2-Methyl-4-oxopentan-2-aminium 2-sulfamoylbenzoate

Rafique, M.; Hussain, G.; Siddiqui, W.A.; Tahir, M.N.

doi:10.1107/S1600536809027007

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1883

doi:10.1107/S1600536809027007

Open

access

2-Methyl-4-oxopentan-2-aminium 2-sulfamoylbenzoate

Muhammad Rafique,^a Ghulam Hussain,^a Waseeq Ahmad Siddiqui ^a and M. Nawaz Tahir ^b ^*

^aDepartment of Chemistry, University of Sargodha, Sargodha, Pakistan, and ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 4 July 2009; accepted 9 July 2009; online 18 July 2009)

In the title salt, C₆H₁₄NO⁺·C₇H₆NO₄S⁻, the 2-sulfamoylbenzoate anion has two intramolecular hydrogen bonds, forming a five membered C—H⋯O and a seven-membered N—H⋯O twisted ring with ring motifs S(5) and S(7), respectively, while the 2-methyl-4-oxopentan-2-aminium cation also has a stabilizing intramolecular N—H⋯O hydrogen bond with a twisted S(6) ring motif. The anions form inversion-related dimers with R₂²(8) ring motifs through intermolecular N—H⋯O hydrogen bonding. The dimers and cations are further linked and stabilized through intermolecular N—H⋯O and C—H⋯O bonds, forming zigzag-shaped layers that extend along the crystallographic a axis.

Related literature

For related structures, see: Akram et al. (2008 ); Schmidt et al. (1997 ); Siddiqui et al. (2007 ). For the definition of hydrogen-bond patterns used for graph-set analysis, see: Bernstein et al. (1995 ). For applications of aldol condensation, see: Afonso & Crespo (2005 ).

Experimental

Crystal data

C₆H₁₄NO⁺·C₇H₆NO₄S⁻
M_r = 316.37
Orthorhombic, P b c a
a = 21.1917 (9) Å
b = 6.3897 (2) Å
c = 23.3751 (11) Å
V = 3165.2 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 296 K
0.28 × 0.10 × 0.08 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.975, T_max = 0.983
32870 measured reflections
4111 independent reflections
2961 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.110
S = 1.04
4111 reflections
200 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4ⁱ	0.80 (2)	2.21 (2)	3.008 (2)	172 (2)
N1—H1B⋯O2	0.85 (2)	2.10 (2)	2.848 (2)	145.4 (18)
N2—H2A⋯O1	0.89	1.94	2.8124 (18)	167
N2—H2B⋯O2ⁱⁱ	0.89	1.87	2.7622 (18)	176
N2—H2C⋯O5	0.89	2.18	2.824 (2)	129
N2—H2C⋯O1ⁱⁱⁱ	0.89	2.50	2.9878 (17)	115
C3—H3⋯O4	0.93	2.47	2.870 (2)	106
C6—H6⋯O2ⁱⁱⁱ	0.93	2.52	3.444 (2)	170
Symmetry codes: (i) -x, -y, -z+1; (ii) x, y+1, z; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809027007/si2187sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809027007/si2187Isup2.hkl

checkCIF report

Comment top

We reported the crystal structure of Tetraaquabis(2-sulfamoylbenzoato) manganese(II) (Akram et al., 2008). In continuation of synthesizing metal complexes of o-sulfamoylbenzoic acid (Siddiqui et al., 2007), the title compound (I), (Fig. 1) is prepared in a try of tin complex. The crystal structure of bis(2-Methyl-4-oxopent-2-yl)ammonium bis(phthalato) -beryllium(I) (Schmidt et al., 1997) contains the cation, 2-Methyl-4-oxopentan-2-aminium, of (I). The title compound is an example of aldol condensation which is routinely applied to prepare products used in the fields of biological sciences, industrial catalysis and green chemistry (Afonso & Crespo, 2005).

In the title compound, there are two moieties. In the anion, 2-sulfamoylbenzoate, two intramolecular H-bonds form five and seven membered twisted rings [S(5) and S(7)], while the cation, 2-methyl-4-oxopentan-2-aminium, has also an intramolecular H-bonding with a twisted ring S(6) (Bernstein et al., 1995) (Fig. 1). The cations and anions are connected with each other through H-bonding of the N—H···O type. The 2-sulfamoylbenzoate form dimers with R₂²(8) ring motifs through intermolecular H-bonding of type N1—H1A···O4ⁱ (Table 1) [symmetry code: i = -x, -y, -z + 1]. The dimers are linked to 2-methyl-4-oxopentan-2-aminium moietes through intermolecular H-bondings, (Table 1, Fig. 2), forming zigzag shaped layers that extend along the crystallographic a-axis.

Related literature top

For related crystal structures, see: Akram et al. (2008); Schmidt et al. (1997); Siddiqui et al. (2007). For the definition of hydrogen-bond patterns used for graph-set analysis, see: Bernstein et al. (1995). For applications of aldol condensation, see: Afonso & Crespo (2005).

Experimental top

A suspension of (1.0 g, 4.97 mmol) o-sulfamoylbenzoic acid (Siddiqui et al., 2007), tin(II) chloride dihydrate (0.561 g, 2.49 mmol) and sodium carbonate (0.3 g, 2.83 mmol) was subjected to reflux in a mixture of acetone, methanol, water (1:1:1) for 4 h. The volume of the reaction mixture was reduced to half on a rotary evaporator (11 torr) at room temperature and its pH was adjusted to 12, using aqueous ammonia solution and left over night at the same temperature. The white product was filtered, washed with cold distilled water and dried at room temperature. The product was recrystallized at 313 K from aqueous methanol to obtain colorless needle shaped crystals.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title compound with the atom numbering scheme. The thermal ellipsoids are drawn at the 30% probability level. H-atoms are shown by small circles of arbitrary radii. Intramolecular H-bonds are shown by dotted lines.
	Fig. 2. The partial packing (PLATON; Spek, 2009) which shows that molecules form dimers of 2-sulfamoylbenzoate and connected to 2-methyl-4-oxopentan-2-aminium through intermolecular H-bondings.

2-Methyl-4-oxopentan-2-aminium 2-sulfamoylbenzoate top

Crystal data top

C₆H₁₄NO⁺·C₇H₆NO₄S⁻	F(000) = 1344
M_r = 316.37	D_x = 1.328 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4111 reflections
a = 21.1917 (9) Å	θ = 2.6–28.8°
b = 6.3897 (2) Å	µ = 0.23 mm⁻¹
c = 23.3751 (11) Å	T = 296 K
V = 3165.2 (2) Å³	Needle, colorless
Z = 8	0.28 × 0.10 × 0.08 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	4111 independent reflections
Radiation source: fine-focus sealed tube	2961 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 7.40 pixels mm^-1	θ_max = 28.8°, θ_min = 2.6°
ω scans	h = −27→28
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −8→5
T_min = 0.975, T_max = 0.983	l = −31→30
32870 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0482P)² + 1.1665P] where P = (F_o² + 2F_c²)/3
4111 reflections	(Δ/σ)_max < 0.001
200 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₆H₁₄NO⁺·C₇H₆NO₄S⁻	V = 3165.2 (2) Å³
M_r = 316.37	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 21.1917 (9) Å	µ = 0.23 mm⁻¹
b = 6.3897 (2) Å	T = 296 K
c = 23.3751 (11) Å	0.28 × 0.10 × 0.08 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	4111 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2961 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.983	R_int = 0.032
32870 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.32 e Å⁻³
4111 reflections	Δρ_min = −0.29 e Å⁻³
200 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 (Å²) top

	x	y	z	U_iso*/U_eq
O5	0.23168 (8)	0.6184 (3)	0.16582 (7)	0.0740 (6)
N2	0.17797 (6)	0.6721 (2)	0.27542 (6)	0.0367 (4)
C8	0.18387 (11)	0.5283 (3)	0.15179 (8)	0.0534 (6)
C9	0.12913 (9)	0.5023 (3)	0.19207 (8)	0.0451 (5)
C10	0.12064 (7)	0.6719 (3)	0.23730 (7)	0.0368 (5)
C11	0.11386 (9)	0.8877 (3)	0.21123 (9)	0.0504 (6)
C12	0.06400 (8)	0.6216 (3)	0.27479 (9)	0.0523 (6)
C13	0.17685 (15)	0.4323 (5)	0.09405 (10)	0.0902 (10)
S1	0.03137 (2)	0.12048 (7)	0.41313 (2)	0.0366 (1)
O1	0.18858 (5)	0.25236 (19)	0.31033 (5)	0.0426 (3)
O2	0.15851 (5)	−0.02972 (17)	0.35914 (5)	0.0413 (4)
O3	0.02610 (5)	0.1446 (2)	0.35274 (5)	0.0482 (4)
O4	−0.02263 (5)	0.1683 (2)	0.44799 (6)	0.0519 (4)
N1	0.04974 (8)	−0.1189 (2)	0.42641 (8)	0.0464 (5)
C1	0.15011 (7)	0.2984 (2)	0.40450 (6)	0.0307 (4)
C2	0.09432 (7)	0.2818 (2)	0.43663 (6)	0.0317 (4)
C3	0.08632 (8)	0.3954 (3)	0.48632 (7)	0.0408 (5)
C4	0.13337 (9)	0.5284 (3)	0.50512 (8)	0.0465 (6)
C5	0.18748 (9)	0.5514 (3)	0.47338 (8)	0.0473 (6)
C6	0.19563 (8)	0.4383 (3)	0.42347 (7)	0.0405 (5)
C7	0.16605 (7)	0.1638 (2)	0.35297 (7)	0.0324 (4)
H2A	0.18196	0.54745	0.29202	0.0441*
H2B	0.17365	0.77014	0.30218	0.0441*
H2C	0.21218	0.69889	0.25458	0.0441*
H9A	0.13377	0.36904	0.21148	0.0540*
H9B	0.09076	0.49517	0.16952	0.0540*
H11A	0.15160	0.92237	0.19057	0.0605*
H11B	0.10717	0.98862	0.24105	0.0605*
H11C	0.07852	0.88900	0.18554	0.0605*
H12A	0.06955	0.48618	0.29186	0.0628*
H12B	0.02641	0.62158	0.25188	0.0628*
H12C	0.06029	0.72529	0.30432	0.0628*
H13A	0.21496	0.45282	0.07257	0.1083*
H13B	0.14222	0.49701	0.07436	0.1083*
H13C	0.16884	0.28511	0.09803	0.1083*
H1A	0.0454 (10)	−0.141 (3)	0.4599 (10)	0.0557*
H1B	0.0843 (11)	−0.148 (3)	0.4094 (9)	0.0557*
H3	0.04917	0.38246	0.50721	0.0490*
H4	0.12842	0.60205	0.53914	0.0558*
H5	0.21875	0.64337	0.48550	0.0568*
H6	0.23233	0.45630	0.40221	0.0486*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O5	0.0674 (10)	0.0762 (11)	0.0783 (11)	−0.0084 (8)	0.0259 (8)	−0.0127 (9)
N2	0.0321 (6)	0.0351 (7)	0.0430 (8)	−0.0012 (5)	−0.0019 (6)	−0.0067 (6)
C8	0.0666 (13)	0.0476 (10)	0.0461 (10)	0.0138 (10)	0.0033 (9)	−0.0028 (9)
C9	0.0520 (10)	0.0389 (8)	0.0443 (10)	−0.0064 (8)	−0.0092 (8)	−0.0041 (7)
C10	0.0326 (8)	0.0361 (8)	0.0417 (9)	−0.0027 (6)	−0.0045 (7)	−0.0009 (7)
C11	0.0517 (10)	0.0403 (9)	0.0593 (12)	0.0047 (8)	−0.0053 (9)	0.0025 (9)
C12	0.0348 (9)	0.0671 (12)	0.0550 (11)	−0.0065 (8)	−0.0003 (8)	0.0020 (10)
C13	0.110 (2)	0.110 (2)	0.0506 (13)	0.0401 (18)	−0.0048 (13)	−0.0204 (14)
S1	0.0269 (2)	0.0441 (2)	0.0389 (2)	−0.0018 (2)	0.0009 (2)	0.0023 (2)
O1	0.0429 (6)	0.0449 (6)	0.0401 (6)	0.0007 (5)	0.0096 (5)	−0.0001 (5)
O2	0.0435 (6)	0.0334 (6)	0.0469 (7)	0.0033 (5)	0.0055 (5)	−0.0053 (5)
O3	0.0396 (6)	0.0637 (8)	0.0412 (7)	−0.0052 (6)	−0.0085 (5)	0.0042 (6)
O4	0.0308 (6)	0.0665 (8)	0.0583 (8)	0.0012 (5)	0.0095 (5)	0.0013 (7)
N1	0.0480 (8)	0.0423 (8)	0.0489 (9)	−0.0057 (7)	0.0092 (7)	0.0034 (7)
C1	0.0286 (7)	0.0301 (7)	0.0335 (8)	0.0032 (5)	−0.0002 (6)	0.0007 (6)
C2	0.0293 (7)	0.0327 (7)	0.0332 (8)	0.0033 (6)	−0.0012 (6)	0.0027 (6)
C3	0.0397 (8)	0.0444 (9)	0.0383 (9)	0.0057 (7)	0.0050 (7)	−0.0009 (7)
C4	0.0569 (11)	0.0444 (9)	0.0382 (9)	0.0048 (8)	−0.0033 (8)	−0.0103 (8)
C5	0.0493 (10)	0.0416 (9)	0.0511 (10)	−0.0069 (8)	−0.0102 (8)	−0.0071 (8)
C6	0.0348 (8)	0.0415 (8)	0.0452 (10)	−0.0051 (7)	0.0017 (7)	−0.0012 (7)
C7	0.0230 (6)	0.0369 (8)	0.0373 (8)	0.0027 (6)	0.0001 (6)	−0.0021 (6)

Geometric parameters (Å, º) top

S1—O4	1.4377 (13)	C11—H11B	0.9600
S1—N1	1.6086 (14)	C11—H11C	0.9600
S1—C2	1.7731 (15)	C11—H11A	0.9600
S1—O3	1.4244 (13)	C12—H12A	0.9600
O5—C8	1.211 (3)	C12—H12C	0.9600
O1—C7	1.2416 (19)	C12—H12B	0.9600
O2—C7	1.2551 (17)	C13—H13A	0.9600
N2—C10	1.507 (2)	C13—H13B	0.9600
N2—H2B	0.8900	C13—H13C	0.9600
N2—H2C	0.8900	C1—C7	1.518 (2)
N2—H2A	0.8900	C1—C2	1.405 (2)
N1—H1B	0.85 (2)	C1—C6	1.388 (2)
N1—H1A	0.80 (2)	C2—C3	1.380 (2)
C8—C9	1.503 (3)	C3—C4	1.382 (3)
C8—C13	1.490 (3)	C4—C5	1.374 (3)
C9—C10	1.525 (3)	C5—C6	1.383 (3)
C10—C11	1.514 (3)	C3—H3	0.9300
C10—C12	1.521 (2)	C4—H4	0.9300
C9—H9A	0.9700	C5—H5	0.9300
C9—H9B	0.9700	C6—H6	0.9300

S1···O2	3.1262 (12)	H1A···O4^iv	2.21 (2)
O1···N2	2.8124 (18)	H1A···C4ⁱⁱ	3.01 (2)
O1···N2ⁱ	2.9878 (17)	H1B···O2	2.10 (2)
O2···N2ⁱⁱ	2.7622 (18)	H1B···C7	2.95 (2)
O2···S1	3.1262 (12)	H2A···O1	1.9400
O2···N1	2.848 (2)	H2A···H12A	2.4100
O2···O3	3.0227 (15)	H2A···C7	2.8600
O3···C7	2.9683 (18)	H2A···H9A	2.4300
O3···O2	3.0227 (15)	H2B···O2^vii	1.8700
O4···C4ⁱⁱⁱ	3.235 (2)	H2B···H11B	2.4400
O4···N1^iv	3.008 (2)	H2B···H12C	2.4200
O5···C11	3.213 (3)	H2B···C7^vii	2.7900
O5···C13^v	3.255 (3)	H2C···O1^v	2.5000
O5···C8^v	3.189 (3)	H2C···H11A	2.4300
O5···N2	2.824 (2)	H2C···O5	2.1800
O1···H9A	2.6900	H2C···C8	2.7100
O1···H2Cⁱ	2.5000	H3···H3ⁱⁱⁱ	2.5900
O1···H2A	1.9400	H3···O4	2.4700
O1···H6	2.6800	H4···O4ⁱⁱⁱ	2.7000
O1···H11Bⁱⁱ	2.9000	H5···C6^v	2.9900
O2···H2Bⁱⁱ	1.8700	H5···H13A^ix	2.5500
O2···H1B	2.10 (2)	H6···C7^v	2.7800
O2···H12Cⁱⁱ	2.9000	H6···O1	2.6800
O2···H6ⁱ	2.5200	H6···O2^v	2.5200
O3···H12B^vi	2.6900	H9A···O1	2.6900
O3···H11C^vi	2.8600	H9A···H2A	2.4300
O3···H9B^vi	2.7000	H9A···H11Bⁱⁱ	2.5900
O3···H12A	2.7600	H9A···H12A	2.4400
O4···H13B^vi	2.8100	H9B···H13B	2.4800
O4···H3	2.4700	H9B···O3^x	2.7000
O4···H4ⁱⁱⁱ	2.7000	H9B···H11C	2.5600
O4···H1A^iv	2.21 (2)	H9B···H12B	2.4900
O5···H11A	2.6400	H11A···O5	2.6400
O5···H2C	2.1800	H11A···H2C	2.4300
O5···H11Aⁱ	2.8300	H11A···O5^v	2.8300
O5···H13C^v	2.8400	H11A···C8	2.7600
N1···O2	2.848 (2)	H11B···H9A^vii	2.5900
N1···C4ⁱⁱ	3.407 (2)	H11B···H12C	2.4500
N1···O4^iv	3.008 (2)	H11B···O1^vii	2.9000
N2···O1	2.8124 (18)	H11B···H2B	2.4400
N2···O1^v	2.9878 (17)	H11C···H9B	2.5600
N2···O2^vii	2.7622 (18)	H11C···H12B	2.5600
N2···O5	2.824 (2)	H11C···O3^x	2.8600
C4···N1^vii	3.407 (2)	H12A···H9A	2.4400
C4···O4ⁱⁱⁱ	3.235 (2)	H12A···H2A	2.4100
C7···O3	2.9683 (18)	H12A···O3	2.7600
C8···O5ⁱ	3.189 (3)	H12B···H9B	2.4900
C11···O5	3.213 (3)	H12B···O3^x	2.6900
C13···O5ⁱ	3.255 (3)	H12B···H11C	2.5600
C4···H13C^viii	3.0500	H12C···O2^vii	2.9000
C4···H1A^vii	3.01 (2)	H12C···H2B	2.4200
C6···H5ⁱ	2.9900	H12C···H11B	2.4500
C7···H1B	2.95 (2)	H13A···H5^xi	2.5500
C7···H2Bⁱⁱ	2.7900	H13B···H9B	2.4800
C7···H2A	2.8600	H13B···O4^x	2.8100
C7···H6ⁱ	2.7800	H13C···O5ⁱ	2.8400
C8···H2C	2.7100	H13C···C4^xii	3.0500
C8···H11A	2.7600

