Crystal structure of 3-bromo­methyl-2-chloro-6-(di­bromo­meth­yl)quinoline

Abstract

In the title compound, C₁₁H₇Br₃ClN, the quinoline ring system is approximately planar (r.m.s. = 0.011 Å). In the crystal, mol­ecules are linked by C—H⋯Br inter­actions forming chains along [10-1]. The chains are linked by C—H⋯π and π–π inter­actions involving inversion-related pyridine rings [inter­centroid distance = 3.608 (4) Å], forming sheets parallel to (10-1). Within the sheets, there are two significant short inter­actions 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 _r = 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) ų

• 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

• Δρ_max = 1.65 e Å⁻³

• Δρ_min = −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.

Supplementary Material

CCDC reference: 902598

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

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) .

supplementary crystallographic information

S1. Synthesis and crystallization

The title compound was prepared in line with literature methods (Jones, 1977; Lyle et al., 1972). 2-Chloro-3,6-di­methyl-quinoline (0.001 mole) was dissolved in CCl₄. To this benzoyl peroxide (50 mg) was added and the mixture was stirred under ice-cold conditions. To this mixture N-bromo­succinimide (0.005 mole) was added portion wise. The whole mixture was further stirred under ice-cold condition for 1 h. The reaction mixture was then refluxed for about 10 hours. After completion of the reaction, the succinimide was removed (it was insoluble in CCl₄) by filtration and washed with 20 ml of CCl₄. The contents of the filtrate were reduced to half, and the residue was chromatographed on silica gel using petroleum ether and ethyl acetate as eluent (99:1), which gave the titled product (yield: 52%). The white solid obtained was then recrystallized using acetone yielding colourless block-like crystals.

S2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were included in calculated positions and refined using a riding model: C—H = 0.95 - 1.0 Å with U_iso(H) = 1.2U_eq(C). The highest peak in the final difference Fourier map (1.654 eÅ^-3) is close to atom Cl1. Attempts to split this atom were unsuccessful.

S3. Structural commentary

The presence of the quinoline skeleton in the frameworks of pharmacologically active compounds and natural products has spurred on the development of different strategies for their synthesis (Chauhan et al., 2001; Ferrarini et al., 2000; Chen et al., 2001). Bromo­quinolines have been of inter­est for chemists as precursors for heterocyclic compounds with multifunctionality, giving accessibility to a wide variety of compounds. These building blocks have been used in medicinal chemistry as starting materials for numerous compounds with pharmacological activity (Sahin et al., 2008).

The molecular structure of the title compound is shown in Fig. 1. The quinoline ring is planar (r.m.s. = 0.011 Å).

In the crystal, molecules are linked by C—H···Br inter­actions forming chains along [101]; Table 1 and Fig. 2. The chains are linked by C—H···π (Table 1), and π-π inter­actions involving inversion related pyridine rings (N1/C1—C5) with an inter-centroid distance of 3.608 (4) Å, forming sheets parallel to (101). Within the sheets, there are two significant short inter­actions: A Br1···Clⁱ contact of 3.4904 (18) Å and a Br3···Nⁱⁱ contact of 3.187 (6) Å [symmetry codes: (i) -x+3/2, y-1/2, -z+3/2; (ii) x-1/2, -y+3/2, z-1/2], both are significantly shorter than the sum of their van der Waals radii [1.85 Å for Br; 1.75 Å for Cl; 1.55 Å for N; PLATON (Spek, 2009)].

Figures

Fig. 1.

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

Fig. 2.

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.

Crystal data

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

Data collection

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

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

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

Cg2 is the centroid of the C4–C9 ring.

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

Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z+1.