Crystal structure of 1-[(6-chloro-pyridin-3-yl)sulfon-yl]-1,2,3,4-tetra-hydro-quinoline.

The tetra-hydro-pyridine ring of the quinoline system in the title compound, C14H13ClN2O2S, adopts a half-chair conformation with the bond-angle sum at the N atom being 350.0°. The dihedral angle between the least-squares planes of the two aromatic rings is 50.13 (11)°. In the crystal, inversion dimers linked by pairs of C-H⋯O hydrogen bonds generate R 2 (2)(10) loops. Additional inter-molecular C-H⋯O hydrogen bonds generate C(7) chains along [100].

Chemical context

1,2,3,4-Tetra­hydro­quinoline derivatives play a vital role in developing pharmacological agents and they have been considered as potential drugs (White et al., 1994 ▸; Kokwaro & Taylor, 1990 ▸; Omura & Nakagawa, 1981 ▸) and also antagonists for N-methyl-d-aspartate (NMDA) receptors at the glycine recognition site (Cai et al., 1996 ▸).

Recently, we have synthesized a series of 1,2,3,4-tetra­hydro­quinoline derivatives and a few mol­ecules in fact exhibit pharmacological activity (unpublished results). In a contin­uation of our work on the derivatives of 1,2,3,4-tetra­hydro­quinolines (Jeyaseelan et al., 2014 ▸, 2015a ▸,b ▸), we report herein the synthesis and crystal structure of 1-[(6-chloro­pyridin-3-yl)sulfon­yl]-1,2,3,4-tetra­hydro­quinoline, (I).

Structural commentary

The mol­ecular structure of compound (I) is shown in Fig. 1 ▸. The dihedral angle between the planes of the aromatic rings is 50.13 (11)°. In comparison, the dihedral angle in the 1-tosyl-1,2,3,4-tetra­hydro­quinoline, (II), is 47.74 (9)° (Jeyaseelan et al., 2014 ▸), and in 1-benzyl­sulfonyl-1,2,3,4-tetra­hydro­quinoline, (III), it is 74.15 (10)° (Jeyaseelan et al., 2015b ▸). In the structures of compounds (II), (III) and 1-methane­sulfonyl-1,2,3,4-tetra­hydro­quinoline, (IV) (Jeyaseelan et al., 2015a ▸), the tetra­hydro­pyridine (C1/C6–C9/N1) ring is in a half-chair conformation, with the methyl­ene C9 atom as the flap. However, the bond-angle sums at the N atom in (I), (II), (III) and (IV) differ somehow, with values of 350.0, 350.2, 354.61 and 347.9°, respectively.

Figure 1

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

Supra­molecular features

In the crystal, inversion dimers linked by pairs of C11—H11⋯O2 hydrogen bonds generate (10) loops. In addition, mol­ecules are linked by C7—H7A⋯O1 hydrogen bonds, generating C(7) chains along [100], as shown in Fig. 2 ▸. Numerical values of these inter­actions are compiled in Table 1 ▸.

Figure 2

The mol­ecular packing of the title compound. Dashed lines indicate the pairs of C—H⋯O hydrogen bonds which link the mol­ecules into inversion dimers with (10) ring motifs and forming C(7) chains along [100].

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C11H11O2i	0.93	2.60	3.309(3)	134
C7H7AO1ii	0.97	2.66	3.586(5)	160

Symmetry codes: (i) ; (ii) .

Synthesis and crystallization

To an ice-cold solution of 1,2,3,4-tetra­hydro­quinoline (1.332 g, 10 mmol) and tri­ethyl­amine (1.518 g, 15 mmol) in di­chloro­methane (50 ml), a solution of 6-chloro­pyridine-3-sulfonyl chloride (2.332 g, 11 mmol) in di­chloro­methane (20 ml) was added dropwise and stirred for 30 min. The reaction mixture was diluted with di­chloro­methane (150 ml), the organic layer washed with aqueous 5% NaHCO3 solution and brine, and dried over anhydrous Na2SO4. The solvent was evaporated under reduced pressure to give 1-[(6-chloro­pyridin-3-yl)sulfon­yl]-1,2,3,4-tetra­hydro­quinoline, (I). The product was recrystallized from a mixture of di­chloro­methane and n-hexane (1:1 v/v) to obtain crystals suitable for X-ray diffraction studies.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. H atoms were positioned with idealized geometry using a riding-model approximation, with C—H = 0.93 Å and U iso(H) = 1.2U eq(C) for aromatic H atoms and with C—H = 0.97 Å and U iso(H) = 1.2U eq(C) for methyl­ene H atoms.

