Experimental. Crystal data

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1 organic compounds Acta Crystallographica Section E Structure Reports Online ISSN (4-Methylphenylsulfonyl)-2-{[3-methyl- 4-(2,2,2-trifluoroethoxy)pyridin-2-yl]- methylsulfanyl}-1h-1,3-benzimidazole C. M. Shivaprasad, a S. Madan Kumar, b T. R. Swaroop, a K. S. Rangappa a and N. K. Lokanath b * a Department of Studies in Chemistry, Manasagangotri, University of Mysore, Mysore , India, and b Department of Studies in Physics, Manasagangotri, University of Mysore, Mysore , India Correspondence lokanath@physics.uni-mysore.ac.in Received 5 November 2013; accepted 22 November 2013 Experimental Crystal data C 23 H 20 F 3 N 3 O 3 S 2 M r = Triclinic, P1 a = (6) Å b = (6) Å c = (8) Å = (3) = (2) Data collection Bruker X8 Proteum diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2013) T min = 0.615, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections = (3) V = (13) Å 3 Z =2 Cu K radiation = 2.56 mm 1 T = 296 K mm measured reflections 3779 independent reflections 3301 reflections with I > 2(I) R int = parameters H-atom parameters constrained max = 0.32 e Å 3 min = 0.44 e Å 3 Key indicators: single-crystal X-ray study; T = 296 K; mean (C C) = Å; R factor = 0.050; wr factor = 0.144; data-to-parameter ratio = In the title compound, C 23 H 20 F 3 N 3 O 3 S 2, the benzoimidazole unit makes dihedral angles of 5.02 (1) and (1), respectively, with the pyridine and methylbenzene rings; the dihedral angle between the pyridine and methylbenzene rings is (1). In the crystal, molecules are connected by weak C HF, C HO and C HN hydrogen bonds. Weak C H interactions and stacking [centroid centroid distance = (14) Å] are also observed. The overall packing shows a three-dimensional architecture. The crystal structure contains a void of 51 Å 3, but no solvent molecule (hexane or ethyl acetate) is located within it. Related literature For the biological activity of benzoimidazole derivatives, see: Bansal & Silakari (2012); Ates-Alagoz et al. (2004). For hydrogen-bond motifs, see: Bernstein et al. (1995). Table 1 Hydrogen-bond geometry (Å, ). Cg1 is the centroid of the imidazole ring. D HA D H HA DA D HA C2 H2F2 i (4) 156 C15 H15BO3 ii (3) 155 C18 H18N3 iii (3) 136 C18 H18Cg (3) 126 Symmetry codes: (i) x 1; y 1; z 1; (ii) x þ 1; y þ 2; z þ 1; (iii) x; y þ 1; z þ 1. Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: Mercury. The authors are thankful to the IOE, University of Mysore, for providing the single-crystal X-ray diffraction facility. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU5751). References Ates-Alagoz, Z., Can-Eke, B., Coban, T., Iscan, M. & Buyukbingol, E. (2004). Arch. Pharm Bansal, Y. & Silakari, O. (2012). Bioorg. Med. Chem. 20, Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, Sheldrick, G. M. (2008). Acta Cryst. A64, o1846 Shivaprasad et al. doi: /s

2 [doi: /s ] 1-(4-Methylphenylsulfonyl)-2-{[3-methyl-4-(2,2,2-trifluoroethoxy)pyridin-2- yl]methylsulfanyl}-1h-1,3-benzimidazole C. M. Shivaprasad, S. Madan Kumar, T. R. Swaroop, K. S. Rangappa and N. K. Lokanath S1. Comment The benzimidazole derivatives acts as antioxidant (Ates-Alagoz et al., 2004) and show biological activities (Bansal & Silakari, 2012). The ORTEP of the title molecules is shown in figure 1. the benzoimidazole moiety (N2-N3/C1-C7) makes a dihedral angle of 5.02 (1) and (1) with pyridin ring (N1/C9-C13) and phenyl ring (C17-C22), respectively. The dihedral angle betwen the pyridin ring and phenyl moiety is (1). The molecules in the crystal structure are connected with C H F, C H O, C H N and C H O intermolecular hydrogen bonds (Fig. 2 & Table 1). The C2 H2 F2 forms infinite chains along b-axis. C15 H15B O3 shows R 2 2(26) ring motif while C18 H18 N3 shows R 2 2(14) ring motif (Bernstein et al., 1995). Also, short contacts C H π and π π [centroid-centroid distance of (14) Å] is observed. Overall packing of molecules depicts three dimesional architecture. All the above interactions of the molecule generates three-dimensional architecture (Fig. 2). S2. Experimental To a solution of 2-(((3-methyl-4-(2,2,2-trifluoroethoxy)pyridin-2-yl)methyl)thio)-1H-benzo[d] imidazole (10 mmol) and tetrabutyl ammonium bromide (1 mmol) in toluene (20 ml), a solution of 50% KOH (25 ml) was added at 0 C followed by the addition of toluenesulfonyl chloride (12 mmol). The reaction mixture was allowed for vigorous stirring at room temperature for 6 h and the reaction progress was monitored by TLC. After the completion of the reaction, organic phase was separated from the aqueous phase and the organic phase was washed with water (20 ml) and brine (20 ml), dried over anhydrous sodium sulfate and concentrated to give crude product 2-(3-methyl-4-(2,2,2-trifluoroethoxy)pyridin-2-ylthio)-1-tosyl-1H-benzo[d] imidazole which was purified by column chromatography over silica gel using hexane-etoac (6:4) mixture as eluent. S3. Refinement All the H atoms were fixed geometrically (C H = Å) and allowed to ride on their parent atoms with U iso (H) = 1.5U eq (C) for mehtyl H atoms and 1.2U eq (C) for the others. sup-1

3 Figure 1 ORTEP diagram of the title compound with 50% probability ellipsoids. sup-2

4 Figure 2 Packing diagram of molecule, viewed along the crystallographic c axis. Dotted lines indicate hydrogen bonds and short contacts involved. 1-(4-Methylphenylsulfonyl)-2-{[3-methyl-4-(2,2,2-trifluoroethoxy)pyridin-2-yl]methylsulfanyl}-1H-1,3- benzimidazole Crystal data C 23 H 20 F 3 N 3 O 3 S 2 M r = Triclinic, P1 Hall symbol: -P 1 a = (6) Å b = (6) Å c = (8) Å α = (3) β = (2) γ = (3) V = (13) Å 3 Z = 2 F(000) = 524 D x = Mg m 3 Cu Kα radiation, λ = Å Cell parameters from 3779 reflections θ = µ = 2.56 mm 1 T = 296 K Block, colorless mm sup-3

5 Data collection Bruker X8 Proteum diffractometer Radiation source: Bruker MicroStar microfocus rotating anode Helios multilayer optics monochromator Detector resolution: 10.7 pixels mm -1 \φ and \ω scans Absorption correction: multi-scan (SADABS; Bruker, 2013) Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 310 parameters 0 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map T min = 0.615, T max = measured reflections 3779 independent reflections 3301 reflections with I > 2σ(I) R int = θ max = 64.3, θ min = 3.3 h = k = 10 9 l = Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.0866P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.32 e Å 3 Δρ min = 0.44 e Å 3 Extinction correction: SHELXL97 (Sheldrick, 2008), FC * =KFC[ XFC 2 Λ 3 /SIN(2Θ)] -1/4 Extinction coefficient: (2) 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 on F 2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wr and all goodnesses 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 observed criterion of F 2 > σ(f 2 ) is used only for calculating -R-factor-obs 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 (6) (6) (4) (2) S (7) (6) (4) (2) F (4) (6) (3) (2) F (3) (4) (18) (13) F (6) (5) (2) (2) O (2) (2) (13) (7) O (2) (2) (12) (6) O (2) (2) (15) (7) N (2) (2) (15) (7) N (2) (2) (14) (6) N (2) (2) (14) (6) C (2) (2) (17) (7) C (3) (3) (19) (8) C (3) (3) (2) (9) sup-4

