Hydrogen bonding in 4-nitro­benzene-1,2-di­amine and two hydro­halide salts

The structures of 4-nitro­benzene-1,2-di­amine [C₆H₇N₃O₂, (I)], 2-amino-5-nitro­anilinium chloride [C₆H₈N₃O₂⁺·Cl⁻, (II)] and 2-amino-5-nitro­anilinium bromide monohydrate [C₆H₈N₃O₂⁺·Br⁻·H₂O, (III)] are reported and their hydrogen-bonded structures described. The amine group para to the nitro group in (I) adopts an approximately planar geometry, whereas the meta amine group is decidedly pyramidal. In the hydrogen halide salts (II) and (III), the amine group meta to the nitro group is protonated. Compound (I) displays a pleated-sheet hydrogen-bonded two-dimensional structure with R₂²(14) and R₄⁴(20) rings. The sheets are joined by additional hydrogen bonds, resulting in a three-dimensional extended structure. Hydro­halide salt (II) has two formula units in the asymmetric unit that are related by a pseudo-inversion center. The dominant hydrogen-bonding inter­actions involve the chloride ion and result in R₄²(8) rings linked to form a ladder-chain structure. The chains are joined by N—H...Cl and N—H...O hydrogen bonds to form sheets parallel to (010). In hydrated hydro­halide salt (III), bromide ions are hydrogen bonded to amine and ammonium groups to form R₄²(8) rings. The water behaves as a double donor/single acceptor and, along with the bromide anions, forms hydrogen bonds involving the nitro, amine, and ammonium groups. The result is sheets parallel to (001) composed of alternating R₅⁵(15) and R₆⁴(24) rings. Ammonium N—H...Br inter­actions join the sheets to form a three-dimensional extended structure. Energy-minimized structures obtained using DFT and MP2 calculations are consistent with the solid-state structures. Consistent with (II) and (III), calculations show that protonation of the amine group meta to the nitro group results in a structure that is about 1.5 kJ mol⁻¹ more stable than that obtained by protonation of the para-amine group. DFT calculations on single mol­ecules and hydrogen-bonded pairs of mol­ecules based on structural results obtained for (I) and for 3-nitro­benzene-1,2-di­amine, (IV) [Betz & Gerber (2011). Acta Cryst. E67, o1359] were used to estimate the strength of the N—H...O(nitro) inter­actions for three observed motifs. The hydrogen-bonding inter­action between the pairs of mol­ecules examined was found to correspond to 20–30 kJ mol⁻¹.

Computing details

For all compounds, data collection: APEX2 (Bruker, 2013); cell refinement: APEX2 (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

(I) 4-Nitrobenzene-1,2-diamine

Crystal data

C6H7N3O2	Dx = 1.530 Mg m^−3
Mr = 153.15	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 99 reflections
a = 3.7492 (6) Å	θ = 4.6–21.5°
b = 10.2864 (19) Å	µ = 0.12 mm^−1
c = 17.238 (3) Å	T = 199 K
V = 664.8 (2) Å^3	Plate, clear orange
Z = 4	0.65 × 0.50 × 0.05 mm
F(000) = 320

Data collection

Bruker SMART X2S benchtop diffractometer	1170 independent reflections
Radiation source: sealed microfocus tube	1010 reflections with I > 2σ(I)
Doubly curved silicon crystal monochromator	Rint = 0.066
Detector resolution: 8.3330 pixels mm^-1	θmax = 25.0°, θmin = 3.1°
ω scans	h = −4→4
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −12→12
Tmin = 0.46, Tmax = 0.99	l = −20→20
7773 measured reflections

Refinement

Refinement on F^2	Secondary 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) = 0.072	w = 1/[σ^2(Fo^2) + (0.03917P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
1170 reflections	Δρmax = 0.12 e Å^−3
116 parameters	Δρmin = −0.15 e Å^−3
0 restraints	Absolute structure: Flack x determined using 354 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.8 (10)

Special details

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

Refinement. Refined as a 2-component inversion twin.

