4-Nitro-anilinium 3-carb-oxy-4-hy-droxy-benzene-sulfonate monohydrate.

In the title hydrated salt, C6H7N2O2 (+)·C7H5O6S(-)·H2O, the benzene ring of the cation makes a dihedral angle of 1.32 (19)° with the attached nitro group. In the anion, an intra-molecular O-H⋯O hydrogen bond with an S(6) ring motif is formed between the carb-oxyl and hy-droxy groups; the dihedral angle between the carb-oxyl group and the benzene ring is 8.76 (8)°. The crystal structure exhibits inter-molecular N-H⋯O, O-H⋯O, C-H⋯O, and π-π [centroid-centroid distances = 3.6634 (9) and 3.7426 (9) Å] inter-actions to form a three-dimensional network.

Related literature

For mol­ecular compounds with nonlinear optical properties, see: Nalwa & Miyata (1997 ▶). For related structures, see: Asiri et al. (2010 ▶); Krishnakumar et al. (2012 ▶); Sudhahar et al. (2013 ▶).

Experimental

Crystal data

C6H7N2O2 +·C7H5O6S−·H2O

M = 374.32

Orthorhombic,

a = 13.2676 (3) Å

b = 13.5572 (3) Å

c = 17.1246 (4) Å

V = 3080.23 (12) Å3

Z = 8

Mo Kα radiation

μ = 0.27 mm−1

T = 295 K

0.26 × 0.24 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.934, T max = 0.949

15578 measured reflections

3640 independent reflections

3062 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.107

S = 1.03

3640 reflections

236 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.44 e Å−3

Δρmin = −0.34 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813026779/is5308sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813026779/is5308Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813026779/is5308Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C6H7N2O2+·C7H5O6S−·H2O	F(000) = 1552
Mr = 374.32	Dx = 1.614 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3844 reflections
a = 13.2676 (3) Å	θ = 2.4–28.4°
b = 13.5572 (3) Å	µ = 0.27 mm−1
c = 17.1246 (4) Å	T = 295 K
V = 3080.23 (12) Å3	Block, colourless
Z = 8	0.26 × 0.24 × 0.20 mm

Bruker Kappa APEXII CCD diffractometer	3640 independent reflections
Radiation source: fine-focus sealed tube	3062 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ω and φ scan	θmax = 28.4°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→11
Tmin = 0.934, Tmax = 0.949	k = −18→12
15578 measured reflections	l = −22→17

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)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.107	w = 1/[σ2(Fo2) + (0.0571P)2 + 1.2353P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
3640 reflections	Δρmax = 0.44 e Å−3
236 parameters	Δρmin = −0.34 e Å−3
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0019 (4)

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

	x	y	z	Uiso*/Ueq
C1	0.23376 (11)	0.22732 (11)	0.36435 (9)	0.0324 (3)
H1	0.1676	0.2374	0.3805	0.039*
C2	0.31016 (11)	0.22696 (11)	0.41813 (9)	0.0291 (3)
H2	0.2958	0.2364	0.4708	0.035*
C3	0.41012 (10)	0.21236 (10)	0.39384 (8)	0.0249 (3)
C4	0.43237 (10)	0.20070 (10)	0.31573 (8)	0.0267 (3)
H4	0.4989	0.1928	0.2998	0.032*
C5	0.35471 (11)	0.20079 (11)	0.26038 (8)	0.0277 (3)
C6	0.25490 (11)	0.21266 (11)	0.28527 (9)	0.0304 (3)
C7	0.37580 (12)	0.18773 (12)	0.17625 (9)	0.0343 (3)
C8	0.10072 (13)	−0.02919 (13)	0.38844 (10)	0.0402 (4)
H8	0.0307	−0.0320	0.3888	0.048*
C9	0.15443 (12)	−0.02301 (13)	0.45736 (9)	0.0371 (4)
H9	0.1210	−0.0220	0.5051	0.045*
C10	0.25815 (12)	−0.01838 (11)	0.45470 (9)	0.0301 (3)
C11	0.31058 (12)	−0.02335 (11)	0.38520 (10)	0.0359 (4)
H11	0.3807	−0.0228	0.3848	0.043*
C12	0.25710 (13)	−0.02920 (12)	0.31634 (10)	0.0391 (4)
H12	0.2905	−0.0319	0.2686	0.047*
C13	0.15317 (13)	−0.03101 (12)	0.31948 (9)	0.0361 (4)
N1	0.31299 (10)	−0.00774 (10)	0.52813 (8)	0.0351 (3)
H1A	0.2733	0.0208	0.5634	0.053*
H1B	0.3674	0.0294	0.5205	0.053*
H1C	0.3317	−0.0670	0.5452	0.053*
N2	0.09540 (14)	−0.03548 (12)	0.24631 (9)	0.0513 (4)
O1	0.47752 (9)	0.12506 (9)	0.51725 (7)	0.0434 (3)
O2	0.59937 (8)	0.18656 (10)	0.42481 (7)	0.0403 (3)
O3	0.50743 (9)	0.30034 (8)	0.50523 (7)	0.0391 (3)
O4	0.17634 (9)	0.21175 (11)	0.23553 (7)	0.0485 (4)
H4A	0.1969	0.2027	0.1909	0.073*
O5	0.30993 (9)	0.17648 (13)	0.12778 (7)	0.0580 (4)
O6	0.47157 (9)	0.18949 (11)	0.15782 (7)	0.0489 (3)
H6	0.4778	0.1818	0.1106	0.073*
O7	0.14092 (17)	−0.03731 (18)	0.18586 (9)	0.1005 (8)
O8	0.00426 (13)	−0.03699 (16)	0.24947 (10)	0.0834 (6)
O9	0.16700 (15)	0.10629 (14)	0.60925 (13)	0.0740 (5)
S1	0.50511 (2)	0.20521 (3)	0.46557 (2)	0.02593 (12)
H9A	0.152 (3)	0.149 (2)	0.5775 (18)	0.143 (16)*
H9B	0.186 (3)	0.136 (3)	0.6481 (16)	0.167 (19)*

	U11	U22	U33	U12	U13	U23
C1	0.0208 (7)	0.0399 (8)	0.0365 (8)	0.0032 (6)	0.0027 (6)	−0.0022 (6)
C2	0.0273 (7)	0.0328 (7)	0.0273 (7)	0.0014 (6)	0.0032 (6)	−0.0012 (6)
C3	0.0228 (7)	0.0278 (7)	0.0240 (7)	−0.0001 (5)	−0.0020 (5)	0.0014 (5)
C4	0.0208 (6)	0.0333 (7)	0.0260 (7)	0.0000 (5)	0.0008 (5)	0.0018 (6)
C5	0.0250 (7)	0.0336 (7)	0.0245 (7)	−0.0008 (6)	−0.0022 (5)	0.0009 (6)
C6	0.0227 (7)	0.0364 (8)	0.0323 (8)	0.0010 (6)	−0.0050 (6)	0.0002 (6)
C7	0.0281 (8)	0.0483 (9)	0.0266 (7)	−0.0008 (6)	−0.0025 (6)	0.0017 (7)
C8	0.0297 (8)	0.0515 (10)	0.0396 (9)	−0.0019 (7)	−0.0032 (7)	0.0014 (7)
C9	0.0310 (8)	0.0503 (10)	0.0301 (8)	−0.0037 (7)	0.0030 (6)	0.0015 (7)
C10	0.0304 (8)	0.0277 (7)	0.0322 (7)	−0.0013 (6)	−0.0031 (6)	0.0043 (6)
C11	0.0295 (8)	0.0346 (8)	0.0436 (9)	−0.0011 (6)	0.0052 (7)	0.0011 (7)
C12	0.0455 (9)	0.0387 (8)	0.0332 (8)	−0.0023 (7)	0.0086 (7)	0.0014 (7)
C13	0.0426 (9)	0.0348 (8)	0.0307 (8)	−0.0011 (7)	−0.0049 (7)	0.0024 (6)
N1	0.0306 (7)	0.0385 (7)	0.0362 (7)	−0.0016 (5)	−0.0047 (5)	0.0027 (6)
N2	0.0630 (11)	0.0556 (10)	0.0354 (8)	−0.0016 (8)	−0.0099 (7)	0.0018 (7)
O1	0.0402 (6)	0.0507 (7)	0.0394 (6)	−0.0103 (5)	−0.0074 (5)	0.0197 (6)
O2	0.0242 (5)	0.0657 (8)	0.0310 (6)	0.0081 (5)	0.0021 (4)	0.0055 (5)
O3	0.0451 (7)	0.0419 (7)	0.0302 (6)	−0.0013 (5)	−0.0072 (5)	−0.0047 (5)
O4	0.0238 (6)	0.0848 (10)	0.0370 (7)	0.0052 (6)	−0.0083 (5)	−0.0074 (6)
O5	0.0323 (7)	0.1114 (12)	0.0304 (6)	−0.0045 (7)	−0.0071 (5)	−0.0088 (7)
O6	0.0289 (6)	0.0934 (10)	0.0243 (6)	−0.0025 (6)	0.0010 (5)	0.0018 (6)
O7	0.0957 (14)	0.176 (2)	0.0304 (8)	−0.0207 (14)	−0.0011 (8)	0.0029 (10)
O8	0.0567 (11)	0.1344 (19)	0.0590 (10)	0.0062 (10)	−0.0251 (8)	−0.0088 (11)
O9	0.0787 (12)	0.0606 (10)	0.0827 (13)	0.0281 (9)	−0.0161 (10)	−0.0100 (10)
S1	0.0221 (2)	0.0348 (2)	0.02094 (19)	−0.00090 (13)	−0.00073 (12)	0.00349 (13)

C1—C2	1.370 (2)	C10—C11	1.380 (2)
C1—C6	1.397 (2)	C10—N1	1.4599 (19)
C1—H1	0.9300	C11—C12	1.378 (2)
C2—C3	1.4040 (19)	C11—H11	0.9300
C2—H2	0.9300	C12—C13	1.380 (2)
C3—C4	1.379 (2)	C12—H12	0.9300
C3—S1	1.7625 (14)	C13—N2	1.470 (2)
C4—C5	1.400 (2)	N1—H1A	0.8900
C4—H4	0.9300	N1—H1B	0.8900
C5—C6	1.400 (2)	N1—H1C	0.8900
C5—C7	1.478 (2)	N2—O7	1.199 (2)
C6—O4	1.3462 (18)	N2—O8	1.211 (2)
C7—O5	1.2150 (19)	O1—S1	1.4484 (12)
C7—O6	1.309 (2)	O2—S1	1.4544 (11)
C8—C13	1.371 (2)	O3—S1	1.4579 (12)
C8—C9	1.381 (2)	O4—H4A	0.8200
C8—H8	0.9300	O6—H6	0.8200
C9—C10	1.378 (2)	O9—H9A	0.821 (10)
C9—H9	0.9300	O9—H9B	0.815 (10)
C2—C1—C6	120.18 (13)	C11—C10—N1	119.75 (14)
C2—C1—H1	119.9	C12—C11—C10	118.75 (15)
C6—C1—H1	119.9	C12—C11—H11	120.6
C1—C2—C3	120.03 (13)	C10—C11—H11	120.6
C1—C2—H2	120.0	C11—C12—C13	118.81 (15)
C3—C2—H2	120.0	C11—C12—H12	120.6
C4—C3—C2	120.39 (13)	C13—C12—H12	120.6
C4—C3—S1	121.11 (11)	C8—C13—C12	122.71 (16)
C2—C3—S1	118.47 (11)	C8—C13—N2	118.05 (16)
C3—C4—C5	119.94 (13)	C12—C13—N2	119.24 (16)
C3—C4—H4	120.0	C10—N1—H1A	109.5
C5—C4—H4	120.0	C10—N1—H1B	109.5
C4—C5—C6	119.34 (13)	H1A—N1—H1B	109.5
C4—C5—C7	121.36 (13)	C10—N1—H1C	109.5
C6—C5—C7	119.30 (13)	H1A—N1—H1C	109.5
O4—C6—C1	117.34 (13)	H1B—N1—H1C	109.5
O4—C6—C5	122.58 (14)	O7—N2—O8	122.79 (19)
C1—C6—C5	120.08 (13)	O7—N2—C13	118.31 (19)
O5—C7—O6	122.38 (15)	O8—N2—C13	118.91 (17)
O5—C7—C5	123.01 (15)	C6—O4—H4A	109.5
O6—C7—C5	114.61 (13)	C7—O6—H6	109.5
C13—C8—C9	118.38 (16)	H9A—O9—H9B	106 (4)
C13—C8—H8	120.8	O1—S1—O2	112.34 (7)
C9—C8—H8	120.8	O1—S1—O3	112.60 (8)
C10—C9—C8	119.32 (15)	O2—S1—O3	111.05 (7)
C10—C9—H9	120.3	O1—S1—C3	106.64 (7)
C8—C9—H9	120.3	O2—S1—C3	106.86 (7)
C9—C10—C11	121.97 (15)	O3—S1—C3	106.93 (7)
C9—C10—N1	118.28 (14)
C6—C1—C2—C3	0.3 (2)	C8—C9—C10—N1	177.48 (15)
C1—C2—C3—C4	1.6 (2)	C9—C10—C11—C12	2.6 (2)
C1—C2—C3—S1	−176.32 (11)	N1—C10—C11—C12	−177.29 (14)
C2—C3—C4—C5	−1.7 (2)	C10—C11—C12—C13	−0.7 (2)
S1—C3—C4—C5	176.15 (10)	C9—C8—C13—C12	1.5 (3)
C3—C4—C5—C6	−0.1 (2)	C9—C8—C13—N2	−178.74 (15)
C3—C4—C5—C7	−179.54 (14)	C11—C12—C13—C8	−1.3 (3)
C2—C1—C6—O4	178.63 (14)	C11—C12—C13—N2	178.93 (14)
C2—C1—C6—C5	−2.1 (2)	C8—C13—N2—O7	−179.8 (2)
C4—C5—C6—O4	−178.81 (14)	C12—C13—N2—O7	−0.1 (3)
C7—C5—C6—O4	0.7 (2)	C8—C13—N2—O8	0.3 (3)
C4—C5—C6—C1	2.0 (2)	C12—C13—N2—O8	−179.96 (18)
C7—C5—C6—C1	−178.55 (14)	C4—C3—S1—O1	−120.21 (13)
C4—C5—C7—O5	171.57 (17)	C2—C3—S1—O1	57.67 (13)
C6—C5—C7—O5	−7.9 (3)	C4—C3—S1—O2	0.12 (14)
C4—C5—C7—O6	−8.6 (2)	C2—C3—S1—O2	178.00 (11)
C6—C5—C7—O6	171.95 (14)	C4—C3—S1—O3	119.10 (12)
C13—C8—C9—C10	0.3 (3)	C2—C3—S1—O3	−63.02 (13)
C8—C9—C10—C11	−2.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O9	0.89	1.99	2.841 (2)	160
N1—H1B···O1	0.89	1.95	2.8357 (18)	171
O4—H4A···O5	0.82	1.88	2.6028 (18)	146
C9—H9···O9	0.93	2.57	3.141 (3)	121
N1—H1A···O7i	0.89	2.40	2.836 (2)	111
N1—H1C···O2ii	0.89	1.93	2.8069 (18)	168
O4—H4A···O2iii	0.82	2.38	2.9494 (16)	128
O6—H6···O3iv	0.82	1.86	2.6595 (17)	164
O9—H9A···O2v	0.82 (1)	2.33 (3)	3.005 (2)	139 (4)
O9—H9A···O3v	0.82 (1)	2.48 (3)	3.151 (2)	140 (4)
O9—H9B···O4vi	0.82 (1)	2.56 (3)	3.283 (2)	149 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O9	0.89	1.99	2.841 (2)	160
N1—H1B⋯O1	0.89	1.95	2.8357 (18)	171
O4—H4A⋯O5	0.82	1.88	2.6028 (18)	146
C9—H9⋯O9	0.93	2.57	3.141 (3)	121
N1—H1A⋯O7i	0.89	2.40	2.836 (2)	111
N1—H1C⋯O2ii	0.89	1.93	2.8069 (18)	168
O4—H4A⋯O2iii	0.82	2.38	2.9494 (16)	128
O6—H6⋯O3iv	0.82	1.86	2.6595 (17)	164
O9—H9A⋯O2v	0.82 (1)	2.33 (3)	3.005 (2)	139 (4)
O9—H9A⋯O3v	0.82 (1)	2.48 (3)	3.151 (2)	140 (4)
O9—H9B⋯O4vi	0.82 (1)	2.56 (3)	3.283 (2)	149 (4)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .