4,6-Dibromo­isophthalic acid monohydrate

Ye, B.

doi:10.1107/S1600536812033892

organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2642

doi:10.1107/S1600536812033892

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4,6-Dibromoisophthalic acid monohydrate

Bao-fen Ye ^a ^*

^aDepartment of Analytical Chemistry, China Pharmaceutical University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: baofenye@yahoo.com.cn

(Received 22 July 2012; accepted 29 July 2012; online 4 August 2012)

In the crystal structure of the title hydrate, C₈H₄Br₂O₄·H₂O, O—H⋯O hydrogen bonds link the molecules into a two-dimensional network parallel to (10-2). The acid groups of the main molecule and the water molecule are all involved in the supramolecular structure. The dihedral angles between the benzene ring and the acid groups are 37.8 (4) and 36.4 (5)°, while the dihedral angle between the acid groups is 10.9 (4)°.

Related literature

For the synthesis of the title compound, see: Singh & Bedi (1957 ). For a related structure, see: Song et al. (2008 ).

Experimental

Crystal data

C₈H₄Br₂O₄·H₂O
M_r = 341.95
Monoclinic, P 2₁ /c
a = 3.8740 (8) Å
b = 17.366 (4) Å
c = 15.710 (3) Å
β = 90.91 (3)°
V = 1056.8 (4) Å³
Z = 4
Mo Kα radiation
μ = 7.67 mm⁻¹
T = 293 K
0.30 × 0.05 × 0.05 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.207, T_max = 0.700
2206 measured reflections
1910 independent reflections
1109 reflections with I > 2σ(I)
R_int = 0.051
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.089
S = 0.99
1910 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯OW	0.82	1.74	2.554 (8)	176
O4—H4B⋯O1ⁱ	0.82	1.86	2.665 (8)	168
OW—HWB⋯O3ⁱⁱ	0.85	2.08	2.893 (9)	159
OW—HWA⋯O3ⁱⁱⁱ	0.85	2.17	2.903 (9)	144
Symmetry codes: (i) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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 I, global. DOI: 10.1107/S1600536812033892/bh2450sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812033892/bh2450Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812033892/bh2450Isup3.cml

checkCIF report

Comment top

4,6-Dibromoisophthalic acid (DBPA) is an important organic intermediate for organic synthesis, which can be used in many fields such as organic light-emitting materials. We report herein the crystal structure of the hydrate of DBPA (Fig. 1). Bond lengths and angles are within normal ranges (Song et al., 2008). The asymmetric unit contains one 4,6-dibromoisophthalic acid molecule and one water molecule, in general positions. In the crystal, O—H···O hydrogen bonds link the molecules to form a bidimensional framework (Fig. 2), where all OH groups of the DBPA and the water molecules are involved, as well as carbonyl groups. The water molecule serves as donor and acceptor for hydrogen bonding.

Related literature top

For the synthesis of the title compound, see: Singh & Bedi (1957). For a related structure, see: Song et al. (2008).

Experimental top

DBPA was prepared according to the literature method (Singh & Bedi, 1957). Single crystals of the title hydrate suitable for X-ray analysis were obtained by dissolving DBPA (2.0 g) in water (80 ml) and evaporating the solution slowly at room temperature for about 15 days.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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. The molecular structure of the title compound, with displacement ellipsoids at the 30% probability level. Dashed lines are non-bonding contacts.
	Fig. 2. A packing diagram for the title compound, with O—H···O intermolecular hydrogen bonds shown as dashed lines.

4,6-Dibromoisophthalic acid monohydrate top

Crystal data top

C₈H₄Br₂O₄·H₂O	F(000) = 656
M_r = 341.95	D_x = 2.149 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 441–443 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 3.8740 (8) Å	Cell parameters from 25 reflections
b = 17.366 (4) Å	θ = 10–14°
c = 15.710 (3) Å	µ = 7.67 mm⁻¹
β = 90.91 (3)°	T = 293 K
V = 1056.8 (4) Å³	Rodlike, colourless
Z = 4	0.30 × 0.05 × 0.05 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1109 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.051
Graphite monochromator	θ_max = 25.2°, θ_min = 1.8°
ω/2θ scans	h = −4→4
Absorption correction: ψ scan (North et al., 1968)	k = 0→20
T_min = 0.207, T_max = 0.700	l = 0→18
2206 measured reflections	3 standard reflections every 200 reflections
1910 independent reflections	intensity decay: none

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.02P)²] where P = (F_o² + 2F_c²)/3
1910 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.63 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³
0 constraints

