N-(2,3-Dichloro­phen­yl)methane­sulfonamide

In the structure of the title compound, C₇H₇Cl₂NO₂S, the conformation of the N—H bond is syn to both ortho- and meta-chloro substituents, in contrast to it lying between syn and anti to the methyl substituents at the ortho- and meta-positions in N-(2,3-dimethyl­phenyl)­methane­sulfonamide and the chloro substituents in N-(2-chloro­phen­yl)methane­sulfonamide and N-(3-chloro­phen­yl)methane­sulfonamide. The bond parameters are similar to those of other methyl­sulfonanilides, except for some differences in the bond and torsion angles. The amide H atom is available to a receptor mol­ecule during its biological activity, as it lies on one side of the plane of the benzene ring, while the methane­sulfonyl group is on the opposite side of the plane, similar to what is observed in other methyl­sulfonanilides. The mol­ecules in the title compound are packed into chains through N—H...O hydrogen bonding.

Key indicators

• Single-crystal X-ray study
• T = 303 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.054
• wR factor = 0.152
• Data-to-parameter ratio = 15.9

checkCIF/PLATON results

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S1. Comment

The structural studies of alkyl sulphonanilides are of interest as their biological activity is thought to be due to the hydrogen of the phenyl N—H portion of the sulphonanilide molecules as it can align itself, in relation to a receptor site. In the present work, the structure of N-(2,3-dichlorophenyl)-methanesulfonamide (23DCPMSA) has been determined to explore the substituent effects on the solid state structures of sulfonanilides (Gowda et al., 2007a-k). The structure of 23DCPMSA (Fig. 1) resembles those of N-(phenyl)-methanesulfonamide (PMSA) (Klug, 1968) and other methylsulfonanilides (Gowda et al., 2007a-k). The conformation of the N—H bond in 23DCPMSA is syn to both ortho and meta chloro substituents, in contrast to it lying between syn and anti conformations to the methyl substituents at ortho and meta positions, in N-(2,3-dimethylphenyl)-methanesulfonamide (23DMPMSA)(Gowda et al., 2007h) and chloro substituents in N-(2-chlorophenyl)- methanesulfonamide (2CPMSA)(Gowda et al., 2007k) and N-(3-chlorophenyl)-methanesulfonamide (3CPMSA)(Gowda et al., 2007e). Chloro substitutions at both ortho and meta positions in PMSA do not change its space group, in contrast to change over from monoclinic P2₁/c to orthorhombic P2₁2₁2₁ space group on methyl substitutions at both ortho and meta positions in PMSA to form 23DMPMSA (Gowda et al., 2007h). The bond parameters in 23DCPMSA are similar to those in PMSA, 23DMPMSA and other methylsulfonanilides, except for some difference in the bond and torsional angles. The amide hydrogen is available to a receptor molecule during its biological activity as it sits alone on one side of the plane of the phenyl group, while the whole methanesulfonyl group is on the opposite side of the plane, similar to that in other methylsulfonanilides. The molecules in 23DCPMSA are packed into chains in the direction of b axis (Fig. 2) through N—H···O hydrogen bonds (Fig. 3 and Table 1).

Related literature

For related literature, see: Gowda et al. (2007a,b,c,d,e,f,g,h,i,j,k); Jayalakshmi & Gowda (2004); Klug (1968); Spek (2003).

S2. Experimental

The title compound was prepared according to the literature method (Jayalakshmi & Gowda, 2004). The purity of the compound was checked by determining its melting point. It was characterized by recording its infrared and NMR spectra (Jayalakshmi & Gowda, 2004). Single crystals of the title compound were obtained from a slow evaporation of its ethanolic solution and used for X-ray diffraction studied at room temperature.

S3. Refinement

The H atom of the NH group was located in a diffrerence map and its position refined. The carbon-bound H atoms were positioned with idealized geometry and refined using a riding model with C—H = 0.93 Å (CH aromatic) or 0.96 Å (CH₃). Isotropic displacement parameters for all H atoms were set equal to 1.2U_eq (parent atom).

