Crystal structure of 3-bromo-methyl-2-chloro-6-(di-bromo-meth-yl)quinoline.

In the title compound, C11H7Br3ClN, the quinoline ring system is approximately planar (r.m.s. = 0.011 Å). In the crystal, mol-ecules are linked by C-H⋯Br inter-actions forming chains along [10-1]. The chains are linked by C-H⋯π and π-π inter-actions involving inversion-related pyridine rings [inter-centroid distance = 3.608 (4) Å], forming sheets parallel to (10-1). Within the sheets, there are two significant short inter-actions involving a Br⋯Cl contact of 3.4904 (18) Å and a Br⋯N contact of 3.187 (6) Å, both of which are significantly shorter than the sum of their van der Waals radii.

Related literature

The title compound is an important inter­mediate in the manufacture of materials such as organic light-emitting devices. For the synthesis of the title compound, see: Jones (1977 ▸); Lyle et al. (1972 ▸). For the biological activity of quinoline derivatives, see: Chauhan & Srivastava (2001 ▸); Ferrarini et al. (2000 ▸); Chen et al. (2001 ▸); Sahin et al. (2008 ▸).

Experimental

Crystal data

C11H7Br3ClN

M = 428.36

Monoclinic,

a = 8.9042 (5) Å

b = 9.3375 (4) Å

c = 15.5107 (7) Å

β = 104.553 (5)°

V = 1248.23 (11) Å3

Z = 4

Mo Kα radiation

μ = 9.88 mm−1

T = 120 K

0.42 × 0.36 × 0.30 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 Gemini ultra diffractometer

Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2010 ▸) T min = 0.056, T max = 0.153

8597 measured reflections

2259 independent reflections

1889 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.143

S = 1.09

2259 reflections

145 parameters

H-atom parameters constrained

Δρmax = 1.65 e Å−3

Δρmin = −1.19 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: PLATON (Spek, 2009 ▸) and Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: SHELXL2014 and PLATON.

Crystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989015008002/su5096sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015008002/su5096Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015008002/su5096Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015008002/su5096fig1.tif

The mol­ecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.

a . DOI: 10.1107/S2056989015008002/su5096fig2.tif

A view along the a axis of the crystal packing of the title compound. The C—H⋯Br hydrogen bonds, C—H⋯π inter­actions (Table 1) and the Br⋯Cl and Br⋯N short contacts are shown as dashed lines.

CCDC reference: 902598

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

C11H7Br3ClN	F(000) = 808
Mr = 428.36	Dx = 2.279 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.9042 (5) Å	Cell parameters from 4382 reflections
b = 9.3375 (4) Å	θ = 2.6–29.0°
c = 15.5107 (7) Å	µ = 9.88 mm−1
β = 104.553 (5)°	T = 120 K
V = 1248.23 (11) Å3	Block, colourless
Z = 4	0.42 × 0.36 × 0.30 mm

Oxford Diffraction Xcalibur Sapphire3 Gemini ultra diffractometer	2259 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1889 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 16.1511 pixels mm-1	θmax = 25.3°, θmin = 2.4°
ω scans	h = −10→10
Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2010)	k = −11→11
Tmin = 0.056, Tmax = 0.153	l = −18→12
8597 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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0713P)2 + 10.6242P] where P = (Fo2 + 2Fc2)/3
2259 reflections	(Δ/σ)max < 0.001
145 parameters	Δρmax = 1.65 e Å−3
0 restraints	Δρmin = −1.19 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.

	x	y	z	Uiso*/Ueq
Br1	0.63474 (10)	0.04489 (9)	0.60991 (6)	0.0370 (3)
Br3	0.45280 (10)	0.74291 (9)	0.12751 (6)	0.0381 (3)
Br2	0.70035 (11)	0.53886 (11)	0.08299 (6)	0.0429 (3)
Cl1	0.8069 (2)	0.38929 (19)	0.67965 (10)	0.0226 (4)
N1	0.7951 (7)	0.4817 (7)	0.5207 (4)	0.0242 (13)
C1	0.7245 (8)	0.3973 (8)	0.5630 (4)	0.0215 (15)
C2	0.5903 (8)	0.3156 (7)	0.5249 (4)	0.0179 (14)
C3	0.5309 (8)	0.3292 (7)	0.4361 (5)	0.0201 (14)
H3	0.4411	0.2763	0.4074	0.024*
C4	0.6012 (8)	0.4213 (7)	0.3857 (4)	0.0175 (14)
C5	0.7359 (8)	0.4957 (8)	0.4305 (5)	0.0197 (14)
C6	0.8084 (8)	0.5892 (9)	0.3828 (5)	0.0274 (17)
H6	0.8991	0.6397	0.4129	0.033*
C7	0.7505 (9)	0.6079 (9)	0.2946 (5)	0.0279 (17)
H7	0.8002	0.6722	0.2631	0.034*
C8	0.6160 (8)	0.5326 (8)	0.2483 (5)	0.0217 (15)
C9	0.5450 (8)	0.4423 (7)	0.2927 (4)	0.0201 (14)
H9	0.4555	0.3916	0.2612	0.024*
C10	0.5174 (9)	0.2212 (8)	0.5792 (5)	0.0234 (15)
H10A	0.4102	0.1981	0.5456	0.028*
H10B	0.5120	0.2718	0.6344	0.028*
C11	0.5499 (9)	0.5552 (8)	0.1511 (5)	0.0250 (16)
H11	0.4683	0.4809	0.1295	0.030*

	U11	U22	U33	U12	U13	U23
Br1	0.0423 (5)	0.0311 (5)	0.0363 (5)	0.0018 (4)	0.0073 (4)	0.0085 (3)
Br3	0.0415 (5)	0.0292 (5)	0.0416 (5)	0.0098 (4)	0.0068 (4)	0.0091 (3)
Br2	0.0437 (5)	0.0546 (6)	0.0369 (5)	0.0031 (4)	0.0225 (4)	−0.0033 (4)
Cl1	0.0252 (9)	0.0296 (9)	0.0114 (7)	−0.0033 (7)	0.0013 (6)	0.0017 (6)
N1	0.022 (3)	0.025 (3)	0.024 (3)	−0.001 (3)	0.003 (2)	0.000 (3)
C1	0.020 (4)	0.026 (4)	0.018 (3)	0.001 (3)	0.005 (3)	−0.001 (3)
C2	0.019 (3)	0.012 (3)	0.023 (3)	0.002 (3)	0.007 (3)	0.002 (3)
C3	0.020 (3)	0.012 (3)	0.027 (4)	0.003 (3)	0.004 (3)	−0.001 (3)
C4	0.017 (3)	0.013 (3)	0.024 (3)	0.001 (3)	0.008 (3)	−0.002 (3)
C5	0.019 (3)	0.020 (3)	0.021 (3)	0.002 (3)	0.005 (3)	0.000 (3)
C6	0.018 (4)	0.030 (4)	0.031 (4)	−0.003 (3)	0.000 (3)	−0.002 (3)
C7	0.023 (4)	0.033 (4)	0.029 (4)	−0.007 (3)	0.008 (3)	0.004 (3)
C8	0.022 (4)	0.018 (4)	0.026 (4)	0.005 (3)	0.010 (3)	0.002 (3)
C9	0.021 (4)	0.016 (3)	0.020 (3)	0.001 (3)	−0.001 (3)	0.000 (3)
C10	0.024 (4)	0.023 (4)	0.025 (4)	0.003 (3)	0.008 (3)	0.003 (3)
C11	0.030 (4)	0.021 (4)	0.026 (4)	−0.001 (3)	0.009 (3)	0.004 (3)

