2-Bromo-ethyl 2-chloro-6-methyl-quinoline-3-carboxyl-ate.

In the title compound, C(13)H(11)BrClNO(2), the two rings of the quinoline group are fused in an axial fashion at a dihedral angle of 1.28 (9)°. In the crystal, molecules are arranged in zigzag layers along the c axis. The crystal packing is stabilized by weak C-H⋯O hydrogen bonds and inter-molecular inter-actions between Br and O atoms [Br⋯O= 3.076 (2) Å], resulting in the formation of a three-dimensional network.

Related literature

For our previous work on the preparation of quinoline derivatives, see: Benzerka et al. (2008 ▶); Ladraa et al. (2009 ▶, 2010 ▶). For radical bromination, see: Kikichi et al. (1998 ▶); Xu et al. (2003 ▶); Djerassi (1948 ▶); Newman & Lee (1972 ▶). For radical bromination of ketone and acetal functions, see: Marvell & Joncich (1951 ▶); Markees (1958 ▶).

Experimental

Crystal data

C13H11BrClNO2

M = 328.59

Monoclinic,

a = 6.1740 (4) Å

b = 29.0515 (14) Å

c = 7.2875 (4) Å

β = 99.167 (3)°

V = 1290.42 (13) Å3

Z = 4

Mo Kα radiation

μ = 3.39 mm−1

T = 100 K

0.45 × 0.38 × 0.11 mm

Data collection

Bruker APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ▶) T min = 0.238, T max = 0.689

11364 measured reflections

2938 independent reflections

2430 reflections with I > 2σ(I)

R int = 0.054

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.092

S = 1.02

2938 reflections

164 parameters

H-atom parameters constrained

Δρmax = 0.74 e Å−3

Δρmin = −0.85 e Å−3

Data collection: APEX2 (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg & Berndt, 2001 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810010160/bq2201sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810010160/bq2201Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C13H11BrClNO2	F(000) = 656
Mr = 328.59	Dx = 1.691 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.1740 (4) Å	Cell parameters from 3765 reflections
b = 29.0515 (14) Å	θ = 2.8–27.3°
c = 7.2875 (4) Å	µ = 3.39 mm−1
β = 99.167 (3)°	T = 100 K
V = 1290.42 (13) Å3	Prism, colourless
Z = 4	0.45 × 0.38 × 0.11 mm

Bruker APEXII diffractometer	2938 independent reflections
Radiation source: Enraf–Nonius FR590	2430 reflections with I > 2σ(I)
graphite	Rint = 0.054
CCD rotation images, thick slices scans	θmax = 27.5°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −7→7
Tmin = 0.238, Tmax = 0.689	k = −37→37
11364 measured reflections	l = −9→9

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0397P)2 + 1.2764P] where P = (Fo2 + 2Fc2)/3
2938 reflections	(Δ/σ)max = 0.001
164 parameters	Δρmax = 0.74 e Å−3
0 restraints	Δρmin = −0.85 e Å−3

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.

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.

	x	y	z	Uiso*/Ueq
C1	0.7808 (4)	0.08966 (9)	0.2084 (4)	0.0164 (5)
C2	1.0027 (4)	0.10023 (8)	0.2862 (4)	0.0152 (5)
C3	1.1423 (4)	0.06355 (9)	0.3242 (4)	0.0151 (5)
H3	1.2874	0.0687	0.3775	0.018*
C4	1.0694 (4)	0.01828 (9)	0.2837 (4)	0.0147 (5)
C5	1.2083 (4)	−0.02083 (9)	0.3149 (4)	0.0167 (6)
H5	1.3551	−0.0169	0.3657	0.02*
C6	1.1299 (4)	−0.06439 (9)	0.2713 (4)	0.0161 (5)
C7	0.9057 (5)	−0.06973 (9)	0.1919 (4)	0.0180 (6)
H7	0.8517	−0.0991	0.1616	0.022*
C8	0.7665 (4)	−0.03275 (9)	0.1586 (4)	0.0181 (6)
H8	0.6206	−0.0371	0.1057	0.022*
C9	0.8464 (4)	0.01207 (9)	0.2053 (4)	0.0147 (5)
C10	1.2752 (5)	−0.10631 (9)	0.3046 (4)	0.0204 (6)
H10A	1.425	−0.0968	0.3394	0.031*
H10B	1.2613	−0.1244	0.193	0.031*
H10C	1.2317	−0.1244	0.4027	0.031*
C11	1.0855 (4)	0.14836 (9)	0.3158 (4)	0.0188 (6)
C12	1.3409 (5)	0.19567 (9)	0.5055 (5)	0.0263 (7)
H12A	1.3736	0.2075	0.3885	0.032*
H12B	1.4788	0.1915	0.5883	0.032*
C13	1.2040 (5)	0.23018 (9)	0.5886 (5)	0.0247 (7)
H13A	1.065	0.2342	0.507	0.03*
H13B	1.2789	0.2596	0.6002	0.03*
N1	0.7035 (4)	0.04864 (7)	0.1709 (3)	0.0164 (5)
O1	1.0343 (4)	0.17987 (7)	0.2112 (3)	0.0292 (5)
O2	1.2320 (3)	0.15146 (6)	0.4733 (3)	0.0199 (4)
Cl1	0.58811 (11)	0.13419 (2)	0.16345 (10)	0.02179 (17)
Br1	1.15019 (5)	0.209908 (9)	0.83386 (5)	0.02814 (11)

