cis-[3-(2-Chloro-6-methyl­quinolin-3-yl)oxiran-2-yl](p-tol­yl)methanone

Preveena, N.; Hosamani, A.A.; Praveen, M.; Nagendrappa, G.; Guru Row, T.N.

doi:10.1107/S2414314617004345

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 3| March 2017| x170434

https://doi.org/10.1107/S2414314617004345

Open

access

cis-[3-(2-Chloro-6-methylquinolin-3-yl)oxiran-2-yl](p-tolyl)methanone

Narasimhamurthy Preveena,^a ^* Amar A. Hosamani,^b Managutti Praveen,^b Gopalpur Nagendrappa ^c and Tayur N. Guru Row ^d

^aP.G. Department of Chemistry, Centre for Post Graduation Studies, Jain University, 3rd Block, Jayanagar, Bangalore 560 011, Karnataka, India, ^bSolid state and Structural Chemistry Unit, Indian Institute of Science, C.V. Raman Avenue, Bangalore 560 012, Karnataka, India, ^cP.G. Department of Chemistry, Centre for Post Graduation Studies, Jain, University, 3rd Block, Jayanagar, Bangalore 560 011, Karnataka, India, and ^dSolid state and Structural Chemistry Unit, Indian Institute of Science, C.V., Raman Avenue, Bangalore 560 012, Karnataka, India
^*Correspondence e-mail: praveena.molecularconnection@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 4 February 2017; accepted 18 March 2017; online 24 March 2017)

In the title compound, C₂₀H₁₆ClNO₂, the dihedral angle between the quinolyl ring system and the p-tolyl ring is 65.80 (7)°. The rings are bridged by a functionalized epoxide system, with the exocyclic bonds in a cis configuration. In the crystal, weak C—H⋯O and C—H⋯Cl interactions link the molecules into [100] chains.

Keywords: crystal structure; synthesis; hydrogen bonding; supramolecular chemistry.

CCDC reference: 1477410

Structure description

The synthesis and pharmacological properties of quinolinyl epoxy ketones have been reported by us recently (Preveena et al., 2015 ). 2-Chloroquinoline-3-carbaldehydes have not been exploited for Darzens condensations, a powerful procedure for the formation of a carbon–carbon bond with a simultaneous generation of epoxy function group next to the keto or ester function, except for one report (Boulcina et al., 2008 ) that describes the synthesis of a few quinolinyl epoxy ketones under stronger conditions and much longer duration, with modest yields of products. The structure of a related quinoline derivative was reported by the same workers (Boulcina et al., 2007 ). Here we report the synthesis and crystal structure of the title compound (Fig. 1).

Figure 1
The molecular structure of the title compound, showing 50% probability displacement ellipsoids.

The dihedral angle between the quinoline ring system and the p-tolyl ring is 65.80 (7)°. The conformation about the epoxide group is cis. There are two types of weak intermolecular hydrogen-bonding interactions in the crystal: C5—H5⋯Cl1 and C12—H12⋯O2 (Table 1). Together, these lead to [100] chains in the (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯Cl1ⁱ	0.93	2.87	3.788 (2)	168
C12—H12⋯O2ⁱⁱ	0.93	2.63	3.426 (3)	144
Symmetry codes: (i) x+1, y, z; (ii) x-1, y, z.

Figure 2
Fragment of the crystal structure of the title compound, showing the formation of the [100] chains.

Synthesis and crystallization

1.0 g (4.86 mmol) of 2-chloro-6-methylquinoline-3-carbaldehyde was dissolved in DMF (4 ml); to this was added 1.25 g (5.86 mmol) of 2-bromo-1-p-tolylethanone and 0.20 g (1.45 mmol) of K₂CO₃ and was stirred at room temperature for about 6 h. The progress of reaction was periodically monitored by TLC. At the end of the reaction, the mixture was added to crushed ice and the precipitate obtained was filtered and purified by column chromatography on silica gel using a petroleum ether–ethyl acetate mixture (96:4) as eluting solvent to obtain the title compound (Preveena et al., 2015) in 88% yield. Colourless blocks were recrystallized from ethyl acetate solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₀H₁₆ClNO₂
M_r	337.79
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	298
a, b, c (Å)	7.412 (2), 10.963 (4), 11.070 (4)
α, β, γ (°)	105.124 (18), 95.633 (18), 104.398 (17)
V (Å³)	828.2 (5)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.24
Crystal size (mm)	0.25 × 0.24 × 0.23

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.686, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	11538, 2880, 2411
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.124, 1.13
No. of reflections	2880
No. of parameters	219
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.18
Computer programs: APEX2 and SAINT (Bruker, 2012), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1477410

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617004345/hb4122sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617004345/hb4122Isup2.hkl

abstract and crystal data. DOI: https://doi.org/10.1107/S2414314617004345/hb4122sup3.docx

Supporting information file. DOI: https://doi.org/10.1107/S2414314617004345/hb4122Isup4.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

cis-[3-(2-Chloro-6-methylquinolin-3-yl)oxiran-2-yl](p-tolyl)methanone top

Crystal data top

C₂₀H₁₆ClNO₂	Z = 2
M_r = 337.79	F(000) = 352
Triclinic, P1	D_x = 1.355 Mg m⁻³
a = 7.412 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.963 (4) Å	Cell parameters from 5696 reflections
c = 11.070 (4) Å	θ = 2.3–27.1°
α = 105.124 (18)°	µ = 0.24 mm⁻¹
β = 95.633 (18)°	T = 298 K
γ = 104.398 (17)°	Block, clear light colourless
V = 828.2 (5) Å³	0.25 × 0.24 × 0.23 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	2880 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	2411 reflections with I > 2σ(I)
Mirror optics monochromator	R_int = 0.045
Detector resolution: 7.9 pixels mm^-1	θ_max = 25.0°, θ_min = 1.9°
ω and φ scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2012)	k = −13→13
T_min = 0.686, T_max = 0.746	l = −13→13
11538 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.124	w = 1/[σ²(F_o²) + (0.0588P)² + 0.1667P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max < 0.001
2880 reflections	Δρ_max = 0.23 e Å⁻³
219 parameters	Δρ_min = −0.18 e Å⁻³
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	−0.14999 (6)	0.54946 (5)	0.24404 (5)	0.0599 (2)
O1	0.38544 (19)	0.45396 (13)	0.34241 (13)	0.0574 (4)
O2	0.58876 (19)	0.71396 (15)	0.45887 (14)	0.0631 (4)
N1	0.0398 (2)	0.66501 (15)	0.10097 (14)	0.0472 (4)
C1	0.6831 (3)	0.8368 (3)	−0.1198 (2)	0.0716 (6)
H1A	0.7900	0.8139	−0.0859	0.107*
H1B	0.7136	0.9308	−0.1020	0.107*
H1C	0.6520	0.7961	−0.2101	0.107*
C2	0.5166 (3)	0.7893 (2)	−0.05940 (18)	0.0526 (5)
C3	0.5226 (3)	0.7133 (2)	0.01956 (18)	0.0499 (5)
H3	0.6322	0.6895	0.0365	0.060*
C4	0.3657 (2)	0.66963 (18)	0.07658 (16)	0.0435 (4)
C5	0.3670 (3)	0.59374 (18)	0.16096 (17)	0.0463 (5)
H5	0.4748	0.5690	0.1809	0.056*
C6	0.2119 (2)	0.55591 (17)	0.21394 (16)	0.0433 (4)
C7	0.2094 (3)	0.47792 (18)	0.30524 (18)	0.0488 (5)
H7	0.0948	0.4052	0.2931	0.059*
C8	0.3164 (3)	0.53792 (19)	0.43619 (18)	0.0478 (4)
