Crystal structures of 2-[(4,6-di-amino-pyrimidin-2-yl)sulfan-yl]-N-(naphthalen-1-yl)acetamide and 2-[(4,6-di-amino-pyrimidin-2-yl)sulfan-yl]-N-(4-fluoro-phen-yl)acetamide.

The title compounds, C16H15N5OS, (I), and C12H12FN5OS, (II), are [(di-amino-pyrimidine)-sulfan-yl]acetamide derivatives. In (I), the pyrimidine ring is inclined to the naphthalene ring system by 55.5 (1)°, while in (II), the pyrimidine ring is inclined to the benzene ring by 58.93 (8)°. In (II), there is an intra-molecular N-H⋯N hydrogen bond and a short C-H⋯O contact. In the crystals of (I) and (II), mol-ecules are linked by pairs of N-H⋯N hydrogen bonds, forming inversion dimers with R22(8) ring motifs. In the crystal of (I), the dimers are linked by bifurcated N-H⋯(O,O) and C-H⋯O hydrogen bonds, forming layers parallel to (100). In the crystal of (II), the dimers are linked by N-H⋯O hydrogen bonds, also forming layers parallel to (100). The layers are linked by C-H⋯F hydrogen bonds, forming a three-dimensional architecture.

Chemical context

As a result of the innate ability of bacteria to develop resistance to available anti­biotics, there is a critical need to develop new agents to treat more strains that are resilient. Several classes of di­amino­pyrimidines have been reported as new therapeutic agents. Derivatives of di­amino­pyrimidines also exhibit anti-cancer activity (Xu et al., 2010 ▸), immune suppressant activity (Blumenkopf et al., 2002 ▸), hair-growth-stimulant properties, anti-bacterial (Kandeel et al., 1994 ▸) and potential anti-microbial properties (Holla et al., 2006 ▸). They are also used as potential anti-AIDS agents (Nogueras et al., 1993 ▸) and anti-viral agents (Hocková et al., 2004 ▸). In this connection, the title 4,6-di­amino­pyrimidine-based analogues have been synthesized as potential anti­viral agents against dengue for targeting NS2B/NS3 protease.

Structural commentary

The mol­ecular structure of compound (I) is shown in Fig. 1 ▸. The pyrimidine ring is twisted with respect to the thio­acetamide unit with the N1—C11—C12—S1 torsion angle being 140.88 (18)°. The pyrimidine ring (C13–C16/N2/N3) makes a dihedral angle of 55.5 (1)° with the naphthalene ring system (C1–C10). The amine nitro­gen atoms, N4 and N5, deviate by 0.0235 and 0.0291 Å, respectively, from the plane of the pyrimidine ring.

Figure 1

The mol­ecular structure of compound (I), showing the atom labelling and displacement ellipsoids drawn at the 50% probability level.

The mol­ecular structure of compound (II) is shown in Fig. 2 ▸. Here, the pyrimidine ring is twisted with respect to the thio­acetamide unit with the N1—C7—C8—S1 torsion angle being −82.44 (14)°. The pyrimidine ring (C9–C12/N2/N3) makes a dihedral angle of 58.93 (8)° with the benzene ring (C1–C6). The amine nitro­gen atoms, N4 and N5, deviate by 0.0247 and 0.0564 Å, respectively, from the pyrimidine ring. In compound (II), there is an intra­molecular N—H⋯N hydrogen bond and a short C—H⋯O inter­action present (Table 2 ▸ and Fig. 2 ▸).

Figure 2

The mol­ecular structure of compound (II), showing the atom labelling and displacement ellipsoids drawn at the 50% probability level.

Table 2

Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N3	0.86	2.25	2.990 (2)	145
C3—H3⋯O1	0.93	2.31	2.903 (2)	121
N5—H5A⋯N2i	0.86	2.29	3.139 (2)	169
N4—H4A⋯O1ii	0.86	2.23	2.9852 (18)	146
C2—H2⋯F1iii	0.93	2.48	3.404 (3)	172

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

Supra­molecular features

In the crystal of compound (I), mol­ecules are linked by pairs of N5—H5A⋯N3i hydrogen bonds, forming inversion dimers with an (8) ring motif (Table 1 ▸ and Fig. 3 ▸). The dimers are linked by bifurcated N—H⋯(O,O) and C—H⋯O hydrogen bonds, forming layers parallel to the bc plane (Table 1 ▸ and Fig. 3 ▸).

Table 1

Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯N3i	0.86	2.27	3.110 (4)	167
N1—H1A⋯O1ii	0.86	2.05	2.890 (3)	165
N4—H4B⋯O1iii	0.86	2.36	2.964 (3)	127
C12—H12A⋯O1ii	0.97	2.58	3.408 (3)	143

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

Figure 3

A view along the b axis, of the crystal packing of compound (I). Hydrogen bonds are shown as dashed lines (see Table 1 ▸). For clarity, only the NH and NH2 hydrogens and the C-bound H atoms involved in hydrogen bonding have been included.

In the crystal of compound (II), inversion dimers, with an (8), ring motif, are also formed via pairs of N5—H5A⋯N2i hydrogen bonds (Table 2 ▸ and Fig. 4 ▸). This time the dimers are linked by N—H⋯O hydrogen bonds and also form layers parallel to the bc plane (Table 2 ▸ and Fig. 4 ▸). The layers are linked by C—H⋯F hydrogen bonds, forming a three-dimensional architecture (Table 2 ▸ and Fig. 4 ▸).

Figure 4

The crystal packing of compound (II) viewed along the b axis. Hydrogen bonds are shown as dashed lines (see Table 2 ▸). For clarity, only the NH and NH2 hydrogens and the C-bound H atoms involved in hydrogen bonding have been included.

Database survey

A search of the Cambridge Structural Database (Version 5.37, update May 2016; Groom et al., 2016 ▸) for 2-(pyrimidin-2-yl)-N-phenyl­acetamide yielded only five hits. They include two 4,6-di­methyl­pyrimidine analogues viz. 2-(4,6-di­methyl­pyrimidin-2-ylsulfan­yl)-N-phenyl acetamide (DIWXAJ; Gao et al., 2008 ▸) and N-(2-chloro­phen­yl)-2-(4,6-di­methyl­pyrimidin-2-ylsulfan­yl)acetamide (QOTQEW; Li et al., 2009 ▸), and three 4,6-di­amino­pyrimidine compounds viz. 2-[(4,6-di­amino­pyrim­idin-2-yl)sulfan­yl]-N-2-methyl­phen­yl)acetamide (GOKWIO; Subasri et al., 2014 ▸), 2-[(4,6-di­amino­pyrimidin-2-yl)sulfan­yl]-N-(3-nitro­phen­yl)acetamide (Subasri et al., 2014 ▸) and 2-[(4,6-di­amino­pyrimidin-2-yl)sulfan­yl]-N-(2-chloro­phen­yl)acetamide (Subasri et al., 2014 ▸).

Synthesis and crystallization

Compound (I) To a solution of 4,6-di­amino-pyrimidine-2-thiol (0.5 g, 3.52 mmol) in 25 ml of ethanol, potassium hydroxide (0.2 g, 3.52 mmol) was added and the mixture refluxed for 30 min. Then 3.52 mmol of 2-chloro-N-(naphthalen-1-yl)acetamide was added and the mixture refluxed for 2.5 h. On completion of the reaction (monitored by TLC), the ethanol was evaporated in vacuo and cold water was added. The precipitate that formed was filtered and dried to give compound (I) as a crystalline powder (yield 92%).

Compound (II) To a solution of 4,6-di­amino-pyrimidine-2-thiol (0.5 g, 3.52 mmol) in 25 ml of ethanol, potassium hydroxide (0.2 g, 3.52 mmol) was added and the mixture refluxed for 30 min. Then 3.52 mmol of 2-chloro-N-(4-fluoro­phen­yl)acetamide was added and the mixture refluxed for 4 h. On completion of the reaction (monitored by TLC), ethanol was evaporated in vacuo and cold water was added and the precipitate formed was filtered and dried to give compound (II) as a crystalline powder (yield 88%).

Colourless block-like crystals were obtained by slow evaporation of a solution in CH3OH for compound (I) and C4H8O2 for compound (II).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. For both compounds the hydrogen atoms were placed in calculated positions and refined as riding: C—H = 0.93–0.97 Å, N—H = 0.86 Å with U iso(H) = 1.2U eq(N,C).

