Structural and theoretical analysis of 2-chloro-4-nitro­aniline and 2-methyl-6-nitro­aniline salts

The crystal structures of five new salts of 2-chloro-4-nitro­aniline (2Cl4na) and 2-methyl-6-nitro­aniline (2m6na) with inorganic acids, namely, 2-chloro-4-nitro­anilinium bromide, C₆H₆ClN₂O₂⁺·Br⁻ (1), 2-chloro-4-nitro­anilinium hydrogen sulfate, C₆H₆ClN₂O₂⁺·HSO₄⁻ (2), 2-methyl-6-nitro­anilinium bromide, C₇H₉N₂O₂⁺·Br⁻ (3), 2-methyl-6-nitro­anilinium triiodide, C₇H₉N₂O₂⁺·I₃⁻ (4), and 2-methyl-6-nitro­anilinium hydrogen sulfate, C₇H₉N₂O₂⁺·HSO₄⁻ (5), were determined by single-crystal X-ray diffraction. Theoretical calculations of the relaxed potential energy surface (rPES) revealed that the energy barriers for the rotation of the nitro group for isolated H2Cl4na⁺ and H2m6na⁺ cations are 4.6 and 11.6 kcal mol⁻¹, respectively. The ammonium group and respective anions form hydrogen bonds which are the most important inter­actions and are arranged in zero- (in 3), one- (in 1 and 4) or two-dimensional (in 2 and 5) networks. Hydrogen-bonding patterns were analyzed by means of mathematical relationships between graph-set descriptors and com­pared with previously reported nitro­aniline salts. Hirshfeld surface analysis indicates that the nitro group plays a dominant role among the weak inter­actions, i.e. C—H...O(NO₂), NO₂...π(Ar) and O(NO₂)...π(NO₂). The frequency of the ν_sNO₂ vibration is correlated with the type of inter­action in which the NO₂ group is involved. Analysis of the ν_sNO₂ band observed in the IR and Raman spectra allowed an assessment of its shift in the sequence (H2m6na)I₃ (4) < (H2m6na)HSO₄ (5) < (H2m6na)Br (3) < (H2Cl4na)Br (1) < (H2Cl4na)HSO₄ (2).

Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2015) for (1), (2), (3), (5); CrysAlis PRO (Rigaku OD, 2018) for (4). Cell refinement: CrysAlis PRO (Rigaku OD, 2015) for (1), (2), (3), (5); CrysAlis PRO (Rigaku OD, 2018) for (4). Data reduction: CrysAlis PRO (Rigaku OD, 2015) for (1), (2), (3), (5); CrysAlis PRO (Rigaku OD, 2018) for (4). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (1), (2); SHELXT (Sheldrick, 2015a) for (3), (4), (5). For all structures, program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2008) and OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

2-Chloro-4-nitroanilinium bromide (1)

Crystal data

C6H6ClN2O2^+·Br^−	Dx = 1.837 Mg m^−3
Mr = 253.49	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 7548 reflections
a = 5.72152 (9) Å	θ = 2.8–27.4°
b = 7.90017 (17) Å	µ = 4.74 mm^−1
c = 20.2729 (4) Å	T = 295 K
V = 916.35 (3) Å^3	Block, clear yellowish colourless
Z = 4	0.36 × 0.26 × 0.22 mm
F(000) = 496

Data collection

Rigaku Xcalibur Atlas diffractometer	2669 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2340 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
Detector resolution: 10.6249 pixels mm^-1	θmax = 30.0°, θmin = 2.8°
ω scans	h = −8→8
Absorption correction: analytical {CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)]	k = −11→11
Tmin = 0.300, Tmax = 0.446	l = −28→28
18773 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.028	w = 1/[σ^2(Fo^2) + (0.0322P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.062	(Δ/σ)max = 0.002
S = 1.13	Δρmax = 0.33 e Å^−3
2669 reflections	Δρmin = −0.70 e Å^−3
113 parameters	Absolute structure: Flack x determined using 881 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: −0.008 (4)
Primary atom site location: structure-invariant direct methods

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. X-ray diffraction data were collected on an Oxford Diffraction four-circle single crystal diffractometer equipped with a CCD detector using graphite-monochromatized Mo Kα radiation (λ = 0.71073 Å). The raw data were treated with the CrysAlis Data Reduction Program, version 1.171.38.34a or 1.171.39.46. The intensities of the reflection were corrected for Lorentz and polarization effects. The crystal structures were solved by direct methods (Sheldrick, 2008) and refined by full-matrix least-squares methods using the SHELXL2017 program (Sheldrick, 2015) and OLEX2 software (Dolomanov et al., 2009).

