N-(2,5-Dichloro­phen­yl)methane­sulfonamide

The conformation of the N—H bond in the structure of the title compound, C₇H₇Cl₂NO₂S, is nearly syn to the ortho-chloro group and anti to the meta-chloro group, similar to that in N-(2,5-dimethyl­phen­yl)methane­sulfonamide determined under identical conditions. This is in contrast to the syn conformations observed with respect to both ortho- and meta-chloro substituents in N-(2,3-dichloro­phen­yl)methane­sulfon­amide and the conformation lying between syn and anti to the chloro substituents at ortho or meta positions in N-(2-chloro­phen­yl)­methane­sulfonamide and N-(3-chloro­phen­yl)­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 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 that in other methane­sulfonanilides. The mol­ecules in the title compound are packed into chains through N—H...O and N—H...Cl hydrogen bonding.

Key indicators

• Single-crystal X-ray study
• T = 299 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.048
• wR factor = 0.125
• Data-to-parameter ratio = 12.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.78
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
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 =          5
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          6
PLAT731_ALERT_1_C Bond    Calc     0.85(3), Rep   0.857(10) ......       3.00 su-Ra
              N5   -H5N     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(3), Rep   0.857(10) ......       3.00 su-Ra
              N5   -H5N     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(3), Rep   0.857(10) ......       3.00 su-Ra
              N5   -H5N     1.555   1.555

Alert level G
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
   8 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   5 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
   4 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 as their biological activity is thought to be due to the amide hydrogen portion of the molecules as it can align itself in relation to a receptor site. In the present work, the structure of N-(2,5-dichlorophenyl)-methanesulfonamide (25DCPMSA) has been determined to explore the substituent effects on the solid state structures of sulfonanilides (Gowda et al., 2007a-m). The structure of 25DCPMSA (Fig. 1) is similar to those of N-(phenyl)- methanesulfonamide (PMSA) (Klug, 1968), N-(2-chlorophenyl)- methanesulfonamide (2CPMSA)(Gowda et al., 2007m), N-(2,3-dichlorophenyl)-methanesulfonamide (23DCPMSA)(Gowda et al., 2007k), N-(2,5-dimethylphenyl)-methanesulfonamide (25DMPMSA) (Gowda et al., 2007m) and other alkyl sulfonanilides (Gowda et al., 2007a-i). The conformation of the N—H bond in 25DCPMSA is nearly syn to the ortho chloro group and anti to the meta chloro group, similar to that in 25DMPMSA determined under identical conditions (Gowda et al., 2007m). This is in contrast to the syn conformations observed with respect to both ortho and meta chloro substituents in 23DCPMSA (Gowda et al., 2007k) and the conformation lying between syn and anti conformations to the chloro substituents at ortho or meta positions in 2CPMSA (Gowda et al., 2007m)and N-(3-chlorophenyl)-methanesulfonamide (3CPMSA) (Gowda et al., 2007e). The ortho substitution of either a chloro or methyl group in PMSA changes its space group from monoclinic P2₁/c to triclinic P-1 (Gowda et al., 2007d,m,k). But the Substitution of an additional chloro group in the second meta position of 2CPMSA to produce 25DCPMSA does not further alter the space group, in contrast to the change over from triclinic P-1 to monoclinic P2₁/c on Substitution of an additional methyl group at the second meta position in N-(2-methylphenyl)- methanesulfonamide (2MPMSA) to form 25DMPMSA (Gowda et al., 2007m). Further, monoclinic P2₁/c space group is observed with 23DCPMSA (Gowda et al., 2007k). The geometric parameters in 25DCPMSA are similar to those in PMSA, 2CPMSA, 23DCPMSA, 25DMPMSA and other methanesulfonanilides except for some difference in the bond and torsional angles. The amide 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 in other alkyl sulfonanilides. The amide hydrogen is thus available to a receptor molecule during its biological activity. The molecules in 25DCPMSA are packed into chains in the direction of b axis (Fig. 2) through N—H···O and N—H···Cl 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,kl,m); 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 atoms were located in difference map and their positions refined, with U_iso = 1.2 U_eq of the 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.
	Fig. 3. Hydrogen bonding in the title compound. Hydrogen bonds are shown as dashed lines.