Crystal data top

C₈H₄Br₂O₄·H₂O	V = 1056.8 (4) Å³
M_r = 341.95	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.8740 (8) Å	µ = 7.67 mm⁻¹
b = 17.366 (4) Å	T = 293 K
c = 15.710 (3) Å	0.30 × 0.05 × 0.05 mm
β = 90.91 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1109 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.051
T_min = 0.207, T_max = 0.700	3 standard reflections every 200 reflections
2206 measured reflections	intensity decay: none
1910 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 0.99	Δρ_max = 0.63 e Å⁻³
1910 reflections	Δρ_min = −0.50 e Å⁻³
136 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
OW	0.6960 (16)	0.0557 (3)	−0.0592 (4)	0.079 (2)
HWB	0.8013	0.0536	−0.0114	0.094*
HWA	0.6946	0.0116	−0.0828	0.094*
Br1	−0.1479 (2)	0.52659 (5)	−0.24930 (5)	0.0486 (3)
O1	0.6060 (18)	0.2282 (4)	−0.0212 (4)	0.073 (2)
C1	−0.041 (2)	0.3595 (5)	−0.3421 (5)	0.041 (2)
Br2	0.3840 (2)	0.38158 (6)	0.03673 (5)	0.0473 (3)
C2	0.4568 (19)	0.2307 (5)	−0.0891 (5)	0.0314 (19)
O2	0.4320 (16)	0.1710 (3)	−0.1373 (4)	0.071 (2)
H2A	0.5248	0.1342	−0.1136	0.107*
C3	0.0622 (17)	0.3658 (4)	−0.2523 (5)	0.0297 (19)
O3	−0.0053 (17)	0.4099 (4)	−0.3936 (4)	0.070 (2)
C4	0.1931 (18)	0.3018 (5)	−0.2089 (5)	0.034 (2)
H4A	0.2057	0.2556	−0.2385	0.041*
O4	−0.1724 (15)	0.2937 (4)	−0.3616 (3)	0.0598 (18)
H4B	−0.2295	0.2935	−0.4121	0.090*
C5	0.3038 (18)	0.3022 (5)	−0.1261 (4)	0.0294 (19)
C6	0.2627 (17)	0.3713 (5)	−0.0796 (4)	0.0315 (19)
C7	0.1313 (18)	0.4354 (5)	−0.1184 (5)	0.036 (2)
H7A	0.1089	0.4807	−0.0873	0.043*
C8	0.0319 (18)	0.4341 (4)	−0.2022 (4)	0.0293 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
OW	0.131 (6)	0.051 (4)	0.053 (4)	0.036 (4)	−0.027 (4)	−0.007 (4)
Br1	0.0605 (6)	0.0433 (5)	0.0422 (5)	0.0132 (5)	0.0028 (4)	0.0097 (5)
O1	0.131 (6)	0.049 (4)	0.039 (4)	0.029 (4)	−0.031 (4)	0.003 (3)
C1	0.057 (6)	0.040 (6)	0.027 (5)	−0.004 (5)	−0.007 (4)	0.006 (5)
Br2	0.0647 (6)	0.0517 (6)	0.0254 (4)	0.0066 (5)	−0.0047 (4)	−0.0072 (5)
C2	0.036 (5)	0.039 (5)	0.019 (4)	0.000 (4)	0.003 (4)	0.001 (4)
O2	0.126 (6)	0.038 (4)	0.050 (4)	0.023 (4)	−0.025 (4)	−0.006 (4)
C3	0.029 (5)	0.032 (5)	0.028 (4)	0.004 (4)	0.000 (3)	0.000 (4)
O3	0.125 (6)	0.061 (5)	0.024 (3)	−0.023 (4)	−0.011 (3)	0.006 (4)
C4	0.039 (5)	0.025 (4)	0.038 (5)	−0.002 (4)	0.002 (4)	−0.003 (4)
O4	0.097 (5)	0.056 (5)	0.026 (3)	−0.024 (4)	−0.014 (3)	0.005 (3)
C5	0.035 (5)	0.031 (5)	0.022 (4)	0.000 (4)	0.007 (4)	0.002 (4)
C6	0.038 (5)	0.037 (5)	0.020 (4)	0.001 (4)	0.005 (3)	0.004 (4)
C7	0.037 (5)	0.036 (5)	0.034 (5)	0.002 (4)	0.001 (4)	−0.005 (4)
C8	0.038 (5)	0.026 (4)	0.024 (4)	0.001 (4)	0.003 (3)	0.007 (4)

