3-(2,4-Dichloro­phen­yl)-5-methyl-1,2,4-oxadiazole

Fun, H.-K.; Rosli, M.M.; Rai, S.; Isloor, A.M.; Shetty, P.

doi:10.1107/S1600536810007932

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o772

doi:10.1107/S1600536810007932

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3-(2,4-Dichlorophenyl)-5-methyl-1,2,4-oxadiazole

Hoong-Kun Fun,^a ^*‡ Mohd Mustaqim Rosli,^a Sankappa Rai,^b Arun M Isloor ^c and Prakash Shetty ^d

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bSyngene International Ltd, Biocon Park, Plot Nos 2 & 3, Bommasandra 4^th Phase, Jigani Link Rd, Bangalore 560100, India, ^cDepartment of Chemistry, Organic Chemistry Division, National Institute of Technology-Karnataka, Surathkal, Mangalore 575 025, India, and ^dDepartment of Printing, Manipal Institute of Technology, Manipal 576 104, India
^*Correspondence e-mail: hkfun@usm.my

(Received 24 February 2010; accepted 2 March 2010; online 6 March 2010)

In the title compound, C₉H₆Cl₂N₂O, the dihedral angle between the oxadiazole and benzene rings is 1.7 (2)°. In the crystal, the molecules are linked into chains along the b axis by short intermolecular Cl⋯O contacts [3.019 (3) Å].

Related literature

For general background and the biological activity of oxadiazole compounds, see: Andersen et al. (1994 ); Clitherow et al. (1996 ); Showell et al. (1991 ); Swain et al. (1991 ); Watjen et al. (1989 ). For a related structure, see: Wang et al. (2006 ). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₉H₆Cl₂N₂O
M_r = 229.06
Monoclinic, P 2₁ /c
a = 3.8252 (7) Å
b = 21.678 (4) Å
c = 11.0833 (19) Å
β = 92.421 (4)°
V = 918.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.67 mm⁻¹
T = 100 K
0.28 × 0.17 × 0.11 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.833, T_max = 0.929
7920 measured reflections
2076 independent reflections
1709 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.155
S = 1.20
2076 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810007932/ci5045sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810007932/ci5045Isup2.hkl

checkCIF report

Comment top

Heterocyclic compounds are important in recent years due to pharmacological activities. Nitrogen, oxygen containing five- and six-membered heterocyclic compounds have enormous significance in the field of medicinal chemistry. Oxadiazoles play a very vital role in the preparation of various biologically active drugs with anti-inflammatory (Andersen et al., 1994), anti-cancer (Showell et al., 1991), anti-HIV (Watjen et al., 1989), anti-diabetic and anti-microbial (Swain et al., 1991) properties. The results of biological studies showed that oxadiazole derivatives are molecules with maximum anti-inflammatory, analgesic and minimum ulcerogenic and lipid per-oxidation (Clitherow et al., 1996) properties.

Bond lengths and angles are normal (Wang et al., 2006). The mean plane of the oxadiazole ring (C1/C2/N1/N2/O1) is almost coplanar with the mean plane of the C3–C8 benzene ring (Fig. 1), with a dihedral angle of 1.7 (2)°.

The molecules are linked by Cl2···O1(-x, 1/2+y, 3/2-z) short contacts [3.019 (3) Å;] to form chains along the b axis (Fig.2).

Related literature top

For general background and the biological activity of oxadiazole compounds, see: Andersen et al. (1994); Clitherow et al. (1996); Showell et al. (1991); Swain et al. (1991); Watjen et al. (1989). For a related structure, see: Wang et al. (2006). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).

Experimental top

The title compound was prepared by heating a solution of 2,4-dichloro-N'-hydroxy-benzamidine (1 g, 0.0042 mol) and acetyl chloride (0.38 g, 0.004 mol) in pyridine (30 ml) at 387 K for 1.5 h and the contents were concentrated under vacuum. Further purification was done by column chromatography. The solid obtained was recrystallized using dichloromethane (yield: 1.0 g (76%); m.p. 371-372 K).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The crystal structure of the title compound, showing chains along the b axis.

3-(2,4-Dichlorophenyl)-5-methyl-1,2,4-oxadiazole top

Crystal data top

C₉H₆Cl₂N₂O	F(000) = 464
M_r = 229.06	D_x = 1.657 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3719 reflections
a = 3.8252 (7) Å	θ = 2.6–31.1°
b = 21.678 (4) Å	µ = 0.67 mm⁻¹
c = 11.0833 (19) Å	T = 100 K
β = 92.421 (4)°	Block, colourless
V = 918.3 (3) Å³	0.28 × 0.17 × 0.11 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2076 independent reflections
Radiation source: fine-focus sealed tube	1709 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ϕ and ω scans	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −4→4
T_min = 0.833, T_max = 0.929	k = −26→28
7920 measured reflections	l = −13→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.155	H-atom parameters constrained
S = 1.20	w = 1/[σ²(F_o²) + (0.0428P)² + 4.0517P] where P = (F_o² + 2F_c²)/3
2076 reflections	(Δ/σ)_max = 0.001
128 parameters	Δρ_max = 0.72 e Å⁻³
0 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

C₉H₆Cl₂N₂O	V = 918.3 (3) Å³
M_r = 229.06	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.8252 (7) Å	µ = 0.67 mm⁻¹
b = 21.678 (4) Å	T = 100 K
c = 11.0833 (19) Å	0.28 × 0.17 × 0.11 mm
β = 92.421 (4)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2076 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1709 reflections with I > 2σ(I)
T_min = 0.833, T_max = 0.929	R_int = 0.048
7920 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.155	H-atom parameters constrained
S = 1.20	Δρ_max = 0.72 e Å⁻³
2076 reflections	Δρ_min = −0.56 e Å⁻³
128 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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

	x	y	z	U_iso*/U_eq
Cl1	0.2530 (2)	0.40084 (4)	0.92173 (8)	0.0163 (2)
Cl2	0.1238 (3)	0.63730 (4)	0.78985 (9)	0.0185 (3)
O1	−0.2054 (8)	0.27327 (13)	0.6574 (3)	0.0220 (7)
N1	−0.3467 (8)	0.35961 (15)	0.5636 (3)	0.0158 (7)
N2	−0.0709 (10)	0.32171 (16)	0.7322 (3)	0.0194 (7)
C1	−0.3637 (11)	0.30045 (18)	0.5605 (4)	0.0173 (8)
C2	−0.1651 (10)	0.37119 (18)	0.6715 (3)	0.0140 (8)
C3	−0.0869 (9)	0.43519 (17)	0.7088 (3)	0.0124 (7)
C4	0.0928 (10)	0.45392 (18)	0.8165 (3)	0.0137 (8)
C5	0.1523 (9)	0.51553 (18)	0.8418 (4)	0.0136 (7)
H5A	0.2684	0.5272	0.9136	0.016*
C6	0.0369 (10)	0.56000 (17)	0.7588 (3)	0.0127 (7)
C7	−0.1429 (10)	0.54398 (18)	0.6533 (4)	0.0151 (8)
H7A	−0.2240	0.5740	0.5990	0.018*
C8	−0.1993 (10)	0.48214 (18)	0.6303 (4)	0.0153 (8)
H8A	−0.3186	0.4712	0.5586	0.018*
C9	−0.5226 (12)	0.2592 (2)	0.4666 (4)	0.0237 (9)
H9A	−0.6428	0.2835	0.4055	0.036*
H9B	−0.6856	0.2319	0.5028	0.036*
H9C	−0.3422	0.2354	0.4308	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0168 (5)	0.0182 (5)	0.0138 (5)	0.0028 (3)	−0.0011 (3)	0.0023 (4)
Cl2	0.0197 (5)	0.0140 (4)	0.0219 (5)	−0.0024 (3)	0.0025 (4)	−0.0017 (4)
O1	0.0309 (17)	0.0139 (14)	0.0213 (15)	−0.0017 (12)	0.0017 (12)	−0.0018 (12)
N1	0.0130 (15)	0.0175 (16)	0.0172 (17)	0.0000 (12)	0.0018 (12)	−0.0022 (13)
N2	0.0257 (19)	0.0147 (16)	0.0178 (18)	−0.0002 (14)	0.0018 (14)	−0.0032 (13)
C1	0.0148 (19)	0.0194 (19)	0.018 (2)	0.0000 (15)	0.0051 (15)	−0.0007 (15)
C2	0.0103 (17)	0.0185 (19)	0.0138 (18)	0.0022 (14)	0.0081 (14)	0.0000 (14)
C3	0.0078 (17)	0.0152 (18)	0.0150 (18)	0.0009 (13)	0.0080 (14)	−0.0011 (14)
C4	0.0126 (18)	0.0171 (19)	0.0119 (19)	0.0043 (13)	0.0054 (14)	0.0016 (14)
C5	0.0070 (16)	0.0208 (19)	0.0132 (18)	0.0017 (14)	0.0022 (13)	−0.0021 (15)
C6	0.0106 (17)	0.0134 (17)	0.0144 (18)	−0.0008 (13)	0.0033 (13)	−0.0027 (14)
C7	0.0106 (18)	0.0174 (19)	0.0177 (19)	0.0033 (14)	0.0056 (14)	0.0033 (15)
C8	0.0114 (17)	0.0181 (19)	0.017 (2)	0.0005 (14)	0.0055 (14)	0.0004 (15)
C9	0.025 (2)	0.018 (2)	0.029 (2)	−0.0030 (16)	0.0041 (18)	−0.0072 (17)

