Prof. 18

organic compounds Acta Crystallographica Section E = 92.786 (2) V = 595.06 (6) Å3 Z=2 Mo K radiation Structure Reports Online  = 3.43 mm 1 T = 296 K 0.30  0.14  0.12 mm ISSN 1600-5368 Data collection N-(4-Bromobenzylidene)-3,4-dimethylisoxazol-5-amine Bruker Kappa APEXII CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2005) Tmin = 0.568, Tmax = 0.665 Abdullah M. Asiri,a,b Salman A. Khanb and M. Nawaz Tahirc* Refinement a The 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 Key indicators: single-crystal X-ray study; T = 296 K; mean (C–C) = 0.004 Å; R factor = 0.025; wR factor = 0.059; data-to-parameter ratio = 14.4. 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 – interactions are present between the benzene rings at a centroid–centroid distance of 3.7862 (14) Å. 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 Acta Cryst. (2010). E66, o2077 147 parameters H-atom parameters constrained
max = 0.20 e Å 3
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. The authors would like to thank the Chemistry Department, King Abdul Aziz University, Jeddah, Saudi Arabia, for the provision of research facilities. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BQ2226). Related literature C12H11BrN2O Mr = 279.14 Triclinic, P1 a = 7.6406 (4) Å R[F 2 > 2(F 2)] = 0.025 wR(F 2) = 0.059 S = 1.03 2119 reflections 8212 measured reflections 2119 independent reflections 1643 reflections with I > 2(I) Rint = 0.022 b = 8.8709 (5) Å c = 9.1052 (5) Å = 97.024 (2) = 102.961 (1) References Asiri, A. M., Khan, S. A., Tan, K. W. & Ng, S. W. (2010). Acta Cryst. E66, o1783. Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. Fun, H.-K., Hemamalini, M., Asiri, A. M. & Khan, S. A. (2010a). Acta Cryst. E66, o1037–o1038. Fun, H.-K., Hemamalini, M., Asiri, A. M., Khan, S. A. & Khan, K. A. (2010b). Acta Cryst. E66, o773–o774. Shad, H. A., Chohan, Z. H., Tahir, M. N. & Khan, I. U. (2008). Acta Cryst. E64, o635. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Spek, A. L. (2009). Acta Cryst. D65, 148–155. Tahir, M. N., Chohan, Z. H., Shad, H. A. & Khan, I. U. (2008). Acta Cryst. E64, o720. doi:10.1107/S1600536810027893 Asiri et al. o2077 supplementary materials supplementary materials [ doi:10.1107/S1600536810027893 ] Acta Cryst. (2010). E66, o2077 N-(4-Bromobenzylidene)-3,4-dimethylisoxazol-5-amine A. M. Asiri, S. A. Khan and M. N. Tahir 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 methyl]phenolate structures (Shad of et 4-chloro-2al., 2008), [(E)-({4-[N-(3,4-dimethylisoxazol-5-yl)sulfamoyl]phenyl}iminio) 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]-3,4dimethylisoxazol-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]. 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). 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 aryl H-atoms. 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. sup-1 supplementary materials 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 a = 7.6406 (4) Å b = 8.8709 (5) Å Mo Kα radiation, λ = 0.71073 Å Cell parameters from 1643 reflections θ = 2.3–25.3° c = 9.1052 (5) Å µ = 3.43 mm−1 T = 296 K Needle, brown 0.30 × 0.14 × 0.12 mm α = 97.024 (2)° β = 102.961 (1)° γ = 92.786 (2)° V = 595.06 (6) Å3 Data collection Bruker Kappa APEXII CCD diffractometer Radiation source: fine-focus sealed tube graphite Detector resolution: 8.10 pixels mm-1 ω scans Absorption correction: multi-scan (SADABS; Bruker, 2005) Tmin = 0.568, Tmax = 0.665 2119 independent reflections 1643 reflections with I > 2σ(I) Rint = 0.022 θmax = 25.3°, θmin = 2.3° h = −9→9 k = −10→10 l = −10→10 8212 measured reflections Refinement R[F2 > 2σ(F2)] = 0.025 Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites wR(F2) = 0.059 H-atom parameters constrained Refinement on F2 Least-squares matrix: full S = 1.03 w = 1/[σ2(Fo2) + (0.0225P)2 + 0.2246P] where P = (Fo2 + 2Fc2)/3 2119 reflections (Δ/σ)max = 0.001 147 parameters Δρmax = 0.20 e Å−3 0 restraints Δρmin = −0.17 e Å−3 sup-2 supplementary materials 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 Rfactors(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) Br1 O1 N1 N2 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 H2 H3 H5 H6 H7 H11A H11B H11C H12A H12B H12C x y z Uiso*/Ueq −0.32255 (4) 0.4539 (2) 0.1487 (3) 0.5503 (3) 0.0706 (3) −0.1140 (3) −0.2317 (3) −0.1622 (3) 0.0186 (4) 0.1356 (3) 0.1988 (3) 0.2749 (3) 0.2501 (3) 0.4265 (3) 0.4836 (4) 0.0764 (4) −0.15915 −0.35551 0.06270 0.25905 0.32075 0.61269 0.43483 0.43975 −0.02153 0.07209 0.06658 1.00984 (3) 0.51578 (18) 0.55019 (19) 0.4289 (3) 0.7262 (2) 0.7008 (2) 0.7844 (3) 0.8940 (2) 0.9215 (3) 0.8365 (3) 0.6429 (2) 0.4794 (2) 0.3744 (2) 0.3478 (3) 0.2423 (3) 0.3028 (3) 0.62688 0.76687 0.99657 0.85335 0.65805 0.24881 0.27080 0.13964 0.34332 0.19462 0.32433 0.72075 (3) 0.30328 (18) 0.3071 (2) 0.2111 (3) 0.4987 (2) 0.4413 (3) 0.5070 (3) 0.6301 (3) 0.6888 (3) 0.6240 (3) 0.4298 (3) 0.2430 (3) 0.1180 (3) 0.1044 (3) −0.0149 (3) 0.0200 (3) 0.35786 0.46887 0.77139 0.66457 0.47691 0.00435 −0.11341 −0.01207 0.05809 0.02086 −0.08221 0.0712 (1) 0.0572 (6) 0.0440 (6) 0.0656 (8) 0.0421 (8) 0.0471 (8) 0.0509 (8) 0.0489 (9) 0.0571 (9) 0.0538 (9) 0.0455 (8) 0.0433 (8) 0.0457 (8) 0.0517 (9) 0.0745 (11) 0.0659 (10) 0.0565* 0.0611* 0.0686* 0.0646* 0.0546* 0.1118* 0.1118* 0.1118* 0.0989* 0.0989* 0.0989* Atomic displacement parameters (Å2) Br1 O1 U11 0.0760 (2) 0.0487 (11) U22 0.0641 (2) 0.0650 (10) U33 0.0851 (2) 0.0542 (10) U12 0.0188 (1) 0.0090 (8) U13 0.0448 (2) 0.0134 (8) U23 0.0012 (1) −0.0109 (8) sup-3 supplementary materials N1 N2 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 0.0499 (12) 0.0549 (14) 0.0501 (15) 0.0523 (16) 0.0448 (15) 0.0598 (17) 0.0624 (19) 0.0456 (15) 0.0449 (14) 0.0476 (15) 0.0590 (16) 0.0652 (17) 0.089 (2) 0.073 (2) 0.0408 (10) 0.0742 (14) 0.0399 (12) 0.0422 (12) 0.0493 (13) 0.0419 (12) 0.0568 (15) 0.0632 (15) 0.0482 (13) 0.0428 (12) 0.0397 (12) 0.0456 (13) 0.0725 (18) 0.0616 (16) 0.0421 (11) 0.0684 (15) 0.0394 (13) 0.0466 (14) 0.0603 (16) 0.0521 (15) 0.0492 (15) 0.0486 (15) 0.0446 (14) 0.0410 (13) 0.0398 (13) 0.0482 (15) 0.0698 (19) 0.0553 (16) 0.0068 (8) 0.0155 (11) 0.0059 (10) 0.0001 (10) 0.0033 (10) 0.0077 (10) 0.0015 (12) 0.0020 (11) 0.0075 (10) 0.0081 (10) 0.0087 (10) 0.0143 (12) 0.0249 (15) 0.0060 (13) 0.0138 (9) 0.0226 (12) 0.0163 (10) 0.0157 (11) 0.0164 (12) 0.0271 (12) 0.0174 (12) 0.0104 (11) 0.0117 (10) 0.0119 (10) 0.0140 (11) 0.0209 (13) 0.0379 (16) 0.0070 (14) 0.0023 (9) −0.0074 (12) 0.0061 (10) −0.0006 (10) 0.0063 (12) 0.0063 (11) −0.0115 (12) −0.0063 (12) 0.0071 (11) 0.0065 (10) 0.0045 (10) 0.0037 (11) −0.0036 (14) −0.0075 (13) Geometric parameters (Å, °) Br1—C4 O1—N2 O1—C8 N1—C7 N1—C8 N2—C10 C1—C2 C1—C6 C1—C7 C2—C3 C3—C4 C4—C5 C5—C6 C8—C9 1.899 (2) 1.420 (3) 1.361 (3) 1.274 (3) 1.374 (3) 1.307 (4) 1.387 (3) 1.390 (3) 1.460 (3) 1.384 (3) 1.378 (4) 1.363 (4) 1.382 (4) 1.351 (3) C9—C10 C9—C12 C10—C11 C2—H2 C3—H3 C5—H5 C6—H6 C7—H7 C11—H11A C11—H11B C11—H11C C12—H12A C12—H12B C12—H12C 1.409 (3) 1.486 (4) 1.500 (4) 0.9300 0.9300 0.9300 0.9300 0.9300 0.9600 0.9600 0.9600 0.9600 0.9600 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···C2iv 3.481 (3) 2.3400 iv O1···H7 iv 3.426 (3) 3.512 (3) C8···C3 viii 3.595 (3) 2.6000 C11···Br1 H2···N1 2.6000 2.7600 vii 2.7400 2.7100 H3···O1vii 2.6900 N2···H2iii 2.7400 H6···H7 2.4200 N2···H11Bvi 2.9100 H7···O1 2.3400 3.426 (3) H7···H6 N1···C2 N1···H2 N1···H12A H2···N2 N1···H12Cv C2···N1 iv 3.481 (3) H11B···N2 vii 3.355 (3) H12A···N1 C2···C7 C3···O1 iv C3···C8 sup-4 2.4200 iv 3.512 (3) vi H12C···N1 v 2.9100 2.7600 2.7100 supplementary materials N2—O1—C8 C7—N1—C8 O1—N2—C10 C2—C1—C6 C2—C1—C7 C6—C1—C7 C1—C2—C3 C2—C3—C4 Br1—C4—C3 Br1—C4—C5 C3—C4—C5 C4—C5—C6 C1—C6—C5 N1—C7—C1 O1—C8—N1 O1—C8—C9 N1—C8—C9 C8—C9—C10 C8—C9—C12 C10—C9—C12 N2—C10—C9 N2—C10—C11 C9—C10—C11 107.76 (18) 119.9 (2) 105.0 (2) 118.9 (2) 122.08 (18) 119.0 (2) 120.6 (2) 118.8 (2) 119.17 (18) 119.02 (19) 121.8 (2) 119.2 (2) 120.6 (2) 122.0 (2) 120.5 (2) 110.4 (2) 129.2 (2) 103.9 (2) 127.6 (2) 128.5 (2) 113.0 (2) 118.9 (2) 128.1 (2) C1—C2—H2 C3—C2—H2 C2—C3—H3 C4—C3—H3 C4—C5—H5 C6—C5—H5 C1—C6—H6 C5—C6—H6 N1—C7—H7 C1—C7—H7 C10—C11—H11A C10—C11—H11B C10—C11—H11C H11A—C11—H11B H11A—C11—H11C H11B—C11—H11C C9—C12—H12A C9—C12—H12B C9—C12—H12C H12A—C12—H12B H12A—C12—H12C H12B—C12—H12C 120.00 120.00 121.00 121.00 120.00 120.00 120.00 120.00 119.00 119.00 109.00 109.00 109.00 109.00 109.00 109.00 109.00 109.00 109.00 110.00 109.00 109.00 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, °) D—H···A C7—H7···O1 D—H 0.9300 H···A 2.3400 D···A 2.702 (3) D—H···A 103.00 sup-5 supplementary materials Fig. 1 sup-6