4-Di­chloro­methyl-4-methyl-5-(nitro­meth­yl)cyclo­hex-2-enone

Abstract

In the title compound, C₉H₁₁Cl₂NO₃, the six-membered ring adopts a screw-chair conformation. In the crystal, two different C—H⋯O hydrogen bonds involving the same acceptor atom connect the mol­ecules into a chain extending along the c-axis direction.

Related literature  

For the synthetic procedure, see: Wenkert et al. (1969 ▶). For polyfunctionalized products obtained by similar Michael reactions with carbanions, see: Stefanović et al. (1983 ▶); Solujić et al. (1991 ▶, 1999 ▶). For a related crystal structure, see: Yang & Carter (2010 ▶).

Experimental  

Crystal data  

• C₉H₁₁Cl₂NO₃

• M _r = 252.09

• Monoclinic,

• a = 13.8922 (7) Å

• b = 10.4531 (9) Å

• c = 7.8696 (5) Å

• β = 101.682 (6)°

• V = 1119.12 (13) ų

• Z = 4

• Cu Kα radiation

• μ = 5.14 mm⁻¹

• T = 293 K

• 0.11 × 0.10 × 0.05 mm

Data collection  

• Agilent Gemini S diffractometer

• Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ▶) T _min = 0.288, T _max = 1.000

• 4083 measured reflections

• 2160 independent reflections

• 1674 reflections with I > 2σ(I)

• R _int = 0.016

Refinement  

• R[F ² > 2σ(F ²)] = 0.073

• wR(F ²) = 0.214

• S = 1.13

• 2160 reflections

• 137 parameters

• H-atom parameters constrained

• Δρ_max = 0.44 e Å⁻³

• Δρ_min = −0.46 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2013 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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, 2012 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶), PLATON (Spek, 2009 ▶) and PARST (Nardelli, 1995 ▶).

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O3i	0.98	2.24	3.189 (5)	164
C1—H1a⋯O3i	0.97	2.56	3.503 (6)	164

Symmetry code: (i) .

supplementary crystallographic information

1. Comment

4-Dichloromethyl-4-methylcyclohexa-2,5-dienone, as a conjugated enone, readily undergo Michael reaction with carbanions, giving synthetically valuable polyfunctionalized products (Wenkert et al., 1969). Utilizing this reaction, some natural products (Stefanović et al., 1983), as well as some bioactive compounds (Solujić et al., 1991; 1999) were successfully synthesized. We report now on synthesis of the title compound (I) by the same reaction using carbanion obtained from nitromethane.

The crystal structure of (I) is shown in Figure 1. None of the oxygen atoms of the nitro group is involved in hydrogen bonding. Similarly, two chlorine atoms also remain without the appropriate intermolecular donor, while there are two bent C—H···Cl intramolecular contacts shorter then the sum of van der Waals radii for H and Cl atoms [C6—H6a = 0.97, H6···Cl1 = 2.76 Å, C6—H6···Cl1 =106 °; C2—H2 = 0.98, H2···Cl2 = 2.66 Å, C2—H2···Cl2 = 112 °]. The most significant interaction in the crystal structure is a bifurcated C—H···O hydrogen bond [C8—H8 = 0.98; H8···O3ⁱ = 2.24 Å; C8—H8···O3 = 164° and C1—H1a = 0.97; H1a···O3ⁱ = 2.56 Å; C1—H1a···O3 = 164°] (symmetry code: i = x, y, z - 1)] which connects the molecules into chains extended along the c axis (Figure 2).

2. Experimental

Following the literature protocol (Wenkert et al., 1969), to freshly prepared sodium methoxide in methanol a nitromethane solution of 4-(dichloromethyl)-4-methylcyclohex-2,5-dienone in dry methanol was added dropwise. After one hour stirring of the obtained solution, the solvent was evaporated and the rest quenched with diluted hydrochloric acid. The obtained mixture was extracted with toluene, the organic layer dried overnight (anh. sodium sulfate) and the solvent evaporated. The crude solid was recrystallized from hot toluene to give pure 4-(dichloromethyl)-4-methyl-5-(nitromethyl)cyclohex-2-enon.

3. Refinement

All H atoms were placed at geometrically calculated positions and included in the refinement in the riding model approximation, with C—H lengths of 0.93 (aromatic CH), 0.96 (CH₃), 0.97 (CH₂), and 0.98 Å (CH). U_iso of the H atoms were set at 1.5U_eq of the parent C for the methyl group and at 1.2U_eq otherwise.

Figures

Fig. 1.

The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms.

Fig. 2.

Segment of the crystal packing. A bifurcated C—H···O hydrogen bond connects the molecules into chains extended along c axis.

Crystal data

C9H11Cl2NO3	F(000) = 520
Mr = 252.09	Dx = 1.496 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ybc	Cell parameters from 927 reflections
a = 13.8922 (7) Å	θ = 4.2–70.2°
b = 10.4531 (9) Å	µ = 5.14 mm−1
c = 7.8696 (5) Å	T = 293 K
β = 101.682 (6)°	Prismatic, colourless
V = 1119.12 (13) Å3	0.11 × 0.10 × 0.05 mm
Z = 4

Data collection

Agilent Gemini S diffractometer	2160 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1674 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
Detector resolution: 16.3280 pixels mm-1	θmax = 72.7°, θmin = 5.3°
ω scans	h = −16→17
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −12→7
Tmin = 0.288, Tmax = 1.000	l = −9→9
4083 measured reflections

Refinement

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)] = 0.073	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.214	H-atom parameters constrained
S = 1.13	w = 1/[σ2(Fo2) + (0.0912P)2 + 0.9148P] where P = (Fo2 + 2Fc2)/3
2160 reflections	(Δ/σ)max < 0.001
137 parameters	Δρmax = 0.44 e Å−3
0 restraints	Δρmin = −0.46 e Å−3

Special details

Experimental. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. 'CrysAlisPro (Agilent Technologies, 2013)'

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.42318 (8)	0.42826 (19)	0.16338 (17)	0.1132 (6)
Cl2	0.37776 (11)	0.67949 (16)	0.2702 (2)	0.1229 (7)
N1	0.0336 (2)	0.6681 (4)	0.1987 (4)	0.0681 (9)
O1	0.0509 (4)	0.7541 (5)	0.2925 (9)	0.184 (3)
O2	−0.0380 (4)	0.6677 (7)	0.1028 (8)	0.195 (3)
C1	0.1041 (3)	0.5609 (4)	0.1953 (5)	0.0634 (9)
H1A	0.1335	0.5699	0.0942	0.076*
H1B	0.0686	0.4804	0.1849	0.076*
C2	0.1853 (2)	0.5576 (3)	0.3579 (4)	0.0521 (8)
H2	0.2108	0.6447	0.3804	0.063*
C3	0.1430 (3)	0.5148 (5)	0.5143 (5)	0.0699 (11)
H3A	0.0917	0.5739	0.5301	0.084*
H3B	0.1135	0.4309	0.4909	0.084*
C4	0.2196 (4)	0.5091 (6)	0.6783 (5)	0.0854 (13)
C5	0.3186 (3)	0.4765 (5)	0.6616 (5)	0.0719 (11)
H5	0.3671	0.4682	0.7614	0.086*
C6	0.3420 (2)	0.4579 (4)	0.5085 (5)	0.0605 (9)
H6	0.4067	0.4358	0.5073	0.073*
C7	0.2720 (2)	0.4699 (3)	0.3368 (4)	0.0506 (8)
C8	0.3265 (3)	0.5283 (5)	0.2041 (5)	0.0746 (12)
H8	0.2791	0.5396	0.0946	0.090*
C9	0.2362 (3)	0.3356 (4)	0.2733 (6)	0.0744 (11)
H9A	0.2912	0.2782	0.2889	0.112*
H9B	0.2057	0.3394	0.1525	0.112*
H9C	0.1895	0.3056	0.3387	0.112*
O3	0.1993 (4)	0.5259 (7)	0.8183 (4)	0.165 (3)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0604 (7)	0.1947 (17)	0.0927 (9)	0.0257 (8)	0.0351 (6)	−0.0027 (9)
Cl2	0.0976 (10)	0.1148 (12)	0.1631 (15)	−0.0342 (8)	0.0423 (9)	0.0388 (10)
N1	0.0521 (17)	0.086 (2)	0.0644 (18)	0.0131 (16)	0.0081 (14)	0.0057 (17)
O1	0.140 (4)	0.128 (4)	0.239 (6)	0.069 (3)	−0.066 (4)	−0.086 (4)
O2	0.124 (4)	0.229 (6)	0.187 (5)	0.107 (4)	−0.075 (4)	−0.105 (4)
C1	0.0504 (18)	0.080 (3)	0.058 (2)	0.0105 (17)	0.0056 (15)	−0.0045 (18)
C2	0.0448 (16)	0.063 (2)	0.0486 (16)	0.0008 (14)	0.0095 (13)	−0.0015 (14)
C3	0.0533 (19)	0.100 (3)	0.061 (2)	0.0049 (19)	0.0235 (16)	0.000 (2)
C4	0.083 (3)	0.125 (4)	0.051 (2)	0.006 (3)	0.0212 (19)	0.007 (2)
C5	0.066 (2)	0.097 (3)	0.0485 (19)	−0.004 (2)	0.0008 (16)	0.0104 (19)
C6	0.0432 (16)	0.076 (2)	0.060 (2)	−0.0024 (15)	0.0035 (14)	0.0088 (17)
C7	0.0409 (15)	0.063 (2)	0.0481 (16)	−0.0011 (13)	0.0105 (12)	−0.0021 (14)
C8	0.0508 (19)	0.115 (3)	0.060 (2)	0.004 (2)	0.0181 (16)	0.013 (2)
C9	0.060 (2)	0.069 (2)	0.092 (3)	0.0047 (18)	0.0090 (19)	−0.020 (2)
O3	0.131 (3)	0.317 (8)	0.0541 (19)	0.061 (4)	0.035 (2)	0.004 (3)

