A novel hydrogen-bonding N-oxide–sul­fon­amide–nitro N—H...O synthon determining the architecture of benzene­sul­fon­amide cocrystals

The structures of novel cocrystals of 4-nitro­pyridine N-oxide with benzene­sul­fon­amide derivatives, namely, 4-nitro­benzene­sul­fon­amide–4-nitro­pyridine N-oxide (1/1), C₅H₄N₂O₃·C₆H₆N₂O₄S, and 4-chloro­benzene­sul­fon­amide–4-nitro­pyridine N-oxide (1/1), C₆H₆ClNO₂S·C₅H₄N₂O₃, are stabilized by N—H...O hydrogen bonds, with the sul­fon­amide group acting as a proton donor. The O atoms of the N-oxide and nitro groups are acceptors in these inter­actions. The latter is a double acceptor of bifurcated hydrogen bonds. Previous studies on similar crystal structures indicated com­petition between these functional groups in the formation of hydrogen bonds, with the priority being for the N-oxide group. In contrast, the present X-ray studies indicate the existence of a hydrogen-bonding synthon including N—H...O(N-oxide) and N—H...O(nitro) bridges. We present here a more detailed analysis of the N-oxide–sul­fon­amide–nitro N—H...O ternary com­plex with quantum theory com­putations and the Quantum Theory of Atoms in Mol­ecules (QTAIM) approach. Both inter­actions are present in the crystals, but the O atom of the N-oxide group is found to be a more effective proton acceptor in hydrogen bonds, with an inter­action energy about twice that of the nitro-group O atoms.

Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2015) for structure_I; CrysAlis PRO (Rigaku OD, 2019) for structure_II. Cell refinement: CrysAlis PRO (Rigaku OD, 2015) for structure_I; CrysAlis PRO (Rigaku OD, 2019) for structure_II. Data reduction: CrysAlis PRO (Rigaku OD, 2015) for structure_I; CrysAlis PRO (Rigaku OD, 2019) for structure_II. For both structures, program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b).

4-Nitrobenzenesulfonamide–4-nitropyridine N-oxide (1/1) (structure_I)

Crystal data

C5H4N2O3·C6H6N2O4S	F(000) = 704
Mr = 342.29	Dx = 1.662 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54184 Å
a = 9.8459 (2) Å	Cell parameters from 7021 reflections
b = 10.9530 (2) Å	θ = 5.3–76.2°
c = 12.6881 (3) Å	µ = 2.57 mm^−1
β = 91.524 (2)°	T = 293 K
V = 1367.83 (5) Å^3	Plate, yellow
Z = 4	0.35 × 0.25 × 0.18 mm

Data collection

Rigaku OD SuperNova Dual source diffractometer with an Atlas detector	2848 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	2704 reflections with I > 2σ(I)
Detector resolution: 10.4052 pixels mm^-1	Rint = 0.018
ω scans	θmax = 76.5°, θmin = 5.3°
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2015)	h = −12→12
Tmin = 0.889, Tmax = 0.942	k = −13→10
11842 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.080	w = 1/[σ^2(Fo^2) + (0.0435P)^2 + 0.6523P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
2848 reflections	Δρmax = 0.24 e Å^−3
216 parameters	Δρmin = −0.49 e Å^−3
0 restraints

Special details

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.

