organic compounds
5,7-Dibromo-8-methoxyquinoline
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
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.
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 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.
The packing of the title compound viewed down the b axis is shown in Fig. 2. The 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.
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 .
details are summarized in Table 2Structural data
CCDC reference: 1546956
https://doi.org/10.1107/S2414314617006435/hb4142sup1.cif
contains datablock I. DOI: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
Data collection: APEX2 (Bruker, 2007); cell
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).C10H7Br2NO | F(000) = 608 |
Mr = 316.99 | Dx = 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 |
Bruker APEXII CCD diffractometer | 1604 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.052 |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | θmax = 26.3°, θmin = 3.4° |
Tmin = 0.603, Tmax = 0.745 | h = −20→19 |
16733 measured reflections | k = −4→4 |
2048 independent reflections | l = −21→21 |
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(Fo2) + (0.0218P)2 + 1.0875P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
2048 reflections | Δρmax = 0.55 e Å−3 |
127 parameters | Δρmin = −0.51 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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) |
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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