Crystal structure of 1-methanesulfonyl- 1,2,3,4-tetrahydroquinoline S. Jeyaseelan, a S. L. Nagendra Babu, b G. Venkateshappa, c P. Raghav endra Kumar c and B. S. Palakshamurthy b * a Department of Physics, St Philomenas College (Autonomous), Mysore, Karnataka 570 015, India, b Department of Studies and Research in Physics, U.C.S., Tumkur University, Tumkur, Karnataka 572 103, India, and c Department of Chemistry, Tumkur University, Tumkur, Karnataka 572 103, India. *Correspondence e-mail: [email protected]Received 9 November 2014; accepted 19 November 2014 Edited by W. T. A. Harrison, University of Aberdeen, Scotland In the titl e compo und, C 10 H 13 NO 2 S, the het eroc ycl ic ring adopts a half-chair conformation and the bond-angle sum at the N atom is 347.9 . In the crystal, inversion dimers linked by pairs of C—HO hydrogen bonds generate R 2 2 (8) loops. Keywords:crystal structure; 1,2,3,4-tetrahydroquinoline; physiological activities; photosensitizers. CCDC reference: 1034951 1. Related literature For background to tetrahydroquinolines, see: Chulakovet al. (2012); Kadutskii et al. (2012); Katritsky et al. (1996); Keith etal.(2001). For a related structure, see: Jeyaseelan et al. (2014). 2. Experimental 2.1. Crystal data C 10 H 13 NO 2 S Mr= 211.27 Triclinic, P1 a= 5.5865 (2) A ˚ b= 9.2195 (4) A ˚ c= 10.1924 (4) A ˚ = 85.798 (2) = 84.686 (2) = 77.166 (2) V= 508.89 (4) A ˚ 3 Z= 2 MoKradiation = 0.29 mm 1 T= 294 K 0.24 0.20 0.16 mm 2.2. Data collection Bruker APEXII CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2013) Tmin = 0.933, Tmax = 0.955 7417 measured reflections 1973 independent reflections 1844 reflections with I> 2( I) R int = 0.042 2.3. Refinement R[F2 > 2(F2 )] = 0.038 wR(F2 ) = 0.106 S= 1.07 1973 reflections 128 parameters H-atom parameters constrained max = 0.24 e A ˚ 3 min = 0.31 e A ˚ 3 Table 1 Hydrogen-bond geometry (A ˚ , ). D—HA D—H HA DA D—HA C10—H10CO2 i 0.96 2.50 3.431 (2) 164 Symmetry code: (i) x; y þ 1; z þ 2. Data collec tion: APEX2 (Bruke r, 2013); cell refinement: SAINT(Bruker , 2013); data reduct ion: SAINT; program(s) used to solve structure: SHELXS97(Sheldrick, 2008);; program(s) used to refine structure: SHELXL2014 (Shel dric k, 200 8); mole cul ar grap hic s: ORTEP-3 for Windows (Farrugia, 2012) andMercury(Macrae et al., 20 08 ); soft wa re used to prepar e m at e ri al for publ ic at ion: SHELXL2014. Acknowledgements SJ thanks Vis ion Gr oup on Sc ie nc e and T ec hnol ogy , Gov ern ment of Kar nat aka, for awa rdi ng a maj or proj ect under CISE scheme (refe rence No. VGST/CISE/GRD-19 2/ 2013–14). BSP thanks Rajegowda, Department of Studies and Research in Physics, UCS, Tumkur University, Karnataka 572 103, India, for his support. Sup por ting inf ormati on for this pap er is ava ila ble from the IUCr electronic archives (Reference: HB7314). References Bruker (2013). APEX2, SAINTand SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Chul akov, E. N., Levit , G. L., Tumashov, A. A., Sadretdi nova, L. Sh. & Krasnov, V. P. (2012). Chem. Heterocycl. Compd, 48, 724–732. Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Jeyasee lan, S., Asha, K. V ., Venkateshappa, G., Raghavendrakumar , P . & Palakshamurthy, B. S. (2014). Acta Cryst. E70, o1176. Kadutskii, A. P., Kozlov, N. G., Frolova, L. L., Alekseev, I. N. & Kuchin, A. V. (2012).Chem. Nat. Compd, 48, 404–411. Katritsky, A. R., Rachwal, S. & Rachwal, B. (1996). Tetrahedron, 52, 15031– 15070. Keith, J. M., Larrow, J. F. & Jacobsen, E. N. (2001). Adv. Synth. Catal. 343, 5–27. 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, 466–470. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. data reports o20 Jeyaseelanet al. doi:10.1107/S2056989014025353 Acta Cryst. (2015). E71, o20 ISSN 2056-9890
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Crystal structure of 1-methanesulfonyl-1,2,3,4-tetrahydroquinoline