Geometric parameters (Å, º) top

OW—HWB	0.8500	O2—H2A	0.8200
OW—HWA	0.8502	C3—C4	1.394 (10)
Br1—C8	1.896 (7)	C3—C8	1.430 (10)
O1—C2	1.205 (9)	C4—C5	1.363 (9)
C1—O3	1.201 (9)	C4—H4A	0.9300
C1—O4	1.285 (10)	O4—H4B	0.8200
C1—C3	1.465 (10)	C5—C6	1.414 (10)
Br2—C6	1.888 (7)	C6—C7	1.363 (10)
C2—O2	1.287 (9)	C7—C8	1.367 (10)
C2—C5	1.491 (10)	C7—H7A	0.9300

HWB—OW—HWA	110.2	C1—O4—H4B	109.5
O3—C1—O4	122.5 (7)	C4—C5—C6	117.4 (7)
O3—C1—C3	124.2 (8)	C4—C5—C2	119.0 (7)
O4—C1—C3	113.3 (8)	C6—C5—C2	123.6 (6)
O1—C2—O2	121.4 (8)	C7—C6—C5	120.4 (7)
O1—C2—C5	123.9 (8)	C7—C6—Br2	116.2 (6)
O2—C2—C5	114.6 (6)	C5—C6—Br2	123.4 (6)
C2—O2—H2A	109.5	C6—C7—C8	121.0 (8)
C4—C3—C8	115.1 (6)	C6—C7—H7A	119.5
C4—C3—C1	120.2 (7)	C8—C7—H7A	119.5
C8—C3—C1	124.7 (7)	C7—C8—C3	121.3 (7)
C5—C4—C3	124.7 (8)	C7—C8—Br1	117.3 (6)
C5—C4—H4A	117.7	C3—C8—Br1	121.4 (5)
C3—C4—H4A	117.7

O3—C1—C3—C4	−144.6 (9)	C4—C5—C6—C7	−2.9 (11)
O4—C1—C3—C4	34.9 (11)	C2—C5—C6—C7	177.8 (7)
O3—C1—C3—C8	37.0 (13)	C4—C5—C6—Br2	177.5 (5)
O4—C1—C3—C8	−143.5 (8)	C2—C5—C6—Br2	−1.9 (10)
C8—C3—C4—C5	−3.2 (11)	C5—C6—C7—C8	1.0 (12)
C1—C3—C4—C5	178.2 (7)	Br2—C6—C7—C8	−179.3 (6)
C3—C4—C5—C6	4.1 (11)	C6—C7—C8—C3	−0.1 (12)
C3—C4—C5—C2	−176.5 (7)	C6—C7—C8—Br1	179.9 (6)
O1—C2—C5—C4	169.0 (8)	C4—C3—C8—C7	1.0 (11)
O2—C2—C5—C4	−8.0 (10)	C1—C3—C8—C7	179.5 (7)
O1—C2—C5—C6	−11.7 (13)	C4—C3—C8—Br1	−178.9 (5)
O2—C2—C5—C6	171.3 (7)	C1—C3—C8—Br1	−0.4 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···OW	0.82	1.74	2.554 (8)	176
O4—H4B···O1ⁱ	0.82	1.86	2.665 (8)	168
OW—HWB···O3ⁱⁱ	0.85	2.08	2.893 (9)	159
OW—HWA···O3ⁱⁱⁱ	0.85	2.17	2.903 (9)	144
C4—H4A···O2	0.93	2.33	2.692 (10)	103

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

Experimental details

Crystal data
Chemical formula	C₈H₄Br₂O₄·H₂O
M_r	341.95
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	3.8740 (8), 17.366 (4), 15.710 (3)
β (°)	90.91 (3)
V (Å³)	1056.8 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	7.67
Crystal size (mm)	0.30 × 0.05 × 0.05

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.207, 0.700
No. of measured, independent and observed [I > 2σ(I)] reflections	2206, 1910, 1109
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.089, 0.99
No. of reflections	1910
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.50

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), 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
O2—H2A···OW	0.8200	1.7400	2.554 (8)	176.00
O4—H4B···O1ⁱ	0.8200	1.8600	2.665 (8)	168.00
OW—HWB···O3ⁱⁱ	0.8500	2.0800	2.893 (9)	159.00
OW—HWA···O3ⁱⁱⁱ	0.8500	2.1700	2.903 (9)	144.00

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

Acknowledgements

The author thanks the Center of Testing and Analysis, Nanjing University, for support.

References

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Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
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Singh, T. & Bedi, S. N. (1957). J. Indian Chem. Soc. 34, 321–323. CAS Google Scholar
Song, G.-L., Liu, S., Liu, H.-J., Zeng, T. & Zhu, H.-J. (2008). Acta Cryst. E64, o1860. Web of Science CSD CrossRef IUCr Journals Google Scholar