3-(4-Chloro­benzene­sulfonamido)-5-methyl­cyclo­hex-2-en-1-one

Jackson, P.L.; North, H.; Alexander, M.S.; Assey, G.E.; Scott, K.R.; Butcher, R.J.

doi:10.1107/S1600536811030662

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 9| September 2011| Pages o2272-o2273

doi:10.1107/S1600536811030662

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3-(4-Chlorobenzenesulfonamido)-5-methylcyclohex-2-en-1-one

Patrice L. Jackson,^a Henry North,^b Mariano S. Alexander,^b Gervas E. Assey,^c Kenneth R. Scott ^b and Ray J. Butcher ^c ^*

^aCollege of Pharmacy, University of Maryland Eastern Shore, Princess Anne, MD 21853, USA, ^bDepartment of Pharmaceutical Sciences, Howard University, 2300 4th Street NW, Washington, DC 20059, USA, and ^cDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
^*Correspondence e-mail: rbutcher99@yahoo.com

(Received 25 July 2011; accepted 29 July 2011; online 6 August 2011)

For the title compound, C₁₃H₁₄ClNO₃S, geometrical parameters, determined using X-ray diffraction techniques, are compared with those calculated by density functional theory (DFT), using hybrid exchange-correlation functional, B3LYP methods. The dihedral angle between the benzene ring and the conjugated part of the cyclohexene ring is 87.47 (5)°. The cyclohexene ring and its substituents are disordered over two conformations, with occupancies of 0.786 (3) and 0.214 (3). In the crystal, molecules are linked into chains in the c-axis direction by intermolecular N—H⋯O(C=O) hydrogen bonds. C—H⋯O interactions are also observed.

Related literature

For the crystal growth of the title compound, see: Assey (2010 ). For related enaminone structures and properties, see: Edafiogho et al. (2006 , 2007 ); Eddington et al. (2000 ); Jackson (2009 ); Michael et al. (1996 , 2001 ). For their anti-convulsant activity, see: Stables & Kupferburg (1997 ). For information related to GAUSSIAN software, see: Frisch et al. (2004 )

Experimental

Crystal data

C₁₃H₁₄ClNO₃S
M_r = 299.76
Monoclinic, P 2₁ /c
a = 10.2031 (2) Å
b = 10.3267 (3) Å
c = 14.1217 (3) Å
β = 108.989 (3)°
V = 1406.95 (6) Å³
Z = 4
Cu Kα radiation
μ = 3.83 mm⁻¹
T = 295 K
0.76 × 0.61 × 0.31 mm

Data collection

Oxford Diffraction Gemini R diffractometer
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ), based on expressions derived by Clark & Reid (1995 )] T_min = 0.119, T_max = 0.355
5137 measured reflections
2778 independent reflections
2547 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.083
wR(F²) = 0.250
S = 1.07
2778 reflections
205 parameters
18 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.26 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H1N⋯O3B′ⁱ	0.83 (2)	1.91 (2)	2.729 (10)	166 (2)
N—H1N⋯O3A′ⁱ	0.83 (2)	1.95 (2)	2.777 (3)	171 (2)
C5—H5A⋯O2ⁱⁱ	0.93	2.53	3.337 (3)	145
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811030662/hg5071sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811030662/hg5071Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811030662/hg5071Isup3.cml

checkCIF report

Comment top

Enaminone analogues are reported to possess antiflammatory (Eddington et al., 2000) antimalarial (Edafiogho et al., 2006), antibacterial (Michael et al., 1996, 2001), and anticonvulsant properties (Edafiogho et al., 2007). Over recent years studies have shown that enaminones and their derivatives have played a major role in anti-epileptic activity and a number of structurally diverse anticonvulsant active enaminone analogues have been synthesized in our laboratory. We have provided several enaminones and their derivatives that are highly active in anticonvulsant studies. Our recent research has produced a novel series of benzene sulfonamide enaminones that are active in anticonvulsant studies. One of the compounds, [3-[(4'-chloro)benzenesulfonylamino]-5-methylcyclohex-2-enone, has been studied by pharmacology, X-ray and DFT studies (Jackson, 2009; Assey, 2010). Pharmacology was performed at the National Institute of Neurological Disorders and Stroke (NINDS), National Institute of Health (NIH) (Stables & Kupferburg, 1997). Density-functional theory (DFT) and Hartree-Fock calculations and full-geometry optimizations were performed by means of the GAUSSIAN 03 W package (Frisch, et al., 2004). The selected bond lengths and angles obtained from HF and DFT/B3LYP are given in Table 2.