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

	x	y	z	Uiso*/Ueq
Br1	0.52443 (5)	0.84406 (4)	0.58461 (2)	0.04093 (10)
Cl1	−0.31036 (14)	0.35586 (13)	0.53964 (4)	0.0489 (2)
O1	0.0516 (5)	−0.1126 (3)	0.68972 (13)	0.0555 (7)
O2	0.2906 (5)	0.0104 (4)	0.75612 (13)	0.0684 (8)
N1	0.0211 (4)	0.6339 (3)	0.57628 (13)	0.0376 (6)
H1A	0.139212	0.703405	0.585339	0.051 (11)*
H1B	−0.112446	0.680764	0.589483	0.061 (12)*
H1C	0.015304	0.615323	0.533010	0.058 (12)*
N2	0.1576 (5)	0.0117 (4)	0.70883 (14)	0.0435 (7)
C1	0.0557 (5)	0.4735 (4)	0.61076 (14)	0.0315 (6)
C2	−0.0893 (5)	0.3361 (4)	0.59723 (13)	0.0316 (6)
C3	−0.0560 (5)	0.1838 (4)	0.62907 (14)	0.0353 (6)
H3	−0.150708	0.090853	0.620220	0.042*
C4	0.1227 (5)	0.1743 (4)	0.67451 (14)	0.0336 (6)
C5	0.2665 (6)	0.3069 (5)	0.68918 (16)	0.0411 (8)
H5	0.385125	0.295483	0.720224	0.049*
C6	0.2312 (6)	0.4597 (4)	0.65653 (15)	0.0384 (7)
H6	0.326256	0.552208	0.665712	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.03208 (15)	0.03898 (17)	0.05173 (17)	−0.00640 (13)	−0.00074 (12)	0.00111 (15)
Cl1	0.0427 (4)	0.0490 (5)	0.0550 (4)	−0.0100 (4)	−0.0201 (3)	0.0017 (4)
O1	0.0662 (17)	0.0372 (14)	0.0631 (15)	−0.0065 (13)	0.0010 (13)	0.0077 (11)
O2	0.073 (2)	0.064 (2)	0.0680 (17)	0.0007 (16)	−0.0280 (15)	0.0191 (16)
N1	0.0321 (12)	0.0338 (13)	0.0470 (14)	−0.0041 (11)	−0.0043 (11)	0.0024 (11)
N2	0.0447 (16)	0.0424 (18)	0.0433 (14)	0.0014 (14)	0.0024 (13)	0.0069 (14)
C1	0.0283 (14)	0.0320 (15)	0.0342 (13)	−0.0022 (12)	0.0033 (11)	0.0001 (12)
C2	0.0273 (12)	0.0336 (15)	0.0339 (13)	−0.0016 (12)	−0.0019 (9)	−0.0050 (14)
C3	0.0364 (14)	0.0300 (16)	0.0395 (14)	−0.0072 (12)	0.0003 (12)	−0.0037 (13)
C4	0.0358 (14)	0.0310 (16)	0.0340 (13)	−0.0002 (14)	0.0020 (11)	0.0009 (14)
C5	0.0368 (16)	0.046 (2)	0.0409 (16)	−0.0033 (15)	−0.0098 (13)	0.0050 (15)
C6	0.0343 (16)	0.0383 (18)	0.0424 (15)	−0.0106 (14)	−0.0076 (13)	0.0005 (15)

Geometric parameters (Å, º)

Cl1—C2	1.729 (3)	C1—C6	1.371 (4)
O1—N2	1.217 (4)	C2—C3	1.379 (4)
O2—N2	1.224 (4)	C3—H3	0.9300
N1—H1A	0.8900	C3—C4	1.378 (4)
N1—H1B	0.8900	C4—C5	1.365 (5)
N1—H1C	0.8900	C5—H5	0.9300
N1—C1	1.461 (4)	C5—C6	1.391 (5)
N2—C4	1.475 (4)	C6—H6	0.9300
C1—C2	1.393 (4)
H1A—N1—H1B	109.5	C3—C2—C1	120.4 (3)
H1A—N1—H1C	109.5	C2—C3—H3	121.2
H1B—N1—H1C	109.5	C4—C3—C2	117.6 (3)
C1—N1—H1A	109.5	C4—C3—H3	121.2
C1—N1—H1B	109.5	C3—C4—N2	117.6 (3)
C1—N1—H1C	109.5	C5—C4—N2	119.0 (3)
O1—N2—O2	123.5 (3)	C5—C4—C3	123.4 (3)
O1—N2—C4	119.0 (3)	C4—C5—H5	120.8
O2—N2—C4	117.5 (3)	C4—C5—C6	118.3 (3)
C2—C1—N1	120.1 (3)	C6—C5—H5	120.8
C6—C1—N1	119.5 (3)	C1—C6—C5	119.8 (3)
C6—C1—C2	120.5 (3)	C1—C6—H6	120.1
C1—C2—Cl1	119.9 (2)	C5—C6—H6	120.1
C3—C2—Cl1	119.7 (2)
Cl1—C2—C3—C4	179.9 (2)	C1—C2—C3—C4	0.6 (4)
O1—N2—C4—C3	10.1 (5)	C2—C1—C6—C5	0.7 (5)
O1—N2—C4—C5	−170.2 (3)	C2—C3—C4—N2	179.7 (3)
O2—N2—C4—C3	−168.8 (3)	C2—C3—C4—C5	−0.1 (5)
O2—N2—C4—C5	10.9 (5)	C3—C4—C5—C6	−0.1 (5)
N1—C1—C2—Cl1	−0.1 (4)	C4—C5—C6—C1	−0.2 (5)
N1—C1—C2—C3	179.3 (3)	C6—C1—C2—Cl1	179.7 (2)
N1—C1—C6—C5	−179.5 (3)	C6—C1—C2—C3	−0.9 (4)
N2—C4—C5—C6	−179.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1	0.89	2.47	3.329 (2)	163
N1—H1B···Br1^i	0.89	2.45	3.295 (2)	159
N1—H1C···Br1^ii	0.89	2.41	3.266 (3)	163
C3—H3···Br1^iii	0.93	2.79	3.712 (3)	172
C5—H5···O2^iv	0.93	2.56	3.199 (4)	126

Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+3/2, −z+1; (iii) x−1, y−1, z; (iv) −x+1, y+1/2, −z+3/2.

2-Chloro-4-nitroanilinium hydrogen sulfate (2)

Crystal data

C6H6ClN2O2^+·HSO4^−	F(000) = 552
Mr = 270.65	Dx = 1.783 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.1771 (6) Å	Cell parameters from 1898 reflections
b = 4.95335 (16) Å	θ = 3.2–31.7°
c = 12.8431 (5) Å	µ = 0.60 mm^−1
β = 101.584 (4)°	T = 295 K
V = 1008.17 (7) Å^3	Plate, clear light colourless
Z = 4	0.56 × 0.46 × 0.06 mm

Data collection

Rigaku Xcalibur Atlas diffractometer	2923 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2351 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 10.6249 pixels mm^-1	θmax = 30.0°, θmin = 2.6°
ω scans	h = −22→22
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −6→6
Tmin = 0.967, Tmax = 1.000	l = −9→18
6028 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.036	Hetero
wR(F^2) = 0.099	w = 1/[σ^2(Fo^2) + (0.0452P)^2 + 0.2615P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
2923 reflections	Δρmax = 0.52 e Å^−3
161 parameters	Δρmin = −0.55 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. X-ray diffraction data were collected on an Oxford Diffraction four-circle single crystal diffractometer equipped with a CCD detector using graphite-monochromatized Mo Kα radiation (λ = 0.71073 Å). The raw data were treated with the CrysAlis Data Reduction Program, version 1.171.38.34a or 1.171.39.46. The intensities of the reflection were corrected for Lorentz and polarization effects. The crystal structures were solved by direct methods (Sheldrick, 2008) and refined by full-matrix least-squares methods using the SHELXL2017 program (Sheldrick, 2015) and OLEX2 software (Dolomanov et al., 2009).

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

	x	y	z	Uiso*/Ueq
Cl1	0.23626 (3)	0.96745 (10)	−0.12914 (4)	0.03739 (14)
O1	0.53464 (9)	0.7499 (4)	0.09311 (14)	0.0535 (4)
O2	0.52394 (9)	0.4068 (4)	0.19099 (14)	0.0506 (4)
N1	0.14105 (9)	0.5553 (3)	−0.03115 (12)	0.0241 (3)
H1A	0.1199 (14)	0.422 (5)	0.0078 (17)	0.035 (6)*
H1B	0.1317 (16)	0.517 (5)	−0.101 (2)	0.054 (8)*
H1C	0.1168 (16)	0.706 (5)	−0.021 (2)	0.052 (7)*
N2	0.49334 (10)	0.5802 (4)	0.12857 (14)	0.0347 (4)
C1	0.23101 (10)	0.5733 (3)	0.01443 (13)	0.0224 (3)
C2	0.28109 (11)	0.7520 (3)	−0.02814 (13)	0.0251 (3)
C3	0.36733 (11)	0.7586 (4)	0.01055 (15)	0.0295 (4)
H3	0.401763	0.877371	−0.017358	0.035*
C4	0.40055 (11)	0.5844 (4)	0.09144 (14)	0.0275 (4)
C5	0.35195 (12)	0.4124 (4)	0.13820 (15)	0.0322 (4)
H5	0.376323	0.302298	0.194717	0.039*
C6	0.26607 (11)	0.4079 (4)	0.09890 (14)	0.0299 (4)
H6	0.231691	0.293888	0.129073	0.036*
S1	0.06905 (2)	0.00369 (7)	0.15958 (3)	0.01902 (11)
O3	0.09583 (8)	0.0670 (2)	0.06133 (9)	0.0258 (3)
O4	0.06204 (9)	−0.3111 (3)	0.15478 (11)	0.0306 (3)
H4	0.0475 (16)	−0.361 (5)	0.207 (2)	0.053 (8)*
O5	−0.01424 (8)	0.1079 (3)	0.16332 (10)	0.0300 (3)
O6	0.13091 (8)	0.0741 (3)	0.25338 (10)	0.0318 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0396 (3)	0.0372 (3)	0.0332 (3)	−0.0025 (2)	0.0022 (2)	0.0149 (2)
O1	0.0321 (7)	0.0656 (11)	0.0619 (11)	−0.0164 (7)	0.0077 (7)	0.0142 (9)
O2	0.0323 (8)	0.0582 (10)	0.0568 (10)	0.0050 (7)	−0.0022 (7)	0.0171 (9)
N1	0.0234 (7)	0.0278 (7)	0.0210 (7)	0.0009 (6)	0.0043 (6)	0.0016 (6)
N2	0.0275 (8)	0.0424 (9)	0.0328 (8)	−0.0029 (7)	0.0030 (7)	−0.0017 (7)
C1	0.0219 (7)	0.0256 (8)	0.0195 (7)	−0.0003 (6)	0.0039 (6)	−0.0016 (6)
C2	0.0302 (8)	0.0243 (8)	0.0209 (8)	0.0013 (7)	0.0057 (7)	0.0026 (6)
C3	0.0292 (8)	0.0304 (9)	0.0300 (9)	−0.0057 (7)	0.0082 (7)	0.0026 (7)
C4	0.0224 (8)	0.0326 (9)	0.0266 (8)	−0.0023 (7)	0.0027 (7)	−0.0014 (7)
C5	0.0285 (9)	0.0369 (10)	0.0289 (9)	−0.0017 (8)	0.0000 (7)	0.0108 (8)
C6	0.0296 (9)	0.0333 (9)	0.0258 (8)	−0.0059 (7)	0.0034 (7)	0.0069 (7)
S1	0.0229 (2)	0.01866 (19)	0.01607 (18)	−0.00072 (14)	0.00517 (14)	−0.00065 (14)
O3	0.0324 (6)	0.0278 (6)	0.0195 (6)	−0.0037 (5)	0.0106 (5)	0.0018 (5)
O4	0.0476 (8)	0.0195 (6)	0.0290 (7)	−0.0035 (5)	0.0176 (6)	−0.0006 (5)
O5	0.0296 (6)	0.0379 (7)	0.0241 (6)	0.0082 (6)	0.0088 (5)	−0.0004 (5)
O6	0.0331 (7)	0.0390 (7)	0.0207 (6)	−0.0071 (6)	−0.0005 (5)	−0.0011 (5)

Geometric parameters (Å, º)

