Crystal structures of the co-crystalline adduct 5-(4-bromo-phen-yl)-1,3,4-thia-diazol-2-amine-4-nitro-benzoic acid (1/1) and the salt 2-amino-5-(4-bromo-phen-yl)-1,3,4-thia-diazol-3-ium 2-carb-oxy-4,6-di-nitro-phenolate.

The structures of the 1:1 co-crystalline adduct C8H6BrN3S·C7H5NO4, (I), and the salt C8H7BrN3S(+)·C7H3N2O7 (-), (II), obtained from the inter-action of 5-(4-bromo-phen-yl)-1,3,4-thia-diazol-2-amine with 4-nitro-benzoic acid and 3,5-di-nitro-salicylic acid, respectively, have been determined. The primary inter-species association in both (I) and (II) is through duplex R (2) 2(8) (N-H⋯O/O-H⋯O) or (N-H⋯O/N-H⋯O) hydrogen bonds, respectively, giving heterodimers. In (II), these are close to planar [the dihedral angles between the thia-diazole ring and the two phenyl rings are 2.1 (3) (intra) and 9.8 (2)° (inter)], while in (I) these angles are 22.11 (15) and 26.08 (18)°, respectively. In the crystal of (I), the heterodimers are extended into a chain along b through an amine N-H⋯Nthia-diazole hydrogen bond but in (II), a centrosymmetric cyclic hetero-tetra-mer structure is generated through N-H⋯O hydrogen bonds to phenol and nitro O-atom acceptors and features, together with the primary R (2) 2(8) inter-action, conjoined R (4) 6(12), R (2) 1(6) and S(6) ring motifs. Also present in (I) are π-π inter-actions between thia-diazole rings [minimum ring-centroid separation = 3.4624 (16) Å], as well as short Br⋯Onitro inter-actions in both (I) and (II) [3.296 (3) and 3.104 (3) Å, respectively].

Chemical context

1,3,4-Thia­diazole (TZ) and its derivatives, particularly the 2-amino-substituted analogues (ATZ), which are commonly phenyl-substituted at the 5-site of the thia­diazole ring, exhibit a broad range of biological activities (Jain et al., 2013 ▶). In the solid state, these 2-amino-1,3,4-thia­diazo­les usually inter­act through duplex N—H⋯N hydrogen bonds, giving a centrosymmetric cyclic (8) hydrogen-bonding homodimer motif, which may be discrete e.g. the 5-(3-fluoro­phen­yl)-ATZ deriv­ative (Wang et al., 2009 ▶) or more often is extended into a one-dimensional chain structure through the second 2-amino H-atom by an N—H⋯N4thia­diazole hydrogen bond, e.g. in the 5-(4-bromo­phen­yl)-ATZ derivative (Lynch, 2009a ▶) and the 5-(4-bromo-2-nitro­phen­yl)-ATZ derivative (Zhang et al., 2011 ▶).

With an inter­est in the formation of co-crystalline adducts as opposed to proton-transfer salt formation between Lewis bases and aromatic carb­oxy­lic acids, we have looked at some of these 5-phenyl-substituted ATZ analogues and have reported examples of both structure types: one-dimensional chain structures in the 1:1 adduct of 5-(4-meth­oxy­phen­yl)-2-amino-1,3,4-thia­diazol-2-amine with 4-nitro­benzoic acid (Lynch, 2009b ▶) and 5-(4-bromo­phen­yl)-2-amino-1,3,4-thia­diazol-2-amine (BATZ) with 2-(naphthalen-2-yl­oxy)acetic acid (Smith & Lynch, 2013 ▶), as well as the salt of BATZ with 3,5-di­nitro­benzoic acid (Smith & Lynch, 2013 ▶). In this salt structure, the carboxyl­ate group gives the previously mentioned primary cyclic (8) association through carboxyl O⋯H—N and amine N—H⋯O hydrogen bonds but instead of forming the chain structure, a centrosymmetric hetero­tetra­mer is formed through a cyclic (8) hydrogen-bonding motif.

Herein we report the structures of the 1:1 co-crystalline adduct, C8H6BrN3S·C7H5NO4, (I), and the salt C8H7BrN3S+·C7H3N2O7 −, (II), obtained from the inter­action of BATZ with 4-nitro­benzoic acid (PNBA) and 3,5-di­nitro­salicylic acid (DNSA), respectively. The strong acid DNSA (pK a = 2.18) has been employed extensively for the formation of crystalline salts with Lewis bases, forming mainly phenolates (Smith et al., 2007 ▶), whereas the weaker acid PNBA (pK a = 3.44) provides examples of both salts (Byriel et al., 1992 ▶) and co-crystalline adducts (Aakeröy et al., 2004 ▶).

