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

Novaković, S.B.; Rodić, M.V.; Jaćimović, Ž.K.; Ratković, Z.; Sukdolak, S.

doi:10.1107/S1600536813027517

organic compounds

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ISSN: 2056-9890

Volume 69| Part 11| November 2013| Page o1638

doi:10.1107/S1600536813027517

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

Sladjana B. Novaković,^a Marko V. Rodić,^b Željko K. Jaćimović,^c ^* Zoran Ratković ^d and Slobodan Sukdolak ^d

^aVinča Institute of Nuclear Sciences, Laboratory of Theoretical Physics and Condensed Matter Physics, PO Box 522, University of Belgrade, 11001 Belgrade, Serbia, ^bFaculty of Sciences, University of Novi Sad, Trg Dositeja Obradovića 3, 21000 Novi Sad, Serbia, ^cFaculty of Metallurgy and Technology, University of Montenegro, Cetinjski put bb, 81000 Podgorica, Montenegro, and ^dFaculty of Sciences, Department of Chemistry, University of Kragujevac, R. Domanovića 12, 34000 Kragujevac, Serbia
^*Correspondence e-mail: zeljkoj@ac.me

(Received 1 October 2013; accepted 8 October 2013; online 16 October 2013)

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.

CCDC reference: 965241

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, P 2₁ /c
a = 13.8922 (7) Å
b = 10.4531 (9) Å
c = 7.8696 (5) Å
β = 101.682 (6)°
V = 1119.12 (13) Å³
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[F² > 2σ(F²)] = 0.073
wR(F²) = 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

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) x, y, z-1.

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 ).

Supporting information

CCDC reference: 965241

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813027517/bt6936sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813027517/bt6936Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813027517/bt6936Isup3.cml

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); 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).

Figures top

	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.

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

Crystal data top

C₉H₁₁Cl₂NO₃	F(000) = 520
M_r = 252.09	D_x = 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 top

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

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)] = 0.073	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.214	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0912P)² + 0.9148P] where P = (F_o² + 2F_c²)/3
2160 reflections	(Δ/σ)_max < 0.001
137 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

C₉H₁₁Cl₂NO₃	V = 1119.12 (13) Å³
M_r = 252.09	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 13.8922 (7) Å	µ = 5.14 mm⁻¹
b = 10.4531 (9) Å	T = 293 K
c = 7.8696 (5) Å	0.11 × 0.10 × 0.05 mm
β = 101.682 (6)°

Data collection top

Agilent Gemini S diffractometer	2160 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	1674 reflections with I > 2σ(I)
T_min = 0.288, T_max = 1.000	R_int = 0.016
4083 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.073	0 restraints
wR(F²) = 0.214	H-atom parameters constrained
S = 1.13	Δρ_max = 0.44 e Å⁻³
2160 reflections	Δρ_min = −0.46 e Å⁻³
137 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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) top

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) top

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.

Hydrogen-bond geometry (Å, º) top

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.

Acknowledgements

This work was supported by the Ministry of Education, Science and Technological Development of the Republic of Serbia (project Nos. 172014, 172035 and 172034).

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