Geometric parameters (Å, º)

Cl1—C8	1.782 (4)	C3—H3B	0.9700
Cl2—C8	1.768 (5)	C4—O3	1.204 (5)
N1—O2	1.119 (5)	C4—C5	1.448 (6)
N1—O1	1.157 (5)	C5—C6	1.324 (5)
N1—C1	1.493 (5)	C5—H5	0.9300
C1—C2	1.525 (5)	C6—C7	1.502 (5)
C1—H1A	0.9700	C6—H6	0.9300
C1—H1B	0.9700	C7—C8	1.536 (5)
C2—C3	1.534 (5)	C7—C9	1.538 (5)
C2—C7	1.549 (5)	C8—H8	0.9800
C2—H2	0.9800	C9—H9A	0.9600
C3—C4	1.498 (6)	C9—H9B	0.9600
C3—H3A	0.9700	C9—H9C	0.9600
O2—N1—O1	118.3 (4)	C6—C5—C4	122.0 (3)
O2—N1—C1	118.8 (4)	C6—C5—H5	119.0
O1—N1—C1	122.8 (4)	C4—C5—H5	119.0
N1—C1—C2	112.3 (3)	C5—C6—C7	124.9 (3)
N1—C1—H1A	109.2	C5—C6—H6	117.5
C2—C1—H1A	109.2	C7—C6—H6	117.5
N1—C1—H1B	109.2	C6—C7—C8	109.0 (3)
C2—C1—H1B	109.2	C6—C7—C9	108.9 (3)
H1A—C1—H1B	107.9	C8—C7—C9	108.2 (3)
C1—C2—C3	110.0 (3)	C6—C7—C2	109.2 (3)
C1—C2—C7	112.5 (3)	C8—C7—C2	109.8 (3)
C3—C2—C7	110.2 (3)	C9—C7—C2	111.6 (3)
C1—C2—H2	108.0	C7—C8—Cl2	112.3 (3)
C3—C2—H2	108.0	C7—C8—Cl1	112.5 (3)
C7—C2—H2	108.0	Cl2—C8—Cl1	107.7 (2)
C4—C3—C2	112.5 (3)	C7—C8—H8	108.0
C4—C3—H3A	109.1	Cl2—C8—H8	108.0
C2—C3—H3A	109.1	Cl1—C8—H8	108.0
C4—C3—H3B	109.1	C7—C9—H9A	109.5
C2—C3—H3B	109.1	C7—C9—H9B	109.5
H3A—C3—H3B	107.8	H9A—C9—H9B	109.5
O3—C4—C5	121.3 (4)	C7—C9—H9C	109.5
O3—C4—C3	121.7 (5)	H9A—C9—H9C	109.5
C5—C4—C3	116.9 (3)	H9B—C9—H9C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O3i	0.98	2.24	3.189 (5)	164
C1—H1a···O3i	0.97	2.56	3.503 (6)	164

Symmetry code: (i) x, y, z−1.