PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 February 1; 66(Pt 2): o438.
Published online 2010 January 23. doi:  10.1107/S1600536810002060
PMCID: PMC2979924

3-Chloro­azepan-2-one

Abstract

In the title compound, C6H10ClNO, an inter­mediate for the production of lysine, there are intra­molecular C—H(...)Cl hydrogen bonds.

Related literature

For the preparation of the title compound, see: Wineman et al. (1958 [triangle]). For puckering parameters, see: Cremer & Pople (1975 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o438-scheme1.jpg

Experimental

Crystal data

  • C6H10ClNO
  • M r = 147.60
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o438-efi1.jpg
  • a = 18.776 (4) Å
  • b = 7.3440 (15) Å
  • c = 11.109 (2) Å
  • β = 103.65 (3)°
  • V = 1488.6 (5) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.43 mm−1
  • T = 293 K
  • 0.30 × 0.20 × 0.20 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.881, T max = 0.918
  • 2654 measured reflections
  • 1345 independent reflections
  • 1107 reflections with I > 2σ(I)
  • R int = 0.020
  • 3 standard reflections every 200 reflections intensity decay: 1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.148
  • S = 1.01
  • 1345 reflections
  • 82 parameters
  • H-atom parameters constrained
  • Δρmax = 0.36 e Å−3
  • Δρmin = −0.33 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810002060/gw2071sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810002060/gw2071Isup2.hkl

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

Acknowledgments

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

supplementary crystallographic information

Comment

Some derivatives of 3-chloroazepan-2-one is important chemical material. We report here the crystal structure of the title compound, (I). The molecular structure of (I) is shown in Fig. 1, and the selected geometric parameters are given in Table 1. The bond lengths and angles (Table 1) are within normal ranges (Allen et al., 1987). The seven-membered ring A (N/C1-C6) is not planar, having total puckering amplitude, QT, of 0.702 (2) Å (Cremer & Pople, 1975).

The molecular structure of (I) is shown in Fig. 1. A packing diagram of (I) is shown in Fig. 2, where the dash line indicates C—H···Cl hydrogen bond.

Experimental

18.2 g (100 mmol) 3,3-dichloro-2-oxohexamethyleneimine, 2 g. 5% palladium-on-charcoal and 18 g. (220 mmol) sodium acetate were added into 100 ml glacial acetic acid. The mixture was placed in in a shaker under hydrogen (2 atm. initial pressure) until one equivalent of hydrogen was absorbed. The catalyst and sodium chloride were removed by filtration. The filtrate was neutralized and extracted with chloroform and concentrated, and then recrystallized by n-hexane to give 18.1g white solid (87.4%). (Wineman et al., 1958) Pure compound (I) was obstained by crystallizing from acetic acid. Crystals of (I) suitable for X-ray diffraction were obstained by slow evaporation of an ethanol solution.

Refinement

All H atoms bonded to the C atoms were placed geometrically at the distances of 0.93–0.97 Å, and included in the refinement in riding motion approximation with Uiso(H) = 1.2 or 1.5Ueq of the carrier atom.

Figures

Fig. 1.
The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids at the 30% probability level.
Fig. 2.
A packing diagram of (I). The intermolecular hydrogen bonds are shown as dashed lines.

Crystal data

C6H10ClNOF(000) = 624
Mr = 147.60Dx = 1.317 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 25 reflections
a = 18.776 (4) Åθ = 9–14°
b = 7.3440 (15) ŵ = 0.43 mm1
c = 11.109 (2) ÅT = 293 K
β = 103.65 (3)°Block, colourless
V = 1488.6 (5) Å30.30 × 0.20 × 0.20 mm
Z = 8

Data collection

Enraf–Nonius CAD-4 diffractometer1107 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.020
graphiteθmax = 25.3°, θmin = 2.2°
ω/2θ scansh = 0→22
Absorption correction: ψ scan (North et al., 1968)k = −8→8
Tmin = 0.881, Tmax = 0.918l = −13→12
2654 measured reflections3 standard reflections every 200 reflections
1345 independent reflections intensity decay: 1%

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.148H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.1P)2 + 0.650P] where P = (Fo2 + 2Fc2)/3
1345 reflections(Δ/σ)max < 0.001
82 parametersΔρmax = 0.36 e Å3
0 restraintsΔρmin = −0.33 e Å3

