Crystal structures of five 6-mercaptopurine derivatives.

The crystal structures of five 6-mercaptopurine derivatives, viz. 2-[(9-acetyl-9H-purin-6-yl)sulfan-yl]-1-(3-meth-oxy-phen-yl)ethan-1-one (1), C16H14N4O3S, 2-[(9-acetyl-9H-purin-6-yl)sulfan-yl]-1-(4-meth-oxy-phen-yl)ethan-1-one (2), C16H14N4O3S, 2-[(9-acetyl-9H-purin-6-yl)sulfan-yl]-1-(4-chloro-phen-yl)ethan-1-one (3), C15H11ClN4O2S, 2-[(9-acetyl-9H-purin-6-yl)sulfan-yl]-1-(4-bromo-phen-yl)ethan-1-one (4), C15H11BrN4O2S, and 1-(3-meth-oxy-phen-yl)-2-[(9H-purin-6-yl)sulfan-yl]ethan-1-one (5), C14H12N4O2S. Compounds (2), (3) and (4) are isomorphous and accordingly their mol-ecular and supra-molecular structures are similar. An analysis of the dihedral angles between the purine and exocyclic phenyl rings show that the mol-ecules of (1) and (5) are essentially planar but that in the case of the three isomorphous compounds (2), (3) and (4), these rings are twisted by a dihedral angle of approximately 38°. With the exception of (1) all mol-ecules are linked by weak C-H⋯O hydrogen bonds in their crystals. There is π-π stacking in all compounds. A Cambridge Structural Database search revealed the existence of 11 deposited compounds containing the 1-phenyl-2-sulfanyl-ethanone scaffold; of these, only eight have a cyclic ring as substituent, the majority of these being heterocycles.

Chemical context

<span class="Chemical">Purines, <span class="Chemical">purine <span class="Chemical">nucleosides and their analogs, are nitro­gen-containing heterocycles ubiquitous in nature and present in biological systems like man, plants and marine organisms (Legraverend, 2008 ▸). These types of heterocycles take part of the core structure of guanine and adenine in nucleic acids (DNA and RNA) being involved in diverse in vivo catabolic and anabolic metabolic pathways.

<span class="Chemical">6-Mercaptopurine is a <span class="Chemical">water insoluble <span class="Chemical">purine analogue, which attracted attention due to its anti­tumor and immunosuppressive properties. The drug is used, among others, in the treatment of rheumathologic disorders, cancer and prevention of rejection of organ transplantation. The main problem associated with the pharmacological treatment with 6-mercaptopurine is the low bioavailability of the oral absorption and the short half-life in plasma. Strategies that have been adopted to circumvent those problems include the administration of 6-mercaptopurine analogues that act as prodrugs or by the chemical protection of the thiol group.

Chemically, the <span class="Chemical">6-mercaptopurine scaffold can also be modulated by an appropriate selection of the substituents that can be located at C-2, N-1, C-6, N-3, C-8, N-7 and N-9 positions, generating a variety of derivatives with potential biological applications (Legraverend & Grierson, 2006 ▸; Tunçbilek, et al., 2009 ▸).

Within this framework, the goal of this project has been focused on the functionalization of <span class="Chemical">6-mercapto purinen> at positions 6 and 9. Here we describe the syntheses and characterization of five <span class="Chemical">6-mercaptopurine derivatives: 2-[(9-acetyl-9H-purin-6-yl)sulfan­yl]-1-(3-meth­oxy­phen­yl)ethan-1-one (1), 2-[(9-acetyl-9H-purin-6-yl)sulfan­yl]-1-(4-meth­oxy­phen­yl)ethan-1-one (2), 2-[(9-acetyl-9H-purin-6-yl)sulfan­yl]-1-(4-chloro­phen­yl)ethan-1-one (3), 2-[(9-acetyl-9H-purin-6-yl)sulf­an­yl]-1-(4-<span class="Chemical">bromo­phen­yl)ethan-1-one (4) and 1-(3-meth­oxy­phen­yl)-2-[(9H-purin-6-yl)sulfan­yl]ethan-1-one (5).

Structural commentary

Compounds (1)–(5) are shown in the scheme and their ellipsoid plots are shown in Figs. 1 ▸–5 ▸ ▸ ▸ ▸. Compounds (1) and (5) have similar a and c axes and (2), (3) and (4) are isostructural and isomorphous.

Figure 1

A view of the asymmetric unit of (1), with displacement ellipsoids are drawn at the 70% probability level.

Figure 2

A view of the asymmetric unit of (2), with displacement ellipsoids are drawn at the 70% probability level.

Figure 3

A view of the asymmetric unit of (3), with displacement ellipsoids are drawn at the 70% probability level.

Figure 4

A view of the asymmetric unit of (4), with displacement ellipsoids are drawn at the 70% probability level.

Figure 5

A view of the asymmetric unit of (5), with displacement ellipsoids are drawn at the 70% probability level.

These compounds can be envisaged as two building blocks, a substituted phenyl­<span class="Chemical">ethanonen> grouping and a substituted <span class="Chemical">6-mercaptopurine moiety, bonded together by the <span class="Chemical">mercapto ethanone residue. Since both purine and phenyl rings are essentially planar, the structural conformations of those compounds are conditioned by the –SCH2CO spacer (Fig. 6 ▸) which permits rotations around the following bonds: Pu—S6, S6—C61, C61—C62 and C62—Ph bonds. The sp 3 character of the central carbon atom may also direct the relative positions of the aceto­phenone residue out of the main plane constituted by the mercaptopurine, which is not the case of the present compounds. Selected geometric parameters for compounds (1)–(5) are given in Tables 1 ▸–5 ▸ ▸ ▸ ▸, respectively.

Figure 6

Diagram of the S–CH2–C(=O)– linkage.

Table 1

Selected geometric parameters (Å, °) for (1)

S6—C6	1.7438 (19)	C61—C62	1.520 (3)
S6—C61	1.8017 (18)	C62—C631	1.491 (3)
C6—S6—C61	100.76 (9)
C6—S6—C61—C62	−178.05 (13)	S6—C61—C62—C631	−172.56 (14)
S6—C61—C62—O6	8.5 (2)

Table 2

Selected geometric parameters (Å, °) for (2)

S6—C6	1.741 (3)	C61—C62	1.510 (4)
S6—C61	1.807 (3)	C62—C631	1.474 (3)
C6—S6—C61	100.88 (12)
C6—S6—C61—C62	170.8 (2)	S6—C61—C62—C631	175.8 (2)
S6—C61—C62—O6	−7.7 (3)

Table 3

Selected geometric parameters (Å, °) for (3)

S6—C6	1.7446 (18)	C61—C62	1.513 (2)
S6—C61	1.8038 (17)	C62—C631	1.493 (2)
C6—S6—C61	100.50 (8)
C6—S6—C61—C62	177.77 (12)	S6—C61—C62—C631	177.32 (12)
S6—C61—C62—O6	−4.5 (2)

Table 4

Selected geometric parameters (Å, °) for (4)

S6—C6	1.755 (3)	C61—C62	1.528 (4)
S6—C61	1.812 (3)	C62—C631	1.496 (4)
C6—S6—C61	100.33 (15)
C6—S6—C61—C62	−177.8 (2)	S6—C61—C62—C631	−178.1 (2)
S6—C61—C62—O6	3.2 (4)

Table 5

Selected geometric parameters (Å, °) for (5)

S6—C6	1.7477 (12)	C61—C62	1.5162 (16)
S6—C61	1.8109 (13)	C62—C631	1.4887 (17)
C6—S6—C61	100.77 (6)
C6—S6—C61—C62	179.54 (8)	S6—C61—C62—C631	−175.65 (9)
S6—C61—C62—O6	5.56 (14)

The Pu—S6 bond tends to be coplanar with the <span class="Chemical">purinen> residue. In fact, the <span class="Chemical">6-mercaptopurine itself may appear in the <span class="Chemical">thione form, e.g. 3,7-di­hydro­purine-6-thione, as a consequence of the high degree of electron delocalization within the 6-mercaptopurine environment. The tendency for the Pu—S6 bond to assume partial double-bond character is also seen in the present compounds, for which the corresponding Pu—S6 bond lengths lie between 1.741 (3) Å for (2) and 1.755 (3) Å for (4). In contrast, the S6—C61 bond lengths are longer, with values lying between 1.8017 (18) Å in (1) and 1.812 (3) Å in (4). This bond can also be bent with respect to the main mercaptopurine plane. The degree of bending may be evaluated by the distance of the C62 carbon atom from the mean plane consisting of the mercapto­pyrimidine atoms. Those values [0.307 (3), 0.272 (4), 0.333 (2), 0.332 (4) and 0.164 (2) for (1)–(5), respectively] show that the degree of bending is higher in (1)–(4) than in (5). As regards the ethanone group, the C61—C62 bond lengths lie in the range 1.510 (4) Å (2) to 1.528 (4) Å, (4) and are normal for a Csp 3—Csp 3 bond while the C62—Ph bond lengths are shorter and lie in the range 1.474 (3) Å (2) to 1.496 (4) (4), suggesting that the electron density is delocalized from the phenyl ring.

The dihedral angles between the mean planes of the of the <span class="Chemical">purine and phenyl ring, θ1, those between the mean plane of the <span class="Chemical">purine ring and the plane defined by the S6—C61—C62—O6 atoms, θ2, and those between the mean planes of the phenyl ring and the plane defined by the S6—C61—C62—O6 atoms, θ3 are given in Table 6 ▸. These values show that the mol­ecules of (1) and (5) are essentially planar. However, in the case of the three isomorphous compounds (2), (3) and (4), the <span class="Chemical">purine and exocyclic phenyl rings are both twisted in the opposite direction from the plane of the bridging unit, resulting in a dihedral angle of approximately 38°. This is due to the rotations and bending around the bonds connecting the bridging unit to the purine and exocyclic phenyl rings as discussed above. The dihedral angles θ2 are higher than θ3; the former are mainly due to the rotations around the S6—C61 bond while the latter are mainly the result of the bending of the C62—Ph bond.

Table 6

Selected dihedral angles (°)

θ1 is the dihedral angle between the mean planes of the purine and phenyl rings and the phenyl ring. θ2 is the dihedral angles between the mean planes of the purine ring and the plane defined by the S6/C61/C62/O6 atoms. θ3 is the dihedral angle between the mean planes of the phenyl ring and the plane defined by the S6/C61/C62/O6 atoms.

Compound	θ1°	θ2°	θ3°
(1)	2.95 (7)	8.45 (8)	5.87 (9)
(2)	38.89 (9)	17.05 (12)	22.72 (13)
(3)	38.67 (6)	14.23 (8)	27.82 (8)
(4)	37.11 (10)	13.58 (13)	26.82 (14)
(5)	4.74 (5)	5.30 (5)	3.42 (8)

The maximum deviations from the mean plane of the S–C–C–O bridging unit are for compounds (1)–(5) are 0.0457 (13), −0.041 (2), −0.023 (11), −0.017 (2) and 0.0302 (8) Å respectively. In all cases it is atom C42 which shows the maximum deviation.

Supra­molecular features

There are no weak C—H⋯O or C—H⋯N contacts in (1). <span class="Chemical">Hydrogenn> bonds for (2)–(5) are listed in Tables 7 ▸–10 ▸ ▸ ▸, respectively. Since (2), (3) and (4) are isomorphous, their supra­molecular structures follow similar patterns. Accordingly, hydrogen-bonding diagrams are given for (2) only. Atom C8 acts as a donor to O9 (−x − 1, −y + 1, −z + 1), via H8 forming an (10) centrosymmetric dimer across the inversion centre at (−1/2, 1/2, 1/2), Fig. 7 ▸. Atom C61 makes a <span class="Chemical">hydrogen bond with O6 (−x + 1, y + , −z + ), via H61A, forming a C4 chain, which runs parallel to the b axis, Fig. 8 ▸, generated by the twofold screw axis at (1/2, y, 1/4). In (2), there is a short contact between C6 and the 4-meth­oxy atom O64 (−x + 2, y + , −z + ), forming a C12 chain, Fig. 9 ▸, which runs parallel to the b axis and is generated by the twofold screw axis at (1, y, ). In (5), the N9—H9⋯N9 (x − , −y + , z − ) hydrogen bond, Fig. 10 ▸, links the mol­ecules into a C4 chain which runs parallel to [01] and which is generated by the n-glide plane at (0, , 0).