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

	x	y	z	Uiso*/Ueq
O1	0.9592 (5)	1.03420 (17)	1.12307 (9)	0.0569 (6)
O2	0.7070 (5)	0.85290 (16)	1.08963 (9)	0.0520 (5)
N1	0.9475 (7)	1.1026 (2)	0.76269 (11)	0.0475 (6)
H1A	1.060 (7)	1.174 (3)	0.7478 (15)	0.067 (10)*
H1B	0.850 (7)	1.055 (3)	0.7259 (15)	0.055 (8)*
N2	0.6432 (6)	0.8605 (2)	0.79985 (12)	0.0391 (5)
H2A	0.543 (7)	0.902 (3)	0.7594 (17)	0.056 (8)*
H2B	0.525 (8)	0.804 (3)	0.8184 (17)	0.066 (10)*
N3	0.8486 (5)	0.95831 (19)	1.07251 (9)	0.0363 (5)
C1	0.9249 (6)	1.0660 (2)	0.83812 (11)	0.0300 (5)
C2	0.7666 (6)	0.9449 (2)	0.85884 (11)	0.0286 (5)
C3	0.7492 (5)	0.90992 (19)	0.93576 (11)	0.0294 (5)
H3	0.6461	0.8291	0.9502	0.035*
C4	0.8828 (5)	0.9931 (2)	0.99237 (11)	0.0289 (5)
C5	1.0380 (5)	1.11164 (19)	0.97364 (12)	0.0299 (5)
H5	1.1292	1.1671	1.013	0.036*
C6	1.0567 (6)	1.1467 (2)	0.89689 (12)	0.0323 (5)
H6	1.1615	1.2276	0.8833	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0906 (14)	0.0496 (11)	0.0305 (8)	−0.0074 (11)	−0.0053 (9)	−0.0078 (8)
O2	0.0811 (13)	0.0360 (9)	0.0389 (9)	−0.0070 (10)	0.0097 (9)	0.0071 (8)
N1	0.0657 (16)	0.0484 (13)	0.0282 (10)	−0.0118 (12)	−0.0008 (10)	0.0069 (10)
N2	0.0504 (13)	0.0339 (11)	0.0329 (10)	−0.0044 (11)	−0.0031 (10)	−0.0060 (9)
N3	0.0470 (12)	0.0314 (11)	0.0304 (9)	0.0057 (9)	0.0025 (8)	−0.0011 (9)
C1	0.0306 (11)	0.0293 (12)	0.0301 (10)	0.0047 (9)	0.0025 (9)	0.0018 (9)
C2	0.0298 (12)	0.0248 (10)	0.0312 (10)	0.0044 (10)	−0.0001 (9)	−0.0042 (9)
C3	0.0324 (11)	0.0212 (10)	0.0347 (10)	0.0026 (10)	0.0039 (11)	−0.0014 (9)
C4	0.0335 (12)	0.0249 (11)	0.0282 (10)	0.0058 (10)	0.0022 (8)	−0.0013 (8)
C5	0.0318 (12)	0.0264 (11)	0.0316 (10)	0.0009 (10)	0.0002 (10)	−0.0050 (9)
C6	0.0335 (11)	0.0253 (10)	0.0380 (11)	−0.0010 (10)	0.0023 (9)	0.0009 (9)

Geometric parameters (Å, º)

O1—N3	1.241 (2)	C1—C6	1.399 (3)
O2—N3	1.243 (2)	C1—C2	1.426 (3)
N1—C1	1.356 (3)	C2—C3	1.375 (3)
N1—H1A	0.88 (3)	C3—C4	1.391 (3)
N1—H1B	0.88 (3)	C3—H3	0.95
N2—C2	1.415 (3)	C4—C5	1.389 (3)
N2—H2A	0.90 (3)	C5—C6	1.373 (3)
N2—H2B	0.80 (3)	C5—H5	0.95
N3—C4	1.433 (3)	C6—H6	0.95
C1—N1—H1A	122.5 (18)	N2—C2—C1	119.50 (18)
C1—N1—H1B	120.8 (17)	C2—C3—C4	119.89 (19)
H1A—N1—H1B	117 (2)	C2—C3—H3	120.1
C2—N2—H2A	113.6 (18)	C4—C3—H3	120.1
C2—N2—H2B	110 (2)	C5—C4—C3	121.86 (18)
H2A—N2—H2B	115 (3)	C5—C4—N3	118.74 (18)
O1—N3—O2	121.65 (17)	C3—C4—N3	119.36 (18)
O1—N3—C4	119.33 (19)	C6—C5—C4	118.40 (19)
O2—N3—C4	119.02 (18)	C6—C5—H5	120.8
N1—C1—C6	120.5 (2)	C4—C5—H5	120.8
N1—C1—C2	120.6 (2)	C5—C6—C1	121.6 (2)
C6—C1—C2	118.94 (17)	C5—C6—H6	119.2
C3—C2—N2	121.1 (2)	C1—C6—H6	119.2
C3—C2—C1	119.32 (18)
N1—C1—C2—C3	179.6 (2)	O2—N3—C4—C5	179.37 (18)
C6—C1—C2—C3	−0.4 (3)	O1—N3—C4—C3	−178.08 (19)
N1—C1—C2—N2	2.1 (3)	O2—N3—C4—C3	1.6 (3)
C6—C1—C2—N2	−177.9 (2)	C3—C4—C5—C6	0.3 (3)
N2—C2—C3—C4	177.97 (19)	N3—C4—C5—C6	−177.4 (2)
C1—C2—C3—C4	0.5 (3)	C4—C5—C6—C1	−0.2 (3)
C2—C3—C4—C5	−0.5 (3)	N1—C1—C6—C5	−179.8 (2)
C2—C3—C4—N3	177.19 (19)	C2—C1—C6—C5	0.2 (3)
O1—N3—C4—C5	−0.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2^i	0.88 (3)	2.37 (3)	3.249 (3)	177 (2)
N1—H1B···O1^ii	0.88 (3)	2.31 (3)	3.178 (3)	169 (2)
N1—H1B···O2^ii	0.88 (3)	2.54 (3)	3.073 (3)	120 (2)
N2—H2A···O1^ii	0.90 (3)	2.44 (3)	3.257 (3)	151 (2)
N2—H2B···O2^iii	0.80 (3)	2.55 (3)	3.335 (3)	165 (3)
C3—H3···O2^iii	0.95	2.59	3.411 (3)	145

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

(II) 2-Amino-5-nitroanilinium chloride

Crystal data

C6H8N3O2^+·Cl^−	F(000) = 392
Mr = 189.60	Dx = 1.547 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 4.4743 (11) Å	Cell parameters from 123 reflections
b = 29.757 (7) Å	θ = 0.2–20.7°
c = 6.1706 (15) Å	µ = 0.43 mm^−1
β = 97.774 (8)°	T = 200 K
V = 814.0 (3) Å^3	Plate, colourless
Z = 4	0.50 × 0.20 × 0.05 mm

Data collection

Bruker SMART X2S benchtop diffractometer	2353 independent reflections
Radiation source: sealed microfocus tube	1707 reflections with I > 2σ(I)
Doubly curved silicon crystal monochromator	Rint = 0.073
Detector resolution: 8.3330 pixels mm^-1	θmax = 25.1°, θmin = 2.7°
ω scans	h = −5→4
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −34→35
Tmin = 0.58, Tmax = 0.98	l = −7→7
5088 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.102	w = 1/[σ^2(Fo^2) + (0.0358P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.94	(Δ/σ)max < 0.001
2353 reflections	Δρmax = 0.44 e Å^−3
251 parameters	Δρmin = −0.29 e Å^−3
1 restraint	Absolute structure: Flack x determined using 460 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.50 (12)

Special details

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

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.