Table 2

Experimental details

Crystal data
Chemical formula	C14H13ClN2O2S
M r	308.77
Crystal system, space group	Triclinic, P
Temperature (K)	296
a, b, c ()	6.5661(10), 10.2595(18), 11.3490(19)
, , ()	69.101(7), 88.219(7), 77.238(7)
V (3)	695.6(2)
Z	2
Radiation type	Mo K
(mm1)	0.43
Crystal size (mm)	0.23 0.18 0.16
Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2013 ▸)
T min, T max	0.912, 0.934
No. of measured, independent and observed [I > 2(I)] reflections	9865, 2454, 1980
R int	0.053
(sin /)max (1)	0.595
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.050, 0.146, 1.09
No. of reflections	2454
No. of parameters	181
H-atom treatment	H-atom parameters constrained
max, min (e 3)	0.59, 0.43

Computer programs: APEX2 and SAINT (Bruker, 2013 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸) and Mercury (Macrae et al., 2008 ▸).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015008099/wm5147sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015008099/wm5147Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015008099/wm5147Isup3.cml

CCDC reference: 1061311

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

C14H13ClN2O2S	F(000) = 320
Mr = 308.77	prism
Triclinic, P1	Dx = 1.474 Mg m−3
Hall symbol: -P 1	Melting point: 413 K
a = 6.5661 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.2595 (18) Å	Cell parameters from 1980 reflections
c = 11.3490 (19) Å	θ = 1.9–25.0°
α = 69.101 (7)°	µ = 0.43 mm−1
β = 88.219 (7)°	T = 296 K
γ = 77.238 (7)°	Prism, colourless
V = 695.6 (2) Å3	0.23 × 0.18 × 0.16 mm
Z = 2

Bruker APEXII CCD diffractometer	2454 independent reflections
Radiation source: fine-focus sealed tube	1980 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
Detector resolution: 2.01 pixels mm-1	θmax = 25.0°, θmin = 1.9°
phi and ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −12→12
Tmin = 0.912, Tmax = 0.934	l = −13→13
9865 measured reflections

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.146	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0677P)2 + 0.3614P] where P = (Fo2 + 2Fc2)/3
2454 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 0.59 e Å−3
0 restraints	Δρmin = −0.43 e Å−3
0 constraints

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.

	x	y	z	Uiso*/Ueq
O1	0.3014 (3)	0.1696 (3)	0.3092 (2)	0.0753 (7)
S	0.40371 (11)	0.28345 (8)	0.24768 (6)	0.0562 (3)
Cl1	1.24374 (14)	0.01308 (10)	0.08760 (9)	0.0853 (3)
C10	0.6392 (4)	0.2111 (3)	0.1933 (2)	0.0479 (6)
N1	0.4673 (3)	0.3394 (2)	0.35739 (19)	0.0532 (6)
O2	0.3005 (3)	0.4047 (2)	0.14401 (19)	0.0712 (6)
C11	0.7513 (4)	0.2997 (3)	0.1091 (2)	0.0504 (6)
H11	0.6991	0.3983	0.0764	0.060*
N2	0.9018 (4)	0.0058 (3)	0.2047 (2)	0.0657 (7)
C1	0.5901 (4)	0.4468 (3)	0.3217 (2)	0.0479 (6)
C13	1.0055 (4)	0.0935 (3)	0.1264 (2)	0.0545 (7)
C6	0.7874 (4)	0.4136 (3)	0.3794 (3)	0.0542 (7)
C12	0.9387 (4)	0.2403 (3)	0.0750 (3)	0.0545 (7)
H12	1.0188	0.2965	0.0190	0.065*
C14	0.7193 (5)	0.0656 (3)	0.2371 (3)	0.0615 (8)
H14	0.6417	0.0064	0.2921	0.074*
C2	0.5110 (5)	0.5812 (3)	0.2320 (3)	0.0678 (8)
H2	0.3760	0.6042	0.1966	0.081*
C5	0.9038 (5)	0.5175 (4)	0.3419 (3)	0.0690 (8)
H5	1.0362	0.4975	0.3798	0.083*
C9	0.5138 (5)	0.2322 (4)	0.4875 (3)	0.0733 (10)
H9A	0.4544	0.2766	0.5470	0.088*
H9B	0.4466	0.1542	0.4963	0.088*
C3	0.6339 (7)	0.6804 (3)	0.1957 (3)	0.0812 (10)
H3	0.5830	0.7694	0.1335	0.097*
C4	0.8292 (6)	0.6494 (4)	0.2502 (3)	0.0766 (10)
H4	0.9112	0.7169	0.2255	0.092*
C7	0.8693 (6)	0.2732 (4)	0.4825 (4)	0.0796 (10)
H7A	0.9980	0.2263	0.4563	0.096*
H7B	0.9042	0.2917	0.5566	0.096*
C8	0.7326 (7)	0.1753 (5)	0.5187 (4)	0.124 (2)
H8A	0.7792	0.1037	0.4804	0.149*
H8B	0.7507	0.1261	0.6095	0.149*

	U11	U22	U33	U12	U13	U23
O1	0.0680 (14)	0.0963 (16)	0.0687 (13)	−0.0494 (13)	0.0085 (11)	−0.0202 (12)
S	0.0469 (4)	0.0698 (5)	0.0465 (4)	−0.0217 (3)	−0.0027 (3)	−0.0090 (3)
Cl1	0.0736 (6)	0.0948 (7)	0.0859 (6)	0.0056 (5)	−0.0027 (5)	−0.0446 (5)
C10	0.0520 (15)	0.0511 (15)	0.0373 (12)	−0.0186 (12)	−0.0063 (11)	−0.0069 (11)
N1	0.0489 (12)	0.0633 (14)	0.0406 (11)	−0.0183 (11)	0.0032 (9)	−0.0072 (10)
O2	0.0547 (12)	0.0850 (15)	0.0553 (11)	−0.0067 (11)	−0.0148 (9)	−0.0068 (11)
C11	0.0571 (16)	0.0441 (14)	0.0429 (13)	−0.0133 (12)	−0.0019 (12)	−0.0056 (11)
N2	0.0813 (19)	0.0509 (14)	0.0591 (15)	−0.0116 (13)	−0.0060 (13)	−0.0140 (12)
C1	0.0511 (15)	0.0463 (14)	0.0435 (13)	−0.0087 (12)	0.0095 (11)	−0.0146 (11)
C13	0.0566 (16)	0.0595 (17)	0.0472 (14)	−0.0088 (13)	−0.0096 (12)	−0.0203 (13)
C6	0.0566 (16)	0.0517 (16)	0.0551 (15)	−0.0155 (13)	0.0029 (13)	−0.0184 (13)
C12	0.0561 (16)	0.0596 (17)	0.0482 (14)	−0.0218 (14)	0.0053 (12)	−0.0149 (13)
C14	0.078 (2)	0.0509 (17)	0.0508 (15)	−0.0255 (16)	0.0011 (14)	−0.0056 (13)
C2	0.0673 (19)	0.0558 (18)	0.0628 (18)	−0.0001 (15)	0.0048 (15)	−0.0088 (14)
C5	0.070 (2)	0.070 (2)	0.077 (2)	−0.0312 (17)	0.0105 (16)	−0.0290 (17)
C9	0.079 (2)	0.093 (2)	0.0399 (15)	−0.0443 (19)	0.0005 (14)	−0.0004 (15)
C3	0.105 (3)	0.0411 (16)	0.081 (2)	−0.0057 (18)	0.025 (2)	−0.0101 (15)
C4	0.098 (3)	0.060 (2)	0.084 (2)	−0.0356 (19)	0.033 (2)	−0.0315 (18)
C7	0.066 (2)	0.068 (2)	0.086 (2)	−0.0170 (17)	−0.0195 (17)	−0.0029 (17)
C8	0.110 (3)	0.118 (3)	0.089 (3)	−0.050 (3)	−0.042 (3)	0.047 (3)

O1—S	1.428 (2)	C6—C5	1.385 (4)
S—O2	1.423 (2)	C6—C7	1.492 (4)
S—O1	1.428 (2)	C12—H12	0.9300
S—N1	1.644 (2)	C14—H14	0.9300
S—C10	1.756 (3)	C2—C3	1.378 (5)
Cl1—C13	1.723 (3)	C2—H2	0.9300
C10—C14	1.376 (4)	C5—C4	1.374 (5)
C10—C11	1.383 (3)	C5—H5	0.9300
N1—C1	1.443 (3)	C9—C8	1.430 (5)
N1—C9	1.484 (3)	C9—H9A	0.9700
C11—C12	1.358 (4)	C9—H9B	0.9700
C11—H11	0.9300	C3—C4	1.362 (5)
N2—C13	1.314 (4)	C3—H3	0.9300
N2—C14	1.325 (4)	C4—H4	0.9300
C1—C2	1.386 (4)	C7—C8	1.437 (5)
C1—C6	1.387 (4)	C7—H7A	0.9700
C13—C12	1.378 (4)	C8—H8A	0.9700
O2—S—O1	120.12 (13)	C3—C2—C1	119.5 (3)
O2—S—N1	108.30 (13)	C3—C2—H2	120.2
O1—S—N1	106.51 (12)	C1—C2—H2	120.2
O2—S—C10	106.62 (12)	C4—C5—C6	121.9 (3)
O1—S—C10	107.97 (14)	C4—C5—H5	119.1
N1—S—C10	106.63 (12)	C6—C5—H5	119.1
C14—C10—C11	118.8 (3)	C8—C9—N1	113.3 (3)
C14—C10—S	120.6 (2)	C8—C9—H9A	108.9
C11—C10—S	120.6 (2)	N1—C9—H9A	108.9
C1—N1—C9	115.2 (2)	C8—C9—H9B	108.9
C1—N1—S	117.64 (16)	N1—C9—H9B	108.9
C9—N1—S	117.2 (2)	H9A—C9—H9B	107.7
C12—C11—C10	118.9 (3)	C4—C3—C2	120.7 (3)
C12—C11—H11	120.6	C4—C3—H3	119.6
C10—C11—H11	120.6	C2—C3—H3	119.6
C13—N2—C14	116.3 (2)	C3—C4—C5	119.4 (3)
C2—C1—C6	120.7 (3)	C3—C4—H4	120.3
C2—C1—N1	120.4 (3)	C5—C4—H4	120.3
C6—C1—N1	118.8 (2)	C8—C7—C6	116.5 (3)
N2—C13—C12	125.4 (3)	C8—C7—H7A	108.2
N2—C13—Cl1	115.3 (2)	C6—C7—H7A	108.2
C12—C13—Cl1	119.2 (2)	C8—C7—H7B	108.2
C5—C6—C1	117.8 (3)	C6—C7—H7B	108.2
C5—C6—C7	120.7 (3)	H7A—C7—H7B	107.3
C1—C6—C7	121.5 (2)	C9—C8—C7	118.0 (4)
C11—C12—C13	117.4 (3)	C9—C8—H8A	107.8
C11—C12—H12	121.3	C7—C8—H8A	107.8
C13—C12—H12	121.3	C9—C8—H8B	107.8
N2—C14—C10	123.1 (3)	C7—C8—H8B	107.8
N2—C14—H14	118.4	H8A—C8—H8B	107.1
C10—C14—H14	118.4
O2—S—C10—C14	−145.4 (2)	C9—N1—C1—C6	27.0 (4)
O2—S—C10—C14	−145.4 (2)	S—N1—C1—C6	−117.9 (2)
O1—S—C10—C14	−15.0 (3)	C14—N2—C13—C12	−1.0 (4)
O1—S—C10—C14	−15.0 (3)	C14—N2—C13—Cl1	179.2 (2)
O1—S—C10—C14	−15.0 (3)	C2—C1—C6—C5	−1.8 (4)
N1—S—C10—C14	99.1 (2)	N1—C1—C6—C5	178.8 (2)
O2—S—C10—C11	37.0 (2)	C2—C1—C6—C7	175.7 (3)
O2—S—C10—C11	37.0 (2)	N1—C1—C6—C7	−3.7 (4)
O1—S—C10—C11	167.3 (2)	C10—C11—C12—C13	0.4 (4)
O1—S—C10—C11	167.3 (2)	N2—C13—C12—C11	0.9 (4)
O1—S—C10—C11	167.3 (2)	Cl1—C13—C12—C11	−179.2 (2)
N1—S—C10—C11	−78.6 (2)	C13—N2—C14—C10	−0.3 (4)
O2—S—N1—C1	−54.9 (2)	C11—C10—C14—N2	1.5 (4)
O2—S—N1—C1	−54.9 (2)	S—C10—C14—N2	−176.1 (2)
O1—S—N1—C1	174.7 (2)	C6—C1—C2—C3	3.1 (4)
O1—S—N1—C1	174.7 (2)	N1—C1—C2—C3	−177.6 (3)
O1—S—N1—C1	174.7 (2)	C1—C6—C5—C4	−0.3 (5)
C10—S—N1—C1	59.5 (2)	C7—C6—C5—C4	−177.8 (3)
O2—S—N1—C9	161.0 (2)	C1—N1—C9—C8	−46.6 (5)
O2—S—N1—C9	161.0 (2)	S—N1—C9—C8	98.4 (4)
O1—S—N1—C9	30.5 (2)	C1—C2—C3—C4	−2.3 (5)
O1—S—N1—C9	30.5 (2)	C2—C3—C4—C5	0.2 (5)
O1—S—N1—C9	30.5 (2)	C6—C5—C4—C3	1.1 (5)
C10—S—N1—C9	−84.6 (2)	C5—C6—C7—C8	177.1 (4)
C14—C10—C11—C12	−1.6 (4)	C1—C6—C7—C8	−0.3 (6)
S—C10—C11—C12	176.12 (19)	N1—C9—C8—C7	43.5 (6)
C9—N1—C1—C2	−152.4 (3)	C6—C7—C8—C9	−20.5 (7)
S—N1—C1—C2	62.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O2i	0.93	2.60	3.309 (3)	134
C7—H7A···O1ii	0.97	2.66	3.586 (5)	160