3,3′-Dibromo-6,6′-dimethoxy­biphenyl-2,2′-dicarboxylic acid ethanol monosolvate

Xiao Zhang; Long Li; Le Zhou; Baoming Ji

doi:10.1107/S1600536810013279

. 2010 Apr 24;66(Pt 5):o1144. doi: 10.1107/S1600536810013279

3,3′-Dibromo-6,6′-dimethoxybiphenyl-2,2′-dicarboxylic acid ethanol monosolvate

Xiao Zhang ^a,^b, Long Li ^a,^b, Le Zhou ^a, Baoming Ji ^b,^*

PMCID: PMC2979244 PMID: 21579192

Abstract

In the title compound, C₁₆H₁₂Br₂O₆·C₂H₅OH, the two benzene rings are twisted by 80.64 (5)° and the carboxyl groups form dihedral angles of 72.48 (3) and 89.41 (2)° with the corresponding benzene rings. In the crystal structure, the biphenyl molecules are connected by intermolecular O—H⋯O and O—H⋯Br hydrogen bonds, resulting in a chain along the b axis.

Related literature

For complexes containing diphenic acids, see: Wang et al. (2007 ▶); Yang et al. (2007 ▶). For the synthesis of the title compound, see: Choi et al. (2007 ▶).

Experimental

Crystal data

C₁₆H₁₂Br₂O₆·C₂H₆O
M _r = 506.14
Monoclinic,
a = 9.9872 (9) Å
b = 23.230 (2) Å
c = 8.3967 (7) Å
β = 90.143 (1)°
V = 1948.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 4.20 mm⁻¹
T = 296 K
0.41 × 0.34 × 0.32 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.278, T _max = 0.347
14693 measured reflections
3606 independent reflections
2825 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.069
S = 1.02
3606 reflections
250 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810013279/hg2670sup1.cif

e-66-o1144-sup1.cif^{(20.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013279/hg2670Isup2.hkl

e-66-o1144-Isup2.hkl^{(176.8KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O7	0.82	1.79	2.594 (3)	165
O6—H6⋯O3ⁱ	0.82	1.89	2.711 (3)	174
O7—H7⋯O5ⁱⁱ	0.82	2.07	2.879 (3)	167
O7—H7⋯Br1ⁱⁱ	0.82	3.04	3.445 (2)	113

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

We are grateful to the National Natural Sciences Foundation of China (grant No. 20872057) and the Natural Science Foundation of Henan Province (No. 082300420040) for financial support.

supplementary crystallographic information

Comment

Diphenic acid and its derivatives have been proved to be a kind of multifunctional and flexible ligand in the construction of complexes possessing novel and interesting topological structures (Choi et al. 2007). Our interest in these compounds has led us to prepare the title compound according to the literature methods (Choi et al. 2007). In this contribution, we report the synthesis and crystal structure of the title compound.

The molecule of the title compound (Fig. 1.), is built up form one benzene ring connected to the other benzene ring through the 2 and 2' carbon atoms, in which the bond lengths and angles are within ranges as reported by Wang et al.. (2007). In the crystal structure, except the carboxyl group, both methoxyl group and bromino group lie in the corresponding benzene ring plane, with an r.m.s. deviation of 0.0180 (1) Å and 0.0124 (1) Å.respectively. And, the dihedral angle between the two benzene rings is 80.64 (5)°. It must be pointed out that the striking feature of the title compound is the interesting arrangement of the tilte molecules, which connected each other by the formation of intermolecular O—H···O hydrogen bonds to form one-dimensional chain along the b axis (Fig.2.). Interestingly, the solvent molecules interact with the carboxylate oxygen atoms and bromine atoms from the chains via O—H···O and O—H···Br hydrogen bonds respectively, resulting in the formation of a 2D supramolecular network with 1D channels along the c axis. Detail hydrogen bonds are given in Table 1.

Experimental

2,2'-Dimethoxy-6,6'-Diacetylbiphenyl (0.298 mg, 1 mmol) was suspended and stirred in 1,4-dioxane (24 ml). NaOH (1.76 g, 30.1 mmol) was dissolved in 11.8 ml of water. At 0 °C, bromine (0.80 ml) was added to the NaOH solution which was stirred for 15 min. The NaOBr solution was added gradually to the 1,4-dioxane solution at room temperature, then was stirred at 60 °C for 2 h and cooled to room temperature. The mixture was acidified with conc. HCl (pH < 2) and filtered, washed with water (5 × 100 ml). The products were dried under vacuum, gave the title compounds as white solid (0.253 g, yield 84%).