Structural commentary

In the structure of the (1:1) PNBA adduct with BATZ, (I), the primary inter-species (8) hydrogen-bonded heterodimer is formed (Fig. 1 ▶), in which the 4-bromo­phenyl ring substituent is rotated slightly out of the thia­diazole plane [dihedral angles between the thia­diazole ring and the two benzene rings are 22.11 (15) (intra) and 26.08 (18)° (inter)]. The carb­oxy­lic acid and nitro substituent groups on the PNBA mol­ecule are rotated slightly out of the benzene plane [torsion angles: C2A—C1A—C11A—O11A = −170.2 (3) and C3A— C4A—N4A—O42A = 172.03 (3)°]. This ‘planar’ conformation is found in the parent acid (Bolte, 2009 ▶) and in its adducts, e.g. with 3-(N,N-di­methyl­amino)­benzoic acid (Aakeröy et al., 2004 ▶).

Figure 1

Mol­ecular conformation and atom-numbering scheme for adduct (I), with inter-species hydrogen bonds shown as dashed lines. Non-H atoms are shown as 50% probability displacement ellipsoids.

In the DNSA salt (II) (Fig. 2 ▶), the primary association is also the expected cyclic (8) heterodimer, which is essentially planar [comparative dihedral angles 9.8 (2) (intra) and 2.1 (2)° (inter)]. The DNSA anionic moiety is a phenolate with the anti-related carb­oxy­lic acid H atom forming the common intra­molecular S(6) hydrogen bond which is found in ca. 70% of DNSA salt structures (Smith et al., 2007 ▶). The nitro group at C3A in this anion is rotated significantly out of the benzene plane [torsion angle: C2A—C3A—N3A—O32A = −147.8 (4)°] whereas the second nitro group and the carboxyl­ate group lie essentially in the plane [torsion angles: C6A—C5A— N5A—O51A = 179.5 (4) and C2A—C1A— C11A—O11A = −178.0 (4)°].

Figure 2

Mol­ecular conformation and atom-numbering scheme for salt (II), with inter-species hydrogen bonds shown as dashed lines. Non-H atoms are shown as 50% probability displacement ellipsoids.

Supra­molecular features

In (I), the heterodimers are linked through amine N21B—H21B⋯N4B i hydrogen bonds (Table 1 ▶) forming chains which extend along b (Fig. 3 ▶). This is similar to the structure of the BATZ adduct with 2-naphthoxyacetic acid (Smith & Lynch, 2013 ▶) and the 5-(4-meth­oxy­phen­yl)thia­diazin-2-amine adduct with 4-NBA (Lynch, 2009b ▶). A weak aromatic C55B—H55B⋯O41A ii hydrogen-bonding association links the chains across c [for symmetry codes, see Table 1 ▶] and together with π–π inter­actions between thia­diazole rings [minimum ring-centroid separation = 3.4624 (16) Å], give a two-dimensional supra­molecular structure.

Table 1

Hydrogen-bond geometry (, ) for (I)

DHA	DH	HA	D A	DHA
O11AH11AN3B	0.90	1.75	2.648(3)	175
N21BH21BO12A	0.82	2.04	2.859(4)	172
N21BH22BN4B i	0.92	2.16	3.052(3)	162
C55BH55BO41A ii	0.95	2.47	3.302(4)	146

Symmetry codes: (i) ; (ii) .

Figure 3

A perspective view of the one-dimensional hydrogen-bonded extension in the structure of (I). Hydrogen bonds are shown as dashed lines.

