5,7-Dibromo-2-methyl­quinolin-8-ol

Schmidt, N.; Schwarzer, A.; Weber, E.

doi:10.1107/S1600536811007434

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o794

doi:10.1107/S1600536811007434

Open

access

5,7-Dibromo-2-methylquinolin-8-ol

Nicole Schmidt,^a Anke Schwarzer ^a and Edwin Weber ^a ^*

^aInstitut für Organische Chemie, TU Bergakademie Freiberg, Leipziger Strasse 29, D-09596 Freiberg/Sachsen, Germany
^*Correspondence e-mail: edwin.weber@chemie.tu-freiberg.de

(Received 9 February 2011; accepted 27 February 2011; online 5 March 2011)

In the title compound, C₁₀H₇Br₂NO, the molecule possesses a planar geometry with an r.m.s deviation of 0.0383 Å for all non-H atoms. The crystal structure displays O—H⋯N and C—H⋯O hydrogen bonding, as well as Br⋯Br contacts [3.6284 (4) Å].

Related literature

For a review of hydroxyquinolines in supramolecular chemistry, see: Albrecht et al. (2008 ). Bei et al. (1997 ) report on group 4 metal alkyl complexes. The crystal structure of the parent 8-hydroxyquinoline is described by Banerjee & Saha (1986 ) and Roychowdhury et al. (1978 ). Choi & Chi (2004 ) used the title compound as the starting material for alkylamino-substituted quinoline-5,8-diones. For halogen interactions in molecular crystal structures, see: Awwadi et al. (2006 ); Brammer et al. (2001 ); Metrangolo et al. (2008 ).

Experimental

Crystal data

C₁₀H₇Br₂NO
M_r = 316.99
Monoclinic, C 2/c
a = 22.2221 (5) Å
b = 4.0479 (1) Å
c = 21.7221 (4) Å
β = 102.167 (1)°
V = 1910.07 (7) Å³
Z = 8
Mo Kα radiation
μ = 8.45 mm⁻¹
T = 93 K
0.40 × 0.24 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.133, T_max = 0.258
13437 measured reflections
1727 independent reflections
1629 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.017
wR(F²) = 0.046
S = 1.11
1727 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.84	1.92	2.707 (2)	157
C10—H10A⋯O1ⁱⁱ	0.98	2.52	3.342 (3)	141
Symmetry codes: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-1, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811007434/im2267sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811007434/im2267Isup2.hkl

checkCIF report

Comment top

The molecular shape of the title compound is best described by the planarity of the molecule (Fig. 1), expressed by the RMS deviation of all non-hydrogen fitted atoms being 0.0383 Å. Molecular dimers are formed by a conventional hydrogen bridge, O1—H1···N1 [d = 2.707 (2) Å, θ = 157°] (Fig. 2) that is also found in the structure of the parent 8-hydroxyquinoline (Banerjee & Saha, 1986). In addition, a C—H···O contact creates chains along the crystallographic b axis. Distances between adjacent aromatic planes of 4.1 Å indicate the absence of π stacking interactions. However, halogen interactions of type I mode (Awwadi et al. 2006) represented by the Br2···Br2 contact [d = 3.6284 (4) Å, θ₁ = θ₂ = 143.3°] connect the formed dimers. Considering analogous dimer formation in the parent 8-hydroxyquinoline, this particular halogen contact is largely attributable to crystal packing effects.

Related literature top

For a reviewed discussion of hydroxyquinolines in supramolecular chemistry, see: Albrecht et al. (2008). Bei et al. (1997) report on group 4 metal alkyl complexes. The crystal structure of the parent 8-hydroxyquinoline is decribed by Banerjee & Saha (1986) and Roychowdhury et al. (1978). Choi & Chi (2004) used the title compound as the starting material for alkylamino-substituted quinoline-5,8-diones. For halogen interactions in molecular crystal structures, see: Awwadi et al. (2006); Brammer et al. (2001); Metrangolo et al. (2008).

