3-Hy­droxy­anilinium p-toluene­sulfonate

Bincy, I.P.; Gopalakrishnan, R.

doi:10.1107/S1600536813018692

organic compounds

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ISSN: 2056-9890

Volume 69| Part 8| August 2013| Page o1277

doi:10.1107/S1600536813018692

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3-Hydroxyanilinium p-toluenesulfonate

Impichira Pykkat Bincy ^a and Rengasamy Gopalakrishnan ^a ^*

^aDepartment of Physics, Anna University, Chennai 600 025, India
^*Correspondence e-mail: krgkrishnan@annauniv.edu

(Received 19 June 2013; accepted 5 July 2013; online 20 July 2013)

The asymmetric unit of the title salt, C₆H₈NO⁺·C₇H₇O₃S⁻, contains two cations and two anions. In the crystal, the cations and anions are linked through extensive N—H⋯O and O—H⋯O hydrogen-bonding interactions, which result in R₄⁴(18) and R₂¹(4) ring motifs, forming a three-dimensional network.

Related literature

For related structures of 4-toluenesulfonate salts, see: Koshima et al. (2004 ); Biradha & Mahata (2005 ); Sivakumar et al. (2012 ).

Experimental

Crystal data

C₆H₈NO⁺·C₇H₇O₃S⁻
M_r = 281.32
Triclinic, $[P \overline 1]$
a = 9.5775 (3) Å
b = 10.8224 (3) Å
c = 14.1445 (4) Å
α = 96.787 (2)°
β = 109.701 (1)°
γ = 91.324 (2)°
V = 1367.50 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.910, T_max = 0.953
32207 measured reflections
8651 independent reflections
6679 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.122
S = 1.03
8651 reflections
372 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7⋯O6ⁱ	0.82	1.95	2.7657 (16)	173 (2)
N2—H2C⋯O4ⁱ	0.89 (1)	2.06 (1)	2.9441 (18)	170 (2)
N2—H2B⋯O3ⁱ	0.89 (1)	2.31 (2)	2.9020 (17)	124 (2)
N2—H2A⋯O3ⁱⁱ	0.90 (1)	1.89 (1)	2.7784 (18)	170 (2)
N2—H2B⋯O5ⁱⁱ	0.89 (1)	2.20 (2)	2.9395 (19)	141 (2)
N1—H1B⋯O5ⁱⁱⁱ	0.89 (1)	2.15 (2)	2.9406 (19)	147 (2)
N1—H1B⋯O6ⁱⁱⁱ	0.89 (1)	2.32 (2)	3.1087 (19)	147 (2)
N1—H1C⋯O2^iv	0.89 (1)	1.86 (1)	2.7410 (18)	177 (2)
O8—H8⋯O1	0.82	1.94	2.7216 (17)	160
N1—H1A⋯O1	0.90 (1)	1.95 (1)	2.8007 (17)	158 (2)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x-1, y, z; (iii) -x+2, -y+1, -z+1; (iv) -x+2, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813018692/kp2454sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813018692/kp2454Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813018692/kp2454Isup3.cml

checkCIF report

Comment top

The asymmetric unit of the title salt (Fig.1) contains two hydroxyanilinium cations [C₆H₈N₁O₁]⁺ and two 4-toluenesulfonate anions [C₇H₇O₃S₁]^-. The aminophenol molecule exists as hydroxyanilinium cation due to the protonation. The 4-toluenesulfonic acid exists as 4-toluenesulfonate due to a proton transfer. The hydroxyl oxygen atoms O7 and O8 attached to the phenyl ring deviate from the ring plane by 0.0528 (1)° and 0.0157 (1)Å, respectively. The crystal packing is stabilsed by intermolcular N—H···O and O—H···O hydrogen bonds (Table 1, Fig.2) involving R⁴₄(18), R¹₂(4) ring motifs.

Related literature top

For related structures of 4-toluenesulfonate salts, see: Koshima et al. (2004); Biradha & Mahata (2005); Sivakumar et al. (2012).

Experimental top

The title compound was obtained by addition of 3-aminophenol and 4-toluenesulfonic acid in an equimolar ratio using methanol as solvent. After a filtration of resulting solution into a clean beaker, which was covered and kept at room temperature for slow evaporation. After a period of 2 weeks, block-like colourless crystals suitable for X-ray diffraction analysis were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. The crystal packing of the title compound viewed down a axis. H-atoms not involved in H-bonds have been excluded for clarity.