S. Jeyaseelan, S. L. Nagendra Babu, G. Venkateshappa, P. Raghavendra Kumar and B. S.
Palakshamurthy
S1. Chemical context
Derivatives of tetrahydroquinolines display a wide range of physiological activities, they been found to be pesticides,
antioxidants, photosensitizers, and dyes (Katritsky et al., 1996). Heterocyclic compounds of 1,2,3,4-tetrahydroquinoline
derivatives play important role in synthesize efficient kinetic resolution with predominant (S,S)-(R,R)-diastereoisomers
(Chulakov et al., 2012), optically active camphor moieties (Kadutskii et al., 2012), and biologically active compounds,synthetic intermediates (Keith et al., 2001).
In due course of our study, we have synthised a series of 1,2,3,4-tetrahydroquinoline with derivatives of suloponyl
chlorides they exhibit a few pharmacological activities (our unpublished data). As a part of our study we have undertaken
crystal structure determination of the title compound and the results are compared with crystal structure of 1-
tosyl-1,2,3,4-tetrahydroquinoline(II) (Jeyaseelan et al., 2014) .
S2. Structural commentary
The molecular structure of the title compound(I) is shown in Fig. 1. In both the compounds (I) and (II), the C1/C6–C9/N1
rings are in a half-chair conformation, with the methylene C9 atom as the flap, but the bond-angle sum at the N atom in
the compound (I) and (II) are 347.9° and 350.2°, respectively.
S3. Supramolecular features
In the crystal, inversion dimers linked by pairs of C10—H10C···O2 hydrogen bonds generate R 22(8) ring motifs.
S4. Database survey
S5. Synthesis and crystallization
To a stirred solution of 1,2,3,4-tetrahydroquinoline (10 mmol) in 30 ml dry methylene dichloride, triethylamine (15
mmol) was added at 0 - 5°C. To this reaction mixture methanesulfonyl chloride (12 mmol) in 10 ml dry dichloromethane
was added drop wise. After 2h of stirring at 15 - 20°C, the reaction mixture was washed with 5% Na2CO3 and brine. The
organic phase was dried over Na2SO4 and then it was concentrated on vacuum to yield titled compound as colourless
solid. The crude product was recrystallized from a slovent mixture of ethyl acetate and hexane(1:2) to yield colourless
prisms of (I).
S6. Refinement details
Crystal data, data collection and structure refinement details are summarized in Table 1. The H atoms were positioned
with idealized geometry using a riding model with C—H = 0.93-0.99 Å. All H-atoms were refined with isotropic
displacement parameters (set to 1.2-1.5 times of the U eq of the parent atom).
Least-squares matrix: full R[ F 2 > 2σ ( F 2)] = 0.038wR( F 2) = 0.106S = 1.07
1973 reflections128 parameters0 restraints0 constraintsPrimary atom site location: difference Fourier
map
Secondary atom site location: difference Fouriermap
Hydrogen site location: inferred fromneighbouring sites
H-atom parameters constrained
w = 1/[σ 2( F o2) + (0.0543 P )2 + 0.1542 P ]where P = ( F o2 + 2 F c2)/3
(∆/σ )max = 0.001∆ ρmax = 0.24 e Å−3
∆ ρmin = −0.31 e Å−3
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the fullcovariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles andtorsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry.An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2 )