5,7-Di­bromo-8-meth­oxy­quinoline

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

doi:10.1107/S2414314617006435

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 5| May 2017| x170643

https://doi.org/10.1107/S2414314617006435

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5,7-Dibromo-8-methoxyquinoline

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

^aDepartment of Physics, Faculty of Sciences, Cumhuriyet University, 58140 Sivas, Turkey, ^bDepartment of Maths and Science Education, Division of Science Education, Faculty of Education, Kırıkkale University, 71450, Yahşihan, Kırıkkale, Turkey, ^cDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^dDepartment of Physics, Faculty of Arts and Sciences, Sinop University, 57010 Sinop, 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 25 April 2017; accepted 28 April 2017; online 5 May 2017)

In the title compound, C₁₀H₇Br₂NO, the methoxy C atom deviates from the quinoline ring system (r.m.s deviation = 0.003 Å) by 1.204 (4) Å. In the crystal, C—H⋯O hydrogen bonds link the molecules into infinite chains along the b-axis direction. Aromatic π–π stacking interactions [centroid-to-centroid distance = 3.7659 (19) Å] are also observed.

Keywords: crystal structure; quinoline ring system; hydrogen bonds; π–π stacking interactions.

CCDC reference: 1546956

Structure description

The treatment of several dihalogenated quinoline derivatives with NaOMe in basic solutions afforded mono methoxide analogues (Politanskaya et al., 2005 ). Our own work has studied the bromination reactions of substituted quinolines (Ökten & Çakmak, 2015 ; Ökten et al., 2015 ). The present study presents the crystal structure of 5,7-dibromo-8-hydroxyquinoline.

In the title compound (Fig. 1), the Br—C bond lengths are 1.889 (3) and 1.901 (3) Å, and the Br—C—C bond angles vary from 117.6 (2) to 120.2 (2)°. The relatively wide range of Br—C—C angles may be due to the alternation of the bond-lengths in the bromine-substituted six-membered ring, which vary from 1.357 (4) to 1.425 (4) Å.

Figure 1
View of the title compound with displacement ellipsoids for non-H atoms drawn at the 50% probability level.

The packing of the title compound viewed down the b axis is shown in Fig. 2. The crystal structure features C—H⋯O hydrogen bonds, which lead to the formation of chains along the b-axis direction (Fig. 3 and Table 1). Furthermore, aromatic π–π stacking interactions [Cg1⋯Cg2(x, 1 + y, z) = 3.7659 (19) Å; Cg1 and Cg2 are the centroids of the N1/C1–C5 pyridine and C4–C9 benzene rings, respectively] in the [010] direction are also observed.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10C⋯O1ⁱ	0.96	2.48	3.418 (5)	166
Symmetry code: (i) x, y-1, z.

Figure 2
The packing of the title compound down the b axis.

Figure 3
View of the C—H⋯O hydrogen bonds along the b axis, shown down the a axis.

Synthesis and crystallization

5,7-Dibromoquinolin-8-ol (1.0 g, 3.3 mmol) was added to a solution of NaOH (132 mg, 3.3 mmol) in distilled water (100 ml). Me₂SO₄ (416 mg, 3.3 mmol) was added dropwise to the mixture at 263 K for 1 h while being stirred. The mixture was heated to 343–353 K for 1 h. After completion of the reaction (the colour of the mixture changed, 2 h), the solid was dissolved in CHCl₃ (50 ml). The organic layer was successively washed with 10% Na₂CO₃ (2 × 15 ml) and 10% NaOH (2 × 15 ml), dried over Na₂SO₄, and the solvent was removed under vacuum. The crude material (2.12 g) was passed through a short alumina column and eluted with EtOAc–hexane (1:6, 150 ml) to obtain the title compound (1 g, 95%) as colourless needles, m.p. 372–375 K. ¹H NMR (400 MHz, CDCl₃): (δ/p.p.m.): 9.00 (dd, J₂₃ = 3.2 Hz, J₂₄ = 1.6 Hz, 1H, H-2), 8.52 (dd, 1H, H-4, J₄₃ = 8 Hz, J₄₂ = 1.6 Hz), 8.02 (s, 1H, H-6) 7.58 (dd, 1H, H-3, J₃₄= 8.4 Hz, J₃₂ = 3.2 Hz), 4.19 (s, 3H, OCH₃); ¹³C NMR (100 MHz, CDCl₃) (δ/p.p.m.): 153.3, 150.9, 143.8, 136.1, 133.7, 128.3, 122.5, 116.3, 116.5, 62.1 (OCH₃); IR (ν/cm⁻¹): 2919, 2850, 1733, 1600, 1578, 1490, 1462, 1383, 1370, 1353, 1086.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₇Br₂NO
M_r	316.99
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	16.158 (3), 3.9960 (6), 17.551 (3)
β (°)	115.316 (5)
V (Å³)	1024.4 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	7.88
Crystal size (mm)	0.11 × 0.07 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007 )
T_min, T_max	0.603, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	16733, 2048, 1604
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.623

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.059, 1.03
No. of reflections	2048
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.51
Computer programs: APEX2 and SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2003 ).

Structural data

CCDC reference: 1546956

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617006435/hb4142sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617006435/hb4142Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617006435/hb4142Isup3.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, 2003).

5,7-Dibromo-8-methoxyquinoline top

Crystal data top

C₁₀H₇Br₂NO	F(000) = 608
M_r = 316.99	D_x = 2.055 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.158 (3) Å	Cell parameters from 5051 reflections
b = 3.9960 (6) Å	θ = 3.4–25.1°
c = 17.551 (3) Å	µ = 7.88 mm⁻¹
β = 115.316 (5)°	T = 296 K
V = 1024.4 (3) Å³	Needle, colourless
Z = 4	0.11 × 0.07 × 0.05 mm

Data collection top

Bruker APEXII CCD diffractometer	1604 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.052
Absorption correction: multi-scan (SADABS; Bruker, 2007)	θ_max = 26.3°, θ_min = 3.4°
T_min = 0.603, T_max = 0.745	h = −20→19
16733 measured reflections	k = −4→4
2048 independent reflections	l = −21→21

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.028	H-atom parameters constrained
wR(F²) = 0.059	w = 1/[σ²(F_o²) + (0.0218P)² + 1.0875P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
2048 reflections	Δρ_max = 0.55 e Å⁻³
127 parameters	Δρ_min = −0.51 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	0.1048 (2)	0.9036 (9)	0.4918 (2)	0.0462 (9)
H1	0.049584	1.009212	0.459273	0.055*
C2	0.1639 (2)	0.8352 (9)	0.4542 (2)	0.0462 (9)
H2	0.147908	0.895425	0.398488	0.055*
C3	0.2447 (2)	0.6799 (8)	0.5000 (2)	0.0378 (8)
H3	0.284548	0.632227	0.475841	0.045*
C4	0.2681 (2)	0.5908 (7)	0.58455 (18)	0.0291 (7)
C5	0.2035 (2)	0.6703 (7)	0.61719 (19)	0.0303 (7)
C6	0.2236 (2)	0.5909 (7)	0.70229 (19)	0.0310 (7)
C7	0.3056 (2)	0.4440 (8)	0.75154 (18)	0.0319 (7)
C8	0.3698 (2)	0.3624 (7)	0.72035 (19)	0.0325 (7)
H8	0.425118	0.262233	0.755195	0.039*
C9	0.3503 (2)	0.4313 (7)	0.63871 (19)	0.0296 (7)
C10	0.0821 (3)	0.4740 (10)	0.7055 (3)	0.0544 (10)
H10A	0.043928	0.547100	0.731777	0.082*
H10B	0.049547	0.498501	0.645482	0.082*
H10C	0.098083	0.243169	0.719059	0.082*
N1	0.12264 (18)	0.8276 (7)	0.57021 (17)	0.0391 (7)
O1	0.16339 (15)	0.6720 (6)	0.73544 (14)	0.0417 (6)
BR1	0.33604 (3)	0.34441 (9)	0.86565 (2)	0.04622 (12)
BR2	0.43774 (2)	0.30825 (9)	0.59799 (2)	0.04253 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.038 (2)	0.053 (2)	0.037 (2)	0.0093 (17)	0.0060 (16)	0.0077 (17)
C2	0.044 (2)	0.059 (2)	0.0286 (18)	0.0025 (18)	0.0091 (16)	0.0056 (17)
C3	0.0425 (19)	0.0418 (19)	0.0315 (17)	−0.0029 (16)	0.0180 (15)	−0.0033 (15)
C4	0.0312 (17)	0.0264 (16)	0.0299 (16)	−0.0036 (13)	0.0133 (14)	−0.0053 (12)
C5	0.0294 (17)	0.0296 (16)	0.0303 (16)	−0.0028 (14)	0.0113 (14)	−0.0025 (13)
C6	0.0337 (17)	0.0314 (17)	0.0329 (17)	−0.0017 (13)	0.0189 (15)	−0.0057 (13)
C7	0.0399 (19)	0.0312 (17)	0.0262 (16)	−0.0016 (14)	0.0158 (14)	−0.0009 (13)
C8	0.0296 (17)	0.0302 (17)	0.0351 (18)	0.0031 (13)	0.0113 (15)	0.0015 (13)
C9	0.0310 (17)	0.0290 (16)	0.0340 (17)	−0.0020 (13)	0.0190 (14)	−0.0037 (13)
C10	0.047 (2)	0.058 (2)	0.071 (3)	−0.0053 (19)	0.038 (2)	−0.007 (2)
N1	0.0311 (15)	0.0442 (17)	0.0384 (16)	0.0068 (13)	0.0113 (13)	0.0025 (13)
O1	0.0409 (13)	0.0489 (14)	0.0437 (14)	0.0024 (11)	0.0261 (11)	−0.0078 (11)
BR1	0.0589 (2)	0.0512 (2)	0.03332 (19)	0.00706 (18)	0.02425 (17)	0.00917 (16)
BR2	0.0370 (2)	0.0521 (2)	0.0452 (2)	0.00375 (16)	0.02407 (16)	−0.00531 (16)

