3-Chloro-N-cyclo­hexyl­benzamide

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

doi:10.1107/S1600536809017012

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1265

doi:10.1107/S1600536809017012

Open

access

3-Chloro-N-cyclohexylbenzamide

M. Khawar Rauf,^a Michael Bolte ^b and Amin Badshah ^c ^*

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, ^bInstitut für Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany, and ^cDepartment of Chemistry, Islamia University of Bahawalpur, Pakistan
^*Correspondence e-mail: aminbadshah@yahoo.com

(Received 29 April 2009; accepted 5 May 2009; online 14 May 2009)

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

Experimental

Crystal data

C₁₃H₁₆ClNO
M_r = 237.72
Orthorhombic, P 2₁ 2₁ 2₁
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 ; Blessing, 1995 )] 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[F² > 2σ(F²)] = 0.030
wR(F²) = 0.069
S = 0.98
2737 reflections
150 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ), 1128 Friedel pairs
Flack parameter: 0.03 (5)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.868 (18)	2.052 (18)	2.9161 (15)	173.3 (16)
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Data collection: X-AREA (Stoe & Cie, 2001 ); cell refinement: X-AREA; data reduction: X-AREA; 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.

Supporting information

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

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

checkCIF report

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%.

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

	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.

3-Chloro-N-cyclohexylbenzamide top

Crystal data top

C₁₃H₁₆ClNO	F(000) = 504
M_r = 237.72	D_x = 1.291 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6652 reflections
a = 8.4963 (6) Å	θ = 3.4–27.7°
b = 11.4891 (7) Å	µ = 0.29 mm⁻¹
c = 12.5318 (11) Å	T = 173 K
V = 1223.29 (16) Å³	Block, colourless
Z = 4	0.38 × 0.22 × 0.22 mm

Data collection top

Stoe IPDS II two-circle diffractometer	2737 independent reflections
Radiation source: fine-focus sealed tube	2429 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω scans	θ_max = 27.5°, θ_min = 3.4°
Absorption correction: multi-scan [MULABS (Spek, 2003; Blessing, 1995)]	h = −11→11
T_min = 0.898, T_max = 0.939	k = −14→11
6758 measured reflections	l = −16→13

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.030	w = 1/[σ²(F_o²) + (0.0419P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.069	(Δ/σ)_max = 0.001
S = 0.98	Δρ_max = 0.18 e Å⁻³
2737 reflections	Δρ_min = −0.17 e Å⁻³
150 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.021 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1128 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.03 (5)

Crystal data top

C₁₃H₁₆ClNO	V = 1223.29 (16) Å³
M_r = 237.72	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.4963 (6) Å	µ = 0.29 mm⁻¹
b = 11.4891 (7) Å	T = 173 K
c = 12.5318 (11) Å	0.38 × 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)
T_min = 0.898, T_max = 0.939	R_int = 0.035
6758 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.069	Δρ_max = 0.18 e Å⁻³
S = 0.98	Δρ_min = −0.17 e Å⁻³
2737 reflections	Absolute structure: Flack (1983), 1128 Friedel pairs
150 parameters	Absolute structure parameter: 0.03 (5)
0 restraints

