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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): o2127.
Published online 2010 July 31. doi:  10.1107/S1600536810029284
PMCID: PMC3007510

N-(4-Chloro­benzyl­idene)-3,4-dimethyl­isoxazol-5-amine

Abstract

The mol­ecule of the title compound, C12H11ClN2O, has E configuration at the azomethine double bond and is virtually planar with a dihedral angle of 1.25 (13)° between the benzene and isoxazole rings. C—H(...)π inter­actions stabilize the crystal structure.

Related literature

For related structures, see: Asiri et al. (2010a [triangle],b [triangle]); Fun et al. (2010a [triangle],b [triangle]); Shad et al. (2008 [triangle]); Tahir et al. (2008 [triangle]). For graph-set notation, see: Bernstein et al. (1995 [triangle]).

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Object name is e-66-o2127-scheme1.jpg

Experimental

Crystal data

  • C12H11ClN2O
  • M r = 234.68
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2127-efi1.jpg
  • a = 5.0877 (2) Å
  • b = 24.5197 (9) Å
  • c = 9.4673 (4) Å
  • β = 94.871 (2)°
  • V = 1176.77 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.30 mm−1
  • T = 296 K
  • 0.30 × 0.16 × 0.14 mm

Data collection

  • Bruker Kappa APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.868, T max = 0.965
  • 9016 measured reflections
  • 2112 independent reflections
  • 1539 reflections with I > 2σ(I)
  • R int = 0.030

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.120
  • S = 1.07
  • 2112 reflections
  • 147 parameters
  • H-atom parameters constrained
  • Δρmax = 0.15 e Å−3
  • Δρmin = −0.14 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks text, I. DOI: 10.1107/S1600536810029284/gk2296sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810029284/gk2296Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors would like to thank the Chemistry Department, King Abdul Aziz University, Jeddah, Saudi Arabia for providing research facilities.

supplementary crystallographic information

Comment

The title compound (Fig. 1) has been prepared in continuation of our work on the synthesis of Schiff bases of 3,4-dimethyisoxazol-5-amine. We have recently reported the crystal structure of N-(4-bromobenzylidene)-3,4-dimethylisoxazol-5-amine (Asiri et al., 2010a), which is isostructural with the title compound.

The crystal structures of 4-chloro-2- [(E)-({4-[N-(3,4-dimethylisoxazol-5-yl)sulfamoyl]phenyl}iminio) methyl]phenolate (Shad et al., 2008), 4-bromo-2-((E)-{4-[(3,4-dimethylisoxazol-5-yl)sulfamoyl]phenyl} iminiomethyl)phenolate (Tahir et al., 2008), 2-[(E)-(3,4-dimethylisoxazol-5-yl)iminomethyl]phenol (Fun et al., 2010a), 1-[(E)-(3,4-dimethylisoxazol-5-yl)iminomethyl]-2-naphthol (Fun et al., 2010b) and N-[4-(dimethylamino)benzylidene]-3,4-dimethylisoxazol-5-amine (Asiri et al., 2010b) have also been published previously, which contain the 5-amino-3,4-dimethylisoxazole moiety.

In the title compound, the 4-chlorobenzylidene moiety A (C1—C7/CL1) and 5-amino-3,4-dimethylisoxazole moiety B (N1/C8—C12/N2/O1) are planar with r. m. s. deviation of 0.0042 and 0.0076 Å, respectively. The dihedral angle between A/B is 1.10 (11)°. R. m. s. deviation from the plane of all non-hydrogen atoms in the molecule is 0.0200 Å, with the largest deviation of the CL1 atom [0.0534 (11) Å]. Weak intramolecular H-bonding of C—H···O type (Table 1, Fig. 1) exists and complete an S(5) ring motif (Bernstein et al., 1995). There exists no π···π interaction. The C—H···π interaction (Table 1) play an important role in stabilizing the molecules.

Experimental

A mixture of 4-chlorobenzaldehyde (0.30 g, 2.2 mmol) and 5-amino-3,4-dimethylisoxazole (0.24 g, 2.2 mmol) in ethanol (15 ml) was refluxed for 5 h with stirring to give a light brown precipitate. This material was filtered off and washed with ethanol to give the pure Schiff base (m.p. 397 K; yield: 78.5%)

1H-NMR (CDCl3) δ: 9.97 (s, 1H, CHolefinic), 7.79 (d, H3, CHaromatic J = 5.4 Hz), 7.75 (dd, H4, CHaromatic, J = 8.4 Hz), 7.69 (dd, H5, CHaromatic J = 8.4 Hz), 7.61 (d, H6 CHaromatic, J = 4.8 Hz), 2.25 (s, N—CH3), 1.76 (s,-CH3).

Refinement

The H-atoms were positioned geometrically (C–H = 0.93–0.96 Å) and refined as riding with Uiso(H) = xUeq(C), where x = 1.5 for methyl and x = 1.2 for other H-atoms.

Figures

Fig. 1.
View of the title compound with the atom numbering scheme. The displacement ellipsoids are drawn at the 50% probability level. H-atoms are shown as small spheres of arbitrary radii. The dotted line indicates the intramolecular hydrogen H-bond.

Crystal data

C12H11ClN2OF(000) = 488
Mr = 234.68Dx = 1.325 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1539 reflections
a = 5.0877 (2) Åθ = 2.3–25.3°
b = 24.5197 (9) ŵ = 0.30 mm1
c = 9.4673 (4) ÅT = 296 K
β = 94.871 (2)°Needle, light brown
V = 1176.77 (8) Å30.30 × 0.16 × 0.14 mm
Z = 4

Data collection

Bruker KAPPA APEXII CCD diffractometer2112 independent reflections
Radiation source: fine-focus sealed tube1539 reflections with I > 2σ(I)
graphiteRint = 0.030
Detector resolution: 8.10 pixels mm-1θmax = 25.3°, θmin = 2.3°
ω scansh = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 2005)k = −29→29
Tmin = 0.868, Tmax = 0.965l = −11→11
9016 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120H-atom parameters constrained
S = 1.07w = 1/[σ2(Fo2) + (0.0521P)2 + 0.2476P] where P = (Fo2 + 2Fc2)/3
2112 reflections(Δ/σ)max < 0.001
147 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = −0.14 e Å3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles
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)