Table 3

Experimental details

	(I)	(II)
Crystal data
Chemical formula	C16H15N5OS	C12H12FN5OS
M r	325.39	293.33
Crystal system, space group	Monoclinic, P21/c	Monoclinic, P21/c
Temperature (K)	293	293
a, b, c (Å)	25.1895 (16), 6.9411 (4), 8.9697 (6)	21.7358 (7), 7.3726 (3), 8.4487 (3)
β (°)	90.943 (4)	93.092 (1)
V (Å3)	1568.08 (17)	1351.93 (9)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm−1)	0.22	0.25
Crystal size (mm)	0.30 × 0.25 × 0.20	0.31 × 0.25 × 0.20
Data collection
Diffractometer	Bruker SMART APEXII area-detector	Bruker SMART APEXII area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008 ▸)	Multi-scan (SADABS; Bruker, 2008 ▸)
T min, T max	0.752, 0.831	0.652, 0.753
No. of measured, independent and observed [I > 2σ(I)] reflections	14522, 3849, 2095	12316, 3312, 2829
R int	0.063	0.025
(sin θ/λ)max (Å−1)	0.669	0.667
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.052, 0.153, 0.98	0.037, 0.109, 1.05
No. of reflections	3849	3312
No. of parameters	208	181
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.38, −0.23	0.22, −0.22

Computer programs: APEX2 and SAINT (Bruker, 2008 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2016 (Sheldrick, 2015 ▸) and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989017001293/su5347sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017001293/su5347Isup2.hkl

Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989017001293/su5347IIsup3.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989017001293/su5347Isup4.cml

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989017001293/su5347IIsup5.cml

CCDC references: 1529608, 1529607

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

C16H15N5OS	F(000) = 680
Mr = 325.39	Dx = 1.378 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 25.1895 (16) Å	Cell parameters from 3849 reflections
b = 6.9411 (4) Å	θ = 1.6–28.4°
c = 8.9697 (6) Å	µ = 0.22 mm−1
β = 90.943 (4)°	T = 293 K
V = 1568.08 (17) Å3	Block, colourless
Z = 4	0.30 × 0.25 × 0.20 mm

Bruker SMART APEXII area-detector diffractometer	2095 reflections with I > 2σ(I)
ω and φ scans	Rint = 0.063
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θmax = 28.4°, θmin = 1.6°
Tmin = 0.752, Tmax = 0.831	h = −33→33
14522 measured reflections	k = −7→9
3849 independent reflections	l = −11→12

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.153	H-atom parameters constrained
S = 0.98	w = 1/[σ2(Fo2) + (0.0671P)2 + 0.3358P] where P = (Fo2 + 2Fc2)/3
3849 reflections	(Δ/σ)max = 0.001
208 parameters	Δρmax = 0.38 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

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

	x	y	z	Uiso*/Ueq
N5	0.49526 (12)	−0.2169 (5)	0.6491 (4)	0.1242 (15)
H5A	0.517831	−0.151383	0.599131	0.149*
H5B	0.505205	−0.319772	0.695198	0.149*
C1	0.15258 (14)	−0.2816 (4)	0.5842 (3)	0.0706 (9)
H1	0.156295	−0.401205	0.538876	0.085*
C2	0.10801 (13)	−0.2407 (5)	0.6613 (3)	0.0696 (9)
H2	0.081326	−0.332820	0.667315	0.084*
C3	0.10145 (10)	−0.0625 (4)	0.7317 (3)	0.0562 (7)
C4	0.05553 (12)	−0.0167 (6)	0.8124 (3)	0.0725 (9)
H4	0.028614	−0.107749	0.819483	0.087*
C5	0.04960 (12)	0.1557 (6)	0.8794 (3)	0.0740 (9)
H5	0.019065	0.181697	0.932778	0.089*
C6	0.08929 (11)	0.2952 (5)	0.8688 (3)	0.0634 (8)
H6	0.085036	0.413896	0.915302	0.076*
C7	0.13418 (10)	0.2591 (4)	0.7911 (3)	0.0501 (6)
H7	0.160100	0.354018	0.784284	0.060*
C8	0.14195 (9)	0.0796 (4)	0.7205 (2)	0.0452 (6)
C9	0.18804 (10)	0.0334 (4)	0.6386 (2)	0.0432 (6)
C10	0.19288 (11)	−0.1441 (4)	0.5729 (3)	0.0576 (7)
H10	0.223334	−0.173379	0.520215	0.069*
C11	0.26297 (9)	0.1951 (3)	0.5182 (2)	0.0413 (6)
C12	0.30711 (10)	0.3383 (4)	0.5478 (3)	0.0483 (6)
H12A	0.310700	0.357511	0.654569	0.058*
H12B	0.297111	0.460871	0.503592	0.058*
C13	0.38351 (10)	0.0615 (3)	0.5853 (2)	0.0422 (6)
C14	0.44443 (12)	−0.1587 (5)	0.6552 (3)	0.0688 (8)
C15	0.40599 (12)	−0.2535 (4)	0.7352 (3)	0.0668 (8)
H15	0.414154	−0.364339	0.789169	0.080*
C16	0.35572 (11)	−0.1801 (4)	0.7331 (3)	0.0481 (6)
N1	0.22916 (8)	0.1726 (3)	0.6311 (2)	0.0438 (5)
H1A	0.232751	0.249634	0.705663	0.053*
N2	0.34334 (7)	−0.0183 (3)	0.6559 (2)	0.0427 (5)
N3	0.43337 (8)	0.0052 (3)	0.5783 (2)	0.0540 (6)
N4	0.31453 (10)	−0.2587 (3)	0.8082 (2)	0.0607 (6)
H4A	0.283743	−0.205232	0.803960	0.073*
H4B	0.319286	−0.361782	0.859841	0.073*
O1	0.25760 (7)	0.1132 (3)	0.39688 (16)	0.0502 (5)
S1	0.37019 (3)	0.26816 (10)	0.47685 (8)	0.0554 (2)

	U11	U22	U33	U12	U13	U23
N5	0.0625 (18)	0.132 (3)	0.179 (3)	0.0403 (19)	0.033 (2)	0.099 (3)
C1	0.092 (2)	0.0530 (19)	0.0668 (19)	−0.0148 (18)	0.0000 (17)	−0.0022 (14)
C2	0.077 (2)	0.064 (2)	0.0671 (19)	−0.0257 (17)	−0.0050 (16)	0.0057 (15)
C3	0.0522 (17)	0.065 (2)	0.0511 (14)	−0.0107 (14)	0.0013 (12)	0.0105 (13)
C4	0.0508 (18)	0.102 (3)	0.0654 (18)	−0.0192 (18)	0.0071 (14)	0.0168 (18)
C5	0.0437 (17)	0.113 (3)	0.0657 (18)	0.0019 (19)	0.0160 (13)	0.008 (2)
C6	0.0519 (17)	0.082 (2)	0.0570 (16)	0.0086 (16)	0.0112 (13)	−0.0039 (15)
C7	0.0420 (14)	0.0617 (18)	0.0467 (14)	0.0001 (13)	0.0078 (11)	−0.0006 (12)
C8	0.0440 (14)	0.0538 (16)	0.0380 (12)	−0.0021 (12)	0.0010 (10)	0.0044 (11)
C9	0.0475 (14)	0.0455 (15)	0.0370 (11)	−0.0025 (12)	0.0051 (10)	0.0015 (10)
C10	0.0686 (19)	0.0518 (17)	0.0526 (15)	−0.0014 (15)	0.0095 (13)	−0.0034 (13)
C11	0.0460 (14)	0.0401 (14)	0.0383 (12)	0.0119 (11)	0.0109 (10)	0.0039 (10)
C12	0.0532 (16)	0.0384 (14)	0.0538 (14)	0.0032 (12)	0.0137 (12)	0.0049 (11)
C13	0.0452 (14)	0.0398 (14)	0.0417 (12)	−0.0040 (12)	0.0053 (10)	0.0008 (10)
C14	0.0571 (19)	0.070 (2)	0.080 (2)	0.0153 (16)	0.0118 (15)	0.0257 (17)
C15	0.069 (2)	0.0556 (19)	0.0763 (19)	0.0123 (16)	0.0136 (16)	0.0266 (15)
C16	0.0615 (17)	0.0387 (15)	0.0444 (13)	−0.0024 (13)	0.0094 (12)	0.0017 (11)
N1	0.0465 (12)	0.0458 (12)	0.0395 (10)	−0.0020 (10)	0.0129 (8)	−0.0056 (9)
N2	0.0477 (12)	0.0369 (12)	0.0437 (10)	−0.0037 (9)	0.0069 (9)	0.0039 (9)
N3	0.0437 (13)	0.0538 (14)	0.0646 (13)	0.0023 (11)	0.0074 (10)	0.0137 (11)
N4	0.0713 (16)	0.0460 (14)	0.0656 (14)	−0.0062 (12)	0.0217 (12)	0.0134 (11)
O1	0.0575 (11)	0.0562 (11)	0.0373 (9)	0.0086 (9)	0.0110 (7)	−0.0004 (8)
S1	0.0494 (4)	0.0524 (5)	0.0651 (4)	0.0038 (3)	0.0200 (3)	0.0208 (3)