Cl1—C2	1.7233 (17)	C3—H3	0.9300
O1—N2	1.218 (2)	C3—C4	1.374 (3)
O2—N2	1.211 (2)	C4—C5	1.376 (3)
N1—H1A	0.93 (2)	C5—H5	0.9300
N1—H1B	0.90 (3)	C5—C6	1.380 (2)
N1—H1C	0.87 (3)	C6—H6	0.9300
N1—C1	1.458 (2)	S1—O3	1.4483 (12)
N2—C4	1.481 (2)	S1—O4	1.5636 (13)
C1—C2	1.384 (2)	S1—O5	1.4526 (12)
C1—C6	1.387 (2)	S1—O6	1.4457 (12)
C2—C3	1.384 (2)	O4—H4	0.79 (3)
H1A—N1—H1B	112 (2)	C4—C3—H3	121.0
H1A—N1—H1C	108 (2)	C3—C4—N2	117.99 (16)
H1B—N1—H1C	110 (2)	C3—C4—C5	123.21 (17)
C1—N1—H1A	105.8 (13)	C5—C4—N2	118.79 (17)
C1—N1—H1B	111.5 (16)	C4—C5—H5	120.9
C1—N1—H1C	109.6 (17)	C4—C5—C6	118.16 (17)
O1—N2—C4	117.82 (17)	C6—C5—H5	120.9
O2—N2—O1	123.73 (17)	C1—C6—H6	120.0
O2—N2—C4	118.45 (17)	C5—C6—C1	120.01 (16)
C2—C1—N1	119.76 (15)	C5—C6—H6	120.0
C2—C1—C6	120.46 (16)	O3—S1—O4	102.32 (7)
C6—C1—N1	119.77 (15)	O3—S1—O5	113.18 (8)
C1—C2—Cl1	120.14 (13)	O5—S1—O4	107.17 (8)
C3—C2—Cl1	119.80 (13)	O6—S1—O3	113.31 (8)
C3—C2—C1	120.06 (16)	O6—S1—O4	107.83 (8)
C2—C3—H3	121.0	O6—S1—O5	112.21 (8)
C4—C3—C2	117.99 (16)	S1—O4—H4	107.9 (19)
Cl1—C2—C3—C4	179.72 (14)	C1—C2—C3—C4	−0.1 (3)
O1—N2—C4—C3	7.3 (3)	C2—C1—C6—C5	−2.8 (3)
O1—N2—C4—C5	−173.56 (19)	C2—C3—C4—N2	176.51 (16)
O2—N2—C4—C3	−171.69 (19)	C2—C3—C4—C5	−2.6 (3)
O2—N2—C4—C5	7.5 (3)	C3—C4—C5—C6	2.6 (3)
N1—C1—C2—Cl1	4.0 (2)	C4—C5—C6—C1	0.1 (3)
N1—C1—C2—C3	−176.13 (16)	C6—C1—C2—Cl1	−177.08 (14)
N1—C1—C6—C5	176.11 (17)	C6—C1—C2—C3	2.8 (3)
N2—C4—C5—C6	−176.51 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3	0.93 (2)	1.96 (2)	2.854 (2)	161 (2)
N1—H1B···O6^i	0.90 (3)	1.92 (3)	2.813 (2)	171 (2)
N1—H1C···O3^ii	0.87 (3)	2.14 (3)	2.952 (2)	156 (2)
N1—H1C···O5^iii	0.87 (3)	2.39 (3)	2.911 (2)	119 (2)
C3—H3···O1^iv	0.93	2.41	3.326 (2)	168
C6—H6···O3	0.93	2.47	3.184 (2)	134
O4—H4···O5^v	0.79 (3)	1.85 (3)	2.6350 (18)	167 (3)

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, y+1, z; (iii) −x, −y+1, −z; (iv) −x+1, −y+2, −z; (v) −x, y−1/2, −z+1/2.

2-Methyl-6-nitroanilinium bromide (3)

Crystal data

C7H9N2O2^+·Br^−	Z = 2
Mr = 233.07	F(000) = 232
Triclinic, P1	Dx = 1.775 Mg m^−3
a = 6.8920 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.7281 (3) Å	Cell parameters from 6602 reflections
c = 8.9210 (2) Å	θ = 2.8–29.2°
α = 76.646 (3)°	µ = 4.67 mm^−1
β = 73.897 (2)°	T = 295 K
γ = 76.045 (2)°	Block, clear yellowish colourless
V = 436.12 (2) Å^3	0.46 × 0.33 × 0.18 mm

Data collection

Rigaku Xcalibur Atlas diffractometer	2299 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	1986 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 10.6249 pixels mm^-1	θmax = 29.0°, θmin = 3.1°
ω scans	h = −9→9
Absorption correction: gaussian {CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)]	k = −10→10
Tmin = 0.947, Tmax = 0.973	l = −12→12
15285 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.061	w = 1/[σ^2(Fo^2) + (0.0284P)^2 + 0.0941P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.001
2299 reflections	Δρmax = 0.33 e Å^−3
122 parameters	Δρmin = −0.39 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. X-ray diffraction data were collected on an Oxford Diffraction four-circle single crystal diffractometer equipped with a CCD detector using graphite-monochromatized Mo Kα radiation (λ = 0.71073 Å). The raw data were treated with the CrysAlis Data Reduction Program, version 1.171.38.34a or 1.171.39.46. The intensities of the reflection were corrected for Lorentz and polarization effects. The crystal structures were solved by direct methods (Sheldrick, 2008) and refined by full-matrix least-squares methods using the SHELXL2017 program (Sheldrick, 2015) and OLEX2 software (Dolomanov et al., 2009).

