4-(4-Nitro­benz­yl)pyridinium 3-carb­oxy-4-hy­droxy­benzene­sulfonate

Smith, G.; Wermuth, U.D.

doi:10.1107/S1600536813000093

organic compounds

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ISSN: 2056-9890

Volume 69| Part 2| February 2013| Page o206

doi:10.1107/S1600536813000093

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4-(4-Nitrobenzyl)pyridinium 3-carboxy-4-hydroxybenzenesulfonate

Graham Smith ^a ^* and Urs D. Wermuth ^a

^aScience and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia
^*Correspondence e-mail: g.smith@qut.edu.au

(Received 20 December 2012; accepted 2 January 2013; online 9 January 2013)

In the title salt, C₁₂H₁₁N₂O₂⁺·C₇H₅O₆S⁻, the dihedral angle between the benzene and pyridine rings in the 4-(4-nitrobenzyl)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 interact through duplex anion carboxylic acid O—H⋯O_sulfonate hydrogen bonds, giving a centrosymmetric cyclic association [graph set R₂²(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_r = 432.41
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.071
wR(F²) = 0.173
S = 1.21
3671 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.54 e Å⁻³

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⋯O53Aⁱ	0.94	1.65	2.583 (4)	172
Symmetry code: (i) -x+2, -y, -z+1.

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813000093/bh2470sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536813000093/bh2470Isup3.cml

checkCIF report

Comment top

The Lewis base 4-(4-nitrobenzyl)pyridine (NBPY) is an analogue of 2-(2,4-dinitrobenzyl)pyridine (DNBPY) which is significant because of its unusual photochromic behaviour in the solid state, although NBPY does not possess such properties. The structure of NBPY is not known but both the structures of a 2:1 co-crystal adduct with 4-aminobenzoic acid (Smith et al., 1997) and a 5-nitrosalicylate salt (Smith & Wermuth, 2010) have been reported. Our reaction of NBPY with 3-carboxy-4-hydroxybenzenesulfonic acid (5-sulfosalicylic acid = 5-SSA) gave the title compound, C₁₂H₁₁N₂O₂⁺ C₇H₅O₆S^-, the structure of which is reported herein. The structures of a number of 1:1 salts of 5-SSA are known (Raj et al., 2003; Smith et al., 2004).

With the title compound (Fig. 1), the dihedral angle between the phenyl and pyridine rings in the 4-(4-nitrobenzyl)pyridinium cation is 82.7 (2)° and this forms a single N⁺—H···O_sulfonate hydrogen bond with the anion. These cation–anion pairs inter-associate through duplex anion carboxylic acid O—H···O_sulfonate hydrogen bonds (Table 1, Fig. 2) giving a centrosymmetric cyclic motif [graph set R²₂(16) (Etter et al., 1990)]. Crystals of the compound are non-merohedrally twinned [BASF factor 0.3201 (Sheldrick, 2008); see Refinement section].

In the 5-SSA monoanion, the usual intramolecular phenol O–H···O_carboxyl hydrogen bond [2.613 (5) Å] is present, essentially maintaining coplanarity of the carboxylic acid group and the benzene ring [torsion angle C2A—C1A—C11A—O11A, -176.6 (4)°] (Raj et al., 2003; Smith et al., 2004).

Related literature top

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 top

The title compound was synthesized by heating together under reflux for 10 minutes, 1 mmol quantities of 4-(4-nitrobenzyl)pyridine with 5-sulfosalicylic acid in 50 ml of 50% ethanol–water. After concentration to ca. 30 ml, partial room temperature evaporation of the hot-filtered solution gave colourless crystals from which a block section was cleaved for the X-ray analysis.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); 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 (Spek, 2009).

Figures top

	Fig. 1. Molecular configuration and atom naming scheme for the hydrogen-bonded NBPY cation and 5-SSA monoanion species in the title salt. Hydrogen bonds are shown as dashed lines and displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. A perspective view of the crystal packing in the unit cell showing the centrosymmetric anion-associated hydrogen-bonded cation–anion pairs. For symmetry code (i), see Table 1.

4-(4-Nitrobenzyl)pyridinium 3-carboxy-4-hydroxybenzenesulfonate top

Crystal data top

C₁₂H₁₁N₂O₂⁺·C₇H₅O₆S⁻	F(000) = 896
M_r = 432.41	D_x = 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

Data collection top

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	R_int = 0.049
Detector resolution: 16.077 pixels mm^-1	θ_max = 26.0°, θ_min = 3.2°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −15→15
T_min = 0.916, T_max = 0.980	l = 0→24
14534 measured reflections

Refinement top

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(F_o²) + (0.0464P)² + 2.5904P] where P = (F_o² + 2F_c²)/3
3671 reflections	(Δ/σ)_max < 0.001
272 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.54 e Å⁻³
0 constraints

Crystal data top

C₁₂H₁₁N₂O₂⁺·C₇H₅O₆S⁻	V = 1875.8 (3) Å³
M_r = 432.41	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.4154 (7) Å	µ = 0.23 mm⁻¹
b = 12.8896 (10) Å	T = 200 K
c = 19.649 (2) Å	0.25 × 0.20 × 0.15 mm
β = 92.848 (9)°

Data collection top

Oxford Diffraction Gemini-S CCD-detector diffractometer	3671 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	2631 reflections with I > 2σ(I)
T_min = 0.916, T_max = 0.980	R_int = 0.049
14534 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.071	0 restraints
wR(F²) = 0.173	H-atom parameters constrained
S = 1.21	Δρ_max = 0.39 e Å⁻³
3671 reflections	Δρ_min = −0.54 e Å⁻³
272 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···O52A^iv	0.93	2.44	3.024 (5)	120
C6—H6···O52A^iv	0.93	2.59	3.087 (6)	114
C6A—H6A···O11A	0.93	2.40	2.724 (5)	100
C61—H61···O51A^v	0.93	2.51	3.394 (5)	160
C42—H421···O41^vi	0.97	2.55	3.427 (6)	151

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₁N₂O₂⁺·C₇H₅O₆S⁻
M_r	432.41
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	7.4154 (7), 12.8896 (10), 19.649 (2)
β (°)	92.848 (9)
V (Å³)	1875.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Oxford Diffraction Gemini-S CCD-detector diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2012)
T_min, T_max	0.916, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	14534, 3671, 2631
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.071, 0.173, 1.21
No. of reflections	3671
No. of parameters	272
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.54

Computer programs: CrysAlis PRO (Agilent, 2012), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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

Symmetry code: (i) −x+2, −y, −z+1.

Acknowledgements

The authors acknowledge financial support from the Australian Research Council, the Science and Engineering Faculty and the University Library, Queensland University of Technology.

References

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