N-(3-Chloro­phen­yl)methane­sulfonamide

The conformation of the N—H bond in the structure of the title compound (3CPMSA), C₇H₈ClNO₂S, is neither syn nor anti to the meta-chloro substituent, in contrast to the anti conformations observed for the stronger electron-withdrawing meta-nitro substituted (3NPMSA) and electron-donating meta-methyl substituted compounds (3MPMSA). The substitution of the Cl atom at the meta position of N-(phen­yl)-methane­sulfonamde (PMSA) changes its space group from P2₁/c to C2/c compared to the change over from monoclinic P2₁/c to ortho­rhom­bic Pccn on meta-substitution of the electron-donating methyl group in PMSA and from monoclinic P2₁/c to triclinic P, on meta-substitution of the stronger electron-withdrawing nitro group. The bond parameters in PMSA, 3CPMSA, 3MPMSA and 3NPMSA are similar except for some differences in the S—N—C—C torsion angles. As in other alkyl sulfonanilides, 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 benzene ring, while the whole methane­sulfonyl group is on the opposite side of the plane. The mol­ecules in the title compound are packed into chains in the b-axis direction via N—H...O hydrogen bonds [H...O = 2.06, N...O = 2.979 (3) Å and N—H...O 169°].

Key indicators

• Single-crystal X-ray study
• T = 299 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.064
• wR factor = 0.177
• Data-to-parameter ratio = 14.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.94
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.75 mm
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.939
            Tmax scaled      0.179 Tmin scaled      0.061

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The stereochemistry of the biologically significant alkyl sulfonanilides, particularly in the vicinity of the phenyl-N—H portion is of interest in explaining their biological activity. The latter is thought to be due to the hydrogen atom of the phenyl N—H portion of the sulfonanilides as it can align itself, in relation to a receptor site. Therefore the structural studies of sulfonanilides are of interest. In the present work, the structure of N-(3-chlorophenyl)-methanesulfonamde (3CPMSA) has been determined to explore the substituent effects on the structures of sulfonanilides (Gowda et al., 2007a, b). The conformation of the N—H bond in 3CPMSA is neither syn nor anti to the meta-chloro substituent (Fig. 1), in contrast to the anti conformations observed for the sulfonanilide with the stronger electron withdrawing meta-nitro substituent (3NPMSA)(Gowda et al., 2007a) and for the compound with the electron donating meta - methyl substituent (3MPMSA)(Gowda et al., 2007b). The substitution of Cl atom at the meta position of N-(phenyl)-methanesulfonamde (PMSA) changes its space group from P21/c (Klug, 1968) to C 2/c compared to the change over from monoclinic P21/c to orthorhombic Pccn on meta substitution of electron donating methyl group in PMSA and from monoclinic P21/c to triclinic P-1, on meta substitution of stronger electron withdrawing nitro group. The bond parameters in the 4 compounds, PMSA, 3CPMSA, 3MPMSA and 3NPMSA are similar except some difference in the torsional angles, S2N5C6C7, S2N5C6C11: 75.5 (2)°,-106.6 (2)° (PMSA); 61.7 (3)°, -120.0 (3)° (3CPMSA);68.1 (4)°, -114.3 (3)° (3MPMSA); 41.1 (3)°, -140.8 (2)° (3NPMSA), respectively. The data included for PMSA are the values determined under the present conditions as the literature values were determined by Klug, 1968. The N—H hydrogen 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 observed in PMSA, 3NPMSA and 3MPMSA. The amide hydrogen is thus available to a receptor molecule during biological activity. The molecules in the title compound are packed into chain structure in the direction of b axis through N—H···O hydrogen bond (Table 1 & Fig. 2).

Related literature

For related literature, see: Gowda et al. (2007a, 2007b); Jayalakshmi & Gowda (2004); Klug (1968).

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

All H atoms attached to C atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (CH aromatic) or 0.96 Å (CH₃) with U_iso(H) = 1.2 U_eq. The H atom of the NH group was located in a diffrerence map and its position refined.

Computing details

Data collection: CAD-4-PC (Enraf–Nonius, 1996); cell refinement: CAD-4-PC; data reduction: REDU4 (Stoe & Cie, 1987); 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 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Hydrogen bonding in the title compound. Hydrogen bonds are shown as dashed lines.

N-(3-Chlorophenyl)methanesulfonamide

Crystal data

C7H8ClNO2S	F(000) = 848
Mr = 205.65	Dx = 1.549 Mg m^−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 23.488 (7) Å	θ = 7.9–25.4°
b = 8.523 (2) Å	µ = 5.73 mm^−1
c = 9.216 (2) Å	T = 299 K
β = 107.05 (2)°	Long prism, colourless
V = 1763.8 (8) Å^3	0.75 × 0.47 × 0.30 mm
Z = 8

Data collection

Enraf–Nonius CAD-4 diffractometer	1486 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.097
Graphite monochromator	θmax = 67.0°, θmin = 3.9°
ω/2θ scans	h = −26→28
Absorption correction: ψ scan (North et al., 1968)	k = 0→10
Tmin = 0.065, Tmax = 0.191	l = −10→1
1675 measured reflections	3 standard reflections every 120 min
1563 independent reflections	intensity decay: 1.2%

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)] = 0.064	H-atom parameters constrained
wR(F^2) = 0.177	w = 1/[σ^2(Fo^2) + (0.1311P)^2 + 1.4214P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.006
1563 reflections	Δρmax = 0.40 e Å^−3
110 parameters	Δρmin = −0.87 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0224 (18)

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
Cl12	0.01500 (4)	0.28125 (12)	0.56573 (12)	0.0759 (5)
S2	0.18925 (3)	0.58669 (7)	0.33977 (7)	0.0419 (4)
O3	0.16237 (10)	0.6527 (2)	0.4463 (2)	0.0517 (6)
O4	0.20627 (12)	0.6889 (3)	0.2374 (3)	0.0647 (7)
N5	0.14299 (11)	0.4624 (3)	0.2333 (2)	0.0480 (7)
H5N	0.1531	0.4357	0.1457	0.058*
C1	0.25175 (15)	0.4810 (4)	0.4443 (4)	0.0577 (8)
H1A	0.2799	0.5516	0.5088	0.069*
H1B	0.2698	0.4298	0.3761	0.069*
H1C	0.2398	0.4038	0.5055	0.069*
C6	0.11753 (12)	0.3372 (3)	0.2964 (3)	0.0420 (7)
C7	0.08190 (12)	0.3679 (4)	0.3865 (3)	0.0451 (7)
H7	0.0736	0.4707	0.4074	0.054*
C8	0.05832 (13)	0.2427 (4)	0.4464 (3)	0.0493 (7)
C9	0.06830 (15)	0.0902 (4)	0.4126 (4)	0.0576 (9)
H9	0.0522	0.0075	0.4534	0.069*
C10	0.10249 (15)	0.0622 (4)	0.3175 (4)	0.0618 (9)
H10	0.1085	−0.0405	0.2912	0.074*
C11	0.12804 (14)	0.1837 (4)	0.2603 (4)	0.0527 (7)
H11	0.1521	0.1633	0.1983	0.063*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl12	0.0730 (7)	0.0799 (7)	0.0904 (8)	−0.0152 (4)	0.0484 (5)	0.0030 (5)
S2	0.0540 (6)	0.0361 (5)	0.0403 (5)	−0.0044 (2)	0.0215 (3)	−0.0007 (2)
O3	0.0674 (13)	0.0441 (11)	0.0497 (11)	0.0002 (9)	0.0268 (9)	−0.0063 (8)
O4	0.0914 (18)	0.0536 (13)	0.0583 (14)	−0.0144 (12)	0.0362 (12)	0.0058 (10)
N5	0.0604 (15)	0.0514 (14)	0.0350 (11)	−0.0112 (11)	0.0181 (10)	−0.0024 (10)
C1	0.0527 (16)	0.0536 (18)	0.0658 (18)	0.0022 (14)	0.0157 (14)	−0.0049 (14)
C6	0.0422 (13)	0.0455 (15)	0.0347 (12)	−0.0080 (11)	0.0056 (10)	0.0002 (10)
C7	0.0443 (14)	0.0451 (14)	0.0450 (14)	−0.0048 (12)	0.0118 (11)	−0.0020 (11)
C8	0.0412 (15)	0.0550 (17)	0.0509 (15)	−0.0105 (12)	0.0126 (11)	0.0017 (12)
C9	0.0519 (17)	0.0496 (18)	0.067 (2)	−0.0133 (13)	0.0103 (14)	0.0069 (13)
C10	0.0582 (18)	0.0421 (15)	0.078 (2)	−0.0052 (13)	0.0083 (16)	−0.0063 (15)
C11	0.0554 (17)	0.0473 (15)	0.0548 (16)	−0.0018 (13)	0.0150 (13)	−0.0067 (13)

Geometric parameters (Å, º)

Cl12—C8	1.735 (3)	C6—C7	1.366 (4)
S2—O4	1.425 (2)	C6—C11	1.390 (4)
S2—O3	1.429 (2)	C7—C8	1.389 (4)
S2—N5	1.625 (2)	C7—H7	0.9300
S2—C1	1.751 (3)	C8—C9	1.372 (5)
N5—C6	1.428 (4)	C9—C10	1.372 (5)
N5—H5N	0.9344	C9—H9	0.9300
C1—H1A	0.9600	C10—C11	1.377 (5)
C1—H1B	0.9600	C10—H10	0.9300
C1—H1C	0.9600	C11—H11	0.9300
O4—S2—O3	118.70 (14)	C11—C6—N5	118.8 (3)
O4—S2—N5	105.47 (13)	C6—C7—C8	118.8 (3)
O3—S2—N5	108.64 (13)	C6—C7—H7	120.6
O4—S2—C1	109.04 (17)	C8—C7—H7	120.6
O3—S2—C1	107.00 (15)	C9—C8—C7	121.5 (3)
N5—S2—C1	107.54 (15)	C9—C8—Cl12	119.6 (2)
C6—N5—S2	121.81 (17)	C7—C8—Cl12	118.8 (2)
C6—N5—H5N	114.4	C8—C9—C10	118.7 (3)
S2—N5—H5N	112.7	C8—C9—H9	120.6
S2—C1—H1A	109.5	C10—C9—H9	120.6
S2—C1—H1B	109.5	C9—C10—C11	121.0 (3)
H1A—C1—H1B	109.5	C9—C10—H10	119.5
S2—C1—H1C	109.5	C11—C10—H10	119.5
H1A—C1—H1C	109.5	C10—C11—C6	119.3 (3)
H1B—C1—H1C	109.5	C10—C11—H11	120.4
C7—C6—C11	120.6 (3)	C6—C11—H11	120.4
C7—C6—N5	120.6 (3)
O4—S2—N5—C6	178.0 (2)	C6—C7—C8—Cl12	178.0 (2)
O3—S2—N5—C6	−53.7 (3)	C7—C8—C9—C10	0.1 (5)
C1—S2—N5—C6	61.7 (3)	Cl12—C8—C9—C10	179.7 (2)
S2—N5—C6—C7	62.3 (3)	C8—C9—C10—C11	2.0 (5)
S2—N5—C6—C11	−119.8 (3)	C9—C10—C11—C6	−1.8 (5)
C11—C6—C7—C8	2.6 (4)	C7—C6—C11—C10	−0.5 (4)
N5—C6—C7—C8	−179.6 (2)	N5—C6—C11—C10	−178.4 (3)
C6—C7—C8—C9	−2.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5N···O3^i	0.93	2.06	2.979 (3)	169

Symmetry code: (i) x, −y+1, z−1/2.