Experimental top

As described by Choi & Chi (2004), 5 ml of bromine in MeOH (50 ml) was added to a mixture of 8-hydroxy-2-methylquinoline (5.0 g, 31.4 mmol), NaHCO₃ (5 g) and MeOH (50 ml). After stirring for 5 min at room temperature, Na₂SO₃ (2.5 g) was added, and then the mixture was filtered and washed with H₂O (100 ml). The white solid was dried in vacuo to give the title compound as raw product (8.9 g, 89%). Recrystallization from boiling and slowly cooling to room temperature ethanol yielded single crystals suitable for X-ray crystallography.

Computing details top

Data collection: SMART (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: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Perspective view of (I), showing 50% probability displacementellipsoids for the non-H atoms.
	Fig. 2. View of the crystal packing of the title compound along the crystallographic b axis. C–H···O, O–H···N and Br···Br contacts are shown as broken lines.

5,7-Dibromo-2-methylquinolin-8-ol top

Crystal data top

C₁₀H₇Br₂NO	F(000) = 1216
M_r = 316.99	D_x = 2.205 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9610 reflections
a = 22.2221 (5) Å	θ = 2.4–29.2°
b = 4.0479 (1) Å	µ = 8.45 mm⁻¹
c = 21.7221 (4) Å	T = 93 K
β = 102.167 (1)°	Piece, colourless
V = 1910.07 (7) Å³	0.40 × 0.24 × 0.22 mm
Z = 8

Data collection top

Bruker SMART CCD area-detector diffractometer	1727 independent reflections
Radiation source: fine-focus sealed tube	1629 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 25.2°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −26→25
T_min = 0.133, T_max = 0.258	k = −4→4
13437 measured reflections	l = −26→26

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)] = 0.017	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.046	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0262P)² + 2.9807P] where P = (F_o² + 2F_c²)/3
1727 reflections	(Δ/σ)_max = 0.001
129 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.60 e Å⁻³

Crystal data top

C₁₀H₇Br₂NO	V = 1910.07 (7) Å³
M_r = 316.99	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 22.2221 (5) Å	µ = 8.45 mm⁻¹
b = 4.0479 (1) Å	T = 93 K
c = 21.7221 (4) Å	0.40 × 0.24 × 0.22 mm
β = 102.167 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1727 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1629 reflections with I > 2σ(I)
T_min = 0.133, T_max = 0.258	R_int = 0.025
13437 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.017	0 restraints
wR(F²) = 0.046	H-atom parameters constrained
S = 1.11	Δρ_max = 0.36 e Å⁻³
1727 reflections	Δρ_min = −0.60 e Å⁻³
129 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) 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
Br1	0.226304 (10)	0.34054 (6)	0.083369 (10)	0.02104 (8)
Br2	0.431764 (10)	1.01225 (5)	0.033388 (9)	0.02065 (8)
N1	0.42288 (8)	0.6326 (4)	0.26148 (8)	0.0151 (4)
O1	0.47717 (7)	0.9601 (4)	0.17443 (7)	0.0197 (3)
H1	0.5012	0.8441	0.2009	0.030*
C1	0.39566 (10)	0.4874 (5)	0.30307 (10)	0.0168 (4)
C2	0.33816 (10)	0.3287 (5)	0.28492 (10)	0.0198 (5)
H2	0.3204	0.2213	0.3157	0.024*
C3	0.30807 (10)	0.3291 (5)	0.22338 (10)	0.0186 (5)
H3	0.2693	0.2223	0.2111	0.022*
C4	0.33477 (10)	0.4888 (5)	0.17805 (10)	0.0144 (4)
C5	0.30664 (10)	0.5140 (5)	0.11344 (10)	0.0155 (4)
C6	0.33502 (10)	0.6709 (5)	0.07179 (10)	0.0174 (4)
H6	0.3154	0.6859	0.0286	0.021*
C7	0.39324 (10)	0.8094 (5)	0.09334 (10)	0.0150 (4)
C8	0.42345 (10)	0.8007 (5)	0.15583 (10)	0.0145 (4)
C9	0.39347 (10)	0.6360 (5)	0.19921 (9)	0.0137 (4)
C10	0.42720 (11)	0.4996 (6)	0.37143 (10)	0.0224 (5)
H10A	0.4668	0.3840	0.3774	0.034*
H10B	0.4012	0.3923	0.3968	0.034*
H10C	0.4342	0.7303	0.3847	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01485 (13)	0.02683 (14)	0.02053 (13)	−0.00403 (8)	0.00170 (9)	−0.00389 (8)
Br2	0.02015 (14)	0.02857 (14)	0.01417 (13)	−0.00252 (9)	0.00577 (9)	0.00366 (8)
N1	0.0131 (9)	0.0189 (9)	0.0133 (8)	0.0042 (7)	0.0024 (7)	0.0016 (7)
O1	0.0130 (8)	0.0279 (9)	0.0169 (8)	−0.0037 (6)	0.0001 (6)	0.0048 (6)
C1	0.0168 (11)	0.0181 (11)	0.0160 (10)	0.0068 (8)	0.0048 (9)	0.0025 (8)
C2	0.0196 (12)	0.0220 (12)	0.0198 (11)	0.0029 (9)	0.0088 (9)	0.0040 (9)
C3	0.0142 (11)	0.0193 (11)	0.0233 (11)	0.0004 (8)	0.0063 (9)	0.0011 (9)
C4	0.0124 (11)	0.0144 (10)	0.0172 (11)	0.0037 (8)	0.0045 (8)	−0.0007 (8)
C5	0.0114 (10)	0.0159 (10)	0.0187 (10)	0.0005 (8)	0.0021 (8)	−0.0027 (8)
C6	0.0174 (11)	0.0210 (11)	0.0133 (10)	0.0041 (9)	0.0022 (8)	−0.0015 (8)
C7	0.0157 (11)	0.0168 (10)	0.0143 (10)	0.0023 (8)	0.0071 (8)	0.0017 (8)
C8	0.0113 (10)	0.0153 (10)	0.0174 (10)	0.0032 (8)	0.0039 (8)	0.0003 (8)
C9	0.0131 (11)	0.0152 (10)	0.0130 (10)	0.0043 (8)	0.0030 (8)	−0.0011 (8)
C10	0.0236 (13)	0.0286 (13)	0.0152 (11)	0.0026 (9)	0.0047 (9)	0.0035 (9)