xyzUiso*/Ueq
Cl1−0.59118 (13)0.19483 (3)−0.44471 (7)0.0894 (3)
O10.5343 (3)0.03641 (6)0.15781 (16)0.0736 (6)
N10.3653 (3)0.11804 (7)0.05045 (17)0.0608 (6)
N20.7399 (4)0.02071 (8)0.2600 (2)0.0763 (7)
C1−0.0022 (4)0.11701 (8)−0.1255 (2)0.0576 (7)
C2−0.1918 (4)0.08576 (9)−0.2009 (2)0.0676 (8)
C3−0.3750 (4)0.10921 (9)−0.2987 (2)0.0701 (8)
C4−0.3674 (4)0.16448 (9)−0.3200 (2)0.0630 (8)
C5−0.1824 (5)0.19639 (9)−0.2446 (3)0.0775 (9)
C6−0.0019 (4)0.17261 (10)−0.1484 (3)0.0724 (8)
C70.1915 (4)0.09088 (9)−0.0251 (2)0.0622 (7)
C80.5459 (4)0.09160 (9)0.1431 (2)0.0576 (7)
C90.7462 (4)0.11227 (8)0.2291 (2)0.0575 (7)
C100.8603 (4)0.06588 (9)0.2988 (2)0.0617 (7)
C111.0916 (4)0.06456 (11)0.4077 (2)0.0785 (9)
C120.8318 (4)0.16992 (9)0.2438 (3)0.0778 (9)
H2−0.196090.04832−0.185540.0811*
H3−0.501490.08784−0.349210.0842*
H5−0.180160.23391−0.258950.0930*
H60.122980.19425−0.097570.0869*
H70.188240.05313−0.015780.0746*
H11A1.153180.027720.420020.1177*
H11B1.039400.078210.496130.1177*
H11C1.230560.086920.376650.1177*
H12A0.720030.192300.180850.1168*
H12B1.010970.173120.220230.1168*
H12C0.819710.181680.339720.1168*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0947 (5)0.0856 (5)0.0842 (4)0.0155 (3)−0.0142 (3)0.0044 (3)
O10.0787 (10)0.0567 (9)0.0821 (10)−0.0045 (7)−0.0123 (8)−0.0012 (7)
N10.0579 (10)0.0613 (11)0.0634 (10)−0.0002 (8)0.0067 (8)−0.0017 (8)
N20.0797 (12)0.0638 (12)0.0816 (12)0.0000 (10)−0.0161 (10)0.0055 (10)
C10.0568 (11)0.0568 (12)0.0597 (11)0.0007 (9)0.0079 (9)−0.0057 (9)
C20.0741 (14)0.0517 (12)0.0761 (14)−0.0019 (10)0.0014 (11)−0.0053 (11)
C30.0702 (14)0.0664 (14)0.0715 (14)−0.0028 (11)−0.0071 (11)−0.0110 (11)
C40.0642 (13)0.0644 (14)0.0602 (12)0.0080 (10)0.0041 (10)−0.0028 (10)
C50.0836 (16)0.0537 (13)0.0932 (17)−0.0027 (11)−0.0041 (13)0.0021 (12)
C60.0709 (14)0.0617 (14)0.0822 (15)−0.0064 (11)−0.0074 (11)−0.0056 (12)
C70.0663 (13)0.0559 (12)0.0647 (12)0.0006 (10)0.0077 (10)−0.0048 (10)
C80.0589 (12)0.0548 (12)0.0598 (11)0.0013 (9)0.0099 (9)−0.0006 (9)
C90.0565 (11)0.0618 (13)0.0552 (11)−0.0041 (10)0.0102 (9)−0.0011 (10)
C100.0633 (12)0.0647 (13)0.0575 (11)−0.0039 (11)0.0082 (9)0.0004 (10)
C110.0716 (14)0.0913 (18)0.0708 (14)−0.0056 (12)−0.0044 (11)0.0059 (12)
C120.0793 (15)0.0613 (14)0.0921 (16)−0.0106 (12)0.0026 (12)−0.0055 (12)

Geometric parameters (Å, °)

