Manpreet Kaur, Jerry P. Jasinski, Thammarse S. Yamuna, H. S. Yathirajan and K. Byrappa

Transcription

1 Acta Crystallographica Section E Structure Reports Online ISSN {2-[(2-Bromo-5-methoxybenzylidene)amino]-4,5,6,7-tetrahydrobenzo[b ]thiophen-3-yl}(phenyl)methanone Manpreet Kaur, Jerry P. Jasinski, Thammarse S. Yamuna, H. S. Yathirajan and K. Byrappa This open-access article is distributed under the terms of the Creative Commons Attribution Licence which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited. Acta Crystallographica Section E: Structure Reports Online is the IUCr s highly popular open-access structural journal. It provides a simple and easily accessible publication mechanism for the growing number of inorganic, metal-organic and organic crystal structure determinations. The electronic submission, validation, refereeing and publication facilities of the journal ensure very rapid and high-quality publication, whilst key indicators and validation reports provide measures of structural reliability. The average publication time is less than one month. Articles are published in a short-format style with enhanced supplementary materials. Each publication consists of a complete package the published article, HTML and PDF supplements, CIF, structure factors, graphics, and any other submitted supplementary files. Crystallography Journals Online is available from journals.iucr.org Kaur et al. C 23 H 20 BrNO 2 S

2 organic compounds Acta Crystallographica Section E Structure Reports Online ISSN {2-[(2-Bromo-5-methoxybenzylidene)- amino]-4,5,6,7-tetrahydrobenzo[b]thiophen-3-yl}(phenyl)methanone Manpreet Kaur, a Jerry P. Jasinski, b * Thammarse S. Yamuna, a H. S. Yathirajan a and K. Byrappa c a Department of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore , India, b Department of Chemistry, Keene State College, 229 Main Street, Keene, NH , USA, and c Materials Science Center, University of Mysore, Vijyana Bhavan Building, Manasagangothri, Mysore , India Correspondence jjasinski@keene.edu Received 3 April 2014; accepted 12 April 2014 Experimental Crystal data C 23 H 20 BrNO 2 S M r = Monoclinic, P2 1 =n a = (17) Å b = (2) Å c = (4) Å = (2) Data collection Agilent Eos Gemini diffractometer Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012) T min = 0.725, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections V = (7) Å 3 Z =4 Cu K radiation = 3.92 mm 1 T = 173 K mm measured reflections 3853 independent reflections 3440 reflections with I > 2(I) R int = parameters H-atom parameters constrained max = 0.56 e Å 3 min = 0.31 e Å 3 Key indicators: single-crystal X-ray study; T = 173 K; mean (C C) = Å; disorder in main residue; R factor = 0.032; wr factor = 0.087; data-to-parameter ratio = In the title compound, C 23 H 20 BrNO 2 S, disorder was modeled for the outer two C atoms of the cyclohexene ring over two sets of sites with an occupancy ratio of (11):0.420 (11). Both rings have a half-chair conformation. The dihedral angles between the mean plane of the thiophene ring and the benzene and phenyl rings are 9.2 (2) and 66.1 (2), respectively. The benzene and phenyl rings are inclined to each other by 74.8 (8). In the crystal, molecules are linked by pairs of C HO hydrogen bonds, forming inversion dimers. Related literature For applications of 2-aminothiophene derivatives, see: Sabnis et al. (1999); Puterová et al. (2010). For the biological and industrial importance of Schiff bases, see: Desai et al. (2001); Karia & Parsania (1999); Samadhiya & Halve (2001); Singh & Dash (1988); Aydogan et al. (2001); Taggi et al. (2002). For a related structure, see: Kubicki et al. (2012). For puckering parameters, see: Cremer & Pople (1975). For standard bond lengths, see: Allen et al. (1987). Table 1 Hydrogen-bond geometry (Å, ). D HA D H HA DA D HA C20 H20O2 i (3) 132 Symmetry code: (i) x; y þ 1; z þ 1. Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and PLATON. MK is grateful to the CPEPA UGC for the award of a Junior Research Fellowship and thanks the University of Mysore for research facilities. JPJ acknowledges the NSF MRI program (grant No. CHE ) for funds to purchase the X-ray diffractometer. Supporting information for this paper is available from the IUCr electronic archives (Reference: SU2721). References Agilent (2012). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, England. Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1 19. Aydogan, F., Ocal, N., Turgut, Z. & Yolacan, C. (2001). Bull. Korean Chem. Soc. 22, Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, Desai, S. B., Desai, P. B. & Desai, K. R. (2001). Hetrocycl. Commun. 7, Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, Karia, F. D. & Parsania, P. H. (1999). Asian J. Chem. 11, Kubicki, M., Dutkiewicz, G., Yathirajan, H. S., Dawar, P., Ramesha, A. R. & Dayananda, A. S. (2012). Crystals, 2, doi: /s Kaur et al. o581

3 organic compounds 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, Palatinus, L. & Chapuis, G. (2007). J. Appl. Cryst. 40, Puterová, Z., Krutošiková, A.& Végh, D. (2010). Arkivoc, (i), Sabnis, R. W., Rangnekar, D. W. & Sonawane, N. D. (1999). J. Heterocycl. Chem. 36, Samadhiya, S. & Halve, A. (2001). Orient. J. Chem Sheldrick, G. M. (2008). Acta Cryst. A64, Singh, W. M. & Dash, B. C. (1988). Pesticides, 22, Spek, A. L. (2009). Acta Cryst. D65, Taggi, A. E., Hafez, A. M., Wack, H., Young, B., Ferraris, D. & Lectka, T. (2002). J. Am. Chem. Soc. 124, o582 Kaur et al. C 23 H 20 BrNO 2 S

4 supplementary materials [doi: /s ] {2-[(2-Bromo-5-methoxybenzylidene)amino]-4,5,6,7-tetrahydrobenzo[b]thiophen-3-yl}(phenyl)methanone Manpreet Kaur, Jerry P. Jasinski, Thammarse S. Yamuna, H. S. Yathirajan and K. Byrappa 1. Comment 2-Aminothiophene derivatives have been used in a number of applications in pesticides, dyes and pharmaceuticals (Sabnis et al. 1999; Puterová et al. 2010). Schiff base compounds show biological activities including antibacterial, antifungal, anticancer and herbicidal activities (Desai et al., 2001; Karia & Parsania, 1999; Samadhiya & Halve, 2001; Singh & Dash, 1988) and have been used as starting materials in the synthesis of compounds of industrial (Aydogan et al., 2001) and biological interest such as β-lactams (Taggi et al., 2002). In continuation of our work on the Schiff base derivatives of 2-aminothiophenes (Kubicki et al., 2012), we report herein on the crystal structure of the title compound. In the title compound, Fig. 1, disorder was modeled for atoms C5 and C6 of the cyclohexene ring over two sites (A and B) with an occupancy ratio of (11):0.420 (11). Both rings have half-chair conformations with puckering parameters (Cremer & Pople, 1975) Q,θ, and φ being = (6) Å, 49.9 (4) and (6), respectively, for ring A and being = (8) Å, (5) and (7), respectively, for ring B. The dihedral angles between the mean plane of the thiophene ring and the benzene and phenyl rings are 9.2 (2) and 66.1 (2), respectively. The benzene and phenyl rings are twisted with respect to each other by 74.8 (8). Bond lengths are in normal ranges (Allen et al., 1987). In the crystal, molecules are linked by pairs of C-H O hydrogen bonds forming inversion dimers (Table 1 and Fig. 2). 2. Experimental To a solution of (2-amino-4,5,6,7-tetrahydro-benzo[b]thiophen-3-yl)- phenyl-methanone (200 mg, 0.79 mmol) in 10 ml of methanol an equimolar amount of 2-bromo-5-methoxybenzaldehyde (170 mg, 0.79 mmol) was added with constant stirring. The mixture was then refluxed for 6 hours and a yellow precipitate was obtained. The reaction completion was confirmed by thin layer chromatography. The precipitate was filtered and dried at room temperature overnight. Slow evaporation of a solution in CH 2 Cl 2 gave yellow block-like crystals of the title compound. 3. Refinement All H atoms were placed in calculated positions and refined as riding atoms: C H = Å with U iso (H) = 1.5U eq (C-methyl) and = 1.2U eq (C) for other H atoms. Atoms C5 and C6, of the tetrahydrobenzothiophenyl ring, are disordered over two sites (A and B) and were refined with an occupancy ratio of (11):0.426 (11). sup-1

5 Figure 1 A view of the molecular structure of the title molecule, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level (the minor component atoms C5B and C6B are not shown). Figure 2 A view along the b axis of the crystal packing of the title compound. The C H O hydrogen bonds are shown as dashed lines (see Table 1 for details; H atoms not involved in hydrogen bonding have been omitted for clarity; the minor component atoms C5B and C6B are not shown). sup-2

6 {2-[(2-Bromo-5-methoxybenzylidene)amino]-4,5,6,7-tetrahydrobenzo[b]thiophen-3-yl}(phenyl)methanone Crystal data C 23 H 20 BrNO 2 S M r = Monoclinic, P2 1 /n a = (17) Å b = (2) Å c = (4) Å β = (2) V = (7) Å 3 Z = 4 Data collection Agilent Eos Gemini diffractometer Radiation source: Enhance (Cu) X-ray Source ω scans Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012) T min = 0.725, T max = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 273 parameters 0 restraints F(000) = 928 D x = Mg m 3 Cu Kα radiation, λ = Å Cell parameters from 5917 reflections θ = µ = 3.92 mm 1 T = 173 K Irregular, yellow mm measured reflections 3853 independent reflections 3440 reflections with I > 2σ(I) R int = θ max = 71.3, θ min = 4.3 h = k = l = Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.0539P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max < Δρ max = 0.56 e Å 3 Δρ min = 0.31 e Å 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. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq Occ. (<1) Br (3) (2) (2) (10) S (6) (4) (3) (12) O (2) (12) (8) (4) O (19) (12) (10) (4) N (18) (13) (9) (3) C (2) (15) (11) (4) C (2) (15) (11) (4) C (2) (15) (10) (4) C (2) (16) (12) (4) H4AA * (11) H4AB * (11) sup-3

7 H4BC * (11) H4BD * (11) C5A (8) (3) (3) (14) (11) H5AA * (11) H5AB * (11) C6A (10) (3) (3) (14) (11) H6AA * (11) H6AB * (11) C5B (11) (5) (4) (18) (11) H5BA * (11) H5BB * (11) C6B (12) (5) (4) (17) (11) H6BA * (11) H6BB * (11) C (3) (15) (12) (4) H7AA * (11) H7AB * (11) H7BC * (11) H7BD * (11) C (2) (15) (11) (4) C (2) (15) (11) (4) C (2) (15) (10) (4) C (2) (17) (12) (4) H * C (3) (2) (14) (5) H * C (3) (19) (15) (6) H * C (3) (18) (14) (5) H * C (3) (16) (12) (4) H * C (2) (15) (11) (4) H * C (2) (16) (11) (4) C (2) (16) (11) (4) C (2) (18) (12) (4) H * C (2) (17) (12) (5) H * C (2) (16) (12) (4) C (2) (16) (11) (4) H * C (3) (17) (14) (5) H23A * H23B * H23C * sup-4

8 Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Br (15) (15) (15) (8) (10) (8) S (3) (2) (2) (17) (2) (17) O (10) (7) (7) (7) (7) (6) O (9) (7) (9) (6) (7) (7) N (8) (8) (8) (6) (6) (6) C (9) (9) (10) (7) (7) (7) C (9) (9) (9) (7) (7) (7) C (8) (9) (9) (7) (7) (7) C (10) (10) (11) (8) (8) (8) C5A (3) (2) (3) (19) (3) (17) C6A (4) (2) (3) (2) (3) (18) C5B (4) (3) (3) (3) (3) (2) C6B (4) (3) (4) (3) (3) (2) C (11) (10) (11) (8) (9) (8) C (9) (9) (10) (7) (7) (7) C (9) (8) (9) (7) (7) (7) C (9) (9) (9) (7) (7) (7) C (10) (11) (11) (8) (8) (8) C (12) (14) (13) (10) (10) (10) C (15) (12) (15) (11) (12) (11) C (15) (10) (13) (10) (12) (9) C (12) (10) (11) (8) (9) (8) C (9) (9) (9) (7) (7) (7) C (9) (10) (10) (7) (7) (8) C (9) (10) (10) (7) (8) (8) C (9) (12) (10) (8) (8) (9) C (10) (11) (11) (8) (9) (9) C (9) (10) (11) (7) (8) (8) C (9) (10) (9) (7) (8) (8) C (12) (12) (13) (9) (10) (9) Geometric parameters (Å, º) Br1 C (2) C6B C (7) S1 C (19) C7 H7AA S1 C (19) C7 H7AB O1 C (2) C7 H7BC O2 C (3) C7 H7BD O2 C (3) C7 C (3) N1 C (3) C10 C (3) N1 C (2) C10 C (3) C1 C (3) C11 H C1 C (3) C11 C (3) C2 C (3) C12 H C2 C (3) C12 C (4) C3 C (3) C13 H C3 C (3) C13 C (4) sup-5

9 C4 H4AA C14 H C4 H4AB C14 C (3) C4 H4BC C15 H C4 H4BD C16 H C4 C5A (4) C16 C (3) C4 C5B (6) C17 C (3) C5A H5AA C17 C (3) C5A H5AB C18 C (3) C5A C6A (8) C19 H C6A H6AA C19 C (3) C6A H6AB C20 H C6A C (5) C20 C (3) C5B H5BA C21 C (3) C5B H5BB C22 H C5B C6B (12) C23 H23A C6B H6BA C23 H23B C6B H6BB C23 H23C C8 S1 C (9) C8 C7 H7AA C21 O2 C (16) C8 C7 H7AB C16 N1 C (17) C8 C7 H7BC O1 C1 C (18) C8 C7 H7BD O1 C1 C (18) C3 C8 S (14) C2 C1 C (17) C3 C8 C (18) C3 C2 C (17) C7 C8 S (15) C9 C2 C (17) N1 C9 S (14) C9 C2 C (17) C2 C9 S (15) C2 C3 C (17) C2 C9 N (18) C8 C3 C (17) C11 C10 C (18) C8 C3 C (17) C15 C10 C (18) C3 C4 H4AA C15 C10 C (19) C3 C4 H4AB C10 C11 H C3 C4 H4BC C12 C11 C (2) C3 C4 H4BD C12 C11 H C3 C4 C5B (3) C11 C12 H H4AA C4 H4AB C11 C12 C (2) H4BC C4 H4BD C13 C12 H C5A C4 C (2) C12 C13 H C5A C4 H4AA C14 C13 C (2) C5A C4 H4AB C14 C13 H C5B C4 H4BC C13 C14 H C5B C4 H4BD C13 C14 C (2) C4 C5A H5AA C15 C14 H C4 C5A H5AB C10 C15 C (2) C4 C5A C6A (5) C10 C15 H H5AA C5A H5AB C14 C15 H C6A C5A H5AA N1 C16 H C6A C5A H5AB N1 C16 C (18) C5A C6A H6AA C17 C16 H sup-6

10 C5A C6A H6AB C18 C17 C (18) C5A C6A C (5) C18 C17 C (18) H6AA C6A H6AB C22 C17 C (17) C7 C6A H6AA C17 C18 Br (15) C7 C6A H6AB C19 C18 Br (15) C4 C5B H5BA C19 C18 C (19) C4 C5B H5BB C18 C19 H H5BA C5B H5BB C20 C19 C (19) C6B C5B C (6) C20 C19 H C6B C5B H5BA C19 C20 H C6B C5B H5BB C19 C20 C (19) C5B C6B H6BA C21 C20 H C5B C6B H6BB O2 C21 C (18) C5B C6B C (6) O2 C21 C (19) H6BA C6B H6BB C22 C21 C (19) C7 C6B H6BA C17 C22 H C7 C6B H6BB C21 C22 C (18) C6A C7 H7AA C21 C22 H C6A C7 H7AB O2 C23 H23A C6B C7 H7BC O2 C23 H23B C6B C7 H7BD O2 C23 H23C H7AA C7 H7AB H23A C23 H23B H7BC C7 H7BD H23A C23 H23C C8 C7 C6A (2) H23B C23 H23C C8 C7 C6B (3) Br1 C18 C19 C (17) C5B C6B C7 C (8) O1 C1 C2 C (3) C6B C7 C8 S (4) O1 C1 C2 C (2) C6B C7 C8 C (5) O1 C1 C10 C (19) C8 S1 C9 N (17) O1 C1 C10 C (3) C8 S1 C9 C (15) O2 C21 C22 C (19) C8 C3 C4 C5A 13.9 (4) N1 C16 C17 C (19) C8 C3 C4 C5B 19.7 (5) N1 C16 C17 C (3) C9 S1 C8 C (15) C1 C2 C3 C4 4.7 (3) C9 S1 C8 C (17) C1 C2 C3 C (17) C9 N1 C16 C (17) C1 C2 C9 S (15) C9 C2 C3 C (18) C1 C2 C9 N1 2.1 (3) C9 C2 C3 C8 0.4 (2) C1 C10 C11 C (19) C10 C1 C2 C (19) C1 C10 C15 C (19) C10 C1 C2 C (3) C2 C1 C10 C (3) C10 C11 C12 C (3) C2 C1 C10 C (18) C11 C10 C15 C (3) C2 C3 C4 C5A (3) C11 C12 C13 C (4) C2 C3 C4 C5B (4) C12 C13 C14 C (4) C2 C3 C8 S1 1.2 (2) C13 C14 C15 C (3) C2 C3 C8 C (18) C15 C10 C11 C (3) C3 C2 C9 S1 0.5 (2) C16 N1 C9 S1 3.8 (3) C3 C2 C9 N (17) C16 N1 C9 C (19) C3 C4 C5A C6A 46.7 (7) C16 C17 C18 Br1 3.6 (3) sup-7

11 C3 C4 C5B C6B 53.2 (8) C16 C17 C18 C (19) C4 C3 C8 S (15) C16 C17 C22 C (18) C4 C3 C8 C7 0.1 (3) C17 C18 C19 C (3) C4 C5A C6A C (8) C18 C17 C22 C (3) C4 C5B C6B C (9) C18 C19 C20 C (3) C5A C4 C5B C6B 43.5 (7) C19 C20 C21 O (2) C5A C6A C7 C6B 51.1 (7) C19 C20 C21 C (3) C5A C6A C7 C (7) C20 C21 C22 C (3) C6A C7 C8 S (4) C22 C17 C18 Br (14) C6A C7 C8 C (4) C22 C17 C18 C (3) C5B C4 C5A C6A 48.4 (6) C23 O2 C21 C (19) C5B C6B C7 C6A 46.2 (7) C23 O2 C21 C (3) Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A C20 H20 O2 i (3) 132 Symmetry code: (i) x, y+1, z+1. sup-8