6-Bromo­quinoline-8-carbo­nitrile

Çelik, Í.; Akkurt, M.; Ökten, S.; Çakmak, O.; Ersanlı, C.C.

doi:10.1107/S2414314617009300

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 7| July 2017| x170930

https://doi.org/10.1107/S2414314617009300

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6-Bromoquinoline-8-carbonitrile

Ísmail Çelik,^a Mehmet Akkurt,^b ^* Salih Ökten,^c Osman Çakmak ^d and Cem Cüneyt Ersanlı ^e

^aDepartment of Physics, Faculty of Sciences, Cumhuriyet University, 58140 Sivas, Turkey, ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^cDepartment of Maths and Science Education, Division of Science Education, Faculty of Education, Kırıkkale University, 71450, Yahşihan, Kırıkkale, Turkey, ^dDepartment of Nutrition and Dietetics, School of Health Sciences, İstanbul Gelişim University, 34315 Avcılar, İstanbul, Turkey, and ^eDepartment of Physics, Faculty of Arts and Sciences, Sinop University, 57010 Sinop, Turkey
^*Correspondence e-mail: akkurt@erciyes.edu.tr

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 11 June 2017; accepted 20 June 2017; online 7 July 2017)

In the title compound, C₁₀H₅BrN₂, the whole molecule is essentially planar (r.m.s. deviation = 0.005 Å). The crystal packing features face-to-face π–π stacking interactions [centroid–centroid distance = 3.755 (3) Å] between the pyridine and benzene rings of the quinoline ring systems of adjacent molecules, along the a-axis direction. Short Br⋯Br contacts of 3.5908 (12) Å (compared to a van der Waals separation of 3.70 Å) are also observed.

Keywords: crystal structure; quinoline ring; π–π stacking interactions; synthesis.

CCDC reference: 1557337

Structure description

The asymmetric syntheses of 2-cyano-substituted dihydro and tetrahydroquinolines have been achieved using the Reissert reaction (Pauvert et al., 2005 ) while 8-cyano substituted quinolines have been prepared by the treatment of cyano substituted aniline with several ketones in polar solvents (Ekiz et al., 2016 ). As the cyclization methods using cyano-substituted benzene or cyclohexane allow only the synthesis of mono cyano-substituted quinolines, the synthesis of two or more cyano-substituted quinolines has been limited (Ökten & Çakmak, 2015 ). As part of our studies in this area, the crystal structure of the title compound is now reported.

The title molecule (Fig. 1) is essentially planar, with a maximum deviation of 0.063 (1) Å for atom Br1. All bond lengths and angles are in normal ranges and are comparable with those reported for similar compounds: 2-chloro-8-methyl-3-[(pyrimidin-4-yloxy)methyl]quinoline (Khan et al., 2010 ), 6,8-dibromoquinoline (Çelik et al., 2010a ), 3,6,8-tribromoquinoline (Çelik et al., 2010b ) and 5,7-dibromo-8-methoxyquinoline (Çelik et al., 2017 ).

Figure 1
View of the title compound, with displacement ellipsoids drawn at the 50% probability level.

In the crystal, the packing features face-to-face π–π stacking interactions [Cg1⋯Cg2ⁱ = 3.755 (3) Å; symmetry code: (i) −1 + x, y, z] between the pyridine (N1/C1–C4/C9; centroid Cg1) and benzene (C4–C9; centroid Cg2) rings of the quinoline ring systems of adjacent molecules, along the a-axis direction. Short Br⋯Br contacts [3.5908 (12) Å compared to a van der Waals separation of 3.70 Å] are also observed. The packing viewed down the a-axis direction is shown in Fig. 2.

Figure 2
View of the packing of the title compound down the a axis.

