μ-Biphenyl-3,3′,4,4′-tetra­carboxyl­ato-κ2 O 3:O 3′-bis­[triaqua­(2,2′-bipyridyl-κ2 N,N′)nickel(II)] hexa­hydrate

Dong Zhou; Min Shao; Xiang He; Yongmei Zhao; Shourong Zhu

doi:10.1107/S1600536809014639

. 2009 Apr 25;65(Pt 5):m562–m563. doi: 10.1107/S1600536809014639

μ-Biphenyl-3,3′,4,4′-tetracarboxylato-κ² O ³:O ^3′-bis[triaqua(2,2′-bipyridyl-κ² N,N′)nickel(II)] hexahydrate

Dong Zhou ^a, Min Shao ^b, Xiang He ^b, Yongmei Zhao ^b, Shourong Zhu ^a,^*

PMCID: PMC2977608 PMID: 21583794

Abstract

The asymmetric unit of the title complex, [Ni₂(C₁₆H₆O₈)(C₁₀H₈N₂)₂(H₂O)₆]·6H₂O, contains one Ni^II atom, one 2,2′-bipyridine ligand, three coordinated water molecules, one-half of a fully deprotonated biphenyl-3,3′,4,4′-tetracarboxylate anion and three lattice water molecules. The Ni^II atom displays a distorted NiN₂O₄ octahedral coordination formed by one carboxylate O atom, three water O atoms and two N atoms of the chelating ligand. The complete biphenyl-3,3′,4,4′-tetracarboxylate ligand displays inversion symmetry and links two symmetry-related Ni^II atoms into a binuclear complex. Neighbouring complex molecules are linked through O—H⋯O hydrogen bonds into a three-dimensional structure. Additional O—H⋯O hydrogen bonds between the lattice water molecules help to consolidate the crystal packing.

Related literature

For other metal complexes with biphenyl-3,3′,4,4′-tetracarboxylate as ligand, see: Hao et al. (2005 ▶); Wang et al. (2005 ▶, 2006 ▶, 2007 ▶). For related structures containing biphenyl-3,3′,4,4′-tetracarboxylate and neutral chelating ligands, see: Zhu et al. (2008a ▶,b ▶).

Experimental

Crystal data

[Ni₂(C₁₆H₆O₈)(C₁₀H₈N₂)₂(H₂O)₆]·6H₂O
M _r = 972.19
Triclinic,
a = 7.5126 (14) Å
b = 12.088 (2) Å
c = 12.285 (2) Å
α = 105.445 (2)°
β = 98.075 (2)°
γ = 92.162 (3)°
V = 1061.4 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.97 mm⁻¹
T = 296 K
0.20 × 0.20 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.829, T _max = 0.868
5556 measured reflections
3698 independent reflections
2526 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.062
wR(F ²) = 0.172
S = 1.05
3698 reflections
280 parameters
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2006 ▶) and ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809014639/wm2225sup1.cif

e-65-0m562-sup1.cif^{(20KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809014639/wm2225Isup2.hkl

e-65-0m562-Isup2.hkl^{(181.3KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Ni1—N2	2.063 (4)
Ni1—N1	2.064 (4)
Ni1—O2W	2.067 (3)
Ni1—O1	2.069 (3)
Ni1—O3W	2.075 (3)
Ni1—O1W	2.076 (4)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O4ⁱ	0.82	1.91	2.720 (5)	168
O1W—H1WB⋯O3	0.85	2.04	2.889 (5)	176
O2W—H2WA⋯O2	0.82	1.99	2.708 (5)	146
O2W—H2WB⋯O3ⁱⁱ	0.84	2.06	2.715 (5)	135
O3W—H3WA⋯O3ⁱ	0.85	1.88	2.723 (5)	168
O3W—H3WB⋯O4W	0.82	1.97	2.793 (6)	178
O4W—H4WA⋯O2ⁱⁱⁱ	0.87	1.87	2.715 (6)	164
O4W—H4WB⋯O5W	0.85	2.22	2.803 (8)	125
O5W—H5WB⋯O6W^iv	0.83	2.18	2.770 (15)	128
O6W—H6WA⋯O2	0.85	2.44	3.091 (11)	134
O6W—H6WA⋯O2	0.85	2.44	3.091 (11)	134

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

Acknowledgments

The authors thank Shanghai University for financial support.

supplementary crystallographic information

Comment

Coordination compounds of biphenyl-3,3',4,4'-tetracarboxylic acid have been investigated previously. As expected, the deprotonated ligand coordinates to metal ions in a versatile mode due to its multidentate character (Hao et al., 2005; Wang et al., 2005; 2006; 2007). Upon adding chelating ligands, such as 2,2'-bipyridine or 1,10-phenanthroline, ternary coordination polymers can be formed (Zhu et al., 2008a). In all these complexes, biphenyl-3,3',4,4'-tetracarboxylate acts as counter ion and/or multidentate ligand. Here we present the crystal structure of the dinuclear complex [Ni₂(C₁₀H₈N₂)₂(C₁₆H₆O₈)(H₂O)₆]^.6H₂O, (I).

The unique Ni atom in the structure of complex (I) (Fig. 1) is in a distorted octahedral coordination sphere formed by one carboxylate O, three water O and two N atoms with Ni—O and Ni—N bond lengths in the range 2.063 (4) Å - 2.076 (4) Å with σ=0.87 (Zhu et al., 2008b). The fully deprotonated biphenyl-3,3',4,4'-tetracarboxylate ligand displays inversion symmetry and links two symmetry-related Ni^II atoms. Due to symmetric reason, the two benzene rings of the biphenyl ligand are coplanar. The two pyridine rings in the 2,2'-bipyridine molecule have a torsion angle of 4.7 (8)°. The carboxylate group that coordinate to nickel is almost coplanar with the benzene ring (torsion angle 8.6 (8)°), while the free carboxylate has a torsion angle of 72.2 (7)° with the benzene ring which is almost perpendicular each other. The intramolecular distance between the two nickel(II) ions is 14.788 (11) Å.

As expected, there are considerable hydrogen bonds in the structure. Table 2 lists bond distances and angles. These H-bonds link dinuclear complex together to a three-dimensional structure (Fig 2.). The uncoordinated crystal lattice water molecules interact through additional hydrogen bonds, as shown in Fig. 3, and thus help to consolidate the crystal packing.

Experimental

A mixture of biphenyl-3,3',4,4'-tetracarboxylic acid dianhydride (0.5 mmol), 2,2'-bipyridine (0.5 mmol), NaOH (2 mmol) and Ni(NO₃)₂ (1 mmol) in 8 ml H₂O was placed in a 25 ml Teflon reactor, which was sealed and heated in a oven at 433 K for 72 h. Then the autoclave was cooled to room temperature at the rate of 10 K to get light-blue flat crystals of the title compound (in ca 85% yield based on biphenyltetracarboxylic dianhydride). The crystals were isolated by filtration and washed with water.