O3—S1—C2	107.65 (7)	C10—C11—H11B	109.00
O3—S1—O4	118.44 (7)	H12A—C12—H12C	109.00
O3—S1—N1	108.25 (9)	H12A—C12—H12B	109.00
N1—S1—C2	108.12 (8)	C10—C12—H12C	109.00
O4—S1—N1	106.58 (9)	H12B—C12—H12C	109.00
O4—S1—C2	107.44 (7)	C10—C12—H12A	109.00
H2B—N2—H2C	109.00	C10—C12—H12B	109.00
H2A—N2—H2C	109.00	C8—C13—H13A	109.00
H2A—N2—H2B	109.00	H13A—C13—H13B	109.00
C10—N2—H2A	109.00	C8—C13—H13B	109.00
C10—N2—H2B	109.00	C8—C13—H13C	109.00
C10—N2—H2C	109.00	H13B—C13—H13C	109.00
H1A—N1—H1B	121 (2)	H13A—C13—H13C	109.00
S1—N1—H1B	109.0 (13)	C6—C1—C7	117.63 (13)
S1—N1—H1A	109.2 (14)	C2—C1—C7	124.66 (12)
C9—C8—C13	116.4 (2)	C2—C1—C6	117.57 (13)
O5—C8—C9	121.92 (18)	S1—C2—C1	120.76 (10)
O5—C8—C13	121.7 (2)	S1—C2—C3	118.30 (12)
C8—C9—C10	116.54 (16)	C1—C2—C3	120.91 (14)
N2—C10—C9	108.40 (13)	C2—C3—C4	120.16 (16)
C9—C10—C12	110.03 (15)	C3—C4—C5	119.76 (17)
C11—C10—C12	110.46 (15)	C4—C5—C6	120.26 (17)
N2—C10—C11	108.28 (14)	C1—C6—C5	121.28 (16)
N2—C10—C12	107.21 (13)	O1—C7—O2	126.17 (15)
C9—C10—C11	112.29 (15)	O1—C7—C1	117.67 (12)
C8—C9—H9B	108.00	O2—C7—C1	116.02 (13)
C8—C9—H9A	108.00	C2—C3—H3	120.00
H9A—C9—H9B	107.00	C4—C3—H3	120.00
C10—C9—H9A	108.00	C3—C4—H4	120.00
C10—C9—H9B	108.00	C5—C4—H4	120.00
C10—C11—H11C	109.00	C4—C5—H5	120.00
H11B—C11—H11C	109.00	C6—C5—H5	120.00
H11A—C11—H11B	109.00	C1—C6—H6	119.00
H11A—C11—H11C	109.00	C5—C6—H6	119.00
C10—C11—H11A	109.00