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

	x	y	z	Uiso*/Ueq
Br1	0.81600 (3)	0.10038 (3)	0.85182 (2)	0.04788 (9)
O1	0.2903 (3)	0.0584 (2)	0.53501 (18)	0.0519 (4)
N1	0.3605 (3)	0.1243 (2)	0.7969 (2)	0.0356 (3)
H1A	0.359 (4)	0.044 (4)	0.739 (3)	0.062 (7)*
H1B	0.281 (4)	0.095 (3)	0.889 (3)	0.057 (7)*
H1C	0.492 (4)	0.108 (3)	0.811 (3)	0.052 (6)*
C1	0.2937 (2)	0.3101 (2)	0.7213 (2)	0.0294 (3)
O2	0.3704 (3)	0.2520 (2)	0.32372 (17)	0.0638 (5)
N2	0.3158 (2)	0.2116 (2)	0.46776 (19)	0.0397 (4)
C2	0.2568 (3)	0.4475 (2)	0.8078 (2)	0.0354 (4)
C3	0.1993 (3)	0.6251 (3)	0.7319 (3)	0.0457 (5)
H3	0.168936	0.719362	0.788371	0.055*
C4	0.1863 (3)	0.6645 (3)	0.5753 (3)	0.0484 (5)
H4	0.148182	0.784148	0.528182	0.058*
C5	0.2291 (3)	0.5293 (3)	0.4892 (2)	0.0411 (4)
H5	0.224223	0.555655	0.383067	0.049*
C6	0.2799 (2)	0.3522 (2)	0.5636 (2)	0.0316 (3)
C7	0.2796 (4)	0.4061 (3)	0.9765 (2)	0.0500 (5)
H7A	0.195481	0.320174	1.038442	0.075*
H7B	0.237042	0.515587	1.020032	0.075*
H7C	0.420924	0.356305	0.978274	0.075*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.04293 (13)	0.05194 (14)	0.04204 (12)	−0.01063 (9)	−0.01413 (9)	0.01167 (9)
O1	0.0688 (10)	0.0404 (8)	0.0518 (8)	−0.0171 (7)	−0.0158 (7)	−0.0094 (7)
N1	0.0429 (9)	0.0296 (8)	0.0318 (8)	−0.0052 (7)	−0.0110 (7)	0.0008 (6)
C1	0.0251 (7)	0.0285 (8)	0.0321 (8)	−0.0079 (6)	−0.0049 (6)	0.0004 (6)
O2	0.0869 (12)	0.0773 (12)	0.0324 (7)	−0.0260 (10)	−0.0152 (8)	−0.0074 (8)
N2	0.0372 (8)	0.0496 (10)	0.0364 (8)	−0.0109 (7)	−0.0127 (6)	−0.0078 (7)
C2	0.0296 (8)	0.0352 (9)	0.0401 (9)	−0.0094 (7)	−0.0023 (7)	−0.0078 (7)
C3	0.0372 (10)	0.0312 (9)	0.0673 (14)	−0.0099 (8)	−0.0045 (9)	−0.0116 (9)
C4	0.0407 (10)	0.0310 (9)	0.0690 (14)	−0.0103 (8)	−0.0186 (10)	0.0108 (9)
C5	0.0355 (9)	0.0397 (10)	0.0463 (10)	−0.0140 (8)	−0.0167 (8)	0.0116 (8)
C6	0.0270 (8)	0.0327 (8)	0.0353 (9)	−0.0094 (7)	−0.0099 (7)	0.0005 (7)
C7	0.0571 (13)	0.0552 (13)	0.0402 (10)	−0.0122 (10)	−0.0065 (9)	−0.0177 (10)

Geometric parameters (Å, º)

O1—N2	1.228 (2)	C2—C7	1.508 (3)
N1—H1A	0.90 (3)	C3—H3	0.9300
N1—H1B	0.86 (3)	C3—C4	1.383 (3)
N1—H1C	0.92 (3)	C4—H4	0.9300
N1—C1	1.461 (2)	C4—C5	1.366 (3)
C1—C2	1.389 (3)	C5—H5	0.9300
C1—C6	1.394 (2)	C5—C6	1.383 (2)
O2—N2	1.222 (2)	C7—H7A	0.9600
N2—C6	1.467 (2)	C7—H7B	0.9600
C2—C3	1.399 (3)	C7—H7C	0.9600
H1A—N1—H1B	105 (2)	C4—C3—H3	119.1
H1A—N1—H1C	108 (2)	C3—C4—H4	119.7
H1B—N1—H1C	108 (2)	C5—C4—C3	120.57 (18)
C1—N1—H1A	111.5 (17)	C5—C4—H4	119.7
C1—N1—H1B	112.9 (17)	C4—C5—H5	120.8
C1—N1—H1C	110.7 (15)	C4—C5—C6	118.49 (18)
C2—C1—N1	118.04 (15)	C6—C5—H5	120.8
C2—C1—C6	120.05 (16)	C1—C6—N2	122.02 (15)
C6—C1—N1	121.77 (16)	C5—C6—C1	121.68 (17)
O1—N2—C6	118.93 (15)	C5—C6—N2	116.30 (16)
O2—N2—O1	122.57 (17)	C2—C7—H7A	109.5
O2—N2—C6	118.50 (17)	C2—C7—H7B	109.5
C1—C2—C3	117.32 (17)	C2—C7—H7C	109.5
C1—C2—C7	121.11 (17)	H7A—C7—H7B	109.5
C3—C2—C7	121.57 (18)	H7A—C7—H7C	109.5
C2—C3—H3	119.1	H7B—C7—H7C	109.5
C4—C3—C2	121.83 (19)
O1—N2—C6—C1	24.5 (2)	C2—C1—C6—N2	−179.47 (15)
O1—N2—C6—C5	−154.82 (17)	C2—C1—C6—C5	−0.2 (3)
N1—C1—C2—C3	178.02 (16)	C2—C3—C4—C5	0.3 (3)
N1—C1—C2—C7	−1.5 (3)	C3—C4—C5—C6	1.8 (3)
N1—C1—C6—N2	4.9 (2)	C4—C5—C6—C1	−1.8 (3)
N1—C1—C6—C5	−175.88 (16)	C4—C5—C6—N2	177.48 (16)
C1—C2—C3—C4	−2.3 (3)	C6—C1—C2—C3	2.2 (2)
O2—N2—C6—C1	−155.44 (18)	C6—C1—C2—C7	−177.35 (17)
O2—N2—C6—C5	25.3 (2)	C7—C2—C3—C4	177.29 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.90 (3)	1.98 (3)	2.693 (2)	135 (2)
N1—H1B···Br1^i	0.86 (3)	2.47 (3)	3.2717 (17)	155 (2)
N1—H1C···Br1	0.92 (3)	2.34 (3)	3.2650 (18)	174 (2)

Symmetry code: (i) −x+1, −y, −z+2.

2-Methyl-6-nitroanilinium triiodide (4)

Crystal data

C7H9N2O2^+·I3^−	F(000) = 960
Mr = 533.86	Dx = 2.681 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.0840 (2) Å	Cell parameters from 6876 reflections
b = 11.5247 (4) Å	θ = 3.0–26.6°
c = 16.3921 (6) Å	µ = 7.07 mm^−1
β = 98.738 (3)°	T = 295 K
V = 1322.73 (8) Å^3	Block, clear dark black
Z = 4	0.21 × 0.11 × 0.09 mm

Data collection

Rigaku Xcalibur Atlas diffractometer	5822 measured reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	5822 independent reflections
Graphite monochromator	3181 reflections with I > 2σ(I)
Detector resolution: 10.6249 pixels mm^-1	θmax = 29.7°, θmin = 3.1°
ω scans	h = −9→9
Absorption correction: gaussian {CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)]	k = −15→15
Tmin = 0.966, Tmax = 0.988	l = −22→22

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.031	H-atom parameters constrained
wR(F^2) = 0.059	w = 1/[σ^2(Fo^2) + (0.0302P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.80	(Δ/σ)max = 0.001
5822 reflections	Δρmax = 0.70 e Å^−3
130 parameters	Δρmin = −0.78 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. Refined as a 2-component twin.

