1-Benzoyl-3-chloro­azepan-2-one

Liu, H.-Q.; Fan, D.-M.; Wang, D.-C.; Ou-Yang, P.-K.

doi:10.1107/S1600536809033510

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2383

doi:10.1107/S1600536809033510

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1-Benzoyl-3-chloroazepan-2-one

Hua-Quan Liu,^a Dong-Mei Fan,^a De-Cai Wang ^a ^* and Ping-Kai Ou-Yang ^a

^aState Key Laboratory of Materials-Oriented Chemical Engineering, College of Life Science and Pharmaceutical Engineering, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: dcwang@njut.edu.cn

(Received 8 August 2009; accepted 22 August 2009; online 9 September 2009)

In the crystal structure of the title compound, C₁₃H₁₄ClNO₂, intermolecular C—H⋯O interactions link the molecules into a two-dimensional network.

Related literature

For related structures, see: Tull et al. (1964 ); Largman et al. (1979 ). For ring-puckering parameters, see: Cremer & Pople (1975 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₃H₁₄ClNO₂
M_r = 251.70
Orthorhombic, P n a 2₁
a = 19.564 (4) Å
b = 7.6500 (15) Å
c = 8.4050 (17) Å
V = 1257.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 294 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.917, T_max = 0.971
2413 measured reflections
1229 independent reflections
968 reflections with I > 2σ(I)
R_int = 0.027
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.109
S = 1.01
1229 reflections
155 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983 ), 1184 Friedel pairs
Flack parameter: 0.07 (12)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯O1ⁱ	0.93	2.43	3.335 (6)	163
C12—H12A⋯O2ⁱⁱ	0.98	2.56	3.319 (5)	134
Symmetry codes: (i) x, y+1, z; (ii) $[-x, -y+1, z-{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97 and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809033510/hk2754sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809033510/hk2754Isup2.hkl

checkCIF report

Comment top

N-substituted-3-chlorocaprolactams are used as medicines and as intermediate compounds for producing various organic chemicals. We report herein the crystal structure of the title compound.

In the molecule of the title compound, (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Ring A (C1-C6) is, of course, planar, while the seven-membered ring B (N/C8-C13) is not planar, having total puckering amplitude, Q_T, of 0.841 (2) Å (Cremer & Pople, 1975).

In the crystal structure, intermolecular C-H···O interactions (Table 1) link the molecules into a two dimensional network (Fig. 2), in which they may be efective in the stabilization of the structure.

Related literature top

For related structures, see: Tull et al. (1964); Largman et al. (1979). For ring-puckering parameters, see: Cremer & Pople (1975). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was prepared according to a literature method (Tull et al., 1964). The purity of the compound was checked by determining its melting point. It was characterized by recording its infrared and NMR spectra (Largman et al., 1979). Crystals suitable for X-ray analysis were obtained from slow evaporation of an ethanol solution.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at 30% probability level.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

1-Benzoyl-3-chloroazepan-2-one top

Crystal data top

C₁₃H₁₄ClNO₂	F(000) = 528
M_r = 251.70	D_x = 1.329 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 25 reflections
a = 19.564 (4) Å	θ = 10–13°
b = 7.6500 (15) Å	µ = 0.29 mm⁻¹
c = 8.4050 (17) Å	T = 294 K
V = 1257.9 (4) Å³	Block, colorless
Z = 4	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	968 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.027
Graphite monochromator	θ_max = 25.3°, θ_min = 2.1°
ω/2θ scans	h = −23→23
Absorption correction: ψ scan (North et al., 1968)	k = 0→9
T_min = 0.917, T_max = 0.971	l = 0→10
2413 measured reflections	3 standard reflections every 120 min
1229 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.040	w = 1/[σ²(F_o²) + (0.068P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.109	(Δ/σ)_max < 0.001
S = 1.01	Δρ_max = 0.17 e Å⁻³
1229 reflections	Δρ_min = −0.16 e Å⁻³
155 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.020 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1184 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.07 (12)

Crystal data top

C₁₃H₁₄ClNO₂	V = 1257.9 (4) Å³
M_r = 251.70	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 19.564 (4) Å	µ = 0.29 mm⁻¹
b = 7.6500 (15) Å	T = 294 K
c = 8.4050 (17) Å	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	968 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.027
T_min = 0.917, T_max = 0.971	3 standard reflections every 120 min
2413 measured reflections	intensity decay: 1%
1229 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.109	Δρ_max = 0.17 e Å⁻³
S = 1.01	Δρ_min = −0.16 e Å⁻³
1229 reflections	Absolute structure: Flack (1983), 1184 Friedel pairs
155 parameters	Absolute structure parameter: 0.07 (12)
1 restraint

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
Cl	0.11953 (5)	0.57305 (14)	0.24751 (14)	0.0715 (4)
O1	−0.1309 (2)	0.1107 (4)	0.1382 (6)	0.1086 (15)
O2	−0.00941 (14)	0.4326 (3)	0.3449 (4)	0.0675 (9)
N	−0.03396 (16)	0.2690 (4)	0.1259 (4)	0.0536 (8)
C1	−0.2327 (2)	0.5048 (9)	0.3917 (8)	0.0978 (18)
H1A	−0.2664	0.4839	0.4674	0.117*
C2	−0.1934 (2)	0.3696 (7)	0.3412 (7)	0.0795 (14)
H2A	−0.2007	0.2575	0.3804	0.095*
C3	−0.14219 (19)	0.4004 (5)	0.2300 (6)	0.0595 (10)
C4	−0.1317 (2)	0.5660 (5)	0.1702 (6)	0.0682 (12)
H4A	−0.0972	0.5876	0.0968	0.082*
C5	−0.1740 (3)	0.6992 (7)	0.2223 (7)	0.0935 (17)
H5A	−0.1688	0.8113	0.1811	0.112*
C6	−0.2244 (3)	0.6671 (9)	0.3359 (9)	0.0995 (19)
H6A	−0.2520	0.7577	0.3725	0.119*
C7	−0.1033 (2)	0.2489 (5)	0.1659 (5)	0.0664 (11)
C8	−0.0071 (2)	0.1496 (5)	0.0028 (5)	0.0667 (12)
H8A	0.0183	0.2172	−0.0749	0.080*
H8B	−0.0452	0.0950	−0.0518	0.080*
C9	0.0390 (3)	0.0080 (5)	0.0694 (6)	0.0801 (14)
H9A	0.0200	−0.0327	0.1693	0.096*
H9B	0.0392	−0.0901	−0.0038	0.096*
C10	0.1113 (3)	0.0645 (6)	0.0972 (7)	0.0812 (15)
H10A	0.1315	0.0921	−0.0052	0.097*
H10B	0.1362	−0.0344	0.1402	0.097*
C11	0.1229 (2)	0.2193 (5)	0.2068 (5)	0.0695 (12)
H11A	0.1712	0.2481	0.2068	0.083*
H11B	0.1105	0.1859	0.3143	0.083*
C12	0.08196 (19)	0.3832 (4)	0.1600 (4)	0.0524 (9)
H12A	0.0820	0.3955	0.0439	0.063*
C13	0.00874 (18)	0.3694 (4)	0.2188 (4)	0.0493 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0725 (6)	0.0733 (7)	0.0686 (7)	−0.0204 (5)	0.0016 (6)	−0.0118 (7)
O1	0.103 (3)	0.0654 (18)	0.158 (5)	−0.0333 (17)	−0.006 (3)	−0.010 (3)
O2	0.0634 (16)	0.086 (2)	0.0532 (18)	−0.0064 (14)	0.0031 (14)	−0.0231 (17)
N	0.0711 (19)	0.0486 (16)	0.0411 (16)	−0.0102 (15)	−0.0084 (15)	−0.0033 (15)
C1	0.057 (3)	0.139 (5)	0.098 (4)	−0.001 (3)	−0.003 (3)	−0.006 (4)
C2	0.059 (2)	0.096 (3)	0.083 (3)	−0.016 (2)	−0.009 (3)	0.022 (3)
C3	0.0542 (19)	0.068 (2)	0.056 (2)	−0.0110 (18)	−0.015 (2)	0.007 (2)
C4	0.083 (3)	0.060 (2)	0.061 (3)	−0.007 (2)	−0.014 (2)	0.008 (2)
C5	0.120 (4)	0.068 (3)	0.093 (4)	0.007 (3)	−0.040 (4)	0.004 (3)
C6	0.066 (3)	0.116 (5)	0.117 (5)	0.027 (3)	−0.029 (4)	−0.027 (4)
C7	0.078 (3)	0.057 (2)	0.064 (3)	−0.016 (2)	−0.020 (2)	0.006 (2)
C8	0.104 (3)	0.055 (2)	0.041 (2)	−0.008 (2)	−0.009 (2)	−0.011 (2)
C9	0.141 (4)	0.047 (2)	0.052 (3)	0.003 (3)	0.000 (3)	−0.006 (2)
C10	0.115 (4)	0.056 (3)	0.073 (3)	0.022 (2)	0.009 (3)	0.007 (3)
C11	0.083 (3)	0.066 (2)	0.059 (3)	0.014 (2)	−0.006 (2)	0.005 (2)
C12	0.065 (2)	0.052 (2)	0.0396 (19)	−0.0011 (17)	0.0015 (19)	−0.0028 (17)
C13	0.062 (2)	0.0466 (18)	0.039 (2)	−0.0036 (16)	−0.0013 (17)	−0.0010 (17)

Geometric parameters (Å, º) top

Cl—C12	1.786 (4)	C5—H5A	0.9300
O1—C7	1.210 (5)	C6—H6A	0.9300
O2—C13	1.218 (5)	C8—C9	1.517 (6)
N—C7	1.406 (5)	C8—H8A	0.9700
N—C8	1.477 (5)	C8—H8B	0.9700
N—C13	1.377 (5)	C9—C10	1.497 (7)
C1—C6	1.338 (8)	C9—H9A	0.9700
C1—C2	1.357 (7)	C9—H9B	0.9700
C1—H1A	0.9300	C10—C11	1.518 (7)
C2—C3	1.390 (6)	C10—H10A	0.9700
C2—H2A	0.9300	C10—H10B	0.9700
C3—C4	1.378 (5)	C11—C12	1.539 (5)
C3—C7	1.487 (6)	C11—H11A	0.9700
C4—C5	1.384 (7)	C11—H11B	0.9700
C4—H4A	0.9300	C12—C13	1.519 (5)
C5—C6	1.394 (8)	C12—H12A	0.9800

C7—N—C8	116.3 (3)	H8A—C8—H8B	107.7
C13—N—C7	120.7 (3)	C10—C9—C8	114.4 (4)
C13—N—C8	121.7 (3)	C10—C9—H9A	108.7
C6—C1—C2	121.9 (6)	C8—C9—H9A	108.7
C6—C1—H1A	119.1	C10—C9—H9B	108.7
C2—C1—H1A	119.1	C8—C9—H9B	108.7
C1—C2—C3	119.4 (5)	H9A—C9—H9B	107.6
C1—C2—H2A	120.3	C9—C10—C11	117.5 (4)
C3—C2—H2A	120.3	C9—C10—H10A	107.9
C4—C3—C2	120.5 (4)	C11—C10—H10A	107.9
C4—C3—C7	120.5 (4)	C9—C10—H10B	107.9
C2—C3—C7	118.7 (4)	C11—C10—H10B	107.9
C3—C4—C5	118.2 (5)	H10A—C10—H10B	107.2
C3—C4—H4A	120.9	C10—C11—C12	113.8 (4)
C5—C4—H4A	120.9	C10—C11—H11A	108.8
C4—C5—C6	120.6 (5)	C12—C11—H11A	108.8
C4—C5—H5A	119.7	C10—C11—H11B	108.8
C6—C5—H5A	119.7	C12—C11—H11B	108.8
C1—C6—C5	119.3 (5)	H11A—C11—H11B	107.7
C1—C6—H6A	120.3	C13—C12—C11	110.6 (3)
C5—C6—H6A	120.3	C13—C12—Cl	108.1 (2)
O1—C7—N	118.7 (4)	C11—C12—Cl	110.0 (3)
O1—C7—C3	121.5 (4)	C13—C12—H12A	109.4
N—C7—C3	119.7 (3)	C11—C12—H12A	109.4
N—C8—C9	113.3 (3)	Cl—C12—H12A	109.4
N—C8—H8A	108.9	O2—C13—N	122.5 (4)
C9—C8—H8A	108.9	O2—C13—C12	122.0 (3)
N—C8—H8B	108.9	N—C13—C12	115.2 (3)
C9—C8—H8B	108.9

C6—C1—C2—C3	1.1 (8)	C13—N—C8—C9	60.9 (5)
C1—C2—C3—C4	−0.7 (7)	C7—N—C8—C9	−106.4 (4)
C1—C2—C3—C7	−175.1 (5)	N—C8—C9—C10	−82.1 (5)
C2—C3—C4—C5	−0.8 (7)	C8—C9—C10—C11	57.4 (6)
C7—C3—C4—C5	173.5 (4)	C9—C10—C11—C12	−53.5 (6)
C3—C4—C5—C6	2.0 (7)	C10—C11—C12—C13	80.6 (5)
C2—C1—C6—C5	0.1 (9)	C10—C11—C12—Cl	−160.0 (3)
C4—C5—C6—C1	−1.6 (8)	C7—N—C13—O2	6.3 (5)
C13—N—C7—O1	−145.6 (5)	C8—N—C13—O2	−160.5 (3)
C8—N—C7—O1	21.9 (6)	C7—N—C13—C12	−178.7 (3)
C13—N—C7—C3	38.8 (5)	C8—N—C13—C12	14.5 (5)
C8—N—C7—C3	−153.7 (4)	C11—C12—C13—O2	94.8 (4)
C4—C3—C7—O1	−136.6 (5)	Cl—C12—C13—O2	−25.7 (4)
C2—C3—C7—O1	37.8 (7)	C11—C12—C13—N	−80.3 (4)
C4—C3—C7—N	38.9 (6)	Cl—C12—C13—N	159.2 (3)
C2—C3—C7—N	−146.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O1ⁱ	0.93	2.43	3.335 (6)	163
C12—H12A···O2ⁱⁱ	0.98	2.56	3.319 (5)	134

Symmetry codes: (i) x, y+1, z; (ii) −x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₄ClNO₂
M_r	251.70
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	294
a, b, c (Å)	19.564 (4), 7.6500 (15), 8.4050 (17)
V (Å³)	1257.9 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.917, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	2413, 1229, 968
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.109, 1.01
No. of reflections	1229
No. of parameters	155
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.16
Absolute structure	Flack (1983), 1184 Friedel pairs
Absolute structure parameter	0.07 (12)

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O1ⁱ	0.93	2.43	3.335 (6)	163
C12—H12A···O2ⁱⁱ	0.98	2.56	3.319 (5)	134

Symmetry codes: (i) x, y+1, z; (ii) −x, −y+1, z−1/2.

Acknowledgements

The authors thank the Innovation Fund for Doctoral Theses (BSCX200811), Nanjing University of Technology, for support.

References

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