V = (14) Å 3 Z =8 Cu K radiation. Data collection. Refinement

Transcription

1 organic compounds Acta Crystallographica Section E Structure Reports Online ISSN (E)-4-Amino-N-(1,2-dihydropyridin-2-ylidene)benzenesulfonamide nitromethane monosolvate Mostafa M. Ghorab, a Mansour S. Al-Said, a Hazem A. Ghabbour, b Suchada Chantrapromma c and Hoong-Kun Fun d * V = (14) Å 3 Z =8 Cu K radiation Data collection Bruker SMART APEXII CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2009) T min = 0.392, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 196 parameters = 2.14 mm 1 T = 296 K mm measured reflections 2799 independent reflections 2386 reflections with I > 2(I) R int = H atoms treated by a mixture of independent and constrained refinement max = 0.25 e Å 3 min = 0.42 e Å 3 a Medicinal, Aromatic and Poisonous Plants Research Center (MAPPRC), College of Pharmacy, King Saud University, PO Box 2457, Riyadh 11451, Saudi Arabia, b Department of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, PO Box 2457, Riyadh 11451, Saudi Arabia, c Crystal Materials Research Unit, Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand, and d X-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, USM, Penang, Malaysia Correspondence hkfun@usm.my Received 27 February 2012; accepted 6 March 2012 Key indicators: single-crystal X-ray study; T = 296 K; mean (C C) = Å; R factor = 0.045; wr factor = 0.144; data-to-parameter ratio = In the title solvate, C 11 H 11 N 3 O 2 SCH 3 NO 2, the dihedral angle between the benzene ring and the N-containing ring is (11), and an approximate V shape arises for the sulfonamide molecule. In the crystal, N HO and N HN hydrogen bonds and weak C HO interactions link the sulfonamide molecules into a three-dimensional network. The nitromethane solvent molecules are located in the interstitial sites in the sulfonamide network. Related literature For background to the applications of sulfonamide compounds, see: Ghorab et al. (2009); Table 1 Hydrogen-bond geometry (Å, ). D HA D H HA DA D HA N2 H1N2O2 i (3) 174 N2 H2N2O1 ii (3) 157 N3 H1N3N1 iii 0.86 (2) 2.09 (2) (2) 178 (2) C8 H8AO1 iii (3) 126 Symmetry codes: (i) x; y 1 2 ; z þ 1 2 ; (ii) x 1 2 ; y 1 2 ; z; (iii) x; y þ 1; z. Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); 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). The authors are grateful for the sponsorship of the Research Center, College of Pharmacy and the Deanship of Scientific Research, King Saud University, Riyadh, Saudi Arabia. HKF and SC thank Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/ HKF also thanks the King Saud University, Riyadh, Saudi Arabia, for the award of a visiting Professorship (December 23rd 2011 to January 14th 2012). Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB6660). Experimental Crystal data C 11 H 11 N 3 O 2 SCH 3 NO 2 M r = Orthorhombic, Pbca a = (3) Å b = (3) Å c = (6) Å References Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Ghorab, M. M., Ragab, F. A., Alqasoumi, S. I., Alafeefy, A. M. & Aboulmaged, S. A. (2009). Eur. J. Med. Chem. 45, Sheldrick, G. M. (2008). Acta Cryst. A64, Spek, A. L. (2009). Acta Cryst. D65, Thomson Reuters ResearcherID: A College of Pharmacy (Visiting Professor), King Saud University, PO Box 2457, Riyadh 11451, Saudi Arabia. Thomson Reuters ResearcherID: A o1030 Ghorab et al. doi: /s