Table 7

Hydrogen-bond geometry (Å, °) for (2)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O64i	0.95	2.48	3.375 (3)	157
C8—H8⋯O9ii	0.95	2.37	3.319 (3)	178
C61—H61A⋯O6iii	0.99	2.33	3.269 (3)	159

Symmetry codes: (i) ; (ii) ; (iii) .

Table 8

Hydrogen-bond geometry (Å, °) for (3)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O9i	0.95	2.31	3.262 (2)	176
C61—H61A⋯O6ii	0.99	2.40	3.354 (2)	162

Symmetry codes: (i) ; (ii) .

Table 9

Hydrogen-bond geometry (Å, °) for (4)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O9i	0.95	2.42	3.367 (4)	177
C61—H61B⋯O6ii	0.99	2.45	3.396 (4)	160

Symmetry codes: (i) ; (ii) .

Table 10

Hydrogen-bond geometry (Å, °) for (5)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N9—H9⋯N7i	0.88	1.90	2.7715 (14)	171

Symmetry code: (i) .

Figure 7

Compound (2): view of the C8—H8⋯O9 centrosymetric (16) ring structure centred on (−½, ½, −½). Symmetry code: (i) −x − 1, −y + 1, −z + 1. H atoms not involved in the hydrogen bonding are omitted.

Figure 8

Compound (2): the simple C4 chain formed by the C61—H61A⋯O6 weak hydrogen bond. This chain extends along the b axis and is generated by the twofold screw axis at (, y, ). Symmetry codes: (i) −x + 1, y + , −z + ; (ii) −x + 1, y − , −z + . H atoms not involved in the hydrogen bonding are omitted.

Figure 9

Compound (2): the simple C12 chain formed by the C2—H2⋯O64 weak hydrogen bond. This chain extends along the b axis and is generated by the twofold screw-axis at (1, y, ). Symmetry codes: (i) −x + 2, y + , −z + ; (ii) −x + 2, y − , −z + . H atoms not involved in the hydrogen bonding are omitted.

Figure 10

Compound (5): the simple C4 chain formed by the N9—H9⋯O64 weak hydrogen bond. This chain extends along the b axis and is generated by the n-glide plane at (0, , 0). Symmetry codes: (i) x − , −y + , −z − ; (ii) x − , −y + , −z + . H atoms not involved in the hydrogen bonding are omitted.

Since those compounds have three rings, the <span class="Chemical">imidazole ring (with centroid Cg1), the <span class="Chemical">pyrimidine ring (with centroid Cg2) and the benzyl ring (with centroid Cg3), it would be expected that π–π contacts were part of the supra­molecular structure. Table 11 ▸ lists the possible π–π contacts for (1)–(5). As may be seen in the Table, the <span class="Chemical">pyrimidine ring establishes π–π contacts with the benzyl ring for all compounds. In (1), two mol­ecules centrosymmetrically related across the inversion centre at (0, ½, ½) are involved in π–π stacking in which the purine ring stacks above the exocyclic phenyl ring. In (2), (3) and (4), the π–π stacking is between imidazole rings while in (1) and (5), the contact is between an imidazole ring and a benzyl ring. In particular, in (1) and (5) two mol­ecules centrosymmetrically related across the centre of symmetry at (0, ½, ½) are involved in π–π stacking in which the purine rings stack above the exocyclic phenyl ring, Table 11 ▸.

Table 11

Selected π–π contacts (Å, °)

CgI(J) is plane I(J); Cg⋯Cg is the distance between ring centroids; α is the dihedral angle between planes I and J; CgI perp is the perpendicular distance of Cg(I) on ring J; CgJ perp is the perpendicular distance of Cg(J) on ring I; Slippage is the distance between Cg(I) and the perpendicular projection of Cg(J) on ring I. Plane 1 is through the imadazole ring, plane 2 the pyrimidine ring and plane 3 the exocyclic benzene ring.

Compound	CgI	CgJ	Cg⋯Cg	α	CgI perp	CgJ perp	Slippage
(1)	Cg1	Cg3(−x, 1 − y, 1 − z)	3.6923 (14)	2.62 (12)	3.4547 (9)	−3.3985 (9)
	Cg2	Cg3(−x, 1 − y, 1 − z)	3.6019 (12)	3.26 (11)	−3.3477 (9)	−3.4071 (9)
(2)	Cg1	Cg1(−x, 1 − y, −z)	3.8561 (16)	0.00 (15)	3.3156 (11)	3.3156 (11)	1.969
	Cg2	Cg3(1 − x,  + y,  − z)	3.8270 (16)	0.80 (12)	−3.2463 (10)	−3.2391 (11)
(3)	Cg1	Cg1(−x, 1 − y, −z)	3.7799 (11)	0	3.2016 (7)	3.2016 (7)	2.009
	Cg2	Cg3(1 − x,  + y,  − z)	4.0620 (10)	6.70 (8)	−3.4438 (7)	−3.1708 (7)
(4)	Cg1	Cg1(1 − x, 1 − y, 1 − z)	3.8319 (18)	0.04 (18)	3.1987 (13)	3.1987 (13)	2.110
	Cg2	Cg3(1 − x,  + y,  − z)	4.1601 (18)	6.27 (15)	−3.4328 (12)	−3.1701 (13)
(5)	Cg1	Cg3(−x, 1 − y, 1 − z)	3.6359 (8)	5.35 (7)	−3.4757 (5)	−3.4162 (5)
	Cg2	Cg3(−x, 1 − y, 1 − z)	3.5204 (8)	4.43 (6)	−3.3669 (5)	−3.4160 (5)

Database survey

A search made in the Cam<span class="Chemical">bridge Structural Database (Groom & Allen, 2014 ▸) revealed the existence of 11 deposited compounds containing the 2-thio-1-phenyl­<span class="Chemical">ethanone scaffold (see supplementary Figure). Of those, only eight have a cyclic ring as substituent, the majority of these being heterocycles: MUCCUJ: 2-(1,3-benzoxazol-2-ylsulfan­yl)-1-phenyl­<span class="Chemical">ethanone (Loghmani-Khouzani et al., 2009a ▸); NENFAO: 3-(benzoyl­methyl­thio)-1,5-diphenyl-1H-1,2,4-triazole (Liu et al., 2006 ▸); PUFGED: 2-(1,3-benzo­thia­zol-2-ylsulfan­yl)-1-phenyl­ethan­one (Loghmani-Khouzani et al., 2009b ▸); IKAXOI: 6-cyclohexyl­methyl-5-ethyl-2-[(2-oxo-2-phenyl­eth­yl)sulfan­yl]pyrimidin-4(3H)-οne (Yan et al., 2011 ▸); SILGAW: 2-(benzoylmethyl­sulfan­yl)-6-benzyl-5-iso­propyl­pyrimidin-4(3H)-one (Rao et al., 2007 ▸); ETEWOP: 2-(benzoyl­methyl­sulphan­yl)-6-meth­oxy-1H-benzamide (Lynch & McLenaghan, 2004 ▸); XEBWEI: 2-(1,3-benzimidazolol-2-ylsulfan­yl)phenyl­ethan­one (Abdel-Aziz et al., 2012 ▸); UGITUA: 2-[(4-meth­oxy­benz­yl)sulfan­yl]-1-phenyl­ethanone (Heravi et al., 2009 ▸).

The R—S bond distances for these compounds are similar to those of the studied compounds and they assume a partial double-bond character with the exception of UGITUA where the S atom is bonded to a phenyl ring, suggesting a tendency for delocalization of the electron density through the <span class="Chemical">sulfurn> atom when the ring has heteroatoms. The S—<span class="Chemical">CH2 bond distances vary between 1.80 and 1.81 Å with exception of SILGAW (1.79 Å) and ETEWOP (1.82 Å). The supplementary figure also gives information about the distances of the –<span class="Chemical">CH2– carbon atom to the best plane made up of the atoms of the heterocycles (CH2– distance). These values were computed in order to evaluate the degree of bending of the S—CH2 bond with respect to the main plane of the substituted rings. There are two main groups of compounds, one in which the distance is shorter than 0.3 Å and the other, which contains the CNH fragment in the heterocyclic ring, in which this distance is greater than 1.2 Å. As noted above, the sp 3 character of the β-carbon atom of the ethanone fragment may also direct the relative positions of the aceto­phenone residue out of the main plane constituted by the substituted heteroaromatic ring. This is the case for SILGAW and IKAXOI. Thus, despite the small sample size, there is a wide range of adopted conformations.

Synthesis and crystallization

The <span class="Chemical">6-mercaptopurine derivatives (1)–(5) were obtained in moderate yields by a two-step synthetic strategy. Firstly, <span class="Chemical">6-mercaptopurine was alkyl­ated using diverse mono<span class="Chemical">bromide aceto­phenone derivatives in DMF/potassium carbonate medium at room temperature (Lambertucci, et al. 2009 ▸). After thiol alkyl­ation, the purine nucleus was acyl­ated in position 9 with acetic anhydride in tri­ethyl­amine and anhydrous DMF for (1)–(4) under an argon atmosphere at room temperature (Masai, et al. 2002 ▸). All compounds were recrystallized from di­chloro­methane solution: 2-[(9-acetyl-9H-purin-6-yl)sulfan­yl]-1-(3-meth­oxy­phen­yl)ethan-1-one (1): overall yield: 48%; m.p. 432–435 K; 2-[(9-acetyl-9H-purin-6-yl)sulfan­yl]-1-(4-meth­oxy­phen­yl)ethan-1-one (2): overall yield: 17%; m.p. 460–463 K; 2-[(9-acetyl-9H-purin-6-yl)sulfan­yl]-1-(4-chloro­phen­yl)ethan-1-one (3): overall yield: 26%; m.p. 453–457 K; 2-[(9-acetyl-9H-purin-6-yl)sulfan­yl]-1-(4-bromo­phen­yl)ethan-1-one (4): overall yield: 10%; m.p. 449–451 K; 1-(3-meth­oxy­phen­yl)-2-[(9H-purin-6-yl)sulfan­yl]ethan-1-one (5): overall yield: 55%; m.p. 461–464 K.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 12 ▸. H atoms were treated as riding atoms with C—H(aromatic), 0.95 Å, with U iso = 1.2U <span class="Chemical">eqn>(C), C—<span class="Chemical">H2(methyl­ene), 0.99 Å, with U iso = 1.2U <span class="Chemical">eq(C),C—H(meth­yl) 0.98 Å with U iso = 1.5U eq(C) and in (5) only, N—H, 0.88 Å, with U iso = 1.2U eq(C). The positions of the methyl groups were checked on a final difference map as was that of the N—H hydrogen atom in (5). In (4), the high difference map peaks were associated with the Br atom.

