4,4′-Bipyridine-1,1′-diium 2,3,5,6-tetra­bromo­terephthalate dihydrate

Hitoshi Kumagai; Satoshi Kawata

doi:10.1107/S1600536811035926

. 2011 Sep 14;67(Pt 10):o2636. doi: 10.1107/S1600536811035926

4,4′-Bipyridine-1,1′-diium 2,3,5,6-tetrabromoterephthalate dihydrate

Hitoshi Kumagai ^a,^*, Satoshi Kawata ^b

PMCID: PMC3201235 PMID: 22064366

Abstract

The title compound, C₁₀H₁₀N₂ ²⁺·C₈Br₄O₄ ²⁻·2H₂O, consists of a tetrabromoterephthalate dianion, a 4,4′-bipyridinium dication and two solvent water molecules. Crystallographic inversion centers are situated at the center of the aromatic ring of the dianion as well as at the midpoint of the carbon–carbon bond connecting the pyridine rings in the dication. In the crystal, intermolecular N—H⋯O hydrogen-bonding interactions between tetrabromoterephthalate dianions and protonated 4,4′-bipyridinium dications result in the formation of a chain-like structure. Further O—H⋯O hydrogen bonds between carboxylate O atoms and water molecules lead to the formation of a two-dimensional network in the crystal structure.

Related literature

For hydrogen-bonded assemblies, see: Desiraju & Steiner (1999 ▶); Jia et al. (2009 ▶); Soleimannejad et al. (2009 ▶). For proton transfer, see: Kawata et al. (2002 ▶).

Experimental

Crystal data

C₁₀H₁₀N₂ ²⁺·C₈Br₄O₄ ²⁻·2H₂O
M _r = 673.93
Triclinic,
a = 6.503 (3) Å
b = 9.249 (4) Å
c = 9.987 (4) Å
α = 64.119 (14)°
β = 85.868 (18)°
γ = 73.737 (14)°
V = 517.9 (4) Å³
Z = 1
Mo Kα radiation
μ = 7.83 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Rigaku Mercury70 diffractometer
Absorption correction: multi-scan (REQAB; Rigaku, 1998 ▶) T _min = 0.126, T _max = 0.209
5065 measured reflections
2336 independent reflections
2116 reflections with F ² > 2.0σ(F ²)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.086
S = 1.19
2336 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −1.55 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: IL MILIONE (Burla et al., 2007 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalMaker (Palmer, 2004 ▶); software used to prepare material for publication: CrystalStructure (Rigaku, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811035926/im2306sup1.cif

e-67-o2636-sup1.cif^{(14.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811035926/im2306Isup2.hkl

e-67-o2636-Isup2.hkl^{(114.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811035926/im2306Isup3.cdx

Supplementary material file. DOI: 10.1107/S1600536811035926/im2306Isup4.cml

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
O3—H6⋯O2ⁱ	0.963	1.944	2.822 (4)	150.5
O3—H7⋯O2	1.002	1.765	2.766 (3)	177.2
N1—H5⋯O1ⁱⁱ	0.941	1.670	2.606 (4)	172.9

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

Acknowledgments

HK thanks the Japan Society for the Promotion of Science for his postdoctoral fellowship.

supplementary crystallographic information

Comment

Hydrogen bonded inorganic and organic compounds are of great current interest in recent years due to fundamental scientific and technological applications (Desiraju & Steiner,1999; Kawata et al., 2002). Here we report the synthesis and single-crystal structure of the title compound [(C₈Br₄O₄)(C₁₀H₁₀N₂).2H₂O)]. It consists of a tetrabromoterephthalate dianion, a 4,4'-bipyridinium dication and solvent water molecules. Intermolecular N–H···O hydrogen bonding interactions between tetrabromoterephthalate dianions and protonated 4,4'-bipyridinium dications result in the formation of a one-dimensional chain-like structure. Further O–H···O hydrogen bonds between oxygen atoms of carboxylates and water molecules lead to the formation of a two-dimensional network in the crystal structure.

Experimental

An aqueous solution (2 ml) of cerium nitrate hexahydrate (0.43 g, 1 mmolL^-1) was transferred to a glass tube, then a mixture of tetrabromoterephthalic acid (0.48 g, 1 mmolL^-1), NaOH (0.08 g, 2 mmolL^-1) and 4,4'-bpy (0.15 g, 1 mmolL^-1) in ethanol/water (2 ml) was poured into the glass tube without mixing the two solutions. Colorless crystals began to form at ambient temperature during 1 month. One of these crystals was used for X-ray crystallography.