3-Hydroxyanilinium p-toluenesulfonate top

Crystal data top

C₆H₈NO⁺·C₇H₇O₃S⁻	Z = 4
M_r = 281.32	F(000) = 592
Triclinic, P1	D_x = 1.366 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5775 (3) Å	Cell parameters from 7098 reflections
b = 10.8224 (3) Å	θ = 2.3–30.8°
c = 14.1445 (4) Å	µ = 0.25 mm⁻¹
α = 96.787 (2)°	T = 293 K
β = 109.701 (1)°	Block, colourless
γ = 91.324 (2)°	0.30 × 0.25 × 0.20 mm
V = 1367.50 (7) Å³

Data collection top

Bruker SMART APEXII area-detector diffractometer	8651 independent reflections
Radiation source: fine-focus sealed tube	6679 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω and ϕ scans	θ_max = 31.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −13→13
T_min = 0.910, T_max = 0.953	k = −15→15
32207 measured reflections	l = −20→20

Refinement top

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)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.122	w = 1/[σ²(F_o²) + (0.0591P)² + 0.346P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
8651 reflections	Δρ_max = 0.35 e Å⁻³
372 parameters	Δρ_min = −0.33 e Å⁻³
6 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: 0.048 (2)

Crystal data top

C₆H₈NO⁺·C₇H₇O₃S⁻	γ = 91.324 (2)°
M_r = 281.32	V = 1367.50 (7) Å³
Triclinic, P1	Z = 4
a = 9.5775 (3) Å	Mo Kα radiation
b = 10.8224 (3) Å	µ = 0.25 mm⁻¹
c = 14.1445 (4) Å	T = 293 K
α = 96.787 (2)°	0.30 × 0.25 × 0.20 mm
β = 109.701 (1)°

Data collection top

Bruker SMART APEXII area-detector diffractometer	8651 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	6679 reflections with I > 2σ(I)
T_min = 0.910, T_max = 0.953	R_int = 0.031
32207 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	6 restraints
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.35 e Å⁻³
8651 reflections	Δρ_min = −0.33 e Å⁻³
372 parameters

