organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

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

aDepartment of Organic Chemistry, Ivan Franko National University of Lviv, Kyryla and Mefodiya 6, Lviv, 79005, Ukraine, and bFaculty of Chemistry, University of Wrocław, 14 Joliot-Curie St, 50-383 Wrocław, Poland
*Correspondence e-mail: dangercorp@gmail.com

(Received 29 October 2008; accepted 14 November 2008; online 22 November 2008)

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 ππ 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[McEvoy, F. J., Greenblatt, E. N., Osterrerg, A. C. & Allen, G. R. Jr (1968). J. Med. Chem. 11, 1248-1250.]); Hester et al. (1989[Hester, J. B., Ludens, J. H., Emmert, D. E. & West, B. E. (1989). J. Med. Chem. 32, 1157-1163.]); Walsh et al. (1990[Walsh, D. A., Moran, H. W., Shamblee, D. A. & Welstead, W. J. (1990). J. Med. Chem. 33, 2296-2304.]); Angibaud et al. (2003[Angibaud, P., et al. (2003). Bioorg. Med. Chem. Lett. 13, 1543-1548.]). For details of the synthesis, see: Davis & Pizzini (1960[Davis, R. B. & Pizzini, L. C. (1960). J. Org. Chem. 25, 1884-1888.]). For hydrogen-bond motifs, see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]).

[Scheme 1]

Experimental

Crystal data
  • C14H7Cl2NO2

  • Mr = 292.11

  • Monoclinic, C 2/c

  • 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[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, Oxfordshire, England.]) Tmin = 0.21, Tmax = 0.66

  • 9609 measured reflections

  • 2413 independent reflections

  • 2131 reflections with I > 2σ(I)

  • Rint = 0.068

Refinement
  • R[F2 > 2σ(F2)] = 0.044

  • wR(F2) = 0.126

  • S = 1.05

  • 2413 reflections

  • 173 parameters

  • H-atom parameters constrained

  • Δρmax = 0.30 e Å−3

  • Δρmin = −0.60 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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
Symmetry codes: (i) [-x+{\script{1\over 2}}, -y+{\script{5\over 2}}, -z]; (ii) [-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (iii) [-x+1, y, -z+{\script{1\over 2}}].

Data collection: CrysAlis CCD (Oxford Diffraction, 2006[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, Oxfordshire, England.]); cell refinement: CrysAlis RED (Oxford Diffraction, 2006[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, Oxfordshire, England.]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg, 2005[Brandenburg, K. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: publCIF (Westrip, 2008[Westrip, S. P. (2008). publCIF. In preparation.]).

Supporting information


Comment top

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).

Related literature top

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 related literature, see: Bernstein et al. (1995).

Experimental top

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%).

Refinement top

All H atoms were found in difference-Fourier maps. In the final refinement cycles, H atoms were positioned geometrically and treated as riding atoms, with C–H = 0.95 Å and with Uiso(H) = 1.2 Ueq(C).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); 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).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with the atom labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Packing diagram of the title compound viewed along the b axis, showing intermolecular hydrogen bonds (dashed lines) and weak hydrogen interactions (dotted lines). Symmetry codes are as in Table 1.
3-(4-Chlorophenyl)-2,1-benzisoxazole-5-carbonyl chloride top
Crystal data top
C14H7Cl2NO2F(000) = 1184
Mr = 292.11Dx = 1.619 Mg m3
Monoclinic, C2/cMelting point: 453-454 K K
Hall symbol: -C 2ycCu Kα radiation, λ = 1.54180 Å
a = 30.337 (6) ÅCell parameters from 9042 reflections
b = 3.828 (1) Åθ = 2.2–76.9°
c = 21.000 (4) ŵ = 4.85 mm1
β = 100.67 (3)°T = 100 K
V = 2396.6 (9) Å3Needle, yellow
Z = 80.80 × 0.15 × 0.12 mm
Data collection top
Xcalibur PX κ-geometry
diffractometer with CCD Onyx camera
2413 independent reflections
Radiation source: fine-focus sealed tube2131 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.068
ω and ϕ scansθmax = 76.7°, θmin = 4.3°
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2006)
h = 3821
Tmin = 0.21, Tmax = 0.66k = 44
9609 measured reflectionsl = 2026
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.126 w = 1/[σ2(Fo2) + (0.1002P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
2413 reflectionsΔρmax = 0.30 e Å3
173 parametersΔρmin = 0.60 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00084 (17)
Crystal data top
C14H7Cl2NO2V = 2396.6 (9) Å3
Mr = 292.11Z = 8
Monoclinic, C2/cCu Kα radiation
a = 30.337 (6) ŵ = 4.85 mm1
b = 3.828 (1) ÅT = 100 K
c = 21.000 (4) Å0.80 × 0.15 × 0.12 mm
β = 100.67 (3)°
Data collection top
Xcalibur PX κ-geometry
diffractometer with CCD Onyx camera
2413 independent reflections
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2006)
2131 reflections with I > 2σ(I)
Tmin = 0.21, Tmax = 0.66Rint = 0.068
9609 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.126H-atom parameters constrained
S = 1.05Δρmax = 0.30 e Å3
2413 reflectionsΔρmin = 0.60 e Å3
173 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.226537 (14)0.66461 (14)0.17672 (2)0.0394 (2)
Cl20.440884 (15)0.22145 (13)0.50018 (2)0.0379 (2)
O20.44488 (4)0.9282 (4)0.21086 (6)0.0344 (3)
O10.22228 (5)0.9426 (5)0.06384 (7)0.0531 (4)
N10.43252 (5)1.0756 (5)0.14821 (8)0.0373 (4)
C30.40860 (5)0.8178 (5)0.23358 (8)0.0276 (4)
C10.38838 (6)1.0480 (5)0.13517 (8)0.0305 (4)
C20.37105 (5)0.8870 (5)0.18709 (8)0.0272 (4)
C70.35923 (6)1.1558 (5)0.07744 (9)0.0348 (4)
H70.37061.26600.04330.042*
C60.31470 (6)1.0960 (5)0.07275 (8)0.0341 (4)
H60.29461.16680.03470.041*
C50.29704 (5)0.9272 (5)0.12426 (8)0.0286 (4)
C40.32426 (5)0.8258 (5)0.18041 (8)0.0277 (4)
H40.31220.71710.21410.033*
C80.41646 (5)0.6636 (5)0.29788 (8)0.0277 (4)
C90.38161 (5)0.6433 (5)0.33305 (8)0.0312 (4)
H90.35260.72610.31430.037*
C100.38894 (5)0.5044 (5)0.39469 (8)0.0325 (4)
H100.36520.49050.41830.039*
C110.43141 (6)0.3854 (5)0.42168 (8)0.0297 (4)
C120.46655 (5)0.3991 (5)0.38806 (8)0.0316 (4)
H120.49540.31480.40720.038*
C130.45895 (5)0.5378 (5)0.32618 (8)0.0314 (4)
H130.48280.54780.30260.038*
C150.24813 (6)0.8697 (5)0.11157 (9)0.0338 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0264 (2)0.0502 (4)0.0408 (3)0.00458 (17)0.00416 (19)0.00756 (19)
Cl20.0379 (3)0.0451 (3)0.0291 (3)0.00141 (18)0.00193 (19)0.00423 (17)
O20.0246 (6)0.0479 (8)0.0318 (6)0.0032 (5)0.0085 (5)0.0005 (5)
O10.0335 (7)0.0836 (13)0.0381 (8)0.0006 (8)0.0038 (6)0.0134 (8)
N10.0319 (8)0.0487 (10)0.0329 (8)0.0029 (7)0.0102 (6)0.0036 (7)
C30.0230 (7)0.0322 (9)0.0288 (8)0.0031 (6)0.0074 (6)0.0050 (6)
C10.0315 (8)0.0325 (9)0.0296 (8)0.0017 (7)0.0112 (7)0.0012 (7)
C20.0268 (8)0.0288 (9)0.0268 (8)0.0006 (6)0.0069 (6)0.0022 (6)
C70.0394 (9)0.0377 (10)0.0292 (9)0.0014 (7)0.0116 (7)0.0045 (7)
C60.0373 (9)0.0380 (10)0.0268 (8)0.0056 (7)0.0050 (7)0.0033 (7)
C50.0275 (8)0.0311 (9)0.0271 (8)0.0003 (6)0.0045 (6)0.0016 (7)
C40.0250 (8)0.0327 (9)0.0256 (8)0.0003 (6)0.0054 (6)0.0001 (6)
C80.0228 (7)0.0328 (9)0.0270 (8)0.0023 (6)0.0035 (6)0.0034 (6)
C90.0211 (7)0.0429 (10)0.0293 (8)0.0034 (7)0.0037 (6)0.0020 (7)
C100.0232 (7)0.0445 (11)0.0298 (8)0.0001 (7)0.0051 (6)0.0034 (7)
C110.0290 (8)0.0323 (9)0.0268 (8)0.0007 (7)0.0028 (6)0.0023 (7)
C120.0231 (7)0.0381 (10)0.0320 (8)0.0036 (7)0.0006 (6)0.0013 (7)
C130.0197 (7)0.0416 (10)0.0331 (8)0.0006 (7)0.0054 (6)0.0041 (7)
C150.0293 (8)0.0410 (10)0.0296 (8)0.0010 (7)0.0016 (7)0.0007 (8)
Geometric parameters (Å, º) top
Cl1—C151.803 (2)C6—H60.9500
Cl2—C111.7373 (18)C5—C41.365 (2)
O2—C31.3461 (19)C5—C151.475 (2)
O2—N11.417 (2)C4—H40.9500
O1—C151.186 (2)C8—C91.400 (2)
N1—C11.320 (2)C8—C131.401 (2)
C3—C21.382 (2)C9—C101.379 (3)
C3—C81.452 (2)C9—H90.9500
C1—C71.423 (3)C10—C111.385 (2)
C1—C21.434 (2)C10—H100.9500
C2—C41.420 (2)C11—C121.384 (2)
C7—C61.356 (3)C12—C131.383 (2)
C7—H70.9500C12—H120.9500
C6—C51.446 (2)C13—H130.9500
C3—O2—N1111.15 (13)C2—C4—H4120.9
C1—N1—O2104.15 (13)C9—C8—C13118.86 (16)
O2—C3—C2108.11 (15)C9—C8—C3120.21 (15)
O2—C3—C8116.92 (15)C13—C8—C3120.92 (15)
C2—C3—C8134.97 (15)C10—C9—C8120.70 (16)
N1—C1—C7126.85 (16)C10—C9—H9119.6
N1—C1—C2112.17 (16)C8—C9—H9119.6
C7—C1—C2120.98 (15)C9—C10—C11119.16 (16)
C3—C2—C4135.77 (16)C9—C10—H10120.4
C3—C2—C1104.42 (14)C11—C10—H10120.4
C4—C2—C1119.77 (16)C12—C11—C10121.64 (16)
C6—C7—C1117.82 (16)C12—C11—Cl2119.33 (14)
C6—C7—H7121.1C10—C11—Cl2119.02 (13)
C1—C7—H7121.1C13—C12—C11118.92 (15)
C7—C6—C5121.57 (17)C13—C12—H12120.5
C7—C6—H6119.2C11—C12—H12120.5
C5—C6—H6119.2C12—C13—C8120.72 (15)
C4—C5—C6121.66 (15)C12—C13—H13119.6
C4—C5—C15122.78 (16)C8—C13—H13119.6
C6—C5—C15115.56 (16)O1—C15—C5127.12 (18)
C5—C4—C2118.18 (15)O1—C15—Cl1117.88 (15)
C5—C4—H4120.9C5—C15—Cl1115.00 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4···Cl10.952.583.015 (2)108
C6—H6···O1i0.952.533.378 (2)149
C9—H9···Cl1ii0.952.963.813 (2)150
C13—H13···O2iii0.952.693.492 (2)142
Symmetry codes: (i) x+1/2, y+5/2, z; (ii) x+1/2, y+1/2, z+1/2; (iii) x+1, y, z+1/2.

