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

Gayathri, K.; Mohan, P.S.; Howard, J.A.K.; Sparkes, H.A.

doi:10.1107/S2056989015008002

organic compounds

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Volume 71| Part 5| May 2015| Pages o354-o355

https://doi.org/10.1107/S2056989015008002

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

Kasirajan Gayathri,^a Palathurai S. Mohan,^a ^* Judith A. K. Howard ^b and Hazel A. Sparkes ^b,^c

^aDepartment of Chemistry, Bharathiar University, Coimbatore 641 046, Tamil Nadu, India, ^bDepartment of Chemistry, University of Durham, South Road, Durham DH1 3LE, England, and ^cUniveristy of Bristol, Department of Chemistry, Cantock's Close, Bristol BS8 1TS, England
^*Correspondence e-mail: psmohan59@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 18 March 2015; accepted 22 April 2015; online 30 April 2015)

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.

Keywords: crystal structure; quinoline; bromoquinolines; halogen–halogen contacts; Br⋯Cl contacts; Br⋯N contacts; C—H⋯Br hydrogen bonds; π–π interactions.

CCDC reference: 902598

1. 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 ).

2. Experimental

2.1. Crystal data

C₁₁H₇Br₃ClN
M_r = 428.36
Monoclinic, P 2₁ /n
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

2.2. Data collection

Oxford Diffraction Xcalibur Sapphire3 Gemini ultra diffractometer
Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.056, T_max = 0.153
8597 measured reflections
2259 independent reflections
1889 reflections with I > 2σ(I)
R_int = 0.029

2.3. Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 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

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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.

Supporting information

CCDC reference: 902598

Crystal structure: contains datablocks I, Global. DOI: https://doi.org/10.1107/S2056989015008002/su5096sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015008002/su5096Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015008002/su5096Isup3.cml

checkCIF report

Synthesis and crystallization top

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.

Refinement top

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.

Structural commentary top

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)].

Related literature top

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).

Structure description top

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

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).

Synthesis and crystallization top

Refinement details top

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); 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 (Sheldrick, 2015) and PLATON (Spek, 2009).

Figures top

	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.

3-Bromomethyl-2-chloro-6-(dibromomethyl)quinoline top

Crystal data top

C₁₁H₇Br₃ClN	F(000) = 808
M_r = 428.36	D_x = 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 top

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	R_int = 0.029
Detector resolution: 16.1511 pixels mm^-1	θ_max = 25.3°, θ_min = 2.4°
ω scans	h = −10→10
Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2010)	k = −11→11
T_min = 0.056, T_max = 0.153	l = −18→12
8597 measured reflections

Refinement top

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(F_o²) + (0.0713P)² + 10.6242P] where P = (F_o² + 2F_c²)/3
2259 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 1.65 e Å⁻³
0 restraints	Δρ_min = −1.19 e Å⁻³

Crystal data top

C₁₁H₇Br₃ClN	V = 1248.23 (11) Å³
M_r = 428.36	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.9042 (5) Å	µ = 9.88 mm⁻¹
b = 9.3375 (4) Å	T = 120 K
c = 15.5107 (7) Å	0.42 × 0.36 × 0.30 mm
β = 104.553 (5)°

Data collection top

Oxford Diffraction Xcalibur Sapphire3 Gemini ultra diffractometer	2259 independent reflections
Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2010)	1889 reflections with I > 2σ(I)
T_min = 0.056, T_max = 0.153	R_int = 0.029
8597 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0713P)² + 10.6242P] where P = (F_o² + 2F_c²)/3
2259 reflections	Δρ_max = 1.65 e Å⁻³
145 parameters	Δρ_min = −1.19 e Å⁻³

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
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 (Å²) top

	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) top

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) top

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.

Hydrogen-bond geometry (Å, º) top

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.

Acknowledgements

HAS is grateful to the Leverhulme Trust and Durham University for financial support.

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