N-(2,5-dichlorophenyl)methanesulfonamide

Crystal data

C7H7Cl2NO2S	Z = 2
Mr = 240.10	F(000) = 244
Triclinic, P1	Dx = 1.659 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54180 Å
a = 5.8889 (5) Å	Cell parameters from 25 reflections
b = 8.4810 (6) Å	θ = 6.6–23.8°
c = 9.937 (1) Å	µ = 7.85 mm^−1
α = 95.45 (1)°	T = 299 K
β = 103.30 (1)°	Block, colourless
γ = 90.16 (1)°	0.10 × 0.10 × 0.08 mm
V = 480.64 (7) Å^3

Data collection

Enraf–Nonius CAD-4 diffractometer	1271 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.051
Graphite monochromator	θmax = 66.9°, θmin = 4.6°
ω/2θ scans	h = −6→7
Absorption correction: psi-scan (North et al., 1968)	k = −10→10
Tmin = 0.411, Tmax = 0.534	l = −11→1
1804 measured reflections	3 standard reflections every 120 min
1683 independent reflections	intensity decay: 1.2%

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0578P)^2 + 0.4897P] where P = (Fo^2 + 2Fc^2)/3
1683 reflections	(Δ/σ)max = 0.018
139 parameters	Δρmax = 0.29 e Å^−3
1 restraint	Δρmin = −0.47 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	0.2881 (10)	0.1936 (7)	0.4766 (6)	0.0609 (14)
H1A	0.312 (10)	0.114 (6)	0.549 (6)	0.073*
H1B	0.370 (10)	0.286 (7)	0.510 (6)	0.073*
H1C	0.323 (10)	0.138 (6)	0.395 (6)	0.073*
C6	−0.0009 (7)	0.3162 (4)	0.1698 (4)	0.0323 (8)
C7	−0.1735 (8)	0.2222 (5)	0.0805 (4)	0.0381 (9)
H7	−0.305 (8)	0.192 (5)	0.106 (5)	0.046*
C8	−0.1542 (8)	0.1785 (5)	−0.0540 (4)	0.0396 (9)
C9	0.0319 (9)	0.2282 (5)	−0.1024 (4)	0.0487 (11)
H9	0.028 (9)	0.204 (5)	−0.196 (5)	0.058*
C10	0.2017 (9)	0.3234 (5)	−0.0152 (4)	0.0456 (11)
H10	0.344 (9)	0.354 (5)	−0.036 (5)	0.055*
C11	0.1899 (7)	0.3666 (4)	0.1211 (4)	0.0370 (9)
N5	−0.0228 (7)	0.3644 (4)	0.3072 (3)	0.0387 (8)
H5N	0.042 (7)	0.455 (3)	0.338 (4)	0.046*
O3	−0.0774 (7)	0.3234 (4)	0.5373 (3)	0.0672 (11)
O4	−0.1353 (6)	0.0990 (4)	0.3569 (3)	0.0585 (9)
S2	−0.0073 (2)	0.23883 (12)	0.42304 (10)	0.0421 (3)
Cl12	0.4089 (2)	0.48370 (14)	0.23125 (12)	0.0552 (3)
Cl13	−0.3795 (2)	0.06441 (14)	−0.16473 (11)	0.0585 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.066 (4)	0.069 (3)	0.044 (3)	0.000 (3)	0.000 (2)	0.014 (2)
C6	0.041 (2)	0.0312 (18)	0.0277 (18)	0.0049 (16)	0.0132 (16)	0.0047 (14)
C7	0.044 (3)	0.038 (2)	0.035 (2)	−0.0001 (18)	0.0144 (18)	0.0044 (17)
C8	0.049 (3)	0.037 (2)	0.033 (2)	0.0007 (18)	0.0107 (18)	0.0021 (16)
C9	0.070 (3)	0.048 (2)	0.033 (2)	0.006 (2)	0.022 (2)	0.0046 (18)
C10	0.045 (3)	0.056 (3)	0.043 (2)	0.000 (2)	0.024 (2)	0.008 (2)
C11	0.043 (3)	0.035 (2)	0.037 (2)	0.0021 (17)	0.0161 (18)	0.0083 (16)
N5	0.055 (2)	0.0314 (17)	0.0336 (17)	−0.0078 (15)	0.0196 (16)	−0.0023 (14)
O3	0.115 (3)	0.0538 (19)	0.0468 (19)	−0.007 (2)	0.051 (2)	−0.0047 (15)
O4	0.085 (3)	0.0476 (17)	0.0419 (17)	−0.0273 (17)	0.0133 (16)	0.0029 (14)
S2	0.0621 (7)	0.0392 (5)	0.0283 (5)	−0.0106 (5)	0.0193 (4)	−0.0022 (4)
Cl12	0.0469 (7)	0.0661 (7)	0.0535 (7)	−0.0147 (5)	0.0155 (5)	0.0020 (5)
Cl13	0.0740 (9)	0.0577 (7)	0.0393 (6)	−0.0099 (6)	0.0091 (5)	−0.0080 (5)

Geometric parameters (Å, º)

C1—S2	1.753 (6)	C8—Cl13	1.739 (4)
C1—H1A	1.02 (6)	C9—C10	1.367 (7)
C1—H1B	0.91 (6)	C9—H9	0.93 (5)
C1—H1C	0.96 (6)	C10—C11	1.386 (6)
C6—C7	1.380 (6)	C10—H10	0.95 (5)
C6—C11	1.402 (5)	C11—Cl12	1.728 (4)
C6—N5	1.422 (4)	N5—S2	1.629 (3)
C7—C8	1.384 (5)	N5—H5N	0.857 (10)
C7—H7	0.91 (5)	O3—S2	1.427 (3)
C8—C9	1.374 (6)	O4—S2	1.423 (3)
S2—C1—H1A	111 (3)	C8—C9—H9	118 (3)
S2—C1—H1B	108 (4)	C9—C10—C11	120.7 (4)
H1A—C1—H1B	112 (5)	C9—C10—H10	125 (3)
S2—C1—H1C	104 (3)	C11—C10—H10	114 (3)
H1A—C1—H1C	105 (4)	C10—C11—C6	120.1 (4)
H1B—C1—H1C	117 (5)	C10—C11—Cl12	120.2 (3)
C7—C6—C11	118.9 (3)	C6—C11—Cl12	119.7 (3)
C7—C6—N5	119.8 (3)	C6—N5—S2	121.9 (3)
C11—C6—N5	121.3 (4)	C6—N5—H5N	112 (3)
C6—C7—C8	119.6 (4)	S2—N5—H5N	115 (3)
C6—C7—H7	122 (3)	O4—S2—O3	118.8 (2)
C8—C7—H7	118 (3)	O4—S2—N5	107.90 (18)
C9—C8—C7	121.7 (4)	O3—S2—N5	105.64 (18)
C9—C8—Cl13	120.1 (3)	O4—S2—C1	108.9 (3)
C7—C8—Cl13	118.2 (3)	O3—S2—C1	108.4 (3)
C10—C9—C8	119.0 (4)	N5—S2—C1	106.5 (2)
C10—C9—H9	123 (3)
C11—C6—C7—C8	0.5 (6)	C7—C6—C11—C10	0.8 (6)
N5—C6—C7—C8	178.6 (4)	N5—C6—C11—C10	−177.2 (4)
C6—C7—C8—C9	−0.9 (6)	C7—C6—C11—Cl12	−179.7 (3)
C6—C7—C8—Cl13	−178.2 (3)	N5—C6—C11—Cl12	2.3 (5)
C7—C8—C9—C10	−0.1 (7)	C7—C6—N5—S2	68.5 (5)
Cl13—C8—C9—C10	177.2 (3)	C11—C6—N5—S2	−113.6 (4)
C8—C9—C10—C11	1.4 (7)	C6—N5—S2—O4	−42.0 (4)
C9—C10—C11—C6	−1.8 (7)	C6—N5—S2—O3	−170.0 (3)
C9—C10—C11—Cl12	178.7 (4)	C6—N5—S2—C1	74.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5N···O3^i	0.86 (1)	2.13 (2)	2.923 (4)	153 (4)
N5—H5N···Cl12	0.86 (1)	2.63 (4)	3.012 (4)	108 (3)

Symmetry code: (i) −x, −y+1, −z+1.