2,2-Dichloro-1-(3,3,6-trimethyl-9-oxo-1,5-diaza­bicyclo­[4.3.0]nonan-5-yl)ethanone

Fu, Y.; Ye, F.

doi:10.1107/S1600536811027176

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2020

doi:10.1107/S1600536811027176

Open

access

2,2-Dichloro-1-(3,3,6-trimethyl-9-oxo-1,5-diazabicyclo[4.3.0]nonan-5-yl)ethanone

Ying Fu ^a and Fei Ye ^a ^*

^aCollege of Science, Northeast Agricultural University, Harbin 150030, People's Republic of China
^*Correspondence e-mail: yefei@neau.edu.cn

(Received 27 June 2011; accepted 7 July 2011; online 13 July 2011)

In the title molecule, C₁₂H₁₈Cl₂N₂O₂, the six-membered ring is in a chair conformation and the five-membered ring is in an envelope conformation. In the crystal, weak intermolecular bifurcated (C—H)₂⋯O hydrogen bonds connect molecules into chains along [010].

Related literature

For synthetic applications of 1,5-diazabicyclo compounds, see: Hutton & Bartlett (2007); Koptelov et al. (2011 ); Taylor et al. (2010 ). For the bioactivity of N-dichloroacety diazabicyclo derivatives, see: Burton et al. (1994 ); Hatzios (2004 ); Loniovereror (1993 ). For the synthetic procedure, see: Sun & Ye (2010 ).

Experimental

Crystal data

C₁₂H₁₈Cl₂N₂O₂
M_r = 293.18
Monoclinic, P 2₁ /c
a = 9.4442 (18) Å
b = 14.116 (3) Å
c = 11.7555 (16) Å
β = 115.067 (11)°
V = 1419.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 298 K
0.42 × 0.40 × 0.28 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.832, T_max = 0.884
10829 measured reflections
3492 independent reflections
2556 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.129
S = 1.04
3492 reflections
166 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O2ⁱ	0.98	2.23	3.200 (3)	170
C3—H3B⋯O2ⁱ	0.97	2.50	3.390 (2)	153
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811027176/lh5271sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811027176/lh5271Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811027176/lh5271Isup3.cml

checkCIF report

Comment top

1,5-Diazabicyclo compounds are important synthetic targets due to their biological activity (Hutton & Bartlett, 2007, Koptelov et al., 2011) and catalytic activity (Taylor et al., 2010). It was discovered that N-dichloroacetyl-1,5-diazabicyclo compounds act as herbicide safeners and these compounds have drawn widespread attention in agricultural biochemistry (Burton et al., 1994, Hatzios, 2004, Loniovereror, 1993). As a part of our ongoing investigation on the bioactivities of safeners we have determined the crystal structure of the title compound.

The molecular structure of the title compound is shown in Fig. 1. In the crystal, weak interolecular bifurcated (C—H)₂···O hydrogen bonds connect molecules into one-dimensional chains along [010]. (Fig. 2).

Related literature top

For synthetic applications of 1,5-diazabicyclo compounds, see: Hutton & Bartlett (2007); Koptelov et al. (2011); Taylor et al. (2010). For the bioactivity of N-dichloroacety diazabicyclo derivatives, see: Burton et al. (1994); Hatzios (2004); Loniovereror (1993). For the synthetic procedure, see: Sun & Ye (2010).

Experimental top

The title compound was prepared according to the literature procedure (Sun et al., 2010). The single-crystal suitable for X-ray structural analysis was obtained by slow evaporation of a solution of the title compound in petroleum ether and ethyl acetate at room temperature.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure showing the weak intermolecular C—H···O hydrogen bonds as dashed lines.

2,2-Dichloro-1-(3,3,6-trimethyl-9-oxo-1,5-diazabicyclo[4.3.0]nonan-5-yl)ethanone top

Crystal data top

C₁₂H₁₈Cl₂N₂O₂	F(000) = 616
M_r = 293.18	D_x = 1.372 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3515 reflections
a = 9.4442 (18) Å	θ = 2.4–27.1°
b = 14.116 (3) Å	µ = 0.45 mm⁻¹
c = 11.7555 (16) Å	T = 298 K
β = 115.067 (11)°	Block, colourless
V = 1419.6 (4) Å³	0.42 × 0.40 × 0.28 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	3492 independent reflections
Radiation source: fine-focus sealed tube	2556 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.832, T_max = 0.884	k = −18→18
10829 measured reflections	l = −9→15

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) = 0.129	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0683P)² + 0.2384P] where P = (F_o² + 2F_c²)/3
3492 reflections	(Δ/σ)_max < 0.001
166 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

C₁₂H₁₈Cl₂N₂O₂	V = 1419.6 (4) Å³
M_r = 293.18	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.4442 (18) Å	µ = 0.45 mm⁻¹
b = 14.116 (3) Å	T = 298 K
c = 11.7555 (16) Å	0.42 × 0.40 × 0.28 mm
β = 115.067 (11)°

Data collection top

Bruker SMART CCD diffractometer	3492 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2556 reflections with I > 2σ(I)
T_min = 0.832, T_max = 0.884	R_int = 0.027
10829 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.04	Δρ_max = 0.33 e Å⁻³
3492 reflections	Δρ_min = −0.48 e Å⁻³
166 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
Cl1	0.38732 (6)	−0.01048 (4)	0.34216 (5)	0.05901 (18)
Cl2	0.21200 (7)	−0.01735 (4)	0.07141 (6)	0.0696 (2)
O1	0.43042 (15)	−0.18995 (10)	0.24212 (16)	0.0618 (4)
O2	0.06902 (18)	−0.54370 (10)	0.24058 (16)	0.0638 (4)
N1	0.17907 (15)	−0.24099 (9)	0.17670 (13)	0.0342 (3)
N2	0.10521 (16)	−0.40443 (10)	0.15860 (14)	0.0388 (3)
C1	0.2408 (2)	−0.07096 (12)	0.21585 (17)	0.0419 (4)
H1	0.1428	−0.0703	0.2257	0.050*
C2	0.29300 (19)	−0.17366 (12)	0.21273 (17)	0.0399 (4)
C3	0.01328 (18)	−0.21728 (12)	0.09737 (15)	0.0364 (4)
H3A	−0.0029	−0.2147	0.0102	0.044*
H3B	−0.0089	−0.1549	0.1205	0.044*
C4	−0.10098 (18)	−0.28847 (12)	0.10984 (15)	0.0366 (4)
C5	−0.2656 (2)	−0.26170 (16)	0.0151 (2)	0.0581 (5)
H5A	−0.2699	−0.2615	−0.0679	0.087*
H5B	−0.2913	−0.1998	0.0346	0.087*
H5C	−0.3392	−0.3070	0.0193	0.087*
C6	−0.0909 (2)	−0.28828 (14)	0.24271 (18)	0.0485 (4)
H6A	−0.1645	−0.3329	0.2480	0.073*
H6B	−0.1148	−0.2261	0.2627	0.073*
H6C	0.0128	−0.3057	0.3011	0.073*
C7	−0.0579 (2)	−0.38544 (12)	0.07744 (17)	0.0419 (4)
H7A	−0.1235	−0.4337	0.0893	0.050*
H7B	−0.0742	−0.3866	−0.0098	0.050*
C8	0.22976 (19)	−0.33990 (11)	0.16558 (16)	0.0367 (4)
C9	0.2611 (2)	−0.34929 (15)	0.04896 (19)	0.0516 (5)
H9A	0.2991	−0.4119	0.0457	0.077*
H9B	0.3380	−0.3035	0.0525	0.077*
H9C	0.1660	−0.3384	−0.0247	0.077*
C10	0.3679 (2)	−0.37342 (13)	0.28688 (18)	0.0477 (4)
H10A	0.4655	−0.3695	0.2784	0.057*
H10B	0.3763	−0.3353	0.3582	0.057*
C11	0.3290 (2)	−0.47623 (14)	0.3029 (2)	0.0531 (5)
H11A	0.3784	−0.5195	0.2666	0.064*
H11B	0.3628	−0.4917	0.3909	0.064*
C12	0.1545 (2)	−0.48091 (12)	0.23385 (19)	0.0454 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0585 (3)	0.0609 (3)	0.0632 (3)	−0.0227 (2)	0.0313 (3)	−0.0199 (2)
Cl2	0.0747 (4)	0.0676 (4)	0.0629 (4)	0.0028 (3)	0.0257 (3)	0.0219 (3)
O1	0.0345 (7)	0.0509 (8)	0.0934 (12)	−0.0021 (6)	0.0206 (7)	−0.0014 (7)
O2	0.0683 (9)	0.0460 (7)	0.0921 (12)	0.0003 (7)	0.0483 (9)	0.0128 (8)
N1	0.0325 (7)	0.0336 (6)	0.0362 (7)	−0.0005 (5)	0.0141 (6)	−0.0005 (5)
N2	0.0405 (8)	0.0346 (7)	0.0426 (8)	−0.0015 (6)	0.0189 (6)	−0.0034 (6)
C1	0.0399 (9)	0.0389 (9)	0.0505 (10)	−0.0074 (7)	0.0226 (8)	−0.0032 (8)
C2	0.0360 (9)	0.0392 (8)	0.0431 (9)	−0.0025 (7)	0.0156 (8)	−0.0012 (7)
C3	0.0345 (8)	0.0391 (8)	0.0329 (8)	0.0000 (6)	0.0116 (7)	0.0019 (7)
C4	0.0336 (8)	0.0387 (8)	0.0359 (8)	−0.0028 (6)	0.0133 (7)	−0.0029 (7)
C5	0.0363 (10)	0.0621 (12)	0.0633 (13)	−0.0026 (9)	0.0089 (9)	0.0008 (10)
C6	0.0567 (11)	0.0495 (10)	0.0487 (11)	−0.0041 (8)	0.0313 (9)	−0.0047 (8)
C7	0.0418 (9)	0.0404 (9)	0.0412 (9)	−0.0073 (7)	0.0153 (8)	−0.0097 (7)
C8	0.0367 (8)	0.0344 (8)	0.0414 (9)	−0.0001 (6)	0.0189 (7)	−0.0026 (7)
C9	0.0573 (11)	0.0563 (11)	0.0524 (11)	0.0039 (9)	0.0342 (10)	−0.0030 (9)
C10	0.0419 (10)	0.0461 (10)	0.0507 (11)	0.0072 (8)	0.0153 (9)	0.0024 (8)
C11	0.0530 (11)	0.0509 (11)	0.0594 (12)	0.0123 (9)	0.0278 (10)	0.0129 (9)
C12	0.0565 (11)	0.0381 (9)	0.0533 (11)	0.0051 (8)	0.0345 (10)	0.0008 (8)

Geometric parameters (Å, º) top

Cl1—C1	1.7627 (18)	C5—H5B	0.9600
Cl2—C1	1.7715 (19)	C5—H5C	0.9600
O1—C2	1.215 (2)	C6—H6A	0.9600
O2—C12	1.224 (2)	C6—H6B	0.9600
N1—C2	1.362 (2)	C6—H6C	0.9600
N1—C3	1.482 (2)	C7—H7A	0.9700
N1—C8	1.499 (2)	C7—H7B	0.9700
N2—C12	1.348 (2)	C8—C9	1.526 (2)
N2—C7	1.452 (2)	C8—C10	1.544 (2)
N2—C8	1.462 (2)	C9—H9A	0.9600
C1—C2	1.537 (2)	C9—H9B	0.9600
C1—H1	0.9800	C9—H9C	0.9600
C3—C4	1.527 (2)	C10—C11	1.528 (3)
C3—H3A	0.9700	C10—H10A	0.9700
C3—H3B	0.9700	C10—H10B	0.9700
C4—C7	1.522 (2)	C11—C12	1.499 (3)
C4—C6	1.524 (2)	C11—H11A	0.9700
C4—C5	1.528 (2)	C11—H11B	0.9700
C5—H5A	0.9600

C2—N1—C3	121.54 (13)	C4—C6—H6C	109.5
C2—N1—C8	115.95 (13)	H6A—C6—H6C	109.5
C3—N1—C8	116.53 (12)	H6B—C6—H6C	109.5
C12—N2—C7	123.66 (15)	N2—C7—C4	108.86 (13)
C12—N2—C8	114.61 (15)	N2—C7—H7A	109.9
C7—N2—C8	121.72 (14)	C4—C7—H7A	109.9
C2—C1—Cl1	109.38 (12)	N2—C7—H7B	109.9
C2—C1—Cl2	107.50 (13)	C4—C7—H7B	109.9
Cl1—C1—Cl2	110.34 (9)	H7A—C7—H7B	108.3
C2—C1—H1	109.9	N2—C8—N1	107.82 (13)
Cl1—C1—H1	109.9	N2—C8—C9	110.68 (14)
Cl2—C1—H1	109.9	N1—C8—C9	110.48 (14)
O1—C2—N1	124.36 (16)	N2—C8—C10	101.88 (14)
O1—C2—C1	119.10 (15)	N1—C8—C10	112.40 (13)
N1—C2—C1	116.54 (14)	C9—C8—C10	113.16 (15)
N1—C3—C4	113.10 (13)	C8—C9—H9A	109.5
N1—C3—H3A	109.0	C8—C9—H9B	109.5
C4—C3—H3A	109.0	H9A—C9—H9B	109.5
N1—C3—H3B	109.0	C8—C9—H9C	109.5
C4—C3—H3B	109.0	H9A—C9—H9C	109.5
H3A—C3—H3B	107.8	H9B—C9—H9C	109.5
C7—C4—C6	110.55 (14)	C11—C10—C8	104.57 (15)
C7—C4—C3	107.05 (14)	C11—C10—H10A	110.8
C6—C4—C3	110.96 (14)	C8—C10—H10A	110.8
C7—C4—C5	109.74 (15)	C11—C10—H10B	110.8
C6—C4—C5	110.41 (16)	C8—C10—H10B	110.8
C3—C4—C5	108.05 (15)	H10A—C10—H10B	108.9
C4—C5—H5A	109.5	C12—C11—C10	104.01 (15)
C4—C5—H5B	109.5	C12—C11—H11A	111.0
H5A—C5—H5B	109.5	C10—C11—H11A	111.0
C4—C5—H5C	109.5	C12—C11—H11B	111.0
H5A—C5—H5C	109.5	C10—C11—H11B	111.0
H5B—C5—H5C	109.5	H11A—C11—H11B	109.0
C4—C6—H6A	109.5	O2—C12—N2	124.68 (19)
C4—C6—H6B	109.5	O2—C12—C11	126.95 (18)
H6A—C6—H6B	109.5	N2—C12—C11	108.34 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2ⁱ	0.98	2.23	3.200 (3)	170
C3—H3B···O2ⁱ	0.97	2.50	3.390 (2)	153

Symmetry code: (i) −x, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₈Cl₂N₂O₂
M_r	293.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	9.4442 (18), 14.116 (3), 11.7555 (16)
β (°)	115.067 (11)
V (Å³)	1419.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.45
Crystal size (mm)	0.42 × 0.40 × 0.28

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.832, 0.884
No. of measured, independent and observed [I > 2σ(I)] reflections	10829, 3492, 2556
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.129, 1.04
No. of reflections	3492
No. of parameters	166
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.48

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2ⁱ	0.98	2.23	3.200 (3)	170
C3—H3B···O2ⁱ	0.97	2.50	3.390 (2)	153

Symmetry code: (i) −x, y+1/2, −z+1/2.

Acknowledgements

We thank the Heilongjiang Province Foundation for Young Scholars (QC2009C44) for generously supporting this study.

References

Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burton, J. D., Maness, E. P., Monks, D. W. & Robinson, D. K. (1994). Pestic. Biochem. Phys. 48, 163–172. CrossRef Web of Science Google Scholar
Hatzios, K. K. (2004). Weed Sci. 52, 454–467. Web of Science CrossRef CAS Google Scholar
Hutton, C. A. & Bartlett, P. A. (2007). J. Org. Chem. 72, 6865–6872. Web of Science CrossRef PubMed CAS Google Scholar
Koptelov, Y. B., Saik, S. P., Molchanov, A. P. & Selivanov, S. I. (2011). Russ. J. Org. Chem. 47, 421–432. Web of Science CrossRef CAS Google Scholar
Loniovereror, G. L. (1993). Weed Res. 33, 311–318. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sun, T. F. & Ye, F. (2010). Chem. Online, 73, 669–672. CAS Google Scholar
Taylor, J. E., Jones, M. D., Williams, J. M. J. & Bull, S. D. (2010). Org. Lett. 12, 5740–5743. Web of Science CSD CrossRef CAS PubMed 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.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2020

doi:10.1107/S1600536811027176

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

2,2-Di­chloro-1-(3,3,6-tri­methyl-9-oxo-1,5-di­aza­bi­cyclo­[4.3.0]nonan-5-yl)ethanone

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2,2-Dichloro-1-(3,3,6-trimethyl-9-oxo-1,5-diazabicyclo[4.3.0]nonan-5-yl)ethanone