(4S)-4-[(R)-Chloro­(4-nitro­phen­yl)meth­yl]-1,3-oxazolidin-2-one

V Gaumet; C Denis; M Madesclaire; V P Zaitsev

doi:10.1107/S1600536813010398

. 2013 Apr 24;69(Pt 5):o783. doi: 10.1107/S1600536813010398

(4S)-4-[(R)-Chloro(4-nitrophenyl)methyl]-1,3-oxazolidin-2-one

V Gaumet ^a,^*, C Denis ^a, M Madesclaire ^b, V P Zaitsev ^c

PMCID: PMC3648307 PMID: 23723927

Abstract

In the title compound, C₁₀H₉ClN₂O₄, the oxazolidinone ring adopts a near-planar conformation, with mean and maximum deviations of 0.0204 (8) and 0.0328 (8) Å, respectively. The nitro group is twisted slightly from the plane of the benzene ring, making a dihedral angle of 6.79 (3)°. The dihedral angle between the mean oxazolidinone plane and the benzene ring is 56.21 (3)°. In the crystal, N—H⋯O hydrogen bonds and N—O⋯π interactions [O⋯centroid distances = 3.478 (1) and 3.238 (1) Å] dominate the packing, forming infinite zigzag chains along the b-axis direction. Neighbouring chains are linked together through C—H⋯O and C—H⋯Cl interactions. The absolute configuration of the two stereogenic centres was determined using the anomalous dispersion of the Cl atom.

Related literature

For the biological activity of oxazolidinone derivatives, see: Michalska et al. (2012 ▶); Mathur et al. (2013 ▶); Jindal et al. (2013 ▶). For related structures, see: Bach et al. (2001 ▶); Tsui et al. (2013 ▶). For detailed of the synthesis, see: Madesclaire et al. (2013 ▶). graphic file with name e-69-0o783-scheme1.jpg

Experimental

Crystal data

C₁₀H₉ClN₂O₄
M _r = 256.64
Monoclinic,
a = 7.2372 (1) Å
b = 6.6726 (1) Å
c = 11.7126 (2) Å
β = 106.715 (1)°
V = 541.71 (1) Å³
Z = 2
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 296 K
0.52 × 0.49 × 0.34 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2012 ▶) T _min = 0.915, T _max = 1.000
12895 measured reflections
6114 independent reflections
5384 reflections with I > 2σ(I)
R _int = 0.014

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.098
S = 1.06
6114 reflections
158 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.44 e Å⁻³
Absolute structure: Flack (1983 ▶), 2348 Friedel pairs
Flack parameter: −0.03 (3)

Data collection: APEX2 (Bruker, 2012 ▶); cell refinement: SAINT (Bruker, 2012 ▶); 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 for Windows (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(20.7KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813010398/kp2451sup1.cif

e-69-0o783-sup1.cif^{(20.7KB, cif)}

Click here for additional data file.^{(299.3KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813010398/kp2451Isup2.hkl

e-69-0o783-Isup2.hkl^{(299.3KB, hkl)}

Click here for additional data file.^{(4.5KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813010398/kp2451Isup3.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
N3—H3⋯O15ⁱ	0.77 (2)	2.32 (2)	3.095 (1)	179 (2)
C6—H6⋯O16ⁱⁱ	0.98	2.46	3.309 (2)	145
C11—H11⋯Cl17ⁱⁱⁱ	0.93	2.83	3.582 (1)	139

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

supplementary crystallographic information

Comment

Oxazolidinones are a new class of synthetic antimicrobial agents. Linezolid is the first oxazolidinone approved for human use in the treatment of multidrug-resistant gram-positive bacterial infections (Michalska et al., 2012; Mathur et al., 2013). Linezolid may also offer novel disease modifying and symptomatic therapeutic potential for the treatment of anxiety disorders (Jindal et al., 2013).

The molecular structure of the title compound (Fig. 1) reveals a planar oxazolidinone ring with a mean deviation of 0.0204 (8) Å, maximum deviation from planarity being 0.0328 (8) Å for atom C5. The dihedral angle between the mean oxazolidinone plane and the phenyl ring is 56.21 (3)°. The p-NO₂ group form a interplanar angle of 6.79° with the benzene ring. In the crystal, molecules are linked through N3—H3···O15 hydrogen bonds into infinite zigzag chains extending along the b axis (Table 1, Fig. 2). In chains, molecules are regularly arranged in head-to-tail sequence allowing N—O···π stacking interactions which reinforce the chain cohesion (Fig. 2 and 3). These stacking forces are characterized by two N13—O15···C_g^{i, iv} [symmetry code: i: -x + 1, y + 1/2, -z + 1; iv: -x + 1, y - 1/2, -z + 1] interactions with distances of 3.478 (1) Å and 3.238 (1) Å between the O15 atom and centroid, C_g, of the (C7—C12) aromatic rings. Adjacent chains build the three dimensional network via C6—H6···O16 and C11—H11···Cl17 interactions (Table 1).

The title coumpound exhibits structural similarities with related structures (Bach et al., 2001; Tsui et al., 2013).

Experimental

The title compound was obtained as a by-product from the reaction of 4-[hydroxy(4-nitrophenyl)methyl]-1,3-oxazolidin-2-one and benzenesulfonyl chloride with pyridine in chloroform. The synthesis process is described by Madesclaire et al. (2013). After isolation and purification by column chromatography, crystals suitable for X-ray analysis were obtained by slow evaporation from a mixture of ethyl acetate-cyclohexane (1:1 vol.) solution.