The structure of the title compound, 3-[(4'-chloro)benzenesulfonylamino]-5-methylcyclohex-2-enone, C₁₃H₁₄ClNO₃S, the shape of the molecule is important in determining binding to the receptor sites thus it is of interest to note that the dihedral angle between the phenyl ring and the conjugated part of the cyclohexene ring is 87.47 (5)°. The cyclohexene and its substituents are disordered over two conformations with occupancies of 0.786 (3) and 0.214 (3), respectively. The molecules are linked in chains in the c direction by intermolecular N—H···O(C=O) hydrogen bonds.

Related literature top

For the crystal growth of the title compound, see: Assey (2010). For related enaminone structures and properties, see: Edafiogho et al. (2006, 2007); Eddington et al. (2000); Jackson (2009); Michael et al. (1996, 2001). For their anti-convulsant activity, see: Stables & Kupferburg (1997). For information related to GAUSSIAN software, see: Frisch et al. (2004)

Experimental top

3-amino-5-methylcyclohex-2-enone (2.00 g, 16 mmol) and NaH (1.07 g, 44.8 mmol) in dry THF refluxed for 1 h. After cooling, a solution of p-chlorobenzenesulfonyl chloride (3.42 g, 16.2 mmol) in 30 ml of dry THF was added dropwise. The reaction mixture was allowed to reflux for 1 h. Upon workup, the mixture is cooled to room temperature and quenched with 150 ml of deionized H₂O and acidified with 12 ml of concentrated HCl. The aqueous solution was extracted with dichloromethane (2 x 100 ml) and the organic layer washed with 80 ml of water. The organic phase was dried over MgSO₄, filtered, and evaporated in vacuo at a temperature not exceeding 35°C (32% yield) (1.54 g), as a white powder from methylene chloride, mp 191–193°C. νmax (cm^-1) = νNH 3093 (w); νsp² 3031 (CH stretch; w); νC=O 1615 (m); νC=C 1609 and 1476 (aromatic); νS=O 1332(asymmetric; m) and 1141 (symmetric; m); νCN 1164 (s, sh); and νCl-aryl 1088 (m, sh). ¹H NMR: δ (DMSO-d₆) 0.915 (3H, d, CH3); 1.86–2.40 (5H, m, cyclohexene ring); 5.54 (1H, s, =CH); 7.76–7.86 (4H, dd, aromatic ring); 10.90 (1H, s, NH). Anal. Calculated for C¹³H¹⁴ClN²O⁵S: C, 52.09; H, 4.71; N, 4.67; S, 10.70. Found: C, 52.03; H, 4.59; N, 4.30; S, 10.67. Crystals of 3-[(4'-chloro)benzenesulfonylamino]-5-methylcyclohex-2-enone were obtained by slow evaporation from acetonitrile.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Diagram of 3-[(4'-chloro)benzenesulfonylamino]-5-methylcyclohex-2-enone showing the major component. Thermal ellipsoids drawn at the 30% probability level.
	Fig. 2. The molecular packing for 3-[(4'-chloro)benzenesulfonylamino]-5-methylcyclohex-2-enone viewed down the a axis. Intermolecular interactions are shown by dashed lines.

3-(4-Chlorobenzenesulfonamido)-5-methylcyclohex-2-en-1-one top

Crystal data top

C₁₃H₁₄ClNO₃S	F(000) = 624
M_r = 299.76	D_x = 1.415 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 4047 reflections
a = 10.2031 (2) Å	θ = 4.3–77.2°
b = 10.3267 (3) Å	µ = 3.83 mm⁻¹
c = 14.1217 (3) Å	T = 295 K
β = 108.989 (3)°	Large plate, colorless
V = 1406.95 (6) Å³	0.76 × 0.61 × 0.31 mm
Z = 4

Data collection top

Oxford Diffraction Gemini R diffractometer	2778 independent reflections
Radiation source: fine-focus sealed tube	2547 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
Detector resolution: 10.5081 pixels mm^-1	θ_max = 77.7°, θ_min = 4.6°
ϕ and ω scans	h = −12→11
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2009), based on expressions derived by Clark & Reid (1995)]	k = −11→12
T_min = 0.119, T_max = 0.355	l = −17→16
5137 measured reflections

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)] = 0.083	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.250	w = 1/[σ²(F_o²) + (0.183P)² + 0.6772P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
2778 reflections	Δρ_max = 1.26 e Å⁻³
205 parameters	Δρ_min = −0.65 e Å⁻³
18 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: 0.0074 (13)

Crystal data top

C₁₃H₁₄ClNO₃S	V = 1406.95 (6) Å³
M_r = 299.76	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 10.2031 (2) Å	µ = 3.83 mm⁻¹
b = 10.3267 (3) Å	T = 295 K
c = 14.1217 (3) Å	0.76 × 0.61 × 0.31 mm
β = 108.989 (3)°

Data collection top

Oxford Diffraction Gemini R diffractometer	2778 independent reflections
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2009), based on expressions derived by Clark & Reid (1995)]	2547 reflections with I > 2σ(I)
T_min = 0.119, T_max = 0.355	R_int = 0.047
5137 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.083	18 restraints
wR(F²) = 0.250	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 1.26 e Å⁻³
2778 reflections	Δρ_min = −0.65 e Å⁻³
205 parameters

