3-(4-Chloro­phen­yl)-2,1-benzisoxazole-5-carbonyl chloride

Yuriy Teslenko; Vasyl Matiychuk; Mykola Obushak; Vasyl Kinzhybalo; Katarzyna Ślepokura

doi:10.1107/S1600536808037872

. 2008 Nov 22;64(Pt 12):o2420. doi: 10.1107/S1600536808037872

3-(4-Chlorophenyl)-2,1-benzisoxazole-5-carbonyl chloride

Yuriy Teslenko ^a,^*, Vasyl Matiychuk ^a, Mykola Obushak ^a, Vasyl Kinzhybalo ^b, Katarzyna Ślepokura ^b

PMCID: PMC2959907 PMID: 21581388

Abstract

The molecule of the title compound, C₁₄H₇Cl₂NO₂, is not planar; the dihedral angle between the mean planes of the chlorophenyl and benzisoxazole rings is 20.32 (7)°. The carbonyl chloride group is twisted with respect to the benzisoxazole ring by 2.5 (1)°. The molecular conformation is stabilized by an intramolecular C—H⋯Cl hydrogen bond. In the crystal packing, adjacent molecules are linked into dimers by intermolecular C—H⋯O hydrogen bonds. The dimers are further stacked into columns along the unique axis direction by π–π stacking interactions, with a centroid⋯centroid distance of 3.828 (5) Å. Other weak intermolecular C—H⋯O and C—H⋯Cl interactions are also present.

Related literature

For the applications and biological activities of benzo[c]isoxazoles, see: McEvoy et al. (1968 ▶); Hester et al. (1989 ▶); Walsh et al. (1990 ▶); Angibaud et al. (2003 ▶). For details of the synthesis, see: Davis & Pizzini (1960 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₄H₇Cl₂NO₂
M _r = 292.11
Monoclinic,
a = 30.337 (6) Å
b = 3.828 (1) Å
c = 21.000 (4) Å
β = 100.67 (3)°
V = 2396.6 (9) Å³
Z = 8
Cu Kα radiation
μ = 4.85 mm⁻¹
T = 100 (2) K
0.80 × 0.15 × 0.12 mm

Data collection

Oxford Xcalibur PX κ-geometry diffractometer with Onyx CCD camera
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006 ▶) T _min = 0.21, T _max = 0.66
9609 measured reflections
2413 independent reflections
2131 reflections with I > 2σ(I)
R _int = 0.068

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.126
S = 1.05
2413 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2005 ▶); software used to prepare material for publication: publCIF (Westrip, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536808037872/rz2265sup1.cif

e-64-o2420-sup1.cif^{(15.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037872/rz2265Isup2.hkl

e-64-o2420-Isup2.hkl^{(118.7KB, 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
C4—H4⋯Cl1	0.95	2.58	3.015 (2)	108
C6—H6⋯O1ⁱ	0.95	2.53	3.378 (2)	149
C9—H9⋯Cl1ⁱⁱ	0.95	2.96	3.813 (2)	150
C13—H13⋯O2ⁱⁱⁱ	0.95	2.69	3.492 (2)	142

Open in a new tab

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

supplementary crystallographic information

Comment

Our interest in benzo[c]isoxazoles is concerned with their biological activity and their application as precursors of the variety of bioactive compounds (Angibaud et al., 2003; Walsh et al., 1990; Hester et al., 1989; McEvoy et al., 1968). The title compound will be used in our further investigations as a building block for modifications by nucleophiles.

The asymmetric unit of the title compound is shown in Figure 1. The planarity of the molecule is disturbed by intramolecular attractive and repulsive interactions of the C–H···Cl, C–H···O and C–H···H–C types. The dihedral angle between the least-square mean planes of the chlorophenyl and benzisoxazole rings is 20.32 (7)°. The carbonyl chloride group is rotated by 2.5 (1)° with respect to the benzisoxazole ring. An intramolecular C—H···Cl hydrogen bonding interactions is observed (Table 1). The crystal packing (Fig. 2) is governed by intermolecular interactions of the C–H..O type and by π-π stacking interactions. The C–H···O type hydrogen bonds connect adjacent molecules into dimers, forming ten-membered rings of graph set motif R²₂(10) (Bernstein et al., 1995). The dimers are further linked along the unique axis direction by π-π stacking interactions: Cg1···Cg1ⁱ = Cg2···Cg2ⁱ = 3.828 (5) Å (Cg1 and Cg2 are the centroids of the C1/C2/C4–C7 and C8–C13 aromatic rings, respectively; symmetry code: (i) x, 1+y, z); the corresponding perpendicular interplanar distances are 3.429 (4) and 3.475 (4) Å, respectively, and the centroid-centroid offsets are 1.702 (4) and 1.605 (3) Å, respectively. Additionally, two weak C–H···O and C—H···Cl interactions are present in the structure (shown as dotted lines in Figure 2).

Experimental

To 40 ml of an ethanol solution of potassium hydroxide (4 g, 0.1 mol) p-nitrobenzoic acid (1.67 g, 10 mmol) was added with stirring. Then 5 ml of an ethanol solution of 4-chlorophenylacetonitrile (1.82 g, 12 mmol) was added to the reaction mixture. The suspension was stirred for 4 h at 323 K and left overnight at room temperature. The reaction mixture was poured into 150 ml of water and acidified with hydrochloric acid. The precipitate was isolated by filtration, washed with water and dried. Crude acid was added to a solution of thionyl chloride (1.19 ml, 20 mmol) in benzene (15 ml) and heated under reflux until a clear solution was obtained. Yellow needles of the title compound were obtained by slow cooling of the reaction solution (m.p. 453–454 K; 2 g, yield 70%).