Geometric parameters (Å, º) top

Br1—C5	1.901 (2)	C3—H3	0.9500
Br2—C7	1.890 (2)	C4—C5	1.415 (3)
N1—C1	1.326 (3)	C4—C9	1.420 (3)
N1—C9	1.373 (3)	C5—C6	1.364 (3)
O1—C8	1.342 (3)	C6—C7	1.397 (3)
O1—H1	0.8400	C6—H6	0.9500
C1—C2	1.410 (3)	C7—C8	1.382 (3)
C1—C10	1.503 (3)	C8—C9	1.429 (3)
C2—C3	1.363 (3)	C10—H10A	0.9800
C2—H2	0.9500	C10—H10B	0.9800
C3—C4	1.409 (3)	C10—H10C	0.9800

C1—N1—C9	119.01 (18)	C5—C6—H6	120.3
C8—O1—H1	109.5	C7—C6—H6	120.3
N1—C1—C2	121.88 (19)	C8—C7—C6	122.87 (19)
N1—C1—C10	118.3 (2)	C8—C7—Br2	119.40 (16)
C2—C1—C10	119.8 (2)	C6—C7—Br2	117.73 (15)
C3—C2—C1	120.1 (2)	O1—C8—C7	120.03 (19)
C3—C2—H2	119.9	O1—C8—C9	122.33 (18)
C1—C2—H2	119.9	C7—C8—C9	117.52 (19)
C2—C3—C4	119.6 (2)	N1—C9—C4	121.94 (19)
C2—C3—H3	120.2	N1—C9—C8	117.59 (18)
C4—C3—H3	120.2	C4—C9—C8	120.45 (18)
C3—C4—C5	124.3 (2)	C1—C10—H10A	109.5
C3—C4—C9	117.38 (19)	C1—C10—H10B	109.5
C5—C4—C9	118.34 (19)	H10A—C10—H10B	109.5
C6—C5—C4	121.5 (2)	C1—C10—H10C	109.5
C6—C5—Br1	118.43 (16)	H10A—C10—H10C	109.5
C4—C5—Br1	120.05 (16)	H10B—C10—H10C	109.5
C5—C6—C7	119.32 (19)