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
Cl0.05987 (4)0.14400 (11)0.65254 (6)0.0703 (3)
O0.24623 (10)0.2773 (2)0.75479 (18)0.0609 (5)
N0.17420 (10)0.4720 (2)0.62946 (16)0.0436 (5)
H0A0.20350.55670.66450.052*
C10.08706 (17)0.2590 (4)0.3877 (2)0.0647 (8)
H1A0.08400.22640.30200.078*
H1B0.03830.24710.40220.078*
C20.11018 (17)0.4574 (4)0.4058 (2)0.0671 (8)
H2A0.15870.47020.39060.081*
H2B0.07680.53050.34460.081*
C30.11132 (14)0.5312 (3)0.5331 (2)0.0552 (7)
H3A0.11130.66320.52950.066*
H3B0.06680.49360.55600.066*
C40.19194 (12)0.3048 (3)0.66976 (19)0.0402 (5)
C50.14703 (13)0.1426 (3)0.6099 (2)0.0458 (6)
H5A0.17310.03340.64750.055*
C60.13727 (15)0.1235 (4)0.4704 (2)0.0579 (7)
H6B0.18530.13200.45250.069*
H6A0.11880.00210.44690.069*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl0.0684 (5)0.0767 (6)0.0696 (5)−0.0248 (4)0.0237 (4)0.0048 (3)
O0.0615 (10)0.0416 (9)0.0627 (10)0.0047 (8)−0.0190 (9)0.0013 (8)
N0.0462 (10)0.0336 (10)0.0451 (10)−0.0026 (8)−0.0014 (8)0.0018 (8)
C10.0739 (18)0.0727 (18)0.0402 (13)−0.0032 (15)−0.0014 (12)−0.0069 (12)
C20.0781 (19)0.0712 (18)0.0448 (14)−0.0010 (15)−0.0001 (13)0.0173 (12)
C30.0559 (14)0.0410 (13)0.0606 (15)0.0059 (11)−0.0024 (12)0.0090 (11)
C40.0426 (11)0.0364 (11)0.0389 (11)0.0013 (9)0.0040 (9)0.0006 (9)
C50.0488 (12)0.0370 (11)0.0469 (12)−0.0012 (10)0.0022 (10)0.0003 (10)
C60.0648 (16)0.0545 (15)0.0516 (14)−0.0012 (12)0.0084 (12)−0.0158 (11)

Geometric parameters (Å, °)

Cl—C51.808 (3)C2—H2A0.9700
O—C41.232 (3)C2—H2B0.9700
N—C41.322 (3)C3—H3A0.9700
N—C31.460 (3)C3—H3B0.9700
N—H0A0.8600C4—C51.519 (3)
C1—C21.520 (4)C5—C61.524 (3)
C1—C61.521 (4)C5—H5A0.9800
C1—H1A0.9700C6—H6B0.9700
C1—H1B0.9700C6—H6A0.9700
C2—C31.510 (4)
C4—N—C3128.35 (19)N—C3—H3B108.7
C4—N—H0A115.8C2—C3—H3B108.7
C3—N—H0A115.8H3A—C3—H3B107.6
C2—C1—C6115.5 (2)O—C4—N120.6 (2)
C2—C1—H1A108.4O—C4—C5118.68 (19)
C6—C1—H1A108.4N—C4—C5120.71 (18)
C2—C1—H1B108.4C4—C5—C6116.0 (2)
C6—C1—H1B108.4C4—C5—Cl108.92 (15)
H1A—C1—H1B107.5C6—C5—Cl111.58 (17)
C3—C2—C1114.1 (2)C4—C5—H5A106.6
C3—C2—H2A108.7C6—C5—H5A106.6
C1—C2—H2A108.7Cl—C5—H5A106.6
C3—C2—H2B108.7C1—C6—C5117.6 (2)
C1—C2—H2B108.7C1—C6—H6B107.9
H2A—C2—H2B107.6C5—C6—H6B107.9
N—C3—C2114.2 (2)C1—C6—H6A107.9
N—C3—H3A108.7C5—C6—H6A107.9
C2—C3—H3A108.7H6B—C6—H6A107.2
C6—C1—C2—C3−62.8 (3)N—C4—C5—C655.0 (3)
C4—N—C3—C2−63.1 (3)O—C4—C5—Cl109.8 (2)
C1—C2—C3—N76.1 (3)N—C4—C5—Cl−71.8 (2)
C3—N—C4—O−178.0 (2)C2—C1—C6—C561.3 (4)
C3—N—C4—C53.6 (4)C4—C5—C6—C1−71.6 (3)
O—C4—C5—C6−123.4 (2)Cl—C5—C6—C153.9 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C1—H1B···Cl0.972.823.215 (3)105
C3—H3B···Cl0.972.803.374 (3)119

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GW2071).

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.
  • Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc.97, 1354–1358.
  • Enraf–Nonius (1989). CAD-4 Software Enraf–Nonius, Delft, The Netherlands.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
  • Wineman, R. J., Hsu, E.-P. T. & Anagnostopoulos, C. E. (1958). J. Am. Chem. Soc.80, 6233–6237.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography