Crystal structure of 1-[(6-chloro­pyridin-3-yl)sulfon­yl]-1,2,3,4-tetra­hydro­quinoline

In the crystal structure of 1-[(6-chloro­pyridin-3-yl)sulfon­yl]-1,2,3,4-tetra­hydro­quinoline, the tetra­hydro­pyridine ring of the quinoline system adopts a half-chair conformation and the bond-angle sum at the N atom is 350.0°.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.050
• wR factor = 0.146
• Data-to-parameter ratio = 13.6

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Alert level C
PLAT241_ALERT_2_C High      Ueq as Compared to Neighbors for .....         C8 Check
PLAT242_ALERT_2_C Low       Ueq as Compared to Neighbors for .....         C9 Check
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0048 Ang.
PLAT360_ALERT_2_C Short  C(sp3)-C(sp3) Bond  C8     -   C9     ...       1.43 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H7A    ..  O1      ..       2.66 Ang.

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S1. 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a series of 1,2,3,4-tetra­hydro­quinoline derivatives and a few molecules in fact exhibit pharmacological activity (unpublished results).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).

S2. 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 related 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.

S3. Supra­molecular features

In the crystal, inversion dimers linked by pairs of C11—H11···O2 hydrogen bonds generate R₂²(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.

S4. 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.

S5. 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.

Related literature

For pharmacological background of tetrahydroquinolines, see: White et al., (1994); Kokwaro et al., (1990); Omura et al., (1981); Cai et al., (1996). For a related structures, see: Jeyaseelan et al., (2014); Jeyaseelan and Palakshamurthy et al., (2015); Jeyaseelan et al., (2015).

Computing details

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: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Figures

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.
	Fig. 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 R2^2(10) ring motifs and forming C(7) chains along [100].

1-[(6-Chloropyridin-3-yl)sulfonyl]-1,2,3,4-tetrahydroquinoline

Crystal data

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) Å^3	0.23 × 0.18 × 0.16 mm
Z = 2

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.146	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0677P)^2 + 0.3614P] where P = (Fo^2 + 2Fc^2)/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

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 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O2^i	0.93	2.60	3.309 (3)	134
C7—H7A···O1^ii	0.97	2.66	3.586 (5)	160

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x+1, y, z.