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

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 R₂²(8) loops.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• R factor = 0.038
• wR factor = 0.106
• Data-to-parameter ratio = 15.4

checkCIF/PLATON results

No syntax errors found


No errors found in this datablock

---

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with derivatives of suloponyl chlorides they exhibit a few pharmacological activities (our unpublished data).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).

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).

Structure description

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) .

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.

In the crystal, inversion dimers linked by pairs of C10—H10C···O2 hydrogen bonds generate R₂²(8) ring motifs.

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).

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).

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).

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

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 indicates the inversion dimers linked by pairs of C—H···O hydrogen bonds with R2^2(8) ring motifs.

1-Methanesulfonyl-1,2,3,4-tetrahydroquinoline

Crystal data

C10H13NO2S	F(000) = 224
Mr = 211.27	Prism
Triclinic, P1	Dx = 1.379 Mg m^−3
Hall symbol: -P 1	Melting point: 414 K
a = 5.5865 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.2195 (4) Å	Cell parameters from 1844 reflections
c = 10.1924 (4) Å	θ = 2.0–26.0°
α = 85.798 (2)°	µ = 0.29 mm^−1
β = 84.686 (2)°	T = 294 K
γ = 77.166 (2)°	Prism, colourless
V = 508.89 (4) Å^3	0.24 × 0.20 × 0.16 mm
Z = 2

Data collection

Bruker APEXII CCD diffractometer	1973 independent reflections
Radiation source: fine-focus sealed tube	1844 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
Detector resolution: 1.09 pixels mm^-1	θmax = 26.0°, θmin = 2.0°
phi and ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −11→11
Tmin = 0.933, Tmax = 0.955	l = −12→12
7417 measured reflections

Refinement

Refinement on F^2	Primary atom site location: difference Fourier map
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0543P)^2 + 0.1542P] where P = (Fo^2 + 2Fc^2)/3
1973 reflections	(Δ/σ)max = 0.001
128 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.31 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	−0.0188 (3)	0.52244 (15)	0.71208 (15)	0.0682 (4)
C1	0.3459 (3)	0.12140 (16)	0.73875 (15)	0.0323 (3)
C2	0.2249 (4)	0.0388 (2)	0.83231 (18)	0.0478 (4)
H2	0.0635	0.0778	0.8639	0.057*
C3	0.3448 (4)	−0.1007 (2)	0.8780 (2)	0.0620 (6)
H3	0.2647	−0.1549	0.9413	0.074*
C4	0.5827 (4)	−0.1601 (2)	0.8300 (2)	0.0593 (5)
H4	0.6643	−0.2534	0.8619	0.071*
C5	0.6980 (3)	−0.0810 (2)	0.73512 (18)	0.0480 (4)
H5	0.8574	−0.1227	0.7022	0.058*
C6	0.5840 (3)	0.06025 (17)	0.68628 (15)	0.0359 (4)
C7	0.7133 (3)	0.1364 (2)	0.57329 (19)	0.0489 (4)
H7A	0.8788	0.1355	0.5955	0.059*
H7B	0.7273	0.0797	0.4954	0.059*
C8	0.5850 (4)	0.2949 (2)	0.54063 (19)	0.0537 (5)
H8A	0.6378	0.3244	0.4512	0.064*
H8B	0.6293	0.3604	0.6001	0.064*
C9	0.3091 (4)	0.3101 (2)	0.55315 (16)	0.0461 (4)
H9A	0.2296	0.4127	0.5318	0.055*
H9B	0.2648	0.2483	0.4903	0.055*
N1	0.2186 (2)	0.26547 (14)	0.68785 (12)	0.0343 (3)
C10	0.3540 (4)	0.4495 (2)	0.8543 (2)	0.0548 (5)
H10A	0.4427	0.4978	0.7856	0.082*
H10B	0.4619	0.3619	0.8890	0.082*
H10C	0.2931	0.5165	0.9235	0.082*
O2	−0.0312 (3)	0.33906 (15)	0.89749 (14)	0.0592 (4)
S1	0.10556 (7)	0.39877 (4)	0.78957 (4)	0.03662 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0777 (10)	0.0463 (8)	0.0683 (9)	0.0213 (7)	−0.0239 (8)	−0.0061 (7)
C1	0.0337 (7)	0.0307 (7)	0.0331 (7)	−0.0068 (6)	−0.0033 (6)	−0.0056 (6)
C2	0.0479 (10)	0.0421 (9)	0.0499 (10)	−0.0084 (8)	0.0107 (8)	−0.0023 (7)
C3	0.0783 (15)	0.0417 (10)	0.0591 (12)	−0.0096 (10)	0.0141 (10)	0.0071 (9)
C4	0.0768 (14)	0.0358 (9)	0.0578 (11)	0.0021 (9)	−0.0054 (10)	0.0022 (8)
C5	0.0419 (9)	0.0425 (9)	0.0553 (10)	0.0027 (7)	−0.0041 (8)	−0.0117 (8)
C6	0.0336 (8)	0.0364 (8)	0.0390 (8)	−0.0080 (6)	−0.0024 (6)	−0.0093 (6)
C7	0.0381 (9)	0.0537 (10)	0.0543 (10)	−0.0125 (8)	0.0100 (8)	−0.0084 (8)
C8	0.0626 (12)	0.0528 (11)	0.0455 (10)	−0.0200 (9)	0.0140 (9)	−0.0013 (8)
C9	0.0606 (11)	0.0445 (9)	0.0308 (8)	−0.0067 (8)	−0.0049 (7)	0.0003 (7)
N1	0.0350 (7)	0.0333 (7)	0.0336 (7)	−0.0043 (5)	−0.0030 (5)	−0.0042 (5)
C10	0.0488 (10)	0.0674 (12)	0.0529 (11)	−0.0158 (9)	−0.0023 (8)	−0.0261 (9)
O2	0.0526 (8)	0.0569 (8)	0.0645 (9)	−0.0122 (6)	0.0261 (7)	−0.0179 (7)
S1	0.0304 (2)	0.0346 (3)	0.0418 (3)	0.00108 (16)	−0.00305 (16)	−0.00688 (17)

Geometric parameters (Å, º)

O1—S1	1.4227 (13)	C7—H7B	0.9700
C1—C2	1.396 (2)	C8—C9	1.511 (3)
C1—C6	1.398 (2)	C8—H8A	0.9700
C1—N1	1.4446 (18)	C8—H8B	0.9700
C2—C3	1.381 (3)	C9—N1	1.480 (2)
C2—H2	0.9300	C9—H9A	0.9700
C3—C4	1.379 (3)	C9—H9B	0.9700
C3—H3	0.9300	N1—S1	1.6446 (13)
C4—C5	1.369 (3)	C10—S1	1.7555 (18)
C4—H4	0.9300	C10—H10A	0.9600
C5—C6	1.394 (2)	C10—H10B	0.9600
C5—H5	0.9300	C10—H10C	0.9600
C6—C7	1.515 (2)	O2—S1	1.4279 (13)
C7—C8	1.505 (3)	S1—O1	1.4227 (13)
C7—H7A	0.9700
C2—C1—C6	120.12 (15)	C9—C8—H8A	109.6
C2—C1—N1	120.16 (14)	C7—C8—H8B	109.6
C6—C1—N1	119.53 (13)	C9—C8—H8B	109.6
C3—C2—C1	120.02 (17)	H8A—C8—H8B	108.1
C3—C2—H2	120.0	N1—C9—C8	111.80 (14)
C1—C2—H2	120.0	N1—C9—H9A	109.3
C4—C3—C2	120.28 (18)	C8—C9—H9A	109.3
C4—C3—H3	119.9	N1—C9—H9B	109.3
C2—C3—H3	119.9	C8—C9—H9B	109.3
C5—C4—C3	119.56 (18)	H9A—C9—H9B	107.9
C5—C4—H4	120.2	C1—N1—C9	114.89 (12)
C3—C4—H4	120.2	C1—N1—S1	119.76 (10)
C4—C5—C6	122.06 (16)	C9—N1—S1	117.41 (10)
C4—C5—H5	119.0	S1—C10—H10A	109.5
C6—C5—H5	119.0	S1—C10—H10B	109.5
C5—C6—C1	117.87 (15)	H10A—C10—H10B	109.5
C5—C6—C7	119.39 (15)	S1—C10—H10C	109.5
C1—C6—C7	122.61 (15)	H10A—C10—H10C	109.5
C8—C7—C6	114.00 (14)	H10B—C10—H10C	109.5
C8—C7—H7A	108.8	O1—S1—O2	118.38 (10)
C6—C7—H7A	108.8	O1—S1—N1	106.54 (8)
C8—C7—H7B	108.8	O2—S1—N1	108.22 (7)
C6—C7—H7B	108.8	O1—S1—C10	108.39 (10)
H7A—C7—H7B	107.6	O2—S1—C10	107.06 (9)
C7—C8—C9	110.45 (15)	N1—S1—C10	107.85 (8)
C7—C8—H8A	109.6
C6—C1—C2—C3	3.1 (3)	C6—C1—N1—C9	22.44 (19)
N1—C1—C2—C3	178.13 (17)	C2—C1—N1—S1	59.22 (18)
C1—C2—C3—C4	−1.0 (3)	C6—C1—N1—S1	−125.77 (13)
C2—C3—C4—C5	−1.1 (3)	C8—C9—N1—C1	−51.15 (19)
C3—C4—C5—C6	1.2 (3)	C8—C9—N1—S1	97.83 (15)
C4—C5—C6—C1	0.9 (3)	C1—N1—S1—O1	−176.90 (12)
C4—C5—C6—C7	−174.89 (18)	C9—N1—S1—O1	35.68 (15)
C2—C1—C6—C5	−3.1 (2)	C1—N1—S1—O1	−176.90 (12)
N1—C1—C6—C5	−178.07 (13)	C9—N1—S1—O1	35.68 (15)
C2—C1—C6—C7	172.62 (15)	C1—N1—S1—O2	−48.59 (13)
N1—C1—C6—C7	−2.4 (2)	C9—N1—S1—O2	163.98 (12)
C5—C6—C7—C8	−173.18 (16)	C1—N1—S1—O2	−48.59 (13)
C1—C6—C7—C8	11.2 (2)	C9—N1—S1—O2	163.98 (12)
C6—C7—C8—C9	−38.3 (2)	C1—N1—S1—C10	66.91 (14)
C7—C8—C9—N1	58.9 (2)	C9—N1—S1—C10	−80.52 (14)
C2—C1—N1—C9	−152.58 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10C···O2^i	0.96	2.50	3.431 (2)	164

Symmetry code: (i) −x, −y+1, −z+2.