Br1—C10	1.944 (7)	C4—C9	1.417 (9)
Br3—C11	1.948 (7)	C5—C6	1.404 (11)
Br2—C11	1.910 (8)	C6—C7	1.345 (10)
Cl1—C1	1.776 (7)	C6—H6	0.9500
N1—C1	1.286 (10)	C7—C8	1.419 (10)
N1—C5	1.371 (9)	C7—H7	0.9500
C1—C2	1.416 (10)	C8—C9	1.343 (10)
C2—C3	1.352 (10)	C8—C11	1.489 (10)
C2—C10	1.478 (10)	C9—H9	0.9500
C3—C4	1.409 (10)	C10—H10A	0.9900
C3—H3	0.9500	C10—H10B	0.9900
C4—C5	1.409 (10)	C11—H11	1.0000
C1—N1—C5	117.8 (6)	C6—C7—H7	119.7
N1—C1—C2	126.0 (6)	C8—C7—H7	119.7
N1—C1—Cl1	114.6 (5)	C9—C8—C7	119.9 (7)
C2—C1—Cl1	119.5 (5)	C9—C8—C11	119.4 (7)
C3—C2—C1	116.6 (6)	C7—C8—C11	120.7 (7)
C3—C2—C10	121.5 (6)	C8—C9—C4	121.2 (6)
C1—C2—C10	121.9 (6)	C8—C9—H9	119.4
C2—C3—C4	120.5 (6)	C4—C9—H9	119.4
C2—C3—H3	119.8	C2—C10—Br1	111.0 (5)
C4—C3—H3	119.8	C2—C10—H10A	109.4
C5—C4—C3	118.0 (6)	Br1—C10—H10A	109.4
C5—C4—C9	118.2 (6)	C2—C10—H10B	109.4
C3—C4—C9	123.8 (6)	Br1—C10—H10B	109.4
N1—C5—C6	119.2 (6)	H10A—C10—H10B	108.0
N1—C5—C4	121.2 (6)	C8—C11—Br2	113.3 (5)
C6—C5—C4	119.6 (6)	C8—C11—Br3	111.2 (5)
C7—C6—C5	120.5 (7)	Br2—C11—Br3	107.9 (3)
C7—C6—H6	119.8	C8—C11—H11	108.1
C5—C6—H6	119.8	Br2—C11—H11	108.1
C6—C7—C8	120.6 (7)	Br3—C11—H11	108.1
C5—N1—C1—C2	0.4 (11)	N1—C5—C6—C7	−178.3 (7)
C5—N1—C1—Cl1	−178.6 (5)	C4—C5—C6—C7	−0.2 (11)
N1—C1—C2—C3	−0.7 (11)	C5—C6—C7—C8	−0.5 (12)
Cl1—C1—C2—C3	178.3 (5)	C6—C7—C8—C9	0.4 (12)
N1—C1—C2—C10	180.0 (7)	C6—C7—C8—C11	178.8 (7)
Cl1—C1—C2—C10	−1.0 (9)	C7—C8—C9—C4	0.5 (11)
C1—C2—C3—C4	−0.2 (10)	C11—C8—C9—C4	−177.9 (6)
C10—C2—C3—C4	179.1 (6)	C5—C4—C9—C8	−1.2 (10)
C2—C3—C4—C5	1.2 (10)	C3—C4—C9—C8	179.4 (7)
C2—C3—C4—C9	−179.4 (7)	C3—C2—C10—Br1	103.9 (7)
C1—N1—C5—C6	178.7 (7)	C1—C2—C10—Br1	−76.8 (8)
C1—N1—C5—C4	0.7 (10)	C9—C8—C11—Br2	−131.1 (6)
C3—C4—C5—N1	−1.5 (10)	C7—C8—C11—Br2	50.5 (8)
C9—C4—C5—N1	179.1 (6)	C9—C8—C11—Br3	107.2 (7)
C3—C4—C5—C6	−179.5 (7)	C7—C8—C11—Br3	−71.3 (8)
C9—C4—C5—C6	1.0 (10)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···Br1i	1.00	2.92	3.709 (8)	137
C10—H10B···Cg2ii	0.99	2.70	3.438 (8)	131

Table 1

Hydrogen-bond geometry (, )

Cg2 is the centroid of the C4C9 ring.

DHA	DH	HA	D A	DHA
C11H11Br1i	1.00	2.92	3.709(8)	137
C10H10B Cg2ii	0.99	2.70	3.438(8)	131

Symmetry codes: (i) ; (ii) .