2,4-Dibromo­naphthalen-1-ol

Raza, A.R.; Sultan, A.; Tahir, M.N.

doi:10.1107/S160053681103011X

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2199

doi:10.1107/S160053681103011X

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2,4-Dibromonaphthalen-1-ol

Abdul Rauf Raza,^a Aeysha Sultan ^a and M. Nawaz Tahir ^b ^*

^aUniversity of Sargodha, Department of Chemistry, Sargodha, Pakistan, and ^bUniversity of Sargodha, Department of Physics, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 25 July 2011; accepted 26 July 2011; online 30 July 2011)

In the essentially planar (r.m.s. deviation = 0.023 Å) title compound, C₁₀H₆Br₂O, an intramolecular O—H⋯Br hydrogen bond generates an S(5) ring. In the crystal, molecules are linked by an ⋯O—H⋯O—H⋯O— C(2) chain extending along [100], which involves the same H atom that participates in the intramolecular hydrogen bond. Aromatic π–π interactions [centroid–centroid separation = 3.737 (4) Å] help to consolidate the packing.

Related literature

For a related structure, see: Chanh et al. (1973 ): For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₀H₆Br₂O
M_r = 301.97
Orthorhombic, P 2₁ 2₁ 2₁
a = 4.1225 (3) Å
b = 14.4441 (11) Å
c = 16.0490 (14) Å
V = 955.65 (13) Å³
Z = 4
Mo Kα radiation
μ = 8.44 mm⁻¹
T = 296 K
0.32 × 0.14 × 0.12 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.254, T_max = 0.365
5060 measured reflections
2239 independent reflections
1410 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.089
S = 0.96
2239 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.41 e Å⁻³
Absolute structure: Flack (1983 ), 863 Friedel pairs
Flack parameter: −0.01 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯Br1	0.82	2.60	3.107 (5)	122
O1—H1⋯O1ⁱ	0.82	2.21	2.893 (6)	141
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681103011X/hb6335sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681103011X/hb6335Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681103011X/hb6335Isup3.cml

checkCIF report

Comment top

The crystal structure of 2-bromonaphthalene (Chanh, et al., 1973) has been published which is related to the title compound (Fig. 1).

The molecule of the title compound is planar with r.m.s. deviation of 0.0234 Å. The Br2 atom has maximum deviation from the mean plane and its value is 0.0574 (27) Å. There exists an intra-molecular hydrogen bond of O—H···Br type (Table 1, Fig. 1) and complete S(5) ring motif (Bernstein et al., 1995). The molecules are stabilized in the form of polymeric chains due to intermolecular H-bonding of O—H···O type (Table 1, Fig. 2). Due to these hydrogen bonds a chain of ···O—H···O—H···O— exists. The π–π interactions between the benzene rings (C1—C6) and (C1/C6—C10) of the naphthalen group at a distance of 3.737 (4) Å help to consolidate the packing.

Related literature top

For a related crystal structure, see: Chanh et al. (1973): For graph-set notation, see: Bernstein et al. (1995).

Experimental top

Bromine (2.9 ml, 9.2 g, 30 mmol, 2 eq) was added as drops to an ice-chilled solution of α,β-unsaturated-1-tetralone (2.2 g, 15 mmol, 1 eq) in CHCl₃ (50 ml) and was stirred for 1 h. Et₃N (3 ml, 2.2 g, 22 mmol, 1.5 eq) was added to the reaction mixture followed by 2 h stirring at room temperature. After the commencement of reaction, the reaction mixture was neutralized with aq HCl (15 ml). The organic layer was washed with H₂O (3 × 25 ml), dried over anhydrous Na₂SO₄ and concentrated under reduced pressure to afford the colorless needles of (I).

Yield: 2.4 g, 52%, m.p. 499 K.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title compound with displacement ellipsoids drawn at the 50% probability level. The dotted line indicates the intramolecular H-bond.
	Fig. 2. The partial packing of (I), which shows that molecules form polymeric chains.

2,4-Dibromonaphthalen-1-ol top

Crystal data top

C₁₀H₆Br₂O	F(000) = 576
M_r = 301.97	D_x = 2.099 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1410 reflections
a = 4.1225 (3) Å	θ = 2.8–27.9°
b = 14.4441 (11) Å	µ = 8.44 mm⁻¹
c = 16.0490 (14) Å	T = 296 K
V = 955.65 (13) Å³	Needle, colorless
Z = 4	0.32 × 0.14 × 0.12 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2239 independent reflections
Radiation source: fine-focus sealed tube	1410 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 7.60 pixels mm^-1	θ_max = 27.9°, θ_min = 2.8°
ω scans	h = −5→5
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −15→19
T_min = 0.254, T_max = 0.365	l = −20→20
5060 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.089	w = 1/[σ²(F_o²) + (0.0309P)²] where P = (F_o² + 2F_c²)/3
S = 0.96	(Δ/σ)_max < 0.001
2239 reflections	Δρ_max = 0.47 e Å⁻³
119 parameters	Δρ_min = −0.41 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 863 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (3)

Crystal data top

C₁₀H₆Br₂O	V = 955.65 (13) Å³
M_r = 301.97	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 4.1225 (3) Å	µ = 8.44 mm⁻¹
b = 14.4441 (11) Å	T = 296 K
c = 16.0490 (14) Å	0.32 × 0.14 × 0.12 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2239 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1410 reflections with I > 2σ(I)
T_min = 0.254, T_max = 0.365	R_int = 0.045
5060 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.089	Δρ_max = 0.47 e Å⁻³
S = 0.96	Δρ_min = −0.41 e Å⁻³
2239 reflections	Absolute structure: Flack (1983), 863 Friedel pairs
119 parameters	Absolute structure parameter: −0.01 (3)
0 restraints

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 e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	0.45967 (15)	0.18900 (4)	0.18041 (4)	0.0493 (2)
Br2	1.06884 (18)	−0.15734 (4)	0.19773 (5)	0.0624 (3)
O1	0.6998 (11)	0.1798 (3)	−0.0029 (3)	0.0463 (16)
C1	0.9478 (14)	0.0326 (3)	0.0024 (3)	0.0333 (17)
C2	0.7730 (14)	0.1034 (4)	0.0449 (4)	0.0343 (19)
C3	0.6882 (14)	0.0934 (4)	0.1244 (4)	0.036 (2)
C4	0.7718 (13)	0.0149 (4)	0.1698 (4)	0.039 (2)
C5	0.9399 (15)	−0.0536 (4)	0.1318 (4)	0.0417 (19)
C6	1.0379 (14)	−0.0490 (4)	0.0474 (3)	0.0377 (19)
C7	1.2132 (16)	−0.1172 (4)	0.0024 (5)	0.048 (3)
C8	1.2958 (16)	−0.1080 (5)	−0.0777 (4)	0.058 (3)
C9	1.2149 (16)	−0.0287 (5)	−0.1202 (5)	0.059 (3)
C10	1.0428 (15)	0.0408 (4)	−0.0816 (3)	0.045 (2)
H1	0.57717	0.21391	0.02304	0.0692*
H4	0.71293	0.00947	0.22552	0.0471*
H7	1.27375	−0.17112	0.03010	0.0583*
H8	1.40791	−0.15515	−0.10460	0.0694*
H9	1.27695	−0.02190	−0.17559	0.0702*
H10	0.98850	0.09384	−0.11132	0.0537*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0513 (4)	0.0432 (3)	0.0535 (4)	−0.0002 (3)	0.0022 (4)	−0.0087 (3)
Br2	0.0679 (5)	0.0465 (4)	0.0727 (5)	0.0007 (3)	−0.0084 (4)	0.0200 (4)
O1	0.049 (3)	0.034 (2)	0.056 (3)	0.002 (2)	0.002 (2)	0.007 (2)
C1	0.030 (3)	0.036 (3)	0.034 (3)	−0.005 (3)	−0.008 (3)	−0.005 (3)
C2	0.034 (3)	0.030 (3)	0.039 (4)	−0.008 (3)	−0.009 (3)	0.003 (3)
C3	0.033 (3)	0.036 (4)	0.038 (4)	−0.008 (3)	0.000 (3)	−0.006 (3)
C4	0.041 (4)	0.039 (3)	0.038 (4)	−0.008 (3)	−0.006 (3)	0.005 (3)
C5	0.039 (3)	0.037 (3)	0.049 (4)	−0.006 (3)	−0.014 (3)	0.008 (3)
C6	0.033 (3)	0.031 (3)	0.049 (4)	−0.007 (3)	−0.012 (3)	−0.002 (3)
C7	0.047 (4)	0.042 (4)	0.056 (5)	0.004 (3)	−0.017 (4)	−0.012 (4)
C8	0.052 (4)	0.063 (5)	0.059 (6)	0.011 (4)	−0.004 (4)	−0.026 (5)
C9	0.052 (5)	0.081 (6)	0.043 (5)	−0.001 (4)	0.003 (4)	−0.006 (4)
C10	0.042 (4)	0.049 (3)	0.044 (4)	−0.002 (3)	−0.012 (3)	0.001 (3)

Geometric parameters (Å, º) top

Br1—C3	1.898 (6)	C5—C6	1.415 (8)
Br2—C5	1.910 (6)	C6—C7	1.419 (9)
O1—C2	1.377 (7)	C7—C8	1.337 (10)
O1—H1	0.8200	C8—C9	1.374 (10)
C1—C2	1.425 (8)	C9—C10	1.377 (9)
C1—C10	1.409 (7)	C4—H4	0.9300
C1—C6	1.431 (7)	C7—H7	0.9300
C2—C3	1.331 (9)	C8—H8	0.9300
C3—C4	1.391 (8)	C9—H9	0.9300
C4—C5	1.353 (8)	C10—H10	0.9300

C2—O1—H1	110.00	C1—C6—C5	116.6 (5)
C2—C1—C6	118.7 (5)	C6—C7—C8	123.4 (6)
C2—C1—C10	122.6 (5)	C7—C8—C9	119.9 (7)
C6—C1—C10	118.7 (5)	C8—C9—C10	120.6 (7)
O1—C2—C1	114.8 (5)	C1—C10—C9	120.8 (5)
O1—C2—C3	124.3 (5)	C3—C4—H4	121.00
C1—C2—C3	120.9 (5)	C5—C4—H4	120.00
Br1—C3—C4	117.9 (5)	C6—C7—H7	118.00
C2—C3—C4	121.7 (6)	C8—C7—H7	118.00
Br1—C3—C2	120.4 (5)	C7—C8—H8	120.00
C3—C4—C5	119.1 (6)	C9—C8—H8	120.00
Br2—C5—C6	119.2 (4)	C8—C9—H9	120.00
C4—C5—C6	122.9 (6)	C10—C9—H9	120.00
Br2—C5—C4	117.8 (5)	C1—C10—H10	120.00
C1—C6—C7	116.6 (5)	C9—C10—H10	120.00
C5—C6—C7	126.9 (6)

C6—C1—C2—O1	179.3 (5)	Br1—C3—C4—C5	−178.8 (4)
C6—C1—C2—C3	−1.5 (8)	C2—C3—C4—C5	−0.9 (9)
C10—C1—C2—O1	1.0 (8)	C3—C4—C5—Br2	176.9 (4)
C10—C1—C2—C3	−179.8 (6)	C3—C4—C5—C6	0.5 (9)
C2—C1—C6—C5	1.0 (8)	Br2—C5—C6—C1	−176.9 (4)
C2—C1—C6—C7	−179.7 (5)	Br2—C5—C6—C7	3.8 (9)
C10—C1—C6—C5	179.4 (5)	C4—C5—C6—C1	−0.5 (9)
C10—C1—C6—C7	−1.3 (8)	C4—C5—C6—C7	−179.8 (6)
C2—C1—C10—C9	179.2 (6)	C1—C6—C7—C8	0.4 (9)
C6—C1—C10—C9	0.9 (9)	C5—C6—C7—C8	179.6 (6)
O1—C2—C3—Br1	−1.5 (8)	C6—C7—C8—C9	1.0 (10)
O1—C2—C3—C4	−179.4 (5)	C7—C8—C9—C10	−1.5 (10)
C1—C2—C3—Br1	179.3 (4)	C8—C9—C10—C1	0.5 (10)
C1—C2—C3—C4	1.4 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Br1	0.82	2.60	3.107 (5)	122
O1—H1···O1ⁱ	0.82	2.21	2.893 (6)	141

Symmetry code: (i) x−1/2, −y+1/2, −z.

Experimental details

Crystal data
Chemical formula	C₁₀H₆Br₂O
M_r	301.97
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	4.1225 (3), 14.4441 (11), 16.0490 (14)
V (Å³)	955.65 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	8.44
Crystal size (mm)	0.32 × 0.14 × 0.12

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.254, 0.365
No. of measured, independent and observed [I > 2σ(I)] reflections	5060, 2239, 1410
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.089, 0.96
No. of reflections	2239
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.41
Absolute structure	Flack (1983), 863 Friedel pairs
Absolute structure parameter	−0.01 (3)

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Br1	0.82	2.60	3.107 (5)	122
O1—H1···O1ⁱ	0.82	2.21	2.893 (6)	141

Symmetry code: (i) x−1/2, −y+1/2, −z.

Acknowledgements

The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Ex-Vice Chancellor, University of Sargodha, Pakistan. ARR also acknowledges the Higher Education Commission, Government of Pakistan, for generous support of this research project (No. 20-819).

References

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