Crystal structure of 1-methane­sulfonyl-1,2,3,4-tetra­hydro­quinoline

S Jeyaseelan; S L Nagendra Babu; G Venkateshappa; P Raghavendra Kumar; B S Palakshamurthy

doi:10.1107/S2056989014025353

. 2015 Jan 1;71(Pt 1):o20. doi: 10.1107/S2056989014025353

Crystal structure of 1-methanesulfonyl-1,2,3,4-tetrahydroquinoline

S Jeyaseelan ^a, S L Nagendra Babu ^b, G Venkateshappa ^c, P Raghavendra Kumar ^c, B S Palakshamurthy ^b,^*

PMCID: PMC4331909 PMID: 25705484

Abstract

In the title compound, C₁₀H₁₃NO₂S, the heterocyclic 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—H⋯O hydrogen bonds generate R ₂ ²(8) loops.

Keywords: crystal structure; 1,2,3,4-tetrahydroquinoline; physiological activities; photosensitizers

Related literature

For background to tetrahydroquinolines, see: Chulakov et al. (2012 ▸); Kadutskii et al. (2012 ▸); Katritsky et al. (1996 ▸); Keith et al. (2001 ▸). For a related structure, see: Jeyaseelan et al. (2014 ▸). graphic file with name e-71-00o20-scheme1.jpg

Experimental

Crystal data

C₁₀H₁₃NO₂S
M _r = 211.27
Triclinic,
a = 5.5865 (2) Å
b = 9.2195 (4) Å
c = 10.1924 (4) Å
α = 85.798 (2)°
β = 84.686 (2)°
γ = 77.166 (2)°
V = 508.89 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 294 K
0.24 × 0.20 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013 ▸) T _min = 0.933, T _max = 0.955
7417 measured reflections
1973 independent reflections
1844 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.106
S = 1.07
1973 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.31 e Å⁻³

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: SHELXL2014 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: SHELXL2014.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989014025353/hb7314sup1.cif

e-71-00o20-sup1.cif^{(252.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014025353/hb7314Isup2.hkl

e-71-00o20-Isup2.hkl^{(108.6KB, hkl)}

Click here for additional data file.^{(4.1KB, cml)}

Supporting information file. DOI: 10.1107/S2056989014025353/hb7314Isup3.cml

Click here for additional data file.^{(1.7MB, tif)}

. DOI: 10.1107/S2056989014025353/hb7314fig1.tif

The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.

Click here for additional data file.^{(1.3MB, tif)}

. DOI: 10.1107/S2056989014025353/hb7314fig2.tif

The molecular packing of the title compound, dashed lines indicates the inversion dimers linked by pairs of C—H⋯O hydrogen bonds with Inline graphic (8) ring motifs.

CCDC reference: 1034951

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C10H10CO2ⁱ	0.96	2.50	3.431(2)	164

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Symmetry code: (i) Inline graphic .

Acknowledgments

SJ thanks Vision Group on Science and Technology, Government of Karnataka, for awarding a major project under CISE scheme (reference No. VGST/CISE/GRD-192/2013–14). BSP thanks Rajegowda, Department of Studies and Research in Physics, UCS, Tumkur University, Karnataka 572 103, India, for his support.

supplementary crystallographic information

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 R₂²(8) ring motifs.

S4. 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).

S5. 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).