Special details top

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. 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 > 2sigma(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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.79378 (15)	0.72105 (13)	0.22287 (10)	0.0342 (3)
C2	0.7663 (2)	0.82072 (15)	0.16737 (13)	0.0509 (4)
H2	0.7882	0.9023	0.1999	0.061*
C3	0.7056 (2)	0.79676 (18)	0.06283 (13)	0.0595 (5)
H3	0.6879	0.8634	0.0253	0.071*
C4	0.67079 (19)	0.67706 (18)	0.01284 (12)	0.0515 (4)
C5	0.6972 (2)	0.57994 (17)	0.06995 (12)	0.0521 (4)
H5	0.6734	0.4985	0.0375	0.063*
C6	0.75833 (18)	0.60085 (14)	0.17446 (11)	0.0435 (3)
H6	0.7754	0.5341	0.2118	0.052*
C7	0.6075 (3)	0.6510 (2)	−0.10113 (13)	0.0735 (6)
H7A	0.5010	0.6440	−0.1227	0.110*
H7B	0.6424	0.5744	−0.1236	0.110*
H7C	0.6390	0.7180	−0.1297	0.110*
C8	0.86225 (15)	0.26820 (13)	0.17460 (10)	0.0367 (3)
C9	0.97997 (17)	0.32943 (17)	0.16045 (12)	0.0495 (4)
H9	1.0607	0.3644	0.2160	0.059*
C10	0.9775 (2)	0.3387 (2)	0.06314 (13)	0.0576 (4)
H10	1.0577	0.3796	0.0543	0.069*
C11	0.8593 (2)	0.28898 (18)	−0.02095 (12)	0.0526 (4)
C12	0.7423 (2)	0.2290 (2)	−0.00521 (13)	0.0596 (5)
H12	0.6609	0.1954	−0.0608	0.072*
C13	0.74287 (18)	0.21754 (18)	0.09124 (13)	0.0526 (4)
H13	0.6630	0.1758	0.1000	0.063*
C14	0.8580 (3)	0.3018 (3)	−0.12599 (15)	0.0793 (7)
H14A	0.7661	0.2648	−0.1748	0.119*
H14B	0.9395	0.2603	−0.1375	0.119*
H14C	0.8677	0.3886	−0.1326	0.119*
C15	0.75233 (16)	0.93763 (12)	0.64225 (10)	0.0366 (3)
C16	0.60302 (16)	0.91742 (13)	0.58994 (11)	0.0371 (3)
H16	0.5676	0.9027	0.5195	0.044*
C17	0.50499 (17)	0.91922 (13)	0.64370 (12)	0.0410 (3)
C18	0.5603 (2)	0.93703 (17)	0.74827 (13)	0.0548 (4)
H18	0.4956	0.9377	0.7847	0.066*
C19	0.7110 (2)	0.9538 (2)	0.79838 (13)	0.0652 (5)
H19	0.7474	0.9644	0.8688	0.078*
C20	0.8098 (2)	0.95514 (19)	0.74635 (13)	0.0553 (4)
H20	0.9117	0.9675	0.7806	0.066*
C21	0.27809 (14)	0.53847 (13)	0.42602 (9)	0.0326 (3)
C22	0.31807 (15)	0.65362 (13)	0.40693 (10)	0.0362 (3)
H22	0.2743	0.7247	0.4240	0.043*
C23	0.42514 (15)	0.66067 (13)	0.36166 (10)	0.0358 (3)
C24	0.48849 (15)	0.55399 (14)	0.33565 (10)	0.0389 (3)
H24	0.5606	0.5592	0.3054	0.047*
C25	0.44440 (15)	0.44001 (14)	0.35467 (11)	0.0395 (3)
H25	0.4866	0.3685	0.3366	0.047*
C26	0.33822 (15)	0.43084 (13)	0.40027 (10)	0.0357 (3)
H26	0.3083	0.3541	0.4132	0.043*
N1	0.85435 (15)	0.94075 (12)	0.58541 (10)	0.0397 (3)
N2	0.17042 (14)	0.53203 (13)	0.47848 (10)	0.0419 (3)
O1	0.76020 (13)	0.81258 (14)	0.38830 (9)	0.0607 (3)
O2	1.00677 (13)	0.82598 (12)	0.38221 (10)	0.0594 (3)
O3	0.89749 (14)	0.62868 (11)	0.39024 (8)	0.0508 (3)
O4	0.74946 (13)	0.33688 (11)	0.31395 (9)	0.0509 (3)
O5	1.00949 (12)	0.29535 (12)	0.36731 (8)	0.0513 (3)
O6	0.82415 (14)	0.12609 (10)	0.29910 (9)	0.0522 (3)
O7	0.35802 (13)	0.90516 (13)	0.58862 (9)	0.0551 (3)
H7	0.3104	0.8967	0.6262	0.083*
O8	0.46157 (13)	0.77577 (11)	0.34359 (10)	0.0525 (3)
H8	0.5470	0.7784	0.3432	0.079*
S1	0.87120 (4)	0.74922 (3)	0.35574 (2)	0.03467 (9)
S2	0.86039 (4)	0.25714 (3)	0.29790 (3)	0.03551 (9)