Refinement. All XRD data were collected on a four-circle Oxford Diffraction Supernova Dual diffractometer using a two-dimensional area CCD. Integration of the intensities and corrections for Lorentz effects, polarization effects, and analytical absorption were performed with CrysAlis PRO. The crystal structures were solved by direct methods and refined on F² with a full-matrix least-squares procedure (SHELXL2014; Sheldrick, 2015).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1A	0.31764 (10)	0.50837 (8)	0.45407 (8)	0.0230 (2)
O12	0.10353 (10)	0.75433 (9)	0.72598 (8)	0.0256 (2)
O42A	0.14780 (10)	−0.02804 (9)	0.50911 (9)	0.0262 (2)
O11	0.11632 (10)	0.53536 (9)	0.67629 (9)	0.0262 (2)
O41A	0.35783 (11)	−0.03833 (9)	0.56319 (9)	0.0285 (2)
O42	0.80474 (10)	0.73469 (11)	0.84559 (9)	0.0314 (3)
O41	0.81244 (10)	0.54216 (10)	0.80761 (9)	0.0305 (2)
N1A	0.30350 (11)	0.39244 (10)	0.47247 (9)	0.0180 (2)
N4	0.75210 (11)	0.64031 (12)	0.81260 (9)	0.0234 (3)
N1	0.16751 (11)	0.69435 (11)	0.54861 (9)	0.0189 (2)
N4A	0.25935 (12)	0.01884 (10)	0.52868 (9)	0.0202 (2)
C4A	0.27484 (13)	0.14912 (11)	0.50865 (10)	0.0171 (3)
C1	0.34092 (13)	0.65172 (11)	0.71663 (10)	0.0175 (3)
C4	0.60776 (13)	0.64406 (13)	0.77847 (10)	0.0197 (3)
C6A	0.41091 (13)	0.32742 (12)	0.51232 (11)	0.0194 (3)
H6A	0.493261	0.366381	0.526673	0.023*
C5A	0.39829 (13)	0.20443 (12)	0.53149 (10)	0.0192 (3)
H5A	0.471077	0.159563	0.559145	0.023*
C2	0.40708 (14)	0.53959 (12)	0.72214 (10)	0.0196 (3)
H2	0.360433	0.468133	0.705121	0.023*
C3A	0.16510 (13)	0.21481 (13)	0.46808 (11)	0.0209 (3)
H3A	0.082402	0.176748	0.453070	0.025*
C6	0.40727 (14)	0.76026 (12)	0.74346 (10)	0.0196 (3)
H6	0.360890	0.834190	0.740295	0.024*
C2A	0.18167 (13)	0.33763 (12)	0.45061 (11)	0.0216 (3)
H2A	0.109343	0.383653	0.423704	0.026*
C5	0.54317 (14)	0.75675 (13)	0.77490 (11)	0.0209 (3)
H5	0.589761	0.827876	0.793093	0.025*
C3	0.54311 (14)	0.53514 (12)	0.75320 (10)	0.0206 (3)
H3	0.589553	0.461271	0.756953	0.025*
S1	0.16876 (3)	0.65721 (3)	0.67104 (2)	0.01723 (10)
H1A	0.211 (2)	0.638 (2)	0.5094 (16)	0.038 (5)*
H1B	0.1897 (19)	0.765 (2)	0.5379 (15)	0.034 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.0232 (5)	0.0131 (4)	0.0327 (5)	−0.0020 (4)	0.0048 (4)	−0.0013 (4)
O12	0.0216 (5)	0.0289 (5)	0.0263 (5)	0.0059 (4)	0.0024 (4)	−0.0044 (4)
O42A	0.0236 (5)	0.0203 (5)	0.0347 (6)	−0.0067 (4)	0.0020 (4)	0.0006 (4)
O11	0.0218 (5)	0.0195 (5)	0.0371 (6)	−0.0039 (4)	−0.0021 (4)	0.0089 (4)
O41A	0.0299 (5)	0.0226 (5)	0.0327 (6)	0.0053 (4)	−0.0047 (4)	0.0067 (4)
O42	0.0215 (5)	0.0396 (6)	0.0328 (6)	−0.0025 (4)	−0.0050 (4)	−0.0088 (5)
O41	0.0231 (5)	0.0373 (6)	0.0309 (6)	0.0115 (4)	−0.0016 (4)	0.0005 (5)
N1A	0.0177 (5)	0.0156 (5)	0.0208 (5)	−0.0012 (4)	0.0025 (4)	−0.0023 (4)
N4	0.0177 (5)	0.0355 (7)	0.0169 (5)	0.0024 (5)	−0.0008 (4)	−0.0001 (5)
N1	0.0197 (5)	0.0163 (5)	0.0205 (6)	0.0004 (4)	−0.0017 (4)	0.0009 (4)
N4A	0.0230 (5)	0.0183 (5)	0.0194 (5)	−0.0001 (4)	0.0017 (4)	0.0000 (4)
C4A	0.0181 (6)	0.0155 (6)	0.0178 (6)	−0.0004 (5)	0.0005 (5)	−0.0006 (4)
C1	0.0193 (6)	0.0183 (6)	0.0148 (6)	0.0016 (5)	0.0000 (5)	0.0018 (4)
C4	0.0177 (6)	0.0260 (7)	0.0153 (6)	0.0020 (5)	−0.0015 (5)	0.0002 (5)
C6A	0.0141 (6)	0.0212 (6)	0.0230 (6)	−0.0010 (5)	−0.0001 (5)	−0.0042 (5)
C5A	0.0160 (6)	0.0218 (6)	0.0196 (6)	0.0014 (5)	−0.0015 (5)	−0.0020 (5)
C2	0.0227 (6)	0.0163 (6)	0.0197 (6)	0.0011 (5)	−0.0008 (5)	0.0007 (5)
C3A	0.0148 (6)	0.0206 (6)	0.0273 (7)	−0.0020 (5)	−0.0018 (5)	−0.0008 (5)
C6	0.0224 (6)	0.0169 (6)	0.0195 (6)	0.0029 (5)	−0.0007 (5)	0.0003 (5)
C2A	0.0155 (6)	0.0200 (6)	0.0292 (7)	0.0005 (5)	−0.0029 (5)	0.0001 (5)
C5	0.0227 (6)	0.0211 (7)	0.0188 (6)	−0.0019 (5)	−0.0017 (5)	−0.0011 (5)
C3	0.0229 (6)	0.0201 (6)	0.0188 (6)	0.0051 (5)	−0.0009 (5)	0.0013 (5)
S1	0.01570 (16)	0.01613 (17)	0.01985 (17)	0.00064 (10)	0.00024 (11)	0.00184 (11)

Geometric parameters (Å, º)

O1A—N1A	1.2992 (15)	C1—C6	1.3944 (18)
O12—S1	1.4331 (10)	C1—S1	1.7775 (13)
O42A—N4A	1.2317 (15)	C4—C3	1.3857 (19)
O11—S1	1.4332 (10)	C4—C5	1.3887 (19)
O41A—N4A	1.2253 (15)	C6A—C5A	1.3750 (19)
O42—N4	1.2251 (17)	C6A—H6A	0.9300
O41—N4	1.2308 (16)	C5A—H5A	0.9300
N1A—C6A	1.3612 (17)	C2—C3	1.3869 (19)
N1A—C2A	1.3632 (17)	C2—H2	0.9300
N4—C4	1.4752 (17)	C3A—C2A	1.3737 (19)
N1—S1	1.6055 (12)	C3A—H3A	0.9300
N1—H1A	0.91 (2)	C6—C5	1.3866 (19)
N1—H1B	0.82 (2)	C6—H6	0.9300
N4A—C4A	1.4582 (16)	C2A—H2A	0.9300
C4A—C5A	1.3819 (18)	C5—H5	0.9300
C4A—C3A	1.3858 (18)	C3—H3	0.9300
C1—C2	1.3910 (18)
O1A—N1A—C6A	119.48 (11)	C4A—C5A—H5A	120.8
O1A—N1A—C2A	119.46 (11)	C3—C2—C1	119.52 (12)
C6A—N1A—C2A	121.05 (11)	C3—C2—H2	120.2
O42—N4—O41	123.65 (12)	C1—C2—H2	120.2
O42—N4—C4	118.19 (12)	C2A—C3A—C4A	118.27 (12)
O41—N4—C4	118.15 (12)	C2A—C3A—H3A	120.9
S1—N1—H1A	111.6 (13)	C4A—C3A—H3A	120.9
S1—N1—H1B	114.0 (14)	C5—C6—C1	119.27 (12)
H1A—N1—H1B	114.5 (19)	C5—C6—H6	120.4
O41A—N4A—O42A	123.50 (12)	C1—C6—H6	120.4
O41A—N4A—C4A	118.49 (11)	N1A—C2A—C3A	120.40 (12)
O42A—N4A—C4A	118.01 (11)	N1A—C2A—H2A	119.8
C5A—C4A—C3A	121.53 (12)	C3A—C2A—H2A	119.8
C5A—C4A—N4A	119.21 (12)	C6—C5—C4	118.13 (12)
C3A—C4A—N4A	119.26 (12)	C6—C5—H5	120.9
C2—C1—C6	121.65 (12)	C4—C5—H5	120.9
C2—C1—S1	119.18 (10)	C4—C3—C2	118.01 (12)
C6—C1—S1	119.15 (10)	C4—C3—H3	121.0
C3—C4—C5	123.40 (12)	C2—C3—H3	121.0
C3—C4—N4	118.49 (12)	O12—S1—O11	120.13 (6)
C5—C4—N4	118.10 (12)	O12—S1—N1	106.89 (6)
N1A—C6A—C5A	120.35 (12)	O11—S1—N1	106.70 (6)
N1A—C6A—H6A	119.8	O12—S1—C1	107.62 (6)
C5A—C6A—H6A	119.8	O11—S1—C1	107.16 (6)
C6A—C5A—C4A	118.39 (12)	N1—S1—C1	107.83 (6)
C6A—C5A—H5A	120.8
O41A—N4A—C4A—C5A	−1.58 (18)	C2—C1—C6—C5	1.0 (2)
O42A—N4A—C4A—C5A	178.98 (11)	S1—C1—C6—C5	−177.37 (10)
O41A—N4A—C4A—C3A	179.01 (12)	O1A—N1A—C2A—C3A	179.09 (12)
O42A—N4A—C4A—C3A	−0.44 (18)	C6A—N1A—C2A—C3A	−0.3 (2)
O42—N4—C4—C3	−172.31 (12)	C4A—C3A—C2A—N1A	0.3 (2)
O41—N4—C4—C3	6.78 (18)	C1—C6—C5—C4	−0.10 (19)
O42—N4—C4—C5	6.74 (18)	C3—C4—C5—C6	−0.6 (2)
O41—N4—C4—C5	−174.18 (12)	N4—C4—C5—C6	−179.61 (11)
O1A—N1A—C6A—C5A	−179.45 (12)	C5—C4—C3—C2	0.4 (2)
C2A—N1A—C6A—C5A	−0.07 (19)	N4—C4—C3—C2	179.42 (11)
N1A—C6A—C5A—C4A	0.43 (19)	C1—C2—C3—C4	0.5 (2)
C3A—C4A—C5A—C6A	−0.4 (2)	C2—C1—S1—O12	147.09 (11)
N4A—C4A—C5A—C6A	−179.84 (12)	C6—C1—S1—O12	−34.50 (12)
C6—C1—C2—C3	−1.2 (2)	C2—C1—S1—O11	16.61 (13)
S1—C1—C2—C3	177.18 (10)	C6—C1—S1—O11	−164.99 (10)
C5A—C4A—C3A—C2A	0.1 (2)	C2—C1—S1—N1	−97.93 (11)
N4A—C4A—C3A—C2A	179.50 (12)	C6—C1—S1—N1	80.48 (12)

4-Chlorobenzenesulfonamide–4-nitropyridine N-oxide (1/1) (structure_II)

Crystal data

C6H6ClNO2S·C5H4N2O3	F(000) = 680
Mr = 331.73	Dx = 1.623 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.392 (2) Å	Cell parameters from 8998 reflections
b = 11.2356 (8) Å	θ = 3.1–31.5°
c = 16.674 (19) Å	µ = 0.46 mm^−1
β = 101.33 (5)°	T = 293 K
V = 1357.8 (16) Å^3	Plate, yellow
Z = 4	0.69 × 0.18 × 0.09 mm

Data collection

Rigaku OD SuperNova Dual source diffractometer with an Atlas detector	3430 independent reflections
Radiation source: micro-focus sealed X-ray tube	2577 reflections with I > 2σ(I)
Detector resolution: 10.4052 pixels mm^-1	Rint = 0.046
ω scans	θmax = 28.5°, θmin = 3.1°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2019)	h = −9→9
Tmin = 0.459, Tmax = 1.000	k = −13→15
17382 measured reflections	l = −20→22

Refinement

Refinement on F^2	Primary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.088	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.183	w = 1/[σ^2(Fo^2) + (0.0148P)^2 + 8.5074P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
3430 reflections	Δρmax = 1.47 e Å^−3
286 parameters	Δρmin = −1.05 e Å^−3
21 restraints

Special details

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.

