N-(3,4-Dichloro­phen­yl)methane­sulfonamide

In the structure of the title compound, C₇H₇Cl₂NO₂S, the conformation of the N—H bond is syn to the meta-chloro group, in contrast with the anti conformation observed for the meta-methyl group in N-(3,4-dimethyl­phenyl)­methane­sulfonamide and the conformation lying between syn and anti to the meta-chloro substituent in N-(3-chloro­phen­yl)methane­sulfonamide. The bond parameters are similar to those in other methane­sulfonanilides, except for some differences in the bond and torsion angles. There are N—H...O hydrogen bonds, resulting in the formation of dimers. C—H...O inter­actions between the dimers lead to a ribbon-like structure.

Key indicators

• Single-crystal X-ray study
• T = 299 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.034
• wR factor = 0.094
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.91
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        100 Ang.
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)       1000 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          6
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         S2

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      0.909
            Tmax scaled      0.451 Tmin scaled      0.298
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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 structural studies of sulphonanilides are of interest due to their biological activity as the latter is thought to be due to the amide hydrogen portion of the molecules. In the present work, the structure of N-(3,4-dichlorophenyl)-methanesulfonamde (34DCPMSA) has been determined as part of our study of the substituent effects on the solid state structures of methanesulfonanilides (Gowda et al., 2007a, b, c, d, e, f). The structure of 34DCPMSA (Fig. 1) is similar to those of other methanesulfonanilides(Gowda et al., 2007a,b,c,d,e,f). The conformation of the N—H bond in 34DCPMSA is syn to the meta chloro group in contrast to the anti conformation observed for the meta methyl group in N-(3,4-dimethylphenyl)-methanesulfonamde (34DMPMSA)(Gowda et al., 2007c) and the conformation lying between syn and anti to the meta-chloro substituent in N-(3-chlorophenyl)- methanesulfonamde (3CPMSA)(Gowda et al., 2007b). The substitution of Cl atom at the meta position of N-(phenyl)-methanesulfonamde (PMSA)to produce 3CPMSA changes its space group from monoclinic P2₁/c (Klug, 1968) to C 2/c (Gowda et al., 2007b). The substitution of an additional chloro group at the para position of 3CPMSA to produce 34DCPMSA changes the space group from monoclinic C 2/c to triclinic P-1 in contrast to change over from orthorhombic Pccn to monoclinic P2₁ on substitution of an additional methyl group at the para position in N-(3-methylphenyl)-methanesulfonamde to produce 34DMPMSA (Gowda et al., 2007c). The bond parameters in 34DCPMSA are similar to those in PMSA (Klug, 1968), 3CPMSA (Gowda et al., 2007b), 34DMPMSA (Gowda et al., 2007c) and other methanesulpfonanilides (Gowda et al., 2007a, d, e, f), except for some difference in the bond and torsional angles. The amide H atom is nearly in the plane of the dichlorophenyl group, the N atom is 0.110 (3) Å above the plane whereas the S atom is -0.426 (2) Å below the plane. The methyl group is clearly below the plane. The N—H···O hydrogen bonds (Table 1) result in the formation of dimers. The C—H···O interactions among the dimers in turn develop into ribbon like structures (Fig. 2).

Related literature

For related structures, see: Gowda et al. (2007a,b,c,d,e,f); Klug (1968). For the synthetic procedure, see: Jayalakshmi & Gowda (2004).

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

H atoms attached to C atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) or 0.96 Å (CH₃) and with U_iso(H) = 1.2U_eq(aromatic) or U_iso(H) = 1.5U_eq(CH₃). H atom attached to N was refined using a N—H restraint of 0.85 (1) Å.

Computing details

Data collection: CAD-4-PC Software (Enraf–Nonius, 1996); cell refinement: CAD-4-PC Software; data reduction: REDU4 (Stoe, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and 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. Partial packing view showing the formation of the ribbon through N—H···O and C—H···O hydrogen bonding interactions. H bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry code: (i) -x, -y + 1, -z; (ii) -x, -y + 1, -z + 1].

N-(3,4-Dichlorophenyl)methanesulfonamide

Crystal data

C7H7Cl2NO2S	Z = 2
Mr = 240.10	F(000) = 244
Triclinic, P1	Dx = 1.681 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54180 Å
a = 5.192 (1) Å	Cell parameters from 25 reflections
b = 8.452 (1) Å	θ = 5.3–27.1°
c = 11.031 (1) Å	µ = 7.95 mm^−1
α = 79.72 (1)°	T = 299 K
β = 89.72 (1)°	Prism, colourless
γ = 84.89 (1)°	0.40 × 0.15 × 0.10 mm
V = 474.38 (12) Å^3

Data collection

Enraf–Nonius CAD-4 diffractometer	1536 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.015
Graphite monochromator	θmax = 66.9°, θmin = 4.1°
ω/2θ scans	h = −6→1
Absorption correction: ψ scan (North et al., 1968)	k = −10→10
Tmin = 0.328, Tmax = 0.496	l = −13→13
1916 measured reflections	3 standard reflections every 120 min
1685 independent reflections	intensity decay: 1.0%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0543P)^2 + 0.2324P] where P = (Fo^2 + 2Fc^2)/3
1685 reflections	(Δ/σ)max < 0.001
123 parameters	Δρmax = 0.27 e Å^−3
1 restraint	Δρmin = −0.33 e Å^−3