Synthesis and crystallization

The title compound was prepared according to the reported method (Ökten et al., 2013 ). Colourless prisms were obtained by recrystallization from mixed solvents of AcOEt/hexane (1:2).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₁₀H₅BrN₂
M_r	233.07
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	3.8484 (8), 12.634 (3), 18.042 (4)
β (°)	92.918 (7)
V (Å³)	876.0 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	4.64
Crystal size (mm)	0.15 × 0.12 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003 )
T_min, T_max	0.565, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	26227, 2203, 1501
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.672

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.120, 1.22
No. of reflections	2203
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.61
Computer programs: APEX2 and SAINT (Bruker, 2007 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP3for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1557337

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617009300/hb4153sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617009300/hb4153Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617009300/hb4153Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP3for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

6-Bromoquinoline-8-carbonitrile top

Crystal data top

C₁₀H₅BrN₂	F(000) = 456
M_r = 233.07	D_x = 1.767 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 3.8484 (8) Å	Cell parameters from 9362 reflections
b = 12.634 (3) Å	θ = 3.2–25.3°
c = 18.042 (4) Å	µ = 4.64 mm⁻¹
β = 92.918 (7)°	T = 296 K
V = 876.0 (3) Å³	Prism, colourless
Z = 4	0.15 × 0.12 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	1501 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.073
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	θ_max = 28.5°, θ_min = 3.2°
T_min = 0.565, T_max = 0.746	h = −4→5
26227 measured reflections	k = −16→16
2203 independent reflections	l = −24→24

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.058	H-atom parameters constrained
wR(F²) = 0.120	w = 1/[σ²(F_o²) + (0.0088P)² + 3.5104P] where P = (F_o² + 2F_c²)/3
S = 1.22	(Δ/σ)_max < 0.001
2203 reflections	Δρ_max = 0.53 e Å⁻³
118 parameters	Δρ_min = −0.61 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
C1	0.0305 (16)	0.4253 (5)	0.8151 (3)	0.0491 (15)
H1	−0.0601	0.4759	0.8462	0.059*
C2	0.1004 (16)	0.3254 (5)	0.8451 (3)	0.0482 (15)
H2	0.0526	0.3104	0.8940	0.058*
C3	0.2403 (15)	0.2500 (5)	0.8014 (3)	0.0449 (14)
H3	0.2927	0.1832	0.8206	0.054*
C4	0.3047 (14)	0.2741 (4)	0.7272 (3)	0.0346 (11)
C5	0.4372 (14)	0.1998 (4)	0.6781 (3)	0.0375 (12)
H5	0.4966	0.1322	0.6948	0.045*
C6	0.4792 (14)	0.2268 (4)	0.6057 (3)	0.0339 (11)
C7	0.3995 (14)	0.3287 (4)	0.5793 (3)	0.0371 (12)
H7	0.4317	0.3460	0.5300	0.045*
C8	0.2738 (14)	0.4027 (4)	0.6266 (3)	0.0337 (11)
C9	0.2174 (13)	0.3781 (4)	0.7021 (2)	0.0332 (10)
C10	0.1862 (16)	0.5105 (5)	0.5988 (3)	0.0438 (14)
N1	0.0822 (12)	0.4542 (4)	0.7461 (2)	0.0412 (11)
N2	0.1305 (16)	0.5879 (4)	0.5762 (3)	0.0606 (15)
Br1	0.63809 (18)	0.12498 (5)	0.53862 (3)	0.0525 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.052 (4)	0.058 (4)	0.038 (3)	−0.006 (3)	0.006 (3)	−0.015 (3)
C2	0.049 (4)	0.068 (4)	0.028 (3)	−0.008 (3)	0.006 (2)	−0.003 (3)
C3	0.049 (4)	0.050 (3)	0.035 (3)	−0.003 (3)	0.002 (2)	0.008 (2)
C4	0.035 (3)	0.036 (3)	0.031 (2)	−0.005 (2)	−0.004 (2)	0.000 (2)
C5	0.039 (3)	0.033 (3)	0.040 (3)	−0.002 (2)	0.001 (2)	0.002 (2)
C6	0.033 (3)	0.033 (3)	0.035 (2)	−0.002 (2)	0.001 (2)	−0.003 (2)
C7	0.037 (3)	0.043 (3)	0.031 (2)	−0.001 (2)	0.003 (2)	0.001 (2)
C8	0.037 (3)	0.030 (3)	0.034 (2)	−0.004 (2)	−0.004 (2)	0.0005 (19)
C9	0.036 (3)	0.033 (2)	0.031 (2)	−0.003 (2)	0.0006 (19)	−0.002 (2)
C10	0.056 (4)	0.047 (3)	0.029 (2)	0.002 (3)	0.007 (2)	−0.001 (2)
N1	0.043 (3)	0.043 (3)	0.038 (2)	−0.004 (2)	0.004 (2)	−0.0097 (19)
N2	0.085 (5)	0.047 (3)	0.051 (3)	0.010 (3)	0.011 (3)	−0.001 (2)
Br1	0.0572 (4)	0.0517 (4)	0.0490 (3)	0.0076 (3)	0.0052 (2)	−0.0145 (3)