Geometric parameters (Å, º) top

Cl1—C4	1.732 (4)	C4—C5	1.382 (5)
Cl2—C6	1.740 (4)	C5—C6	1.391 (5)
O1—C1	1.346 (5)	C5—H5A	0.93
O1—N2	1.421 (4)	C6—C7	1.376 (5)
N1—C1	1.285 (5)	C7—C8	1.380 (6)
N1—C2	1.381 (5)	C7—H7A	0.93
N2—C2	1.308 (5)	C8—H8A	0.93
C1—C9	1.483 (6)	C9—H9A	0.96
C2—C3	1.475 (5)	C9—H9B	0.96
C3—C8	1.396 (5)	C9—H9C	0.96
C3—C4	1.411 (5)

C1—O1—N2	106.4 (3)	C6—C5—H5A	120.3
C1—N1—C2	103.2 (3)	C7—C6—C5	121.3 (4)
C2—N2—O1	102.8 (3)	C7—C6—Cl2	119.7 (3)
N1—C1—O1	113.3 (4)	C5—C6—Cl2	119.0 (3)
N1—C1—C9	129.8 (4)	C6—C7—C8	118.1 (4)
O1—C1—C9	116.9 (4)	C6—C7—H7A	121.0
N2—C2—N1	114.4 (4)	C8—C7—H7A	121.0
N2—C2—C3	125.4 (4)	C7—C8—C3	123.5 (4)
N1—C2—C3	120.2 (3)	C7—C8—H8A	118.3
C8—C3—C4	116.4 (3)	C3—C8—H8A	118.3
C8—C3—C2	117.2 (3)	C1—C9—H9A	109.5
C4—C3—C2	126.4 (3)	C1—C9—H9B	109.5
C5—C4—C3	121.3 (3)	H9A—C9—H9B	109.5
C5—C4—Cl1	117.1 (3)	C1—C9—H9C	109.5
C3—C4—Cl1	121.6 (3)	H9A—C9—H9C	109.5
C4—C5—C6	119.4 (3)	H9B—C9—H9C	109.5
C4—C5—H5A	120.3

C1—O1—N2—C2	0.1 (4)	C8—C3—C4—C5	0.0 (5)
C2—N1—C1—O1	−0.4 (5)	C2—C3—C4—C5	179.8 (3)
C2—N1—C1—C9	−179.1 (4)	C8—C3—C4—Cl1	−179.1 (3)
N2—O1—C1—N1	0.2 (5)	C2—C3—C4—Cl1	0.6 (5)
N2—O1—C1—C9	179.1 (3)	C3—C4—C5—C6	−0.8 (6)
O1—N2—C2—N1	−0.4 (4)	Cl1—C4—C5—C6	178.4 (3)
O1—N2—C2—C3	−179.3 (3)	C4—C5—C6—C7	1.6 (6)
C1—N1—C2—N2	0.5 (5)	C4—C5—C6—Cl2	−178.3 (3)
C1—N1—C2—C3	179.5 (3)	C5—C6—C7—C8	−1.5 (6)
N2—C2—C3—C8	178.0 (4)	Cl2—C6—C7—C8	178.4 (3)
N1—C2—C3—C8	−0.8 (5)	C6—C7—C8—C3	0.7 (6)
N2—C2—C3—C4	−1.8 (6)	C4—C3—C8—C7	0.1 (6)
N1—C2—C3—C4	179.4 (4)	C2—C3—C8—C7	−179.7 (4)

Experimental details

Crystal data
Chemical formula	C₉H₆Cl₂N₂O
M_r	229.06
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	3.8252 (7), 21.678 (4), 11.0833 (19)
β (°)	92.421 (4)
V (Å³)	918.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.67
Crystal size (mm)	0.28 × 0.17 × 0.11

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.833, 0.929
No. of measured, independent and observed [I > 2σ(I)] reflections	7920, 2076, 1709
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.155, 1.20
No. of reflections	2076
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.72, −0.56

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

HKF and MMR thank the Malaysian Government and Universiti Sains Malaysia (USM) for the Research University Golden Goose Grant (1001/PFIZIK/811012). AMI is grateful to Professor Sandeep Sancheti, Director, National Institute of Technology-Karnataka, India, for providing research facilities and encouragement.

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