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

	x	y	z	Uiso*/Ueq
Cl1	0.8425 (4)	0.50092 (5)	0.4491 (3)	0.0314 (5)
Cl2	0.4721 (4)	0.45202 (5)	0.9346 (3)	0.0304 (4)
N3	0.3963 (13)	0.2867 (2)	0.0126 (10)	0.0315 (15)
O1	0.3220 (15)	0.24711 (17)	−0.0179 (10)	0.0579 (18)
O2	0.5645 (12)	0.30679 (18)	−0.0977 (9)	0.0437 (15)
N6	1.0347 (14)	0.1643 (2)	0.6032 (11)	0.0345 (17)
O3	1.2238 (12)	0.14523 (19)	0.5058 (10)	0.0452 (15)
O4	0.9319 (14)	0.20114 (19)	0.5553 (10)	0.0528 (18)
N1	−0.0631 (16)	0.3809 (2)	0.6825 (11)	0.0326 (16)
H1A	0.021 (16)	0.405 (2)	0.725 (12)	0.04 (2)*
H1B	−0.182 (17)	0.363 (3)	0.748 (14)	0.05 (3)*
N2	0.3191 (14)	0.4262 (2)	0.4200 (12)	0.0296 (17)
H2A	0.428 (19)	0.428 (3)	0.508 (15)	0.044*
H2B	0.174 (14)	0.458 (2)	0.461 (12)	0.044*
H2C	0.435 (18)	0.436 (2)	0.336 (14)	0.044*
C1	0.0597 (15)	0.3576 (2)	0.5228 (13)	0.0244 (17)
C2	0.2439 (15)	0.3784 (2)	0.3848 (12)	0.0230 (16)
C3	0.3534 (14)	0.3556 (2)	0.2208 (12)	0.0235 (17)
H3	0.4796	0.3701	0.1303	0.028*
C4	0.2770 (14)	0.3110 (2)	0.1892 (12)	0.0251 (17)
C5	0.0995 (16)	0.2888 (2)	0.3176 (12)	0.0280 (17)
H5	0.0506	0.2581	0.291	0.034*
C6	−0.0098 (16)	0.3116 (2)	0.4882 (13)	0.0311 (19)
H6	−0.1301	0.2963	0.5804	0.037*
N4	0.6182 (17)	0.0721 (2)	1.2972 (12)	0.0339 (17)
H4A	0.728 (15)	0.049 (2)	1.367 (12)	0.04 (2)*
H4B	0.538 (19)	0.086 (3)	1.364 (14)	0.04 (3)*
N5	1.0075 (15)	0.0276 (2)	1.0387 (11)	0.0276 (16)
H5A	1.093 (18)	0.018 (2)	0.937 (13)	0.041*
H5B	0.796 (16)	0.007 (2)	1.028 (11)	0.041*
H5C	1.152 (16)	0.025 (2)	1.176 (14)	0.041*
C7	0.7333 (15)	0.0956 (2)	1.1374 (12)	0.0241 (17)
C8	0.9220 (15)	0.0750 (2)	1.0006 (12)	0.0245 (17)
C9	1.0259 (16)	0.0970 (2)	0.8319 (12)	0.0271 (17)
H9	1.1573	0.0825	0.7452	0.032*
C10	0.9352 (16)	0.1412 (2)	0.7896 (12)	0.0276 (16)
C11	0.7525 (15)	0.1635 (2)	0.9185 (13)	0.0300 (19)
H11	0.6961	0.194	0.89	0.036*
C12	0.6552 (15)	0.1405 (2)	1.0886 (12)	0.0253 (17)
H12	0.5294	0.1556	1.1772	0.03*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0422 (11)	0.0317 (10)	0.0222 (10)	−0.0059 (8)	0.0111 (8)	−0.0012 (8)
Cl2	0.0399 (11)	0.0302 (9)	0.0231 (10)	−0.0051 (8)	0.0111 (8)	−0.0013 (8)
N3	0.034 (4)	0.037 (4)	0.025 (4)	0.005 (3)	0.009 (3)	−0.002 (3)
O1	0.087 (5)	0.029 (3)	0.066 (5)	−0.002 (3)	0.041 (4)	−0.015 (3)
O2	0.054 (4)	0.050 (3)	0.034 (4)	−0.002 (3)	0.030 (3)	−0.002 (3)
N6	0.045 (4)	0.035 (4)	0.025 (4)	−0.009 (3)	0.011 (3)	0.000 (3)
O3	0.054 (4)	0.054 (4)	0.032 (3)	−0.001 (3)	0.022 (3)	0.005 (3)
O4	0.089 (5)	0.029 (3)	0.045 (5)	0.004 (3)	0.025 (4)	0.017 (3)
N1	0.044 (4)	0.032 (4)	0.025 (4)	−0.012 (3)	0.017 (3)	−0.005 (3)
N2	0.038 (4)	0.029 (4)	0.023 (4)	−0.006 (3)	0.008 (3)	0.001 (3)
C1	0.023 (4)	0.027 (4)	0.023 (5)	0.000 (3)	0.004 (3)	−0.003 (3)
C2	0.027 (4)	0.022 (4)	0.021 (4)	0.000 (3)	0.005 (3)	0.004 (3)
C3	0.021 (4)	0.029 (4)	0.022 (5)	0.000 (3)	0.009 (3)	0.001 (3)
C4	0.024 (4)	0.026 (4)	0.026 (5)	0.006 (3)	0.007 (3)	−0.003 (3)
C5	0.036 (4)	0.024 (3)	0.024 (5)	−0.005 (3)	0.005 (3)	0.000 (3)
C6	0.039 (5)	0.031 (4)	0.025 (5)	−0.004 (3)	0.010 (4)	0.003 (3)
N4	0.047 (5)	0.032 (4)	0.026 (4)	0.007 (4)	0.018 (4)	0.004 (3)
N5	0.035 (4)	0.027 (4)	0.022 (4)	0.011 (3)	0.011 (3)	0.000 (3)
C7	0.027 (4)	0.030 (4)	0.017 (4)	−0.006 (3)	0.008 (3)	−0.003 (3)
C8	0.028 (4)	0.026 (4)	0.019 (4)	0.004 (3)	0.001 (3)	0.003 (3)
C9	0.033 (4)	0.029 (4)	0.022 (5)	0.000 (3)	0.013 (4)	−0.006 (3)
C10	0.036 (4)	0.029 (4)	0.020 (4)	−0.004 (3)	0.011 (3)	0.002 (3)
C11	0.034 (4)	0.020 (3)	0.038 (5)	0.002 (3)	0.013 (4)	0.002 (3)
C12	0.025 (4)	0.029 (4)	0.024 (4)	0.007 (3)	0.009 (3)	−0.010 (3)

Geometric parameters (Å, º)

N3—O1	1.232 (8)	C5—C6	1.395 (10)
N3—O2	1.235 (8)	C5—H5	0.95
N3—C4	1.467 (9)	C6—H6	0.95
N6—O4	1.210 (8)	N4—C7	1.366 (9)
N6—O3	1.240 (8)	N4—H4A	0.91 (7)
N6—C10	1.460 (9)	N4—H4B	0.72 (8)
N1—C1	1.379 (9)	N5—C8	1.473 (9)
N1—H1A	0.84 (7)	N5—H5A	0.83 (8)
N1—H1B	0.89 (8)	N5—H5B	1.12 (7)
N2—C2	1.471 (9)	N5—H5C	1.00 (8)
N2—H2A	0.68 (8)	C7—C12	1.403 (9)
N2—H2B	1.19 (7)	C7—C8	1.412 (9)
N2—H2C	0.83 (9)	C8—C9	1.364 (10)
C1—C2	1.407 (9)	C9—C10	1.390 (9)
C1—C6	1.411 (9)	C9—H9	0.95
C2—C3	1.364 (9)	C10—C11	1.385 (10)
C3—C4	1.378 (8)	C11—C12	1.373 (10)
C3—H3	0.95	C11—H11	0.95
C4—C5	1.364 (10)	C12—H12	0.95
O1—N3—O2	123.4 (7)	C5—C6—C1	119.5 (7)
O1—N3—C4	117.8 (6)	C5—C6—H6	120.3
O2—N3—C4	118.8 (6)	C1—C6—H6	120.3
O4—N6—O3	123.9 (7)	C7—N4—H4A	119 (5)
O4—N6—C10	118.2 (7)	C7—N4—H4B	112 (7)
O3—N6—C10	117.9 (7)	H4A—N4—H4B	117 (9)
C1—N1—H1A	117 (5)	C8—N5—H5A	111 (5)
C1—N1—H1B	110 (5)	C8—N5—H5B	108 (3)
H1A—N1—H1B	130 (8)	H5A—N5—H5B	104 (6)
C2—N2—H2A	109 (8)	C8—N5—H5C	110 (4)
C2—N2—H2B	132 (3)	H5A—N5—H5C	107 (7)
H2A—N2—H2B	96 (8)	H5B—N5—H5C	117 (5)
C2—N2—H2C	113 (5)	N4—C7—C12	122.4 (7)
H2A—N2—H2C	92 (9)	N4—C7—C8	121.6 (7)
H2B—N2—H2C	106 (6)	C12—C7—C8	115.9 (6)
N1—C1—C2	122.2 (6)	C9—C8—C7	122.8 (6)
N1—C1—C6	119.7 (7)	C9—C8—N5	118.3 (6)
C2—C1—C6	118.0 (7)	C7—C8—N5	118.9 (6)
C3—C2—C1	121.9 (6)	C8—C9—C10	118.5 (7)
C3—C2—N2	119.6 (6)	C8—C9—H9	120.8
C1—C2—N2	118.5 (7)	C10—C9—H9	120.8
C2—C3—C4	118.5 (7)	C11—C10—C9	121.7 (7)
C2—C3—H3	120.7	C11—C10—N6	119.6 (6)
C4—C3—H3	120.7	C9—C10—N6	118.7 (7)
C5—C4—C3	122.4 (7)	C12—C11—C10	118.2 (6)
C5—C4—N3	119.6 (6)	C12—C11—H11	120.9
C3—C4—N3	118.1 (7)	C10—C11—H11	120.9
C4—C5—C6	119.7 (7)	C11—C12—C7	123.0 (7)
C4—C5—H5	120.2	C11—C12—H12	118.5
C6—C5—H5	120.2	C7—C12—H12	118.5
N1—C1—C2—C3	−177.0 (6)	N4—C7—C8—C9	176.2 (7)
C6—C1—C2—C3	0.3 (10)	C12—C7—C8—C9	0.5 (10)
N1—C1—C2—N2	3.0 (10)	N4—C7—C8—N5	−2.9 (10)
C6—C1—C2—N2	−179.7 (6)	C12—C7—C8—N5	−178.5 (6)
C1—C2—C3—C4	0.8 (10)	C7—C8—C9—C10	−1.8 (11)
N2—C2—C3—C4	−179.2 (6)	N5—C8—C9—C10	177.3 (6)
C2—C3—C4—C5	−0.8 (10)	C8—C9—C10—C11	2.3 (11)
C2—C3—C4—N3	−179.9 (6)	C8—C9—C10—N6	−177.3 (6)
O1—N3—C4—C5	2.4 (10)	O4—N6—C10—C11	−6.5 (10)
O2—N3—C4—C5	−177.7 (7)	O3—N6—C10—C11	172.3 (6)
O1—N3—C4—C3	−178.5 (6)	O4—N6—C10—C9	173.1 (7)
O2—N3—C4—C3	1.4 (9)	O3—N6—C10—C9	−8.1 (10)
C3—C4—C5—C6	−0.2 (11)	C9—C10—C11—C12	−1.5 (11)
N3—C4—C5—C6	178.9 (6)	N6—C10—C11—C12	178.1 (6)
C4—C5—C6—C1	1.3 (11)	C10—C11—C12—C7	0.2 (11)
N1—C1—C6—C5	176.0 (7)	N4—C7—C12—C11	−175.3 (7)
C2—C1—C6—C5	−1.3 (10)	C8—C7—C12—C11	0.3 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl2	0.84 (7)	2.64 (7)	3.410 (7)	152 (6)
N1—H1B···O2^i	0.89 (8)	2.30 (8)	3.176 (9)	170 (7)
N2—H2A···Cl2	0.68 (8)	2.70 (9)	3.249 (7)	139 (10)
N2—H2B···Cl1^ii	1.19 (7)	1.95 (7)	3.103 (7)	161 (5)
N2—H2C···Cl1	0.83 (9)	2.69 (7)	3.217 (6)	123 (7)
N2—H2C···Cl2^iii	0.83 (9)	2.55 (9)	3.254 (7)	143 (7)
C3—H3···Cl2^iii	0.95	2.72	3.449 (7)	134
C5—H5···O4^ii	0.95	2.46	3.134 (9)	128
C6—H6···O2^i	0.95	2.58	3.390 (10)	144
N4—H4A···Cl1^iv	0.91 (7)	2.54 (7)	3.426 (8)	164 (6)
N4—H4B···O3^i	0.72 (8)	2.48 (8)	3.182 (10)	166 (9)
N5—H5A···Cl1^v	0.83 (8)	2.49 (8)	3.269 (6)	157 (7)
N5—H5A···Cl2^iv	0.83 (8)	2.80 (7)	3.225 (6)	114 (6)
N5—H5B···Cl2^vi	1.12 (7)	2.06 (7)	3.128 (7)	157 (5)
N5—H5C···Cl1^iv	1.00 (8)	2.42 (8)	3.240 (7)	139 (6)
N5—H5C···N4^vii	1.00 (8)	2.54 (7)	3.253 (10)	128 (6)

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

(III) 2-Amino-4-nitroanilinium bromide monohydrate

Crystal data

C6H8N3O2^+·Br^−·H2O	Dx = 1.791 Mg m^−3
Mr = 252.08	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Iba2	Cell parameters from 3357 reflections
a = 14.352 (2) Å	θ = 2.8–24.6°
b = 20.086 (3) Å	µ = 4.38 mm^−1
c = 6.4851 (9) Å	T = 200 K
V = 1869.5 (5) Å^3	Plate, clear yellow
Z = 8	0.40 × 0.40 × 0.05 mm
F(000) = 1008

Data collection

Bruker SMART X2S benchtop diffractometer	1695 independent reflections
Radiation source: sealed microfocus tube	1387 reflections with I > 2σ(I)
Doubly curved silicon crystal monochromator	Rint = 0.069
Detector resolution: 8.3330 pixels mm^-1	θmax = 25.3°, θmin = 2.8°
ω scans	h = −17→16
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −24→24
Tmin = 0.48, Tmax = 0.81	l = −7→7
8617 measured reflections

Refinement

Refinement on F^2	Secondary 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) = 0.071	w = 1/[σ^2(Fo^2) + (0.0314P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.96	(Δ/σ)max < 0.001
1695 reflections	Δρmax = 0.40 e Å^−3
146 parameters	Δρmin = −0.34 e Å^−3
1 restraint	Absolute structure: Flack x determined using 554 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.006 (13)

Special details

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

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.

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

	x	y	z	Uiso*/Ueq
Br1	0.40567 (3)	0.86365 (3)	1.00289 (17)	0.0284 (2)
O1S	0.1940 (4)	0.8047 (3)	0.9423 (9)	0.0418 (16)
H1SA	0.240 (6)	0.830 (4)	0.969 (13)	0.07 (3)*
H1SB	0.153 (5)	0.827 (3)	0.933 (10)	0.02 (2)*
N1	0.1130 (4)	0.5386 (3)	1.0132 (19)	0.0363 (14)
H1A	0.069 (4)	0.567 (3)	0.973 (12)	0.030 (19)*
H1B	0.105 (4)	0.500 (4)	1.002 (19)	0.041 (19)*
N2	0.1359 (4)	0.6782 (3)	1.0088 (19)	0.0291 (12)
H2A	0.152 (4)	0.721 (4)	1.008 (19)	0.05 (2)*
H2B	0.108 (6)	0.671 (6)	1.15 (2)	0.09 (4)*
H2C	0.099 (5)	0.675 (5)	0.918 (14)	0.04 (3)*
N3	0.4682 (4)	0.6423 (3)	0.8891 (10)	0.0387 (15)
O1	0.4761 (3)	0.7017 (3)	0.8467 (10)	0.0555 (16)
O2	0.5364 (3)	0.6047 (3)	0.9039 (8)	0.0497 (15)
C1	0.1988 (4)	0.5642 (3)	0.9848 (15)	0.0283 (15)
C2	0.2146 (4)	0.6330 (3)	0.9782 (16)	0.0242 (16)
C3	0.3024 (5)	0.6591 (4)	0.9466 (9)	0.0316 (19)
H3	0.3118	0.7059	0.9422	0.038*
C4	0.3762 (4)	0.6159 (4)	0.9216 (11)	0.0293 (17)
C5	0.3645 (5)	0.5471 (4)	0.9300 (11)	0.038 (2)
H5	0.4164	0.5181	0.9156	0.046*
C6	0.2769 (4)	0.5222 (4)	0.9592 (10)	0.036 (2)
H6	0.2683	0.4753	0.9624	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0240 (3)	0.0334 (3)	0.0277 (3)	−0.0004 (3)	0.0005 (5)	−0.0017 (6)
O1S	0.028 (3)	0.032 (3)	0.065 (5)	−0.003 (3)	−0.002 (3)	0.007 (3)
N1	0.034 (3)	0.024 (3)	0.051 (4)	−0.003 (2)	−0.005 (5)	0.000 (6)
N2	0.029 (3)	0.026 (3)	0.033 (3)	−0.003 (2)	−0.008 (5)	−0.004 (5)
N3	0.030 (3)	0.039 (4)	0.047 (4)	−0.001 (3)	0.003 (3)	−0.003 (3)
O1	0.030 (3)	0.043 (4)	0.093 (5)	−0.002 (3)	0.003 (3)	−0.001 (3)
O2	0.026 (2)	0.046 (3)	0.078 (4)	0.010 (3)	0.003 (3)	−0.004 (3)
C1	0.032 (3)	0.030 (3)	0.022 (4)	0.000 (2)	−0.005 (4)	0.000 (4)
C2	0.023 (2)	0.031 (3)	0.019 (5)	0.003 (2)	−0.002 (4)	0.003 (3)
C3	0.034 (4)	0.039 (4)	0.022 (5)	0.000 (3)	−0.004 (3)	−0.002 (3)
C4	0.019 (3)	0.037 (4)	0.032 (4)	0.002 (3)	−0.001 (3)	−0.002 (3)
C5	0.031 (4)	0.034 (4)	0.049 (5)	0.009 (3)	−0.006 (3)	−0.004 (3)
C6	0.036 (3)	0.029 (4)	0.042 (6)	0.001 (3)	−0.007 (3)	0.002 (3)

Geometric parameters (Å, º)

O1S—H1SA	0.85 (8)	N3—C4	1.439 (9)
O1S—H1SB	0.74 (7)	C1—C2	1.401 (8)
N1—C1	1.347 (8)	C1—C6	1.413 (8)
N1—H1A	0.89 (6)	C2—C3	1.380 (9)
N1—H1B	0.79 (7)	C3—C4	1.379 (9)
N2—C2	1.462 (8)	C3—H3	0.95
N2—H2A	0.89 (7)	C4—C5	1.393 (10)
N2—H2B	1.03 (12)	C5—C6	1.366 (9)
N2—H2C	0.80 (8)	C5—H5	0.95
N3—O1	1.229 (7)	C6—H6	0.95
N3—O2	1.239 (7)
H1SA—O1S—H1SB	106 (8)	C3—C2—C1	121.8 (6)
C1—N1—H1A	112 (4)	C3—C2—N2	119.3 (6)
C1—N1—H1B	120 (5)	C1—C2—N2	118.9 (5)
H1A—N1—H1B	120 (6)	C4—C3—C2	118.6 (7)
C2—N2—H2A	113 (4)	C4—C3—H3	120.7
C2—N2—H2B	110 (6)	C2—C3—H3	120.7
H2A—N2—H2B	104 (10)	C3—C4—C5	121.8 (6)
C2—N2—H2C	112 (7)	C3—C4—N3	119.4 (7)
H2A—N2—H2C	104 (10)	C5—C4—N3	118.8 (6)
H2B—N2—H2C	114 (7)	C6—C5—C4	118.6 (6)
O1—N3—O2	122.4 (6)	C6—C5—H5	120.7
O1—N3—C4	118.3 (6)	C4—C5—H5	120.7
O2—N3—C4	119.3 (6)	C5—C6—C1	121.9 (6)
N1—C1—C2	121.9 (6)	C5—C6—H6	119.1
N1—C1—C6	120.9 (6)	C1—C6—H6	119.1
C2—C1—C6	117.2 (6)
N1—C1—C2—C3	−179.2 (9)	O2—N3—C4—C3	167.0 (7)
C6—C1—C2—C3	0.5 (15)	O1—N3—C4—C5	167.7 (7)
N1—C1—C2—N2	1.7 (17)	O2—N3—C4—C5	−12.0 (10)
C6—C1—C2—N2	−178.6 (9)	C3—C4—C5—C6	1.5 (11)
C1—C2—C3—C4	−0.2 (14)	N3—C4—C5—C6	−179.5 (6)
N2—C2—C3—C4	178.9 (9)	C4—C5—C6—C1	−1.2 (11)
C2—C3—C4—C5	−0.8 (11)	N1—C1—C6—C5	179.9 (8)
C2—C3—C4—N3	−179.8 (7)	C2—C1—C6—C5	0.2 (14)
O1—N3—C4—C3	−13.3 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1S—H1SA···Br1	0.85 (8)	2.48 (8)	3.284 (6)	158 (7)
O1S—H1SB···O2^i	0.74 (7)	2.17 (7)	2.914 (8)	178 (7)
N1—H1A···Br1^i	0.89 (6)	2.73 (6)	3.565 (6)	156 (6)
N1—H1B···Br1^ii	0.79 (7)	2.74 (7)	3.524 (6)	173 (10)
N2—H2A···O1S	0.89 (7)	1.83 (8)	2.708 (7)	166 (12)
N2—H2B···Br1^iii	1.03 (12)	2.38 (13)	3.366 (12)	160 (7)
N2—H2C···Br1^iv	0.80 (8)	2.80 (9)	3.439 (12)	138 (7)
N2—H2C···Br1^i	0.80 (8)	2.93 (8)	3.410 (6)	121 (7)

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