4-(4-Nitro-benz-yl)pyridinium 3-carb-oxy-4-hy-droxy-benzene-sulfonate.

In the title salt, C(12)H(11)N(2)O(2) (+)·C(7)H(5)O(6)S(-), the dihedral angle between the benzene and pyridine rings in the 4-(4-nitro-benz-yl)pyridinium cation is 82.7 (2)°. Within the anion there is an intramolecular hydroxy-O-H⋯O(carboxylic acid) bond. In the crystal, the cation forms a single N(+)-H⋯O(sulfonate) hydrogen bond with the anion. These cation-anion pairs inter-act through duplex anion carb-oxy-lic acid O-H⋯O(sulfonate) hydrogen bonds, giving a centrosymmetric cyclic association [graph set R(2) (2)(16)]. The crystals studied were non-merohedrally twinned.

Related literature

For data on 4-(4-nitro­benz­yl)pyridine adduct and salt structures, see: Smith et al. (1997 ▶); Smith & Wermuth (2010 ▶). For examples of the structures of salts of 5-sulfosalicylic acid, see: Raj et al. (2003 ▶); Smith et al. (2004 ▶). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ▶).

Experimental

Crystal data

C12H11N2O2 +·C7H5O6S−

M = 432.41

Monoclinic,

a = 7.4154 (7) Å

b = 12.8896 (10) Å

c = 19.649 (2) Å

β = 92.848 (9)°

V = 1875.8 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.23 mm−1

T = 200 K

0.25 × 0.20 × 0.15 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T min = 0.916, T max = 0.980

14534 measured reflections

3671 independent reflections

2631 reflections with I > 2σ(I)

R int = 0.049

Refinement

R[F 2 > 2σ(F 2)] = 0.071

wR(F 2) = 0.173

S = 1.21

3671 reflections

272 parameters

H-atom parameters constrained

Δρmax = 0.39 e Å−3

Δρmin = −0.54 e Å−3

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) within WinGX (Farrugia, 2012 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813000093/bh2470sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813000093/bh2470Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813000093/bh2470Isup3.cml

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

C12H11N2O2+·C7H5O6S−	F(000) = 896
Mr = 432.41	Dx = 1.531 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3757 reflections
a = 7.4154 (7) Å	θ = 3.2–28.8°
b = 12.8896 (10) Å	µ = 0.23 mm−1
c = 19.649 (2) Å	T = 200 K
β = 92.848 (9)°	Block, colourless
V = 1875.8 (3) Å3	0.25 × 0.20 × 0.15 mm
Z = 4

Oxford Diffraction Gemini-S CCD-detector diffractometer	3671 independent reflections
Radiation source: Enhance (Mo) X-ray source	2631 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
Detector resolution: 16.077 pixels mm-1	θmax = 26.0°, θmin = 3.2°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −15→15
Tmin = 0.916, Tmax = 0.980	l = 0→24
14534 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.173	H-atom parameters constrained
S = 1.21	w = 1/[σ2(Fo2) + (0.0464P)2 + 2.5904P] where P = (Fo2 + 2Fc2)/3
3671 reflections	(Δ/σ)max < 0.001
272 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.54 e Å−3
0 constraints

	x	y	z	Uiso*/Ueq
O41	0.5308 (6)	1.2075 (3)	0.6714 (2)	0.0669 (15)
O42	0.4378 (6)	1.1939 (3)	0.5666 (2)	0.0580 (16)
N1	0.6089 (5)	0.4772 (3)	0.58094 (19)	0.0343 (14)
N41	0.4750 (5)	1.1565 (3)	0.6224 (2)	0.0374 (14)
C2	0.6921 (7)	0.5677 (4)	0.5906 (3)	0.0433 (19)
C3	0.6005 (7)	0.6507 (4)	0.6162 (3)	0.0363 (16)
C4	0.4226 (6)	0.6405 (3)	0.6324 (2)	0.0265 (14)
C5	0.3420 (6)	0.5439 (3)	0.6213 (2)	0.0332 (16)
C6	0.4369 (7)	0.4631 (3)	0.5959 (2)	0.0347 (16)
C11	0.3719 (6)	0.8367 (3)	0.6512 (2)	0.0304 (16)
C21	0.4350 (8)	0.8981 (4)	0.7051 (2)	0.0439 (19)
C31	0.4738 (7)	1.0020 (4)	0.6955 (3)	0.0447 (19)
C41	0.4452 (6)	1.0441 (3)	0.6322 (2)	0.0294 (16)
C42	0.3137 (7)	0.7262 (3)	0.6619 (2)	0.0351 (16)
C51	0.3888 (6)	0.9853 (4)	0.5774 (2)	0.0328 (16)
C61	0.3547 (6)	0.8809 (3)	0.5871 (2)	0.0305 (14)
S5A	0.96726 (16)	0.31180 (8)	0.53828 (6)	0.0283 (3)
O2A	1.0084 (6)	−0.0013 (3)	0.75787 (17)	0.0573 (14)
O11A	0.8687 (5)	−0.0882 (2)	0.55774 (16)	0.0372 (10)
O12A	0.9140 (5)	−0.1398 (2)	0.66576 (17)	0.0427 (11)
O51A	0.7756 (5)	0.3169 (2)	0.51826 (16)	0.0385 (11)
O52A	1.0352 (5)	0.4070 (2)	0.56822 (18)	0.0433 (11)
O53A	1.0709 (5)	0.2754 (2)	0.48221 (18)	0.0503 (13)
C1A	0.9474 (6)	0.0393 (3)	0.6394 (2)	0.0317 (16)
C2A	1.0008 (7)	0.0680 (4)	0.7061 (2)	0.0363 (16)
C3A	1.0483 (7)	0.1698 (4)	0.7204 (2)	0.0443 (17)
C4A	1.0432 (7)	0.2439 (4)	0.6695 (2)	0.0361 (17)
C5A	0.9863 (6)	0.2161 (3)	0.6031 (2)	0.0250 (12)
C6A	0.9407 (6)	0.1142 (3)	0.5884 (2)	0.0273 (14)
C11A	0.9080 (6)	−0.0709 (3)	0.6227 (2)	0.0304 (14)
H1	0.66760	0.42610	0.56460	0.0410*
H2	0.81240	0.57490	0.58020	0.0520*
H3	0.65890	0.71410	0.62250	0.0440*
H5	0.22190	0.53430	0.63130	0.0400*
H6	0.38210	0.39880	0.58900	0.0420*
H21	0.45160	0.86920	0.74840	0.0520*
H31	0.51860	1.04250	0.73170	0.0540*
H51	0.37360	1.01480	0.53430	0.0390*
H61	0.31950	0.83990	0.54990	0.0370*
H421	0.31140	0.71450	0.71060	0.0420*
H422	0.19060	0.71940	0.64330	0.0420*
H2A	0.97480	−0.06270	0.73320	0.0860*
H3A	1.08390	0.18860	0.76480	0.0530*
H4A	1.07740	0.31190	0.67930	0.0430*
H6A	0.90540	0.09560	0.54390	0.0320*
H11A	0.88000	−0.15700	0.54300	0.0560*

	U11	U22	U33	U12	U13	U23
O41	0.098 (3)	0.0271 (19)	0.074 (3)	−0.016 (2)	−0.012 (3)	−0.020 (2)
O42	0.082 (3)	0.033 (2)	0.059 (3)	−0.008 (2)	0.004 (2)	0.0134 (19)
N1	0.040 (3)	0.027 (2)	0.036 (2)	0.0075 (19)	0.0044 (18)	0.0012 (18)
N41	0.034 (2)	0.024 (2)	0.054 (3)	−0.0013 (18)	−0.001 (2)	−0.006 (2)
C2	0.032 (3)	0.034 (3)	0.065 (4)	0.000 (2)	0.013 (3)	0.008 (3)
C3	0.039 (3)	0.020 (2)	0.050 (3)	−0.004 (2)	0.004 (2)	0.003 (2)
C4	0.033 (3)	0.021 (2)	0.025 (2)	−0.002 (2)	−0.0044 (19)	0.0075 (18)
C5	0.030 (3)	0.031 (2)	0.038 (3)	−0.002 (2)	−0.003 (2)	−0.003 (2)
C6	0.043 (3)	0.023 (2)	0.037 (3)	−0.003 (2)	−0.008 (2)	0.001 (2)
C11	0.033 (3)	0.023 (2)	0.035 (3)	0.002 (2)	0.001 (2)	−0.007 (2)
C21	0.069 (4)	0.035 (3)	0.027 (3)	−0.002 (3)	−0.004 (2)	0.000 (2)
C31	0.066 (4)	0.028 (3)	0.039 (3)	0.000 (3)	−0.009 (3)	−0.011 (2)
C41	0.029 (3)	0.023 (2)	0.036 (3)	0.001 (2)	−0.001 (2)	−0.008 (2)
C42	0.040 (3)	0.026 (2)	0.040 (3)	0.003 (2)	0.008 (2)	0.001 (2)
C51	0.036 (3)	0.031 (2)	0.031 (3)	−0.002 (2)	−0.001 (2)	0.001 (2)
C61	0.035 (3)	0.030 (2)	0.026 (2)	−0.006 (2)	−0.002 (2)	−0.007 (2)
S5A	0.0326 (6)	0.0160 (5)	0.0364 (6)	−0.0023 (5)	0.0040 (5)	−0.0030 (5)
O2A	0.093 (3)	0.051 (2)	0.0285 (19)	0.004 (2)	0.0092 (19)	0.0112 (18)
O11A	0.059 (2)	0.0190 (15)	0.0336 (18)	−0.0051 (16)	0.0011 (16)	0.0005 (14)
O12A	0.059 (2)	0.0300 (18)	0.040 (2)	0.0037 (18)	0.0116 (17)	0.0138 (16)
O51A	0.046 (2)	0.0291 (17)	0.0398 (19)	−0.0026 (17)	−0.0037 (15)	−0.0011 (15)
O52A	0.049 (2)	0.0192 (16)	0.061 (2)	−0.0087 (16)	−0.0056 (18)	−0.0087 (16)
O53A	0.079 (3)	0.0230 (16)	0.052 (2)	0.0096 (18)	0.036 (2)	0.0085 (16)
C1A	0.034 (3)	0.028 (2)	0.034 (3)	0.003 (2)	0.011 (2)	0.005 (2)
C2A	0.047 (3)	0.037 (3)	0.026 (2)	0.010 (2)	0.013 (2)	0.004 (2)
C3A	0.057 (3)	0.049 (3)	0.027 (3)	0.002 (3)	0.002 (2)	−0.011 (2)
C4A	0.039 (3)	0.031 (3)	0.039 (3)	−0.004 (2)	0.009 (2)	−0.013 (2)
C5A	0.022 (2)	0.021 (2)	0.032 (2)	−0.0002 (18)	0.0023 (19)	−0.0011 (18)
C6A	0.031 (3)	0.028 (2)	0.023 (2)	−0.002 (2)	0.0027 (19)	−0.0013 (19)
C11A	0.026 (2)	0.031 (2)	0.035 (3)	0.002 (2)	0.009 (2)	0.005 (2)

S5A—C5A	1.774 (4)	C31—C41	1.364 (7)
S5A—O53A	1.452 (4)	C41—C51	1.365 (6)
S5A—O51A	1.457 (4)	C51—C61	1.384 (6)
S5A—O52A	1.441 (3)	C2—H2	0.9300
O41—N41	1.221 (6)	C3—H3	0.9300
O42—N41	1.217 (6)	C5—H5	0.9300
O2A—C2A	1.353 (6)	C6—H6	0.9300
O11A—C11A	1.314 (5)	C21—H21	0.9300
O12A—C11A	1.226 (5)	C31—H31	0.9300
O2A—H2A	0.9500	C42—H422	0.9700
O11A—H11A	0.9400	C42—H421	0.9700
N1—C6	1.336 (6)	C51—H51	0.9300
N1—C2	1.329 (6)	C61—H61	0.9300
N41—C41	1.480 (5)	C1A—C11A	1.484 (6)
N1—H1	0.8600	C1A—C2A	1.400 (6)
C2—C3	1.376 (7)	C1A—C6A	1.391 (6)
C3—C4	1.379 (7)	C2A—C3A	1.384 (7)
C4—C5	1.394 (6)	C3A—C4A	1.382 (6)
C4—C42	1.502 (6)	C4A—C5A	1.398 (6)
C5—C6	1.365 (6)	C5A—C6A	1.383 (6)
C11—C21	1.385 (6)	C3A—H3A	0.9300
C11—C42	1.506 (6)	C4A—H4A	0.9300
C11—C61	1.383 (6)	C6A—H6A	0.9300
C21—C31	1.385 (7)
O51A—S5A—O53A	110.8 (2)	C6—C5—H5	119.00
O51A—S5A—C5A	105.49 (19)	N1—C6—H6	120.00
O52A—S5A—O53A	113.4 (2)	C5—C6—H6	120.00
O52A—S5A—C5A	106.6 (2)	C11—C21—H21	120.00
O53A—S5A—C5A	107.09 (19)	C31—C21—H21	119.00
O51A—S5A—O52A	112.85 (19)	C21—C31—H31	120.00
C2A—O2A—H2A	100.00	C41—C31—H31	120.00
C11A—O11A—H11A	116.00	C4—C42—H422	108.00
C2—N1—C6	122.0 (4)	C11—C42—H421	108.00
O41—N41—O42	123.4 (4)	C11—C42—H422	108.00
O42—N41—C41	118.5 (4)	H421—C42—H422	107.00
O41—N41—C41	118.1 (4)	C4—C42—H421	108.00
C6—N1—H1	119.00	C41—C51—H51	121.00
C2—N1—H1	119.00	C61—C51—H51	121.00
N1—C2—C3	120.1 (5)	C11—C61—H61	119.00
C2—C3—C4	120.4 (5)	C51—C61—H61	119.00
C5—C4—C42	118.9 (4)	C6A—C1A—C11A	120.4 (4)
C3—C4—C5	117.2 (4)	C2A—C1A—C11A	120.2 (4)
C3—C4—C42	123.9 (4)	C2A—C1A—C6A	119.3 (4)
C4—C5—C6	120.9 (4)	O2A—C2A—C3A	118.2 (4)
N1—C6—C5	119.5 (4)	O2A—C2A—C1A	121.9 (4)
C21—C11—C42	121.5 (4)	C1A—C2A—C3A	119.9 (4)
C21—C11—C61	118.3 (4)	C2A—C3A—C4A	120.7 (4)
C42—C11—C61	120.2 (4)	C3A—C4A—C5A	119.6 (4)
C11—C21—C31	120.9 (4)	C4A—C5A—C6A	119.8 (4)
C21—C31—C41	119.0 (5)	S5A—C5A—C4A	120.1 (3)
N41—C41—C31	119.4 (4)	S5A—C5A—C6A	120.0 (3)
N41—C41—C51	118.9 (4)	C1A—C6A—C5A	120.6 (4)
C31—C41—C51	121.7 (4)	O12A—C11A—C1A	122.8 (4)
C4—C42—C11	118.6 (4)	O11A—C11A—O12A	123.1 (4)
C41—C51—C61	118.8 (4)	O11A—C11A—C1A	114.1 (3)
C11—C61—C51	121.1 (4)	C2A—C3A—H3A	120.00
N1—C2—H2	120.00	C4A—C3A—H3A	120.00
C3—C2—H2	120.00	C3A—C4A—H4A	120.00
C4—C3—H3	120.00	C5A—C4A—H4A	120.00
C2—C3—H3	120.00	C1A—C6A—H6A	120.00
C4—C5—H5	120.00	C5A—C6A—H6A	120.00
O53A—S5A—C5A—C6A	−54.6 (4)	C42—C11—C61—C51	172.9 (4)
O52A—S5A—C5A—C4A	5.3 (4)	C11—C21—C31—C41	1.4 (8)
O53A—S5A—C5A—C4A	126.9 (4)	C21—C31—C41—N41	176.1 (5)
O51A—S5A—C5A—C4A	−114.9 (4)	C21—C31—C41—C51	−3.6 (8)
O52A—S5A—C5A—C6A	−176.3 (4)	C31—C41—C51—C61	2.0 (7)
O51A—S5A—C5A—C6A	63.5 (4)	N41—C41—C51—C61	−177.7 (4)
C6—N1—C2—C3	−0.6 (8)	C41—C51—C61—C11	1.9 (7)
C2—N1—C6—C5	0.6 (7)	C2A—C1A—C11A—O11A	−176.6 (4)
O41—N41—C41—C31	2.5 (6)	C2A—C1A—C11A—O12A	2.6 (7)
O42—N41—C41—C51	4.3 (6)	C6A—C1A—C11A—O11A	0.1 (6)
O41—N41—C41—C51	−177.8 (4)	C6A—C1A—C11A—O12A	179.2 (4)
O42—N41—C41—C31	−175.4 (5)	C11A—C1A—C2A—O2A	−3.8 (7)
N1—C2—C3—C4	0.4 (8)	C11A—C1A—C2A—C3A	175.9 (4)
C2—C3—C4—C42	178.7 (5)	C2A—C1A—C6A—C5A	0.0 (7)
C2—C3—C4—C5	−0.4 (7)	C11A—C1A—C6A—C5A	−176.7 (4)
C3—C4—C5—C6	0.5 (6)	C6A—C1A—C2A—O2A	179.4 (5)
C42—C4—C5—C6	−178.6 (4)	C6A—C1A—C2A—C3A	−0.8 (7)
C3—C4—C42—C11	22.4 (6)	O2A—C2A—C3A—C4A	180.0 (5)
C5—C4—C42—C11	−158.6 (4)	C1A—C2A—C3A—C4A	0.2 (8)
C4—C5—C6—N1	−0.6 (6)	C2A—C3A—C4A—C5A	1.2 (8)
C61—C11—C42—C4	69.8 (6)	C3A—C4A—C5A—C6A	−1.9 (7)
C21—C11—C61—C51	−3.9 (7)	C3A—C4A—C5A—S5A	176.5 (4)
C21—C11—C42—C4	−113.5 (5)	S5A—C5A—C6A—C1A	−177.2 (3)
C42—C11—C21—C31	−174.6 (5)	C4A—C5A—C6A—C1A	1.3 (7)
C61—C11—C21—C31	2.3 (8)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O51A	0.86	1.88	2.732 (5)	172
O2A—H2A···O12A	0.95	1.70	2.613 (5)	159
O11A—H11A···O53Ai	0.94	1.65	2.583 (4)	172
C2—H2···O53Aii	0.93	2.47	3.078 (6)	123
C3A—H3A···O12Aiii	0.93	2.60	3.323 (6)	135
C4A—H4A···O52A	0.93	2.51	2.893 (6)	105
C5—H5···O52Aiv	0.93	2.44	3.024 (5)	120
C6—H6···O52Aiv	0.93	2.59	3.087 (6)	114
C6A—H6A···O11A	0.93	2.40	2.724 (5)	100
C61—H61···O51Av	0.93	2.51	3.394 (5)	160
C42—H421···O41vi	0.97	2.55	3.427 (6)	151

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O51A	0.86	1.88	2.732 (5)	172
O2A—H2A⋯O12A	0.95	1.70	2.613 (5)	159
O11A—H11A⋯O53A i	0.94	1.65	2.583 (4)	172

Symmetry code: (i) .