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

Asiri, A.M.; Khan, S.A.; Tahir, M.N.

doi:10.1107/S1600536810027893

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o2077

https://doi.org/10.1107/S1600536810027893

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

Abdullah M. Asiri,^a,^b Salman A. Khan ^b and M. Nawaz Tahir ^c ^*

^aThe Center of Excellence for Advanced Materials Research, King Abdul Aziz University, Jeddah 21589, PO Box 80203, Saudi Arabia, ^bDepartment of Chemistry, Faculty of Science, King Abdul Aziz University, Jeddah 21589, PO Box 80203, Saudi Arabia, and ^cDepartment of Physics, University of Sargodha, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 11 July 2010; accepted 13 July 2010; online 21 July 2010)

In the title compound, C₁₂H₁₁BrN₂O, the 4-bromobenzaldehyde and 5-amino-3,4-dimethylisoxazole units are oriented at a dihedral angle of 4.89 (8)°. In the crystal, weak π–π interactions are present between the benzene rings at a centroid–centroid distance of 3.7862 (14) Å.

Related literature

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

Experimental

Crystal data

C₁₂H₁₁BrN₂O
M_r = 279.14
Triclinic, $[P \overline 1]$
a = 7.6406 (4) Å
b = 8.8709 (5) Å
c = 9.1052 (5) Å
α = 97.024 (2)°
β = 102.961 (1)°
γ = 92.786 (2)°
V = 595.06 (6) Å³
Z = 2
Mo Kα radiation
μ = 3.43 mm⁻¹
T = 296 K
0.30 × 0.14 × 0.12 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.568, T_max = 0.665
8212 measured reflections
2119 independent reflections
1643 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.059
S = 1.03
2119 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.17 e Å⁻³

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810027893/bq2226sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810027893/bq2226Isup2.hkl

checkCIF report

Comment top

Heterocycles such as nitrogen and oxygen containing compounds are abundant in nature and are of great significance to life. We herein report the synthesis and crystal structure of title compound (I, Fig. 1).

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., 2010) have been published previously, which contain the 5-amino-3,4-dimethylisoxazole moiety.

In (I), the 4-bromobenzaldehyde moiety A (C1—C7/BR1) and 5-amino-3,4-dimethylisoxazole moiety B (N1/C8—C12/N2/O1) are planar with r. m. s. deviations of 0.0119 Å and 0.0128 Å, respectively. The dihedral angle between A/B is 4.89 (8)°. The title compound essentially consists of monomers. 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 also π–π interaction between the centroids of phenyl rings at a distance of 3.7862 (14) Å [symmetry code: -x, 2 - y, 1 - z].

Related literature top

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

Experimental top

A mixture of 4-bromobenzaldehyde (0.40 g, 0.0022 mol) and 5-amino-3,4-dimethylisoxazole (0.24 g, 0.0022 mol) in ethanol (15 ml) was refluxed for 5 h with stirring to give a light brown needles of title compound (I).

Structure description top

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

Computing details top

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

Figures top

Fig. 1. View of the title compound with the atom numbering scheme. The thermal ellipsoids are drawn at the 50% probability level. The dotted line indicate the intramolecular H-bond.

N-(4-Bromobenzylidene)-3,4-dimethylisoxazol-5-amine top

Crystal data top

C₁₂H₁₁BrN₂O	Z = 2
M_r = 279.14	F(000) = 280
Triclinic, P1	D_x = 1.558 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6406 (4) Å	Cell parameters from 1643 reflections
b = 8.8709 (5) Å	θ = 2.3–25.3°
c = 9.1052 (5) Å	µ = 3.43 mm⁻¹
α = 97.024 (2)°	T = 296 K
β = 102.961 (1)°	Needle, brown
γ = 92.786 (2)°	0.30 × 0.14 × 0.12 mm
V = 595.06 (6) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	2119 independent reflections
Radiation source: fine-focus sealed tube	1643 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 8.10 pixels mm^-1	θ_max = 25.3°, θ_min = 2.3°
ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −10→10
T_min = 0.568, T_max = 0.665	l = −10→10
8212 measured reflections

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.059	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0225P)² + 0.2246P] where P = (F_o² + 2F_c²)/3
2119 reflections	(Δ/σ)_max = 0.001
147 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₂H₁₁BrN₂O	γ = 92.786 (2)°
M_r = 279.14	V = 595.06 (6) Å³
Triclinic, P1	Z = 2
a = 7.6406 (4) Å	Mo Kα radiation
b = 8.8709 (5) Å	µ = 3.43 mm⁻¹
c = 9.1052 (5) Å	T = 296 K
α = 97.024 (2)°	0.30 × 0.14 × 0.12 mm
β = 102.961 (1)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2119 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1643 reflections with I > 2σ(I)
T_min = 0.568, T_max = 0.665	R_int = 0.022
8212 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.059	H-atom parameters constrained
S = 1.03	Δρ_max = 0.20 e Å⁻³
2119 reflections	Δρ_min = −0.17 e Å⁻³
147 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Br1	−0.32255 (4)	1.00984 (3)	0.72075 (3)	0.0712 (1)
O1	0.4539 (2)	0.51578 (18)	0.30328 (18)	0.0572 (6)
N1	0.1487 (3)	0.55019 (19)	0.3071 (2)	0.0440 (6)
N2	0.5503 (3)	0.4289 (3)	0.2111 (3)	0.0656 (8)
C1	0.0706 (3)	0.7262 (2)	0.4987 (2)	0.0421 (8)
C2	−0.1140 (3)	0.7008 (2)	0.4413 (3)	0.0471 (8)
C3	−0.2317 (3)	0.7844 (3)	0.5070 (3)	0.0509 (8)
C4	−0.1622 (3)	0.8940 (2)	0.6301 (3)	0.0489 (9)
C5	0.0186 (4)	0.9215 (3)	0.6888 (3)	0.0571 (9)
C6	0.1356 (3)	0.8365 (3)	0.6240 (3)	0.0538 (9)
C7	0.1988 (3)	0.6429 (2)	0.4298 (3)	0.0455 (8)
C8	0.2749 (3)	0.4794 (2)	0.2430 (3)	0.0433 (8)
C9	0.2501 (3)	0.3744 (2)	0.1180 (3)	0.0457 (8)
C10	0.4265 (3)	0.3478 (3)	0.1044 (3)	0.0517 (9)
C11	0.4836 (4)	0.2423 (3)	−0.0149 (3)	0.0745 (11)
C12	0.0764 (4)	0.3028 (3)	0.0200 (3)	0.0659 (10)
H2	−0.15915	0.62688	0.35786	0.0565*
H3	−0.35551	0.76687	0.46887	0.0611*
H5	0.06270	0.99657	0.77139	0.0686*
H6	0.25905	0.85335	0.66457	0.0646*
H7	0.32075	0.65805	0.47691	0.0546*
H11A	0.61269	0.24881	0.00435	0.1118*
H11B	0.43483	0.27080	−0.11341	0.1118*
H11C	0.43975	0.13964	−0.01207	0.1118*
H12A	−0.02153	0.34332	0.05809	0.0989*
H12B	0.07209	0.19462	0.02086	0.0989*
H12C	0.06658	0.32433	−0.08221	0.0989*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0760 (2)	0.0641 (2)	0.0851 (2)	0.0188 (1)	0.0448 (2)	0.0012 (1)
O1	0.0487 (11)	0.0650 (10)	0.0542 (10)	0.0090 (8)	0.0134 (8)	−0.0109 (8)
N1	0.0499 (12)	0.0408 (10)	0.0421 (11)	0.0068 (8)	0.0138 (9)	0.0023 (9)
N2	0.0549 (14)	0.0742 (14)	0.0684 (15)	0.0155 (11)	0.0226 (12)	−0.0074 (12)
C1	0.0501 (15)	0.0399 (12)	0.0394 (13)	0.0059 (10)	0.0163 (10)	0.0061 (10)
C2	0.0523 (16)	0.0422 (12)	0.0466 (14)	0.0001 (10)	0.0157 (11)	−0.0006 (10)
C3	0.0448 (15)	0.0493 (13)	0.0603 (16)	0.0033 (10)	0.0164 (12)	0.0063 (12)
C4	0.0598 (17)	0.0419 (12)	0.0521 (15)	0.0077 (10)	0.0271 (12)	0.0063 (11)
C5	0.0624 (19)	0.0568 (15)	0.0492 (15)	0.0015 (12)	0.0174 (12)	−0.0115 (12)
C6	0.0456 (15)	0.0632 (15)	0.0486 (15)	0.0020 (11)	0.0104 (11)	−0.0063 (12)
C7	0.0449 (14)	0.0482 (13)	0.0446 (14)	0.0075 (10)	0.0117 (10)	0.0071 (11)
C8	0.0476 (15)	0.0428 (12)	0.0410 (13)	0.0081 (10)	0.0119 (10)	0.0065 (10)
C9	0.0590 (16)	0.0397 (12)	0.0398 (13)	0.0087 (10)	0.0140 (11)	0.0045 (10)
C10	0.0652 (17)	0.0456 (13)	0.0482 (15)	0.0143 (12)	0.0209 (13)	0.0037 (11)
C11	0.089 (2)	0.0725 (18)	0.0698 (19)	0.0249 (15)	0.0379 (16)	−0.0036 (14)
C12	0.073 (2)	0.0616 (16)	0.0553 (16)	0.0060 (13)	0.0070 (14)	−0.0075 (13)

