6-Bromo-1,2,3,4-tetra­hydro­quinoline-8-carbo­nitrile

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

doi:10.1107/S241431461601854X

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 11| November 2016| x161854

https://doi.org/10.1107/S241431461601854X

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6-Bromo-1,2,3,4-tetrahydroquinoline-8-carbonitrile

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

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

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 18 November 2016; accepted 19 November 2016; online 25 November 2016)

In the title compound, C₁₀H₉BrN₂, one of the methylene groups of the piperidine ring is disordered over two sets of sites in a 0.692 (8):0.308 (8) ratio, which leads to two envelope conformations. In the crystal, inversion dimers linked by pairs of N—H⋯N hydrogen bonds generate R₂²(12) loops.

Keywords: crystal structure; quinoline; dimer; disorder.

CCDC reference: 1518057

Structure description

Cyano quinoline compounds can deactivate the action of growth factor receptor protein tyrocine kinases (Berger et al., 2008 ) and bind with biological systems (Fleming et al., 2010 ). As part of our ongoing synthetic and structural studies in this area (Ökten & Çakmak, 2015 ), we now describe the title compound (Fig. 1).

Figure 1
A view of the title compound, with displacement ellipsoids drawn at the 50% probability level. The minor component of the disorder is not shown.

The piperidine ring is disordered over two conformations in a 0.692 (8):0.308 (8) ratio. Both disorder components lead to an envelope conformation for the ring, with methylene atom C8 as the flap with it and its attached H atoms either above or below the plane of the other atoms.

In the crystal, inversion dimers linked by pairs of N—H⋯N hydrogen bonds (Table 1 and Fig. 2) generate $[R_{2}^{2}]$ (12) loops. Br⋯Br contacts [3.6394 (14) Å] just shorter than the van der Waals contact distance (3.70 Å) are also observed.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯N2ⁱ	0.85 (2)	2.29 (3)	3.075 (4)	153 (2)
Symmetry code: (i) -x+2, -y+2, -z+1.

Figure 2
A view down the b axis of the dimers linked by pairs of N—H⋯N hydrogen bonds (shown as dashed lines).

Synthesis and crystallization

6-Bromo-8-cyano-1,2,3,4-tetrahydroquinoline was prepared by the literature method (Ökten & Çakmak, 2015). Recrystallization from a CH₂Cl₂/hexane (2:1, 5 ml) solvent mixture gave colourless prisms.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The central carbon atom (C8) and its attached H atoms of the three methylene groups in the piperidine ring are positionally disordered over two sets of sites (C8A and C8B) in a 0.692 (8): 0.308 (8) ratio. The other two methylene C atoms (C6 and C7) in the piperidine ring are also refined as disordered and constrained with the EXYZ and EADP instructions to aid in the location of their attached H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₉BrN₂
M_r	237.09
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	14.189 (5), 5.0064 (14), 14.683 (5)
β (°)	113.008 (13)
V (Å³)	960.1 (5)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	4.23
Crystal size (mm)	0.19 × 0.15 × 0.14

Data collection
Diffractometer	Bruker APEXII CCD
No. of measured, independent and observed [I > 2σ(I)] reflections	35875, 2412, 1837
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.672

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.080, 1.10
No. of reflections	2412
No. of parameters	133
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.47
Computer programs: APEX2 and SAINT (Bruker, 2007 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1518057

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S241431461601854X/hb4099sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461601854X/hb4099Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431461601854X/hb4099Isup3.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: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

6-Bromo-1,2,3,4-tetrahydroquinoline-8-carbonitrile top

Crystal data top

C₁₀H₉BrN₂	F(000) = 472
M_r = 237.09	D_x = 1.640 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9423 reflections
a = 14.189 (5) Å	θ = 3.0–27.8°
b = 5.0064 (14) Å	µ = 4.23 mm⁻¹
c = 14.683 (5) Å	T = 296 K
β = 113.008 (13)°	Prism, colourless
V = 960.1 (5) Å³	0.19 × 0.15 × 0.14 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	R_int = 0.043
φ and ω scans	θ_max = 28.5°, θ_min = 3.0°
35875 measured reflections	h = −19→18
2412 independent reflections	k = −6→6
1837 reflections with I > 2σ(I)	l = −19→19

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.031	w = 1/[σ²(F_o²) + (0.0285P)² + 0.7134P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.080	(Δ/σ)_max = 0.001
S = 1.10	Δρ_max = 0.36 e Å⁻³
2412 reflections	Δρ_min = −0.47 e Å⁻³
133 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0135 (11)

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > 2sigma(F²) is used only for calculating -R-factor-obs 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Br1	0.61037 (2)	0.18750 (7)	0.58211 (2)	0.0649 (1)
N1	1.03058 (15)	0.6179 (5)	0.65068 (16)	0.0490 (7)
N2	0.86937 (18)	0.9940 (5)	0.44726 (18)	0.0611 (8)
C1	0.92333 (18)	0.3281 (4)	0.70001 (16)	0.0394 (7)
C2	0.82674 (19)	0.2339 (5)	0.68257 (17)	0.0446 (8)
C3	0.74161 (17)	0.3303 (5)	0.60479 (17)	0.0431 (7)
C4	0.75099 (17)	0.5260 (5)	0.54363 (16)	0.0426 (7)
C5	0.84797 (17)	0.6238 (5)	0.55964 (16)	0.0388 (7)
C6	0.93628 (16)	0.5253 (4)	0.63672 (15)	0.0373 (7)
C7A	1.12305 (19)	0.5279 (6)	0.7306 (2)	0.0585 (9)	0.692 (8)
C7B	1.12305 (19)	0.5279 (6)	0.7306 (2)	0.0585 (9)	0.308 (8)
C8A	1.0989 (3)	0.4295 (9)	0.8157 (3)	0.0525 (14)	0.692 (8)
C8B	1.1163 (6)	0.2658 (19)	0.7700 (7)	0.051 (3)	0.308 (8)
C9A	1.0160 (2)	0.2262 (6)	0.7852 (2)	0.0527 (8)	0.692 (8)
C9B	1.0160 (2)	0.2262 (6)	0.7852 (2)	0.0527 (8)	0.308 (8)
C10	0.85870 (18)	0.8300 (5)	0.49630 (18)	0.0447 (7)
H7A1	1.17160	0.67400	0.75250	0.0700*	0.692 (8)
H1N	1.037 (2)	0.731 (4)	0.6103 (17)	0.054 (8)*
H2	0.81840	0.10300	0.72380	0.0540*
H7A2	1.15410	0.38510	0.70720	0.0700*	0.692 (8)
H8A1	1.16030	0.35260	0.86540	0.0630*	0.692 (8)
H4	0.69340	0.59240	0.49220	0.0510*
H8A2	1.07860	0.57980	0.84560	0.0630*	0.692 (8)
H9A1	0.99750	0.18500	0.84060	0.0630*	0.692 (8)
H9A2	1.04010	0.06330	0.76580	0.0630*	0.692 (8)
H7B1	1.14110	0.65690	0.78400	0.0700*	0.308 (8)
H7B2	1.17820	0.52530	0.70710	0.0700*	0.308 (8)
H8B1	1.17370	0.24230	0.83280	0.0610*	0.308 (8)
H8B2	1.12130	0.13010	0.72490	0.0610*	0.308 (8)
H9B1	1.00690	0.03740	0.79430	0.0630*	0.308 (8)
H9B2	1.02110	0.31810	0.84510	0.0630*	0.308 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0467 (2)	0.0867 (3)	0.0617 (2)	−0.0181 (1)	0.0216 (1)	−0.0032 (2)
N1	0.0394 (10)	0.0536 (13)	0.0496 (12)	−0.0030 (9)	0.0125 (9)	0.0126 (10)
N2	0.0559 (13)	0.0667 (16)	0.0585 (14)	0.0000 (11)	0.0200 (11)	0.0202 (12)
C1	0.0435 (12)	0.0372 (12)	0.0339 (11)	0.0006 (9)	0.0114 (9)	−0.0004 (9)
C2	0.0499 (13)	0.0471 (14)	0.0375 (12)	−0.0058 (10)	0.0178 (10)	0.0019 (10)
C3	0.0385 (11)	0.0510 (14)	0.0406 (12)	−0.0074 (10)	0.0163 (9)	−0.0061 (11)
C4	0.0392 (11)	0.0488 (14)	0.0352 (11)	0.0017 (10)	0.0097 (9)	−0.0016 (10)
C5	0.0431 (12)	0.0387 (12)	0.0328 (10)	−0.0010 (9)	0.0128 (9)	−0.0001 (9)
C6	0.0406 (11)	0.0364 (12)	0.0331 (11)	−0.0009 (9)	0.0124 (9)	−0.0031 (9)
C7A	0.0393 (13)	0.0695 (19)	0.0601 (16)	0.0044 (12)	0.0122 (12)	0.0094 (14)
C7B	0.0393 (13)	0.0695 (19)	0.0601 (16)	0.0044 (12)	0.0122 (12)	0.0094 (14)
C8A	0.044 (2)	0.060 (3)	0.042 (2)	0.0004 (18)	0.0044 (16)	0.0050 (19)
C8B	0.042 (4)	0.059 (6)	0.046 (5)	0.006 (4)	0.010 (4)	0.006 (4)
C9A	0.0500 (14)	0.0538 (15)	0.0462 (13)	0.0050 (12)	0.0102 (11)	0.0093 (12)
C9B	0.0500 (14)	0.0538 (15)	0.0462 (13)	0.0050 (12)	0.0102 (11)	0.0093 (12)
C10	0.0400 (12)	0.0499 (14)	0.0395 (12)	0.0001 (10)	0.0105 (10)	0.0018 (11)

Geometric parameters (Å, º) top

Br1—C3	1.899 (3)	C8A—C9A	1.486 (5)
N1—C6	1.354 (3)	C8B—C9B	1.537 (10)
N1—C7A	1.448 (4)	C2—H2	0.9300
N1—C7B	1.448 (4)	C4—H4	0.9300
N2—C10	1.141 (4)	C7A—H7A1	0.9700
C1—C2	1.376 (4)	C7A—H7A2	0.9700
C1—C6	1.416 (3)	C7B—H7B1	0.9700
C1—C9A	1.506 (4)	C7B—H7B2	0.9700
C1—C9B	1.506 (4)	C8A—H8A1	0.9700
N1—H1N	0.85 (2)	C8A—H8A2	0.9700
C2—C3	1.385 (4)	C8B—H8B1	0.9700
C3—C4	1.370 (3)	C8B—H8B2	0.9700
C4—C5	1.391 (4)	C9A—H9A1	0.9700
C5—C10	1.437 (4)	C9A—H9A2	0.9700
C5—C6	1.409 (3)	C9B—H9B1	0.9700
C7A—C8A	1.502 (5)	C9B—H9B2	0.9700
C7B—C8B	1.452 (10)

C6—N1—C7A	123.0 (2)	C5—C4—H4	121.00
C6—N1—C7B	123.0 (2)	N1—C7A—H7A1	110.00
C2—C1—C6	119.5 (2)	N1—C7A—H7A2	110.00
C2—C1—C9A	121.4 (2)	C8A—C7A—H7A1	110.00
C2—C1—C9B	121.4 (2)	C8A—C7A—H7A2	110.00
C6—C1—C9A	119.1 (2)	H7A1—C7A—H7A2	108.00
C6—C1—C9B	119.1 (2)	H7B1—C7B—H7B2	108.00
C6—N1—H1N	119.4 (19)	N1—C7B—H7B2	108.00
C7A—N1—H1N	117.5 (19)	C8B—C7B—H7B1	109.00
C7B—N1—H1N	117.5 (19)	N1—C7B—H7B1	108.00
C1—C2—C3	121.2 (2)	C8B—C7B—H7B2	108.00
Br1—C3—C2	119.54 (19)	C7A—C8A—H8A2	109.00
Br1—C3—C4	119.61 (18)	C9A—C8A—H8A1	109.00
C2—C3—C4	120.9 (2)	C7A—C8A—H8A1	109.00
C3—C4—C5	118.9 (2)	H8A1—C8A—H8A2	108.00
C6—C5—C10	119.0 (2)	C9A—C8A—H8A2	109.00
C4—C5—C10	119.4 (2)	C7B—C8B—H8B2	109.00
C4—C5—C6	121.5 (2)	C7B—C8B—H8B1	109.00
N1—C6—C1	120.9 (2)	H8B1—C8B—H8B2	108.00
N1—C6—C5	121.2 (2)	C9B—C8B—H8B1	109.00
C1—C6—C5	117.9 (2)	C9B—C8B—H8B2	109.00
N1—C7A—C8A	110.3 (3)	C1—C9A—H9A2	110.00
N1—C7B—C8B	115.1 (4)	H9A1—C9A—H9A2	108.00
C7A—C8A—C9A	112.6 (3)	C8A—C9A—H9A1	110.00
C7B—C8B—C9B	112.5 (6)	C8A—C9A—H9A2	110.00
C1—C9A—C8A	110.5 (3)	C1—C9A—H9A1	110.00
C1—C9B—C8B	113.1 (4)	C1—C9B—H9B1	109.00
N2—C10—C5	178.6 (3)	C1—C9B—H9B2	109.00
C1—C2—H2	119.00	C8B—C9B—H9B1	109.00
C3—C2—H2	119.00	C8B—C9B—H9B2	109.00
C3—C4—H4	121.00	H9B1—C9B—H9B2	108.00

C7A—N1—C6—C1	−1.1 (4)	C1—C2—C3—C4	−1.0 (4)
C7A—N1—C6—C5	178.2 (2)	Br1—C3—C4—C5	−178.36 (18)
C6—N1—C7A—C8A	−25.7 (4)	C2—C3—C4—C5	1.2 (4)
C6—C1—C2—C3	−0.7 (4)	C3—C4—C5—C10	−179.7 (2)
C9A—C1—C2—C3	179.3 (2)	C3—C4—C5—C6	0.3 (4)
C2—C1—C6—N1	−178.6 (2)	C4—C5—C6—N1	178.7 (2)
C2—C1—C9A—C8A	−154.6 (3)	C4—C5—C6—C1	−2.0 (3)
C6—C1—C9A—C8A	25.3 (3)	C10—C5—C6—N1	−1.3 (3)
C2—C1—C6—C5	2.1 (3)	C10—C5—C6—C1	178.1 (2)
C9A—C1—C6—N1	1.5 (3)	N1—C7A—C8A—C9A	52.7 (4)
C9A—C1—C6—C5	−177.9 (2)	C7A—C8A—C9A—C1	−52.4 (4)
C1—C2—C3—Br1	178.54 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N2ⁱ	0.85 (2)	2.29 (3)	3.075 (4)	153 (2)

Symmetry code: (i) −x+2, −y+2, −z+1.

Acknowledgements

This study was supported financially by grants from the Scientific and Technological Research Council of Turkey (TÜBİTAK, project No. 112 T394). The authors acknowledge the Scientific and Technological Research Application and Research Center, Sinop University, Turkey, for the use of the Bruker D8 QUEST diffractometer.

References

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