6 C (3) (3) (2) (9) C (3) (3) (2) (9) C (2) (3) (17) (7) C (2) (2) (16) (7) C (3) (3) (17) (7) C (2) (2) (17) (7) C (2) (3) (17) (7) C (3) (3) (18) (7) C (3) (3) (19) (8) C (3) (3) (2) (8) C (3) (4) (2) (10) C (3) (3) (2) (9) C (5) (5) (3) (14) C (2) (3) (16) (7) C (3) (3) (18) (8) C (3) (3) (2) (9) C (3) (3) (3) (10) C (4) (3) (2) (11) C (3) (3) (19) (9) C (5) (4) (4) (18) H * H * H * H * H8A * H8B * H * H * H14A * H14B * H14C * H15A * H15B * H * H * H * H * H23A * H23B * H23C * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 S (4) (4) (4) (2) (2) (2) S (4) (4) (3) (3) (2) (2) F (3) (6) (2) (3) (2) (3) F (2) (3) (15) (2) (13) (17) sup-5

7 F (5) (4) (2) (3) (3) (2) O (10) (14) (10) (9) (8) (9) O (12) (12) (9) (10) (8) (8) O (12) (11) (12) (9) (10) (9) N (11) (12) (11) (9) (9) (9) N (10) (11) (10) (8) (8) (8) N (10) (11) (10) (8) (8) (8) C (11) (13) (12) (9) (9) (9) C (14) (16) (13) (12) (11) (11) C (14) (18) (17) (13) (12) (13) C (14) (18) (17) (12) (12) (13) C (13) (17) (14) (12) (11) (12) C (11) (13) (12) (9) (9) (9) C (11) (12) (11) (9) (9) (9) C (12) (13) (12) (10) (10) (10) C (11) (13) (12) (10) (9) (9) C (11) (13) (13) (10) (9) (10) C (12) (14) (12) (10) (9) (10) C (13) (14) (14) (10) (11) (11) C (14) (15) (14) (12) (11) (11) C (16) (2) (15) (14) (12) (13) C (14) (18) (16) (13) (12) (13) C (2) (3) (2) (2) (18) (2) C (11) (13) (11) (9) (9) (9) C (12) (16) (13) (11) (10) (11) C (13) (17) (18) (12) (12) (14) C (14) (16) (2) (11) (14) (15) C (19) (18) (19) (15) (15) (14) C (17) (17) (13) (14) (12) (11) C (3) (2) (4) (19) (3) (2) Geometric parameters (Å, º) S1 C (2) C15 C (5) S1 C (2) C17 C (3) S2 O (18) C17 C (3) S2 O (2) C18 C (4) S2 N (2) C19 C (5) S2 C (3) C20 C (5) F1 C (6) C20 C (5) F2 C (6) C21 C (4) F3 C (6) C2 H O1 C (3) C3 H O1 C (3) C4 H N1 C (3) C5 H N1 C (3) C8 H8A N2 C (3) C8 H8B N2 C (3) C12 H sup-6

8 N3 C (3) C13 H N3 C (3) C14 H14A C1 C (3) C14 H14B C1 C (3) C14 H14C C2 C (4) C15 H15A C3 C (4) C15 H15B C4 C (4) C18 H C5 C (4) C19 H C8 C (3) C21 H C9 C (3) C22 H C10 C (4) C23 H23A C10 C (4) C23 H23B C11 C (4) C23 H23C C12 C (4) C7 S1 C (12) C18 C19 C (3) O2 S2 O (12) C19 C20 C (3) O2 S2 N (10) C19 C20 C (4) O2 S2 C (11) C21 C20 C (4) O3 S2 N (11) C20 C21 C (3) O3 S2 C (11) C17 C22 C (2) N2 S2 C (10) C1 C2 H C11 O1 C (2) C3 C2 H C9 N1 C (2) C2 C3 H S2 N2 C (16) C4 C3 H S2 N2 C (15) C3 C4 H C1 N2 C (17) C5 C4 H C6 N3 C (18) C4 C5 H N2 C1 C (2) C6 C5 H N2 C1 C (19) S1 C8 H8A C2 C1 C (2) S1 C8 H8B C1 C2 C (2) C9 C8 H8A C2 C3 C (3) C9 C8 H8B C3 C4 C (3) H8A C8 H8B C4 C5 C (2) C11 C12 H N3 C6 C (19) C13 C12 H N3 C6 C (2) N1 C13 H C1 C6 C (2) C12 C13 H S1 C7 N (15) C10 C14 H14A S1 C7 N (17) C10 C14 H14B N2 C7 N (18) C10 C14 H14C S1 C8 C (17) H14A C14 H14B N1 C9 C (2) H14A C14 H14C N1 C9 C (19) H14B C14 H14C C8 C9 C (19) O1 C15 H15A C9 C10 C (2) O1 C15 H15B C9 C10 C (2) C16 C15 H15A C11 C10 C (2) C16 C15 H15B sup-7

9 O1 C11 C (2) H15A C15 H15B O1 C11 C (2) C17 C18 H C10 C11 C (2) C19 C18 H C11 C12 C (3) C18 C19 H N1 C13 C (3) C20 C19 H O1 C15 C (3) C20 C21 H F1 C16 F (4) C22 C21 H F1 C16 F (4) C17 C22 H F1 C16 C (4) C21 C22 H F2 C16 F (4) C20 C23 H23A F2 C16 C (3) C20 C23 H23B F3 C16 C (4) C20 C23 H23C S2 C17 C (19) H23A C23 H23B S2 C17 C (19) H23A C23 H23C C18 C17 C (3) H23B C23 H23C C17 C18 C (2) C8 S1 C7 N (17) N2 C1 C6 N3 0.4 (2) C8 S1 C7 N3 0.4 (2) N2 C1 C6 C (2) C7 S1 C8 C (16) C2 C1 C6 N (2) O2 S2 N2 C (2) C2 C1 C6 C5 0.7 (4) O2 S2 N2 C (19) C1 C2 C3 C4 0.3 (4) O3 S2 N2 C (17) C2 C3 C4 C5 0.7 (4) O3 S2 N2 C (2) C3 C4 C5 C6 0.4 (4) C17 S2 N2 C (19) C4 C5 C6 N (3) C17 S2 N2 C (2) C4 C5 C6 C1 0.3 (4) O2 S2 C17 C (2) S1 C8 C9 N1 3.6 (2) O2 S2 C17 C (2) S1 C8 C9 C (17) O3 S2 C17 C (2) N1 C9 C10 C (3) O3 S2 C17 C (2) N1 C9 C10 C (2) N2 S2 C17 C (2) C8 C9 C10 C (2) N2 S2 C17 C (19) C8 C9 C10 C (4) C15 O1 C11 C (2) C9 C10 C11 O (2) C15 O1 C11 C (4) C9 C10 C11 C (4) C11 O1 C15 C (3) C14 C10 C11 O1 2.0 (4) C13 N1 C9 C (2) C14 C10 C11 C (3) C13 N1 C9 C (3) O1 C11 C12 C (3) C9 N1 C13 C (4) C10 C11 C12 C (4) S2 N2 C1 C (3) C11 C12 C13 N1 0.1 (4) S2 N2 C1 C (16) O1 C15 C16 F (5) C7 N2 C1 C (2) O1 C15 C16 F (3) C7 N2 C1 C6 0.2 (2) O1 C15 C16 F (5) S2 N2 C7 S (3) S2 C17 C18 C (2) S2 N2 C7 N (16) C22 C17 C18 C (4) C1 N2 C7 S (14) S2 C17 C22 C (2) C1 N2 C7 N3 0.8 (2) C18 C17 C22 C (4) C7 N3 C6 C1 0.8 (3) C17 C18 C19 C (4) C7 N3 C6 C (3) C18 C19 C20 C (4) sup-8

10 C6 N3 C7 S (17) C18 C19 C20 C (3) C6 N3 C7 N2 1.0 (2) C19 C20 C21 C (5) N2 C1 C2 C (2) C23 C20 C21 C (3) C6 C1 C2 C3 0.4 (4) C20 C21 C22 C (5) Hydrogen-bond geometry (Å, º) Cg1 is the centroid of the imidazole ring. D H A D H H A D A D H A C2 H2 F2 i (4) 156 C15 H15B O3 ii (3) 155 C18 H18 N3 iii (3) 136 C18 H18 Cg (3) 126 Symmetry codes: (i) x 1, y 1, z 1; (ii) x+1, y+2, z+1; (iii) x, y+1, z+1. sup-9