H8	0.2644	0.5009	0.5012	0.057*
C9	0.4290 (2)	0.68091 (19)	0.48030 (16)	0.0456 (4)
C10	0.3345 (2)	0.77642 (18)	0.54584 (16)	0.0443 (4)
C11	0.1419 (3)	0.7400 (2)	0.54987 (19)	0.0531 (5)
H11	0.0717	0.6520	0.5161	0.064*
C12	0.0542 (3)	0.8326 (2)	0.6033 (2)	0.0584 (5)
H12	−0.0749	0.8064	0.6043	0.070*
C13	0.1545 (3)	0.9635 (2)	0.65515 (19)	0.0571 (5)
C14	0.0577 (4)	1.0655 (3)	0.7101 (3)	0.0872 (8)
H14A	−0.0707	1.0386	0.6664	0.131*
H14B	0.1231	1.1486	0.7000	0.131*
H14C	0.0588	1.0745	0.7988	0.131*
C15	0.3474 (3)	0.8234 (2)	−0.0848 (2)	0.0593 (5)
H15	0.3415	0.8753	−0.1387	0.071*
C16	0.1942 (3)	0.7824 (2)	−0.0326 (2)	0.0559 (5)
H16	0.0852	0.8062	−0.0516	0.067*
C17	0.1976 (2)	0.70482 (18)	0.04924 (16)	0.0446 (4)
C18	0.0518 (2)	0.59602 (18)	0.17794 (17)	0.0434 (4)
C19	0.3476 (3)	0.9993 (2)	0.6530 (2)	0.0618 (6)
H19	0.4181	1.0870	0.6888	0.074*
C20	0.4360 (3)	0.9079 (2)	0.59925 (18)	0.0545 (5)
H20	0.5652	0.9343	0.5986	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0448 (3)	0.0745 (4)	0.0624 (4)	0.0206 (2)	0.0093 (2)	0.0201 (3)
O1	0.0665 (9)	0.0583 (8)	0.0578 (8)	0.0356 (7)	0.0060 (7)	0.0199 (7)
O2	0.0465 (8)	0.0728 (10)	0.0708 (10)	0.0140 (7)	0.0126 (7)	0.0245 (8)
N1	0.0433 (8)	0.0526 (9)	0.0473 (9)	0.0246 (7)	0.0020 (7)	0.0091 (7)
C1	0.0675 (14)	0.0770 (16)	0.0745 (16)	0.0218 (12)	0.0203 (12)	0.0256 (13)
C2	0.0541 (11)	0.0539 (11)	0.0479 (11)	0.0185 (9)	0.0065 (9)	0.0098 (9)
C3	0.0438 (10)	0.0571 (12)	0.0470 (11)	0.0224 (9)	0.0017 (8)	0.0072 (9)
C4	0.0433 (9)	0.0456 (10)	0.0391 (9)	0.0192 (8)	−0.0001 (7)	0.0046 (8)
C5	0.0452 (10)	0.0510 (11)	0.0445 (10)	0.0253 (8)	−0.0016 (8)	0.0095 (8)
C6	0.0443 (9)	0.0426 (10)	0.0402 (9)	0.0181 (8)	−0.0003 (7)	0.0049 (8)
C7	0.0509 (10)	0.0428 (10)	0.0537 (11)	0.0189 (8)	0.0046 (9)	0.0126 (9)
C8	0.0512 (10)	0.0514 (11)	0.0486 (10)	0.0215 (8)	0.0091 (8)	0.0215 (9)
C9	0.0452 (10)	0.0540 (11)	0.0400 (10)	0.0135 (8)	0.0014 (8)	0.0207 (8)
C10	0.0472 (10)	0.0479 (10)	0.0369 (9)	0.0085 (8)	0.0037 (7)	0.0172 (8)
C11	0.0467 (10)	0.0474 (11)	0.0558 (11)	0.0057 (8)	0.0043 (9)	0.0083 (9)
C12	0.0478 (11)	0.0585 (12)	0.0612 (12)	0.0131 (9)	0.0070 (9)	0.0078 (10)
C13	0.0729 (13)	0.0545 (12)	0.0457 (11)	0.0226 (10)	0.0093 (10)	0.0141 (9)
C14	0.104 (2)	0.0712 (16)	0.0887 (19)	0.0398 (15)	0.0215 (16)	0.0124 (14)
C15	0.0676 (13)	0.0622 (13)	0.0564 (12)	0.0282 (11)	0.0072 (10)	0.0236 (10)
C16	0.0566 (11)	0.0626 (13)	0.0586 (12)	0.0331 (10)	0.0047 (9)	0.0215 (10)
C17	0.0455 (10)	0.0466 (10)	0.0407 (10)	0.0226 (8)	−0.0006 (8)	0.0051 (8)
C18	0.0411 (9)	0.0439 (10)	0.0407 (9)	0.0162 (8)	0.0006 (7)	0.0035 (8)
C19	0.0773 (15)	0.0419 (11)	0.0585 (13)	0.0035 (10)	0.0129 (11)	0.0142 (9)
C20	0.0550 (11)	0.0528 (12)	0.0512 (11)	0.0027 (9)	0.0109 (9)	0.0193 (9)

Geometric parameters (Å, º) top

Cl1—C18	1.750 (2)	C8—H8	0.9800
O1—C7	1.436 (2)	C8—C9	1.504 (3)
O1—C8	1.424 (2)	C9—C10	1.477 (3)
O2—C9	1.215 (2)	C10—C11	1.392 (3)
N1—C17	1.376 (2)	C10—C20	1.386 (3)
N1—C18	1.289 (2)	C11—H11	0.9300
C1—H1A	0.9600	C11—C12	1.376 (3)
C1—H1B	0.9600	C12—H12	0.9300
C1—H1C	0.9600	C12—C13	1.377 (3)
C1—C2	1.506 (3)	C13—C14	1.506 (3)
C2—C3	1.361 (3)	C13—C19	1.391 (3)
C2—C15	1.417 (3)	C14—H14A	0.9600
C3—H3	0.9300	C14—H14B	0.9600
C3—C4	1.416 (3)	C14—H14C	0.9600
C4—C5	1.405 (3)	C15—H15	0.9300
C4—C17	1.420 (2)	C15—C16	1.355 (3)
C5—H5	0.9300	C16—H16	0.9300
C5—C6	1.364 (3)	C16—C17	1.398 (3)
C6—C7	1.483 (3)	C19—H19	0.9300
C6—C18	1.421 (2)	C19—C20	1.371 (3)
C7—H7	0.9800	C20—H20	0.9300
C7—C8	1.476 (3)

C8—O1—C7	62.16 (12)	C10—C9—C8	117.05 (16)
C18—N1—C17	117.07 (15)	C11—C10—C9	121.83 (16)
H1A—C1—H1B	109.5	C20—C10—C9	119.83 (17)
H1A—C1—H1C	109.5	C20—C10—C11	118.24 (18)
H1B—C1—H1C	109.5	C10—C11—H11	119.6
C2—C1—H1A	109.5	C12—C11—C10	120.79 (18)
C2—C1—H1B	109.5	C12—C11—H11	119.6
C2—C1—H1C	109.5	C11—C12—H12	119.5
C3—C2—C1	121.85 (19)	C11—C12—C13	121.02 (19)
C3—C2—C15	118.32 (19)	C13—C12—H12	119.5
C15—C2—C1	119.8 (2)	C12—C13—C14	121.1 (2)
C2—C3—H3	119.2	C12—C13—C19	118.09 (19)
C2—C3—C4	121.51 (17)	C19—C13—C14	120.8 (2)
C4—C3—H3	119.2	C13—C14—H14A	109.5
C3—C4—C17	119.07 (17)	C13—C14—H14B	109.5
C5—C4—C3	123.48 (16)	C13—C14—H14C	109.5
C5—C4—C17	117.45 (17)	H14A—C14—H14B	109.5
C4—C5—H5	119.6	H14A—C14—H14C	109.5
C6—C5—C4	120.71 (16)	H14B—C14—H14C	109.5
C6—C5—H5	119.6	C2—C15—H15	119.2
C5—C6—C7	122.20 (16)	C16—C15—C2	121.7 (2)
C5—C6—C18	116.50 (17)	C16—C15—H15	119.2
C18—C6—C7	121.30 (17)	C15—C16—H16	119.5
O1—C7—C6	115.74 (16)	C15—C16—C17	120.95 (18)
O1—C7—H7	116.2	C17—C16—H16	119.5
O1—C7—C8	58.52 (12)	N1—C17—C4	121.97 (17)
C6—C7—H7	116.2	N1—C17—C16	119.55 (16)
C8—C7—C6	121.17 (16)	C16—C17—C4	118.47 (18)
C8—C7—H7	116.2	N1—C18—Cl1	115.87 (13)
O1—C8—C7	59.32 (12)	N1—C18—C6	126.28 (18)
O1—C8—H8	116.4	C6—C18—Cl1	117.85 (15)
O1—C8—C9	115.69 (16)	C13—C19—H19	119.3
C7—C8—H8	116.4	C20—C19—C13	121.31 (19)
C7—C8—C9	120.34 (16)	C20—C19—H19	119.3
C9—C8—H8	116.4	C10—C20—H20	119.7
O2—C9—C8	120.14 (17)	C19—C20—C10	120.54 (19)
O2—C9—C10	122.79 (17)	C19—C20—H20	119.7

