Benzoyl­methyl 4-chloro­benzoate

Yi Jin; Jian-Nan Guo; Kan Lin; Guo Tang; Yu-Fen Zhao

doi:10.1107/S1600536807066469

. 2008 Jan 23;64(Pt 2):o507. doi: 10.1107/S1600536807066469

Benzoylmethyl 4-chlorobenzoate

Yi Jin ^a, Jian-Nan Guo ^a,^*, Kan Lin ^a, Guo Tang ^a, Yu-Fen Zhao ^a

PMCID: PMC2960412 PMID: 21201527

Abstract

The asymmetric unit of the title compound, C₁₅H₁₁ClO₃, contains three molecules, A, B, and C. Molecules A and B are aligned edge-to-face, whereas molecules B and C are aligned almost parallel to each other. The crystal structure displays C—H⋯π and π–π [centroid–centroid distances of 3.960 (4), 3.971 (4) and 3.971 (4) for molecules A, B and C, respectively] parallel-displaced interactions, and C—H⋯O hydrogen bonds.

Related literature

For background literature, see: Kelly & Howard (1932 ▶). For the synthesis, see Hendrickson & Kandall (1970 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₅H₁₁ClO₃
M _r = 274.69
Monoclinic,
a = 14.7634 (6) Å
b = 16.4509 (6) Å
c = 15.8214 (5) Å
β = 92.105 (4)°
V = 3840.0 (2) Å³
Z = 12
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 293 (2) K
0.18 × 0.15 × 0.10 mm

Data collection

Bruker APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.948, T _max = 0.971
18809 measured reflections
6647 independent reflections
3093 reflections with I > 2σ(I)
R _int = 0.061

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.071
S = 0.79
6647 reflections
514 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT (Bruker, 2001 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807066469/ng2408sup1.cif

e-64-0o507-sup1.cif^{(31.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807066469/ng2408Isup2.hkl

e-64-0o507-Isup2.hkl^{(325.3KB, 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
C8A—H8AB⋯O3B	0.97	2.55	3.322 (3)	137
C8C—H8CB⋯O3Aⁱ	0.97	2.55	3.212 (3)	126
C11A—H11A⋯Cg1B	0.93	3.46	4.036 (4)	123
C11B—H11B⋯Cg1A	0.93	3.10	3.917 (4)	137

Open in a new tab

Symmetry code: (i) Inline graphic . Cg1A and Cg1B are the centroids of the C1A–C6A and C1B–C6B benzene rings, respectively.

Acknowledgments

The authors acknowledge financial support from the Key Foundation of Science & Technology Project of Fujian Province, China (Key grant No. 2002H011) and also thank Professor G. M. Blackburn and Mr Harry Adams of Sheffield University Chemistry Department for their helpful suggestions.

supplementary crystallographic information

Comment

An X-ray crystal structure determination of the molecule of the title compound, 2-oxo-2-phenylethyl 4-chlorobenzoate, (I) (Scheme. 1), was carried out to determine its conformation and the results are presented here. The bond lengths and angles are within their normal ranges (Allen et al., 1987).

The unit cell has four identical asymmetric units which contain three molecules of (I) each (Fig. 2). In each asymmetric unit, the benzene rings of molecules B and C stack in a parallel-displaced structure, while the benzene rings of molecules A and B form a displaced T-shaped structure (Fig. 1). The two benzene rings within molecule A make a dihedral angle of 61.68 (6)°, while the two benzene rings within molecules B and C make almost identical dihedral angles of 77.66 (6)° and 77.29 (6)° respectively.

Hydrogen bonds C—H···O which are found not only between molecules A and B in the asymmetric unit but also between molecule A and the symmetry- equivalent Ci in the next asymmetric unit (Fig. 3). These C—H···O interactions stabilize the formation of asymmetric units as well as of the whole unit cell (Table 2).

Meanwhile, π—π interactions in stacked, slipped benzene rings from two symmetry-equivalent molecules in adjacent asymmetric units also provide stability for the crystal structure. The distance between Cg1 A and Cg2 Aⁱⁱ is 3.960 (4) Å and the angles between the line through the centroids of these two benzene rings and the normal through Cg1 A is 26.6 (1)° and through Cg2 Aⁱⁱ is 25.0 (1)°. The corresponding values for benzene rings C1B/C6B and C10B/C15Bⁱⁱⁱ are 3.971 (4) Å, 26.4 (1)° and 24.9 (1)°. For C1C/C6C and C10C/C15Cⁱⁱⁱ they are 3.971 (4) Å, 18.1 (1)° and 33.5 (1)°.Cg1X and Cg2X are the centroids of C1/C6 and C10/C15 benzene rings in molecule X (X=A, B, C) respectively [Symmetry code: (ii) x, -y - 1/2, z + 1/2; (iii) x, -y + 1/2, z - 1/2] (Fig. 2). The packing is further stabilized by weak C—H···π interactions(Table 1).The distances and angles correspond to their caculated ranges.

Experimental

Triethylamine (0.84 ml, 6 mmol) was slowly dropped into 2-bromo-1-phenylethanone (796 mg, 4 mmol) and 4-chlorobenzoic acid (630 mg, 4 mmol) dissolved in freshly distilled tetrahydrofuran (10 ml) at rt under nitrogen and stirred overnight. The precipitate was collected at the pump and washed with ethyl acetate. The filtrate and washings were combined and back-washed successively with 1/3 of the volume each of 10% citric acid, 10% sodium bicarbonate, and water and then dried. Solvent was distilled off in vacuo and the residue recrystallized repeatedly from ethyl acetate-petroleum ether giving 1.085 g (98%) as colourless needles, m.p.128°C. (Hendrickson & Kandall, 1970).