2 [ (E)-4-Amino-N-(1,2-dihydropyridin-2-ylidene)benzenesulfonamide nitromethane monosolvate Mostafa M. Ghorab, Mansour S. Al-Said, Hazem A. Ghabbour, Suchada Chantrapromma and Hoong-Kun Fun S1. Comment As part of our ongoing studies of sulfonamides with potential biological activities (Ghorab et al. (2009), the present investigation deals with the synthesis of the title compound, (I), (Fig. 1) a sulfonamide bearing a pyridine moiety to be evaluated as anticancer agent. The environment of S atom is distorted tetrahedral geometry [angles around S atom are (9) (10) ] with two O atoms, one N atom of the amide group and one C atom of the benzene ring. The dihedral angle between the benzene ring and the N atom-containing ring is (11). The amino group is co-planar with its bound benzene ring with r.m.s (2) Å for the seven non H atoms (C1 C6/N2). In the crystal (Fig. 2), the molecules of sulfonamide derivative are linked by N H O and N H N hydrogen bonds and weak C H O interactions (Table 1) into a three dimensional network. The nitromethane solvent molecules are located in the interstitial sites of the sulfonamide network. S2. Experimental A mixture of (E)-3-(dimethylamino)-1-(thiophen-2-yl)prop-2-en-1-one (1.81 g, 0.01 mole) and sulfapyridine (2.49 g, 0.01 mole) in absolute ethanol (30 ml) was heated under reflux for 12 hr. The reaction mixture was filtered and pink blocks of (I) were obtained by the slow evaporation of an ethanol/nitromethane (3:1) solution at room temperature. S3. Refinement Amide H atom was located in a difference map and refined isotropically. The remaining H atoms were placed in calculated positions with d(n-h) = 0.87 Å, d(c-h) = 0.93 for aromatic, and 0.96 Å for CH 3 atoms. The U iso values were constrained to be 1.5U eq of the carrier atom for methyl H atoms and 1.2U eq for the remaining H atoms. A rotating group model was used for the methyl groups. sup-1

3 Figure 1 The structure of (I), showing 30% probability displacement ellipsoids. sup-2

4 Figure 2 The crystal packing of (I) viewed along the a axis, showing three dimensional network. (E)-4-Amino-N-(1,2-dihydropyridin-2-ylidene)benzenesulfonamide nitromethane monosolvate Crystal data C 11 H 11 N 3 O 2 S CH 3 NO 2 M r = Orthorhombic, Pbca Hall symbol: -P 2ac 2ab a = (3) Å b = (3) Å c = (6) Å V = (14) Å 3 Z = 8 Data collection Bruker SMART APEXII CCD diffractometer Radiation source: fine-focus sealed tube Graphite monochromator φ and ω scans Absorption correction: multi-scan (SADABS; Bruker, 2009) T min = 0.392, T max = F(000) = 1296 D x = Mg m 3 Cu Kα radiation, λ = Å Cell parameters from 2799 reflections θ = µ = 2.14 mm 1 T = 296 K Block, pink mm measured reflections 2799 independent reflections 2386 reflections with I > 2σ(I) R int = θ max = 71.6, θ min = 5.7 h = k = l = sup-3

5 Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 196 parameters 0 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H atoms treated by a mixture of independent and constrained refinement w = 1/[σ 2 (F o2 ) + (0.0843P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.25 e Å 3 Δρ min = 0.42 e Å 3 Extinction correction: SHELXTL (Sheldrick, 2008), Fc * =kfc[ xfc 2 λ 3 /sin(2θ)] -1/4 Extinction coefficient: (3) Special details 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 F 2 against ALL reflections. The weighted R-factor wr and goodness of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The threshold expression of F 2 > 2sigma(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 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 (Å 2 ) x y z U iso */U eq S (5) (4) (2) (2) O (16) (11) (7) (4) O (16) (12) (7) (4) N (16) (13) (8) (4) N (19) (17) (10) (6) H1N * H2N * N (17) (14) (8) (4) H1N (2) (17) (10) (6)* C (18) (14) (8) (4) C (2) (16) (9) (5) H2A * C (2) (17) (9) (5) H3A * C (19) (16) (9) (5) C (2) (18) (9) (5) H5A * C (2) (17) (9) (5) H6A * C (18) (15) (9) (4) C (2) (2) (12) (6) H8A * C (3) (2) (14) (8) sup-4

6 H9A * C (3) (2) (14) (8) H10A * C (2) (18) (11) (6) H11A * O (3) (2) (11) (9) O (2) (2) (11) (8) N (3) (3) (15) (9) C (4) (4) (17) (14) H12A * H12B * H12C * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 S (4) (3) (3) (18) (19) (17) O (11) (8) (10) (7) (7) (6) O (10) (9) (10) (7) (8) (7) N (9) (8) (9) (7) (7) (7) N (12) (13) (15) (10) (10) (11) N (10) (9) (10) (8) (8) (8) C (10) (9) (9) (8) (7) (7) C (11) (10) (10) (8) (8) (8) C (10) (11) (11) (8) (8) (9) C (10) (10) (11) (9) (8) (8) C (13) (12) (10) (10) (9) (9) C (11) (11) (11) (9) (8) (8) C (10) (9) (11) (8) (8) (8) C (14) (14) (14) (12) (11) (11) C (17) (15) (19) (14) (14) (14) C (17) (14) (2) (13) (15) (13) C (15) (12) (14) (11) (11) (10) O (18) (2) (17) (17) (14) (15) O (15) (2) (15) (15) (13) (13) N (17) (2) (2) (17) (16) (17) C (3) (4) (2) (3) (2) (2) Geometric parameters (Å, º) S1 O (16) C5 C (3) S1 O (15) C5 H5A S1 N (18) C6 H6A S1 C (19) C7 C (3) N1 C (3) C8 C (4) N2 C (3) C8 H8A N2 H1N C9 C (4) N2 H2N C9 H9A sup-5

7 N3 C (3) C10 C (4) N3 C (3) C10 H10A N3 H1N (2) C11 H11A C1 C (3) O3 N (4) C1 C (3) O4 N (4) C2 C (3) N4 C (5) C2 H2A C12 H12A C3 C (3) C12 H12B C3 H3A C12 H12C C4 C (3) O2 S1 O (10) C5 C6 C (19) O2 S1 N (10) C5 C6 H6A O1 S1 N (9) C1 C6 H6A O2 S1 C (10) N1 C7 N (17) O1 S1 C (9) N1 C7 C (2) N1 S1 C (9) N3 C7 C (19) C7 N1 S (14) C9 C8 N (2) C4 N2 H1N C9 C8 H8A C4 N2 H2N N3 C8 H8A H1N2 N2 H2N C8 C9 C (2) C7 N3 C (19) C8 C9 H9A C7 N3 H1N (15) C10 C9 H9A C8 N3 H1N (16) C11 C10 C (2) C6 C1 C (18) C11 C10 H10A C6 C1 S (15) C9 C10 H10A C2 C1 S (15) C10 C11 C (2) C3 C2 C (18) C10 C11 H11A C3 C2 H2A C7 C11 H11A C1 C2 H2A O4 N4 O (3) C2 C3 C (19) O4 N4 C (3) C2 C3 H3A O3 N4 C (3) C4 C3 H3A N4 C12 H12A N2 C4 C (19) N4 C12 H12B N2 C4 C (19) H12A C12 H12B C5 C4 C (19) N4 C12 H12C C6 C5 C (18) H12A C12 H12C C6 C5 H5A H12B C12 H12C C4 C5 H5A O2 S1 N1 C (19) C3 C4 C5 C6 3.3 (3) O1 S1 N1 C (16) C4 C5 C6 C1 1.3 (3) C1 S1 N1 C (17) C2 C1 C6 C5 1.2 (3) O2 S1 C1 C6 0.9 (2) S1 C1 C6 C (17) O1 S1 C1 C (18) S1 N1 C7 N (14) N1 S1 C1 C (17) S1 N1 C7 C (3) O2 S1 C1 C (16) C8 N3 C7 N (2) O1 S1 C1 C (18) C8 N3 C7 C (3) sup-6

8 N1 S1 C1 C (18) C7 N3 C8 C9 0.8 (4) C6 C1 C2 C3 1.6 (3) N3 C8 C9 C (4) S1 C1 C2 C (16) C8 C9 C10 C (5) C1 C2 C3 C4 0.5 (3) C9 C10 C11 C7 0.7 (4) C2 C3 C4 N (2) N1 C7 C11 C (2) C2 C3 C4 C5 2.9 (3) N3 C7 C11 C (3) N2 C4 C5 C (2) Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A N2 H1N2 O2 i (3) 174 N2 H2N2 O1 ii (3) 157 N3 H1N3 N1 iii 0.86 (2) 2.09 (2) (2) 178 (2) C8 H8A O1 iii (3) 126 Symmetry codes: (i) x, y 1/2, z+1/2; (ii) x 1/2, y 1/2, z; (iii) x, y+1, z. sup-7