X-ray diffraction data were collected on an Oxford Diffraction four-circle single crystal diffractometer equipped with a CCD detector using graphite-monochromatized Mo Kα radiation (λ = 0.71073 Å). The raw data were treated with the CrysAlis Data Reduction Program, version 1.171.38.34a or 1.171.39.46. The intensities of the reflection were corrected for Lorentz and polarization effects. The crystal structures were solved by direct methods (Sheldrick, 2008) and refined by full-matrix least-squares methods using the SHELXL2017 program (Sheldrick, 2015) and OLEX2 software (Dolomanov et al., 2009).

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

	x	y	z	Uiso*/Ueq
I1	0.23412 (5)	0.64676 (3)	0.49174 (2)	0.05463 (12)
O1	0.7268 (7)	0.6352 (3)	0.3066 (3)	0.0872 (15)
N1	0.7262 (6)	0.6691 (3)	0.4628 (2)	0.0498 (11)
H1A	0.705654	0.624493	0.418041	0.060*
H1B	0.632377	0.658951	0.492567	0.060*
H1C	0.837132	0.649941	0.492907	0.060*
C1	0.7319 (7)	0.7911 (4)	0.4380 (3)	0.0384 (11)
O2	0.6924 (7)	0.7754 (4)	0.2194 (3)	0.0901 (15)
N2	0.7129 (7)	0.7393 (5)	0.2892 (3)	0.0615 (13)
C2	0.7435 (7)	0.8734 (4)	0.5006 (3)	0.0435 (12)
C3	0.7455 (7)	0.9904 (4)	0.4768 (3)	0.0493 (13)
H3	0.750588	1.047841	0.516951	0.059*
C4	0.7403 (7)	1.0219 (4)	0.3964 (3)	0.0562 (15)
H4	0.744029	1.099935	0.382326	0.067*
C5	0.7293 (7)	0.9375 (5)	0.3353 (3)	0.0515 (13)
H5	0.724229	0.958706	0.280255	0.062*
C6	0.7262 (7)	0.8236 (4)	0.3568 (3)	0.0405 (12)
C7	0.7513 (9)	0.8411 (4)	0.5907 (3)	0.0653 (17)
H7A	0.637762	0.799188	0.597706	0.098*
H7B	0.759889	0.910330	0.623588	0.098*
H7C	0.861188	0.793308	0.607767	0.098*
I2	0.25651 (6)	0.48323 (3)	0.33199 (2)	0.06088 (13)
I3	0.28580 (6)	0.33035 (3)	0.20403 (2)	0.06437 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0485 (2)	0.0462 (2)	0.0689 (2)	−0.00020 (18)	0.00820 (19)	−0.00626 (17)
O1	0.126 (4)	0.051 (3)	0.089 (3)	−0.006 (3)	0.033 (3)	−0.027 (2)
N1	0.046 (3)	0.039 (2)	0.065 (3)	−0.001 (2)	0.009 (2)	−0.002 (2)
C1	0.031 (3)	0.032 (2)	0.052 (3)	0.000 (2)	0.005 (2)	−0.002 (2)
O2	0.112 (4)	0.109 (4)	0.050 (3)	−0.001 (3)	0.014 (3)	−0.021 (2)
N2	0.051 (3)	0.076 (4)	0.060 (3)	−0.005 (3)	0.017 (3)	−0.017 (3)
C2	0.043 (3)	0.039 (3)	0.049 (3)	0.001 (2)	0.004 (2)	0.005 (2)
C3	0.056 (4)	0.036 (3)	0.057 (4)	0.000 (3)	0.010 (3)	−0.002 (2)
C4	0.057 (4)	0.038 (3)	0.073 (4)	−0.004 (3)	0.010 (3)	0.014 (3)
C5	0.047 (3)	0.055 (3)	0.053 (3)	0.003 (3)	0.008 (3)	0.008 (3)
C6	0.044 (3)	0.041 (3)	0.037 (3)	−0.002 (2)	0.008 (2)	−0.010 (2)
C7	0.097 (5)	0.048 (3)	0.050 (3)	−0.006 (3)	0.008 (3)	0.006 (3)
I2	0.0549 (2)	0.0456 (2)	0.0798 (3)	−0.00325 (19)	0.00274 (19)	0.01677 (19)
I3	0.0536 (3)	0.0606 (3)	0.0816 (3)	0.0035 (2)	0.0189 (2)	0.0096 (2)

Geometric parameters (Å, º)

O1—N2	1.234 (6)	C3—H3	0.9300
N1—H1A	0.8900	C3—C4	1.363 (6)
N1—H1B	0.8900	C4—H4	0.9300
N1—H1C	0.8900	C4—C5	1.389 (7)
N1—C1	1.466 (5)	C5—H5	0.9300
C1—C2	1.391 (6)	C5—C6	1.360 (6)
C1—C6	1.378 (6)	C7—H7A	0.9600
O2—N2	1.205 (6)	C7—H7B	0.9600
N2—C6	1.465 (6)	C7—H7C	0.9600
C2—C3	1.405 (6)	I2—I3	2.7711 (6)
C2—C7	1.515 (6)
H1A—N1—H1B	109.5	C4—C3—H3	119.2
H1A—N1—H1C	109.5	C3—C4—H4	119.9
H1B—N1—H1C	109.5	C3—C4—C5	120.1 (5)
C1—N1—H1A	109.5	C5—C4—H4	119.9
C1—N1—H1B	109.5	C4—C5—H5	120.3
C1—N1—H1C	109.5	C6—C5—C4	119.4 (5)
C2—C1—N1	116.7 (4)	C6—C5—H5	120.3
C6—C1—N1	122.1 (4)	C1—C6—N2	122.6 (4)
C6—C1—C2	121.2 (4)	C5—C6—C1	120.9 (4)
O1—N2—C6	118.5 (5)	C5—C6—N2	116.5 (5)
O2—N2—O1	123.3 (5)	C2—C7—H7A	109.5
O2—N2—C6	118.2 (5)	C2—C7—H7B	109.5
C1—C2—C3	116.8 (4)	C2—C7—H7C	109.5
C1—C2—C7	122.8 (4)	H7A—C7—H7B	109.5
C3—C2—C7	120.4 (4)	H7A—C7—H7C	109.5
C2—C3—H3	119.2	H7B—C7—H7C	109.5
C4—C3—C2	121.6 (4)
O1—N2—C6—C1	−7.5 (8)	C2—C1—C6—N2	−179.6 (5)
O1—N2—C6—C5	173.6 (5)	C2—C1—C6—C5	−0.8 (8)
N1—C1—C2—C3	−178.9 (4)	C2—C3—C4—C5	1.1 (8)
N1—C1—C2—C7	0.4 (7)	C3—C4—C5—C6	−0.7 (8)
N1—C1—C6—N2	0.4 (7)	C4—C5—C6—C1	0.6 (8)
N1—C1—C6—C5	179.2 (5)	C4—C5—C6—N2	179.5 (5)
C1—C2—C3—C4	−1.3 (8)	C6—C1—C2—C3	1.1 (7)
O2—N2—C6—C1	173.9 (5)	C6—C1—C2—C7	−179.6 (5)
O2—N2—C6—C5	−5.0 (7)	C7—C2—C3—C4	179.4 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.89	1.86	2.591 (6)	138
N1—H1B···I1	0.89	2.82	3.598 (4)	146
N1—H1C···I1^i	0.89	2.82	3.566 (4)	143
C5—H5···O1^ii	0.93	2.54	3.304 (6)	140

Symmetry codes: (i) x+1, y, z; (ii) −x+3/2, y+1/2, −z+1/2.

2-Methyl-6-nitroanilinium hydrogen sulfate (5)

Crystal data

C7H9N2O2^+·HSO4^−	F(000) = 520
Mr = 250.23	Dx = 1.622 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.0966 (5) Å	Cell parameters from 5045 reflections
b = 8.3785 (8) Å	θ = 3.0–30.2°
c = 17.5115 (18) Å	µ = 0.33 mm^−1
β = 100.185 (9)°	T = 295 K
V = 1024.81 (16) Å^3	Plate, clear light colourless
Z = 4	0.42 × 0.32 × 0.09 mm

Data collection

Rigaku Xcalibur Atlas diffractometer	4495 measured reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	4495 independent reflections
Graphite monochromator	3463 reflections with I > 2σ(I)
Detector resolution: 10.6249 pixels mm^-1	θmax = 27.5°, θmin = 2.7°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −10→10
Tmin = 0.939, Tmax = 1.000	l = −22→22

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.136	w = 1/[σ^2(Fo^2) + (0.0891P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
4495 reflections	Δρmax = 0.66 e Å^−3
149 parameters	Δρmin = −0.42 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. Refined as a 2-component twin.

X-ray diffraction data were collected on an Oxford Diffraction four-circle single crystal diffractometer equipped with a CCD detector using graphite-monochromatized Mo Kα radiation (λ = 0.71073 Å). The raw data were treated with the CrysAlis Data Reduction Program, version 1.171.38.34a or 1.171.39.46. The intensities of the reflection were corrected for Lorentz and polarization effects. The crystal structures were solved by direct methods (Sheldrick, 2008) and refined by full-matrix least-squares methods using the SHELXL2017 program (Sheldrick, 2015) and OLEX2 software (Dolomanov et al., 2009).

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

	x	y	z	Uiso*/Ueq
S1	0.32295 (8)	0.09177 (8)	0.70227 (4)	0.0348 (2)
O3	0.4440 (3)	0.1334 (4)	0.64969 (14)	0.0759 (8)
O4	0.1257 (3)	0.1015 (3)	0.66720 (14)	0.0616 (6)
O5	0.3759 (3)	−0.0587 (3)	0.73916 (19)	0.0826 (9)
O6	0.3636 (4)	0.2094 (4)	0.76979 (18)	0.1056 (12)
H6	0.281061	0.278984	0.764211	0.158*
O1	0.6922 (3)	0.5681 (3)	0.70497 (17)	0.0655 (7)
N1	0.7908 (3)	0.2815 (3)	0.66155 (12)	0.0339 (5)
H1A	0.814514	0.352634	0.699809	0.041*
H1B	0.888031	0.213257	0.665312	0.041*
H1C	0.683885	0.228555	0.664973	0.041*
C1	0.7677 (3)	0.3634 (3)	0.58742 (14)	0.0296 (5)
O2	0.7360 (4)	0.7746 (3)	0.6394 (2)	0.1016 (11)
N2	0.7261 (3)	0.6306 (3)	0.6464 (2)	0.0544 (7)
C2	0.7659 (3)	0.2709 (3)	0.52187 (15)	0.0376 (6)
C3	0.7550 (4)	0.3499 (5)	0.45104 (17)	0.0550 (8)
H3	0.754673	0.289852	0.406357	0.066*
C4	0.7451 (4)	0.5101 (5)	0.4451 (2)	0.0651 (10)
H4	0.742614	0.558246	0.397108	0.078*
C5	0.7385 (4)	0.6028 (4)	0.5088 (2)	0.0549 (8)
H5	0.727814	0.713202	0.504282	0.066*
C6	0.7481 (3)	0.5294 (3)	0.58028 (18)	0.0391 (6)
C7	0.7704 (4)	0.0907 (4)	0.52610 (19)	0.0540 (8)
H7A	0.888111	0.056721	0.557734	0.081*
H7B	0.761790	0.047517	0.474816	0.081*
H7C	0.664339	0.053420	0.548427	0.081*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0317 (3)	0.0349 (3)	0.0374 (4)	0.0040 (2)	0.0048 (3)	0.0040 (3)
O3	0.0534 (13)	0.121 (2)	0.0551 (15)	−0.0218 (12)	0.0147 (10)	0.0165 (16)
O4	0.0349 (11)	0.0726 (16)	0.0731 (16)	0.0129 (9)	−0.0023 (10)	−0.0071 (13)
O5	0.0546 (13)	0.0609 (16)	0.124 (2)	−0.0057 (10)	−0.0065 (13)	0.0485 (16)
O6	0.104 (2)	0.122 (3)	0.074 (2)	0.0560 (17)	−0.0328 (15)	−0.0527 (19)
O1	0.0745 (15)	0.0624 (17)	0.0601 (16)	0.0092 (11)	0.0136 (12)	−0.0225 (14)
N1	0.0335 (10)	0.0397 (12)	0.0282 (12)	0.0023 (8)	0.0046 (8)	0.0031 (9)
C1	0.0219 (11)	0.0376 (13)	0.0295 (12)	0.0006 (9)	0.0054 (9)	0.0023 (10)
O2	0.125 (2)	0.0362 (15)	0.134 (3)	0.0110 (13)	−0.0042 (19)	−0.0145 (17)
N2	0.0452 (13)	0.0392 (15)	0.072 (2)	0.0068 (10)	−0.0080 (12)	−0.0099 (14)
C2	0.0264 (12)	0.0543 (17)	0.0320 (14)	0.0026 (10)	0.0050 (10)	−0.0027 (12)
C3	0.0445 (16)	0.092 (3)	0.0298 (16)	0.0084 (15)	0.0094 (11)	0.0052 (16)
C4	0.0482 (18)	0.101 (3)	0.046 (2)	0.0019 (17)	0.0090 (15)	0.036 (2)
C5	0.0390 (15)	0.0520 (19)	0.071 (2)	−0.0023 (12)	0.0032 (14)	0.0263 (18)
C6	0.0276 (12)	0.0373 (14)	0.0498 (18)	−0.0007 (10)	0.0002 (11)	0.0044 (13)
C7	0.0558 (18)	0.0529 (19)	0.0512 (18)	0.0083 (13)	0.0037 (14)	−0.0193 (16)

Geometric parameters (Å, º)

S1—O3	1.410 (2)	N2—C6	1.465 (4)
S1—O4	1.428 (2)	C2—C3	1.396 (4)
S1—O5	1.436 (2)	C2—C7	1.512 (4)
S1—O6	1.527 (3)	C3—H3	0.9300
O6—H6	0.8200	C3—C4	1.347 (5)
O1—N2	1.213 (4)	C4—H4	0.9300
N1—H1A	0.8900	C4—C5	1.367 (5)
N1—H1B	0.8900	C5—H5	0.9300
N1—H1C	0.8900	C5—C6	1.385 (4)
N1—C1	1.452 (3)	C7—H7A	0.9600
C1—C2	1.383 (3)	C7—H7B	0.9600
C1—C6	1.401 (4)	C7—H7C	0.9600
O2—N2	1.216 (3)
O3—S1—O4	111.65 (15)	C1—C2—C7	121.5 (2)
O3—S1—O5	111.72 (17)	C3—C2—C7	121.0 (3)
O3—S1—O6	107.0 (2)	C2—C3—H3	118.8
O4—S1—O5	113.72 (14)	C4—C3—C2	122.3 (3)
O4—S1—O6	109.44 (14)	C4—C3—H3	118.8
O5—S1—O6	102.7 (2)	C3—C4—H4	119.6
S1—O6—H6	109.5	C3—C4—C5	120.8 (3)
H1A—N1—H1B	109.5	C5—C4—H4	119.6
H1A—N1—H1C	109.5	C4—C5—H5	120.6
H1B—N1—H1C	109.5	C4—C5—C6	118.8 (3)
C1—N1—H1A	109.5	C6—C5—H5	120.6
C1—N1—H1B	109.5	C1—C6—N2	121.8 (3)
C1—N1—H1C	109.5	C5—C6—C1	120.7 (3)
C2—C1—N1	117.4 (2)	C5—C6—N2	117.5 (3)
C2—C1—C6	119.7 (2)	C2—C7—H7A	109.5
C6—C1—N1	122.9 (2)	C2—C7—H7B	109.5
O1—N2—O2	122.5 (3)	C2—C7—H7C	109.5
O1—N2—C6	118.9 (3)	H7A—C7—H7B	109.5
O2—N2—C6	118.6 (4)	H7A—C7—H7C	109.5
C1—C2—C3	117.5 (3)	H7B—C7—H7C	109.5
O1—N2—C6—C1	−12.4 (4)	C2—C1—C6—N2	172.5 (2)
O1—N2—C6—C5	164.2 (3)	C2—C1—C6—C5	−3.9 (3)
N1—C1—C2—C3	−176.3 (2)	C2—C3—C4—C5	−2.3 (4)
N1—C1—C2—C7	5.2 (3)	C3—C4—C5—C6	1.9 (4)
N1—C1—C6—N2	−7.6 (3)	C4—C5—C6—C1	1.2 (4)
N1—C1—C6—C5	175.9 (2)	C4—C5—C6—N2	−175.5 (2)
C1—C2—C3—C4	−0.5 (4)	C6—C1—C2—C3	3.5 (3)
O2—N2—C6—C1	170.0 (2)	C6—C1—C2—C7	−175.0 (2)
O2—N2—C6—C5	−13.4 (4)	C7—C2—C3—C4	178.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6···O5^i	0.82	1.75	2.568 (3)	173
N1—H1A···O5^ii	0.89	2.39	2.993 (3)	126
N1—H1A···O1	0.89	2.01	2.650 (3)	128
N1—H1B···O4^iii	0.89	1.92	2.802 (3)	169
N1—H1C···O3	0.89	1.86	2.731 (3)	167

Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+3/2, y+1/2, −z+3/2; (iii) x+1, y, z.