Special details top

Experimental. CrysAlis RED (Oxford Diffraction , 2009) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > 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	Occ. (<1)
Cl	1.22572 (8)	0.52485 (10)	0.58620 (7)	0.0804 (3)
S	0.75611 (6)	0.92036 (5)	0.56637 (4)	0.04691 (16)
O1	0.7602 (2)	1.02174 (17)	0.49885 (16)	0.0609 (5)
O2	0.7649 (2)	0.9502 (2)	0.66719 (15)	0.0706 (6)
N	0.60950 (18)	0.84131 (18)	0.52132 (10)	0.0412 (4)
H1N	0.591 (2)	0.802 (2)	0.5668 (14)	0.048 (7)*
C1	0.8877 (2)	0.8073 (2)	0.56969 (17)	0.0441 (5)
C2	0.9599 (3)	0.8170 (3)	0.5024 (2)	0.0538 (6)
H2A	0.9385	0.8817	0.4540	0.065*
C3	1.0638 (3)	0.7296 (3)	0.5081 (2)	0.0605 (7)
H3A	1.1137	0.7351	0.4636	0.073*
C4	1.0935 (2)	0.6346 (3)	0.5792 (2)	0.0557 (7)
C5	1.0217 (3)	0.6238 (3)	0.6468 (2)	0.0596 (7)
H5A	1.0433	0.5585	0.6948	0.072*
C6	0.9181 (2)	0.7110 (3)	0.64169 (19)	0.0534 (6)
H6A	0.8686	0.7054	0.6864	0.064*
O3A'	0.5775 (3)	0.8028 (3)	0.17833 (16)	0.0530 (5)	0.786 (3)
C1A'	0.5533 (3)	0.7962 (2)	0.42417 (12)	0.0339 (4)	0.786 (3)
C2A'	0.6036 (3)	0.8212 (3)	0.34828 (19)	0.0364 (5)	0.786 (3)
H2AA	0.6808	0.8745	0.3599	0.044*	0.786 (3)
C3A'	0.5401 (3)	0.7671 (3)	0.2502 (2)	0.0393 (5)	0.786 (3)
C4A'	0.4276 (3)	0.6688 (3)	0.2359 (2)	0.0466 (7)	0.786 (3)
H4AA	0.4685	0.5832	0.2497	0.056*	0.786 (3)
H4AB	0.3677	0.6704	0.1666	0.056*	0.786 (3)
C5A'	0.3411 (3)	0.6942 (3)	0.3040 (2)	0.0437 (7)	0.786 (3)
H5AA	0.2954	0.7784	0.2855	0.052*	0.786 (3)
C6A'	0.4363 (3)	0.7032 (3)	0.4122 (2)	0.0421 (6)	0.786 (3)
H6AA	0.3828	0.7308	0.4542	0.051*	0.786 (3)
H6AB	0.4738	0.6181	0.4347	0.051*	0.786 (3)
C7A'	0.2296 (4)	0.5931 (4)	0.2902 (3)	0.0558 (9)	0.786 (3)
H7AA	0.1709	0.5922	0.2215	0.084*	0.786 (3)
H7AB	0.1753	0.6132	0.3324	0.084*	0.786 (3)
H7AC	0.2718	0.5096	0.3079	0.084*	0.786 (3)
O3B'	0.5921 (10)	0.7747 (12)	0.1904 (6)	0.0530 (5)	0.214 (3)
C1B'	0.5549 (9)	0.7864 (5)	0.4272 (2)	0.0339 (4)	0.214 (3)
C2B'	0.5841 (11)	0.8367 (12)	0.3478 (6)	0.0364 (5)	0.214 (3)
H2BA	0.6405	0.9093	0.3552	0.044*	0.214 (3)
C3B'	0.5260 (10)	0.7750 (12)	0.2512 (7)	0.0393 (5)	0.214 (3)
C4B'	0.3941 (10)	0.7012 (12)	0.2334 (7)	0.0466 (7)	0.214 (3)
H4BA	0.3842	0.6399	0.1795	0.056*	0.214 (3)
H4BB	0.3169	0.7612	0.2119	0.056*	0.214 (3)
C5B'	0.3867 (10)	0.6284 (10)	0.3246 (6)	0.0437 (7)	0.214 (3)
H5BA	0.4570	0.5600	0.3395	0.052*	0.214 (3)
C6B'	0.4207 (11)	0.7179 (13)	0.4147 (8)	0.0421 (6)	0.214 (3)
H6BA	0.3470	0.7808	0.4053	0.051*	0.214 (3)
H6BB	0.4282	0.6680	0.4744	0.051*	0.214 (3)
C7B'	0.2415 (16)	0.5623 (17)	0.3043 (14)	0.0558 (9)	0.214 (3)
H7BA	0.1711	0.6277	0.2920	0.084*	0.214 (3)
H7BB	0.2423	0.5120	0.3617	0.084*	0.214 (3)
H7BC	0.2225	0.5068	0.2469	0.084*	0.214 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0536 (4)	0.0905 (5)	0.0885 (6)	0.0121 (3)	0.0112 (4)	−0.0009 (4)
S	0.0462 (3)	0.0526 (3)	0.0352 (3)	−0.0116 (2)	0.0040 (2)	−0.00969 (19)
O1	0.0640 (10)	0.0465 (9)	0.0670 (11)	−0.0130 (8)	0.0142 (8)	0.0008 (8)
O2	0.0764 (12)	0.0880 (12)	0.0396 (9)	−0.0123 (11)	0.0081 (8)	−0.0268 (9)
N	0.0399 (8)	0.0581 (10)	0.0253 (7)	−0.0102 (7)	0.0103 (6)	−0.0050 (7)
C1	0.0329 (9)	0.0557 (11)	0.0368 (10)	−0.0111 (8)	0.0019 (8)	0.0004 (8)
C2	0.0531 (11)	0.0599 (13)	0.0486 (12)	−0.0120 (10)	0.0170 (10)	0.0062 (10)
C3	0.0536 (12)	0.0721 (16)	0.0600 (14)	−0.0106 (12)	0.0243 (10)	0.0014 (12)
C4	0.0339 (10)	0.0649 (14)	0.0592 (14)	−0.0056 (10)	0.0026 (9)	−0.0020 (12)
C5	0.0433 (11)	0.0763 (16)	0.0511 (13)	−0.0075 (11)	0.0044 (10)	0.0162 (12)
C6	0.0404 (10)	0.0725 (15)	0.0426 (11)	−0.0100 (10)	0.0070 (9)	0.0114 (10)
O3A'	0.0683 (9)	0.0686 (13)	0.0278 (8)	−0.0041 (9)	0.0235 (7)	0.0011 (7)
C1A'	0.0317 (8)	0.0430 (9)	0.0264 (8)	−0.0005 (7)	0.0083 (6)	0.0000 (7)
C2A'	0.0329 (9)	0.0498 (11)	0.0272 (9)	−0.0061 (9)	0.0108 (7)	−0.0035 (8)
C3A'	0.0405 (10)	0.0513 (11)	0.0274 (9)	0.0008 (9)	0.0129 (8)	−0.0024 (8)
C4A'	0.0476 (14)	0.0558 (16)	0.0347 (11)	−0.0052 (12)	0.0112 (10)	−0.0115 (10)
C5A'	0.0333 (11)	0.0538 (15)	0.0403 (13)	−0.0072 (10)	0.0071 (9)	−0.0063 (11)
C6A'	0.0367 (10)	0.0599 (13)	0.0313 (9)	−0.0072 (9)	0.0132 (8)	0.0001 (9)
C7A'	0.0404 (11)	0.0595 (19)	0.0639 (17)	−0.0150 (12)	0.0122 (11)	−0.0074 (14)
O3B'	0.0683 (9)	0.0686 (13)	0.0278 (8)	−0.0041 (9)	0.0235 (7)	0.0011 (7)
C1B'	0.0317 (8)	0.0430 (9)	0.0264 (8)	−0.0005 (7)	0.0083 (6)	0.0000 (7)
C2B'	0.0329 (9)	0.0498 (11)	0.0272 (9)	−0.0061 (9)	0.0108 (7)	−0.0035 (8)
C3B'	0.0405 (10)	0.0513 (11)	0.0274 (9)	0.0008 (9)	0.0129 (8)	−0.0024 (8)
C4B'	0.0476 (14)	0.0558 (16)	0.0347 (11)	−0.0052 (12)	0.0112 (10)	−0.0115 (10)
C5B'	0.0333 (11)	0.0538 (15)	0.0403 (13)	−0.0072 (10)	0.0071 (9)	−0.0063 (11)
C6B'	0.0367 (10)	0.0599 (13)	0.0313 (9)	−0.0072 (9)	0.0132 (8)	0.0001 (9)
C7B'	0.0404 (11)	0.0595 (19)	0.0639 (17)	−0.0150 (12)	0.0122 (11)	−0.0074 (14)

Geometric parameters (Å, º) top

Cl—C4	1.740 (3)	C4A'—H4AB	0.9700
S—O1	1.426 (2)	C5A'—C7A'	1.509 (5)
S—O2	1.431 (2)	C5A'—C6A'	1.524 (4)
S—N	1.6400 (17)	C5A'—H5AA	0.9800
S—C1	1.768 (2)	C6A'—H6AA	0.9700
N—C1B'	1.384 (2)	C6A'—H6AB	0.9700
N—C1A'	1.3843 (18)	C7A'—H7AA	0.9600
N—H1N	0.833 (16)	C7A'—H7AB	0.9600
C1—C2	1.382 (4)	C7A'—H7AC	0.9600
C1—C6	1.383 (3)	O3B'—C3B'	1.252 (12)
C2—C3	1.375 (4)	C1B'—C2B'	1.355 (10)
C2—H2A	0.9300	C1B'—C6B'	1.499 (11)
C3—C4	1.365 (4)	C2B'—C3B'	1.446 (11)
C3—H3A	0.9300	C2B'—H2BA	0.9300
C4—C5	1.384 (4)	C3B'—C4B'	1.494 (12)
C5—C6	1.373 (4)	C4B'—C5B'	1.514 (12)
C5—H5A	0.9300	C4B'—H4BA	0.9700
C6—H6A	0.9300	C4B'—H4BB	0.9700
O3A'—C3A'	1.251 (4)	C5B'—C6B'	1.519 (12)
C1A'—C2A'	1.356 (4)	C5B'—C7B'	1.570 (18)
C1A'—C6A'	1.498 (4)	C5B'—H5BA	0.9800
C2A'—C3A'	1.437 (3)	C6B'—H6BA	0.9700
C2A'—H2AA	0.9300	C6B'—H6BB	0.9700
C3A'—C4A'	1.496 (4)	C7B'—H7BA	0.9600
C4A'—C5A'	1.525 (4)	C7B'—H7BB	0.9600
C4A'—H4AA	0.9700	C7B'—H7BC	0.9600

O1—S—O2	120.11 (14)	C7A'—C5A'—C4A'	111.5 (3)
O1—S—N	109.11 (10)	C6A'—C5A'—C4A'	109.4 (2)
O2—S—N	104.28 (12)	C7A'—C5A'—H5AA	107.8
O1—S—C1	108.39 (12)	C6A'—C5A'—H5AA	107.8
O2—S—C1	108.34 (13)	C4A'—C5A'—H5AA	107.8
N—S—C1	105.70 (10)	C1A'—C6A'—C5A'	112.1 (2)
C1B'—N—S	127.4 (4)	C1A'—C6A'—H6AA	109.2
C1A'—N—S	125.70 (16)	C5A'—C6A'—H6AA	109.2
C1B'—N—H1N	114.7 (17)	C1A'—C6A'—H6AB	109.2
C1A'—N—H1N	118.3 (16)	C5A'—C6A'—H6AB	109.2
S—N—H1N	110.6 (15)	H6AA—C6A'—H6AB	107.9
C2—C1—C6	121.0 (2)	C2B'—C1B'—N	120.6 (6)
C2—C1—S	120.28 (19)	C2B'—C1B'—C6B'	121.5 (6)
C6—C1—S	118.7 (2)	N—C1B'—C6B'	112.0 (6)
C3—C2—C1	119.1 (2)	C1B'—C2B'—C3B'	118.6 (9)
C3—C2—H2A	120.5	C1B'—C2B'—H2BA	120.7
C1—C2—H2A	120.5	C3B'—C2B'—H2BA	120.7
C4—C3—C2	119.8 (3)	O3B'—C3B'—C2B'	120.0 (9)
C4—C3—H3A	120.1	O3B'—C3B'—C4B'	122.7 (9)
C2—C3—H3A	120.1	C2B'—C3B'—C4B'	117.0 (9)
C3—C4—C5	121.7 (3)	C3B'—C4B'—C5B'	113.7 (8)
C3—C4—Cl	119.5 (2)	C3B'—C4B'—H4BA	108.8
C5—C4—Cl	118.9 (2)	C5B'—C4B'—H4BA	108.8
C6—C5—C4	118.8 (3)	C3B'—C4B'—H4BB	108.8
C6—C5—H5A	120.6	C5B'—C4B'—H4BB	108.8
C4—C5—H5A	120.6	H4BA—C4B'—H4BB	107.7
C5—C6—C1	119.7 (3)	C4B'—C5B'—C6B'	110.5 (9)
C5—C6—H6A	120.2	C4B'—C5B'—C7B'	111.5 (9)
C1—C6—H6A	120.2	C6B'—C5B'—C7B'	111.2 (10)
C2A'—C1A'—N	125.3 (2)	C4B'—C5B'—H5BA	107.8
C2A'—C1A'—C6A'	121.7 (2)	C6B'—C5B'—H5BA	107.8
N—C1A'—C6A'	112.7 (2)	C7B'—C5B'—H5BA	107.8
C1A'—C2A'—C3A'	121.3 (2)	C1B'—C6B'—C5B'	109.7 (8)
C1A'—C2A'—H2AA	119.4	C1B'—C6B'—H6BA	109.7
C3A'—C2A'—H2AA	119.4	C5B'—C6B'—H6BA	109.7
O3A'—C3A'—C2A'	120.4 (3)	C1B'—C6B'—H6BB	109.7
O3A'—C3A'—C4A'	120.9 (2)	C5B'—C6B'—H6BB	109.7
C2A'—C3A'—C4A'	118.7 (3)	H6BA—C6B'—H6BB	108.2
C3A'—C4A'—C5A'	111.9 (2)	C5B'—C7B'—H7BA	109.5
C3A'—C4A'—H4AA	109.2	C5B'—C7B'—H7BB	109.5
C5A'—C4A'—H4AA	109.2	H7BA—C7B'—H7BB	109.5
C3A'—C4A'—H4AB	109.2	C5B'—C7B'—H7BC	109.5
C5A'—C4A'—H4AB	109.2	H7BA—C7B'—H7BC	109.5
H4AA—C4A'—H4AB	107.9	H7BB—C7B'—H7BC	109.5
C7A'—C5A'—C6A'	112.3 (3)

O1—S—N—C1B'	53.1 (4)	C6A'—C1A'—C2A'—C3A'	4.8 (4)
O2—S—N—C1B'	−177.4 (4)	C1A'—C2A'—C3A'—O3A'	171.7 (3)
C1—S—N—C1B'	−63.2 (4)	C1A'—C2A'—C3A'—C4A'	−7.5 (4)
O1—S—N—C1A'	48.0 (2)	O3A'—C3A'—C4A'—C5A'	−146.2 (3)
O2—S—N—C1A'	177.5 (2)	C2A'—C3A'—C4A'—C5A'	33.0 (4)
C1—S—N—C1A'	−68.4 (2)	C3A'—C4A'—C5A'—C7A'	−178.9 (3)
O1—S—C1—C2	−9.0 (2)	C3A'—C4A'—C5A'—C6A'	−54.2 (3)
O2—S—C1—C2	−140.8 (2)	C2A'—C1A'—C6A'—C5A'	−27.7 (4)
N—S—C1—C2	107.90 (19)	N—C1A'—C6A'—C5A'	158.0 (2)
O1—S—C1—C6	169.99 (18)	C7A'—C5A'—C6A'—C1A'	175.5 (3)
O2—S—C1—C6	38.1 (2)	C4A'—C5A'—C6A'—C1A'	51.3 (3)
N—S—C1—C6	−73.15 (19)	C1A'—N—C1B'—C2B'	40 (5)
C6—C1—C2—C3	−0.4 (4)	S—N—C1B'—C2B'	−28.9 (10)
S—C1—C2—C3	178.6 (2)	C1A'—N—C1B'—C6B'	−113 (6)
C1—C2—C3—C4	0.4 (4)	S—N—C1B'—C6B'	177.9 (6)
C2—C3—C4—C5	−0.2 (4)	N—C1B'—C2B'—C3B'	179.2 (8)
C2—C3—C4—Cl	−179.7 (2)	C6B'—C1B'—C2B'—C3B'	−30.1 (15)
C3—C4—C5—C6	0.0 (4)	C1B'—C2B'—C3B'—O3B'	−147.4 (12)
Cl—C4—C5—C6	179.5 (2)	C1B'—C2B'—C3B'—C4B'	26.1 (16)
C4—C5—C6—C1	0.0 (4)	O3B'—C3B'—C4B'—C5B'	135.8 (12)
C2—C1—C6—C5	0.2 (4)	C2B'—C3B'—C4B'—C5B'	−37.6 (15)
S—C1—C6—C5	−178.8 (2)	C3B'—C4B'—C5B'—C6B'	51.1 (13)
C1B'—N—C1A'—C2A'	−121 (6)	C3B'—C4B'—C5B'—C7B'	175.3 (11)
S—N—C1A'—C2A'	−6.9 (4)	C2B'—C1B'—C6B'—C5B'	43.2 (13)
C1B'—N—C1A'—C6A'	53 (6)	N—C1B'—C6B'—C5B'	−163.8 (7)
S—N—C1A'—C6A'	167.16 (19)	C4B'—C5B'—C6B'—C1B'	−51.6 (11)
N—C1A'—C2A'—C3A'	178.3 (3)	C7B'—C5B'—C6B'—C1B'	−175.9 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H1N···O3B′ⁱ	0.83 (2)	1.91 (2)	2.729 (10)	166 (2)
N—H1N···O3A′ⁱ	0.83 (2)	1.95 (2)	2.777 (3)	171 (2)
C5—H5A···O2ⁱⁱ	0.93	2.53	3.337 (3)	145

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₄ClNO₃S
M_r	299.76
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	10.2031 (2), 10.3267 (3), 14.1217 (3)
β (°)	108.989 (3)
V (Å³)	1406.95 (6)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	3.83
Crystal size (mm)	0.76 × 0.61 × 0.31

Data collection
Diffractometer	Oxford Diffraction Gemini R diffractometer
Absorption correction	Analytical [CrysAlis RED (Oxford Diffraction, 2009), based on expressions derived by Clark & Reid (1995)]
T_min, T_max	0.119, 0.355
No. of measured, independent and observed [I > 2σ(I)] reflections	5137, 2778, 2547
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.634

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.083, 0.250, 1.07
No. of reflections	2778
No. of parameters	205
No. of restraints	18
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.26, −0.65

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H1N···O3B'ⁱ	0.833 (16)	1.913 (19)	2.729 (10)	166 (2)
N—H1N···O3A'ⁱ	0.833 (16)	1.951 (17)	2.777 (3)	171 (2)
C5—H5A···O2ⁱⁱ	0.93	2.53	3.337 (3)	145.3

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

Selected geometric parameters (Å, °) calculated with X-ray and DFT top

Parameters	X-ray	DFT/B3LYP(3-21G**)
Cl—C4	1.7404 (12)	1.7556
S—O1	1.4262 (9)	1.4610
S—O2	1.4300 (9)	1.4613
S—N	1.6397 (7)	1.6831
S—C1	1.7675 (10)	1.7663
N—C1A'	1.4049 (11)	1.4055
O3A'—C3A'	1.2376 (14)	1.2415
C5A'—C7A'	1.5102 (18)	1.5477
O1—S—O2	120.12 (5)	123.44
O1—S—N	109.07 (4)	108.92
O2—S—N	104.34 (5)	103.61
O1—S—C1	108.40 (5)	107.79
O2—S—C1	108.31 (5)	108.21
N—S—C1	105.69 (4)	103.02
C6—C1—C2	120.93 (9)	121.18
C6—C1—S	118.79 (8)	120.04
C3—C4—C5	121.65 (11)	121.58
C3—C4—Cl	119.40 (10)	119.14
C5—C4—Cl	118.95 (9)	119.28
C2A'—C1A'—C6A'	122.58 (8)	122.53
C7A'—C5A'—C4A'	110.73 (11)	111.36
C1—S—N—C1A'	-67.84 (8)	76.42
N—S—C1—C6	-73.16 (8)	88.67
N—S—C1—C2	107.82 (8)	-92.03
S—N—C1A'—C2A'	-8.93 (14)	13.37

Acknowledgements

The authors are indebted to Mr James P. Stables, Epilepsy Branch, Division of Convulsive, Developmental and Neuromuscular Disorders, National Institute of Neurological Disorders and Stroke, for helpful discussions and the initial data. The authors wish to acknowledge E. Jeannette Andrews, EdD, Deputy Director of the Center of Excellence at Howard University College of Pharmacy, Nursing and Allied Health Sciences, for her generous assistance in completing this project. RJB wishes to acknowledge the NSF–MRI program (grant CHE-0619278) for funds to purchase the diffractometer.

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