3-Chloro­azepan-2-one

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

doi:10.1107/S1600536810002060

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o438

https://doi.org/10.1107/S1600536810002060

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3-Chloroazepan-2-one

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

^aState Key Laboratory of Materials-Oriented Chemcial 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 6 October 2009; accepted 16 January 2010; online 23 January 2010)

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 ). For puckering parameters, see: Cremer & Pople (1975 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₆H₁₀ClNO
M_r = 147.60
Monoclinic, C 2/c
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 ) 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[F² > 2σ(F²)] = 0.044
wR(F²) = 0.148
S = 1.01
1345 reflections
82 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1B⋯Cl	0.97	2.82	3.215 (3)	105
C3—H3B⋯Cl	0.97	2.80	3.374 (3)	119

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810002060/gw2071Isup2.hkl

checkCIF report

Comment top

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, Q_T, 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.

Related literature top

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

Experimental top

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.

Structure description top

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.

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

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	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.

3-Chloroazepan-2-one top

Crystal data top

C₆H₁₀ClNO	F(000) = 624
M_r = 147.60	D_x = 1.317 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 18.776 (4) Å	θ = 9–14°
b = 7.3440 (15) Å	µ = 0.43 mm⁻¹
c = 11.109 (2) Å	T = 293 K
β = 103.65 (3)°	Block, colourless
V = 1488.6 (5) Å³	0.30 × 0.20 × 0.20 mm
Z = 8

Data collection top

Enraf–Nonius CAD-4 diffractometer	1107 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.020
Graphite monochromator	θ_max = 25.3°, θ_min = 2.2°
ω/2θ scans	h = 0→22
Absorption correction: ψ scan (North et al., 1968)	k = −8→8
T_min = 0.881, T_max = 0.918	l = −13→12
2654 measured reflections	3 standard reflections every 200 reflections
1345 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.148	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.1P)² + 0.650P] where P = (F_o² + 2F_c²)/3
1345 reflections	(Δ/σ)_max < 0.001
82 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₆H₁₀ClNO	V = 1488.6 (5) Å³
M_r = 147.60	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 18.776 (4) Å	µ = 0.43 mm⁻¹
b = 7.3440 (15) Å	T = 293 K
c = 11.109 (2) Å	0.30 × 0.20 × 0.20 mm
β = 103.65 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1107 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.020
T_min = 0.881, T_max = 0.918	3 standard reflections every 200 reflections
2654 measured reflections	intensity decay: 1%
1345 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.148	H-atom parameters constrained
S = 1.01	Δρ_max = 0.36 e Å⁻³
1345 reflections	Δρ_min = −0.33 e Å⁻³
82 parameters

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	0.05987 (4)	0.14400 (11)	0.65254 (6)	0.0703 (3)
O	0.24623 (10)	0.2773 (2)	0.75479 (18)	0.0609 (5)
N	0.17420 (10)	0.4720 (2)	0.62946 (16)	0.0436 (5)
H0A	0.2035	0.5567	0.6645	0.052*
C1	0.08706 (17)	0.2590 (4)	0.3877 (2)	0.0647 (8)
H1A	0.0840	0.2264	0.3020	0.078*
H1B	0.0383	0.2471	0.4022	0.078*
C2	0.11018 (17)	0.4574 (4)	0.4058 (2)	0.0671 (8)
H2A	0.1587	0.4702	0.3906	0.081*
H2B	0.0768	0.5305	0.3446	0.081*
C3	0.11132 (14)	0.5312 (3)	0.5331 (2)	0.0552 (7)
H3A	0.1113	0.6632	0.5295	0.066*
H3B	0.0668	0.4936	0.5560	0.066*
C4	0.19194 (12)	0.3048 (3)	0.66976 (19)	0.0402 (5)
C5	0.14703 (13)	0.1426 (3)	0.6099 (2)	0.0458 (6)
H5A	0.1731	0.0334	0.6475	0.055*
C6	0.13727 (15)	0.1235 (4)	0.4704 (2)	0.0579 (7)
H6B	0.1853	0.1320	0.4525	0.069*
H6A	0.1188	0.0021	0.4469	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0684 (5)	0.0767 (6)	0.0696 (5)	−0.0248 (4)	0.0237 (4)	0.0048 (3)
O	0.0615 (10)	0.0416 (9)	0.0627 (10)	0.0047 (8)	−0.0190 (9)	0.0013 (8)
N	0.0462 (10)	0.0336 (10)	0.0451 (10)	−0.0026 (8)	−0.0014 (8)	0.0018 (8)
C1	0.0739 (18)	0.0727 (18)	0.0402 (13)	−0.0032 (15)	−0.0014 (12)	−0.0069 (12)
C2	0.0781 (19)	0.0712 (18)	0.0448 (14)	−0.0010 (15)	−0.0001 (13)	0.0173 (12)
C3	0.0559 (14)	0.0410 (13)	0.0606 (15)	0.0059 (11)	−0.0024 (12)	0.0090 (11)
C4	0.0426 (11)	0.0364 (11)	0.0389 (11)	0.0013 (9)	0.0040 (9)	0.0006 (9)
C5	0.0488 (12)	0.0370 (11)	0.0469 (12)	−0.0012 (10)	0.0022 (10)	0.0003 (10)
C6	0.0648 (16)	0.0545 (15)	0.0516 (14)	−0.0012 (12)	0.0084 (12)	−0.0158 (11)

Geometric parameters (Å, º) top

Cl—C5	1.808 (3)	C2—H2A	0.9700
O—C4	1.232 (3)	C2—H2B	0.9700
N—C4	1.322 (3)	C3—H3A	0.9700
N—C3	1.460 (3)	C3—H3B	0.9700
N—H0A	0.8600	C4—C5	1.519 (3)
C1—C2	1.520 (4)	C5—C6	1.524 (3)
C1—C6	1.521 (4)	C5—H5A	0.9800
C1—H1A	0.9700	C6—H6B	0.9700
C1—H1B	0.9700	C6—H6A	0.9700
C2—C3	1.510 (4)

C4—N—C3	128.35 (19)	N—C3—H3B	108.7
C4—N—H0A	115.8	C2—C3—H3B	108.7
C3—N—H0A	115.8	H3A—C3—H3B	107.6
C2—C1—C6	115.5 (2)	O—C4—N	120.6 (2)
C2—C1—H1A	108.4	O—C4—C5	118.68 (19)
C6—C1—H1A	108.4	N—C4—C5	120.71 (18)
C2—C1—H1B	108.4	C4—C5—C6	116.0 (2)
C6—C1—H1B	108.4	C4—C5—Cl	108.92 (15)
H1A—C1—H1B	107.5	C6—C5—Cl	111.58 (17)
C3—C2—C1	114.1 (2)	C4—C5—H5A	106.6
C3—C2—H2A	108.7	C6—C5—H5A	106.6
C1—C2—H2A	108.7	Cl—C5—H5A	106.6
C3—C2—H2B	108.7	C1—C6—C5	117.6 (2)
C1—C2—H2B	108.7	C1—C6—H6B	107.9
H2A—C2—H2B	107.6	C5—C6—H6B	107.9
N—C3—C2	114.2 (2)	C1—C6—H6A	107.9
N—C3—H3A	108.7	C5—C6—H6A	107.9
C2—C3—H3A	108.7	H6B—C6—H6A	107.2

C6—C1—C2—C3	−62.8 (3)	N—C4—C5—C6	55.0 (3)
C4—N—C3—C2	−63.1 (3)	O—C4—C5—Cl	109.8 (2)
C1—C2—C3—N	76.1 (3)	N—C4—C5—Cl	−71.8 (2)
C3—N—C4—O	−178.0 (2)	C2—C1—C6—C5	61.3 (4)
C3—N—C4—C5	3.6 (4)	C4—C5—C6—C1	−71.6 (3)
O—C4—C5—C6	−123.4 (2)	Cl—C5—C6—C1	53.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···Cl	0.97	2.82	3.215 (3)	105
C3—H3B···Cl	0.97	2.80	3.374 (3)	119

Experimental details

Crystal data
Chemical formula	C₆H₁₀ClNO
M_r	147.60
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	18.776 (4), 7.3440 (15), 11.109 (2)
β (°)	103.65 (3)
V (Å³)	1488.6 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.43
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.881, 0.918
No. of measured, independent and observed [I > 2σ(I)] reflections	2654, 1345, 1107
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.148, 1.01
No. of reflections	1345
No. of parameters	82
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.33

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···Cl	0.9700	2.8200	3.215 (3)	105.00
C3—H3B···Cl	0.9700	2.8000	3.374 (3)	119.00

Acknowledgements

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

References

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