H1C	0.899 (2)	1.0158 (12)	0.5934 (16)	0.066 (6)*
H1A	0.811 (2)	0.9178 (19)	0.5186 (8)	0.062 (6)*
H2A	0.0884 (16)	0.5712 (18)	0.4500 (14)	0.064 (6)*
H2C	0.206 (2)	0.5702 (19)	0.5421 (9)	0.066 (6)*
H2B	0.141 (2)	0.4533 (11)	0.4761 (16)	0.069 (6)*
H1B	0.928 (2)	0.891 (2)	0.6078 (19)	0.092 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0375 (6)	0.0332 (7)	0.0337 (6)	0.0013 (5)	0.0155 (5)	0.0024 (5)
C2	0.0696 (11)	0.0362 (8)	0.0451 (8)	0.0021 (7)	0.0172 (7)	0.0060 (6)
C3	0.0797 (12)	0.0550 (10)	0.0438 (9)	0.0098 (9)	0.0171 (8)	0.0179 (8)
C4	0.0536 (9)	0.0647 (11)	0.0354 (7)	0.0083 (8)	0.0147 (7)	0.0041 (7)
C5	0.0653 (10)	0.0458 (9)	0.0406 (8)	0.0026 (7)	0.0164 (7)	−0.0067 (6)
C6	0.0576 (9)	0.0340 (7)	0.0384 (7)	0.0036 (6)	0.0165 (6)	0.0025 (6)
C7	0.0775 (13)	0.1009 (17)	0.0358 (8)	0.0106 (12)	0.0123 (8)	0.0051 (9)
C8	0.0357 (6)	0.0386 (7)	0.0367 (6)	0.0019 (5)	0.0155 (5)	−0.0004 (5)
C9	0.0382 (7)	0.0692 (11)	0.0396 (7)	−0.0076 (7)	0.0122 (6)	0.0067 (7)
C10	0.0505 (9)	0.0800 (13)	0.0469 (9)	−0.0038 (8)	0.0217 (7)	0.0131 (8)
C11	0.0571 (9)	0.0631 (11)	0.0393 (8)	0.0100 (8)	0.0186 (7)	0.0063 (7)
C12	0.0554 (10)	0.0741 (13)	0.0395 (8)	−0.0054 (9)	0.0092 (7)	−0.0079 (8)
C13	0.0438 (8)	0.0642 (11)	0.0459 (8)	−0.0128 (7)	0.0159 (7)	−0.0069 (7)
C14	0.0955 (16)	0.1021 (18)	0.0428 (10)	0.0034 (14)	0.0267 (10)	0.0109 (10)
C15	0.0476 (7)	0.0280 (6)	0.0378 (7)	0.0018 (5)	0.0197 (6)	0.0031 (5)
C16	0.0465 (7)	0.0315 (7)	0.0371 (7)	0.0051 (5)	0.0184 (6)	0.0072 (5)
C17	0.0502 (8)	0.0330 (7)	0.0472 (8)	0.0023 (6)	0.0250 (6)	0.0096 (6)
C18	0.0688 (11)	0.0593 (10)	0.0480 (9)	−0.0016 (8)	0.0352 (8)	0.0078 (8)
C19	0.0767 (13)	0.0838 (14)	0.0357 (8)	−0.0047 (11)	0.0225 (8)	0.0020 (8)
C20	0.0539 (9)	0.0676 (11)	0.0404 (8)	−0.0054 (8)	0.0141 (7)	−0.0007 (7)
C21	0.0298 (5)	0.0386 (7)	0.0303 (6)	0.0009 (5)	0.0119 (4)	0.0042 (5)
C22	0.0362 (6)	0.0357 (7)	0.0399 (7)	0.0062 (5)	0.0162 (5)	0.0071 (5)
C23	0.0348 (6)	0.0393 (7)	0.0344 (6)	0.0013 (5)	0.0117 (5)	0.0098 (5)
C24	0.0361 (6)	0.0496 (8)	0.0336 (6)	0.0018 (6)	0.0168 (5)	0.0014 (6)
C25	0.0389 (7)	0.0396 (7)	0.0379 (7)	0.0061 (5)	0.0133 (5)	−0.0036 (5)
C26	0.0355 (6)	0.0326 (7)	0.0362 (6)	−0.0015 (5)	0.0097 (5)	0.0024 (5)
N1	0.0427 (6)	0.0377 (7)	0.0415 (6)	0.0027 (5)	0.0189 (5)	0.0026 (5)
N2	0.0398 (6)	0.0464 (8)	0.0474 (7)	0.0022 (5)	0.0244 (6)	0.0089 (6)
O1	0.0479 (6)	0.0841 (9)	0.0462 (6)	0.0099 (6)	0.0192 (5)	−0.0171 (6)
O2	0.0465 (6)	0.0594 (8)	0.0633 (8)	−0.0198 (5)	0.0110 (5)	0.0007 (6)
O3	0.0629 (7)	0.0467 (6)	0.0389 (5)	−0.0019 (5)	0.0112 (5)	0.0101 (5)
O4	0.0560 (6)	0.0547 (7)	0.0506 (6)	0.0180 (5)	0.0296 (5)	0.0042 (5)
O5	0.0436 (6)	0.0681 (8)	0.0385 (5)	−0.0068 (5)	0.0109 (4)	0.0042 (5)
O6	0.0699 (8)	0.0373 (6)	0.0604 (7)	−0.0009 (5)	0.0379 (6)	0.0036 (5)
O7	0.0474 (6)	0.0701 (8)	0.0574 (7)	0.0041 (5)	0.0281 (5)	0.0147 (6)
O8	0.0503 (6)	0.0459 (6)	0.0711 (8)	0.0014 (5)	0.0294 (6)	0.0210 (6)
S1	0.03290 (16)	0.03659 (18)	0.03343 (16)	−0.00323 (12)	0.01232 (12)	−0.00138 (12)
S2	0.03677 (17)	0.03538 (18)	0.03731 (17)	0.00095 (12)	0.01806 (13)	0.00041 (13)

