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

Jeyaseelan, S.; Asha, K.V.; Venkateshappa, G.; Raghavendrakumar, P.; Palakshamurthy, B.S.

doi:10.1107/S1600536814022181

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 11| November 2014| Page o1176

doi:10.1107/S1600536814022181

Open

access

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

S. Jeyaseelan,^a K.V. Asha,^b G. Venkateshappa,^c P. Raghavendrakumar ^c and B.S. Palakshamurthy ^b ^*

^aDepartment of Physics, St Philomena's College (Autonomous), Mysore, karnataka 570 015, India, ^bDepartment of Studies and Research in Physics, UCS, Tumkur University, Karnataka 572 103, India, and ^cDepartment of Chemistry, UCST, Tumkur University, Karnataka 572 103, India
^*Correspondence e-mail: palaksha.bspm@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 30 September 2014; accepted 8 October 2014; online 24 October 2014)

In the title compound, C₁₆H₁₇NO₂S, the heterocyclic ring adopts a half-chair conformation and the bond-angle sum at the N atom is 350.2°. The dihedral angle between the planes of the aromatic rings is 47.74 (10)°. In the crystal, molecules are linked by C—H⋯O hydrogen bonds to generate [010] chains.

Keywords: crystal structure; quinolines; C—H⋯O interactions; biotransformations; pharmacological activity.

CCDC reference: 1028050

1. Related literature

For reactions related to biotransformations, see: Leresche et al. (2006 ); Astudillo et al. (2009 ). For pharmacological activities, see: Bendale et al. (2007 ); Chen et al. (2007 ); Singer et al. (2005 ).

2. Experimental

2.1. Crystal data

C₁₆H₁₇NO₂S
M_r = 287.37
Monoclinic, P 2₁ /n
a = 8.2176 (7) Å
b = 8.0468 (6) Å
c = 22.2439 (18) Å
β = 98.107 (4)°
V = 1456.2 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 94 K
0.24 × 0.22 × 0.18 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013 ) T_min = 0.949, T_max = 0.961
20017 measured reflections
2568 independent reflections
2327 reflections with I > 2σ(I)
R_int = 0.046

2.3. Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.101
S = 1.09
2568 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯O2ⁱ	0.95	2.53	3.340 (2)	143
Symmetry code: (i) x, y-1, z.

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: ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 1028050

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814022181/hb7292sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814022181/hb7292Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814022181/hb7292Isup3.cml

checkCIF report

Chemical context top

Chemical reactions by biotransformations have a number of advantages because they play an important role in the production of chiral products from racemic mixtures (Leresche et al., 2006) in perticlar the tetrahydroquinoline derivatives can be transformed to other by Mortierella isabelina (Astudillo et al., 2009). The tetrahydroquinoline compounds are core structures in pharmacological activities such as antimalarial activities (Bendale et al., 2007), antipsychotic (Singer et al., 2005), estrogenic receptors (Chen et al., 2007). In the course of our study, we noticed that 1,2,3,4-tetrahydroquinoline derivatives 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 presented here.

Structural commentary top

The molecular structure of the title compound is shown in Fig. 1. In the title molecule, the planes of the C1–C6 and C10–C15 benzene rings form a dihedral angle of 47.74 (9)°. The C1/C6–C9/N1 ring is in a half-chair conformation, with the methylene C9 atom as the flap. The molecular structure is stabilized by intramolecular C9—H9A···O1 and C2—H2···O2 hydrogen bonds (Fig. 2).

Supramolecular features top

In the crystal structure, intermolecular C14—H14···O2 hydrogen bonds link molecules into C(6) chains along [010] (Fig. 2 and Table 1)

Synthesis and crystallization top

To a stirred solution of 1,2,3,4-tetrahydroquinoline (10 mmol) in 30 mL dry dichloroethane, triethylamine (15 mmol) was added at 0 – 5°C. To this reaction mixture 4-methylbenzene-1-sulfonylchloride (12 mmol) was added drop wise. After 2h of stirring at room temperature, the reaction mixture was washed with 5% Na₂CO₃ and brine. 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 in the mixture of ethyl acetate and hexane(1:1) to get colourless prisms.

Refinement top

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 = 0.95-0.99 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).

Related literature top

For reactions related to biotransformations, see: Leresche et al. (2006); Astudillo et al. (2009). For pharmacological activities, see: Bendale et al. (2007); Chen et al. (2007); Singer et al. (2005).

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

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

The molecular packing of the title compound, dashed lines indicate intramolecular C—H···O and intermolecular C—H···O hydrogen bonds forming C(6) chains viewed along [010].

1-Tosyl-1,2,3,4-tetrahydroquinoline top

Crystal data top

C₁₆H₁₇NO₂S	Prism
M_r = 287.37	D_x = 1.311 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 402 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 8.2176 (7) Å	Cell parameters from 2327 reflections
b = 8.0468 (6) Å	θ = 1.9–25.0°
c = 22.2439 (18) Å	µ = 0.22 mm⁻¹
β = 98.107 (4)°	T = 94 K
V = 1456.2 (2) Å³	Prism, colourless
Z = 4	0.24 × 0.22 × 0.18 mm
F(000) = 608

Data collection top

Bruker APEXII CCD diffractometer	2568 independent reflections
Radiation source: fine-focus sealed tube	2327 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
Detector resolution: 1.9 pixels mm^-1	θ_max = 25.0°, θ_min = 1.9°
phi and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −9→9
T_min = 0.949, T_max = 0.961	l = −26→26
20017 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0362P)² + 0.8395P] where P = (F_o² + 2F_c²)/3
2568 reflections	(Δ/σ)_max = 0.001
182 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³
0 constraints

Crystal data top

C₁₆H₁₇NO₂S	V = 1456.2 (2) Å³
M_r = 287.37	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.2176 (7) Å	µ = 0.22 mm⁻¹
b = 8.0468 (6) Å	T = 94 K
c = 22.2439 (18) Å	0.24 × 0.22 × 0.18 mm
β = 98.107 (4)°

Data collection top

Bruker APEXII CCD diffractometer	2568 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2013)	2327 reflections with I > 2σ(I)
T_min = 0.949, T_max = 0.961	R_int = 0.046
20017 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.09	Δρ_max = 0.23 e Å⁻³
2568 reflections	Δρ_min = −0.36 e Å⁻³
182 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion 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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² 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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.5482 (2)	0.4736 (2)	0.17137 (8)	0.0359 (4)
C2	0.5261 (3)	0.6396 (2)	0.15480 (9)	0.0461 (5)
H2	0.4386	0.7015	0.1675	0.055*
C3	0.6312 (3)	0.7140 (3)	0.12003 (10)	0.0565 (6)
H3	0.6146	0.8265	0.1078	0.068*
C4	0.7605 (3)	0.6253 (3)	0.10294 (10)	0.0593 (6)
H4	0.8319	0.6758	0.0782	0.071*
C5	0.7859 (2)	0.4634 (3)	0.12175 (9)	0.0509 (5)
H5	0.8772	0.4043	0.1106	0.061*
C6	0.6818 (2)	0.3838 (2)	0.15666 (8)	0.0400 (4)
C7	0.7232 (3)	0.2110 (3)	0.18038 (11)	0.0553 (6)
H7A	0.7451	0.1398	0.1461	0.066*
H7B	0.8255	0.2161	0.2098	0.066*
C8	0.5908 (3)	0.1313 (3)	0.21082 (11)	0.0553 (6)
H8A	0.6394	0.0426	0.2386	0.066*
H8B	0.5079	0.0799	0.1798	0.066*
C9	0.5085 (3)	0.2589 (3)	0.24637 (9)	0.0505 (5)
H9A	0.4200	0.2043	0.2651	0.061*
H9B	0.5900	0.3033	0.2795	0.061*
C10	0.2228 (2)	0.2132 (2)	0.12881 (8)	0.0368 (4)
C11	0.2794 (3)	0.2300 (3)	0.07339 (9)	0.0536 (5)
H11	0.3210	0.3333	0.0616	0.064*
C12	0.2741 (4)	0.0936 (3)	0.03583 (10)	0.0661 (7)
H12	0.3131	0.1040	−0.0022	0.079*
C13	0.2137 (3)	−0.0582 (3)	0.05179 (10)	0.0577 (6)
C14	0.1579 (3)	−0.0714 (3)	0.10703 (10)	0.0524 (5)
H14	0.1156	−0.1745	0.1187	0.063*
C15	0.1626 (2)	0.0630 (2)	0.14573 (9)	0.0427 (4)
H15	0.1244	0.0520	0.1839	0.051*
C16	0.2090 (4)	−0.2057 (4)	0.00972 (13)	0.0920 (10)
H16A	0.2151	−0.3085	0.0336	0.138*
H16B	0.3025	−0.2004	−0.0131	0.138*
H16C	0.1062	−0.2042	−0.0186	0.138*
O1	0.15775 (18)	0.33842 (19)	0.22946 (7)	0.0548 (4)
O2	0.19664 (17)	0.52807 (17)	0.14578 (7)	0.0532 (4)
N	0.43800 (18)	0.39748 (19)	0.20781 (7)	0.0381 (4)
S	0.24138 (5)	0.38103 (6)	0.17987 (2)	0.03916 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0337 (9)	0.0389 (10)	0.0349 (9)	−0.0051 (8)	0.0038 (7)	−0.0037 (8)
C2	0.0459 (11)	0.0401 (11)	0.0527 (11)	−0.0041 (9)	0.0082 (9)	−0.0020 (9)
C3	0.0605 (14)	0.0486 (12)	0.0607 (13)	−0.0124 (11)	0.0102 (11)	0.0080 (10)
C4	0.0523 (13)	0.0752 (16)	0.0527 (12)	−0.0209 (12)	0.0152 (10)	0.0045 (12)
C5	0.0367 (11)	0.0699 (15)	0.0470 (11)	−0.0057 (10)	0.0092 (9)	−0.0098 (11)
C6	0.0341 (10)	0.0479 (11)	0.0373 (9)	−0.0024 (8)	0.0025 (8)	−0.0061 (8)
C7	0.0451 (12)	0.0545 (13)	0.0660 (14)	0.0119 (10)	0.0070 (10)	−0.0018 (11)
C8	0.0496 (12)	0.0458 (12)	0.0689 (14)	0.0112 (10)	0.0029 (10)	0.0139 (10)
C9	0.0495 (12)	0.0565 (13)	0.0457 (11)	0.0021 (10)	0.0074 (9)	0.0137 (10)
C10	0.0365 (10)	0.0350 (10)	0.0381 (9)	0.0010 (8)	0.0028 (7)	0.0014 (8)
C11	0.0704 (15)	0.0471 (12)	0.0444 (11)	−0.0039 (11)	0.0118 (10)	0.0067 (9)
C12	0.0952 (19)	0.0675 (16)	0.0370 (11)	0.0029 (14)	0.0138 (12)	−0.0015 (11)
C13	0.0697 (15)	0.0497 (13)	0.0498 (12)	0.0089 (11)	−0.0056 (11)	−0.0092 (10)
C14	0.0595 (13)	0.0374 (11)	0.0578 (13)	−0.0024 (10)	−0.0002 (10)	0.0005 (9)
C15	0.0454 (11)	0.0390 (10)	0.0439 (10)	−0.0020 (8)	0.0066 (9)	0.0028 (8)
C16	0.127 (3)	0.0716 (19)	0.0739 (18)	0.0083 (18)	0.0008 (18)	−0.0298 (15)
O1	0.0478 (8)	0.0610 (9)	0.0612 (9)	−0.0083 (7)	0.0268 (7)	−0.0128 (7)
O2	0.0399 (8)	0.0352 (7)	0.0831 (11)	0.0066 (6)	0.0040 (7)	0.0050 (7)
N	0.0361 (8)	0.0379 (8)	0.0410 (8)	−0.0006 (7)	0.0084 (7)	0.0007 (7)
S	0.0332 (3)	0.0345 (3)	0.0516 (3)	0.00026 (18)	0.0119 (2)	−0.0035 (2)

Geometric parameters (Å, º) top

C1—C2	1.390 (3)	C10—C15	1.378 (3)
C1—C6	1.392 (3)	C10—C11	1.384 (3)
C1—N	1.435 (2)	C10—S	1.7577 (19)
C2—C3	1.375 (3)	C11—C12	1.377 (3)
C2—H2	0.9500	C11—H11	0.9500
C3—C4	1.377 (3)	C12—C13	1.384 (3)
C3—H3	0.9500	C12—H12	0.9500
C4—C5	1.375 (3)	C13—C14	1.374 (3)
C4—H4	0.9500	C13—C16	1.508 (3)
C5—C6	1.390 (3)	C14—C15	1.379 (3)
C5—H5	0.9500	C14—H14	0.9500
C6—C7	1.509 (3)	C15—H15	0.9500
C7—C8	1.504 (3)	C16—H16A	0.9800
C7—H7A	0.9900	C16—H16B	0.9800
C7—H7B	0.9900	C16—H16C	0.9800
C8—C9	1.512 (3)	O1—S	1.4213 (14)
C8—H8A	0.9900	O2—S	1.4254 (14)
C8—H8B	0.9900	N—S	1.6526 (16)
C9—N	1.475 (2)	S—O1	1.4213 (14)
C9—H9A	0.9900	S—O2	1.4254 (14)
C9—H9B	0.9900

C2—C1—C6	120.95 (17)	H9A—C9—H9B	107.9
C2—C1—N	119.39 (17)	C15—C10—C11	120.52 (18)
C6—C1—N	119.52 (17)	C15—C10—S	119.94 (14)
C3—C2—C1	119.9 (2)	C11—C10—S	119.40 (15)
C3—C2—H2	120.1	C12—C11—C10	118.5 (2)
C1—C2—H2	120.1	C12—C11—H11	120.8
C2—C3—C4	120.0 (2)	C10—C11—H11	120.8
C2—C3—H3	120.0	C11—C12—C13	122.0 (2)
C4—C3—H3	120.0	C11—C12—H12	119.0
C5—C4—C3	119.8 (2)	C13—C12—H12	119.0
C5—C4—H4	120.1	C14—C13—C12	118.3 (2)
C3—C4—H4	120.1	C14—C13—C16	120.8 (2)
C4—C5—C6	121.8 (2)	C12—C13—C16	120.9 (2)
C4—C5—H5	119.1	C13—C14—C15	121.0 (2)
C6—C5—H5	119.1	C13—C14—H14	119.5
C5—C6—C1	117.40 (19)	C15—C14—H14	119.5
C5—C6—C7	119.59 (18)	C10—C15—C14	119.75 (19)
C1—C6—C7	122.88 (17)	C10—C15—H15	120.1
C8—C7—C6	114.12 (17)	C14—C15—H15	120.1
C8—C7—H7A	108.7	C13—C16—H16A	109.5
C6—C7—H7A	108.7	C13—C16—H16B	109.5
C8—C7—H7B	108.7	H16A—C16—H16B	109.5
C6—C7—H7B	108.7	C13—C16—H16C	109.5
H7A—C7—H7B	107.6	H16A—C16—H16C	109.5
C7—C8—C9	110.59 (19)	H16B—C16—H16C	109.5
C7—C8—H8A	109.5	C1—N—C9	115.09 (15)
C9—C8—H8A	109.5	C1—N—S	118.90 (12)
C7—C8—H8B	109.5	C9—N—S	116.17 (13)
C9—C8—H8B	109.5	O1—S—O2	119.76 (9)
H8A—C8—H8B	108.1	O1—S—N	106.36 (9)
N—C9—C8	112.16 (16)	O2—S—N	107.38 (8)
N—C9—H9A	109.2	O1—S—C10	107.98 (9)
C8—C9—H9A	109.2	O2—S—C10	107.57 (9)
N—C9—H9B	109.2	N—S—C10	107.19 (8)
C8—C9—H9B	109.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O2ⁱ	0.95	2.53	3.340 (2)	143

Symmetry code: (i) x, y−1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O2ⁱ	0.95	2.53	3.340 (2)	143

Symmetry code: (i) x, y−1, z.

Acknowledgements

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). BSPM thanks Rajegowda, Department of Studies and Research in Physics, UCS, Tumkur University, Karnataka 572 103, India, for his suport.

References

Astudillo, L., De la Guarda, W., Gutierrez, M. & San-Martin, A. (2009). Z. Naturforsch. Teil C, 64, 215–218. CAS Google Scholar
Bendale, P., Olepu, S., Kumar, S. P., Buldule, V., Rivas, K. & Nallan, L. (2007). J. Med. Chem. 50, 4585–4605. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, W., Lin, Z., Ning, M., Yang, C., Yan, X. & Xie, Y. (2007). Bioorg. Med. Chem. 15, 5828–5836. Web of Science CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Leresche, J. & Meyer, H. P. (2006). Org. Process Res. Dev. 10, 572–580. Web of Science CrossRef CAS Google Scholar
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. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Singer, J. M., Barr, B. M., Coughenour, L. L. & Walters, M. A. (2005). Bioorg. Med. Chem. Lett. 15, 4560–4563. Web of Science CrossRef PubMed CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 11| November 2014| Page o1176

doi:10.1107/S1600536814022181

Open

access