With (II), a secondary symmetric three-centre hydrogen-bonding inter­action between the second amine-H atom and both the phenolate-O atom (O2B) and the adjacent nitro-O atom (O31A) (Table 2 ▶) gives an enlarged centrosymmetric cyclic (12) association. This generates a hetero­tetra­mer, which comprises a total of seven conjoined cyclic motifs, the central (12) plus two each of (8), (6) and S(6) motifs (Fig. 4 ▶). The hetero­tetra­mers are weakly linked peripherally through both a centrosymmetric cyclic C—H⋯Onitro [C4A—H4A⋯O32A ii] hydrogen-bond pair [graph set (10)] and a linear C56B—H56B⋯O51A iii hydrogen bond, giving a two-dimensional supra­molecular structure (for symmetry codes, see Table 2 ▶). Within the cyclic association there is a short O32A⋯O32A ii non-bonding contact [2.835 (4) Å]. However, unlike in the structure of (I), no π–π ring inter­actions are found in (II) [minimum ring-centroid separation = 4.078 (3) Å].

Table 2

Hydrogen-bond geometry (, ) for (II)

DHA	DH	HA	D A	DHA
O12AH12AO2A	0.87	1.57	2.418(4)	164
N3BH3BO11A	0.88	1.87	2.744(4)	172
N21BH21BO12A	0.88	1.89	2.747(4)	166
N21BH22BO2A i	0.88	2.22	2.897(4)	134
N21BH22BO31A i	0.88	2.19	2.986(5)	150
C4AH4AO32A ii	0.95	2.44	3.284(5)	148
C56BH56BO51A iii	0.95	2.44	3.364(5)	164

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

Figure 4

A perspective view of the centrosymmetric hydrogen-bonded hetero­tetra­mer units in the unit cell of (II), showing conjoined cyclic (12), (8), (6) and S(6) hydrogen-bonded structural motifs.

In both (I) and (II), short Br⋯Onitro contacts are found: for (I) Br1B⋯O42A iii = 3.314 (4) Å, and for (II), Br1B⋯ O52A iv = 3.104 (3) Å [symmetry codes: (iii) x + , −y + , z + ; (iv) −x, −y, −z + 1].

Synthesis and crystallization

The title compounds were prepared by the reaction of 1 mmol (260 mg) of 5-(4-bromo­phen­yl)-1,3,4-thia­diazol-2-amine with 1 mmol of either 4-nitro­benzoic acid (167 mg) [for (I)] or 3,5-di­nitro­salicylic acid (228 mg) [for (II)] in 20 mL of 50% ethanol–water, with 10 min refluxing. Partial evaporation of the solvent gave colourless needles of (I) or yellow plates of (II) from which specimens were cleaved for the X-ray analyses.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3 ▶. Hydrogen atoms potentially involved in hydrogen-bonding inter­actions were located by difference methods but were subsequently included in the refinements with positional parameters fixed and their isotropic displacement parameters riding, with U iso(H) = 1.2U eq(N) or 1.5U eq(O). Other H atoms were included at calculated positions [C—H = 0.95 Å] and also treated as riding, with U iso(H) = 1.2U eq(C).

Table 3

Experimental details

	(I)	(II)
Crystal data
Chemical formula	C8H6BrN3SC7H5NO4	C8H7BrN3S+C7H3N2O7
M r	423.25	484.25
Crystal system, space group	Monoclinic, C2/c	Triclinic, P
Temperature (K)	200	200
a, b, c ()	8.5205(6), 12.0394(7), 31.4321(18)	5.8017(3), 10.1903(5), 15.1592(9)
, , ()	90, 92.982(6), 90	88.884(4), 82.438(5), 85.470(4)
V (3)	3220.0(3)	885.62(8)
Z	8	2
Radiation type	Mo K	Mo K
(mm1)	2.71	2.49
Crystal size (mm)	0.30 0.10 0.05	0.25 0.20 0.18
Data collection
Diffractometer	Oxford Diffraction Gemini-S CCD detector	Oxford Diffraction Gemini-S CCD detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013 ▶)	Multi-scan (CrysAlis PRO; Agilent, 2013 ▶)
T min, T max	0.936, 0.980	0.903, 0.980
No. of measured, independent and observed [I > 2(I)] reflections	6234, 3164, 2446	5742, 3458, 2479
R int	0.029	0.045
(sin /)max (1)	0.617	0.617
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.044, 0.093, 1.05	0.058, 0.134, 1.08
No. of reflections	3164	3458
No. of parameters	226	263
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
max, min (e 3)	0.37, 0.30	0.78, 0.82

Computer programs: CrysAlis PRO (Agilent, 2013 ▶), SIR92 (Altomare et al., 1993 ▶), SHELXL97 (Sheldrick, 2008 ▶) within WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S1600536814021138/lh5731sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814021138/lh5731Isup2.hkl