Geometric parameters (Å, º) top

C1—C6	1.374 (2)	C16—H16	0.9300
C1—C2	1.387 (2)	C17—O7	1.3543 (19)
C1—S1	1.7576 (14)	C17—C18	1.380 (2)
C2—C3	1.384 (2)	C18—C19	1.374 (3)
C2—H2	0.9300	C18—H18	0.9300
C3—C4	1.376 (3)	C19—C20	1.381 (3)
C3—H3	0.9300	C19—H19	0.9300
C4—C5	1.377 (3)	C20—H20	0.9300
C4—C7	1.507 (2)	C21—C26	1.3760 (19)
C5—C6	1.382 (2)	C21—C22	1.3783 (19)
C5—H5	0.9300	C21—N2	1.4641 (16)
C6—H6	0.9300	C22—C23	1.3849 (18)
C7—H7A	0.9600	C22—H22	0.9300
C7—H7B	0.9600	C23—O8	1.3617 (17)
C7—H7C	0.9600	C23—C24	1.385 (2)
C8—C9	1.378 (2)	C24—C25	1.380 (2)
C8—C13	1.381 (2)	C24—H24	0.9300
C8—S2	1.7682 (14)	C25—C26	1.3830 (19)
C9—C10	1.384 (2)	C25—H25	0.9300
C9—H9	0.9300	C26—H26	0.9300
C10—C11	1.378 (2)	N1—H1C	0.885 (9)
C10—H10	0.9300	N1—H1A	0.895 (9)
C11—C12	1.377 (3)	N1—H1B	0.893 (10)
C11—C14	1.504 (2)	N2—H2A	0.895 (9)
C12—C13	1.383 (2)	N2—H2C	0.892 (9)
C12—H12	0.9300	N2—H2B	0.886 (9)
C13—H13	0.9300	O1—S1	1.4497 (11)
C14—H14A	0.9600	O2—S1	1.4370 (11)
C14—H14B	0.9600	O3—S1	1.4444 (12)
C14—H14C	0.9600	O4—S2	1.4435 (11)
C15—C16	1.369 (2)	O5—S2	1.4511 (11)
C15—C20	1.375 (2)	O6—S2	1.4558 (11)
C15—N1	1.4617 (18)	O7—H7	0.8200
C16—C17	1.3923 (19)	O8—H8	0.8200