Refinement. All XRD data were collected on a four-circle Oxford Diffraction Supernova Dual diffractometer using a two-dimensional area CCD. Integration of the intensities and corrections for Lorentz effects, polarization effects, and analytical absorption were performed with CrysAlis PRO. The crystal structures were solved by direct methods and refined on F² with a full-matrix least-squares procedure (SHELXL2014; Sheldrick, 2015).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1A	0.393 (3)	0.475 (3)	0.1781 (19)	0.032 (4)	0.5
N1A	0.3560 (9)	0.5908 (7)	0.1677 (4)	0.0266 (14)	0.5
C6A	0.3887 (18)	0.6301 (11)	0.0952 (8)	0.027 (3)	0.5
H6A	0.412257	0.574480	0.057259	0.032*	0.5
C5A	0.389 (2)	0.7543 (13)	0.0743 (10)	0.024 (3)	0.5
H5A	0.411218	0.781228	0.024428	0.029*	0.5
C4A	0.3518 (11)	0.8309 (10)	0.1347 (6)	0.0218 (16)	0.5
C3A	0.3217 (15)	0.7911 (12)	0.2115 (7)	0.024 (2)	0.5
H3A	0.299857	0.844197	0.251357	0.029*	0.5
C2A	0.3263 (10)	0.6702 (8)	0.2244 (6)	0.0204 (15)	0.5
H2A	0.307994	0.641755	0.274631	0.024*	0.5
N4A	0.3503 (15)	0.9567 (14)	0.1172 (6)	0.031 (2)	0.5
O42A	0.3212 (10)	1.0259 (6)	0.1717 (5)	0.0334 (15)	0.5
O41A	0.3759 (10)	0.9894 (7)	0.0504 (4)	0.0447 (18)	0.5
O42B	0.354 (3)	0.477 (3)	0.181 (2)	0.032 (4)	0.5
O41B	0.4360 (9)	0.4886 (6)	0.0525 (4)	0.0322 (14)	0.5
N4B	0.4042 (9)	0.5342 (7)	0.1155 (4)	0.0276 (15)	0.5
C4B	0.3769 (15)	0.6634 (11)	0.1181 (8)	0.022 (2)	0.5
C3B	0.3428 (11)	0.7169 (11)	0.1890 (6)	0.0268 (17)	0.5
H3B	0.337703	0.671831	0.235277	0.032*	0.5
N1B	0.3267 (13)	0.9025 (10)	0.1222 (6)	0.026 (2)	0.5
C6B	0.3640 (11)	0.8485 (8)	0.0532 (6)	0.0309 (18)	0.5
H6B	0.372484	0.893439	0.007222	0.037*	0.5
C5B	0.389 (2)	0.7251 (14)	0.0530 (11)	0.029 (3)	0.5
H5B	0.414161	0.687216	0.006764	0.034*	0.5
O1B	0.2961 (12)	1.0150 (8)	0.1226 (6)	0.0365 (18)	0.5
C2B	0.3178 (16)	0.8339 (12)	0.1889 (8)	0.028 (2)	0.5
H2B	0.293481	0.870242	0.235796	0.033*	0.5
O11	0.8024 (4)	0.3371 (3)	0.17352 (19)	0.0348 (7)
C1	0.6671 (5)	0.2280 (4)	0.2851 (2)	0.0246 (8)
C6	0.6613 (6)	0.3323 (4)	0.3280 (3)	0.0307 (9)
H6	0.677385	0.405251	0.303934	0.037*
C5	0.6312 (5)	0.3274 (4)	0.4079 (3)	0.0313 (9)
H5	0.628326	0.396864	0.437948	0.038*
C4	0.6054 (5)	0.2172 (4)	0.4421 (3)	0.0287 (9)
C3	0.6126 (5)	0.1122 (4)	0.4004 (3)	0.0270 (9)
H3	0.596926	0.039630	0.424899	0.032*
C2	0.6438 (5)	0.1166 (4)	0.3203 (3)	0.0270 (9)
H2	0.648999	0.046909	0.290753	0.032*
Cl4	0.55992 (15)	0.21104 (12)	0.54090 (7)	0.0403 (3)
S1	0.70284 (16)	0.23043 (12)	0.18306 (7)	0.0351 (3)
O12	0.7782 (6)	0.1188 (3)	0.1669 (2)	0.0496 (10)
N1	0.5043 (6)	0.2425 (6)	0.1225 (3)	0.0662 (17)
H1A	0.431 (8)	0.174 (3)	0.124 (5)	0.099*
H1B	0.430 (8)	0.309 (4)	0.128 (5)	0.099*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.035 (8)	0.022 (5)	0.038 (5)	−0.002 (6)	0.007 (6)	0.003 (4)
N1A	0.021 (3)	0.026 (4)	0.034 (4)	0.003 (3)	0.009 (3)	0.003 (3)
C6A	0.028 (5)	0.019 (7)	0.036 (7)	0.003 (4)	0.010 (4)	−0.006 (4)
C5A	0.024 (5)	0.011 (7)	0.036 (8)	−0.009 (5)	0.005 (5)	−0.003 (5)
C4A	0.020 (4)	0.016 (5)	0.030 (5)	−0.004 (3)	0.005 (3)	0.006 (4)
C3A	0.023 (4)	0.030 (8)	0.019 (6)	−0.004 (5)	0.005 (4)	−0.001 (5)
C2A	0.019 (4)	0.016 (4)	0.028 (4)	−0.003 (3)	0.008 (3)	−0.004 (3)
N4A	0.027 (5)	0.031 (8)	0.033 (4)	−0.006 (5)	0.000 (3)	0.010 (5)
O42A	0.045 (4)	0.020 (3)	0.038 (4)	−0.002 (3)	0.014 (3)	−0.001 (3)
O41A	0.053 (4)	0.048 (5)	0.032 (3)	−0.010 (3)	0.007 (3)	0.016 (3)
O42B	0.035 (8)	0.017 (4)	0.048 (6)	0.001 (6)	0.014 (6)	0.002 (4)
O41B	0.040 (3)	0.026 (3)	0.032 (3)	0.005 (3)	0.011 (3)	−0.007 (2)
N4B	0.022 (3)	0.036 (5)	0.023 (3)	0.001 (3)	0.003 (3)	−0.009 (3)
C4B	0.014 (4)	0.021 (7)	0.032 (6)	−0.002 (4)	0.005 (4)	−0.006 (4)
C3B	0.020 (4)	0.033 (6)	0.029 (5)	−0.002 (4)	0.008 (3)	0.005 (5)
N1B	0.028 (4)	0.011 (6)	0.041 (5)	−0.005 (4)	0.011 (3)	0.004 (4)
C6B	0.028 (4)	0.027 (5)	0.041 (5)	0.000 (3)	0.014 (3)	0.005 (4)
C5B	0.020 (4)	0.016 (7)	0.047 (9)	0.005 (5)	0.000 (5)	−0.011 (5)
O1B	0.045 (5)	0.013 (4)	0.055 (5)	−0.002 (3)	0.019 (4)	−0.003 (4)
C2B	0.024 (4)	0.032 (8)	0.029 (7)	0.000 (5)	0.009 (4)	0.003 (4)
O11	0.0292 (16)	0.0388 (19)	0.0373 (17)	−0.0088 (14)	0.0085 (13)	0.0108 (14)
C1	0.0151 (16)	0.026 (2)	0.032 (2)	−0.0050 (15)	0.0013 (14)	0.0127 (16)
C6	0.0228 (19)	0.025 (2)	0.042 (2)	−0.0059 (16)	−0.0010 (16)	0.0109 (18)
C5	0.0179 (18)	0.029 (2)	0.047 (3)	−0.0022 (16)	0.0052 (16)	−0.0006 (19)
C4	0.0144 (16)	0.040 (3)	0.032 (2)	−0.0010 (16)	0.0045 (14)	0.0055 (18)
C3	0.0217 (18)	0.026 (2)	0.034 (2)	0.0008 (15)	0.0067 (15)	0.0117 (17)
C2	0.0195 (18)	0.030 (2)	0.031 (2)	0.0017 (16)	0.0040 (15)	0.0071 (17)
Cl4	0.0309 (5)	0.0554 (8)	0.0375 (6)	−0.0057 (5)	0.0136 (4)	−0.0022 (5)
S1	0.0331 (5)	0.0416 (7)	0.0274 (5)	−0.0149 (5)	−0.0016 (4)	0.0135 (5)
O12	0.086 (3)	0.037 (2)	0.0280 (17)	−0.0217 (19)	0.0165 (17)	−0.0003 (14)
N1	0.043 (2)	0.106 (4)	0.040 (2)	−0.038 (3)	−0.0141 (19)	0.043 (3)

