(5R)-5-[(1R)-2,2-Dichloro-1-methyl-cyclo-prop-yl]-2-methyl-cyclo-hex-2-en-1-one.

The title compound, C(11)H(14)Cl(2)O, was synthesized by the reaction of a dichloro-methane solution of (R)-carvone and potassium tert-butano-late in the presence of a catalytic amount of benzyl-triethyl-ammonium chloride in chloro-form. The cyclo-hexene ring adopts a half-boat conformation. The cyclo-propyl ring is unsymmetrical, the shortest C-C bond being distal to the alkyl-substituted C atom. The crystal packing is stabilized only by van der Waals inter-actions.

Related literature

For background to and applications of dichloro­cyclo­propane derivatives, see: Hirota et al. (1996 ▶); Künzer et al. (1996 ▶); Ziyat et al. (2004 ▶); Fedorynski (2003 ▶). For the synthesis and structures of optically active dihalogenocylopropanes reported by our group, see: Ziyat et al. (2002 ▶); Boualy et al. (2009 ▶); Ziyat et al. (2006 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C11H14Cl2O

M = 233.12

Monoclinic,

a = 6.5722 (3) Å

b = 8.4802 (4) Å

c = 10.8022 (5) Å

β = 104.435 (4)°

V = 583.04 (5) Å3

Z = 2

Cu Kα radiation

μ = 4.73 mm−1

T = 294 K

0.25 × 0.20 × 0.14 mm

Data collection

Siemens AED diffractometer

Absorption correction: refined from ΔF (DIFABS; Walker & Stuart, 1983 ▶) T min = 0.327, T max = 0.519

2295 measured reflections

1576 independent reflections

1554 reflections with I > 2σ(I)

R int = 0.057

3 standard reflections every 100 reflections intensity decay: 0.3%

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.126

S = 1.09

1576 reflections

130 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.43 e Å−3

Δρmin = −0.30 e Å−3

Absolute structure: Flack (1983 ▶), 394 Friedel pairs

Flack parameter: 0.00 (2)

Data collection: AED (Belletti et al., 1993 ▶); cell refinement: AED; data reduction: AED; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and SCHAKAL97 (Keller, 1997 ▶); software used to prepare material for publication: SHELXL97 and PARST95 (Nardelli, 1995 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811021933/gk2382sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811021933/gk2382Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811021933/gk2382Isup3.cml

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

C11H14Cl2O	F(000) = 244
Mr = 233.12	Dx = 1.328 Mg m−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2yb	Cell parameters from 48 reflections
a = 6.5722 (3) Å	θ = 22.5–35.9°
b = 8.4802 (4) Å	µ = 4.73 mm−1
c = 10.8022 (5) Å	T = 294 K
β = 104.435 (4)°	Irregular block, colourless
V = 583.04 (5) Å3	0.25 × 0.20 × 0.14 mm
Z = 2

Siemens AED diffractometer	1554 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.057
graphite	θmax = 69.8°, θmin = 4.2°
θ/2θ scans	h = −7→6
Absorption correction: part of the refinement model (ΔF) (DIFABS; Walker & Stuart, 1983)	k = −10→6
Tmin = 0.327, Tmax = 0.519	l = −12→13
2295 measured reflections	3 standard reflections every 100 reflections
1576 independent reflections	intensity decay: 0.3%

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.046	w = 1/[σ2(Fo2) + (0.083P)2 + 0.0912P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.126	(Δ/σ)max < 0.001
S = 1.09	Δρmax = 0.43 e Å−3
1576 reflections	Δρmin = −0.30 e Å−3
130 parameters	Extinction correction: SHELXL
1 restraint	Extinction coefficient: 0.014 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 394 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.00 (2)

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
Cl1	1.34023 (13)	0.77757 (15)	0.58246 (8)	0.0824 (4)
Cl2	0.90330 (12)	0.84462 (16)	0.47313 (8)	0.0858 (4)
O1	0.7651 (5)	0.7920 (6)	−0.1253 (3)	0.0987 (12)
C1	1.0031 (5)	0.7536 (6)	0.0774 (3)	0.0693 (10)
H1A	1.0523	0.8597	0.0677	0.083*
H1B	1.1099	0.6805	0.0652	0.083*
C2	0.8020 (5)	0.7244 (5)	−0.0244 (3)	0.0636 (8)
C3	0.6586 (5)	0.6053 (4)	0.0053 (3)	0.0554 (7)
C4	0.7023 (5)	0.5357 (4)	0.1185 (3)	0.0571 (7)
H4	0.6091	0.4590	0.1322	0.069*
C5	0.8894 (4)	0.5702 (4)	0.2264 (3)	0.0548 (7)
H5A	0.9982	0.4927	0.2270	0.066*
H5B	0.8499	0.5627	0.3069	0.066*
C6	0.9740 (4)	0.7342 (4)	0.2127 (3)	0.0496 (6)
H6	0.8668	0.8101	0.2227	0.059*
C7	1.1744 (4)	0.7717 (5)	0.3144 (3)	0.0584 (7)
C8	1.2112 (6)	0.9436 (6)	0.3526 (4)	0.0799 (11)
H8A	1.3547	0.9822	0.3731	0.096*
H8B	1.1062	1.0197	0.3108	0.096*
C9	1.1528 (4)	0.8301 (5)	0.4415 (3)	0.0614 (7)
C10	0.4642 (6)	0.5669 (7)	−0.0993 (4)	0.0791 (11)
H10A	0.3966	0.6630	−0.1344	0.119*
H10B	0.3692	0.5055	−0.0644	0.119*
H10C	0.5037	0.5079	−0.1655	0.119*
C11	1.3618 (5)	0.6704 (8)	0.3127 (4)	0.0909 (15)
H11A	1.3816	0.6673	0.2276	0.136*
H11B	1.3386	0.5654	0.3395	0.136*
H11C	1.4848	0.7138	0.3699	0.136*

	U11	U22	U33	U12	U13	U23
Cl1	0.0728 (5)	0.0887 (7)	0.0691 (5)	0.0062 (4)	−0.0133 (3)	−0.0101 (5)
Cl2	0.0610 (4)	0.1189 (9)	0.0741 (5)	0.0072 (5)	0.0107 (3)	−0.0351 (6)
O1	0.115 (2)	0.115 (3)	0.0616 (14)	−0.024 (2)	0.0147 (13)	0.028 (2)
C1	0.0660 (16)	0.081 (3)	0.0632 (17)	−0.0162 (17)	0.0201 (13)	0.007 (2)
C2	0.0756 (17)	0.066 (2)	0.0503 (15)	−0.0062 (16)	0.0182 (13)	0.0030 (17)
C3	0.0608 (14)	0.0537 (16)	0.0500 (14)	−0.0017 (14)	0.0104 (11)	−0.0062 (15)
C4	0.0616 (15)	0.0554 (17)	0.0544 (16)	−0.0067 (13)	0.0146 (12)	−0.0029 (15)
C5	0.0571 (14)	0.0535 (17)	0.0515 (15)	0.0014 (12)	0.0091 (11)	0.0047 (14)
C6	0.0467 (12)	0.0490 (16)	0.0512 (14)	0.0010 (10)	0.0087 (10)	−0.0009 (13)
C7	0.0443 (12)	0.0613 (18)	0.0666 (17)	−0.0028 (13)	0.0083 (11)	−0.0043 (17)
C8	0.075 (2)	0.064 (2)	0.090 (3)	−0.0173 (18)	0.0005 (17)	−0.001 (2)
C9	0.0511 (13)	0.0621 (19)	0.0632 (15)	0.0017 (13)	−0.0003 (11)	−0.0075 (17)
C10	0.081 (2)	0.086 (3)	0.0612 (18)	−0.019 (2)	0.0007 (15)	−0.007 (2)
C11	0.0462 (15)	0.124 (4)	0.097 (3)	0.015 (2)	0.0073 (16)	−0.027 (3)

Cl1—C9	1.760 (3)	C6—C7	1.523 (4)
Cl2—C9	1.761 (3)	C6—H6	0.9800
O1—C2	1.202 (4)	C7—C9	1.500 (4)
C1—C2	1.514 (4)	C7—C11	1.506 (5)
C1—C6	1.529 (4)	C7—C8	1.518 (6)
C1—H1A	0.9700	C8—C9	1.477 (6)
C1—H1B	0.9700	C8—H8A	0.9700
C2—C3	1.470 (5)	C8—H8B	0.9700
C3—C4	1.323 (4)	C10—H10A	0.9600
C3—C10	1.515 (4)	C10—H10B	0.9600
C4—C5	1.497 (4)	C10—H10C	0.9600
C4—H4	0.9300	C11—H11A	0.9600
C5—C6	1.519 (5)	C11—H11B	0.9600
C5—H5A	0.9700	C11—H11C	0.9600
C5—H5B	0.9700
C2—C1—C6	112.4 (2)	C11—C7—C8	118.4 (3)
C2—C1—H1A	109.1	C9—C7—C6	117.9 (2)
C6—C1—H1A	109.1	C11—C7—C6	115.8 (3)
C2—C1—H1B	109.1	C8—C7—C6	116.5 (3)
C6—C1—H1B	109.1	C9—C8—C7	60.1 (3)
H1A—C1—H1B	107.8	C9—C8—H8A	117.8
O1—C2—C3	122.0 (3)	C7—C8—H8A	117.8
O1—C2—C1	121.5 (3)	C9—C8—H8B	117.8
C3—C2—C1	116.5 (3)	C7—C8—H8B	117.8
C4—C3—C2	120.3 (3)	H8A—C8—H8B	114.9
C4—C3—C10	122.8 (3)	C8—C9—C7	61.3 (3)
C2—C3—C10	116.9 (3)	C8—C9—Cl1	119.2 (2)
C3—C4—C5	125.4 (3)	C7—C9—Cl1	120.2 (2)
C3—C4—H4	117.3	C8—C9—Cl2	119.1 (3)
C5—C4—H4	117.3	C7—C9—Cl2	120.4 (2)
C4—C5—C6	110.7 (3)	Cl1—C9—Cl2	109.55 (18)
C4—C5—H5A	109.5	C3—C10—H10A	109.5
C6—C5—H5A	109.5	C3—C10—H10B	109.5
C4—C5—H5B	109.5	H10A—C10—H10B	109.5
C6—C5—H5B	109.5	C3—C10—H10C	109.5
H5A—C5—H5B	108.1	H10A—C10—H10C	109.5
C5—C6—C7	113.1 (3)	H10B—C10—H10C	109.5
C5—C6—C1	109.1 (3)	C7—C11—H11A	109.5
C7—C6—C1	112.1 (2)	C7—C11—H11B	109.5
C5—C6—H6	107.4	H11A—C11—H11B	109.5
C7—C6—H6	107.4	C7—C11—H11C	109.5
C1—C6—H6	107.4	H11A—C11—H11C	109.5
C9—C7—C11	117.6 (3)	H11B—C11—H11C	109.5
C9—C7—C8	58.6 (3)