Dimethyl 2-(3-chloro­phen­yl)-6-hy­droxy-6-methyl-4-(methyl­amino)­cyclo­hex-3-ene-1,3-dicarboxyl­ate

S Amirthaganesan; S Sundaramoorthy; D Velmurugan; Y T Jeong

doi:10.1107/S1600536811017089

. 2011 May 14;67(Pt 6):o1424. doi: 10.1107/S1600536811017089

Dimethyl 2-(3-chlorophenyl)-6-hydroxy-6-methyl-4-(methylamino)cyclohex-3-ene-1,3-dicarboxylate

S Amirthaganesan ^a, S Sundaramoorthy ^b, D Velmurugan ^b, Y T Jeong ^a,^*

PMCID: PMC3120530 PMID: 21754804

Abstract

In the title compound, C₁₈H₂₂ClNO₅, the cyclohexene ring adopts a distorted half-chair conformation. The molecular structure is stabilized by pairs of intramolecular N—H⋯O and O—H⋯O interactions, generating S(6) motifs. In the crystal, the molecules are linked by intermolecular C—H⋯O interactions, forming centrosymmetric dimers.

Related literature

For the synthesis see: Pandiarajan et al. (2005 ▶). For related structures, see: Amézquita-Valencia et al. (2009, ▶ 2010) ▶; Venter et al. (2010 ▶). For ring conformational analysis, see: Cremer & Pople (1975 ▶); Nardelli (1983 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₈H₂₂ClNO₅
M _r = 367.82
Monoclinic,
a = 11.962 (3) Å
b = 9.118 (4) Å
c = 17.704 (5) Å
β = 104.890 (3)°
V = 1866.1 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 293 K
0.25 × 0.22 × 0.2 mm

Data collection

Bruker SMART APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.944, T _max = 0.955
17431 measured reflections
4638 independent reflections
3337 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.138
S = 1.04
4638 reflections
231 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811017089/bt5540sup1.cif

e-67-o1424-sup1.cif^{(20.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811017089/bt5540Isup2.hkl

e-67-o1424-Isup2.hkl^{(222.6KB, hkl)}

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
N1—H1A⋯O1	0.86	2.0	2.673 (2)	134
O3—H4A⋯O4	0.82	2.39	2.990 (2)	131
C15—H15B⋯O1ⁱ	0.96	2.52	3.327 (3)	142

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Symmetry code: (i) Inline graphic .

Acknowledgments

This study was supported financially by Pukyong National University in the 2009 Post-Doc. Program. SS and DV thank the TBI X-ray Facility, CAS in Crystallography and Biophysics, University of Madras, India, for the data collection and the University Grants Commission (UGC&SAP) for financial support.

supplementary crystallographic information

Comment

The title compound has been obtained as a minor product during the synthesis of 2,4-bismethoxycarbonyl-3-(3-chlorophenyl)- 5-hydroxy-5-methylcyclohexanone (Pandiarajan et al., 2005). The synthesized cyclohexanone has been purified by the recrystallization process in ethanol solvent. The expected compound regenerated and settled as powder along with some small crystals. The obtained crystals were analysed by single-crystal XRD and the results clearly evidence the formation of the title compound.

The ORTEP diagram of the title compound is shown in Fig.1. The cyclohexane ring adopts a distorted half-chair conformation with the puckering parameters (Cremer & Pople, 1975) and the smallest displacement asymmetry parameters (Nardelli, 1983) being q₂ = 0.4038 (16) Å, q₃ = -0.3083 (16) Å, Q_T = 0.5080 (16) Å, and θ = 127.36 (18)°. Atom Cl1 deviates from the plane of the C1—C6 benzene ring by 0.034 (1) Å.

The crystal packing is stabilized by C—H···O intermolecular interactions. The molecular structure is stabilized by N—H···O and O—H···O hydrogen bonds, wherein, atom N1 and O3 act as donor to O1 and O4, to generate S(6) motifs, respectively. In the crystal structure, the molecules at (x, y, z) and (1 - x,1 - y,1 - z) are linked by C(15)—H(15B) ···O(1) hydrogen bonds, generating a centrosymmetric dimeric ring motif R₂²(14) (Bernstein et al., 1995).

Experimental

A mixture of 3-chlorobenzaldehyde (1 equvi) and methyl acetoacetate (2 equvi) and 40% methylamine solution (1 equvi) in ethanol was kept in hot water bath for about 30 minutes. It was kept aside for a day. The separated solid was recrystallized from ethanol.