2-(Dibromo­meth­yl)benzoic acid

Lin, H.-Y.; Fang, S.-K.; Chen, K.-Y.

doi:10.1107/S1600536811052858

organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o109

doi:10.1107/S1600536811052858

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2-(Dibromomethyl)benzoic acid

Hong-Yi Lin,^a Sin-Kai Fang ^a and Kew-Yu Chen ^a ^*

^aDepartment of Chemical Engineering, Feng Chia University, 40724 Taichung, Taiwan
^*Correspondence e-mail: kyuchen@fcu.edu.tw

(Received 3 October 2011; accepted 8 December 2011; online 14 December 2011)

In the crystal structure of the title compound, C₈H₆Br₂O₂, the carboxyl groups are involved in pairs of O—H⋯O hydrogen bonds, which link the molecules into inversion dimers.

Related literature

For the preparation of the title compound, see: Eliel & Rivard (1952 ). For its applications, see: Dey & Mal (2005 ). For graph-set theory, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₈H₆Br₂O₂
M_r = 293.95
Monoclinic, P 2₁ /n
a = 4.9988 (6) Å
b = 25.617 (3) Å
c = 7.1844 (8) Å
β = 97.709 (10)°
V = 911.68 (18) Å³
Z = 4
Mo Kα radiation
μ = 8.85 mm⁻¹
T = 297 K
0.74 × 0.36 × 0.25 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.251, T_max = 1.000
7515 measured reflections
2210 independent reflections
1221 reflections with I > 2σ(I)
R_int = 0.088

Refinement

R[F² > 2σ(F²)] = 0.091
wR(F²) = 0.227
S = 1.13
2210 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.85 e Å⁻³
Δρ_min = −0.93 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O1ⁱ	0.82	1.82	2.641 (11)	176
Symmetry code: (i) -x+2, -y, -z+1.

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); 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 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811052858/lx2208sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811052858/lx2208Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811052858/lx2208Isup3.cml

checkCIF report

Comment top

The title compound is a useful reagent to prepare phthalaldehydic acid (Eliel & Rivard, 1952). In addition, it has been prepared as a potential precursor to an antitumour agent, BE-23254. (Dey & Mal, 2005). The structure of the title compound is shown in Fig. 1. In the crystal structure (Fig. 2), inversion-related molecules are linked by pairs of O–H···O hydrogen bonds, forming a cyclic dimers with R₂²(8) graph-set motif (Table 1) (Bernstein et al., 1995). The intramolecular C–H···O hydrogen bond (Table 1) generates an S(6) ring motif .

Related literature top

For the preparation of the title compound, see: Eliel & Rivard (1952). For its applications, see: Dey & Mal (2005). For graph-set theory, see: Bernstein et al. (1995).

Experimental top

The title compound was synthesized according to the literature (Eliel & Rivard, 1952). Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in chloroform at room temperature for six weeks.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. A view of the O–H···O hydrogen bonds (dotted lines) in the crystal structure of the title compound.

2-(Dibromomethyl)benzoic acid top

Crystal data top

C₈H₆Br₂O₂	F(000) = 560
M_r = 293.95	D_x = 2.142 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2762 reflections
a = 4.9988 (6) Å	θ = 2.9–29.2°
b = 25.617 (3) Å	µ = 8.85 mm⁻¹
c = 7.1844 (8) Å	T = 297 K
β = 97.709 (10)°	Parallelepiped, colorless
V = 911.68 (18) Å³	0.74 × 0.36 × 0.25 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2210 independent reflections
Radiation source: fine-focus sealed tube	1221 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.088
ω scans	θ_max = 29.3°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −6→6
T_min = 0.251, T_max = 1.000	k = −34→34
7515 measured reflections	l = −9→9

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)] = 0.091	Hydrogen site location: difference Fourier map
wR(F²) = 0.227	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0876P)² + 4.8672P] where P = (F_o² + 2F_c²)/3
2210 reflections	(Δ/σ)_max = 0.001
109 parameters	Δρ_max = 0.85 e Å⁻³
0 restraints	Δρ_min = −0.93 e Å⁻³

Crystal data top

C₈H₆Br₂O₂	V = 911.68 (18) Å³
M_r = 293.95	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.9988 (6) Å	µ = 8.85 mm⁻¹
b = 25.617 (3) Å	T = 297 K
c = 7.1844 (8) Å	0.74 × 0.36 × 0.25 mm
β = 97.709 (10)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2210 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1221 reflections with I > 2σ(I)
T_min = 0.251, T_max = 1.000	R_int = 0.088
7515 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.091	0 restraints
wR(F²) = 0.227	H-atom parameters constrained
S = 1.13	Δρ_max = 0.85 e Å⁻³
2210 reflections	Δρ_min = −0.93 e Å⁻³
109 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	0.4317 (3)	0.14770 (6)	0.73655 (16)	0.0676 (5)
Br2	0.6793 (3)	0.22661 (4)	0.4627 (2)	0.0700 (5)
O1	0.8610 (16)	0.0565 (3)	0.5279 (11)	0.055 (2)
O2	0.7203 (17)	−0.0025 (3)	0.3117 (11)	0.057 (2)
H2A	0.8523	−0.0181	0.3649	0.086*
C1	0.613 (2)	0.1540 (4)	0.5132 (14)	0.038 (2)
H1A	0.7859	0.1356	0.5355	0.046*
C2	0.4355 (19)	0.1276 (3)	0.3520 (12)	0.032 (2)
C3	0.216 (2)	0.1550 (4)	0.2570 (14)	0.043 (2)
H3A	0.1840	0.1890	0.2926	0.052*
C4	0.050 (2)	0.1329 (4)	0.1143 (14)	0.045 (3)
H4A	−0.0943	0.1519	0.0528	0.054*
C5	0.093 (2)	0.0821 (4)	0.0596 (14)	0.050 (3)
H5A	−0.0223	0.0667	−0.0375	0.060*
C6	0.307 (2)	0.0547 (4)	0.1501 (14)	0.041 (2)
H6A	0.3367	0.0207	0.1115	0.049*
C7	0.484 (2)	0.0759 (4)	0.2988 (12)	0.033 (2)
C8	0.702 (2)	0.0430 (4)	0.3896 (14)	0.037 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0750 (9)	0.0939 (10)	0.0320 (6)	0.0025 (8)	0.0000 (5)	−0.0081 (6)
Br2	0.0771 (10)	0.0335 (6)	0.0951 (11)	−0.0055 (6)	−0.0039 (8)	−0.0100 (6)
O1	0.060 (5)	0.039 (4)	0.062 (5)	0.013 (4)	−0.013 (4)	−0.011 (4)
O2	0.065 (5)	0.036 (4)	0.065 (5)	0.011 (4)	−0.011 (4)	−0.011 (4)
C1	0.043 (6)	0.028 (5)	0.042 (6)	0.007 (4)	0.003 (5)	−0.010 (4)
C2	0.040 (5)	0.030 (4)	0.024 (4)	0.002 (4)	−0.002 (4)	0.000 (4)
C3	0.056 (7)	0.037 (5)	0.037 (6)	0.004 (5)	0.010 (5)	0.000 (4)
C4	0.039 (6)	0.062 (7)	0.032 (5)	−0.003 (5)	0.000 (4)	0.009 (5)
C5	0.057 (7)	0.060 (7)	0.029 (5)	−0.013 (6)	−0.009 (5)	−0.004 (5)
C6	0.034 (5)	0.045 (6)	0.043 (6)	−0.001 (5)	0.002 (4)	−0.013 (5)
C7	0.044 (6)	0.034 (5)	0.022 (4)	0.000 (4)	0.004 (4)	0.001 (4)
C8	0.042 (6)	0.031 (5)	0.040 (6)	−0.002 (4)	0.016 (5)	−0.001 (4)

Geometric parameters (Å, º) top

Br1—C1	1.951 (10)	C3—C4	1.354 (14)
Br2—C1	1.932 (10)	C3—H3A	0.9300
O1—C8	1.235 (12)	C4—C5	1.386 (15)
O2—C8	1.302 (11)	C4—H4A	0.9300
O2—H2A	0.8200	C5—C6	1.370 (15)
C1—C2	1.519 (13)	C5—H5A	0.9300
C1—H1A	0.9800	C6—C7	1.402 (13)
C2—C3	1.399 (14)	C6—H6A	0.9300
C2—C7	1.409 (12)	C7—C8	1.461 (14)

C8—O2—H2A	109.5	C3—C4—H4A	119.9
C2—C1—Br2	112.5 (7)	C5—C4—H4A	119.9
C2—C1—Br1	107.6 (7)	C6—C5—C4	119.3 (9)
Br2—C1—Br1	110.2 (4)	C6—C5—H5A	120.4
C2—C1—H1A	108.8	C4—C5—H5A	120.4
Br2—C1—H1A	108.8	C5—C6—C7	122.4 (9)
Br1—C1—H1A	108.8	C5—C6—H6A	118.8
C3—C2—C7	119.4 (9)	C7—C6—H6A	118.8
C3—C2—C1	119.2 (8)	C2—C7—C6	117.3 (9)
C7—C2—C1	121.4 (8)	C2—C7—C8	124.5 (9)
C4—C3—C2	121.5 (10)	C6—C7—C8	118.2 (9)
C4—C3—H3A	119.2	O1—C8—O2	121.5 (9)
C2—C3—H3A	119.2	O1—C8—C7	123.9 (9)
C3—C4—C5	120.2 (10)	O2—C8—C7	114.6 (9)

Br2—C1—C2—C3	−40.2 (11)	C1—C2—C7—C6	179.1 (9)
Br1—C1—C2—C3	81.4 (9)	C3—C2—C7—C8	−178.5 (9)
Br2—C1—C2—C7	141.2 (8)	C1—C2—C7—C8	0.1 (15)
Br1—C1—C2—C7	−97.3 (9)	C5—C6—C7—C2	−0.8 (15)
C7—C2—C3—C4	−0.2 (15)	C5—C6—C7—C8	178.3 (10)
C1—C2—C3—C4	−178.9 (9)	C2—C7—C8—O1	2.9 (16)
C2—C3—C4—C5	0.4 (16)	C6—C7—C8—O1	−176.1 (10)
C3—C4—C5—C6	−0.7 (16)	C2—C7—C8—O2	−176.3 (9)
C4—C5—C6—C7	0.9 (17)	C6—C7—C8—O2	4.7 (13)
C3—C2—C7—C6	0.4 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1ⁱ	0.82	1.82	2.641 (11)	176
C1—H1A···O1	0.98	2.06	2.784 (13)	129

Symmetry code: (i) −x+2, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₈H₆Br₂O₂
M_r	293.95
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	297
a, b, c (Å)	4.9988 (6), 25.617 (3), 7.1844 (8)
β (°)	97.709 (10)
V (Å³)	911.68 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	8.85
Crystal size (mm)	0.74 × 0.36 × 0.25

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.251, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7515, 2210, 1221
R_int	0.088
(sin θ/λ)_max (Å⁻¹)	0.689

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.091, 0.227, 1.13
No. of reflections	2210
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.85, −0.93

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1ⁱ	0.82	1.82	2.641 (11)	176
C1—H1A···O1	0.98	2.06	2.784 (13)	129

Symmetry code: (i) −x+2, −y, −z+1.

Acknowledgements

This work was supported by the National Science Council (NSC 99-2113-M-035-001-MY2) and Feng Chia University, Taiwan.

References

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