Geometric parameters (Å, º)

O1A—N1A	1.34 (3)	N1B—C6B	1.376 (13)
N1A—C2A	1.349 (11)	C6B—C5B	1.399 (17)
N1A—C6A	1.353 (16)	C6B—H6B	0.9300
C6A—C5A	1.44 (2)	C5B—H5B	0.9300
C6A—H6A	0.9300	C2B—H2B	0.9300
C5A—C4A	1.391 (15)	O11—S1	1.431 (3)
C5A—H5A	0.9300	C1—C6	1.378 (6)
C4A—C3A	1.415 (13)	C1—C2	1.407 (5)
C4A—N4A	1.443 (14)	C1—S1	1.773 (5)
C3A—C2A	1.375 (15)	C6—C5	1.394 (7)
C3A—H3A	0.9300	C6—H6	0.9300
C2A—H2A	0.9300	C5—C4	1.392 (6)
N4A—O41A	1.222 (12)	C5—H5	0.9300
N4A—O42A	1.247 (15)	C4—C3	1.376 (6)
O42B—N4B	1.38 (3)	C4—Cl4	1.746 (5)
O41B—N4B	1.232 (9)	C3—C2	1.400 (6)
N4B—C4B	1.467 (14)	C3—H3	0.9300
C4B—C5B	1.31 (2)	C2—H2	0.9300
C4B—C3B	1.393 (14)	S1—O12	1.420 (4)
C3B—C2B	1.326 (16)	S1—N1	1.616 (4)
C3B—H3B	0.9300	N1—H1A	0.95 (2)
N1B—O1B	1.284 (12)	N1—H1B	0.94 (2)
N1B—C2B	1.366 (15)
O1A—N1A—C2A	127.8 (15)	C5B—C6B—H6B	120.4
O1A—N1A—C6A	111.5 (15)	C4B—C5B—C6B	119.5 (12)
C2A—N1A—C6A	119.5 (9)	C4B—C5B—H5B	120.2
N1A—C6A—C5A	122.8 (11)	C6B—C5B—H5B	120.2
N1A—C6A—H6A	118.6	C3B—C2B—N1B	122.0 (11)
C5A—C6A—H6A	118.6	C3B—C2B—H2B	119.0
C4A—C5A—C6A	114.5 (13)	N1B—C2B—H2B	119.0
C4A—C5A—H5A	122.7	C6—C1—C2	121.4 (4)
C6A—C5A—H5A	122.7	C6—C1—S1	120.7 (3)
C5A—C4A—C3A	123.2 (12)	C2—C1—S1	117.8 (3)
C5A—C4A—N4A	117.0 (12)	C1—C6—C5	119.3 (4)
C3A—C4A—N4A	119.7 (10)	C1—C6—H6	120.4
C2A—C3A—C4A	116.7 (12)	C5—C6—H6	120.4
C2A—C3A—H3A	121.6	C4—C5—C6	119.2 (4)
C4A—C3A—H3A	121.6	C4—C5—H5	120.4
N1A—C2A—C3A	123.1 (10)	C6—C5—H5	120.4
N1A—C2A—H2A	118.4	C3—C4—C5	122.2 (4)
C3A—C2A—H2A	118.4	C3—C4—Cl4	118.5 (3)
O41A—N4A—O42A	123.9 (14)	C5—C4—Cl4	119.3 (4)
O41A—N4A—C4A	118.8 (13)	C4—C3—C2	118.9 (4)
O42A—N4A—C4A	117.3 (9)	C4—C3—H3	120.6
O41B—N4B—O42B	127.7 (16)	C2—C3—H3	120.6
O41B—N4B—C4B	119.2 (8)	C3—C2—C1	119.0 (4)
O42B—N4B—C4B	111.9 (15)	C3—C2—H2	120.5
C5B—C4B—C3B	122.0 (12)	C1—C2—H2	120.5
C5B—C4B—N4B	117.9 (10)	O12—S1—O11	119.3 (2)
C3B—C4B—N4B	120.1 (11)	O12—S1—N1	107.3 (3)
C2B—C3B—C4B	118.4 (10)	O11—S1—N1	106.5 (2)
C2B—C3B—H3B	120.8	O12—S1—C1	107.9 (2)
C4B—C3B—H3B	120.8	O11—S1—C1	107.2 (2)
O1B—N1B—C2B	120.9 (10)	N1—S1—C1	108.3 (2)
O1B—N1B—C6B	120.2 (11)	S1—N1—H1A	111 (4)
C2B—N1B—C6B	118.8 (11)	S1—N1—H1B	119 (5)
N1B—C6B—C5B	119.2 (11)	H1A—N1—H1B	107 (3)
N1B—C6B—H6B	120.4
O1A—N1A—C6A—C5A	−169.8 (16)	C3B—C4B—C5B—C6B	−1 (2)
C2A—N1A—C6A—C5A	−1.7 (17)	N4B—C4B—C5B—C6B	−179.9 (11)
N1A—C6A—C5A—C4A	0 (2)	N1B—C6B—C5B—C4B	0 (2)
C6A—C5A—C4A—C3A	1.6 (18)	C4B—C3B—C2B—N1B	−0.8 (16)
C6A—C5A—C4A—N4A	179.8 (11)	O1B—N1B—C2B—C3B	177.7 (10)
C5A—C4A—C3A—C2A	−1.4 (16)	C6B—N1B—C2B—C3B	−0.4 (16)
N4A—C4A—C3A—C2A	−179.5 (8)	C2—C1—C6—C5	−0.2 (6)
O1A—N1A—C2A—C3A	168.0 (14)	S1—C1—C6—C5	179.4 (3)
C6A—N1A—C2A—C3A	2.1 (13)	C1—C6—C5—C4	−0.8 (6)
C4A—C3A—C2A—N1A	−0.6 (14)	C6—C5—C4—C3	1.4 (6)
C5A—C4A—N4A—O41A	2.0 (15)	C6—C5—C4—Cl4	−177.9 (3)
C3A—C4A—N4A—O41A	−179.8 (9)	C5—C4—C3—C2	−1.1 (6)
C5A—C4A—N4A—O42A	−178.6 (11)	Cl4—C4—C3—C2	178.2 (3)
C3A—C4A—N4A—O42A	−0.3 (14)	C4—C3—C2—C1	0.1 (6)
O41B—N4B—C4B—C5B	−0.5 (15)	C6—C1—C2—C3	0.5 (6)
O42B—N4B—C4B—C5B	−168.6 (15)	S1—C1—C2—C3	−179.0 (3)
O41B—N4B—C4B—C3B	−179.3 (8)	C6—C1—S1—O12	155.9 (3)
O42B—N4B—C4B—C3B	12.6 (16)	C2—C1—S1—O12	−24.6 (4)
C5B—C4B—C3B—C2B	1.6 (17)	C6—C1—S1—O11	26.2 (4)
N4B—C4B—C3B—C2B	−179.6 (9)	C2—C1—S1—O11	−154.2 (3)
O1B—N1B—C6B—C5B	−177.2 (11)	C6—C1—S1—N1	−88.3 (4)
C2B—N1B—C6B—C5B	0.9 (16)	C2—C1—S1—N1	91.3 (4)