Cl1—C41.737 (2)C9—C101.415 (3)
O1—N21.417 (2)C9—C121.482 (3)
O1—C81.362 (3)C10—C111.498 (3)
N1—C71.277 (3)C2—H20.9300
N1—C81.377 (3)C3—H30.9300
N2—C101.303 (3)C5—H50.9300
C1—C21.382 (3)C6—H60.9300
C1—C61.380 (3)C7—H70.9300
C1—C71.458 (3)C11—H11A0.9600
C2—C31.382 (3)C11—H11B0.9600
C3—C41.371 (3)C11—H11C0.9600
C4—C51.376 (3)C12—H12A0.9600
C5—C61.368 (4)C12—H12B0.9600
C8—C91.348 (3)C12—H12C0.9600
Cl1···H12Ci3.0600C12···H11C3.0700
O1···H72.3400H2···H72.4300
O1···H2ii2.7200H2···O1ii2.7200
N1···H62.5800H3···C11vi3.0200
N1···H12A2.7800H6···N12.5800
N1···H12Biii2.8500H7···O12.3400
C3···C7iii3.570 (3)H7···H22.4300
C7···C3iv3.570 (3)H11B···C3vii3.0800
C7···C9iii3.482 (3)H11C···C8iv2.8400
C9···C7iv3.482 (3)H11C···C123.0700
C3···H11Bi3.0800H12A···N12.7800
C8···H11Ciii2.8400H12B···N1iv2.8500
C11···H3v3.0200H12C···Cl1vii3.0600
N2—O1—C8107.69 (15)C1—C2—H2119.00
C7—N1—C8120.28 (18)C3—C2—H2119.00
O1—N2—C10105.29 (17)C2—C3—H3121.00
C2—C1—C6118.45 (19)C4—C3—H3121.00
C2—C1—C7119.77 (18)C4—C5—H5120.00
C6—C1—C7121.78 (19)C6—C5—H5120.00
C1—C2—C3121.1 (2)C1—C6—H6119.00
C2—C3—C4118.94 (19)C5—C6—H6119.00
Cl1—C4—C3119.90 (16)N1—C7—H7119.00
Cl1—C4—C5119.28 (18)C1—C7—H7119.00
C3—C4—C5120.82 (19)C10—C11—H11A109.00
C4—C5—C6119.6 (2)C10—C11—H11B109.00
C1—C6—C5121.1 (2)C10—C11—H11C109.00
N1—C7—C1122.3 (2)H11A—C11—H11B109.00
O1—C8—N1120.02 (18)H11A—C11—H11C109.00
O1—C8—C9110.42 (18)H11B—C11—H11C109.00
N1—C8—C9129.6 (2)C9—C12—H12A109.00
C8—C9—C10103.81 (18)C9—C12—H12B109.00
C8—C9—C12128.04 (19)C9—C12—H12C109.00
C10—C9—C12128.13 (19)H12A—C12—H12B109.00
N2—C10—C9112.79 (18)H12A—C12—H12C109.00
N2—C10—C11119.9 (2)H12B—C12—H12C110.00
C9—C10—C11127.3 (2)
C8—O1—N2—C10−0.4 (2)C1—C2—C3—C4−0.3 (3)
N2—O1—C8—N1−179.39 (17)C2—C3—C4—Cl1178.75 (15)
N2—O1—C8—C90.1 (2)C2—C3—C4—C5−0.6 (3)
C8—N1—C7—C1−179.45 (18)Cl1—C4—C5—C6−178.59 (19)
C7—N1—C8—O1−2.1 (3)C3—C4—C5—C60.8 (4)
C7—N1—C8—C9178.5 (2)C4—C5—C6—C10.0 (4)
O1—N2—C10—C90.5 (2)O1—C8—C9—C100.2 (2)
O1—N2—C10—C11179.91 (17)O1—C8—C9—C12178.5 (2)
C6—C1—C2—C31.0 (3)N1—C8—C9—C10179.6 (2)
C7—C1—C2—C3−178.80 (18)N1—C8—C9—C12−2.1 (4)
C2—C1—C6—C5−0.8 (3)C8—C9—C10—N2−0.4 (2)
C7—C1—C6—C5179.0 (2)C8—C9—C10—C11−179.78 (19)
C2—C1—C7—N1−177.71 (19)C12—C9—C10—N2−178.7 (2)
C6—C1—C7—N12.5 (3)C12—C9—C10—C111.9 (3)

Symmetry codes: (i) x−1, y, z−1; (ii) −x, −y, −z; (iii) x−1, y, z; (iv) x+1, y, z; (v) x+2, y, z+1; (vi) x−2, y, z−1; (vii) x+1, y, z+1.

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the O1/N2/C10/C9/C8 ring.
D—H···AD—HH···AD···AD—H···A
C7—H7···O10.932.342.704 (3)103
C11—H11C···Cg1iv0.962.913.644 (2)134

Symmetry codes: (iv) x+1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2296).

References

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  • Fun, H.-K., Hemamalini, M., Asiri, A. M., Khan, S. A. & Khan, K. A. (2010b). Acta Cryst. E66, o773–o774. [PMC free article] [PubMed]
  • Shad, H. A., Chohan, Z. H., Tahir, M. N. & Khan, I. U. (2008). Acta Cryst. E64, o635. [PMC free article] [PubMed]
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  • Tahir, M. N., Chohan, Z. H., Shad, H. A. & Khan, I. U. (2008). Acta Cryst. E64, o720. [PMC free article] [PubMed]

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