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

	x	y	z	U_iso*/U_eq
Cl1	0.70767 (6)	1.17100 (4)	0.53982 (4)	0.04673 (13)
C1	0.54914 (14)	0.73267 (12)	0.53979 (11)	0.0203 (3)
O1	0.43572 (10)	0.67397 (9)	0.56950 (7)	0.0245 (2)
N1	0.63351 (13)	0.70808 (10)	0.45221 (9)	0.0233 (2)
H1	0.720 (2)	0.7470 (16)	0.4421 (13)	0.028 (4)*
C11	0.59541 (13)	0.84022 (13)	0.60027 (10)	0.0208 (3)
C12	0.63710 (15)	0.94177 (12)	0.54747 (11)	0.0233 (3)
H12	0.6474	0.9425	0.4720	0.028*
C13	0.66355 (15)	1.04213 (13)	0.60606 (11)	0.0260 (3)
C14	0.65300 (16)	1.04247 (14)	0.71660 (12)	0.0289 (3)
H14	0.6727	1.1117	0.7558	0.035*
C15	0.61351 (17)	0.94075 (15)	0.76869 (12)	0.0300 (3)
H15	0.6069	0.9399	0.8444	0.036*
C16	0.58335 (14)	0.83946 (14)	0.71154 (11)	0.0253 (3)
H16	0.5547	0.7701	0.7479	0.030*
C21	0.59346 (14)	0.61160 (13)	0.38088 (11)	0.0218 (3)
H21	0.4778	0.5966	0.3868	0.026*
C22	0.62972 (17)	0.64688 (13)	0.26615 (11)	0.0274 (3)
H22A	0.7431	0.6654	0.2594	0.033*
H22B	0.5690	0.7176	0.2476	0.033*
C23	0.58727 (17)	0.54859 (16)	0.18917 (12)	0.0334 (4)
H23A	0.4722	0.5353	0.1911	0.040*
H23B	0.6161	0.5717	0.1156	0.040*
C24	0.67181 (18)	0.43660 (15)	0.21786 (13)	0.0340 (3)
H24A	0.7865	0.4471	0.2080	0.041*
H24B	0.6367	0.3735	0.1696	0.041*
C25	0.6385 (2)	0.40235 (15)	0.33291 (14)	0.0373 (4)
H25A	0.7005	0.3322	0.3511	0.045*
H25B	0.5255	0.3827	0.3405	0.045*
C26	0.68006 (17)	0.50066 (13)	0.41084 (12)	0.0292 (3)
H26A	0.6508	0.4774	0.4843	0.035*
H26B	0.7950	0.5148	0.4092	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0806 (3)	0.02269 (18)	0.0369 (2)	−0.00841 (19)	−0.0039 (2)	0.00076 (18)
C1	0.0225 (5)	0.0208 (7)	0.0176 (5)	0.0040 (5)	−0.0026 (5)	0.0014 (6)
O1	0.0244 (4)	0.0256 (5)	0.0236 (5)	−0.0026 (4)	0.0023 (3)	0.0014 (4)
N1	0.0236 (5)	0.0234 (6)	0.0227 (5)	−0.0043 (4)	0.0028 (4)	−0.0057 (5)
C11	0.0203 (5)	0.0220 (7)	0.0202 (6)	0.0036 (5)	−0.0005 (4)	−0.0031 (6)
C12	0.0267 (5)	0.0245 (7)	0.0188 (6)	0.0028 (5)	−0.0008 (5)	−0.0020 (6)
C13	0.0304 (6)	0.0213 (7)	0.0261 (7)	0.0022 (5)	−0.0023 (5)	−0.0004 (6)
C14	0.0312 (6)	0.0291 (8)	0.0264 (7)	0.0030 (6)	−0.0031 (5)	−0.0095 (6)
C15	0.0318 (7)	0.0391 (9)	0.0190 (6)	0.0012 (6)	−0.0012 (5)	−0.0058 (6)
C16	0.0273 (6)	0.0292 (8)	0.0195 (6)	0.0012 (5)	0.0002 (5)	0.0004 (6)
C21	0.0231 (6)	0.0224 (7)	0.0199 (6)	−0.0027 (5)	−0.0008 (5)	−0.0054 (5)
C22	0.0355 (7)	0.0253 (7)	0.0214 (6)	0.0044 (6)	−0.0006 (5)	0.0001 (6)
C23	0.0360 (7)	0.0433 (10)	0.0208 (7)	0.0010 (7)	−0.0008 (5)	−0.0076 (7)
C24	0.0391 (8)	0.0306 (8)	0.0322 (7)	−0.0025 (6)	0.0058 (6)	−0.0122 (7)
C25	0.0532 (9)	0.0209 (8)	0.0377 (9)	−0.0028 (7)	0.0057 (7)	−0.0048 (7)
C26	0.0393 (7)	0.0229 (8)	0.0254 (7)	−0.0008 (6)	−0.0016 (6)	0.0018 (6)

Geometric parameters (Å, º) top

Cl1—C13	1.7383 (16)	C21—C22	1.5253 (19)
C1—O1	1.2337 (16)	C21—H21	1.0000
C1—N1	1.3410 (17)	C22—C23	1.528 (2)
C1—C11	1.5020 (18)	C22—H22A	0.9900
N1—C21	1.4641 (17)	C22—H22B	0.9900
N1—H1	0.868 (18)	C23—C24	1.517 (3)
C11—C12	1.387 (2)	C23—H23A	0.9900
C11—C16	1.3982 (18)	C23—H23B	0.9900
C12—C13	1.385 (2)	C24—C25	1.521 (2)
C12—H12	0.9500	C24—H24A	0.9900
C13—C14	1.388 (2)	C24—H24B	0.9900
C14—C15	1.380 (2)	C25—C26	1.534 (2)
C14—H14	0.9500	C25—H25A	0.9900
C15—C16	1.390 (2)	C25—H25B	0.9900
C15—H15	0.9500	C26—H26A	0.9900
C16—H16	0.9500	C26—H26B	0.9900
C21—C26	1.519 (2)

O1—C1—N1	123.32 (13)	C21—C22—C23	110.54 (13)
O1—C1—C11	120.12 (11)	C21—C22—H22A	109.5
N1—C1—C11	116.52 (11)	C23—C22—H22A	109.5
C1—N1—C21	122.34 (11)	C21—C22—H22B	109.5
C1—N1—H1	117.6 (11)	C23—C22—H22B	109.5
C21—N1—H1	119.8 (11)	H22A—C22—H22B	108.1
C12—C11—C16	119.98 (13)	C24—C23—C22	111.43 (12)
C12—C11—C1	121.20 (11)	C24—C23—H23A	109.3
C16—C11—C1	118.62 (13)	C22—C23—H23A	109.3
C13—C12—C11	119.25 (12)	C24—C23—H23B	109.3
C13—C12—H12	120.4	C22—C23—H23B	109.3
C11—C12—H12	120.4	H23A—C23—H23B	108.0
C12—C13—C14	121.38 (14)	C23—C24—C25	110.85 (13)
C12—C13—Cl1	119.39 (11)	C23—C24—H24A	109.5
C14—C13—Cl1	119.22 (12)	C25—C24—H24A	109.5
C15—C14—C13	119.04 (14)	C23—C24—H24B	109.5
C15—C14—H14	120.5	C25—C24—H24B	109.5
C13—C14—H14	120.5	H24A—C24—H24B	108.1
C14—C15—C16	120.66 (13)	C24—C25—C26	111.71 (13)
C14—C15—H15	119.7	C24—C25—H25A	109.3
C16—C15—H15	119.7	C26—C25—H25A	109.3
C15—C16—C11	119.67 (15)	C24—C25—H25B	109.3
C15—C16—H16	120.2	C26—C25—H25B	109.3
C11—C16—H16	120.2	H25A—C25—H25B	107.9
N1—C21—C26	111.83 (11)	C21—C26—C25	110.41 (13)
N1—C21—C22	109.11 (11)	C21—C26—H26A	109.6
C26—C21—C22	110.99 (11)	C25—C26—H26A	109.6
N1—C21—H21	108.3	C21—C26—H26B	109.6
C26—C21—H21	108.3	C25—C26—H26B	109.6
C22—C21—H21	108.3	H26A—C26—H26B	108.1

O1—C1—N1—C21	2.9 (2)	C14—C15—C16—C11	0.9 (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—C12	40.62 (17)	C1—N1—C21—C26	−92.52 (14)
O1—C1—C11—C16	37.55 (17)	C1—N1—C21—C22	144.31 (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—C23	57.06 (15)
C1—C11—C12—C13	173.54 (11)	C21—C22—C23—C24	−56.47 (16)
C11—C12—C13—C14	1.6 (2)	C22—C23—C24—C25	55.47 (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—C15	178.16 (10)	C22—C21—C26—C25	−56.52 (15)
C13—C14—C15—C16	−0.5 (2)	C24—C25—C26—C21	55.74 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.868 (18)	2.052 (18)	2.9161 (15)	173.3 (16)

Symmetry code: (i) x+1/2, −y+3/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₆ClNO
M_r	237.72
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	173
a, b, c (Å)	8.4963 (6), 11.4891 (7), 12.5318 (11)
V (Å³)	1223.29 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.38 × 0.22 × 0.22

Data collection
Diffractometer	Stoe IPDS II two-circle diffractometer
Absorption correction	Multi-scan [MULABS (Spek, 2003; Blessing, 1995)]
T_min, T_max	0.898, 0.939
No. of measured, independent and observed [I > 2σ(I)] reflections	6758, 2737, 2429
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.069, 0.98
No. of reflections	2737
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)	0.18, −0.17
Absolute structure	Flack (1983), 1128 Friedel pairs
Absolute structure parameter	0.03 (5)

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL-Plus (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.868 (18)	2.052 (18)	2.9161 (15)	173.3 (16)

Symmetry code: (i) x+1/2, −y+3/2, −z+1.

Acknowledgements

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

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Garden, S. J., Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2005). Acta Cryst. C61, o450–o451. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany. Google Scholar
Wardell, J. L., Skakle, J. M. S., Low, J. N. & Glidewell, C. (2005). Acta Cryst. C61, o634–o638. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar