Biphenyl-3,3′,4,4′-tetra­carboxylic acid dihydrate

Fei Li; Wu-Wei Wang; Xing Ji; Chang-Chun Cao; Dong-Ya Zhu

doi:10.1107/S1600536808044012

. 2009 Jan 8;65(Pt 2):o244. doi: 10.1107/S1600536808044012

Biphenyl-3,3′,4,4′-tetracarboxylic acid dihydrate

Fei Li ^a,^*, Wu-Wei Wang ^a, Xing Ji ^a, Chang-Chun Cao ^a, Dong-Ya Zhu ^a,^*

PMCID: PMC2968332 PMID: 21581861

Abstract

The asymmetric unit of the title compound, C₁₆H₁₀O₈·2H₂O, contains one-half of the centrosymmetric organic molecule and one water molecule. The dihedral angles between the carboxylate groups and the adjacent phenyl ring are 71.31 (3) and 16.67 (3)°, while the carboxylate groups are oriented at a dihedral angle of 72.01 (3)°. In the crystal structure, intermolecular O—H⋯O and bifurcated O—H⋯(O,O) hydrogen bonds link the molecules to form a three-dimensional supramolecular network.

Related literature

For general background, see: Du et al. (2006 ▶, 2007 ▶); Desiraju (2003 ▶); Yaghi et al. (2003 ▶); Li et al. (2008 ▶). For a related structure, see: Coles et al. (2002 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₆H₁₀O₈·2H₂O
M _r = 366.27
Triclinic,
a = 5.5858 (16) Å
b = 6.6618 (19) Å
c = 11.086 (3) Å
α = 93.126 (5)°
β = 91.404 (4)°
γ = 109.110 (4)°
V = 388.81 (19) Å³
Z = 1
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 296 (2) K
0.28 × 0.24 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.943, T _max = 0.973
1992 measured reflections
1362 independent reflections
1222 reflections with I > 2σ(I)
R _int = 0.008

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.090
S = 1.08
1362 reflections
120 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.16 e Å⁻³

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: SHELXTL (Sheldrick, 2008 ▶) and ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808044012/hk2568sup1.cif

e-65-0o244-sup1.cif^{(14.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808044012/hk2568Isup2.hkl

e-65-0o244-Isup2.hkl^{(66.8KB, 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
O1—H1⋯O3ⁱ	0.82	1.88	2.683 (3)	168
O4—H4⋯O5ⁱⁱ	0.82	1.79	2.599 (3)	169
O5—H5A⋯O3ⁱⁱⁱ	0.85	2.45	3.129 (3)	137
O5—H5A⋯O2^iv	0.85	2.22	2.892 (3)	136
O5—H5B⋯O2	0.85	1.95	2.801 (3)	175

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

Acknowledgments

We acknowledge Tianjin Normal University for their active cooperation in this work.

supplementary crystallographic information

Comment

Non-covalent intermolecular interactions, mainly hydrogen bonding and aromatic stacking, play the key role to perfectly project and regulate the detailed crystal packing of supramolecular materials (Du et al., 2006; Desiraju, 2003). Aromatic carboxylates have also been proved to be effective building blocks in constructing various architectures (Yaghi et al., 2003; Li et al., 2008; Du et al., 2007). However, the crystal structures of these polycarboxyl acids themselves are rarely reported (Coles et al., 2002). We synthesized the title compound under hydrothermal condition, and report herein its crystal structure.

The asymmetric unit of the title compound (Fig. 1) contains one-half of the centrosymmetric molecule and one water molecule. The bond lengths (Allen et al., 1987) and angles are within normal ranges. The intramolecular O—H···O hydrogen bonding (Table 1) of the carboxylate O2 atom to the water molecule may cause to a small difference in the C1═O2 [1.2031 (18) Å] and C8═O3 [1.2156 (17) Å] double bonds of the carboxylate groups. The dihedral angles between the planar carboxylate groups (O1/C1/O2) and (O3/C8/O4) and the adjacent phenyl ring A (C2–C7) are 71.31 (3)° and 16.67 (3)°, respectively, while the carboxylate groups are oriented at a dihedral angle of 72.01 (3)°.

In the crystal structure, intra- and intermolecular O—H···O hydrogen bonds (Table 1) link the molecules to form a 3-D supramolecular network. Firstly, the O1—H1···O3 hydrogen bonds between the carboxyl units connect them into a 1-D zigzag chain (Fig. 2). Then, water molecules play the acceptor and donor roles, respectively, to participate in the formation of O4—H4···O5 and O5—H5B···O2 hydrogen bonds, giving rise to a 2-D supramolecular layer (Fig. 3). Finally, water molecules further act as donors to interconnect the supramolecular layers into 3-D networks with O5—H5A···O3 and O5—H5A···O2 hydrogen bonds (Fig. 4).

Experimental

The title compound was recrystallized from the mixture of H₂O (15 ml) and HNO₃ (0.5 ml) under the hydrothermal conditions on cooling from 393 K. Colorless block shaped crystals were obtained at room temperature.