O4—S1—C2—C1	−168.62 (11)	C7—C1—C2—S1	−8.69 (19)
O4—S1—C2—C3	9.43 (15)	C7—C1—C2—C3	173.31 (14)
N1—S1—C2—C1	76.71 (14)	C2—C1—C6—C5	2.4 (2)
N1—S1—C2—C3	−105.24 (14)	C7—C1—C6—C5	−173.44 (16)
O3—S1—C2—C1	−40.02 (13)	C2—C1—C7—O1	135.91 (15)
O3—S1—C2—C3	138.03 (13)	C2—C1—C7—O2	−48.2 (2)
O5—C8—C9—C10	29.1 (3)	C6—C1—C7—O1	−48.5 (2)
C13—C8—C9—C10	−152.4 (2)	C6—C1—C7—O2	127.34 (15)
C8—C9—C10—C12	−179.37 (16)	S1—C2—C3—C4	−177.83 (14)
C8—C9—C10—N2	−62.4 (2)	C1—C2—C3—C4	0.2 (2)
C8—C9—C10—C11	57.2 (2)	C2—C3—C4—C5	1.7 (3)
C6—C1—C2—S1	175.74 (12)	C3—C4—C5—C6	−1.5 (3)
C6—C1—C2—C3	−2.3 (2)	C4—C5—C6—C1	−0.6 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4^iv	0.80 (2)	2.21 (2)	3.008 (2)	172 (2)
N1—H1B···O2	0.85 (2)	2.10 (2)	2.848 (2)	145.4 (18)
N2—H2A···O1	0.89	1.94	2.8124 (18)	167
N2—H2B···O2^vii	0.89	1.87	2.7622 (18)	176
N2—H2C···O5	0.89	2.18	2.824 (2)	129
N2—H2C···O1^v	0.89	2.50	2.9878 (17)	115
C3—H3···O4	0.93	2.47	2.870 (2)	106
C6—H6···O2^v	0.93	2.52	3.444 (2)	170

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

Experimental details

Crystal data
Chemical formula	C₆H₁₄NO⁺·C₇H₆NO₄S⁻
M_r	316.37
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	21.1917 (9), 6.3897 (2), 23.3751 (11)
V (Å³)	3165.2 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.28 × 0.10 × 0.08

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.975, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	32870, 4111, 2961
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.678

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.110, 1.04
No. of reflections	4111
No. of parameters	200
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.29

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱ	0.80 (2)	2.21 (2)	3.008 (2)	172 (2)
N1—H1B···O2	0.85 (2)	2.10 (2)	2.848 (2)	145.4 (18)
N2—H2A···O1	0.89	1.94	2.8124 (18)	167
N2—H2B···O2ⁱⁱ	0.89	1.87	2.7622 (18)	176
N2—H2C···O5	0.89	2.18	2.824 (2)	129
N2—H2C···O1ⁱⁱⁱ	0.89	2.50	2.9878 (17)	115
C3—H3···O4	0.93	2.47	2.870 (2)	106
C6—H6···O2ⁱⁱⁱ	0.93	2.52	3.444 (2)	170

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

Acknowledgements

The authors acknowledge the Higher Education Commission, Islamabad, Pakistan, and Bana International, Karachi, Pakistan, for funding the purchase of the diffractometer at GCU, Lahore, and for technical support, respectively.

References

Afonso, C. A. M. & Crespo, J. P. (2005). Green Separation Processes: Fundamentals and Applications 1, p. 363. Basel: Wiley-VCH. Google Scholar
Akram, R., Siddiqui, W. A., Tahir, M. N., Siddiqui, H. L. & Iqbal, A. (2008). Acta Cryst. E64, m1293–m1294. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Schmidt, M., Bauer, A. & Schmidbaur, H. (1997). Inorg. Chem. 36, 2047–2050. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siddiqui, W. A., Ahmad, S., Siddiqui, H. L., Tariq, M. I. & Parvez, M. (2007). Acta Cryst. E63, o4117. Web of Science CSD CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar