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

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.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.025
• wR factor = 0.059
• Data-to-parameter ratio = 14.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         37
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          3

Alert level G
PLAT380_ALERT_4_G Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C12

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

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

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).

S2. Experimental

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).

S3. Refinement

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

Computing details

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

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

Crystal data

C12H11BrN2O	Z = 2
Mr = 279.14	F(000) = 280
Triclinic, P1	Dx = 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) Å^3

Data collection

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

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.059	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0225P)^2 + 0.2246P] where P = (Fo^2 + 2Fc^2)/3
2119 reflections	(Δ/σ)max = 0.001
147 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.17 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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···C11^i	3.595 (3)	C4···C6^ii	3.553 (3)
Br1···C7^ii	3.687 (2)	C6···C4^ii	3.553 (3)
O1···C3^iii	3.355 (3)	C7···Br1^ii	3.687 (2)
O1···H3^iii	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···H2^iii	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)

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