Structure factors: contains datablock(s) II. DOI: 10.1107/S1600536814021138/lh5731IIsup3.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814021138/lh5731Isup4.cml

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814021138/lh5731IIsup5.cml

CCDC references: 1025540, 1025541

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

C8H7BrN3S+·C7H3N2O7−	Z = 2
Mr = 484.25	F(000) = 484
Triclinic, P1	Dx = 1.816 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.8017 (3) Å	Cell parameters from 1277 reflections
b = 10.1903 (5) Å	θ = 3.6–24.8°
c = 15.1592 (9) Å	µ = 2.49 mm−1
α = 88.884 (4)°	T = 200 K
β = 82.438 (5)°	Block, yellow
γ = 85.470 (4)°	0.25 × 0.20 × 0.18 mm
V = 885.62 (8) Å3

Oxford Diffraction Gemini-S CCD detector diffractometer	3458 independent reflections
Radiation source: Enhance (Mo) X-ray source	2479 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
Detector resolution: 16.077 pixels mm-1	θmax = 26.0°, θmin = 3.4°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −11→12
Tmin = 0.903, Tmax = 0.980	l = −18→9
5742 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.058	H-atom parameters constrained
wR(F2) = 0.134	w = 1/[σ2(Fo2) + (0.0545P)2] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max < 0.001
3458 reflections	Δρmax = 0.78 e Å−3
263 parameters	Δρmin = −0.82 e Å−3
0 restraints	Extinction correction: SHELXL97, FC*=KFC[1+0.001XFC2Λ3/SIN(2Θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.042 (3)

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
O2A	0.1351 (5)	0.6524 (3)	0.0207 (2)	0.0330 (9)
O11A	−0.0271 (5)	0.3833 (3)	0.2158 (2)	0.0373 (10)
O12A	0.2276 (5)	0.4583 (3)	0.1075 (2)	0.0374 (10)
O31A	−0.0556 (5)	0.8407 (3)	−0.0818 (2)	0.0360 (10)
O32A	−0.2559 (5)	0.9897 (3)	0.0027 (2)	0.0367 (10)
O51A	−0.8459 (5)	0.8277 (3)	0.2177 (2)	0.0434 (11)
O52A	−0.7757 (5)	0.6493 (3)	0.2912 (2)	0.0447 (11)
N3A	−0.1754 (6)	0.8761 (4)	−0.0119 (2)	0.0298 (11)
N5A	−0.7202 (6)	0.7301 (4)	0.2328 (2)	0.0314 (12)
C1A	−0.1349 (7)	0.5803 (4)	0.1393 (3)	0.0245 (12)
C2A	−0.0684 (7)	0.6698 (4)	0.0697 (3)	0.0255 (12)
C3A	−0.2287 (7)	0.7776 (4)	0.0571 (3)	0.0256 (12)
C4A	−0.4397 (7)	0.7983 (4)	0.1105 (3)	0.0248 (12)
C5A	−0.4948 (7)	0.7078 (4)	0.1777 (3)	0.0251 (12)
C6A	−0.3473 (7)	0.5999 (4)	0.1929 (3)	0.0274 (12)
C11A	0.0285 (7)	0.4637 (4)	0.1578 (3)	0.0294 (14)
Br1B	0.60639 (11)	−0.41426 (5)	0.59418 (3)	0.0574 (2)
S1B	0.68942 (18)	0.05777 (11)	0.23777 (7)	0.0314 (3)
N3B	0.2976 (6)	0.1838 (3)	0.2484 (2)	0.0288 (11)
N4B	0.2693 (6)	0.0962 (3)	0.3171 (2)	0.0303 (11)
N21B	0.5551 (6)	0.2544 (3)	0.1290 (2)	0.0346 (11)
C2B	0.5050 (7)	0.1784 (4)	0.1978 (3)	0.0267 (12)
C5B	0.4588 (7)	0.0224 (4)	0.3197 (3)	0.0289 (12)
C51B	0.4894 (7)	−0.0828 (4)	0.3850 (3)	0.0289 (12)
C52B	0.3110 (8)	−0.1094 (5)	0.4517 (3)	0.0383 (17)
C53B	0.3431 (9)	−0.2075 (5)	0.5136 (3)	0.0433 (17)
C54B	0.5553 (9)	−0.2817 (4)	0.5088 (3)	0.0368 (14)
C55B	0.7313 (9)	−0.2594 (5)	0.4423 (3)	0.0420 (17)
C56B	0.6997 (8)	−0.1610 (5)	0.3807 (3)	0.0386 (17)
H4A	−0.54410	0.87240	0.10140	0.0300*
H6A	−0.39030	0.53950	0.23950	0.0330*
H12A	0.22100	0.52990	0.07550	0.0560*
H3B	0.18380	0.24180	0.23770	0.0350*
H21B	0.44930	0.31390	0.11350	0.0410*
H22B	0.69490	0.24630	0.09820	0.0410*
H52B	0.16500	−0.05930	0.45460	0.0460*
H53B	0.22040	−0.22440	0.55940	0.0520*
H55B	0.87510	−0.31180	0.43860	0.0500*
H56B	0.82260	−0.14590	0.33460	0.0460*

	U11	U22	U33	U12	U13	U23
O2A	0.0266 (15)	0.0346 (17)	0.0350 (17)	0.0035 (14)	0.0012 (13)	0.0106 (13)
O11A	0.0373 (17)	0.0299 (17)	0.0412 (19)	0.0067 (15)	−0.0001 (15)	0.0131 (14)
O12A	0.0308 (17)	0.0316 (17)	0.047 (2)	0.0054 (14)	−0.0018 (15)	0.0162 (14)
O31A	0.0378 (17)	0.0395 (18)	0.0287 (17)	0.0007 (15)	−0.0014 (14)	0.0122 (14)
O32A	0.0308 (16)	0.0224 (16)	0.054 (2)	0.0070 (14)	−0.0025 (15)	0.0143 (14)
O51A	0.0361 (18)	0.0377 (19)	0.050 (2)	0.0159 (16)	0.0058 (15)	0.0097 (16)
O52A	0.0409 (18)	0.043 (2)	0.044 (2)	0.0024 (16)	0.0115 (15)	0.0174 (16)
N3A	0.0237 (19)	0.033 (2)	0.033 (2)	−0.0017 (17)	−0.0063 (17)	0.0097 (17)
N5A	0.030 (2)	0.029 (2)	0.033 (2)	0.0013 (18)	0.0012 (17)	0.0010 (17)
C1A	0.027 (2)	0.019 (2)	0.028 (2)	−0.0007 (18)	−0.0072 (18)	0.0040 (17)
C2A	0.025 (2)	0.025 (2)	0.026 (2)	0.0018 (19)	−0.0040 (18)	0.0008 (18)
C3A	0.027 (2)	0.023 (2)	0.027 (2)	−0.0026 (19)	−0.0055 (18)	0.0093 (17)
C4A	0.024 (2)	0.022 (2)	0.028 (2)	0.0045 (18)	−0.0065 (18)	0.0022 (17)
C5A	0.023 (2)	0.026 (2)	0.025 (2)	0.0037 (18)	−0.0018 (17)	−0.0022 (17)
C6A	0.029 (2)	0.025 (2)	0.028 (2)	−0.0007 (19)	−0.0041 (18)	0.0049 (18)
C11A	0.028 (2)	0.026 (2)	0.034 (3)	0.002 (2)	−0.006 (2)	0.001 (2)
Br1B	0.0977 (5)	0.0413 (3)	0.0352 (3)	−0.0111 (3)	−0.0151 (3)	0.0174 (2)
S1B	0.0254 (6)	0.0321 (6)	0.0341 (6)	0.0043 (5)	0.0000 (5)	0.0122 (5)
N3B	0.0258 (19)	0.0265 (19)	0.032 (2)	0.0067 (16)	−0.0026 (16)	0.0086 (15)
N4B	0.0283 (19)	0.033 (2)	0.028 (2)	0.0002 (17)	0.0002 (16)	0.0068 (16)
N21B	0.0259 (19)	0.034 (2)	0.041 (2)	0.0075 (17)	−0.0015 (17)	0.0154 (17)
C2B	0.026 (2)	0.023 (2)	0.031 (2)	−0.0013 (19)	−0.0047 (19)	0.0041 (18)
C5B	0.031 (2)	0.028 (2)	0.027 (2)	−0.002 (2)	−0.0016 (18)	0.0031 (18)
C51B	0.032 (2)	0.031 (2)	0.024 (2)	−0.007 (2)	−0.0022 (18)	0.0031 (18)
C52B	0.038 (3)	0.039 (3)	0.036 (3)	0.002 (2)	−0.001 (2)	0.000 (2)
C53B	0.048 (3)	0.048 (3)	0.032 (3)	−0.011 (3)	0.005 (2)	0.007 (2)
C54B	0.059 (3)	0.028 (2)	0.025 (2)	−0.009 (2)	−0.009 (2)	0.0066 (19)
C55B	0.047 (3)	0.035 (3)	0.042 (3)	0.006 (2)	−0.006 (2)	0.013 (2)
C56B	0.038 (3)	0.041 (3)	0.033 (3)	0.003 (2)	0.004 (2)	0.015 (2)

Br1B—C54B	1.886 (4)	C1A—C6A	1.387 (6)
S1B—C5B	1.756 (4)	C1A—C11A	1.506 (6)
S1B—C2B	1.720 (4)	C1A—C2A	1.416 (6)
O2A—C2A	1.311 (5)	C2A—C3A	1.409 (6)
O11A—C11A	1.220 (5)	C3A—C4A	1.380 (6)
O12A—C11A	1.296 (5)	C4A—C5A	1.384 (6)
O31A—N3A	1.232 (4)	C5A—C6A	1.374 (6)
O32A—N3A	1.227 (5)	C4A—H4A	0.9500
O51A—N5A	1.222 (5)	C6A—H6A	0.9500
O52A—N5A	1.226 (5)	C5B—C51B	1.461 (6)
O12A—H12A	0.8700	C51B—C56B	1.398 (6)
N3A—C3A	1.456 (6)	C51B—C52B	1.388 (6)
N5A—C5A	1.460 (5)	C52B—C53B	1.376 (7)
N3B—C2B	1.337 (5)	C53B—C54B	1.387 (7)
N3B—N4B	1.360 (4)	C54B—C55B	1.367 (7)
N4B—C5B	1.287 (5)	C55B—C56B	1.375 (7)
N21B—C2B	1.302 (5)	C52B—H52B	0.9500
N3B—H3B	0.8800	C53B—H53B	0.9500
N21B—H22B	0.8800	C55B—H55B	0.9500
N21B—H21B	0.8800	C56B—H56B	0.9500
C2B—S1B—C5B	88.1 (2)	O11A—C11A—O12A	124.5 (4)
C11A—O12A—H12A	104.00	O11A—C11A—C1A	121.4 (4)
O32A—N3A—C3A	117.7 (3)	C3A—C4A—H4A	121.00
O31A—N3A—O32A	123.8 (4)	C5A—C4A—H4A	121.00
O31A—N3A—C3A	118.5 (4)	C5A—C6A—H6A	120.00
O51A—N5A—C5A	118.3 (3)	C1A—C6A—H6A	120.00
O51A—N5A—O52A	123.1 (3)	S1B—C2B—N3B	109.7 (3)
O52A—N5A—C5A	118.5 (4)	S1B—C2B—N21B	126.3 (3)
N4B—N3B—C2B	117.4 (3)	N3B—C2B—N21B	124.0 (4)
N3B—N4B—C5B	110.0 (3)	S1B—C5B—N4B	114.8 (3)
C2B—N3B—H3B	121.00	N4B—C5B—C51B	124.5 (4)
N4B—N3B—H3B	121.00	S1B—C5B—C51B	120.7 (3)
C2B—N21B—H21B	120.00	C5B—C51B—C56B	120.4 (4)
H21B—N21B—H22B	120.00	C52B—C51B—C56B	118.2 (4)
C2B—N21B—H22B	120.00	C5B—C51B—C52B	121.3 (4)
C2A—C1A—C11A	120.1 (4)	C51B—C52B—C53B	120.8 (4)
C6A—C1A—C11A	118.9 (4)	C52B—C53B—C54B	119.7 (4)
C2A—C1A—C6A	121.0 (4)	Br1B—C54B—C53B	120.6 (4)
C1A—C2A—C3A	117.0 (4)	C53B—C54B—C55B	120.5 (4)
O2A—C2A—C3A	122.4 (4)	Br1B—C54B—C55B	118.9 (4)
O2A—C2A—C1A	120.6 (4)	C54B—C55B—C56B	119.8 (5)
N3A—C3A—C2A	121.2 (4)	C51B—C56B—C55B	121.0 (4)
N3A—C3A—C4A	116.4 (4)	C51B—C52B—H52B	120.00
C2A—C3A—C4A	122.4 (4)	C53B—C52B—H52B	120.00
C3A—C4A—C5A	118.0 (4)	C52B—C53B—H53B	120.00
N5A—C5A—C4A	117.3 (4)	C54B—C53B—H53B	120.00
N5A—C5A—C6A	120.2 (4)	C54B—C55B—H55B	120.00
C4A—C5A—C6A	122.4 (4)	C56B—C55B—H55B	120.00
C1A—C6A—C5A	119.2 (4)	C51B—C56B—H56B	120.00
O12A—C11A—C1A	114.2 (4)	C55B—C56B—H56B	119.00
C2B—S1B—C5B—C51B	179.2 (4)	C11A—C1A—C6A—C5A	178.5 (4)
C2B—S1B—C5B—N4B	−1.5 (3)	O2A—C2A—C3A—N3A	0.1 (6)
C5B—S1B—C2B—N3B	1.5 (3)	O2A—C2A—C3A—C4A	−177.8 (4)
C5B—S1B—C2B—N21B	−178.6 (4)	C1A—C2A—C3A—C4A	1.3 (6)
O32A—N3A—C3A—C2A	−147.8 (4)	C1A—C2A—C3A—N3A	179.2 (4)
O31A—N3A—C3A—C4A	−148.7 (4)	C2A—C3A—C4A—C5A	−1.1 (6)
O32A—N3A—C3A—C4A	30.3 (5)	N3A—C3A—C4A—C5A	−179.0 (4)
O31A—N3A—C3A—C2A	33.3 (6)	C3A—C4A—C5A—N5A	−179.1 (4)
O51A—N5A—C5A—C4A	−1.1 (6)	C3A—C4A—C5A—C6A	0.3 (6)
O51A—N5A—C5A—C6A	179.5 (4)	C4A—C5A—C6A—C1A	0.1 (7)
O52A—N5A—C5A—C4A	178.0 (4)	N5A—C5A—C6A—C1A	179.5 (4)
O52A—N5A—C5A—C6A	−1.5 (6)	S1B—C5B—C51B—C52B	178.1 (4)
N4B—N3B—C2B—N21B	178.7 (4)	S1B—C5B—C51B—C56B	−3.0 (6)
C2B—N3B—N4B—C5B	0.3 (5)	N4B—C5B—C51B—C52B	−1.1 (7)
N4B—N3B—C2B—S1B	−1.4 (4)	N4B—C5B—C51B—C56B	177.8 (4)
N3B—N4B—C5B—C51B	−179.8 (4)	C5B—C51B—C52B—C53B	−179.1 (4)
N3B—N4B—C5B—S1B	0.9 (4)	C56B—C51B—C52B—C53B	2.0 (7)
C6A—C1A—C2A—C3A	−0.8 (6)	C5B—C51B—C56B—C55B	179.3 (4)
C6A—C1A—C2A—O2A	178.3 (4)	C52B—C51B—C56B—C55B	−1.7 (7)
C2A—C1A—C6A—C5A	0.2 (6)	C51B—C52B—C53B—C54B	−0.7 (7)
C11A—C1A—C2A—O2A	0.0 (6)	C52B—C53B—C54B—Br1B	178.7 (4)
C11A—C1A—C2A—C3A	−179.1 (4)	C52B—C53B—C54B—C55B	−1.0 (7)
C2A—C1A—C11A—O11A	−178.0 (4)	Br1B—C54B—C55B—C56B	−178.4 (4)
C2A—C1A—C11A—O12A	2.2 (6)	C53B—C54B—C55B—C56B	1.3 (7)
C6A—C1A—C11A—O11A	3.7 (6)	C54B—C55B—C56B—C51B	0.1 (7)
C6A—C1A—C11A—O12A	−176.2 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O12A—H12A···O2A	0.87	1.57	2.418 (4)	164
N3B—H3B···O11A	0.88	1.87	2.744 (4)	172
N21B—H21B···O12A	0.88	1.89	2.747 (4)	166
N21B—H22B···O2Ai	0.88	2.22	2.897 (4)	134
N21B—H22B···O31Ai	0.88	2.19	2.986 (5)	150
C4A—H4A···O32Aii	0.95	2.44	3.284 (5)	148
C56B—H56B···O51Aiii	0.95	2.44	3.364 (5)	164
C56B—H56B···S1B	0.95	2.64	3.081 (5)	109