Crystal structure: contains datablock(s) 1, 2, 3, 4, 5, global. DOI: 10.1107/S2056989016001833/hb7562sup1.cif

Structure factors: contains datablock(s) 1. DOI: 10.1107/S2056989016001833/hb75621sup2.hkl

Structure factors: contains datablock(s) 2. DOI: 10.1107/S2056989016001833/hb75622sup3.hkl

Structure factors: contains datablock(s) 3. DOI: 10.1107/S2056989016001833/hb75623sup4.hkl

Structure factors: contains datablock(s) 4. DOI: 10.1107/S2056989016001833/hb75624sup5.hkl

Structure factors: contains datablock(s) 5. DOI: 10.1107/S2056989016001833/hb75625sup6.hkl

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Supporting information file. DOI: 10.1107/S2056989016001833/hb75621sup7.cml

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Supporting information file. DOI: 10.1107/S2056989016001833/hb75622sup8.cml

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Supporting information file. DOI: 10.1107/S2056989016001833/hb75623sup9.cml

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Supporting information file. DOI: 10.1107/S2056989016001833/hb75624sup10.cml

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Supporting information file. DOI: 10.1107/S2056989016001833/hb75625sup11.cml

CCDC references: 1450945, 1450944, 1450943, 1450942, 1450941

Additional supporting information: crystallographic information; 3D view; checkCIF report

C16H14N4O3S	F(000) = 712
Mr = 342.37	Dx = 1.513 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71075 Å
a = 7.6343 (5) Å	Cell parameters from 18327 reflections
b = 26.2356 (18) Å	θ = 2.7–27.5°
c = 8.1332 (5) Å	µ = 0.24 mm−1
β = 112.725 (2)°	T = 100 K
V = 1502.54 (17) Å3	Plate, orange
Z = 4	0.17 × 0.07 × 0.01 mm

Rigaku AFC12 (Right) diffractometer	3450 independent reflections
Radiation source: Rotating Anode	2817 reflections with I > 2σ(I)
Detector resolution: 28.5714 pixels mm-1	Rint = 0.089
profile data from ω–scans	θmax = 27.5°, θmin = 2.8°
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 20112)	h = −9→9
Tmin = 0, Tmax = 1.000	k = −33→34
20144 measured reflections	l = −10→10

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053	H-atom parameters constrained
wR(F2) = 0.148	w = 1/[σ2(Fo2) + (0.0878P)2 + 0.318P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.002
3450 reflections	Δρmax = 0.81 e Å−3
219 parameters	Δρmin = −0.51 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

	x	y	z	Uiso*/Ueq
S6	0.32576 (7)	0.51901 (2)	0.60919 (6)	0.03400 (17)
O6	0.24518 (19)	0.61509 (5)	0.4576 (2)	0.0421 (4)
O9	0.8227 (2)	0.31676 (6)	1.1619 (2)	0.0427 (4)
O63	−0.20860 (19)	0.72411 (5)	−0.05304 (18)	0.0376 (3)
N1	0.2055 (2)	0.42325 (6)	0.4964 (2)	0.0331 (4)
N3	0.3481 (2)	0.34590 (6)	0.6538 (2)	0.0323 (4)
N7	0.6212 (2)	0.44997 (6)	0.9142 (2)	0.0340 (4)
N9	0.6216 (2)	0.36406 (6)	0.9348 (2)	0.0325 (4)
C2	0.2207 (3)	0.37227 (7)	0.5197 (3)	0.0342 (4)
H2	0.1291	0.3525	0.4292	0.041*
C4	0.4710 (3)	0.37649 (7)	0.7754 (3)	0.0309 (4)
C5	0.4740 (3)	0.42955 (7)	0.7676 (2)	0.0312 (4)
C6	0.3330 (3)	0.45263 (7)	0.6203 (2)	0.0308 (4)
C8	0.7025 (3)	0.41060 (7)	1.0084 (3)	0.0343 (4)
H8	0.8086	0.4132	1.1185	0.041*
C9	0.6911 (3)	0.31650 (7)	1.0206 (3)	0.0344 (4)
C61	0.1558 (3)	0.52851 (7)	0.3849 (2)	0.0321 (4)
H61A	0.1996	0.5115	0.2989	0.039*
H61B	0.0313	0.5139	0.3711	0.039*
C62	0.1376 (3)	0.58558 (7)	0.3504 (3)	0.0322 (4)
C91	0.5932 (3)	0.26954 (7)	0.9240 (3)	0.0396 (5)
H91A	0.6527	0.2394	0.9945	0.059*
H91B	0.6040	0.2678	0.8080	0.059*
H91C	0.4588	0.2707	0.9064	0.059*
C631	−0.0135 (2)	0.60328 (7)	0.1806 (2)	0.0312 (4)
C632	−0.0336 (3)	0.65606 (7)	0.1486 (2)	0.0317 (4)
H632	0.0474	0.6794	0.2332	0.038*
C633	−0.1734 (3)	0.67364 (7)	−0.0084 (3)	0.0328 (4)
C634	−0.2922 (3)	0.63923 (8)	−0.1321 (3)	0.0361 (4)
H634	−0.3883	0.6514	−0.2390	0.043*
C635	−0.2701 (3)	0.58745 (8)	−0.0994 (3)	0.0373 (4)
H635	−0.3502	0.5642	−0.1849	0.045*
C636	−0.1321 (3)	0.56914 (7)	0.0572 (3)	0.0352 (4)
H636	−0.1188	0.5335	0.0798	0.042*
C637	−0.0942 (3)	0.76081 (7)	0.0721 (3)	0.0396 (5)
H63A	0.0390	0.7563	0.0885	0.059*
H63B	−0.1070	0.7561	0.1864	0.059*
H63C	−0.1362	0.7952	0.0271	0.059*

	U11	U22	U33	U12	U13	U23
S6	0.0278 (3)	0.0304 (3)	0.0354 (3)	0.00002 (17)	0.0030 (2)	−0.00035 (17)
O6	0.0327 (7)	0.0341 (7)	0.0442 (8)	−0.0027 (6)	−0.0019 (6)	0.0004 (6)
O9	0.0351 (8)	0.0417 (8)	0.0422 (8)	0.0012 (6)	0.0048 (7)	0.0043 (6)
O63	0.0322 (7)	0.0346 (7)	0.0376 (7)	0.0025 (5)	0.0042 (6)	0.0021 (5)
N1	0.0283 (8)	0.0332 (8)	0.0347 (8)	−0.0007 (6)	0.0088 (6)	−0.0002 (6)
N3	0.0280 (8)	0.0333 (8)	0.0337 (8)	−0.0013 (6)	0.0097 (7)	−0.0008 (6)
N7	0.0244 (8)	0.0361 (8)	0.0368 (9)	−0.0011 (6)	0.0066 (7)	−0.0020 (6)
N9	0.0241 (8)	0.0344 (8)	0.0358 (8)	0.0015 (6)	0.0080 (7)	0.0013 (6)
C2	0.0303 (9)	0.0347 (9)	0.0341 (10)	−0.0021 (7)	0.0087 (8)	−0.0023 (7)
C4	0.0236 (8)	0.0342 (9)	0.0336 (9)	0.0014 (7)	0.0096 (7)	0.0008 (7)
C5	0.0240 (8)	0.0324 (9)	0.0341 (9)	0.0000 (7)	0.0080 (7)	−0.0005 (7)
C6	0.0261 (9)	0.0309 (9)	0.0342 (9)	0.0002 (7)	0.0102 (8)	−0.0010 (7)
C8	0.0246 (8)	0.0378 (10)	0.0366 (10)	−0.0017 (7)	0.0076 (8)	−0.0022 (8)
C9	0.0280 (9)	0.0367 (10)	0.0389 (10)	0.0029 (7)	0.0133 (8)	0.0033 (8)
C61	0.0246 (9)	0.0324 (9)	0.0331 (10)	−0.0005 (7)	0.0041 (7)	0.0007 (7)
C62	0.0245 (8)	0.0342 (9)	0.0344 (9)	−0.0009 (7)	0.0077 (7)	−0.0003 (7)
C91	0.0345 (10)	0.0368 (10)	0.0442 (11)	0.0011 (8)	0.0115 (9)	0.0006 (8)
C631	0.0231 (8)	0.0362 (9)	0.0329 (9)	0.0000 (7)	0.0092 (7)	0.0010 (7)
C632	0.0249 (9)	0.0343 (9)	0.0326 (9)	−0.0007 (7)	0.0076 (7)	−0.0003 (7)
C633	0.0260 (9)	0.0360 (9)	0.0351 (10)	0.0032 (7)	0.0103 (8)	0.0028 (7)
C634	0.0266 (9)	0.0455 (11)	0.0318 (10)	0.0024 (8)	0.0065 (8)	0.0014 (8)
C635	0.0290 (9)	0.0423 (10)	0.0357 (10)	−0.0043 (8)	0.0072 (8)	−0.0058 (8)
C636	0.0301 (9)	0.0349 (9)	0.0374 (10)	−0.0014 (7)	0.0096 (8)	−0.0007 (7)
C637	0.0346 (10)	0.0351 (10)	0.0425 (11)	0.0010 (8)	0.0075 (9)	0.0011 (8)

S6—C6	1.7438 (19)	C61—C62	1.520 (3)
S6—C61	1.8017 (18)	C61—H61A	0.9900
O6—C62	1.217 (2)	C61—H61B	0.9900
O9—C9	1.199 (2)	C62—C631	1.491 (3)
O63—C633	1.372 (2)	C91—H91A	0.9800
O63—C637	1.428 (2)	C91—H91B	0.9800
N1—C6	1.341 (2)	C91—H91C	0.9800
N1—C2	1.350 (2)	C631—C636	1.388 (3)
N3—C4	1.336 (2)	C631—C632	1.407 (3)
N3—C2	1.340 (2)	C632—C633	1.389 (3)
N7—C8	1.293 (2)	C632—H632	0.9500
N7—C5	1.392 (2)	C633—C634	1.395 (3)
N9—C8	1.395 (2)	C634—C635	1.382 (3)
N9—C4	1.399 (2)	C634—H634	0.9500
N9—C9	1.428 (2)	C635—C636	1.388 (3)
C2—H2	0.9500	C635—H635	0.9500
C4—C5	1.394 (3)	C636—H636	0.9500
C5—C6	1.401 (2)	C637—H63A	0.9800
C8—H8	0.9500	C637—H63B	0.9800
C9—C91	1.496 (3)	C637—H63C	0.9800
C6—S6—C61	100.76 (9)	O6—C62—C61	120.45 (17)
C633—O63—C637	117.31 (15)	C631—C62—C61	117.42 (15)
C6—N1—C2	117.76 (16)	C9—C91—H91A	109.5
C4—N3—C2	111.95 (16)	C9—C91—H91B	109.5
C8—N7—C5	104.13 (16)	H91A—C91—H91B	109.5
C8—N9—C4	105.22 (15)	C9—C91—H91C	109.5
C8—N9—C9	122.41 (16)	H91A—C91—H91C	109.5
C4—N9—C9	132.36 (16)	H91B—C91—H91C	109.5
N3—C2—N1	128.47 (17)	C636—C631—C632	120.49 (17)
N3—C2—H2	115.8	C636—C631—C62	121.58 (17)
N1—C2—H2	115.8	C632—C631—C62	117.92 (16)
N3—C4—C5	125.80 (17)	C633—C632—C631	119.17 (17)
N3—C4—N9	129.53 (17)	C633—C632—H632	120.4
C5—C4—N9	104.66 (16)	C631—C632—H632	120.4
N7—C5—C4	111.55 (16)	O63—C633—C632	124.49 (17)
N7—C5—C6	131.72 (17)	O63—C633—C634	115.30 (16)
C4—C5—C6	116.73 (16)	C632—C633—C634	120.20 (17)
N1—C6—C5	119.27 (16)	C635—C634—C633	120.01 (18)
N1—C6—S6	122.38 (14)	C635—C634—H634	120.0
C5—C6—S6	118.31 (14)	C633—C634—H634	120.0
N7—C8—N9	114.43 (17)	C634—C635—C636	120.66 (18)
N7—C8—H8	122.8	C634—C635—H635	119.7
N9—C8—H8	122.8	C636—C635—H635	119.7
O9—C9—N9	118.60 (18)	C631—C636—C635	119.46 (18)
O9—C9—C91	124.84 (18)	C631—C636—H636	120.3
N9—C9—C91	116.55 (17)	C635—C636—H636	120.3
C62—C61—S6	107.55 (12)	O63—C637—H63A	109.5
C62—C61—H61A	110.2	O63—C637—H63B	109.5
S6—C61—H61A	110.2	H63A—C637—H63B	109.5
C62—C61—H61B	110.2	O63—C637—H63C	109.5
S6—C61—H61B	110.2	H63A—C637—H63C	109.5
H61A—C61—H61B	108.5	H63B—C637—H63C	109.5
O6—C62—C631	122.13 (17)
C4—N3—C2—N1	0.3 (3)	C9—N9—C8—N7	−179.35 (18)
C6—N1—C2—N3	0.6 (3)	C8—N9—C9—O9	0.7 (3)
C2—N3—C4—C5	−1.2 (3)	C4—N9—C9—O9	−178.2 (2)
C2—N3—C4—N9	178.84 (19)	C8—N9—C9—C91	−178.60 (18)
C8—N9—C4—N3	179.7 (2)	C4—N9—C9—C91	2.5 (3)
C9—N9—C4—N3	−1.3 (4)	C6—S6—C61—C62	−178.05 (13)
C8—N9—C4—C5	−0.3 (2)	S6—C61—C62—O6	8.5 (2)
C9—N9—C4—C5	178.73 (19)	S6—C61—C62—C631	−172.56 (14)
C8—N7—C5—C4	−0.8 (2)	O6—C62—C631—C636	178.23 (19)
C8—N7—C5—C6	178.5 (2)	C61—C62—C631—C636	−0.7 (3)
N3—C4—C5—N7	−179.29 (18)	O6—C62—C631—C632	−2.1 (3)
N9—C4—C5—N7	0.7 (2)	C61—C62—C631—C632	179.03 (17)
N3—C4—C5—C6	1.3 (3)	C636—C631—C632—C633	−0.2 (3)
N9—C4—C5—C6	−178.75 (16)	C62—C631—C632—C633	−179.87 (17)
C2—N1—C6—C5	−0.5 (3)	C637—O63—C633—C632	−0.7 (3)
C2—N1—C6—S6	−178.35 (15)	C637—O63—C633—C634	178.19 (18)
N7—C5—C6—N1	−179.6 (2)	C631—C632—C633—O63	178.91 (17)
C4—C5—C6—N1	−0.3 (3)	C631—C632—C633—C634	0.1 (3)
N7—C5—C6—S6	−1.6 (3)	O63—C633—C634—C635	−179.39 (18)
C4—C5—C6—S6	177.61 (14)	C632—C633—C634—C635	−0.5 (3)
C61—S6—C6—N1	−12.10 (18)	C633—C634—C635—C636	0.9 (3)
C61—S6—C6—C5	170.02 (16)	C632—C631—C636—C635	0.6 (3)
C5—N7—C8—N9	0.6 (2)	C62—C631—C636—C635	−179.72 (18)
C4—N9—C8—N7	−0.2 (2)	C634—C635—C636—C631	−1.0 (3)