C9—N1—C1—C2	1.8 (3)	C6—C7—C8—O1	−174.87 (19)
C9—N1—C1—C10	−177.25 (18)	Br2—C7—C8—O1	5.8 (3)
N1—C1—C2—C3	−1.8 (3)	C6—C7—C8—C9	1.2 (3)
C10—C1—C2—C3	177.2 (2)	Br2—C7—C8—C9	−178.10 (15)
C1—C2—C3—C4	0.0 (3)	C1—N1—C9—C4	0.0 (3)
C2—C3—C4—C5	−177.7 (2)	C1—N1—C9—C8	178.67 (18)
C2—C3—C4—C9	1.6 (3)	C3—C4—C9—N1	−1.7 (3)
C3—C4—C5—C6	−179.7 (2)	C5—C4—C9—N1	177.67 (18)
C9—C4—C5—C6	1.0 (3)	C3—C4—C9—C8	179.69 (19)
C3—C4—C5—Br1	2.5 (3)	C5—C4—C9—C8	−1.0 (3)
C9—C4—C5—Br1	−176.86 (14)	O1—C8—C9—N1	−2.8 (3)
C4—C5—C6—C7	0.1 (3)	C7—C8—C9—N1	−178.78 (18)
Br1—C5—C6—C7	177.96 (15)	O1—C8—C9—C4	175.90 (18)
C5—C6—C7—C8	−1.3 (3)	C7—C8—C9—C4	−0.1 (3)
C5—C6—C7—Br2	178.09 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.84	1.92	2.707 (2)	157
C10—H10A···O1ⁱⁱ	0.98	2.52	3.342 (3)	141

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1, y−1, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₇Br₂NO
M_r	316.99
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	93
a, b, c (Å)	22.2221 (5), 4.0479 (1), 21.7221 (4)
β (°)	102.167 (1)
V (Å³)	1910.07 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	8.45
Crystal size (mm)	0.40 × 0.24 × 0.22

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.133, 0.258
No. of measured, independent and observed [I > 2σ(I)] reflections	13437, 1727, 1629
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.017, 0.046, 1.11
No. of reflections	1727
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.60

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.84	1.92	2.707 (2)	157
C10—H10A···O1ⁱⁱ	0.98	2.52	3.342 (3)	141

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1, y−1, −z+1/2.

References

Albrecht, M., Fiege, M. & Osetska, O. (2008). Coord. Chem. Rev. 252, 812–824. Web of Science CrossRef CAS Google Scholar
Awwadi, F. F., Willett, R. D., Peterson, K. A. & Twamley, B. (2006). Chem. Eur. J. 12, 8952–8960. Web of Science CrossRef PubMed CAS Google Scholar
Banerjee, T. & Saha, N. N. (1986). Acta Cryst. C42, 1408–1411. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Bei, X., Swenson, D. C. & Jordan, R. F. (1997). Organometallics, 16, 3282–3302. CSD CrossRef CAS Web of Science Google Scholar
Brammer, L., Bruton, E. A. & Sherwood, P. (2001). Cryst. Growth Des. 1, 277–290. Web of Science CrossRef CAS Google Scholar
Bruker (2007). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Choi, H. Y. & Chi, D. Y. (2004). Tetrahedron, 60, 4945–4951. CrossRef CAS Google Scholar
Metrangolo, P., Resnati, G., Pilati, T. & Biella, S. (2008). Halogen Bonding, Structure and Bonding, Vol. 126, edited by P. Metrangolo & G. Resnati, pp. 105–136. Berlin, Heidelberg: Springer. Google Scholar
Roychowdhury, P., Das, B. N. & Basak, B. S. (1978). Acta Cryst. B34, 1047–1048. CSD CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o794

doi:10.1107/S1600536811007434

Open

access