C6—C1—C2	120.23 (14)	O7—C17—C16	116.90 (13)
C6—C1—S1	120.08 (11)	C18—C17—C16	119.50 (15)
C2—C1—S1	119.68 (11)	C19—C18—C17	119.91 (15)
C3—C2—C1	118.87 (15)	C19—C18—H18	120.0
C3—C2—H2	120.6	C17—C18—H18	120.0
C1—C2—H2	120.6	C18—C19—C20	121.41 (16)
C4—C3—C2	121.79 (16)	C18—C19—H19	119.3
C4—C3—H3	119.1	C20—C19—H19	119.3
C2—C3—H3	119.1	C15—C20—C19	117.71 (16)
C3—C4—C5	118.09 (15)	C15—C20—H20	121.1
C3—C4—C7	121.74 (17)	C19—C20—H20	121.1
C5—C4—C7	120.17 (17)	C26—C21—C22	122.64 (12)
C4—C5—C6	121.47 (15)	C26—C21—N2	119.15 (12)
C4—C5—H5	119.3	C22—C21—N2	118.18 (12)
C6—C5—H5	119.3	C21—C22—C23	118.24 (13)
C1—C6—C5	119.52 (14)	C21—C22—H22	120.9
C1—C6—H6	120.2	C23—C22—H22	120.9
C5—C6—H6	120.2	O8—C23—C22	116.68 (13)
C4—C7—H7A	109.5	O8—C23—C24	122.94 (12)
C4—C7—H7B	109.5	C22—C23—C24	120.38 (13)
H7A—C7—H7B	109.5	C25—C24—C23	119.83 (12)
C4—C7—H7C	109.5	C25—C24—H24	120.1
H7A—C7—H7C	109.5	C23—C24—H24	120.1
H7B—C7—H7C	109.5	C24—C25—C26	120.79 (13)
C9—C8—C13	119.39 (14)	C24—C25—H25	119.6
C9—C8—S2	120.82 (11)	C26—C25—H25	119.6
C13—C8—S2	119.77 (11)	C21—C26—C25	118.11 (13)
C8—C9—C10	119.68 (15)	C21—C26—H26	120.9
C8—C9—H9	120.2	C25—C26—H26	120.9
C10—C9—H9	120.2	C15—N1—H1C	112.1 (14)
C11—C10—C9	121.79 (16)	C15—N1—H1A	113.8 (13)
C11—C10—H10	119.1	H1C—N1—H1A	106.9 (19)
C9—C10—H10	119.1	C15—N1—H1B	110.6 (17)
C12—C11—C10	117.65 (15)	H1C—N1—H1B	105 (2)
C12—C11—C14	121.49 (18)	H1A—N1—H1B	108 (2)
C10—C11—C14	120.85 (18)	C21—N2—H2A	112.7 (13)
C11—C12—C13	121.62 (16)	C21—N2—H2C	112.2 (14)
C11—C12—H12	119.2	H2A—N2—H2C	104.0 (19)
C13—C12—H12	119.2	C21—N2—H2B	109.9 (14)
C8—C13—C12	119.86 (16)	H2A—N2—H2B	106.4 (19)
C8—C13—H13	120.1	H2C—N2—H2B	111 (2)
C12—C13—H13	120.1	C17—O7—H7	109.5
C11—C14—H14A	109.5	C23—O8—H8	109.5
C11—C14—H14B	109.5	O2—S1—O3	111.93 (8)
H14A—C14—H14B	109.5	O2—S1—O1	112.03 (8)
C11—C14—H14C	109.5	O3—S1—O1	112.64 (8)
H14A—C14—H14C	109.5	O2—S1—C1	108.04 (7)
H14B—C14—H14C	109.5	O3—S1—C1	106.42 (6)
C16—C15—C20	122.37 (14)	O1—S1—C1	105.28 (7)
C16—C15—N1	118.85 (12)	O4—S2—O5	113.19 (7)
C20—C15—N1	118.79 (14)	O4—S2—O6	112.69 (7)
C15—C16—C17	119.05 (13)	O5—S2—O6	110.65 (8)
C15—C16—H16	120.5	O4—S2—C8	107.33 (7)
C17—C16—H16	120.5	O5—S2—C8	106.67 (6)
O7—C17—C18	123.59 (14)	O6—S2—C8	105.79 (7)

C6—C1—C2—C3	−1.3 (3)	C17—C18—C19—C20	1.0 (3)
S1—C1—C2—C3	179.86 (14)	C16—C15—C20—C19	−1.0 (3)
C1—C2—C3—C4	0.6 (3)	N1—C15—C20—C19	179.00 (17)
C2—C3—C4—C5	0.4 (3)	C18—C19—C20—C15	−0.8 (3)
C2—C3—C4—C7	−178.76 (19)	C26—C21—C22—C23	−1.2 (2)
C3—C4—C5—C6	−0.7 (3)	N2—C21—C22—C23	176.98 (12)
C7—C4—C5—C6	178.48 (18)	C21—C22—C23—O8	179.78 (12)
C2—C1—C6—C5	1.0 (2)	C21—C22—C23—C24	0.7 (2)
S1—C1—C6—C5	179.85 (13)	O8—C23—C24—C25	−178.89 (13)
C4—C5—C6—C1	0.0 (3)	C22—C23—C24—C25	0.2 (2)
C13—C8—C9—C10	−0.4 (3)	C23—C24—C25—C26	−0.5 (2)
S2—C8—C9—C10	−178.85 (14)	C22—C21—C26—C25	0.9 (2)
C8—C9—C10—C11	0.5 (3)	N2—C21—C26—C25	−177.28 (12)
C9—C10—C11—C12	0.0 (3)	C24—C25—C26—C21	0.0 (2)
C9—C10—C11—C14	179.1 (2)	C6—C1—S1—O2	126.15 (13)
C10—C11—C12—C13	−0.6 (3)	C2—C1—S1—O2	−54.99 (14)
C14—C11—C12—C13	−179.7 (2)	C6—C1—S1—O3	5.78 (14)
C9—C8—C13—C12	−0.2 (3)	C2—C1—S1—O3	−175.36 (13)
S2—C8—C13—C12	178.26 (15)	C6—C1—S1—O1	−113.99 (13)
C11—C12—C13—C8	0.7 (3)	C2—C1—S1—O1	64.87 (14)
C20—C15—C16—C17	2.5 (2)	C9—C8—S2—O4	108.94 (14)
N1—C15—C16—C17	−177.51 (13)	C13—C8—S2—O4	−69.52 (15)
C15—C16—C17—O7	176.70 (13)	C9—C8—S2—O5	−12.66 (16)
C15—C16—C17—C18	−2.2 (2)	C13—C8—S2—O5	168.88 (13)
O7—C17—C18—C19	−178.30 (17)	C9—C8—S2—O6	−130.52 (14)
C16—C17—C18—C19	0.5 (3)	C13—C8—S2—O6	51.02 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7···O6ⁱ	0.82	1.95	2.7657 (16)	173 (2)
N2—H2C···O4ⁱ	0.89 (1)	2.06 (1)	2.9441 (18)	170 (2)
N2—H2B···O3ⁱ	0.89 (1)	2.31 (2)	2.9020 (17)	124 (2)
N2—H2A···O3ⁱⁱ	0.90 (1)	1.89 (1)	2.7784 (18)	170 (2)
N2—H2B···O5ⁱⁱ	0.89 (1)	2.20 (2)	2.9395 (19)	141 (2)
N1—H1B···O5ⁱⁱⁱ	0.89 (1)	2.15 (2)	2.9406 (19)	147 (2)
N1—H1B···O6ⁱⁱⁱ	0.89 (1)	2.32 (2)	3.1087 (19)	147 (2)
N1—H1C···O2^iv	0.89 (1)	1.86 (1)	2.7410 (18)	177 (2)
O8—H8···O1	0.82	1.94	2.7216 (17)	160
N1—H1A···O1	0.90 (1)	1.95 (1)	2.8007 (17)	158 (2)

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

Experimental details

Crystal data
Chemical formula	C₆H₈NO⁺·C₇H₇O₃S⁻
M_r	281.32
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.5775 (3), 10.8224 (3), 14.1445 (4)
α, β, γ (°)	96.787 (2), 109.701 (1), 91.324 (2)
V (Å³)	1367.50 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.910, 0.953
No. of measured, independent and observed [I > 2σ(I)] reflections	32207, 8651, 6679
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.724

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.122, 1.03
No. of reflections	8651
No. of parameters	372
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.33

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7···O6ⁱ	0.82	1.95	2.7657 (16)	173 (2)
N2—H2C···O4ⁱ	0.892 (9)	2.062 (10)	2.9441 (18)	170 (2)
N2—H2B···O3ⁱ	0.886 (9)	2.311 (19)	2.9020 (17)	124 (2)
N2—H2A···O3ⁱⁱ	0.895 (9)	1.892 (10)	2.7784 (18)	170 (2)
N2—H2B···O5ⁱⁱ	0.886 (9)	2.201 (16)	2.9395 (19)	141 (2)
N1—H1B···O5ⁱⁱⁱ	0.893 (10)	2.149 (16)	2.9406 (19)	147 (2)
N1—H1B···O6ⁱⁱⁱ	0.893 (10)	2.319 (16)	3.1087 (19)	147 (2)
N1—H1C···O2^iv	0.885 (9)	1.857 (10)	2.7410 (18)	177 (2)
O8—H8···O1	0.82	1.94	2.7216 (17)	160
N1—H1A···O1	0.895 (9)	1.951 (12)	2.8007 (17)	158 (2)

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

Acknowledgements

The authors thank thank Dr Babu Varghese, Senior Scientific Officer, SAIF, IIT Madras, Chennai, India, for the data collection.

References

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Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
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