C16H14N4O3S	F(000) = 712
Mr = 342.37	Dx = 1.530 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.9920 (3) Å	Cell parameters from 5825 reflections
b = 9.9795 (5) Å	θ = 2.2–25.0°
c = 24.9907 (13) Å	µ = 0.24 mm−1
β = 95.977 (5)°	T = 100 K
V = 1486.25 (13) Å3	Plate, colourless
Z = 4	0.05 × 0.04 × 0.01 mm

Rigaku AFC12 (Right) diffractometer	2619 independent reflections
Radiation source: Rotating Anode, Rotating Anode	1852 reflections with I > 2σ(I)
Confocal mirrors, HF Varimax monochromator	Rint = 0.106
Detector resolution: 28.5714 pixels mm-1	θmax = 25.0°, θmin = 2.2°
profile data from ω–scans	h = −7→6
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −11→11
Tmin = 0.439, Tmax = 1.000	l = −29→29
15437 measured reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048	H-atom parameters constrained
wR(F2) = 0.116	w = 1/[σ2(Fo2) + (0.0492P)2 + 0.3956P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
2619 reflections	Δρmax = 0.30 e Å−3
219 parameters	Δρmin = −0.36 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

	x	y	z	Uiso*/Ueq
S6	0.34226 (12)	0.45424 (7)	0.33305 (3)	0.0300 (2)
O6	0.6113 (3)	0.30045 (19)	0.27249 (7)	0.0315 (5)
O9	−0.4124 (3)	0.6642 (2)	0.51385 (8)	0.0386 (6)
O64	1.2947 (3)	0.54050 (18)	0.12232 (7)	0.0331 (5)
N1	0.3919 (4)	0.7064 (2)	0.37258 (9)	0.0274 (6)
N3	0.1587 (4)	0.8075 (2)	0.43517 (9)	0.0282 (6)
N7	−0.0486 (4)	0.4737 (2)	0.41015 (9)	0.0295 (6)
N9	−0.1340 (4)	0.6524 (2)	0.45982 (8)	0.0268 (6)
C2	0.3246 (5)	0.8061 (3)	0.40336 (10)	0.0286 (7)
H2	0.4069	0.8873	0.4023	0.034*
C4	0.0500 (4)	0.6901 (3)	0.43323 (10)	0.0260 (7)
C5	0.0983 (4)	0.5794 (3)	0.40346 (10)	0.0251 (6)
C6	0.2774 (5)	0.5909 (3)	0.37190 (11)	0.0264 (7)
C8	−0.1807 (5)	0.5208 (3)	0.44369 (11)	0.0293 (7)
H8	−0.2989	0.4699	0.4561	0.035*
C9	−0.2672 (5)	0.7242 (3)	0.49399 (11)	0.0316 (7)
C61	0.5465 (5)	0.5280 (3)	0.29356 (11)	0.0296 (7)
H61A	0.4725	0.5938	0.2679	0.036*
H61B	0.6632	0.5752	0.3174	0.036*
C62	0.6521 (5)	0.4179 (3)	0.26328 (10)	0.0265 (7)
C91	−0.2175 (5)	0.8699 (3)	0.50110 (11)	0.0366 (8)
H91A	−0.2266	0.9134	0.4658	0.055*
H91B	−0.0662	0.8814	0.5195	0.055*
H91C	−0.3271	0.9106	0.5226	0.055*
C631	0.8133 (4)	0.4560 (3)	0.22523 (10)	0.0257 (6)
C632	0.9745 (5)	0.3617 (3)	0.21303 (10)	0.0279 (7)
H632	0.9736	0.2748	0.2285	0.033*
C633	1.1329 (5)	0.3927 (3)	0.17933 (10)	0.0278 (7)
H633	1.2425	0.3284	0.1719	0.033*
C634	1.1318 (5)	0.5197 (3)	0.15592 (11)	0.0279 (7)
C635	0.9733 (4)	0.6143 (3)	0.16630 (10)	0.0276 (7)
H635	0.9713	0.6998	0.1496	0.033*
C636	0.8169 (4)	0.5822 (3)	0.20161 (10)	0.0264 (7)
H636	0.7105	0.6477	0.2098	0.032*
C637	1.3246 (5)	0.6732 (3)	0.10294 (12)	0.0362 (8)
H63A	1.4617	0.6770	0.0848	0.054*
H63B	1.3370	0.7360	0.1332	0.054*
H63C	1.1955	0.6977	0.0775	0.054*

	U11	U22	U33	U12	U13	U23
S6	0.0341 (4)	0.0194 (4)	0.0394 (4)	−0.0023 (3)	0.0176 (3)	−0.0022 (3)
O6	0.0380 (12)	0.0199 (12)	0.0388 (11)	−0.0023 (9)	0.0149 (10)	0.0002 (9)
O9	0.0413 (12)	0.0305 (13)	0.0479 (13)	−0.0035 (10)	0.0236 (11)	−0.0003 (10)
O64	0.0377 (12)	0.0206 (12)	0.0448 (12)	0.0004 (9)	0.0228 (10)	0.0014 (9)
N1	0.0290 (13)	0.0206 (14)	0.0340 (13)	−0.0009 (11)	0.0105 (11)	0.0005 (11)
N3	0.0297 (13)	0.0230 (14)	0.0333 (13)	−0.0040 (11)	0.0107 (11)	−0.0009 (10)
N7	0.0326 (14)	0.0206 (14)	0.0372 (13)	−0.0017 (11)	0.0128 (12)	0.0014 (11)
N9	0.0278 (13)	0.0205 (14)	0.0340 (13)	0.0006 (10)	0.0119 (11)	0.0012 (11)
C2	0.0292 (16)	0.0226 (17)	0.0352 (16)	−0.0051 (13)	0.0087 (14)	−0.0006 (13)
C4	0.0273 (16)	0.0251 (17)	0.0267 (15)	−0.0001 (13)	0.0081 (13)	0.0030 (12)
C5	0.0237 (14)	0.0217 (17)	0.0311 (15)	−0.0002 (12)	0.0091 (13)	0.0011 (12)
C6	0.0293 (15)	0.0223 (17)	0.0286 (15)	0.0013 (13)	0.0068 (13)	0.0007 (12)
C8	0.0279 (15)	0.0247 (18)	0.0366 (16)	−0.0026 (13)	0.0101 (14)	0.0031 (13)
C9	0.0320 (16)	0.0287 (18)	0.0358 (16)	0.0032 (14)	0.0116 (14)	0.0017 (13)
C61	0.0370 (17)	0.0208 (17)	0.0336 (16)	0.0006 (13)	0.0160 (14)	0.0024 (12)
C62	0.0305 (16)	0.0195 (17)	0.0296 (15)	0.0010 (13)	0.0030 (13)	−0.0020 (12)
C91	0.0425 (18)	0.0283 (18)	0.0421 (17)	−0.0003 (14)	0.0190 (16)	−0.0020 (14)
C631	0.0272 (15)	0.0210 (16)	0.0298 (15)	−0.0028 (12)	0.0066 (13)	−0.0049 (12)
C632	0.0360 (17)	0.0178 (16)	0.0303 (15)	−0.0002 (13)	0.0054 (14)	−0.0028 (12)
C633	0.0303 (15)	0.0197 (16)	0.0344 (15)	0.0056 (12)	0.0083 (14)	−0.0031 (13)
C634	0.0310 (16)	0.0236 (17)	0.0302 (15)	−0.0045 (13)	0.0090 (13)	−0.0033 (12)
C635	0.0316 (16)	0.0188 (16)	0.0338 (16)	−0.0006 (13)	0.0105 (14)	0.0011 (12)
C636	0.0271 (15)	0.0170 (16)	0.0362 (16)	0.0009 (12)	0.0091 (13)	−0.0033 (12)
C637	0.0448 (19)	0.0243 (17)	0.0430 (18)	−0.0049 (14)	0.0218 (16)	0.0008 (14)

S6—C6	1.741 (3)	C61—C62	1.510 (4)
S6—C61	1.807 (3)	C61—H61A	0.9900
O6—C62	1.224 (3)	C61—H61B	0.9900
O9—C9	1.206 (3)	C62—C631	1.474 (3)
O64—C634	1.368 (3)	C91—H91A	0.9800
O64—C637	1.428 (3)	C91—H91B	0.9800
N1—C6	1.340 (3)	C91—H91C	0.9800
N1—C2	1.345 (3)	C631—C636	1.393 (4)
N3—C2	1.336 (3)	C631—C632	1.404 (4)
N3—C4	1.339 (3)	C632—C633	1.368 (4)
N7—C8	1.299 (3)	C632—H632	0.9500
N7—C5	1.395 (3)	C633—C634	1.395 (4)
N9—C8	1.394 (3)	C633—H633	0.9500
N9—C4	1.396 (3)	C634—C635	1.383 (4)
N9—C9	1.422 (3)	C635—C636	1.389 (3)
C2—H2	0.9500	C635—H635	0.9500
C4—C5	1.379 (4)	C636—H636	0.9500
C5—C6	1.401 (4)	C637—H63A	0.9800
C8—H8	0.9500	C637—H63B	0.9800
C9—C91	1.491 (4)	C637—H63C	0.9800
C6—S6—C61	100.88 (12)	O6—C62—C61	120.0 (2)
C634—O64—C637	118.2 (2)	C631—C62—C61	118.2 (2)
C6—N1—C2	117.4 (2)	C9—C91—H91A	109.5
C2—N3—C4	111.0 (2)	C9—C91—H91B	109.5
C8—N7—C5	103.8 (2)	H91A—C91—H91B	109.5
C8—N9—C4	105.1 (2)	C9—C91—H91C	109.5
C8—N9—C9	122.7 (2)	H91A—C91—H91C	109.5
C4—N9—C9	132.1 (2)	H91B—C91—H91C	109.5
N3—C2—N1	129.3 (3)	C636—C631—C632	118.2 (2)
N3—C2—H2	115.3	C636—C631—C62	123.1 (2)
N1—C2—H2	115.3	C632—C631—C62	118.6 (2)
N3—C4—C5	126.3 (2)	C633—C632—C631	121.3 (3)
N3—C4—N9	128.6 (2)	C633—C632—H632	119.4
C5—C4—N9	105.2 (2)	C631—C632—H632	119.4
C4—C5—N7	111.7 (2)	C632—C633—C634	119.3 (2)
C4—C5—C6	117.0 (2)	C632—C633—H633	120.3
N7—C5—C6	131.2 (2)	C634—C633—H633	120.3
N1—C6—C5	119.0 (2)	O64—C634—C635	124.0 (2)
N1—C6—S6	122.46 (19)	O64—C634—C633	115.0 (2)
C5—C6—S6	118.6 (2)	C635—C634—C633	121.0 (2)
N7—C8—N9	114.2 (2)	C634—C635—C636	118.9 (3)
N7—C8—H8	122.9	C634—C635—H635	120.5
N9—C8—H8	122.9	C636—C635—H635	120.5
O9—C9—N9	118.1 (3)	C635—C636—C631	121.2 (2)
O9—C9—C91	125.4 (2)	C635—C636—H636	119.4
N9—C9—C91	116.5 (2)	C631—C636—H636	119.4
C62—C61—S6	108.70 (19)	O64—C637—H63A	109.5
C62—C61—H61A	109.9	O64—C637—H63B	109.5
S6—C61—H61A	109.9	H63A—C637—H63B	109.5
C62—C61—H61B	109.9	O64—C637—H63C	109.5
S6—C61—H61B	109.9	H63A—C637—H63C	109.5
H61A—C61—H61B	108.3	H63B—C637—H63C	109.5
O6—C62—C631	121.7 (2)
C4—N3—C2—N1	−1.2 (4)	C9—N9—C8—N7	176.4 (2)
C6—N1—C2—N3	1.4 (4)	C8—N9—C9—O9	7.5 (4)
C2—N3—C4—C5	0.7 (4)	C4—N9—C9—O9	−176.6 (3)
C2—N3—C4—N9	−179.0 (3)	C8—N9—C9—C91	−171.1 (3)
C8—N9—C4—N3	179.8 (3)	C4—N9—C9—C91	4.8 (4)
C9—N9—C4—N3	3.4 (5)	C6—S6—C61—C62	170.8 (2)
C8—N9—C4—C5	0.1 (3)	S6—C61—C62—O6	−7.7 (3)
C9—N9—C4—C5	−176.3 (3)	S6—C61—C62—C631	175.8 (2)
N3—C4—C5—N7	−179.5 (3)	O6—C62—C631—C636	160.4 (3)
N9—C4—C5—N7	0.2 (3)	C61—C62—C631—C636	−23.1 (4)
N3—C4—C5—C6	−0.4 (4)	O6—C62—C631—C632	−21.1 (4)
N9—C4—C5—C6	179.3 (2)	C61—C62—C631—C632	155.4 (3)
C8—N7—C5—C4	−0.5 (3)	C636—C631—C632—C633	0.7 (4)
C8—N7—C5—C6	−179.4 (3)	C62—C631—C632—C633	−177.9 (3)
C2—N1—C6—C5	−0.9 (4)	C631—C632—C633—C634	−1.1 (4)
C2—N1—C6—S6	178.9 (2)	C637—O64—C634—C635	9.6 (4)
C4—C5—C6—N1	0.5 (4)	C637—O64—C634—C633	−171.3 (2)
N7—C5—C6—N1	179.4 (3)	C632—C633—C634—O64	−179.2 (2)
C4—C5—C6—S6	−179.3 (2)	C632—C633—C634—C635	0.0 (4)
N7—C5—C6—S6	−0.4 (4)	O64—C634—C635—C636	−179.4 (2)
C61—S6—C6—N1	−8.5 (3)	C633—C634—C635—C636	1.5 (4)
C61—S6—C6—C5	171.3 (2)	C634—C635—C636—C631	−1.9 (4)
C5—N7—C8—N9	0.6 (3)	C632—C631—C636—C635	0.9 (4)
C4—N9—C8—N7	−0.5 (3)	C62—C631—C636—C635	179.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O64i	0.95	2.48	3.375 (3)	157
C8—H8···O9ii	0.95	2.37	3.319 (3)	178
C61—H61A···O6iii	0.99	2.33	3.269 (3)	159

C15H11ClN4O2S	F(000) = 712
Mr = 346.79	Dx = 1.603 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71075 Å
a = 5.9900 (4) Å	Cell parameters from 16488 reflections
b = 9.9169 (7) Å	θ = 2.5–27.5°
c = 24.3238 (17) Å	µ = 0.43 mm−1
β = 96.072 (2)°	T = 100 K
V = 1436.78 (17) Å3	Plate, yellow
Z = 4	0.13 × 0.06 × 0.01 mm

Rigaku AFC12 (Right) diffractometer	3291 independent reflections
Radiation source: Rotating Anode	2677 reflections with I > 2σ(I)
Detector resolution: 28.5714 pixels mm-1	Rint = 0.050
profile data from ω–scans	θmax = 27.5°, θmin = 2.7°
Absorption correction: multi-scan CrystalClear-SM Expert (Rigaku, 20112)	h = −7→7
Tmin = 0.809, Tmax = 1.000	k = −12→12
18353 measured reflections	l = −31→31

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035	H-atom parameters constrained
wR(F2) = 0.092	w = 1/[σ2(Fo2) + (0.0466P)2 + 0.5802P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.001
3291 reflections	Δρmax = 0.34 e Å−3
209 parameters	Δρmin = −0.22 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

	x	y	z	Uiso*/Ueq
Cl64	1.32087 (7)	0.64277 (5)	0.10411 (2)	0.02661 (13)
S6	0.38690 (7)	0.47381 (4)	0.33773 (2)	0.02313 (12)
O6	0.6478 (2)	0.33342 (12)	0.26796 (5)	0.0267 (3)
O9	−0.4321 (2)	0.65965 (14)	0.51215 (6)	0.0325 (3)
N1	0.3921 (2)	0.73219 (15)	0.37483 (6)	0.0219 (3)
N3	0.1372 (2)	0.82388 (15)	0.43621 (6)	0.0227 (3)
N7	−0.0233 (2)	0.47859 (16)	0.41129 (6)	0.0242 (3)
N9	−0.1394 (2)	0.65498 (15)	0.46015 (6)	0.0223 (3)
C2	0.3079 (3)	0.82958 (18)	0.40503 (7)	0.0235 (4)
H2	0.3800	0.9148	0.4041	0.028*
C4	0.0447 (3)	0.70149 (19)	0.43464 (7)	0.0210 (3)
C5	0.1118 (3)	0.59112 (18)	0.40522 (7)	0.0209 (4)
C6	0.2939 (3)	0.61023 (18)	0.37446 (7)	0.0209 (4)
C8	−0.1682 (3)	0.52134 (18)	0.44384 (7)	0.0233 (4)
H8	−0.2836	0.4657	0.4554	0.028*
C9	−0.2805 (3)	0.72219 (19)	0.49567 (7)	0.0247 (4)
C61	0.5765 (3)	0.55799 (18)	0.29613 (7)	0.0231 (4)
H61A	0.4932	0.6245	0.2714	0.028*
H61B	0.6936	0.6065	0.3202	0.028*
C62	0.6837 (3)	0.45309 (18)	0.26215 (7)	0.0215 (4)
C91	−0.2263 (3)	0.8664 (2)	0.50911 (8)	0.0309 (4)
H91A	−0.2262	0.9181	0.4748	0.046*
H91B	−0.0778	0.8721	0.5302	0.046*
H91C	−0.3393	0.9036	0.5312	0.046*
C631	0.8399 (3)	0.50213 (18)	0.22261 (7)	0.0209 (4)
C632	1.0125 (3)	0.41672 (18)	0.20934 (7)	0.0235 (4)
H632	1.0258	0.3290	0.2250	0.028*
C633	1.1644 (3)	0.45870 (19)	0.17350 (7)	0.0238 (4)
H633	1.2840	0.4018	0.1653	0.029*
C634	1.1368 (3)	0.58612 (18)	0.15003 (7)	0.0215 (4)
C635	0.9650 (3)	0.67191 (18)	0.16161 (7)	0.0225 (4)
H635	0.9483	0.7580	0.1445	0.027*
C636	0.8181 (3)	0.63008 (18)	0.19851 (7)	0.0214 (4)
H636	0.7018	0.6887	0.2075	0.026*

	U11	U22	U33	U12	U13	U23
Cl64	0.0226 (2)	0.0260 (2)	0.0333 (2)	0.00033 (17)	0.01226 (17)	−0.00087 (18)
S6	0.0242 (2)	0.0180 (2)	0.0288 (2)	−0.00324 (17)	0.01066 (17)	−0.00245 (17)
O6	0.0289 (7)	0.0185 (7)	0.0338 (7)	−0.0011 (5)	0.0085 (5)	0.0000 (5)
O9	0.0269 (7)	0.0309 (8)	0.0423 (8)	−0.0021 (6)	0.0161 (6)	0.0031 (6)
N1	0.0208 (7)	0.0204 (8)	0.0250 (8)	−0.0025 (6)	0.0051 (6)	−0.0009 (6)
N3	0.0225 (7)	0.0200 (8)	0.0264 (8)	−0.0019 (6)	0.0061 (6)	−0.0013 (6)
N7	0.0215 (7)	0.0220 (8)	0.0300 (8)	−0.0045 (6)	0.0064 (6)	0.0005 (6)
N9	0.0189 (7)	0.0221 (8)	0.0269 (8)	−0.0017 (6)	0.0065 (6)	0.0017 (6)
C2	0.0222 (8)	0.0211 (9)	0.0279 (9)	−0.0047 (7)	0.0062 (7)	−0.0018 (7)
C4	0.0167 (8)	0.0253 (9)	0.0215 (8)	0.0010 (7)	0.0043 (6)	0.0017 (7)
C5	0.0190 (8)	0.0202 (9)	0.0240 (9)	−0.0014 (7)	0.0039 (7)	0.0006 (7)
C6	0.0183 (8)	0.0220 (9)	0.0227 (8)	0.0001 (7)	0.0042 (6)	0.0003 (7)
C8	0.0190 (8)	0.0238 (9)	0.0277 (9)	−0.0027 (7)	0.0046 (7)	0.0032 (7)
C9	0.0204 (8)	0.0272 (10)	0.0273 (9)	0.0006 (7)	0.0063 (7)	0.0018 (7)
C61	0.0255 (9)	0.0184 (9)	0.0270 (9)	−0.0021 (7)	0.0103 (7)	−0.0003 (7)
C62	0.0199 (8)	0.0215 (9)	0.0232 (8)	0.0017 (7)	0.0025 (6)	−0.0008 (7)
C91	0.0274 (9)	0.0307 (11)	0.0366 (11)	−0.0025 (8)	0.0134 (8)	−0.0072 (8)
C631	0.0193 (8)	0.0202 (9)	0.0235 (9)	−0.0001 (7)	0.0045 (7)	−0.0025 (7)
C632	0.0252 (9)	0.0182 (9)	0.0275 (9)	0.0031 (7)	0.0048 (7)	0.0009 (7)
C633	0.0202 (8)	0.0248 (10)	0.0270 (9)	0.0051 (7)	0.0050 (7)	−0.0022 (7)
C634	0.0187 (8)	0.0225 (9)	0.0239 (9)	−0.0017 (7)	0.0058 (7)	−0.0032 (7)
C635	0.0232 (8)	0.0173 (9)	0.0279 (9)	0.0008 (7)	0.0062 (7)	−0.0003 (7)
C636	0.0200 (8)	0.0181 (9)	0.0270 (9)	0.0018 (7)	0.0063 (7)	−0.0030 (7)