Geometric parameters (Å, º) top

Br1—C4	1.899 (2)	C9—C10	1.409 (3)
O1—N2	1.420 (3)	C9—C12	1.486 (4)
O1—C8	1.361 (3)	C10—C11	1.500 (4)
N1—C7	1.274 (3)	C2—H2	0.9300
N1—C8	1.374 (3)	C3—H3	0.9300
N2—C10	1.307 (4)	C5—H5	0.9300
C1—C2	1.387 (3)	C6—H6	0.9300
C1—C6	1.390 (3)	C7—H7	0.9300
C1—C7	1.460 (3)	C11—H11A	0.9600
C2—C3	1.384 (3)	C11—H11B	0.9600
C3—C4	1.378 (4)	C11—H11C	0.9600
C4—C5	1.363 (4)	C12—H12A	0.9600
C5—C6	1.382 (4)	C12—H12B	0.9600
C8—C9	1.351 (3)	C12—H12C	0.9600

Br1···C11ⁱ	3.595 (3)	C4···C6ⁱⁱ	3.553 (3)
Br1···C7ⁱⁱ	3.687 (2)	C6···C4ⁱⁱ	3.553 (3)
O1···C3ⁱⁱⁱ	3.355 (3)	C7···Br1ⁱⁱ	3.687 (2)
O1···H3ⁱⁱⁱ	2.6900	C7···C2^iv	3.481 (3)
O1···H7	2.3400	C8···C3^iv	3.512 (3)
N1···C2^iv	3.426 (3)	C11···Br1^viii	3.595 (3)
N1···H2	2.6000	H2···N1	2.6000
N1···H12A	2.7600	H2···N2^vii	2.7400
N1···H12C^v	2.7100	H3···O1^vii	2.6900
N2···H2ⁱⁱⁱ	2.7400	H6···H7	2.4200
N2···H11B^vi	2.9100	H7···O1	2.3400
C2···N1^iv	3.426 (3)	H7···H6	2.4200
C2···C7^iv	3.481 (3)	H11B···N2^vi	2.9100
C3···O1^vii	3.355 (3)	H12A···N1	2.7600
C3···C8^iv	3.512 (3)	H12C···N1^v	2.7100

N2—O1—C8	107.76 (18)	C1—C2—H2	120.00
C7—N1—C8	119.9 (2)	C3—C2—H2	120.00
O1—N2—C10	105.0 (2)	C2—C3—H3	121.00
C2—C1—C6	118.9 (2)	C4—C3—H3	121.00
C2—C1—C7	122.08 (18)	C4—C5—H5	120.00
C6—C1—C7	119.0 (2)	C6—C5—H5	120.00
C1—C2—C3	120.6 (2)	C1—C6—H6	120.00
C2—C3—C4	118.8 (2)	C5—C6—H6	120.00
Br1—C4—C3	119.17 (18)	N1—C7—H7	119.00
Br1—C4—C5	119.02 (19)	C1—C7—H7	119.00
C3—C4—C5	121.8 (2)	C10—C11—H11A	109.00
C4—C5—C6	119.2 (2)	C10—C11—H11B	109.00
C1—C6—C5	120.6 (2)	C10—C11—H11C	109.00
N1—C7—C1	122.0 (2)	H11A—C11—H11B	109.00
O1—C8—N1	120.5 (2)	H11A—C11—H11C	109.00
O1—C8—C9	110.4 (2)	H11B—C11—H11C	109.00
N1—C8—C9	129.2 (2)	C9—C12—H12A	109.00
C8—C9—C10	103.9 (2)	C9—C12—H12B	109.00
C8—C9—C12	127.6 (2)	C9—C12—H12C	109.00
C10—C9—C12	128.5 (2)	H12A—C12—H12B	110.00
N2—C10—C9	113.0 (2)	H12A—C12—H12C	109.00
N2—C10—C11	118.9 (2)	H12B—C12—H12C	109.00
C9—C10—C11	128.1 (2)

C8—O1—N2—C10	−0.1 (3)	C1—C2—C3—C4	0.3 (4)
N2—O1—C8—C9	0.1 (2)	C2—C3—C4—Br1	179.81 (18)
N2—O1—C8—N1	−178.1 (2)	C2—C3—C4—C5	−0.3 (4)
C7—N1—C8—C9	177.3 (2)	Br1—C4—C5—C6	179.42 (19)
C8—N1—C7—C1	177.18 (18)	C3—C4—C5—C6	−0.5 (4)
C7—N1—C8—O1	−4.8 (3)	C4—C5—C6—C1	1.2 (4)
O1—N2—C10—C9	0.1 (3)	O1—C8—C9—C10	0.0 (3)
O1—N2—C10—C11	179.6 (2)	N1—C8—C9—C12	−2.8 (4)
C2—C1—C6—C5	−1.2 (3)	O1—C8—C9—C12	179.1 (2)
C6—C1—C2—C3	0.4 (3)	N1—C8—C9—C10	178.0 (2)
C7—C1—C2—C3	−178.4 (2)	C8—C9—C10—N2	−0.1 (3)
C7—C1—C6—C5	177.6 (2)	C12—C9—C10—C11	1.4 (4)
C2—C1—C7—N1	5.0 (3)	C8—C9—C10—C11	−179.5 (3)
C6—C1—C7—N1	−173.7 (2)	C12—C9—C10—N2	−179.2 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1	0.9300	2.3400	2.702 (3)	103.00

Experimental details

Crystal data
Chemical formula	C₁₂H₁₁BrN₂O
M_r	279.14
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.6406 (4), 8.8709 (5), 9.1052 (5)
α, β, γ (°)	97.024 (2), 102.961 (1), 92.786 (2)
V (Å³)	595.06 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.43
Crystal size (mm)	0.30 × 0.14 × 0.12

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.568, 0.665
No. of measured, independent and observed [I > 2σ(I)] reflections	8212, 2119, 1643
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.059, 1.03
No. of reflections	2119
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.17

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1	0.9300	2.3400	2.702 (3)	103.00

Acknowledgements

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

References

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