N5—C14	1.345 (4)	C9—N1	1.419 (3)
N5—H5A	0.8600	C10—H10	0.9300
N5—H5B	0.8600	C11—O1	1.234 (3)
C1—C2	1.358 (4)	C11—N1	1.343 (3)
C1—C10	1.398 (4)	C11—C12	1.512 (4)
C1—H1	0.9300	C12—S1	1.789 (2)
C2—C3	1.400 (4)	C12—H12A	0.9700
C2—H2	0.9300	C12—H12B	0.9700
C3—C4	1.411 (4)	C13—N3	1.318 (3)
C3—C8	1.424 (4)	C13—N2	1.324 (3)
C4—C5	1.349 (5)	C13—S1	1.762 (2)
C4—H4	0.9300	C14—N3	1.357 (3)
C5—C6	1.396 (4)	C14—C15	1.382 (4)
C5—H5	0.9300	C15—C16	1.365 (4)
C6—C7	1.362 (3)	C15—H15	0.9300
C6—H6	0.9300	C16—N2	1.353 (3)
C7—C8	1.413 (3)	C16—N4	1.360 (3)
C7—H7	0.9300	N1—H1A	0.8600
C8—C9	1.421 (3)	N4—H4A	0.8600
C9—C10	1.372 (3)	N4—H4B	0.8600
C14—N5—H5A	120.0	C1—C10—H10	119.6
C14—N5—H5B	120.0	O1—C11—N1	123.4 (2)
H5A—N5—H5B	120.0	O1—C11—C12	121.8 (2)
C2—C1—C10	120.1 (3)	N1—C11—C12	114.7 (2)
C2—C1—H1	119.9	C11—C12—S1	114.45 (17)
C10—C1—H1	119.9	C11—C12—H12A	108.6
C1—C2—C3	121.3 (3)	S1—C12—H12A	108.6
C1—C2—H2	119.4	C11—C12—H12B	108.6
C3—C2—H2	119.4	S1—C12—H12B	108.6
C2—C3—C4	122.3 (3)	H12A—C12—H12B	107.6
C2—C3—C8	119.4 (3)	N3—C13—N2	129.4 (2)
C4—C3—C8	118.3 (3)	N3—C13—S1	112.83 (17)
C5—C4—C3	121.8 (3)	N2—C13—S1	117.67 (18)
C5—C4—H4	119.1	N5—C14—N3	114.8 (3)
C3—C4—H4	119.1	N5—C14—C15	123.6 (3)
C4—C5—C6	120.0 (3)	N3—C14—C15	121.6 (3)
C4—C5—H5	120.0	C16—C15—C14	118.2 (3)
C6—C5—H5	120.0	C16—C15—H15	120.9
C7—C6—C5	120.6 (3)	C14—C15—H15	120.9
C7—C6—H6	119.7	N2—C16—N4	114.5 (2)
C5—C6—H6	119.7	N2—C16—C15	121.5 (2)
C6—C7—C8	120.9 (3)	N4—C16—C15	123.9 (2)
C6—C7—H7	119.5	C11—N1—C9	126.0 (2)
C8—C7—H7	119.5	C11—N1—H1A	117.0
C7—C8—C9	123.4 (2)	C9—N1—H1A	117.0
C7—C8—C3	118.4 (2)	C13—N2—C16	114.9 (2)
C9—C8—C3	118.2 (2)	C13—N3—C14	114.3 (2)
C10—C9—N1	121.4 (2)	C16—N4—H4A	120.0
C10—C9—C8	120.2 (2)	C16—N4—H4B	120.0
N1—C9—C8	118.3 (2)	H4A—N4—H4B	120.0
C9—C10—C1	120.8 (3)	C13—S1—C12	100.80 (11)
C9—C10—H10	119.6
C10—C1—C2—C3	−0.5 (5)	O1—C11—C12—S1	−42.3 (3)
C1—C2—C3—C4	180.0 (3)	N1—C11—C12—S1	140.88 (18)
C1—C2—C3—C8	1.0 (4)	N5—C14—C15—C16	179.9 (3)
C2—C3—C4—C5	−179.8 (3)	N3—C14—C15—C16	1.3 (5)
C8—C3—C4—C5	−0.8 (4)	C14—C15—C16—N2	−0.4 (4)
C3—C4—C5—C6	0.7 (5)	C14—C15—C16—N4	−179.3 (3)
C4—C5—C6—C7	0.0 (5)	O1—C11—N1—C9	10.4 (4)
C5—C6—C7—C8	−0.6 (4)	C12—C11—N1—C9	−172.8 (2)
C6—C7—C8—C9	−179.7 (2)	C10—C9—N1—C11	31.7 (4)
C6—C7—C8—C3	0.5 (4)	C8—C9—N1—C11	−150.3 (2)
C2—C3—C8—C7	179.3 (2)	N3—C13—N2—C16	0.8 (4)
C4—C3—C8—C7	0.2 (4)	S1—C13—N2—C16	177.84 (17)
C2—C3—C8—C9	−0.6 (4)	N4—C16—N2—C13	178.5 (2)
C4—C3—C8—C9	−179.7 (2)	C15—C16—N2—C13	−0.5 (3)
C7—C8—C9—C10	−180.0 (2)	N2—C13—N3—C14	0.0 (4)
C3—C8—C9—C10	−0.1 (3)	S1—C13—N3—C14	−177.2 (2)
C7—C8—C9—N1	2.1 (3)	N5—C14—N3—C13	−179.8 (3)
C3—C8—C9—N1	−178.1 (2)	C15—C14—N3—C13	−1.1 (4)
N1—C9—C10—C1	178.4 (2)	N3—C13—S1—C12	−165.84 (19)
C8—C9—C10—C1	0.6 (4)	N2—C13—S1—C12	16.6 (2)
C2—C1—C10—C9	−0.2 (4)	C11—C12—S1—C13	−64.63 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···N3i	0.86	2.27	3.110 (4)	167
N1—H1A···O1ii	0.86	2.05	2.890 (3)	165
N4—H4B···O1iii	0.86	2.36	2.964 (3)	127
C12—H12A···O1ii	0.97	2.58	3.408 (3)	143

C12H12FN5OS	F(000) = 608
Mr = 293.33	Dx = 1.441 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 21.7358 (7) Å	Cell parameters from 3312 reflections
b = 7.3726 (3) Å	θ = 1.9–28.3°
c = 8.4487 (3) Å	µ = 0.25 mm−1
β = 93.092 (1)°	T = 293 K
V = 1351.93 (9) Å3	Block, colourless
Z = 4	0.31 × 0.25 × 0.20 mm

Bruker SMART APEXII area-detector diffractometer	2829 reflections with I > 2σ(I)
ω and φ scans	Rint = 0.025
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θmax = 28.3°, θmin = 1.9°
Tmin = 0.652, Tmax = 0.753	h = −28→28
12316 measured reflections	k = −5→9
3312 independent reflections	l = −7→11

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.055P)2 + 0.3099P] where P = (Fo2 + 2Fc2)/3
3312 reflections	(Δ/σ)max = 0.001
181 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

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

	x	y	z	Uiso*/Ueq
C1	0.43036 (9)	−0.1374 (4)	0.4152 (3)	0.0777 (6)
C2	0.42379 (9)	0.0399 (4)	0.3738 (3)	0.0824 (6)
H2	0.450358	0.092466	0.304272	0.099*
C3	0.37714 (8)	0.1422 (3)	0.4359 (2)	0.0658 (4)
H3	0.372002	0.263568	0.408377	0.079*
C4	0.33831 (6)	0.0600 (2)	0.53966 (17)	0.0480 (3)
C5	0.34659 (8)	−0.1211 (2)	0.5791 (2)	0.0605 (4)
H5	0.320667	−0.175666	0.649109	0.073*
C6	0.39282 (10)	−0.2211 (3)	0.5158 (3)	0.0746 (5)
H6	0.398185	−0.342957	0.541273	0.089*
C7	0.26854 (6)	0.32063 (19)	0.58470 (16)	0.0432 (3)
C8	0.21206 (7)	0.36589 (19)	0.67409 (17)	0.0482 (3)
H8A	0.210250	0.496199	0.688963	0.058*
H8B	0.216105	0.310216	0.778152	0.058*
C9	0.13013 (6)	0.07360 (17)	0.65615 (14)	0.0378 (3)
C10	0.06207 (7)	−0.1564 (2)	0.67975 (18)	0.0501 (3)
C11	0.10494 (7)	−0.2466 (2)	0.77884 (18)	0.0505 (3)
H11	0.095821	−0.358065	0.823502	0.061*
C12	0.16170 (7)	−0.16497 (18)	0.80890 (15)	0.0415 (3)
F1	0.47632 (7)	−0.2347 (3)	0.3527 (2)	0.1187 (6)
N1	0.28896 (5)	0.15094 (17)	0.60807 (15)	0.0480 (3)
H1	0.269193	0.087989	0.674351	0.058*
N2	0.07407 (5)	0.00964 (16)	0.61864 (14)	0.0452 (3)
N3	0.17559 (5)	−0.00336 (14)	0.74173 (12)	0.0390 (2)
N4	0.20765 (7)	−0.23810 (17)	0.90067 (16)	0.0546 (3)
H4A	0.242409	−0.182765	0.912926	0.066*
H4B	0.202291	−0.340228	0.947136	0.066*
N5	0.00588 (8)	−0.2236 (2)	0.6394 (2)	0.0815 (5)
H5A	−0.019470	−0.162080	0.579047	0.098*
H5B	−0.004701	−0.328149	0.674068	0.098*
O1	0.29125 (5)	0.43187 (15)	0.49776 (14)	0.0597 (3)
S1	0.14082 (2)	0.29101 (5)	0.57535 (5)	0.05097 (13)

	U11	U22	U33	U12	U13	U23
C1	0.0526 (10)	0.0988 (16)	0.0819 (13)	0.0139 (10)	0.0035 (9)	−0.0235 (12)
C2	0.0581 (11)	0.1083 (18)	0.0830 (13)	−0.0068 (11)	0.0248 (10)	−0.0037 (13)
C3	0.0548 (9)	0.0710 (11)	0.0728 (11)	−0.0055 (8)	0.0142 (8)	0.0061 (9)
C4	0.0429 (7)	0.0532 (8)	0.0478 (7)	−0.0038 (6)	−0.0002 (6)	−0.0007 (6)
C5	0.0577 (9)	0.0563 (10)	0.0677 (10)	0.0023 (7)	0.0049 (7)	0.0015 (8)
C6	0.0682 (11)	0.0665 (12)	0.0885 (14)	0.0138 (9)	−0.0011 (10)	−0.0103 (10)
C7	0.0453 (7)	0.0420 (7)	0.0418 (6)	−0.0102 (5)	−0.0029 (5)	0.0014 (5)
C8	0.0597 (8)	0.0347 (7)	0.0508 (7)	−0.0064 (6)	0.0081 (6)	−0.0023 (6)
C9	0.0447 (6)	0.0333 (6)	0.0366 (6)	0.0004 (5)	0.0123 (5)	−0.0009 (5)
C10	0.0498 (8)	0.0469 (8)	0.0543 (8)	−0.0080 (6)	0.0102 (6)	0.0061 (6)
C11	0.0604 (9)	0.0395 (7)	0.0521 (8)	−0.0086 (6)	0.0088 (7)	0.0089 (6)
C12	0.0551 (7)	0.0340 (6)	0.0361 (6)	0.0012 (5)	0.0082 (5)	−0.0014 (5)
F1	0.0774 (9)	0.1484 (14)	0.1323 (13)	0.0357 (9)	0.0230 (8)	−0.0415 (11)
N1	0.0499 (6)	0.0442 (6)	0.0508 (6)	−0.0030 (5)	0.0106 (5)	0.0070 (5)
N2	0.0442 (6)	0.0422 (6)	0.0499 (6)	−0.0029 (5)	0.0079 (5)	0.0056 (5)
N3	0.0467 (6)	0.0320 (5)	0.0390 (5)	−0.0001 (4)	0.0081 (4)	0.0003 (4)
N4	0.0677 (8)	0.0397 (6)	0.0557 (7)	−0.0015 (6)	−0.0045 (6)	0.0089 (5)
N5	0.0586 (9)	0.0747 (11)	0.1098 (14)	−0.0267 (8)	−0.0091 (8)	0.0363 (10)
O1	0.0564 (6)	0.0514 (6)	0.0719 (7)	−0.0071 (5)	0.0085 (5)	0.0188 (5)
S1	0.0472 (2)	0.0404 (2)	0.0655 (2)	−0.00120 (14)	0.00437 (16)	0.01690 (16)

C1—C6	1.358 (3)	C8—H8B	0.9700
C1—C2	1.359 (3)	C9—N3	1.3207 (17)
C1—F1	1.359 (2)	C9—N2	1.3288 (17)
C2—C3	1.389 (3)	C9—S1	1.7625 (13)
C2—H2	0.9300	C10—N5	1.345 (2)
C3—C4	1.388 (2)	C10—N2	1.3594 (18)
C3—H3	0.9300	C10—C11	1.388 (2)
C4—C5	1.386 (2)	C11—C12	1.384 (2)
C4—N1	1.4144 (19)	C11—H11	0.9300
C5—C6	1.378 (3)	C12—N4	1.3438 (19)
C5—H5	0.9300	C12—N3	1.3606 (17)
C6—H6	0.9300	N1—H1	0.8600
C7—O1	1.2227 (16)	N4—H4A	0.8600
C7—N1	1.3386 (19)	N4—H4B	0.8600
C7—C8	1.513 (2)	N5—H5A	0.8600
C8—S1	1.8054 (15)	N5—H5B	0.8600
C8—H8A	0.9700
C6—C1—C2	122.69 (18)	H8A—C8—H8B	107.7
C6—C1—F1	118.8 (2)	N3—C9—N2	128.87 (12)
C2—C1—F1	118.5 (2)	N3—C9—S1	119.50 (10)
C1—C2—C3	119.57 (19)	N2—C9—S1	111.64 (10)
C1—C2—H2	120.2	N5—C10—N2	115.21 (15)
C3—C2—H2	120.2	N5—C10—C11	123.17 (14)
C4—C3—C2	118.9 (2)	N2—C10—C11	121.61 (14)
C4—C3—H3	120.6	C12—C11—C10	117.71 (13)
C2—C3—H3	120.6	C12—C11—H11	121.1
C5—C4—C3	119.78 (16)	C10—C11—H11	121.1
C5—C4—N1	116.72 (14)	N4—C12—N3	114.66 (13)
C3—C4—N1	123.49 (16)	N4—C12—C11	123.98 (13)
C6—C5—C4	120.67 (18)	N3—C12—C11	121.34 (13)
C6—C5—H5	119.7	C7—N1—C4	129.45 (13)
C4—C5—H5	119.7	C7—N1—H1	115.3
C1—C6—C5	118.4 (2)	C4—N1—H1	115.3
C1—C6—H6	120.8	C9—N2—C10	114.92 (12)
C5—C6—H6	120.8	C9—N3—C12	115.35 (11)
O1—C7—N1	125.03 (14)	C12—N4—H4A	120.0
O1—C7—C8	121.11 (13)	C12—N4—H4B	120.0
N1—C7—C8	113.84 (12)	H4A—N4—H4B	120.0
C7—C8—S1	113.63 (10)	C10—N5—H5A	120.0
C7—C8—H8A	108.8	C10—N5—H5B	120.0
S1—C8—H8A	108.8	H5A—N5—H5B	120.0
C7—C8—H8B	108.8	C9—S1—C8	103.11 (7)
S1—C8—H8B	108.8
C6—C1—C2—C3	0.2 (3)	O1—C7—N1—C4	−1.5 (2)
F1—C1—C2—C3	179.92 (18)	C8—C7—N1—C4	177.03 (13)
C1—C2—C3—C4	0.2 (3)	C5—C4—N1—C7	−176.10 (15)
C2—C3—C4—C5	−0.1 (3)	C3—C4—N1—C7	3.0 (2)
C2—C3—C4—N1	−179.19 (16)	N3—C9—N2—C10	1.3 (2)
C3—C4—C5—C6	−0.3 (3)	S1—C9—N2—C10	−178.73 (10)
N1—C4—C5—C6	178.83 (15)	N5—C10—N2—C9	−178.64 (15)
C2—C1—C6—C5	−0.6 (3)	C11—C10—N2—C9	2.5 (2)
F1—C1—C6—C5	179.66 (18)	N2—C9—N3—C12	−4.68 (19)
C4—C5—C6—C1	0.7 (3)	S1—C9—N3—C12	175.34 (9)
O1—C7—C8—S1	96.18 (14)	N4—C12—N3—C9	−177.50 (12)
N1—C7—C8—S1	−82.44 (14)	C11—C12—N3—C9	4.35 (18)
N5—C10—C11—C12	178.71 (16)	N3—C9—S1—C8	−11.34 (11)
N2—C10—C11—C12	−2.5 (2)	N2—C9—S1—C8	168.68 (10)
C10—C11—C12—N4	−179.08 (14)	C7—C8—S1—C9	91.88 (11)
C10—C11—C12—N3	−1.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3	0.86	2.25	2.990 (2)	145
C3—H3···O1	0.93	2.31	2.903 (2)	121
N5—H5A···N2i	0.86	2.29	3.139 (2)	169
N4—H4A···O1ii	0.86	2.23	2.9852 (18)	146
C2—H2···F1iii	0.93	2.48	3.404 (3)	172