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. Molecular structure of the title compound showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. The crystal packing of the title compound, viewed down the b axis.
	Fig. 3. Hydrogen bonding in the title compound. Hydrogen bonds are shown as dashed lines.

N-(2,3-dichlorophenyl)methanesulfonamide

Crystal data

C7H7Cl2NO2S	F(000) = 488
Mr = 240.10	Dx = 1.650 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2484 reflections
a = 11.1299 (9) Å	θ = 2.8–26.5°
b = 5.1365 (6) Å	µ = 0.85 mm^−1
c = 16.908 (1) Å	T = 303 K
β = 90.038 (6)°	Long prism, colourless
V = 966.61 (15) Å^3	0.50 × 0.15 × 0.15 mm
Z = 4

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	1694 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.058
Graphite monochromator	θmax = 26.4°, θmin = 4.2°
Rotation method data acquisition using ω scans	h = −13→13
5750 measured reflections	k = −3→6
1939 independent reflections	l = −21→21

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.152	w = 1/[σ^2(Fo^2) + (0.1248P)^2 + 0.7632P] where P = (Fo^2 + 2Fc^2)/3
S = 0.87	(Δ/σ)max = 0.011
1939 reflections	Δρmax = 0.57 e Å^−3
122 parameters	Δρmin = −0.71 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.016 (4)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.1880 (4)	0.2088 (7)	−0.08851 (19)	0.0657 (10)
H1A	0.1995	0.1405	−0.1408	0.099*
H1B	0.2505	0.3317	−0.0768	0.099*
H1C	0.1114	0.2940	−0.0855	0.099*
C6	0.2632 (2)	0.2694 (5)	0.10012 (14)	0.0341 (5)
C7	0.3847 (3)	0.2686 (6)	0.08165 (17)	0.0439 (6)
H7	0.4140	0.1514	0.0444	0.053*
C8	0.4626 (3)	0.4409 (6)	0.1182 (2)	0.0520 (8)
H8	0.5438	0.4368	0.1054	0.062*
C9	0.4221 (3)	0.6189 (6)	0.17337 (18)	0.0485 (7)
H9	0.4750	0.7356	0.1970	0.058*
C10	0.3017 (3)	0.6200 (5)	0.19266 (15)	0.0382 (6)
C11	0.2221 (2)	0.4472 (5)	0.15705 (14)	0.0324 (5)
Cl12	0.07252 (6)	0.44392 (16)	0.18443 (4)	0.0490 (3)
Cl13	0.24995 (7)	0.84109 (15)	0.26233 (4)	0.0517 (3)
N5	0.1792 (2)	0.0930 (5)	0.06667 (14)	0.0425 (6)
H5N	0.107 (3)	0.137 (6)	0.077 (2)	0.051*
O3	0.0884 (2)	−0.2047 (4)	−0.02830 (14)	0.0581 (6)
O4	0.3061 (2)	−0.1694 (4)	−0.02436 (14)	0.0543 (6)
S2	0.19291 (6)	−0.04550 (12)	−0.02004 (4)	0.0371 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.106 (3)	0.0489 (17)	0.0418 (16)	0.0056 (18)	−0.0132 (18)	0.0018 (14)
C6	0.0320 (12)	0.0386 (12)	0.0318 (11)	0.0000 (10)	−0.0014 (9)	−0.0023 (10)
C7	0.0360 (14)	0.0521 (16)	0.0437 (14)	0.0054 (11)	0.0032 (11)	−0.0111 (12)
C8	0.0297 (14)	0.067 (2)	0.0591 (19)	0.0001 (12)	0.0020 (13)	−0.0091 (15)
C9	0.0394 (15)	0.0577 (17)	0.0485 (17)	−0.0056 (13)	−0.0093 (12)	−0.0050 (13)
C10	0.0453 (14)	0.0405 (13)	0.0288 (12)	0.0036 (11)	−0.0034 (10)	−0.0032 (10)
C11	0.0302 (12)	0.0393 (13)	0.0276 (11)	0.0039 (9)	−0.0001 (9)	0.0024 (9)
Cl12	0.0334 (4)	0.0687 (5)	0.0449 (5)	0.0027 (3)	0.0076 (3)	−0.0140 (3)
Cl13	0.0633 (5)	0.0521 (5)	0.0395 (4)	0.0029 (3)	−0.0015 (3)	−0.0138 (3)
N5	0.0334 (12)	0.0530 (13)	0.0412 (12)	−0.0036 (10)	0.0063 (10)	−0.0162 (10)
O3	0.0481 (12)	0.0551 (12)	0.0711 (15)	−0.0108 (10)	0.0010 (10)	−0.0263 (11)
O4	0.0479 (12)	0.0562 (12)	0.0588 (13)	0.0178 (10)	−0.0010 (10)	−0.0168 (10)
S2	0.0386 (4)	0.0353 (4)	0.0373 (4)	0.0039 (2)	−0.0014 (3)	−0.0079 (2)

Geometric parameters (Å, º)

C1—S2	1.746 (3)	C8—H8	0.9300
C1—H1A	0.9600	C9—C10	1.380 (4)
C1—H1B	0.9600	C9—H9	0.9300
C1—H1C	0.9600	C10—C11	1.390 (4)
C6—C7	1.388 (4)	C10—Cl13	1.735 (3)
C6—C11	1.404 (3)	C11—Cl12	1.729 (3)
C6—N5	1.420 (3)	N5—S2	1.637 (2)
C7—C8	1.384 (4)	N5—H5N	0.86 (4)
C7—H7	0.9300	O3—S2	1.428 (2)
C8—C9	1.382 (4)	O4—S2	1.413 (2)
S2—C1—H1A	109.5	C10—C9—H9	120.7
S2—C1—H1B	109.5	C11—C10—C9	120.9 (2)
H1A—C1—H1B	109.5	C11—C10—Cl13	120.0 (2)
S2—C1—H1C	109.5	C9—C10—Cl13	119.1 (2)
H1A—C1—H1C	109.5	C10—C11—C6	120.3 (2)
H1B—C1—H1C	109.5	C10—C11—Cl12	120.22 (19)
C7—C6—C11	118.3 (2)	C6—C11—Cl12	119.45 (19)
C7—C6—N5	123.4 (2)	C6—N5—S2	124.90 (19)
C11—C6—N5	118.3 (2)	C6—N5—H5N	112 (2)
C6—C7—C8	120.5 (3)	S2—N5—H5N	113 (2)
C6—C7—H7	119.8	O4—S2—O3	117.55 (14)
C8—C7—H7	119.8	O4—S2—N5	109.03 (13)
C9—C8—C7	121.3 (3)	O3—S2—N5	105.07 (12)
C9—C8—H8	119.3	O4—S2—C1	109.26 (18)
C7—C8—H8	119.3	O3—S2—C1	109.79 (18)
C8—C9—C10	118.6 (3)	N5—S2—C1	105.41 (15)
C8—C9—H9	120.7
C11—C6—C7—C8	−0.6 (4)	C7—C6—C11—C10	1.0 (4)
N5—C6—C7—C8	−178.0 (3)	N5—C6—C11—C10	178.6 (2)
C6—C7—C8—C9	−0.4 (5)	C7—C6—C11—Cl12	−177.3 (2)
C7—C8—C9—C10	1.0 (5)	N5—C6—C11—Cl12	0.3 (3)
C8—C9—C10—C11	−0.5 (4)	C7—C6—N5—S2	−27.1 (4)
C8—C9—C10—Cl13	179.6 (2)	C11—C6—N5—S2	155.4 (2)
C9—C10—C11—C6	−0.5 (4)	C6—N5—S2—O4	53.1 (3)
Cl13—C10—C11—C6	179.42 (19)	C6—N5—S2—O3	179.9 (2)
C9—C10—C11—Cl12	177.8 (2)	C6—N5—S2—C1	−64.1 (3)
Cl13—C10—C11—Cl12	−2.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5N···O3^i	0.86 (4)	2.35 (4)	3.101 (3)	147 (3)
N5—H5N···Cl12	0.86 (4)	2.43 (3)	2.937 (2)	118 (3)

Symmetry code: (i) −x, −y, −z.