N-(2,4-Dichloro­phen­yl)methane­sulfonamide

The conformation of the N—H bond in the structure of the title compound, C₇H₇Cl₂NO₂S, is nearly syn to the ortho-chloro substituent, similar to the syn conformation observed for the N-(2,4-dimethyl­phen­yl)methane­sulfonamide. The geometric parameters are similar to those in other methane­sulfonanilides, except for some differences in the bond and torsion angles. The amide H atom is readily available to a receptor mol­ecule during its biological activity, as it lies on one side of the plane of the benzene ring, similar to those in other N-aryl­methane­sulfonamides. The mol­ecules are packed into chains through both N—H...O and N—H...Cl hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 299 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.095
• wR factor = 0.277
• Data-to-parameter ratio = 14.3

checkCIF/PLATON results

No syntax errors found



Alert level C
DIFMN02_ALERT_2_C  The minimum difference density is < -0.1*ZMAX*0.75
            _refine_diff_density_min given =     -1.653
            Test value =     -1.275
DIFMN03_ALERT_1_C  The minimum difference density is < -0.1*ZMAX*0.75
            The relevant atom site should be identified.
RFACR01_ALERT_3_C  The value of the weighted R factor is > 0.25
            Weighted R factor given   0.277
PLAT084_ALERT_2_C High R2 Value ..................................       0.28
PLAT098_ALERT_2_C Minimum (Negative) Residual Density ............      -1.65 e/A   
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
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          6

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

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
   0 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 sulfonanilides are of interest due to their biological activity. In the present work, the structure of N-(2,4-dichlorophenyl)-methanesulfonamide (24DCPMSA) has been determined to explore the substituent effects on the solid state structures of sulfonanilides (Gowda et al., 2007a-l). The structure of 24DCPMSA (Fig. 1) resembles those of N-(phenyl)-methanesulfonamide (PMSA) (Klug, 1968), N-(2-chlorophenyl)-methanesulfonamide (2CPMSA) (Gowda et al., 2007l), N-(2,3-dichlorophenyl)- methanesulfonamide (23DCPMSA)(Gowda et al., 2007k), N-(2,4-dimethylphenyl)-methanesulfonamide (24DMPMSA)(Gowda et al., 2007i) and other methylsulfonanilides (Gowda et al., 2007a-h). The conformation of the N—H bond in 24DCPMSA is nearly syn to the ortho-chloro substituent, similar to the syn conformation observed for 24DMPMSA (Gowda et al., 2007i). The ortho substitution of either a chloro or methyl group in PMSA changes its space group from monoclinic P2₁/c to triclinic P-1. But the substitution of an additional chloro group in the para position of 2CPMSA to produce 24DCPMSA does not further alter the space group, in contrast to the change over from triclinic P-1 to monoclinic P2₁/n on substitution of an additional methyl group at the para position in N-(2-methylphenyl)- methanesulfonamide (2MPMSA) (Gowda et al., 2007d) to form 24DMPMSA and monoclinic P2₁/c space group observed for 23DCPMSA (Gowda et al., 2007k). The geometric parameters in 24DCPMSA are similar to those in PMSA, 2CPMSA, 23DCPMSA, 24DMPMSA and other methanesulfonanilides except for some difference in the bond and torsional angles. The amide hydrogen is readily available to a receptor molecule during its biological activity as it sits alone on one side of the plane of the phenyl group similar to those in other N-(aryl)-methanesulfonamides. The molecules in 24DCPMSA are packed into chains in the direction of b axis (Fig. 2) through both N—H···O and N—H···Cl hydrogen bonds (Table 1).

Related literature

For related literature, see:

Gowda et al. (2007a,b,c,d,e,f,g,h,i,j,k,l); 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

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 1.2 U_eq (parent atom).

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 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.