Experimental details

Crystal data
Chemical formulaC14H7Cl2NO2
Mr292.11
Crystal system, space groupMonoclinic, C2/c
Temperature (K)100
a, b, c (Å)30.337 (6), 3.828 (1), 21.000 (4)
β (°) 100.67 (3)
V3)2396.6 (9)
Z8
Radiation typeCu Kα
µ (mm1)4.85
Crystal size (mm)0.80 × 0.15 × 0.12
Data collection
DiffractometerXcalibur PX κ-geometry
diffractometer with CCD Onyx camera
Absorption correctionAnalytical
(CrysAlis RED; Oxford Diffraction, 2006)
Tmin, Tmax0.21, 0.66
No. of measured, independent and
observed [I > 2σ(I)] reflections
9609, 2413, 2131
Rint0.068
(sin θ/λ)max1)0.631
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.126, 1.05
No. of reflections2413
No. of parameters173
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.30, 0.60

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2005), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4···Cl10.952.583.015 (2)108.2
C6—H6···O1i0.952.533.378 (2)149.2
C9—H9···Cl1ii0.952.963.813 (2)149.5
C13—H13···O2iii0.952.693.492 (2)142.3
Symmetry codes: (i) x+1/2, y+5/2, z; (ii) x+1/2, y+1/2, z+1/2; (iii) x+1, y, z+1/2.
 

References

First citationAngibaud, P., et al. (2003). Bioorg. Med. Chem. Lett. 13, 1543–1548.  Web of Science CrossRef PubMed CAS
First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science
First citationBrandenburg, K. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany.
First citationDavis, R. B. & Pizzini, L. C. (1960). J. Org. Chem. 25, 1884–1888.  CrossRef CAS Web of Science
First citationHester, J. B., Ludens, J. H., Emmert, D. E. & West, B. E. (1989). J. Med. Chem. 32, 1157–1163.  CrossRef CAS PubMed Web of Science
First citationMcEvoy, F. J., Greenblatt, E. N., Osterrerg, A. C. & Allen, G. R. Jr (1968). J. Med. Chem. 11, 1248–1250.  CrossRef CAS PubMed Web of Science
First citationOxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, Oxfordshire, England.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationWalsh, D. A., Moran, H. W., Shamblee, D. A. & Welstead, W. J. (1990). J. Med. Chem. 33, 2296–2304.  CrossRef CAS PubMed Web of Science
First citationWestrip, S. P. (2008). publCIF. In preparation.

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds