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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): o1265.
Published online 2009 May 14. doi:  10.1107/S1600536809017012
PMCID: PMC2969806

3-Chloro-N-cyclo­hexyl­benzamide

Abstract

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].

Related literature

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

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Object name is e-65-o1265-scheme1.jpg

Experimental

Crystal data

  • C13H16ClNO
  • M r = 237.72
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1265-efi1.jpg
  • a = 8.4963 (6) Å
  • b = 11.4891 (7) Å
  • c = 12.5318 (11) Å
  • V = 1223.29 (16) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.29 mm−1
  • T = 173 K
  • 0.38 × 0.22 × 0.22 mm

Data collection

  • Stoe IPDS II two-circle diffractometer
  • Absorption correction: multi-scan [MULABS (Spek, 2003 [triangle]; Blessing, 1995 [triangle])] T min = 0.898, T max = 0.939
  • 6758 measured reflections
  • 2737 independent reflections
  • 2429 reflections with I > 2σ(I)
  • R int = 0.035

Refinement

  • R[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.069
  • S = 0.98
  • 2737 reflections
  • 150 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.18 e Å−3
  • Δρmin = −0.17 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1128 Friedel pairs
  • Flack parameter: 0.03 (5)

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809017012/lh2817sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809017012/lh2817Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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

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.

Figures

Fig. 1.
Molecular structure of (I) showing atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
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.

Crystal data

C13H16ClNOF(000) = 504
Mr = 237.72Dx = 1.291 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 6652 reflections
a = 8.4963 (6) Åθ = 3.4–27.7°
b = 11.4891 (7) ŵ = 0.29 mm1
c = 12.5318 (11) ÅT = 173 K
V = 1223.29 (16) Å3Block, colourless
Z = 40.38 × 0.22 × 0.22 mm

Data collection

Stoe IPDS II two-circle diffractometer2737 independent reflections
Radiation source: fine-focus sealed tube2429 reflections with I > 2σ(I)
graphiteRint = 0.035
ω scansθmax = 27.5°, θmin = 3.4°
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

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.030w = 1/[σ2(Fo2) + (0.0419P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.069(Δ/σ)max = 0.001
S = 0.98Δρmax = 0.18 e Å3
2737 reflectionsΔρmin = −0.17 e Å3
150 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction 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)

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 (Å2)

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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH2817).

References

  • Allen, F. H. (2002). Acta Cryst. B58, 380–388. [PubMed]
  • 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. [PubMed]
  • 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. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • 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. [PubMed]

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