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Acta Cryst. (2008). E64, o2092    [ doi:10.1107/S1600536808032157 ]

N-(4-Chloro-2-nitrophenyl)-N-(methylsulfonyl)acetamide

M. Zia-ur-Rehman, N. Akbar, M. N. Arshad and I. U. Khan

Abstract top

The title compound, C9H9ClN2O5S, is of interest as a precursor to biologically active substituted quinolines and related compounds. The structure displays intermolecular C-H...O interactions. Each molecule is linked to two adjacent neighbours via weak centrosymmetric dimer-forming interactions, forming chains in the [101] direction.

Comment top

N-(Substituted phenyl)acetamides are well known for their importance as intermediates in organic synthesis. They are used as precursors for the synthesis of many heterocyclic compounds, e.g. 2,5-piperazinedione (Wen et al., 2006), (quinolin-8-yloxy)acetamide (Zhang, Xu, Wen et al., 2006) and 2,2-(1,3,4-thiadiazolyl-2,5-dithio)diacetamide (Wen et al., 2005). In the present paper, the structure of N-(4-chloro-2-nitrophenyl)-N-(methylsulfonyl)acetamide (I) has been determined as part of a research program involving the synthesis and biological evaluation of sulfur containing heterocyclic compounds (Zia-ur-Rehman et al., 2005, 2006, 2007, 2008).

In the molecule of I (Fig. 1), the bond lengths and bond angles are similar to those in related molecules (Wen et al., 2006; Zhang, Xu, Zou et al., 2006) and are within normal ranges (Allen et al., 1987). The nitro group is slightly twisted out of the plane of the benzene ring, as indicated by O1—N1—C3—C2 and O2—N1—C3—C2 torsion angles of -16.7 (3) and 160.9 (2)°, respectively. Each molecule is linked to its neighbour via a centrosymmetric head-to-tail interaction between the methyl hydrogen H9B and the carbonyl oxygen [C9—H9B···O3]. Adjacent pairs of these molecules are then linked into chains via intermolecular [C2—H5···O5] interactions along the [101] direction (Table 1 and Fig. 2).

Related literature top

For synthesis and biological evaluation of sulfur-containing heterocyclic compounds, see: Zia-ur-Rehman et al. (2005, 2006, 2007, 2008); Wen et al. (2005); Zhang, Xu, Wen et al. (2006). For related molecules, see: (Wen et al., 2006; Zhang, Xu, Zou et al. (2006). For bond-length data, see: Allen et al. (1987).

Experimental top

A mixture of N-(4-chloro-2-nitrophenyl)methane sulfonamide (2.507 g; 10.0 mmoles) and acetic anhydride (10.0 ml) was heated to reflux for half an hour and then poured over crushed ice. Resultant solids were then washed with cold water and dried under reduced pressure. Yellow crystals were obtained by slow evaporation of an ethanolic solution over a period of two days.

Refinement top

H atoms bound to C were placed in geometric positions (C—H distance = 0.95 Å) using a riding model with Uiso(H) = 1.2 Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Perspective view of a portion of the crystal packing, viewed approximately down the b-axis, showing hydrogen bond interactions (dashed lines) along the [101] direction. H atoms not involved in hydrogen bonding have been omitted for clarity.
N-(4-Chloro-2-nitrophenyl)-N-(methylsulfonyl)acetamide top
Crystal data top
C9H9ClN2O5SF(000) = 600
Mr = 292.70Dx = 1.611 Mg m−3
Monoclinic, P21/cMelting point: 401 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 9.8071 (4) ÅCell parameters from 3121 reflections
b = 9.4310 (4) Åθ = 2.7–27.2°
c = 13.5679 (7) ŵ = 0.50 mm−1
β = 105.883 (2)°T = 296 K
V = 1207.00 (9) Å3Needle, light yellow
Z = 40.25 × 0.15 × 0.09 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer		2988 independent reflections
Radiation source: fine-focus sealed tube2077 reflections with I > 2σ(I)
graphiteRint = 0.043
Detector resolution: 7.5 pixels mm-1θmax = 28.3°, θmin = 2.7°
φ and ω scansh = −12→13
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		k = −12→12
Tmin = 0.913, Tmax = 0.956l = −18→17
13383 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0426P)2 + 0.5587P]
where P = (Fo2 + 2Fc2)/3
2981 reflections(Δ/σ)max < 0.001
163 parametersΔρmax = 0.43 e Å−3
0 restraintsΔρmin = −0.31 e Å−3
Crystal data top
C9H9ClN2O5SV = 1207.00 (9) Å3
Mr = 292.70Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.8071 (4) ŵ = 0.50 mm−1
b = 9.4310 (4) ÅT = 296 K
c = 13.5679 (7) Å0.25 × 0.15 × 0.09 mm
β = 105.883 (2)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer		2988 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2077 reflections with I > 2σ(I)
Tmin = 0.913, Tmax = 0.956Rint = 0.043
13383 measured reflectionsθmax = 28.3°
Refinement top
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.104Δρmax = 0.43 e Å−3
S = 1.02Δρmin = −0.31 e Å−3
2981 reflectionsAbsolute structure: ?
163 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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
xyzUiso*/Ueq
S10.43935 (5)0.98058 (6)0.14520 (4)0.03097 (15)
Cl1−0.20712 (6)0.67766 (7)−0.00125 (6)0.0511 (2)
N20.34896 (17)0.91810 (19)0.22582 (14)0.0276 (4)
O50.34507 (18)0.96150 (18)0.04574 (13)0.0439 (4)
C40.2107 (2)0.8605 (2)0.17969 (16)0.0269 (5)
O30.52800 (17)0.97095 (19)0.36537 (13)0.0454 (4)
N10.0872 (2)1.0934 (2)0.18329 (16)0.0361 (5)
C30.0874 (2)0.9425 (2)0.15362 (17)0.0283 (5)
O1−0.0130 (2)1.1651 (2)0.13957 (18)0.0695 (7)
C1−0.0476 (2)0.7464 (3)0.07164 (19)0.0365 (5)
O40.49004 (18)1.11878 (17)0.17659 (15)0.0477 (5)
O20.1842 (2)1.1381 (2)0.25205 (18)0.0651 (6)
C50.1996 (2)0.7188 (2)0.15196 (19)0.0359 (5)
H50.28000.66180.16890.043*
C60.0708 (2)0.6607 (3)0.09955 (19)0.0401 (6)
H60.06390.56470.08330.048*
C70.4104 (2)0.9221 (2)0.33238 (17)0.0315 (5)
C2−0.0409 (2)0.8874 (2)0.09933 (18)0.0327 (5)
H2−0.12150.94410.08160.039*
C80.5815 (3)0.8637 (3)0.1615 (2)0.0501 (7)
H8A0.54630.76900.14600.075*
H8B0.63900.86790.23120.075*
H8C0.63740.88990.11630.075*
C90.3259 (3)0.8606 (3)0.39765 (19)0.0415 (6)
H9A0.22850.88870.37160.062*
H9B0.36210.89440.46660.062*
H9C0.33230.75910.39690.062*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0248 (3)0.0320 (3)0.0347 (3)0.0000 (2)0.0057 (2)0.0040 (2)
Cl10.0311 (3)0.0557 (4)0.0567 (4)−0.0129 (3)−0.0043 (3)−0.0082 (3)
N20.0209 (8)0.0327 (9)0.0269 (10)−0.0027 (7)0.0024 (7)−0.0027 (8)
O50.0386 (9)0.0575 (11)0.0322 (10)−0.0048 (8)0.0039 (8)0.0063 (8)
C40.0208 (9)0.0328 (11)0.0253 (11)−0.0021 (8)0.0032 (8)−0.0017 (9)
O30.0317 (9)0.0564 (11)0.0388 (10)−0.0073 (8)−0.0064 (8)−0.0053 (8)
N10.0334 (10)0.0337 (10)0.0424 (12)0.0039 (8)0.0123 (9)−0.0019 (9)
C30.0268 (10)0.0283 (11)0.0292 (12)−0.0009 (8)0.0066 (9)−0.0012 (9)
O10.0571 (13)0.0447 (11)0.0897 (17)0.0213 (10)−0.0088 (12)−0.0094 (11)
C10.0256 (11)0.0426 (13)0.0364 (14)−0.0069 (10)0.0002 (10)−0.0021 (10)
O40.0457 (10)0.0354 (9)0.0607 (13)−0.0111 (8)0.0124 (9)0.0025 (8)
O20.0447 (11)0.0471 (11)0.0889 (17)0.0022 (9)−0.0063 (11)−0.0287 (11)
C50.0277 (11)0.0326 (11)0.0422 (15)0.0037 (9)0.0010 (10)−0.0035 (10)
C60.0368 (13)0.0329 (12)0.0447 (15)−0.0034 (10)0.0012 (11)−0.0067 (11)
C70.0308 (11)0.0307 (11)0.0291 (13)0.0039 (9)0.0016 (10)−0.0025 (9)
C20.0202 (10)0.0403 (12)0.0356 (13)0.0008 (9)0.0043 (9)0.0024 (10)
C80.0370 (14)0.0579 (17)0.0606 (19)0.0155 (12)0.0219 (13)0.0118 (14)
C90.0489 (14)0.0445 (14)0.0309 (14)0.0029 (11)0.0104 (12)0.0004 (11)
Geometric parameters (Å, °) top
S1—O41.4182 (17)C1—C21.379 (3)
S1—O51.4232 (18)C1—C61.380 (3)
S1—N21.6913 (19)C5—C61.382 (3)
S1—C81.743 (2)C5—H50.9300
Cl1—C11.732 (2)C6—H60.9300
N2—C71.406 (3)C7—C91.487 (3)
N2—C41.435 (2)C2—H20.9300
C4—C51.384 (3)C8—H8A0.9600
C4—C31.397 (3)C8—H8B0.9600
O3—C71.208 (3)C8—H8C0.9600
N1—O11.207 (2)C9—H9A0.9600
N1—O21.212 (3)C9—H9B0.9600
N1—C31.479 (3)C9—H9C0.9600
C3—C21.374 (3)
O4—S1—O5118.97 (11)C4—C5—H5119.5
O4—S1—N2109.18 (10)C1—C6—C5119.4 (2)
O5—S1—N2104.46 (9)C1—C6—H6120.3
O4—S1—C8109.91 (13)C5—C6—H6120.3
O5—S1—C8109.27 (13)O3—C7—N2119.2 (2)
N2—S1—C8103.88 (11)O3—C7—C9124.0 (2)
C7—N2—C4123.11 (18)N2—C7—C9116.74 (19)
C7—N2—S1120.17 (14)C3—C2—C1118.6 (2)
C4—N2—S1116.71 (14)C3—C2—H2120.7
C5—C4—C3117.84 (19)C1—C2—H2120.7
C5—C4—N2118.61 (18)S1—C8—H8A109.5
C3—C4—N2123.35 (18)S1—C8—H8B109.5
O1—N1—O2123.1 (2)H8A—C8—H8B109.5
O1—N1—C3117.83 (19)S1—C8—H8C109.5
O2—N1—C3119.05 (19)H8A—C8—H8C109.5
C2—C3—C4121.92 (19)H8B—C8—H8C109.5
C2—C3—N1116.14 (18)C7—C9—H9A109.5
C4—C3—N1121.95 (18)C7—C9—H9B109.5
C2—C1—C6121.1 (2)H9A—C9—H9B109.5
C2—C1—Cl1119.02 (18)C7—C9—H9C109.5
C6—C1—Cl1119.86 (18)H9A—C9—H9C109.5
C6—C5—C4121.1 (2)H9B—C9—H9C109.5
C6—C5—H5119.5
O4—S1—N2—C7−50.92 (18)O1—N1—C3—C4163.6 (2)
O5—S1—N2—C7−179.19 (16)O2—N1—C3—C4−18.8 (3)
C8—S1—N2—C766.30 (19)C3—C4—C5—C60.5 (4)
O4—S1—N2—C4130.04 (16)N2—C4—C5—C6−174.5 (2)
O5—S1—N2—C41.77 (17)C2—C1—C6—C5−3.1 (4)
C8—S1—N2—C4−112.74 (18)Cl1—C1—C6—C5175.8 (2)
C7—N2—C4—C5−91.8 (3)C4—C5—C6—C12.1 (4)
S1—N2—C4—C587.2 (2)C4—N2—C7—O3179.2 (2)
C7—N2—C4—C393.5 (3)S1—N2—C7—O30.2 (3)
S1—N2—C4—C3−87.5 (2)C4—N2—C7—C91.0 (3)
C5—C4—C3—C2−2.1 (3)S1—N2—C7—C9−178.00 (16)
N2—C4—C3—C2172.6 (2)C4—C3—C2—C11.2 (4)
C5—C4—C3—N1177.6 (2)N1—C3—C2—C1−178.6 (2)
N2—C4—C3—N1−7.7 (3)C6—C1—C2—C31.5 (4)
O1—N1—C3—C2−16.7 (3)Cl1—C1—C2—C3−177.41 (18)
O2—N1—C3—C2160.9 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O5i0.932.553.404 (3)153
C9—H9B···O3ii0.962.583.521 (3)169
Symmetry codes: (i) −x, −y+2, −z; (ii) −x+1, −y+2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O5i0.932.553.404 (3)153
C9—H9B···O3ii0.962.583.521 (3)169
Symmetry codes: (i) −x, −y+2, −z; (ii) −x+1, −y+2, −z+1.
Acknowledgements top

The authors are grateful to the PCSIR Laboratories Complex, Lahore, Pakistan, for provision of the necessary chemicals, and the Higher Education Commission of Pakistan for the purchase of the diffractometer.

references
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