Geometric parameters (Å, º) top

C1—N1	1.321 (7)	C5—H5	0.9300
C1—C2	1.394 (8)	C6—C7	1.401 (7)
C1—H1	0.9300	C6—Br1	1.889 (5)
C2—C3	1.364 (8)	C7—C8	1.371 (7)
C2—H2	0.9300	C7—H7	0.9300
C3—C4	1.408 (7)	C8—C9	1.425 (6)
C3—H3	0.9300	C8—C10	1.484 (7)
C4—C5	1.404 (7)	C9—N1	1.366 (6)
C4—C9	1.425 (7)	C10—N2	1.077 (7)
C5—C6	1.368 (7)

N1—C1—C2	125.5 (5)	C5—C6—C7	121.3 (5)
N1—C1—H1	117.3	C5—C6—Br1	120.0 (4)
C2—C1—H1	117.3	C7—C6—Br1	118.7 (4)
C3—C2—C1	118.8 (5)	C8—C7—C6	119.5 (4)
C3—C2—H2	120.6	C8—C7—H7	120.2
C1—C2—H2	120.6	C6—C7—H7	120.2
C2—C3—C4	119.5 (5)	C7—C8—C9	121.5 (4)
C2—C3—H3	120.3	C7—C8—C10	119.8 (4)
C4—C3—H3	120.3	C9—C8—C10	118.7 (4)
C5—C4—C3	122.9 (5)	N1—C9—C8	118.9 (4)
C5—C4—C9	120.2 (4)	N1—C9—C4	123.7 (4)
C3—C4—C9	116.8 (5)	C8—C9—C4	117.4 (4)
C6—C5—C4	120.0 (5)	N2—C10—C8	177.0 (6)
C6—C5—H5	120.0	C1—N1—C9	115.7 (5)
C4—C5—H5	120.0

N1—C1—C2—C3	1.4 (10)	C7—C8—C9—N1	−178.1 (5)
C1—C2—C3—C4	−1.1 (9)	C10—C8—C9—N1	0.5 (7)
C2—C3—C4—C5	−177.9 (5)	C7—C8—C9—C4	1.5 (8)
C2—C3—C4—C9	0.0 (8)	C10—C8—C9—C4	−179.9 (5)
C3—C4—C5—C6	177.0 (5)	C5—C4—C9—N1	178.9 (5)
C9—C4—C5—C6	−0.8 (8)	C3—C4—C9—N1	1.0 (8)
C4—C5—C6—C7	1.5 (8)	C5—C4—C9—C8	−0.6 (7)
C4—C5—C6—Br1	−177.2 (4)	C3—C4—C9—C8	−178.6 (5)
C5—C6—C7—C8	−0.6 (8)	C2—C1—N1—C9	−0.4 (9)
Br1—C6—C7—C8	178.0 (4)	C8—C9—N1—C1	178.8 (5)
C6—C7—C8—C9	−0.9 (8)	C4—C9—N1—C1	−0.8 (8)
C6—C7—C8—C10	−179.5 (5)

Acknowledgements

The authors thank the X-ray Laboratory of Sinop University Scientific and Technological Applied and Research Center, Sinop, Turkey, for use of the X-ray diffractometer.

Funding information

This study was supported financially by grants from the Scientific and Technological Research Council of Turkey (TÜBİTAK, Project No. 112 T394).

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