O1—C7—C8—C9	103.70 (19)	C7—C6—C18—N1	179.09 (17)
O1—C8—C9—O2	−16.3 (2)	C7—C8—C9—O2	−84.3 (2)
O1—C8—C9—C10	161.95 (14)	C7—C8—C9—C10	93.9 (2)
O2—C9—C10—C11	168.50 (18)	C8—O1—C7—C6	112.25 (18)
O2—C9—C10—C20	−7.9 (3)	C8—C9—C10—C11	−9.7 (2)
C1—C2—C3—C4	179.65 (18)	C8—C9—C10—C20	173.97 (16)
C1—C2—C15—C16	179.8 (2)	C9—C10—C11—C12	−175.15 (17)
C2—C3—C4—C5	−178.43 (17)	C9—C10—C20—C19	175.67 (17)
C2—C3—C4—C17	0.8 (3)	C10—C11—C12—C13	−0.6 (3)
C2—C15—C16—C17	0.3 (3)	C11—C10—C20—C19	−0.8 (3)
C3—C2—C15—C16	0.0 (3)	C11—C12—C13—C14	178.1 (2)
C3—C4—C5—C6	179.25 (16)	C11—C12—C13—C19	−0.5 (3)
C3—C4—C17—N1	179.65 (16)	C12—C13—C19—C20	1.0 (3)
C3—C4—C17—C16	−0.4 (3)	C13—C19—C20—C10	−0.3 (3)
C4—C5—C6—C7	−178.83 (16)	C14—C13—C19—C20	−177.7 (2)
C4—C5—C6—C18	0.7 (3)	C15—C2—C3—C4	−0.6 (3)
C5—C4—C17—N1	−1.1 (3)	C15—C16—C17—N1	179.83 (18)
C5—C4—C17—C16	178.81 (16)	C15—C16—C17—C4	−0.1 (3)
C5—C6—C7—O1	4.9 (2)	C17—N1—C18—Cl1	178.95 (12)
C5—C6—C7—C8	72.2 (2)	C17—N1—C18—C6	−0.6 (3)
C5—C6—C18—Cl1	−179.95 (13)	C17—C4—C5—C6	0.0 (3)
C5—C6—C18—N1	−0.4 (3)	C18—N1—C17—C4	1.3 (3)
C6—C7—C8—O1	−102.98 (19)	C18—N1—C17—C16	−178.55 (16)
C6—C7—C8—C9	0.7 (3)	C18—C6—C7—O1	−174.58 (15)
C7—O1—C8—C9	−111.49 (18)	C18—C6—C7—C8	−107.3 (2)
C7—C6—C18—Cl1	−0.4 (2)	C20—C10—C11—C12	1.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···Cl1ⁱ	0.93	2.87	3.788 (2)	168
C12—H12···O2ⁱⁱ	0.93	2.63	3.426 (3)	144

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

Acknowledgements

The authors are thankful to the authorities of Jain University for their encouragement and financial support for this work, and the Department of Solid State Chemistry, Indian Institute of Science, for the facility provided to record crystal data.

References

Boulcina, R., Belfaitah, A., Rhouati, S. & Debache, A. (2008). J. Soc. Alger. Chim, 18, 61–70. CAS Google Scholar
Boulcina, R., Bouacida, S., Roisnel, T. & Debache, A. (2007). Acta Cryst. E63, o3795–o3796. CSD CrossRef IUCr Journals Google Scholar
Bruker (2012). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Preveena, N., Nagendrappa, G., Suresha Kumara, T. H., Tiwari, A. K., Chaithanya, M. S., Nagananda, G. S., Sujan Ganapathy, P. S., Guru Row, T. N., Amar, A. H. & Chethana, P. R. (2015). Int. J. Phar. Sci. Inv. 4, 53–76. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar