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Acta Cryst. (2009). E65, o1265    [ doi:10.1107/S1600536809017012 ]

3-Chloro-N-cyclohexylbenzamide

M. Khawar Rauf, M. Bolte and A. Badshah

Abstract top

In the title molecule, C13H16ClNO, the mean plane of the atoms in the -CONH- group forms a dihedral angle of 42.0 (4)° with the benzene ring plane. In the crystal structure, molecules are linked by intermolecular N-H...O hydrogen bonds, generating C(4) chains along [100].

Comment top

We report herein the structure of the title compound, (I) (Fig. 1), which was separated from an impure sample of thiourea by column chromatography as a byproduct, as part of our ongoing studies related to N,N'-disubstituted thioureas and heterocyclic compounds. In this class of componds, N—H···O, C—H···O and N—H···N hydrogen bonds, and weak π–π stacking interactions are the only direction-specific intermolecular interactions (Garden et al., 2005; Wardell et al., 2005). In the crystal structure, molecules form intermolecular N—H···O hydrogen bonds to generate C(4) chains (Bernstein et al., 1995) along [100] (Fig. 2). The molecules of (I) are not planar, as evidenced by the torsion angles (C21—N1—C1—O1, 2.9 (02) and C21—N1—C1—C11, -174.88 (11)°) associated with –CONH– moiety, and the amide group adopts the usual trans conformation; the bond lengths (Allen, 2002) and inter-bond angles present no unusual values.

Related literature top

For bond-length data, see: Allen (2002). For related structures, see: Garden et al. (2005); Wardell et al. (2005). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

Freshly prepared and steam distillated 3-chlorobenzoyl isothiocyanate (1.97 g, 10 mmol) was stirred in acetone (30 ml) for 20 min. Neat cyclohexylamin (1.0 g, 10 mmol) was then added and the resulting mixture was stirred for 1 h. The reaction mixture was then poured into 300 ml (approx.) acidified (pH 4) water and stirred well. The solid product was separated and washed with deionized water. One of the fraction obtained during the column chromatography of the target thiourea was recrystallized from methanol/1,1-dichloromethane (1:10 v/v) to give fine crystals of (I), with an overall fractional yield of 15%.

Refinement top

H atoms bonded to C were included in calculated positions and refined as riding on their parent C atom with C—H ranging from 0.93 Å to 1.0 Å and Uiso(H) = 1.2Ueq(C). The H atom bonded to N was freely refined.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) showing atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Part of the crystal structure of (I) viewed onto the ac plane. H atoms are omitted for clarity. Dashed lines are drawn between the non-hydrogen donor and acceptor atoms of hydrogen bonds.
3-Chloro-N-cyclohexylbenzamide top
Crystal data top
C13H16ClNOF000 = 504
Mr = 237.72Dx = 1.291 Mg m−3
Orthorhombic, P212121Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 6652 reflections
a = 8.4963 (6) Åθ = 3.4–27.7º
b = 11.4891 (7) ŵ = 0.29 mm−1
c = 12.5318 (11) ÅT = 173 K
V = 1223.29 (16) Å3Block, colourless
Z = 40.38 × 0.22 × 0.22 mm
Data collection top
Stoe IPDS II two-circle
diffractometer		2737 independent reflections
Radiation source: fine-focus sealed tube2429 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.035
T = 173 Kθmax = 27.5º
ω scansθmin = 3.4º
Absorption correction: multi-scan
[MULABS (Spek, 2003; Blessing, 1995)]		h = −11→11
Tmin = 0.898, Tmax = 0.939k = −14→11
6758 measured reflectionsl = −16→13
Refinement top
Refinement on F2H atoms treated by a mixture of
independent and constrained refinement
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.0419P)2]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.030(Δ/σ)max = 0.001
wR(F2) = 0.069Δρmax = 0.18 e Å−3
S = 0.98Δρmin = −0.17 e Å−3
2737 reflectionsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
150 parametersExtinction coefficient: 0.021 (2)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1128 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.03 (5)
Hydrogen site location: inferred from neighbouring sites
Crystal data top
C13H16ClNOV = 1223.29 (16) Å3
Mr = 237.72Z = 4
Orthorhombic, P212121Mo Kα
a = 8.4963 (6) ŵ = 0.29 mm−1
b = 11.4891 (7) ÅT = 173 K
c = 12.5318 (11) Å0.38 × 0.22 × 0.22 mm
Data collection top
Stoe IPDS II two-circle
diffractometer		2737 independent reflections
Absorption correction: multi-scan
[MULABS (Spek, 2003; Blessing, 1995)]		2429 reflections with I > 2σ(I)
Tmin = 0.898, Tmax = 0.939Rint = 0.035
6758 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.030H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.069Δρmax = 0.18 e Å−3
S = 0.98Δρmin = −0.17 e Å−3
2737 reflectionsAbsolute structure: Flack (1983), 1128 Friedel pairs
150 parametersFlack parameter: 0.03 (5)
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
Cl10.70767 (6)1.17100 (4)0.53982 (4)0.04673 (13)
C10.54914 (14)0.73267 (12)0.53979 (11)0.0203 (3)
O10.43572 (10)0.67397 (9)0.56950 (7)0.0245 (2)
N10.63351 (13)0.70808 (10)0.45221 (9)0.0233 (2)
H10.720 (2)0.7470 (16)0.4421 (13)0.028 (4)*
C110.59541 (13)0.84022 (13)0.60027 (10)0.0208 (3)
C120.63710 (15)0.94177 (12)0.54747 (11)0.0233 (3)
H120.64740.94250.47200.028*
C130.66355 (15)1.04213 (13)0.60606 (11)0.0260 (3)
C140.65300 (16)1.04247 (14)0.71660 (12)0.0289 (3)
H140.67271.11170.75580.035*
C150.61351 (17)0.94075 (15)0.76869 (12)0.0300 (3)
H150.60690.93990.84440.036*
C160.58335 (14)0.83946 (14)0.71154 (11)0.0253 (3)
H160.55470.77010.74790.030*
C210.59346 (14)0.61160 (13)0.38088 (11)0.0218 (3)
H210.47780.59660.38680.026*
C220.62972 (17)0.64688 (13)0.26615 (11)0.0274 (3)
H22A0.74310.66540.25940.033*
H22B0.56900.71760.24760.033*
C230.58727 (17)0.54859 (16)0.18917 (12)0.0334 (4)
H23A0.47220.53530.19110.040*
H23B0.61610.57170.11560.040*
C240.67181 (18)0.43660 (15)0.21786 (13)0.0340 (3)
H24A0.78650.44710.20800.041*
H24B0.63670.37350.16960.041*
C250.6385 (2)0.40235 (15)0.33291 (14)0.0373 (4)
H25A0.70050.33220.35110.045*
H25B0.52550.38270.34050.045*
C260.68006 (17)0.50066 (13)0.41084 (12)0.0292 (3)
H26A0.65080.47740.48430.035*
H26B0.79500.51480.40920.035*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0806 (3)0.02269 (18)0.0369 (2)−0.00841 (19)−0.0039 (2)0.00076 (18)
C10.0225 (5)0.0208 (7)0.0176 (5)0.0040 (5)−0.0026 (5)0.0014 (6)
O10.0244 (4)0.0256 (5)0.0236 (5)−0.0026 (4)0.0023 (3)0.0014 (4)
N10.0236 (5)0.0234 (6)0.0227 (5)−0.0043 (4)0.0028 (4)−0.0057 (5)
C110.0203 (5)0.0220 (7)0.0202 (6)0.0036 (5)−0.0005 (4)−0.0031 (6)
C120.0267 (5)0.0245 (7)0.0188 (6)0.0028 (5)−0.0008 (5)−0.0020 (6)
C130.0304 (6)0.0213 (7)0.0261 (7)0.0022 (5)−0.0023 (5)−0.0004 (6)
C140.0312 (6)0.0291 (8)0.0264 (7)0.0030 (6)−0.0031 (5)−0.0095 (6)
C150.0318 (7)0.0391 (9)0.0190 (6)0.0012 (6)−0.0012 (5)−0.0058 (6)
C160.0273 (6)0.0292 (8)0.0195 (6)0.0012 (5)0.0002 (5)0.0004 (6)
C210.0231 (6)0.0224 (7)0.0199 (6)−0.0027 (5)−0.0008 (5)−0.0054 (5)
C220.0355 (7)0.0253 (7)0.0214 (6)0.0044 (6)−0.0006 (5)0.0001 (6)
C230.0360 (7)0.0433 (10)0.0208 (7)0.0010 (7)−0.0008 (5)−0.0076 (7)
C240.0391 (8)0.0306 (8)0.0322 (7)−0.0025 (6)0.0058 (6)−0.0122 (7)
C250.0532 (9)0.0209 (8)0.0377 (9)−0.0028 (7)0.0057 (7)−0.0048 (7)
C260.0393 (7)0.0229 (8)0.0254 (7)−0.0008 (6)−0.0016 (6)0.0018 (6)
Geometric parameters (Å, °) top
Cl1—C131.7383 (16)C21—C221.5253 (19)
C1—O11.2337 (16)C21—H211.0000
C1—N11.3410 (17)C22—C231.528 (2)
C1—C111.5020 (18)C22—H22A0.9900
N1—C211.4641 (17)C22—H22B0.9900
N1—H10.868 (18)C23—C241.517 (3)
C11—C121.387 (2)C23—H23A0.9900
C11—C161.3982 (18)C23—H23B0.9900
C12—C131.385 (2)C24—C251.521 (2)
C12—H120.9500C24—H24A0.9900
C13—C141.388 (2)C24—H24B0.9900
C14—C151.380 (2)C25—C261.534 (2)
C14—H140.9500C25—H25A0.9900
C15—C161.390 (2)C25—H25B0.9900
C15—H150.9500C26—H26A0.9900
C16—H160.9500C26—H26B0.9900
C21—C261.519 (2)
O1—C1—N1123.32 (13)C21—C22—C23110.54 (13)
O1—C1—C11120.12 (11)C21—C22—H22A109.5
N1—C1—C11116.52 (11)C23—C22—H22A109.5
C1—N1—C21122.34 (11)C21—C22—H22B109.5
C1—N1—H1117.6 (11)C23—C22—H22B109.5
C21—N1—H1119.8 (11)H22A—C22—H22B108.1
C12—C11—C16119.98 (13)C24—C23—C22111.43 (12)
C12—C11—C1121.20 (11)C24—C23—H23A109.3
C16—C11—C1118.62 (13)C22—C23—H23A109.3
C13—C12—C11119.25 (12)C24—C23—H23B109.3
C13—C12—H12120.4C22—C23—H23B109.3
C11—C12—H12120.4H23A—C23—H23B108.0
C12—C13—C14121.38 (14)C23—C24—C25110.85 (13)
C12—C13—Cl1119.39 (11)C23—C24—H24A109.5
C14—C13—Cl1119.22 (12)C25—C24—H24A109.5
C15—C14—C13119.04 (14)C23—C24—H24B109.5
C15—C14—H14120.5C25—C24—H24B109.5
C13—C14—H14120.5H24A—C24—H24B108.1
C14—C15—C16120.66 (13)C24—C25—C26111.71 (13)
C14—C15—H15119.7C24—C25—H25A109.3
C16—C15—H15119.7C26—C25—H25A109.3
C15—C16—C11119.67 (15)C24—C25—H25B109.3
C15—C16—H16120.2C26—C25—H25B109.3
C11—C16—H16120.2H25A—C25—H25B107.9
N1—C21—C26111.83 (11)C21—C26—C25110.41 (13)
N1—C21—C22109.11 (11)C21—C26—H26A109.6
C26—C21—C22110.99 (11)C25—C26—H26A109.6
N1—C21—H21108.3C21—C26—H26B109.6
C26—C21—H21108.3C25—C26—H26B109.6
C22—C21—H21108.3H26A—C26—H26B108.1
O1—C1—N1—C212.9 (2)C14—C15—C16—C110.9 (2)
C11—C1—N1—C21−174.88 (11)C12—C11—C16—C15−0.08 (19)
O1—C1—C11—C12−137.24 (12)C1—C11—C16—C15−174.93 (12)
N1—C1—C11—C1240.62 (17)C1—N1—C21—C26−92.52 (14)
O1—C1—C11—C1637.55 (17)C1—N1—C21—C22144.31 (12)
N1—C1—C11—C16−144.60 (12)N1—C21—C22—C23−179.27 (11)
C16—C11—C12—C13−1.17 (19)C26—C21—C22—C2357.06 (15)
C1—C11—C12—C13173.54 (11)C21—C22—C23—C24−56.47 (16)
C11—C12—C13—C141.6 (2)C22—C23—C24—C2555.47 (17)
C11—C12—C13—Cl1−177.30 (9)C23—C24—C25—C26−55.16 (18)
C12—C13—C14—C15−0.8 (2)N1—C21—C26—C25−178.62 (12)
Cl1—C13—C14—C15178.16 (10)C22—C21—C26—C25−56.52 (15)
C13—C14—C15—C16−0.5 (2)C24—C25—C26—C2155.74 (17)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.868 (18)2.052 (18)2.9161 (15)173.3 (16)
Symmetry codes: (i) x+1/2, −y+3/2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.868 (18)2.052 (18)2.9161 (15)173.3 (16)
Symmetry codes: (i) x+1/2, −y+3/2, −z+1.
Acknowledgements top

MKR is grateful to the HEC, Pakistan, for financial support for a PhD program under scholarship No. ILC-0363104.

references
References top

Allen, F. H. (2002). Acta Cryst. B58, 380–388.

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.

Blessing, R. H. (1995). Acta Cryst. A51, 33–38.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Garden, S. J., Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2005). Acta Cryst. C61, o450–o451.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany.

Wardell, J. L., Skakle, J. M. S., Low, J. N. & Glidewell, C. (2005). Acta Cryst. C61, o634–o638.