2,2-Dichloro-N-(4-methyl­phenyl­sulfonyl)acetamide

Gowda, B.T.; Foro, S.; Nirmala, P.G.; Sowmya, B.P.; Fuess, H.

doi:10.1107/S160053680802134X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1492

doi:10.1107/S160053680802134X

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2,2-Dichloro-N-(4-methylphenylsulfonyl)acetamide

B. Thimme Gowda,^a ^* Sabine Foro,^b P. G. Nirmala,^a B. P. Sowmya ^a and Hartmut Fuess ^b

^aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, and ^bInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287 Darmstadt, Germany
^*Correspondence e-mail: gowdabt@yahoo.com

(Received 9 July 2008; accepted 9 July 2008; online 16 July 2008)

The N—H and C=O bonds in the title compound, C₉H₉Cl₂NO₃S, are trans to each other, similar to what is observed in 2,2,2-trimethyl-N-(phenylsulfonyl)acetamide and 2,2,2-trimethyl-N-(4-methylphenylsulfonyl)acetamide. The bond parameters in the title compound are also similar to those in the aforementioned two structures. N—H⋯O hydrogen bonds connect the molecules into chains running along the a axis.

Related literature

For related literature, see: Gowda et al. (2006 , 2007 , 2008a ,b ).

Experimental

Crystal data

C₉H₉Cl₂NO₃S
M_r = 282.13
Orthorhombic, P b c a
a = 9.6580 (8) Å
b = 10.3177 (8) Å
c = 23.067 (2) Å
V = 2298.6 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.74 mm⁻¹
T = 299 (2) K
0.48 × 0.46 × 0.32 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis RED. Oxford Diffraction Ltd. Köln, Germany.]$ ) T_min = 0.719, T_max = 0.799
8079 measured reflections
2313 independent reflections
1886 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.099
S = 1.14
2313 reflections
150 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O3ⁱ	0.82 (3)	2.03 (3)	2.833 (2)	166 (2)
Symmetry code: (i) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2004 $[Oxford Diffraction (2004). CrysAlis CCD. Oxford Diffraction Ltd. Köln, Germany.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis RED. Oxford Diffraction Ltd. Köln, Germany.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680802134X/bt2744sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680802134X/bt2744Isup2.hkl

checkCIF report

Comment top

As part of a study of the substituent effects on the solid state geometries of N-(aryl)-sulfonamides and substituted amides, the structure of N-(4-methylphenylsulfonyl)-2,2-dichloroacetamide (N4MPSDCAA) has been determined (Gowda et al., 2006, 2007, 2008a, 2008b). The conformation of the N—H and C=O bonds in N4MPSDCAA are anti to each other (Fig. 1), similar to that observed in N-(phenylsulfonyl)-2,2,2-trimethylacetamide (NPSTMAA) (Gowda et al., 2008b), N-(4-chlorophenylsulfonyl)-2,2,2-trimethylacetamide (N4CPSTMAA) and (4-methylphenylsulfonyl)-2,2,2-trimethylacetamide (N4MPSTMAA) (Gowda et al., 2008a, b). The bond parameters in N4MPSDCAA are similar to those in NPSTMAA, N4MPSTMAA, N4CPSTMAA (Gowda et al., 2008a, b), N-(aryl)-2,2-dichloroacetamides (Gowda et al., 2006) and 4-methylbenzenesulfonamide and other arylsulfonamides (Gowda et al., 2007). The N—H···O hydrogen bonds (Table 1) connect the molecules to chains running along the a axis (Fig. 2).

Related literature top

For related literature, see: Gowda et al. (2006, 2007, 2008a,b).

Experimental top

The title compound was prepared by refluxing 4-methylbenzenesulfonamide (0.10 mole) with an excess dichloroacetyl chloride (0.20 mole) for about an hour on a water bath. The reaction mixture was cooled and poured into ice cold water. The resulting solid was separated, washed thoroughly with water and dissolved in warm dilute sodium hydrogen carbonate solution. The title compound was precipitated by acidifying the filtered solution with glacial acetic acid. It was filtered, dried and recrystallized from ethanol. The purity of the compound was checked by determining its melting point. It was characterized by recording its infrared and NMR spectra. Single crystals of the title compound used for X-ray diffraction studies were obtained from a slow evaporation of an ethanolic solution.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2004); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXS97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of (I), showing the atom labeling scheme. The displacement ellipsoids are drawn at the 50% probability level. The H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Molecular packing of (I) with hydrogen bonding shown as dashed lines.

2,2-Dichloro-N-(4-methylphenylsulfonyl)acetamide top

Crystal data top

C₉H₉Cl₂NO₃S	F(000) = 1152
M_r = 282.13	D_x = 1.631 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3825 reflections
a = 9.6580 (8) Å	θ = 2.3–28.0°
b = 10.3177 (8) Å	µ = 0.74 mm⁻¹
c = 23.067 (2) Å	T = 299 K
V = 2298.6 (3) Å³	Prism, colourless
Z = 8	0.48 × 0.46 × 0.32 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2313 independent reflections
Radiation source: fine-focus sealed tube	1886 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Rotation method data acquisition using ω and ϕ scans	θ_max = 26.4°, θ_min = 3.9°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	h = −12→11
T_min = 0.719, T_max = 0.799	k = −12→11
8079 measured reflections	l = −28→28

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0465P)² + 1.5357P] where P = (F_o² + 2F_c²)/3
S = 1.14	(Δ/σ)_max = 0.001
2313 reflections	Δρ_max = 0.34 e Å⁻³
150 parameters	Δρ_min = −0.33 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0216 (12)

Crystal data top

C₉H₉Cl₂NO₃S	V = 2298.6 (3) Å³
M_r = 282.13	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.6580 (8) Å	µ = 0.74 mm⁻¹
b = 10.3177 (8) Å	T = 299 K
c = 23.067 (2) Å	0.48 × 0.46 × 0.32 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2313 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	1886 reflections with I > 2σ(I)
T_min = 0.719, T_max = 0.799	R_int = 0.022
8079 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	Δρ_max = 0.34 e Å⁻³
2313 reflections	Δρ_min = −0.33 e Å⁻³
150 parameters

Special details top

Experimental. CrysAlis RED (Oxford Diffraction, 2007) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.1940 (2)	0.2089 (2)	0.10903 (9)	0.0321 (5)
C2	0.3304 (3)	0.2325 (3)	0.09411 (11)	0.0419 (6)
H2	0.4022	0.1916	0.1138	0.050*
C3	0.3581 (3)	0.3181 (3)	0.04945 (11)	0.0487 (6)
H3	0.4497	0.3348	0.0395	0.058*
C4	0.2532 (3)	0.3796 (2)	0.01912 (10)	0.0440 (6)
C5	0.1181 (3)	0.3514 (3)	0.03428 (12)	0.0480 (6)
H5	0.0463	0.3897	0.0136	0.058*
C6	0.0866 (3)	0.2678 (2)	0.07928 (11)	0.0403 (6)
H6	−0.0050	0.2515	0.0893	0.048*
C7	0.2763 (2)	0.27000 (19)	0.24611 (9)	0.0279 (4)
C8	0.2502 (2)	0.3642 (2)	0.29677 (9)	0.0331 (5)
H8	0.1773	0.4255	0.2859	0.040*
C9	0.2837 (4)	0.4760 (3)	−0.02853 (13)	0.0626 (8)
H9A	0.3703	0.4545	−0.0466	0.075*
H9B	0.2892	0.5616	−0.0124	0.075*
H9C	0.2111	0.4731	−0.0569	0.075*
N1	0.15881 (18)	0.21543 (18)	0.22498 (8)	0.0292 (4)
H1N	0.084 (3)	0.238 (2)	0.2380 (11)	0.035*
O1	0.01360 (18)	0.07170 (18)	0.16642 (7)	0.0438 (4)
O2	0.26226 (19)	0.01713 (16)	0.17765 (7)	0.0433 (4)
O3	0.39079 (15)	0.24827 (17)	0.22726 (7)	0.0385 (4)
Cl1	0.40283 (7)	0.45024 (6)	0.31278 (3)	0.0454 (2)
Cl2	0.19595 (7)	0.27418 (7)	0.35847 (3)	0.0508 (2)
S1	0.15508 (6)	0.11055 (5)	0.16929 (2)	0.03130 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0352 (11)	0.0326 (11)	0.0285 (10)	−0.0022 (9)	−0.0002 (8)	−0.0039 (9)
C2	0.0335 (12)	0.0556 (16)	0.0366 (12)	−0.0025 (11)	0.0009 (10)	0.0018 (11)
C3	0.0431 (14)	0.0605 (17)	0.0424 (13)	−0.0122 (12)	0.0083 (11)	0.0013 (13)
C4	0.0633 (16)	0.0372 (13)	0.0315 (11)	−0.0068 (11)	0.0046 (11)	−0.0024 (10)
C5	0.0556 (16)	0.0421 (14)	0.0463 (14)	0.0060 (12)	−0.0039 (12)	0.0077 (12)
C6	0.0353 (12)	0.0431 (14)	0.0424 (13)	0.0005 (10)	−0.0013 (10)	0.0029 (11)
C7	0.0282 (11)	0.0269 (10)	0.0285 (10)	0.0026 (8)	−0.0035 (8)	0.0052 (8)
C8	0.0323 (11)	0.0314 (11)	0.0355 (11)	0.0042 (9)	−0.0043 (9)	−0.0018 (9)
C9	0.087 (2)	0.0531 (18)	0.0476 (15)	−0.0120 (16)	0.0097 (15)	0.0089 (13)
N1	0.0233 (9)	0.0331 (10)	0.0312 (9)	0.0009 (7)	0.0022 (7)	−0.0022 (8)
O1	0.0407 (10)	0.0470 (10)	0.0436 (9)	−0.0165 (8)	−0.0027 (7)	−0.0009 (8)
O2	0.0524 (10)	0.0314 (9)	0.0462 (9)	0.0083 (8)	0.0008 (8)	−0.0002 (7)
O3	0.0230 (8)	0.0514 (10)	0.0412 (9)	0.0030 (7)	−0.0015 (6)	−0.0083 (7)
Cl1	0.0513 (4)	0.0353 (3)	0.0496 (4)	−0.0104 (3)	−0.0075 (3)	−0.0046 (3)
Cl2	0.0564 (4)	0.0610 (4)	0.0348 (3)	−0.0153 (3)	0.0085 (3)	−0.0048 (3)
S1	0.0327 (3)	0.0290 (3)	0.0322 (3)	−0.0035 (2)	−0.0011 (2)	−0.0005 (2)

Geometric parameters (Å, º) top

C1—C2	1.384 (3)	C7—N1	1.357 (3)
C1—C6	1.384 (3)	C7—C8	1.540 (3)
C1—S1	1.761 (2)	C8—Cl1	1.760 (2)
C2—C3	1.383 (4)	C8—Cl2	1.778 (2)
C2—H2	0.9300	C8—H8	0.9800
C3—C4	1.385 (4)	C9—H9A	0.9600
C3—H3	0.9300	C9—H9B	0.9600
C4—C5	1.381 (4)	C9—H9C	0.9600
C4—C9	1.512 (4)	N1—S1	1.6800 (19)
C5—C6	1.384 (4)	N1—H1N	0.82 (3)
C5—H5	0.9300	O1—S1	1.4256 (17)
C6—H6	0.9300	O2—S1	1.4276 (17)
C7—O3	1.210 (3)

C2—C1—C6	120.8 (2)	C7—C8—Cl1	109.94 (15)
C2—C1—S1	120.07 (18)	C7—C8—Cl2	109.02 (14)
C6—C1—S1	118.98 (18)	Cl1—C8—Cl2	110.02 (12)
C3—C2—C1	118.8 (2)	C7—C8—H8	109.3
C3—C2—H2	120.6	Cl1—C8—H8	109.3
C1—C2—H2	120.6	Cl2—C8—H8	109.3
C2—C3—C4	121.8 (2)	C4—C9—H9A	109.5
C2—C3—H3	119.1	C4—C9—H9B	109.5
C4—C3—H3	119.1	H9A—C9—H9B	109.5
C5—C4—C3	117.8 (2)	C4—C9—H9C	109.5
C5—C4—C9	120.5 (3)	H9A—C9—H9C	109.5
C3—C4—C9	121.7 (3)	H9B—C9—H9C	109.5
C4—C5—C6	121.9 (2)	C7—N1—S1	124.04 (15)
C4—C5—H5	119.0	C7—N1—H1N	119.4 (18)
C6—C5—H5	119.0	S1—N1—H1N	116.4 (18)
C5—C6—C1	118.7 (2)	O1—S1—O2	120.76 (11)
C5—C6—H6	120.6	O1—S1—N1	103.72 (10)
C1—C6—H6	120.6	O2—S1—N1	108.43 (10)
O3—C7—N1	124.0 (2)	O1—S1—C1	109.25 (11)
O3—C7—C8	122.60 (19)	O2—S1—C1	109.93 (11)
N1—C7—C8	113.45 (18)	N1—S1—C1	103.17 (10)

C6—C1—C2—C3	1.1 (4)	N1—C7—C8—Cl2	69.4 (2)
S1—C1—C2—C3	−175.0 (2)	O3—C7—N1—S1	−0.4 (3)
C1—C2—C3—C4	−0.5 (4)	C8—C7—N1—S1	179.19 (14)
C2—C3—C4—C5	−0.9 (4)	C7—N1—S1—O1	174.97 (17)
C2—C3—C4—C9	178.2 (3)	C7—N1—S1—O2	45.5 (2)
C3—C4—C5—C6	1.9 (4)	C7—N1—S1—C1	−71.09 (19)
C9—C4—C5—C6	−177.2 (3)	C2—C1—S1—O1	−164.08 (19)
C4—C5—C6—C1	−1.4 (4)	C6—C1—S1—O1	19.7 (2)
C2—C1—C6—C5	−0.2 (4)	C2—C1—S1—O2	−29.4 (2)
S1—C1—C6—C5	175.97 (19)	C6—C1—S1—O2	154.39 (18)
O3—C7—C8—Cl1	9.7 (3)	C2—C1—S1—N1	86.1 (2)
N1—C7—C8—Cl1	−169.93 (15)	C6—C1—S1—N1	−90.13 (19)
O3—C7—C8—Cl2	−111.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3ⁱ	0.82 (3)	2.03 (3)	2.833 (2)	166 (2)

Symmetry code: (i) x−1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₉H₉Cl₂NO₃S
M_r	282.13
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	299
a, b, c (Å)	9.6580 (8), 10.3177 (8), 23.067 (2)
V (Å³)	2298.6 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.74
Crystal size (mm)	0.48 × 0.46 × 0.32

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
T_min, T_max	0.719, 0.799
No. of measured, independent and observed [I > 2σ(I)] reflections	8079, 2313, 1886
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.099, 1.14
No. of reflections	2313
No. of parameters	150
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.33

Computer programs: CrysAlis CCD (Oxford Diffraction, 2004), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3ⁱ	0.82 (3)	2.03 (3)	2.833 (2)	166 (2)

Symmetry code: (i) x−1/2, y, −z+1/2.

Acknowledgements

BTG thanks the Alexander von Humboldt Foundation, Bonn, Germany, for extensions of his research fellowship.

References

Gowda, B. T., Foro, S., Sowmya, B. P., Nirmala, P. G. & Fuess, H. (2008a). Acta Cryst. E64, o1274. Web of Science CSD CrossRef IUCr Journals Google Scholar
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