N-(2,4-Dichlorophenyl)methanesulfonamide

Crystal data

C7H7Cl2NO2S	Z = 2
Mr = 240.10	F(000) = 244
Triclinic, P1	Dx = 1.660 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54180 Å
a = 7.580 (1) Å	Cell parameters from 25 reflections
b = 8.269 (1) Å	θ = 6.8–25.8°
c = 8.285 (1) Å	µ = 7.85 mm^−1
α = 83.70 (1)°	T = 299 K
β = 87.95 (1)°	Prism, colourless
γ = 68.57 (1)°	0.52 × 0.32 × 0.15 mm
V = 480.47 (10) Å^3

Data collection

Enraf–Nonius CAD-4 diffractometer	1601 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.048
Graphite monochromator	θmax = 66.9°, θmin = 5.4°
ω/2θ scans	h = −9→9
Absorption correction: ψ scan (North et al., 1968)	k = −9→9
Tmin = 0.042, Tmax = 0.307	l = −9→0
1831 measured reflections	3 standard reflections every 120 min
1701 independent reflections	intensity decay: 5.0%

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)] = 0.095	H-atom parameters constrained
wR(F^2) = 0.277	w = 1/[σ^2(Fo^2) + (0.2P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.37	(Δ/σ)max < 0.001
1701 reflections	Δρmax = 0.84 e Å^−3
119 parameters	Δρmin = −1.65 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: 0.130 (17)

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	0.3441 (5)	0.4168 (5)	0.2568 (4)	0.0353 (9)
C2	0.2920 (5)	0.3970 (5)	0.1016 (4)	0.0366 (9)
C3	0.2380 (5)	0.5343 (5)	−0.0203 (5)	0.0402 (10)
H3	0.2052	0.5185	−0.1229	0.048*
C4	0.2337 (5)	0.6943 (5)	0.0135 (5)	0.0402 (10)
C5	0.2829 (6)	0.7203 (5)	0.1657 (5)	0.0435 (10)
H5	0.2785	0.8298	0.1870	0.052*
C6	0.3382 (6)	0.5817 (5)	0.2844 (5)	0.0423 (10)
H6	0.3727	0.5986	0.3860	0.051*
C7	0.1136 (6)	0.1897 (7)	0.4902 (7)	0.0582 (12)
H7A	0.1653	0.0805	0.4440	0.070*
H7B	0.0322	0.2772	0.4122	0.070*
H7C	0.0421	0.1765	0.5853	0.070*
N1	0.4140 (4)	0.2726 (4)	0.3754 (4)	0.0402 (9)
H1N	0.5211	0.1917	0.3592	0.048*
O1	0.4295 (5)	0.1117 (4)	0.6438 (4)	0.0533 (9)
O2	0.2194 (5)	0.4216 (4)	0.6006 (4)	0.0528 (9)
S1	0.29870 (12)	0.25352 (12)	0.54332 (10)	0.0385 (6)
Cl1	0.29909 (18)	0.19478 (13)	0.05738 (13)	0.0544 (6)
Cl2	0.17636 (15)	0.86631 (14)	−0.14033 (13)	0.0542 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0286 (16)	0.0312 (19)	0.0447 (18)	−0.0097 (14)	0.0020 (13)	−0.0028 (15)
C2	0.0343 (17)	0.032 (2)	0.0433 (18)	−0.0125 (15)	0.0027 (14)	−0.0051 (16)
C3	0.0344 (18)	0.038 (2)	0.0462 (19)	−0.0111 (16)	0.0006 (15)	−0.0033 (17)
C4	0.0333 (18)	0.034 (2)	0.052 (2)	−0.0125 (16)	0.0045 (15)	0.0008 (17)
C5	0.046 (2)	0.0310 (19)	0.055 (2)	−0.0157 (16)	0.0037 (17)	−0.0058 (17)
C6	0.0416 (19)	0.038 (2)	0.0489 (19)	−0.0161 (16)	−0.0034 (16)	−0.0044 (17)
C7	0.044 (2)	0.055 (3)	0.080 (3)	−0.023 (2)	0.005 (2)	−0.008 (2)
N1	0.0335 (15)	0.0297 (16)	0.0499 (18)	−0.0041 (12)	0.0024 (13)	−0.0001 (14)
O1	0.062 (2)	0.0393 (17)	0.0464 (15)	−0.0057 (14)	−0.0051 (13)	0.0036 (13)
O2	0.0627 (19)	0.0360 (17)	0.0491 (16)	−0.0054 (14)	0.0043 (14)	−0.0063 (14)
S1	0.0398 (8)	0.0281 (8)	0.0423 (8)	−0.0068 (5)	0.0007 (5)	−0.0011 (5)
Cl1	0.0720 (9)	0.0341 (9)	0.0594 (9)	−0.0207 (6)	−0.0036 (6)	−0.0081 (5)
Cl2	0.0552 (9)	0.0405 (9)	0.0583 (9)	−0.0121 (6)	0.0016 (6)	0.0120 (5)