Geometric parameters (Å, º) top

C1—N1	1.316 (4)	C6—C7	1.367 (4)
C1—C2	1.399 (5)	C6—O1	1.368 (3)
C1—H1	0.9300	C7—C8	1.403 (4)
C2—C3	1.356 (5)	C7—BR1	1.889 (3)
C2—H2	0.9300	C8—C9	1.357 (4)
C3—C4	1.411 (4)	C8—H8	0.9300
C3—H3	0.9300	C9—BR2	1.901 (3)
C4—C9	1.411 (4)	C10—O1	1.428 (4)
C4—C5	1.425 (4)	C10—H10A	0.9600
C5—N1	1.364 (4)	C10—H10B	0.9600
C5—C6	1.422 (4)	C10—H10C	0.9600

N1—C1—C2	124.0 (3)	C6—C7—C8	122.1 (3)
N1—C1—H1	118.0	C6—C7—BR1	120.2 (2)
C2—C1—H1	118.0	C8—C7—BR1	117.6 (2)
C3—C2—C1	119.2 (3)	C9—C8—C7	119.2 (3)
C3—C2—H2	120.4	C9—C8—H8	120.4
C1—C2—H2	120.4	C7—C8—H8	120.4
C2—C3—C4	119.8 (3)	C8—C9—C4	122.0 (3)
C2—C3—H3	120.1	C8—C9—BR2	118.0 (2)
C4—C3—H3	120.1	C4—C9—BR2	120.0 (2)
C3—C4—C9	125.1 (3)	O1—C10—H10A	109.5
C3—C4—C5	116.9 (3)	O1—C10—H10B	109.5
C9—C4—C5	118.0 (3)	H10A—C10—H10B	109.5
N1—C5—C6	117.8 (3)	O1—C10—H10C	109.5
N1—C5—C4	122.5 (3)	H10A—C10—H10C	109.5
C6—C5—C4	119.7 (3)	H10B—C10—H10C	109.5
C7—C6—O1	120.4 (3)	C1—N1—C5	117.6 (3)
C7—C6—C5	118.9 (3)	C6—O1—C10	114.9 (3)
O1—C6—C5	120.6 (3)

N1—C1—C2—C3	0.3 (6)	C5—C6—C7—BR1	178.5 (2)
C1—C2—C3—C4	−0.2 (5)	C6—C7—C8—C9	0.1 (5)
C2—C3—C4—C9	−179.5 (3)	BR1—C7—C8—C9	−179.8 (2)
C2—C3—C4—C5	0.3 (5)	C7—C8—C9—C4	1.6 (5)
C3—C4—C5—N1	−0.5 (4)	C7—C8—C9—BR2	−178.6 (2)
C9—C4—C5—N1	179.3 (3)	C3—C4—C9—C8	177.8 (3)
C3—C4—C5—C6	−179.2 (3)	C5—C4—C9—C8	−1.9 (4)
C9—C4—C5—C6	0.6 (4)	C3—C4—C9—BR2	−1.9 (4)
N1—C5—C6—C7	−177.7 (3)	C5—C4—C9—BR2	178.3 (2)
C4—C5—C6—C7	1.0 (4)	C2—C1—N1—C5	−0.5 (5)
N1—C5—C6—O1	−0.3 (4)	C6—C5—N1—C1	179.3 (3)
C4—C5—C6—O1	178.5 (3)	C4—C5—N1—C1	0.6 (5)
O1—C6—C7—C8	−178.9 (3)	C7—C6—O1—C10	−110.4 (3)
C5—C6—C7—C8	−1.4 (5)	C5—C6—O1—C10	72.2 (4)
O1—C6—C7—BR1	1.0 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Br2	0.93	2.80	3.210 (3)	108
C10—H10B···N1	0.96	2.49	3.065 (6)	118
C10—H10C···O1ⁱ	0.96	2.48	3.418 (5)	166

Symmetry code: (i) x, y−1, z.

Acknowledgements

This work is supported by the Scientific Research Project Fund of Cumhuriyet University under the project number F-513. The authors are indebted to the X-ray laboratory of Sinop University Scientific and Technological Applied and Research Center, Sinop, Turkey, for use of the X-ray diffractometer.

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