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	0.2536 (6)	0.2368 (3)	0.2322 (3)	0.0596 (7)
H1A	0.3692	0.2599	0.2931	0.089*
H1B	0.3441	0.2355	0.1562	0.089*
H1C	0.1904	0.1333	0.2601	0.089*
C6	0.2776 (4)	0.6371 (3)	0.2260 (2)	0.0371 (5)
C7	0.4409 (5)	0.7364 (3)	0.1567 (2)	0.0388 (5)
H7	0.4471	0.7416	0.0718	0.047*
C8	0.5949 (4)	0.8279 (3)	0.2121 (2)	0.0378 (5)
C9	0.5897 (5)	0.8187 (3)	0.3392 (2)	0.0413 (5)
C10	0.4287 (5)	0.7178 (3)	0.4082 (2)	0.0465 (6)
H10	0.4258	0.7106	0.4933	0.056*
C11	0.2715 (5)	0.6270 (3)	0.3533 (2)	0.0443 (5)
H11	0.1626	0.5598	0.4008	0.053*
N5	0.1139 (4)	0.5562 (2)	0.16041 (18)	0.0456 (5)
O3	−0.1591 (4)	0.3621 (2)	0.10627 (16)	0.0565 (5)
O4	−0.1291 (4)	0.3894 (2)	0.32363 (17)	0.0547 (5)
S2	−0.00703 (11)	0.38570 (6)	0.20856 (5)	0.03832 (18)
Cl12	0.79029 (13)	0.95435 (8)	0.12089 (6)	0.0547 (2)
Cl13	0.77694 (14)	0.93584 (9)	0.41041 (7)	0.0603 (2)
H5	0.105 (6)	0.581 (3)	0.0828 (10)	0.054 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0588 (16)	0.0464 (14)	0.0720 (19)	−0.0034 (12)	0.0038 (14)	−0.0075 (13)
C6	0.0464 (12)	0.0306 (10)	0.0340 (11)	−0.0072 (9)	−0.0007 (9)	−0.0028 (8)
C7	0.0507 (13)	0.0343 (11)	0.0302 (11)	−0.0062 (9)	0.0016 (9)	−0.0010 (9)
C8	0.0433 (12)	0.0302 (10)	0.0390 (11)	−0.0074 (9)	0.0024 (9)	−0.0018 (9)
C9	0.0465 (12)	0.0375 (12)	0.0422 (13)	−0.0059 (10)	−0.0019 (10)	−0.0125 (10)
C10	0.0589 (15)	0.0512 (14)	0.0311 (11)	−0.0096 (11)	0.0036 (10)	−0.0094 (10)
C11	0.0553 (14)	0.0451 (13)	0.0332 (12)	−0.0159 (11)	0.0087 (10)	−0.0036 (10)
N5	0.0635 (13)	0.0435 (11)	0.0301 (10)	−0.0233 (9)	−0.0029 (9)	0.0020 (8)
O3	0.0682 (12)	0.0577 (11)	0.0448 (10)	−0.0329 (9)	−0.0079 (8)	0.0010 (8)
O4	0.0618 (11)	0.0587 (11)	0.0464 (10)	−0.0213 (9)	0.0191 (8)	−0.0095 (8)
S2	0.0442 (3)	0.0374 (3)	0.0335 (3)	−0.0145 (2)	0.0033 (2)	−0.0018 (2)
Cl12	0.0603 (4)	0.0482 (4)	0.0546 (4)	−0.0244 (3)	0.0056 (3)	0.0028 (3)
Cl13	0.0638 (4)	0.0656 (4)	0.0600 (4)	−0.0216 (3)	−0.0032 (3)	−0.0260 (3)

Geometric parameters (Å, º)

C1—S2	1.751 (3)	C8—Cl12	1.728 (2)
C1—H1A	0.9600	C9—C10	1.377 (4)
C1—H1B	0.9600	C9—Cl13	1.732 (2)
C1—H1C	0.9600	C10—C11	1.380 (3)
C6—C7	1.378 (3)	C10—H10	0.9300
C6—C11	1.392 (3)	C11—H11	0.9300
C6—N5	1.414 (3)	N5—S2	1.624 (2)
C7—C8	1.376 (3)	N5—H5	0.844 (10)
C7—H7	0.9300	O3—S2	1.4329 (18)
C8—C9	1.390 (3)	O4—S2	1.4201 (18)
S2—C1—H1A	109.5	C8—C9—Cl13	120.81 (18)
S2—C1—H1B	109.5	C9—C10—C11	121.1 (2)
H1A—C1—H1B	109.5	C9—C10—H10	119.4
S2—C1—H1C	109.5	C11—C10—H10	119.4
H1A—C1—H1C	109.5	C10—C11—C6	119.3 (2)
H1B—C1—H1C	109.5	C10—C11—H11	120.4
C7—C6—C11	119.8 (2)	C6—C11—H11	120.4
C7—C6—N5	116.56 (19)	C6—N5—S2	127.66 (16)
C11—C6—N5	123.6 (2)	C6—N5—H5	119 (2)
C8—C7—C6	120.5 (2)	S2—N5—H5	111 (2)
C8—C7—H7	119.7	O4—S2—O3	118.85 (12)
C6—C7—H7	119.7	O4—S2—N5	109.71 (11)
C7—C8—C9	120.1 (2)	O3—S2—N5	104.15 (10)
C7—C8—Cl12	118.80 (17)	O4—S2—C1	107.99 (14)
C9—C8—Cl12	121.13 (18)	O3—S2—C1	108.85 (14)
C10—C9—C8	119.2 (2)	N5—S2—C1	106.67 (13)
C10—C9—Cl13	119.97 (18)
C7—C6—N5—S2	152.95 (19)	C11—C6—N5—S2	−30.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···O3^i	0.84 (1)	2.08 (1)	2.913 (3)	169 (3)
C10—H10···O4^ii	0.93	2.60	3.352 (3)	138

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