Geometric parameters (Å, º)

C1—C6	1.392 (5)	C5—H5	0.9300
C1—C2	1.402 (5)	C6—H6	0.9300
C1—N1	1.409 (5)	C7—S1	1.754 (4)
C2—C3	1.384 (6)	C7—H7A	0.9600
C2—Cl1	1.732 (4)	C7—H7B	0.9600
C3—C4	1.371 (6)	C7—H7C	0.9600
C3—H3	0.9300	N1—S1	1.640 (3)
C4—C5	1.388 (6)	N1—H1N	0.8600
C4—Cl2	1.739 (4)	O1—S1	1.431 (3)
C5—C6	1.374 (6)	O2—S1	1.426 (3)
C6—C1—C2	117.2 (4)	C1—C6—H6	119.1
C6—C1—N1	121.4 (3)	S1—C7—H7A	109.5
C2—C1—N1	121.2 (3)	S1—C7—H7B	109.5
C3—C2—C1	121.9 (4)	H7A—C7—H7B	109.5
C3—C2—Cl1	118.3 (3)	S1—C7—H7C	109.5
C1—C2—Cl1	119.8 (3)	H7A—C7—H7C	109.5
C4—C3—C2	118.6 (4)	H7B—C7—H7C	109.5
C4—C3—H3	120.7	C1—N1—S1	122.4 (2)
C2—C3—H3	120.7	C1—N1—H1N	118.8
C3—C4—C5	121.5 (4)	S1—N1—H1N	118.8
C3—C4—Cl2	119.3 (3)	O2—S1—O1	119.49 (19)
C5—C4—Cl2	119.1 (3)	O2—S1—N1	107.84 (18)
C6—C5—C4	119.0 (3)	O1—S1—N1	105.42 (18)
C6—C5—H5	120.5	O2—S1—C7	108.8 (2)
C4—C5—H5	120.5	O1—S1—C7	108.1 (2)
C5—C6—C1	121.9 (3)	N1—S1—C7	106.5 (2)
C5—C6—H6	119.1
C6—C1—C2—C3	0.4 (5)	Cl2—C4—C5—C6	−176.5 (3)
N1—C1—C2—C3	−174.6 (3)	C4—C5—C6—C1	−0.8 (6)
C6—C1—C2—Cl1	179.1 (3)	C2—C1—C6—C5	0.4 (6)
N1—C1—C2—Cl1	4.1 (5)	N1—C1—C6—C5	175.3 (3)
C1—C2—C3—C4	−0.7 (6)	C6—C1—N1—S1	70.8 (4)
Cl1—C2—C3—C4	−179.4 (3)	C2—C1—N1—S1	−114.4 (3)
C2—C3—C4—C5	0.3 (6)	C1—N1—S1—O2	−40.3 (3)
C2—C3—C4—Cl2	177.2 (3)	C1—N1—S1—O1	−169.0 (3)
C3—C4—C5—C6	0.4 (6)	C1—N1—S1—C7	76.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	0.86	2.40	2.979 (5)	125
N1—H1N···Cl2^ii	0.86	2.80	3.494 (3)	138

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