Cl64—C634	1.7433 (17)	C9—C91	1.495 (3)
S6—C6	1.7446 (18)	C61—C62	1.513 (2)
S6—C61	1.8038 (17)	C61—H61A	0.9900
O6—C62	1.217 (2)	C61—H61B	0.9900
O9—C9	1.203 (2)	C62—C631	1.493 (2)
N1—C2	1.344 (2)	C91—H91A	0.9800
N1—C6	1.344 (2)	C91—H91B	0.9800
N3—C4	1.333 (2)	C91—H91C	0.9800
N3—C2	1.337 (2)	C631—C636	1.398 (2)
N7—C8	1.306 (2)	C631—C632	1.400 (2)
N7—C5	1.395 (2)	C632—C633	1.389 (2)
N9—C8	1.389 (2)	C632—H632	0.9500
N9—C4	1.400 (2)	C633—C634	1.389 (3)
N9—C9	1.435 (2)	C633—H633	0.9500
C2—H2	0.9500	C634—C635	1.387 (2)
C4—C5	1.390 (2)	C635—C636	1.385 (2)
C5—C6	1.400 (2)	C635—H635	0.9500
C8—H8	0.9500	C636—H636	0.9500
C6—S6—C61	100.50 (8)	S6—C61—H61B	110.0
C2—N1—C6	117.46 (15)	H61A—C61—H61B	108.4
C4—N3—C2	111.27 (15)	O6—C62—C631	121.52 (16)
C8—N7—C5	103.57 (15)	O6—C62—C61	121.13 (16)
C8—N9—C4	105.53 (14)	C631—C62—C61	117.33 (15)
C8—N9—C9	123.49 (15)	C9—C91—H91A	109.5
C4—N9—C9	130.97 (15)	C9—C91—H91B	109.5
N3—C2—N1	129.31 (16)	H91A—C91—H91B	109.5
N3—C2—H2	115.3	C9—C91—H91C	109.5
N1—C2—H2	115.3	H91A—C91—H91C	109.5
N3—C4—C5	126.14 (15)	H91B—C91—H91C	109.5
N3—C4—N9	129.20 (16)	C636—C631—C632	119.40 (16)
C5—C4—N9	104.65 (15)	C636—C631—C62	121.92 (15)
C4—C5—N7	111.89 (15)	C632—C631—C62	118.68 (16)
C4—C5—C6	116.91 (16)	C633—C632—C631	120.80 (17)
N7—C5—C6	131.18 (16)	C633—C632—H632	119.6
N1—C6—C5	118.90 (16)	C631—C632—H632	119.6
N1—C6—S6	122.55 (12)	C632—C633—C634	118.25 (16)
C5—C6—S6	118.54 (13)	C632—C633—H633	120.9
N7—C8—N9	114.35 (15)	C634—C633—H633	120.9
N7—C8—H8	122.8	C635—C634—C633	122.19 (16)
N9—C8—H8	122.8	C635—C634—Cl64	117.76 (14)
O9—C9—N9	118.34 (17)	C633—C634—Cl64	120.05 (13)
O9—C9—C91	125.05 (17)	C636—C635—C634	118.94 (16)
N9—C9—C91	116.61 (15)	C636—C635—H635	120.5
C62—C61—S6	108.47 (12)	C634—C635—H635	120.5
C62—C61—H61A	110.0	C635—C636—C631	120.38 (16)
S6—C61—H61A	110.0	C635—C636—H636	119.8
C62—C61—H61B	110.0	C631—C636—H636	119.8
C4—N3—C2—N1	−0.7 (3)	C4—N9—C8—N7	0.2 (2)
C6—N1—C2—N3	0.7 (3)	C9—N9—C8—N7	179.77 (16)
C2—N3—C4—C5	0.2 (3)	C8—N9—C9—O9	−0.1 (3)
C2—N3—C4—N9	−178.24 (17)	C4—N9—C9—O9	179.26 (18)
C8—N9—C4—N3	178.49 (18)	C8—N9—C9—C91	−179.93 (17)
C9—N9—C4—N3	−1.0 (3)	C4—N9—C9—C91	−0.5 (3)
C8—N9—C4—C5	−0.24 (18)	C6—S6—C61—C62	177.77 (12)
C9—N9—C4—C5	−179.73 (17)	S6—C61—C62—O6	−4.5 (2)
N3—C4—C5—N7	−178.60 (16)	S6—C61—C62—C631	177.32 (12)
N9—C4—C5—N7	0.2 (2)	O6—C62—C631—C636	153.51 (18)
N3—C4—C5—C6	0.2 (3)	C61—C62—C631—C636	−28.3 (2)
N9—C4—C5—C6	178.95 (15)	O6—C62—C631—C632	−26.3 (3)
C8—N7—C5—C4	−0.1 (2)	C61—C62—C631—C632	151.92 (17)
C8—N7—C5—C6	−178.58 (19)	C636—C631—C632—C633	1.3 (3)
C2—N1—C6—C5	−0.1 (2)	C62—C631—C632—C633	−178.87 (16)
C2—N1—C6—S6	−179.32 (13)	C631—C632—C633—C634	−1.7 (3)
C4—C5—C6—N1	−0.2 (2)	C632—C633—C634—C635	0.5 (3)
N7—C5—C6—N1	178.25 (17)	C632—C633—C634—Cl64	−179.20 (13)
C4—C5—C6—S6	179.00 (13)	C633—C634—C635—C636	1.1 (3)
N7—C5—C6—S6	−2.5 (3)	Cl64—C634—C635—C636	−179.18 (13)
C61—S6—C6—N1	−11.73 (17)	C634—C635—C636—C631	−1.5 (3)
C61—S6—C6—C5	169.08 (14)	C632—C631—C636—C635	0.3 (3)
C5—N7—C8—N9	−0.1 (2)	C62—C631—C636—C635	−179.47 (16)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O9i	0.95	2.31	3.262 (2)	176
C61—H61A···O6ii	0.99	2.40	3.354 (2)	162

C15H11BrN4O2S	F(000) = 784
Mr = 391.25	Dx = 1.758 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71075 Å
a = 6.0705 (4) Å	Cell parameters from 18109 reflections
b = 10.0668 (7) Å	θ = 2.5–27.5°
c = 24.3492 (17) Å	µ = 2.94 mm−1
β = 96.580 (2)°	T = 100 K
V = 1478.19 (18) Å3	Plate, colourless
Z = 4	0.15 × 0.10 × 0.02 mm

Rigaku AFC12 (Right) diffractometer	3346 independent reflections
Radiation source: Rotating Anode	2944 reflections with I > 2σ(I)
Detector resolution: 28.5714 pixels mm-1	Rint = 0.064
profile data from ω–scans	θmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan CrystalClear-SM Expert (Rigaku, 20112)	h = −7→7
Tmin = 0.658, Tmax = 1.000	k = −12→13
18171 measured reflections	l = −31→31

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.056	H-atom parameters constrained
wR(F2) = 0.153	w = 1/[σ2(Fo2) + (0.1178P)2 + 0.358P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
3346 reflections	Δρmax = 2.91 e Å−3
209 parameters	Δρmin = −0.92 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

	x	y	z	Uiso*/Ueq
Br64	1.32442 (5)	0.33869 (3)	0.10086 (2)	0.02971 (16)
S6	0.38570 (14)	0.51673 (7)	0.33803 (3)	0.0278 (2)
O6	0.6441 (5)	0.6537 (2)	0.26801 (11)	0.0318 (5)
O9	−0.4299 (5)	0.3392 (2)	0.51161 (11)	0.0357 (6)
N1	0.3870 (5)	0.2608 (3)	0.37506 (10)	0.0267 (5)
N3	0.1320 (5)	0.1721 (2)	0.43630 (12)	0.0279 (6)
N7	−0.0199 (5)	0.5157 (3)	0.41162 (11)	0.0274 (5)
N9	−0.1388 (5)	0.3411 (2)	0.46032 (12)	0.0263 (6)
C2	0.3003 (6)	0.1653 (3)	0.40499 (14)	0.0290 (7)
H2	0.3683	0.0806	0.4038	0.035*
C4	0.0420 (5)	0.2942 (3)	0.43479 (12)	0.0260 (6)
C5	0.1121 (5)	0.4027 (3)	0.40513 (12)	0.0262 (6)
C6	0.2904 (5)	0.3823 (3)	0.37469 (12)	0.0255 (6)
C8	−0.1649 (5)	0.4742 (3)	0.44429 (12)	0.0274 (6)
H8	−0.2771	0.5298	0.4559	0.033*
C9	−0.2823 (5)	0.2762 (3)	0.49460 (13)	0.0279 (6)
C61	0.5714 (5)	0.4314 (3)	0.29665 (13)	0.0278 (6)
H61A	0.6861	0.3827	0.3209	0.033*
H61B	0.4876	0.3666	0.2718	0.033*
C62	0.6802 (5)	0.5351 (3)	0.26272 (12)	0.0267 (6)
C91	−0.2352 (6)	0.1307 (4)	0.50629 (16)	0.0346 (7)
H91A	−0.2341	0.0827	0.4713	0.052*
H91B	−0.3506	0.0937	0.5268	0.052*
H91C	−0.0904	0.1214	0.5283	0.052*
C631	0.8358 (5)	0.4855 (3)	0.22393 (12)	0.0248 (6)
C632	1.0055 (6)	0.5701 (3)	0.20986 (13)	0.0292 (6)
H632	1.0178	0.6572	0.2250	0.035*
C633	1.1556 (5)	0.5285 (3)	0.17420 (13)	0.0282 (6)
H633	1.2725	0.5850	0.1657	0.034*
C634	1.1296 (5)	0.4012 (3)	0.15118 (12)	0.0262 (6)
C635	0.9596 (6)	0.3157 (3)	0.16372 (14)	0.0291 (6)
H635	0.9435	0.2301	0.1473	0.035*
C636	0.8144 (6)	0.3585 (3)	0.20067 (14)	0.0273 (6)
H636	0.7005	0.3009	0.2100	0.033*

	U11	U22	U33	U12	U13	U23
Br64	0.0279 (2)	0.0250 (2)	0.0387 (2)	0.00019 (11)	0.01488 (15)	0.00074 (10)
S6	0.0299 (4)	0.0199 (4)	0.0361 (4)	0.0021 (3)	0.0142 (3)	0.0016 (3)
O6	0.0370 (13)	0.0205 (12)	0.0399 (12)	0.0015 (9)	0.0127 (10)	−0.0010 (8)
O9	0.0334 (14)	0.0301 (14)	0.0469 (14)	0.0016 (9)	0.0193 (11)	−0.0011 (9)
N1	0.0255 (13)	0.0225 (13)	0.0335 (12)	0.0028 (10)	0.0101 (10)	0.0010 (10)
N3	0.0316 (15)	0.0206 (13)	0.0328 (13)	0.0045 (10)	0.0095 (11)	0.0032 (9)
N7	0.0258 (13)	0.0214 (13)	0.0366 (13)	0.0036 (10)	0.0104 (10)	−0.0008 (10)
N9	0.0266 (14)	0.0206 (14)	0.0332 (13)	0.0012 (9)	0.0096 (11)	−0.0011 (9)
C2	0.0296 (16)	0.0222 (16)	0.0365 (16)	0.0043 (11)	0.0087 (13)	0.0015 (11)
C4	0.0260 (15)	0.0258 (16)	0.0277 (13)	−0.0002 (12)	0.0091 (11)	−0.0006 (12)
C5	0.0267 (16)	0.0202 (15)	0.0325 (14)	0.0035 (11)	0.0065 (11)	0.0008 (11)
C6	0.0249 (15)	0.0209 (14)	0.0316 (14)	0.0006 (11)	0.0070 (11)	0.0007 (12)
C8	0.0284 (16)	0.0214 (15)	0.0332 (14)	0.0025 (11)	0.0070 (11)	−0.0002 (11)
C9	0.0255 (15)	0.0255 (16)	0.0342 (14)	−0.0002 (12)	0.0097 (11)	−0.0009 (12)
C61	0.0298 (16)	0.0202 (15)	0.0358 (14)	0.0003 (11)	0.0143 (12)	−0.0001 (12)
C62	0.0269 (16)	0.0230 (15)	0.0312 (14)	−0.0026 (11)	0.0081 (11)	−0.0012 (11)
C91	0.0343 (18)	0.0275 (16)	0.0448 (18)	0.0033 (14)	0.0162 (14)	0.0072 (14)
C631	0.0251 (15)	0.0218 (15)	0.0287 (13)	0.0013 (11)	0.0079 (11)	−0.0003 (11)
C632	0.0317 (16)	0.0207 (15)	0.0364 (15)	−0.0020 (12)	0.0098 (12)	−0.0007 (12)
C633	0.0272 (16)	0.0246 (16)	0.0339 (14)	−0.0036 (12)	0.0086 (11)	0.0017 (12)
C634	0.0246 (15)	0.0232 (15)	0.0321 (14)	0.0001 (11)	0.0085 (11)	0.0015 (11)
C635	0.0318 (17)	0.0199 (14)	0.0376 (15)	−0.0025 (12)	0.0127 (13)	−0.0016 (12)
C636	0.0288 (16)	0.0187 (14)	0.0360 (15)	−0.0017 (11)	0.0098 (13)	0.0011 (11)

Br64—C634	1.905 (3)	C9—C91	1.513 (5)
S6—C6	1.755 (3)	C61—C62	1.528 (4)
S6—C61	1.812 (3)	C61—H61A	0.9900
O6—C62	1.224 (4)	C61—H61B	0.9900
O9—C9	1.209 (4)	C62—C631	1.496 (4)
N1—C2	1.349 (4)	C91—H91A	0.9800
N1—C6	1.356 (4)	C91—H91B	0.9800
N3—C4	1.344 (4)	C91—H91C	0.9800
N3—C2	1.345 (5)	C631—C636	1.398 (4)
N7—C8	1.320 (4)	C631—C632	1.409 (5)
N7—C5	1.411 (4)	C632—C633	1.393 (5)
N9—C8	1.399 (4)	C632—H632	0.9500
N9—C4	1.404 (4)	C633—C634	1.400 (4)
N9—C9	1.431 (4)	C633—H633	0.9500
C2—H2	0.9500	C634—C635	1.404 (4)
C4—C5	1.402 (4)	C635—C636	1.398 (5)
C5—C6	1.395 (4)	C635—H635	0.9500
C8—H8	0.9500	C636—H636	0.9500
C6—S6—C61	100.33 (15)	S6—C61—H61B	110.1
C2—N1—C6	116.8 (3)	H61A—C61—H61B	108.4
C4—N3—C2	111.3 (3)	O6—C62—C631	121.7 (3)
C8—N7—C5	103.8 (3)	O6—C62—C61	121.1 (3)
C8—N9—C4	105.5 (3)	C631—C62—C61	117.2 (3)
C8—N9—C9	122.9 (3)	C9—C91—H91A	109.5
C4—N9—C9	131.6 (3)	C9—C91—H91B	109.5
N3—C2—N1	129.7 (3)	H91A—C91—H91B	109.5
N3—C2—H2	115.1	C9—C91—H91C	109.5
N1—C2—H2	115.1	H91A—C91—H91C	109.5
N3—C4—C5	125.4 (3)	H91B—C91—H91C	109.5
N3—C4—N9	129.2 (3)	C636—C631—C632	119.4 (3)
C5—C4—N9	105.4 (3)	C636—C631—C62	121.6 (3)
C6—C5—C4	117.3 (3)	C632—C631—C62	118.9 (3)
C6—C5—N7	131.5 (3)	C633—C632—C631	121.2 (3)
C4—C5—N7	111.1 (3)	C633—C632—H632	119.4
N1—C6—C5	119.4 (3)	C631—C632—H632	119.4
N1—C6—S6	122.1 (2)	C632—C633—C634	118.2 (3)
C5—C6—S6	118.5 (2)	C632—C633—H633	120.9
N7—C8—N9	114.2 (3)	C634—C633—H633	120.9
N7—C8—H8	122.9	C633—C634—C635	121.7 (3)
N9—C8—H8	122.9	C633—C634—Br64	120.7 (2)
O9—C9—N9	119.0 (3)	C635—C634—Br64	117.6 (2)
O9—C9—C91	125.1 (3)	C636—C635—C634	119.0 (3)
N9—C9—C91	115.9 (3)	C636—C635—H635	120.5
C62—C61—S6	108.2 (2)	C634—C635—H635	120.5
C62—C61—H61A	110.1	C635—C636—C631	120.4 (3)
S6—C61—H61A	110.1	C635—C636—H636	119.8
C62—C61—H61B	110.1	C631—C636—H636	119.8
C4—N3—C2—N1	1.4 (5)	C4—N9—C8—N7	−0.1 (4)
C6—N1—C2—N3	−1.6 (5)	C9—N9—C8—N7	−178.5 (3)
C2—N3—C4—C5	−0.5 (5)	C8—N9—C9—O9	−1.6 (5)
C2—N3—C4—N9	178.1 (3)	C4—N9—C9—O9	−179.6 (3)
C8—N9—C4—N3	−178.8 (3)	C8—N9—C9—C91	177.9 (3)
C9—N9—C4—N3	−0.6 (6)	C4—N9—C9—C91	0.0 (5)
C8—N9—C4—C5	0.0 (3)	C6—S6—C61—C62	−177.8 (2)
C9—N9—C4—C5	178.2 (3)	S6—C61—C62—O6	3.2 (4)
N3—C4—C5—C6	−0.1 (5)	S6—C61—C62—C631	−178.1 (2)
N9—C4—C5—C6	−179.0 (3)	O6—C62—C631—C636	−153.8 (3)
N3—C4—C5—N7	179.0 (3)	C61—C62—C631—C636	27.6 (4)
N9—C4—C5—N7	0.1 (3)	O6—C62—C631—C632	25.1 (4)
C8—N7—C5—C6	178.7 (3)	C61—C62—C631—C632	−153.6 (3)
C8—N7—C5—C4	−0.2 (3)	C636—C631—C632—C633	−1.5 (5)
C2—N1—C6—C5	0.8 (4)	C62—C631—C632—C633	179.6 (3)
C2—N1—C6—S6	179.6 (2)	C631—C632—C633—C634	1.9 (5)
C4—C5—C6—N1	−0.1 (4)	C632—C633—C634—C635	−0.8 (5)
N7—C5—C6—N1	−179.0 (3)	C632—C633—C634—Br64	178.7 (2)
C4—C5—C6—S6	−178.9 (2)	C633—C634—C635—C636	−0.8 (5)
N7—C5—C6—S6	2.2 (5)	Br64—C634—C635—C636	179.8 (2)
C61—S6—C6—N1	12.0 (3)	C634—C635—C636—C631	1.2 (5)
C61—S6—C6—C5	−169.3 (3)	C632—C631—C636—C635	−0.1 (5)
C5—N7—C8—N9	0.2 (4)	C62—C631—C636—C635	178.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O9i	0.95	2.42	3.367 (4)	177
C61—H61B···O6ii	0.99	2.45	3.396 (4)	160

C14H12N4O2S	F(000) = 624
Mr = 300.34	Dx = 1.487 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71075 Å
a = 7.6683 (5) Å	Cell parameters from 16870 reflections
b = 21.8004 (15) Å	θ = 2.5–27.5°
c = 8.4131 (5) Å	µ = 0.25 mm−1
β = 107.507 (2)°	T = 100 K
V = 1341.29 (15) Å3	Block, colourless
Z = 4	0.17 × 0.12 × 0.07 mm

Rigaku AFC12 (Right) diffractometer	3063 independent reflections
Radiation source: Rotating Anode	2799 reflections with I > 2σ(I)
Detector resolution: 28.5714 pixels mm-1	Rint = 0.060
profile data from ω–scans	θmax = 27.5°, θmin = 2.7°
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012)	h = −9→9
Tmin = 0.724, Tmax = 1.000	k = −28→28
17441 measured reflections	l = −10→10

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033	H-atom parameters constrained
wR(F2) = 0.093	w = 1/[σ2(Fo2) + (0.055P)2 + 0.4055P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
3063 reflections	Δρmax = 0.30 e Å−3
191 parameters	Δρmin = −0.37 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

	x	y	z	Uiso*/Ueq
S6	0.17185 (4)	0.41173 (2)	0.46144 (3)	0.02043 (11)
O6	0.42208 (12)	0.47291 (4)	0.71480 (12)	0.0275 (2)
O63	0.70355 (13)	0.67387 (4)	0.97072 (11)	0.0288 (2)
N1	−0.06585 (14)	0.44463 (5)	0.16289 (13)	0.0227 (2)
N3	−0.25987 (15)	0.37375 (5)	−0.03578 (13)	0.0240 (2)
N7	0.01119 (14)	0.28258 (5)	0.30139 (13)	0.0211 (2)
N9	−0.21099 (14)	0.26758 (5)	0.06007 (13)	0.0226 (2)
H9	−0.2911	0.2481	−0.0214	0.027*
C2	−0.19450 (17)	0.42912 (6)	0.01862 (15)	0.0247 (3)
H6	−0.2451	0.4623	−0.0538	0.030*
C4	−0.17933 (16)	0.32957 (6)	0.07248 (15)	0.0206 (2)
C5	−0.04241 (16)	0.33841 (5)	0.22326 (14)	0.0195 (2)
C6	0.01075 (15)	0.39879 (6)	0.26754 (14)	0.0194 (2)
C8	−0.09352 (16)	0.24220 (6)	0.19916 (15)	0.0225 (3)
H8	−0.0874	0.1993	0.2207	0.027*
C61	0.21217 (16)	0.49315 (6)	0.44829 (15)	0.0213 (2)
H61A	0.2602	0.5018	0.3537	0.026*
H61B	0.0969	0.5163	0.4312	0.026*
C62	0.35075 (16)	0.51187 (6)	0.61124 (15)	0.0207 (2)
C631	0.39980 (16)	0.57789 (6)	0.63995 (15)	0.0205 (2)
C632	0.52582 (16)	0.59345 (5)	0.79351 (15)	0.0208 (2)
H632	0.5744	0.5626	0.8745	0.025*
C633	0.57924 (17)	0.65409 (6)	0.82667 (16)	0.0230 (3)
C634	0.50351 (18)	0.69940 (6)	0.70857 (17)	0.0259 (3)
H634	0.5385	0.7410	0.7320	0.031*
C635	0.37787 (18)	0.68404 (6)	0.55762 (17)	0.0265 (3)
H635	0.3264	0.7152	0.4785	0.032*
C636	0.32641 (16)	0.62298 (6)	0.52100 (16)	0.0238 (3)
H636	0.2425	0.6123	0.4164	0.029*
C637	0.7840 (2)	0.62823 (6)	1.09270 (17)	0.0301 (3)
H63A	0.8724	0.6476	1.1886	0.045*
H63B	0.8465	0.5976	1.0440	0.045*
H63C	0.6882	0.6081	1.1291	0.045*

	U11	U22	U33	U12	U13	U23
S6	0.02055 (17)	0.02018 (17)	0.01696 (16)	−0.00081 (10)	0.00019 (11)	−0.00014 (10)
O6	0.0294 (5)	0.0212 (5)	0.0250 (5)	−0.0002 (3)	−0.0021 (4)	0.0020 (3)
O63	0.0378 (5)	0.0234 (5)	0.0227 (5)	−0.0077 (4)	0.0053 (4)	−0.0043 (4)
N1	0.0231 (5)	0.0235 (5)	0.0196 (5)	0.0015 (4)	0.0036 (4)	0.0024 (4)
N3	0.0229 (5)	0.0282 (6)	0.0173 (5)	0.0029 (4)	0.0005 (4)	0.0022 (4)
N7	0.0203 (5)	0.0220 (5)	0.0178 (5)	0.0011 (4)	0.0009 (4)	0.0009 (4)
N9	0.0214 (5)	0.0242 (5)	0.0179 (5)	0.0001 (4)	−0.0005 (4)	−0.0024 (4)
C2	0.0250 (6)	0.0272 (7)	0.0185 (6)	0.0038 (5)	0.0016 (5)	0.0042 (5)
C4	0.0188 (5)	0.0249 (6)	0.0161 (5)	0.0011 (4)	0.0023 (4)	−0.0012 (5)
C5	0.0180 (5)	0.0233 (6)	0.0150 (5)	0.0015 (4)	0.0014 (4)	0.0006 (4)
C6	0.0179 (5)	0.0227 (6)	0.0166 (5)	0.0006 (4)	0.0038 (4)	0.0006 (4)
C8	0.0224 (6)	0.0222 (6)	0.0199 (6)	0.0004 (4)	0.0019 (4)	0.0000 (5)
C61	0.0206 (5)	0.0209 (6)	0.0203 (6)	−0.0011 (4)	0.0030 (5)	−0.0002 (4)
C62	0.0183 (5)	0.0225 (6)	0.0204 (6)	0.0000 (4)	0.0046 (4)	−0.0003 (4)
C631	0.0187 (5)	0.0219 (6)	0.0210 (6)	0.0000 (4)	0.0060 (4)	−0.0006 (4)
C632	0.0229 (6)	0.0202 (6)	0.0195 (6)	0.0003 (4)	0.0065 (5)	−0.0007 (4)
C633	0.0248 (6)	0.0240 (6)	0.0216 (6)	−0.0028 (5)	0.0091 (5)	−0.0030 (5)
C634	0.0298 (6)	0.0184 (6)	0.0312 (7)	−0.0018 (5)	0.0118 (5)	−0.0006 (5)
C635	0.0262 (6)	0.0228 (6)	0.0302 (7)	0.0021 (5)	0.0082 (5)	0.0053 (5)
C636	0.0208 (6)	0.0247 (7)	0.0241 (6)	0.0001 (4)	0.0042 (5)	0.0026 (5)
C637	0.0350 (7)	0.0315 (7)	0.0209 (6)	−0.0054 (5)	0.0039 (5)	−0.0024 (5)

S6—C6	1.7477 (12)	C61—C62	1.5162 (16)
S6—C61	1.8109 (13)	C61—H61A	0.9900
O6—C62	1.2219 (15)	C61—H61B	0.9900
O63—C633	1.3669 (15)	C62—C631	1.4887 (17)
O63—C637	1.4293 (17)	C631—C636	1.3949 (17)
N1—C6	1.3446 (16)	C631—C632	1.4025 (17)
N1—C2	1.3566 (16)	C632—C633	1.3871 (17)
N3—C2	1.3342 (17)	C632—H632	0.9500
N3—C4	1.3416 (16)	C633—C634	1.3975 (18)
N7—C8	1.3206 (16)	C634—C635	1.3846 (19)
N7—C5	1.3855 (15)	C634—H634	0.9500
N9—C8	1.3612 (15)	C635—C636	1.3963 (18)
N9—C4	1.3716 (16)	C635—H635	0.9500
N9—H9	0.8800	C636—H636	0.9500
C2—H6	0.9500	C637—H63A	0.9800
C4—C5	1.3954 (16)	C637—H63B	0.9800
C5—C6	1.3950 (17)	C637—H63C	0.9800
C8—H8	0.9500
C6—S6—C61	100.77 (6)	H61A—C61—H61B	108.5
C633—O63—C637	116.88 (10)	O6—C62—C631	121.28 (11)
C6—N1—C2	117.22 (11)	O6—C62—C61	119.95 (11)
C2—N3—C4	111.58 (11)	C631—C62—C61	118.75 (10)
C8—N7—C5	103.95 (10)	C636—C631—C632	120.52 (11)
C8—N9—C4	106.19 (10)	C636—C631—C62	122.49 (11)
C8—N9—H9	126.9	C632—C631—C62	116.99 (11)
C4—N9—H9	126.9	C633—C632—C631	119.72 (12)
N3—C2—N1	129.01 (12)	C633—C632—H632	120.1
N3—C2—H6	115.5	C631—C632—H632	120.1
N1—C2—H6	115.5	O63—C633—C632	124.33 (12)
N3—C4—N9	128.37 (11)	O63—C633—C634	115.92 (11)
N3—C4—C5	125.80 (12)	C632—C633—C634	119.75 (12)
N9—C4—C5	105.83 (10)	C635—C634—C633	120.46 (12)
N7—C5—C6	132.92 (11)	C635—C634—H634	119.8
N7—C5—C4	110.17 (11)	C633—C634—H634	119.8
C6—C5—C4	116.90 (11)	C634—C635—C636	120.36 (12)
N1—C6—C5	119.44 (11)	C634—C635—H635	119.8
N1—C6—S6	122.55 (10)	C636—C635—H635	119.8
C5—C6—S6	117.99 (9)	C631—C636—C635	119.17 (12)
N7—C8—N9	113.85 (11)	C631—C636—H636	120.4
N7—C8—H8	123.1	C635—C636—H636	120.4
N9—C8—H8	123.1	O63—C637—H63A	109.5
C62—C61—S6	107.14 (8)	O63—C637—H63B	109.5
C62—C61—H61A	110.3	H63A—C637—H63B	109.5
S6—C61—H61A	110.3	O63—C637—H63C	109.5
C62—C61—H61B	110.3	H63A—C637—H63C	109.5
S6—C61—H61B	110.3	H63B—C637—H63C	109.5
C4—N3—C2—N1	−0.95 (19)	C4—N9—C8—N7	0.34 (14)
C6—N1—C2—N3	0.9 (2)	C6—S6—C61—C62	179.54 (8)
C2—N3—C4—N9	179.68 (12)	S6—C61—C62—O6	5.56 (14)
C2—N3—C4—C5	−0.74 (18)	S6—C61—C62—C631	−175.65 (9)
C8—N9—C4—N3	178.96 (12)	O6—C62—C631—C636	177.18 (11)
C8—N9—C4—C5	−0.68 (13)	C61—C62—C631—C636	−1.59 (17)
C8—N7—C5—C6	178.02 (13)	O6—C62—C631—C632	−2.42 (17)
C8—N7—C5—C4	−0.60 (13)	C61—C62—C631—C632	178.81 (10)
N3—C4—C5—N7	−178.84 (11)	C636—C631—C632—C633	−0.64 (18)
N9—C4—C5—N7	0.81 (13)	C62—C631—C632—C633	178.98 (11)
N3—C4—C5—C6	2.29 (18)	C637—O63—C633—C632	0.86 (17)
N9—C4—C5—C6	−178.05 (10)	C637—O63—C633—C634	−179.47 (11)
C2—N1—C6—C5	0.84 (17)	C631—C632—C633—O63	−178.68 (11)
C2—N1—C6—S6	−177.49 (9)	C631—C632—C633—C634	1.66 (18)
N7—C5—C6—N1	179.21 (12)	O63—C633—C634—C635	179.22 (11)
C4—C5—C6—N1	−2.24 (17)	C632—C633—C634—C635	−1.09 (19)
N7—C5—C6—S6	−2.39 (18)	C633—C634—C635—C636	−0.5 (2)
C4—C5—C6—S6	176.16 (8)	C632—C631—C636—C635	−0.96 (18)
C61—S6—C6—N1	−7.88 (11)	C62—C631—C636—C635	179.45 (11)
C61—S6—C6—C5	173.78 (9)	C634—C635—C636—C631	1.54 (19)
C5—N7—C8—N9	0.16 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9···N7i	0.88	1.90	2.7715 (14)	171

	(1)	(2)	(3)
Crystal data
Chemical formula	C16H14N4O3S	C16H14N4O3S	C15H11ClN4O2S
M r	342.37	342.37	346.79
Crystal system, space group	Monoclinic, P21/n	Monoclinic, P21/c	Monoclinic, P21/c
Temperature (K)	100	100	100
a, b, c (Å)	7.6343 (5), 26.2356 (18), 8.1332 (5)	5.9920 (3), 9.9795 (5), 24.9907 (13)	5.9900 (4), 9.9169 (7), 24.3238 (17)
β (°)	112.725 (2)	95.977 (5)	96.072 (2)
V (Å3)	1502.54 (17)	1486.25 (13)	1436.78 (17)
Z	4	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm−1)	0.24	0.24	0.43
Crystal size (mm)	0.17 × 0.07 × 0.01	0.05 × 0.04 × 0.01	0.13 × 0.06 × 0.01
Data collection
Diffractometer	Rigaku AFC12 (Right)	Rigaku AFC12 (Right)	Rigaku AFC12 (Right)
Absorption correction	Multi-scan (CrystalClear-SM Expert; Rigaku, 20112)	Multi-scan (CrysAlis PRO; Agilent, 2014 ▸)	Multi-scan CrystalClear-SM Expert (Rigaku, 20112)
T min, T max	0, 1.000	0.439, 1.000	0.809, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	20144, 3450, 2817	15437, 2619, 1852	18353, 3291, 2677
R int	0.089	0.106	0.050
(sin θ/λ)max (Å−1)	0.649	0.595	0.651
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.053, 0.148, 1.05	0.048, 0.116, 1.02	0.035, 0.092, 1.02
No. of reflections	3450	2619	3291
No. of parameters	219	219	209
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.81, −0.51	0.30, −0.36	0.34, −0.22

	(4)	(5)
Crystal data
Chemical formula	C15H11BrN4O2S	C14H12N4O2S
M r	391.25	300.34
Crystal system, space group	Monoclinic, P21/c	Monoclinic, P21/n
Temperature (K)	100	100
a, b, c (Å)	6.0705 (4), 10.0668 (7), 24.3492 (17)	7.6683 (5), 21.8004 (15), 8.4131 (5)
β (°)	96.580 (2)	107.507 (2)
V (Å3)	1478.19 (18)	1341.29 (15)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm−1)	2.94	0.25
Crystal size (mm)	0.15 × 0.10 × 0.02	0.17 × 0.12 × 0.07
Data collection
Diffractometer	Rigaku AFC12 (Right)	Rigaku AFC12 (Right)
Absorption correction	Multi-scan CrystalClear-SM Expert (Rigaku, 20112)	Multi-scan (CrystalClear-SM Expert; Rigaku, 2012 ▸)
T min, T max	0.658, 1.000	0.724, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	18171, 3346, 2944	17441, 3063, 2799
R int	0.064	0.060
(sin θ/λ)max (Å−1)	0.649	0.649
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.056, 0.153, 1.06	0.033, 0.093, 1.03
No. of reflections	3346	3063
No. of parameters	209	191
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	2.91, −0.92	0.30, −0.37

Computer programs: CrystalClear-SM Expert (Rigaku, 2012 ▸), CrysAlis PRO (Agilent, 2014 ▸), SHELXT (Sheldrick, 2015a ▸), ShelXle (Hübschle et al., 2011 ▸), SHELXL2014 (Sheldrick, 2015b ▸), OSCAIL (McArdle et al., 2004 ▸), Mercury (Macrae et al., 2006 ▸), and PLATON (Spek, 2009 ▸).