organic compounds
1-Benzoyl-3-chloroazepan-2-one
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
In the 13H14ClNO2, intermolecular C—H⋯O interactions link the molecules into a two-dimensional network.
of the title compound, CRelated 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
|
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell 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
10.1107/S1600536809033510/hk2754sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809033510/hk2754Isup2.hkl
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.
H atoms were positioned geometrically with C-H = 0.93, 0.98 and 0.97 Å for aromatic, methine and methylene H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell
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).C13H14ClNO2 | F(000) = 528 |
Mr = 251.70 | Dx = 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 |
Enraf–Nonius CAD-4 diffractometer | 968 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.027 |
Graphite monochromator | θmax = 25.3°, θmin = 2.1° |
ω/2θ scans | h = −23→23 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→9 |
Tmin = 0.917, Tmax = 0.971 | l = 0→10 |
2413 measured reflections | 3 standard reflections every 120 min |
1229 independent reflections | intensity decay: 1% |
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(Fo2) + (0.068P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.109 | (Δ/σ)max < 0.001 |
S = 1.01 | Δρmax = 0.17 e Å−3 |
1229 reflections | Δρmin = −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) |
C13H14ClNO2 | V = 1257.9 (4) Å3 |
Mr = 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 |
Enraf–Nonius CAD-4 diffractometer | 968 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.027 |
Tmin = 0.917, Tmax = 0.971 | 3 standard reflections every 120 min |
2413 measured reflections | intensity decay: 1% |
1229 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.109 | Δρmax = 0.17 e Å−3 |
S = 1.01 | Δρmin = −0.16 e Å−3 |
1229 reflections | Absolute structure: Flack (1983), 1184 Friedel pairs |
155 parameters | Absolute structure parameter: 0.07 (12) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.917, 0.971 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2413, 1229, 968 |
Rint | 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 |
Δρmax, Δρmin (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).
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
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Largman, T., Sifniades, S. & Schmehl, L. J. (1979). Synth. Commun. 9, 255–259. CrossRef CAS Web of Science Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tull, R., O'Neill, R. C., McCarthy, E. P., Pappas, J. J. & Chemerda, J. M. (1964). J. Org. Chem. 29, 2425–2426. CrossRef CAS Web of Science Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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, QT, 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.