	U11	U22	U33	U12	U13	U23
C1	0.0161 (13)	0.0178 (12)	0.0153 (13)	0.0059 (10)	0.0026 (11)	0.0012 (11)
C2	0.0163 (13)	0.0125 (11)	0.0176 (13)	−0.0006 (9)	0.0050 (11)	−0.0013 (10)
C3	0.0117 (12)	0.0159 (12)	0.0180 (13)	0.0001 (9)	0.0030 (11)	0.0004 (11)
C4	0.0134 (12)	0.0140 (11)	0.0169 (13)	−0.0012 (9)	0.0035 (11)	0.0000 (10)
C5	0.0124 (12)	0.0174 (12)	0.0200 (14)	0.0012 (10)	0.0018 (11)	−0.0007 (11)
C6	0.0177 (13)	0.0160 (12)	0.0150 (13)	0.0031 (9)	0.0039 (11)	0.0005 (11)
C7	0.0207 (14)	0.0130 (12)	0.0198 (14)	−0.0013 (10)	0.0019 (12)	−0.0006 (11)
C8	0.0151 (13)	0.0179 (12)	0.0202 (14)	−0.0014 (10)	−0.0004 (11)	−0.0036 (11)
C9	0.0147 (13)	0.0142 (12)	0.0151 (13)	0.0016 (9)	0.0017 (11)	0.0002 (10)
C10	0.0207 (14)	0.0147 (12)	0.0261 (16)	0.0042 (10)	0.0045 (12)	−0.0006 (11)
C11	0.0169 (13)	0.0144 (12)	0.0281 (16)	0.0005 (10)	0.0123 (12)	−0.0014 (12)
C12	0.0254 (15)	0.0119 (12)	0.043 (2)	−0.0056 (11)	0.0098 (14)	−0.0054 (13)
C13	0.0291 (16)	0.0125 (12)	0.0335 (18)	−0.0003 (11)	0.0079 (14)	−0.0005 (12)
N1	0.0133 (11)	0.0173 (10)	0.0179 (12)	0.0036 (8)	0.0005 (9)	−0.0005 (10)
O1	0.0349 (12)	0.0158 (9)	0.0376 (13)	0.0016 (8)	0.0084 (11)	0.0066 (10)
O2	0.0208 (10)	0.0117 (8)	0.0280 (11)	−0.0022 (7)	0.0062 (9)	−0.0040 (8)
Cl1	0.0196 (3)	0.0190 (3)	0.0273 (4)	0.0092 (2)	0.0050 (3)	0.0016 (3)
Br1	0.03431 (19)	0.01765 (15)	0.0334 (2)	0.00054 (11)	0.00824 (14)	−0.00443 (13)

C1—N1	1.296 (3)	C8—C9	1.415 (3)
C1—C2	1.430 (4)	C8—H8	0.93
C1—Cl1	1.753 (3)	C9—N1	1.378 (3)
C2—C3	1.371 (3)	C10—H10A	0.96
C2—C11	1.493 (3)	C10—H10B	0.96
C3—C4	1.406 (3)	C10—H10C	0.96
C3—H3	0.93	C11—O1	1.201 (3)
C4—C9	1.416 (4)	C11—O2	1.346 (3)
C4—C5	1.420 (3)	C12—O2	1.451 (3)
C5—C6	1.374 (4)	C12—C13	1.500 (4)
C5—H5	0.93	C12—H12A	0.97
C6—C7	1.422 (4)	C12—H12B	0.97
C6—C10	1.509 (3)	C13—Br1	1.960 (3)
C7—C8	1.373 (4)	C13—H13A	0.97
C7—H7	0.93	C13—H13B	0.97
N1—C1—C2	125.3 (2)	N1—C9—C4	121.9 (2)
N1—C1—Cl1	115.0 (2)	C8—C9—C4	119.6 (2)
C2—C1—Cl1	119.6 (2)	C6—C10—H10A	109.5
C3—C2—C1	116.4 (2)	C6—C10—H10B	109.5
C3—C2—C11	120.6 (2)	H10A—C10—H10B	109.5
C1—C2—C11	122.9 (2)	C6—C10—H10C	109.5
C2—C3—C4	121.0 (2)	H10A—C10—H10C	109.5
C2—C3—H3	119.5	H10B—C10—H10C	109.5
C4—C3—H3	119.5	O1—C11—O2	124.3 (2)
C3—C4—C9	117.5 (2)	O1—C11—C2	125.0 (3)
C3—C4—C5	123.4 (2)	O2—C11—C2	110.7 (2)
C9—C4—C5	119.1 (2)	O2—C12—C13	112.4 (2)
C6—C5—C4	121.2 (2)	O2—C12—H12A	109.1
C6—C5—H5	119.4	C13—C12—H12A	109.1
C4—C5—H5	119.4	O2—C12—H12B	109.1
C5—C6—C7	118.6 (2)	C13—C12—H12B	109.1
C5—C6—C10	121.9 (2)	H12A—C12—H12B	107.9
C7—C6—C10	119.5 (2)	C12—C13—Br1	110.8 (2)
C8—C7—C6	121.9 (2)	C12—C13—H13A	109.5
C8—C7—H7	119.1	Br1—C13—H13A	109.5
C6—C7—H7	119.1	C12—C13—H13B	109.5
C7—C8—C9	119.5 (2)	Br1—C13—H13B	109.5
C7—C8—H8	120.2	H13A—C13—H13B	108.1
C9—C8—H8	120.2	C1—N1—C9	117.9 (2)
N1—C9—C8	118.5 (2)	C11—O2—C12	115.3 (2)
N1—C1—C2—C3	−0.3 (4)	C3—C4—C9—N1	−0.6 (4)
Cl1—C1—C2—C3	177.6 (2)	C5—C4—C9—N1	−179.7 (3)
N1—C1—C2—C11	176.2 (3)	C3—C4—C9—C8	178.7 (3)
Cl1—C1—C2—C11	−5.9 (4)	C5—C4—C9—C8	−0.4 (4)
C1—C2—C3—C4	1.4 (4)	C3—C2—C11—O1	137.8 (3)
C11—C2—C3—C4	−175.2 (3)	C1—C2—C11—O1	−38.6 (4)
C2—C3—C4—C9	−1.0 (4)	C3—C2—C11—O2	−40.1 (4)
C2—C3—C4—C5	178.1 (3)	C1—C2—C11—O2	143.5 (3)
C3—C4—C5—C6	−179.3 (3)	O2—C12—C13—Br1	62.8 (3)
C9—C4—C5—C6	−0.3 (4)	C2—C1—N1—C9	−1.2 (4)
C4—C5—C6—C7	0.6 (4)	Cl1—C1—N1—C9	−179.2 (2)
C4—C5—C6—C10	−179.6 (3)	C8—C9—N1—C1	−177.6 (3)
C5—C6—C7—C8	−0.3 (4)	C4—C9—N1—C1	1.7 (4)
C10—C6—C7—C8	−180.0 (3)	O1—C11—O2—C12	−4.3 (4)
C6—C7—C8—C9	−0.4 (4)	C2—C11—O2—C12	173.6 (2)
C7—C8—C9—N1	−179.9 (3)	C13—C12—O2—C11	81.8 (3)
C7—C8—C9—C4	0.8 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13B···O1i	0.97	2.41	3.347 (4)	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13B⋯O1i	0.97	2.41	3.347 (4)	162

Symmetry code: (i) .