[(1R,3S)-2,2-Dichloro-3-(hy­droxy­meth­yl)cyclo­prop­yl]methanol

Mohammed H Kailani

doi:10.1107/S1600536813000366

. 2013 Jan 12;69(Pt 2):o225. doi: 10.1107/S1600536813000366

[(1R,3S)-2,2-Dichloro-3-(hydroxymethyl)cyclopropyl]methanol

Mohammed H Kailani ^a,^*

PMCID: PMC3569760 PMID: 23424506

Abstract

The title compound, C₅H₈Cl₂O₂, represents a meso isomer crystallizing in a chiral space group with two molecules per asymmetric unit. The molecules form helical associates with a pitch of 6.31 Å along the a axis via O—H⋯O hydrogen bonds. The overall three-dimesional supramolecular architecture is stabilized by C—Cl⋯O halogen bonding, with a Cl⋯O separation of 3.139 (3) Å and a C—Cl⋯O angle of 162.5 (2)°.

Related literature

For background on this class of compounds, see: Kean et al. (2012 ▶); Lenhardt et al. (2009 ▶). For one-handed helical chains caused by hydrogen bonds, see: Abe et al. (2012 ▶). For the preparation of this type of compound, see: Kailani et al. (2012 ▶); Pustovit et al. (1994 ▶).

Experimental

Crystal data

C₅H₈Cl₂O₂
M _r = 171.02
Orthorhombic,
a = 6.3110 (13) Å
b = 15.429 (3) Å
c = 15.433 (3) Å
V = 1502.7 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.79 mm⁻¹
T = 293 K
0.2 × 0.1 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (COLLECT; Nonius, 2004 ▶) T _min = 0.91, T _max = 0.96
6911 measured reflections
2628 independent reflections
1969 reflections with I > 2σ(I)
R _int = 0.047

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.085
S = 1.03
2627 reflections
181 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ▶), 1081 Friedel pairs
Flack parameter: 0.03 (9)

Data collection: COLLECT (Nonius, 2004 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Click here for additional data file.^{(24.7KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813000366/ld2090sup1.cif

e-69-0o225-sup1.cif^{(24.7KB, cif)}

Click here for additional data file.^{(129KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813000366/ld2090Isup2.hkl

e-69-0o225-Isup2.hkl^{(129KB, hkl)}

Click here for additional data file.^{(2.9KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813000366/ld2090Isup3.cml

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
O1A—H4⋯O2B ⁱ	0.76 (3)	1.89 (3)	2.650 (4)	174 (4)
O2B—H3⋯O2A ⁱⁱ	0.84 (4)	1.84 (4)	2.668 (4)	171 (4)
O2A—H2⋯O1B	0.78 (4)	1.90 (4)	2.678 (4)	174 (4)
O1B—H1⋯O1A ⁱⁱⁱ	0.84 (4)	1.86 (4)	2.680 (5)	167 (4)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

Data were collected by Malva Liu Gonzalez (Universitat València–SCSIE, Carrer del Dr Moliner, 50 Edifici de Investigació, Lab-1.46/-1.51, 46100 Burjassot–València, España).

supplementary crystallographic information

Comment

The title compound contains gem-dichlororcyclopropane ring with two symmetrically positioned hydroxy groups. gem-dichlororcyclopropane ring was recently recognized as a mechanophore by Lenhardt et al. (2009) and the title compound was used by Kean et al. (2012) to make polymers with mechanophore properties. Recently, Kailani et al. (2012), also reported enhancement of antimicrobial activity for novel cis-dicarbamates prepared from title compound.

Although the title compound is a meso-isomer, it crystallizes in a chiral supramolecular architecture. Abe et al. (2012) suggested that the presence of two hydroxy groups, which form intramolecular hydrogen bonds, can result in formation of one-handed helical structures in polymers, even in an absence of chiral moieties.

The title compound, (I), crystallizes with two molecules in the asymmetric unit, as shown in Fig. 1. Although the title compound is expected to be achiral in solution due to presence of the internal plane of symmetry, in the solid state both of the molecules are found to lack a plane of symmetry. In addition, both of said molecules were found to be not superimposable with each other, resulting in a chiral, orthorhombic P2(1)2(1)2(1) space group. The structure also has a long range chiral order, helical hydrogen bonded O—H···O chains with a pitch of 6.311 Å, running along the a axis (Fig. 2). These chains are further reinforced by C1B—Cl1B···O1A halogen bonding interactions with interaction parameters of 3.139 (3) Å and 162.5 (2)° resulting in the three-dimensional supramolecular structure, as shown in Fig. 3.

The lack of plane of symmetry in each molecule in the asymmetric unit is mainly caused by the differences in the spatial arrangements of the oxygen atoms within each molecule. This is thought to be caused by the presence of high concentration of strongly associating groups, two hydroxy groups and two Cl atoms, in the relatively small title compound.

Experimental

The title compound was prepared according to literature procedure, Kailani et al. (2012), which was a modification of reported procedure, Pustovit et al. (1994), in order to improve the yield.