Tris(1,10-phenanthroline-κ2 N,N′)nickel(II) bis­(2,4,5-tricarb­oxy­benzo­ate) monohydrate

Kai-Long Zhong; Chao Ni; Ming-Yi Qian

doi:10.1107/S1600536811048914

. 2011 Nov 23;67(Pt 12):m1814–m1815. doi: 10.1107/S1600536811048914

Tris(1,10-phenanthroline-κ² N,N′)nickel(II) bis(2,4,5-tricarboxybenzoate) monohydrate

Kai-Long Zhong ^a,^*, Chao Ni ^a, Ming-Yi Qian ^a

PMCID: PMC3238718 PMID: 22199595

Abstract

In the title compound, [Ni(C₁₂H₈N₂)₃](C₁₀H₅O₈)₂·H₂O, the Ni^II cation is coordinated by six N atoms of the three bidentate chelating 1,10-phenanthroline ligands in a slightly distorted octahedral coordination geometry. The Ni—N bond lengths range from 2.074 (2) to 2.094 (2) Å. The dihedral angles between the three chelating NCCN groups to each other are 85.71 (3), 73.75 (2) and 85.71 (3)°, respectively. The Ni cation, the phenyl ring of the 1,10-phenanthroline ligand and the lattice water molecule are located on special positions (site symmetry 2). In the crystal, the uncoordinated 2,4,5-tricarboxybenzenoate anions join with each other through O—H⋯O hydrogen bonds, forming a two-dimensional hydrogen-bonded layer structure along the bc plane. The layers are further linked via additional O—H⋯O interactions between water and carboxyl groups, resulting in a three-dimensional supramolecular network.

Related literature

For structures of complexes with six-coordinate nickel atoms and background references, see: Li et al. (2003 ▶); Fu et al. (2004 ▶); Fabelo et al. (2008 ▶); Zhong et al. (2009 ▶); Ni et al. (2010 ▶). For background to phenanthroline complexes, see: Wang & Zhong (2011 ▶); Zhu et al. (2006 ▶); Cui et al. (2010 ▶); Zhong (2011a ▶,b ▶,c ▶).

Experimental

Crystal data

[Ni(C₁₂H₈N₂)₃](C₁₀H₅O₈)₂·H₂O
M _r = 1123.62
Monoclinic,
a = 24.2009 (11) Å
b = 14.1546 (5) Å
c = 15.8347 (7) Å
β = 116.271 (5)°
V = 4864.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.49 mm⁻¹
T = 295 K
0.40 × 0.40 × 0.30 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 Gemini ultra diffractometer
Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2009 ▶) T _min = 0.829, T _max = 0.868
12270 measured reflections
4977 independent reflections
3050 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.054
S = 1.02
4977 reflections
369 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811048914/bq2318sup1.cif

e-67-m1814-sup1.cif^{(26.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811048914/bq2318Isup2.hkl

e-67-m1814-Isup2.hkl^{(243.9KB, 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—H4⋯O5ⁱ	0.82	1.87	2.690 (2)	177
O1—H5⋯O6ⁱⁱ	0.82	1.81	2.624 (2)	173
O7—H7⋯O6	0.82	1.63	2.4450 (19)	178
O1W—H1WA⋯O2ⁱⁱⁱ	0.80 (2)	2.10 (3)	2.866 (3)	158 (4)

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

Acknowledgments

This work was supported by the Scientific Research Foundation of Nanjing College of Chemical Technology (grant No. NHKY-2010–17).

supplementary crystallographic information

Comment

1,10-Phenanthroline (Phen) and 1,2,4,5-Benzenetetracarboxylate have also been widely employed as polydentate ligands in coordination reactions and in the construction of supermolecular networks (Li et al., 2003; Fu et al., 2004; Fabelo et al., 2008). Recently we have synthesized and reported many metal-Phen complexes such as cadmium complexe (Zhong, 2011a), cobalt complexes (Wang & Zhong, 2011), copper complexes (Zhong 2011b,c), nickel complexes (Zhong et al., 2009; Ni et al., 2010), manganese complex (Zhu et al., 2006), and zinc complex (Cui et al., 2010). The title compound [Ni(C₁₂H₈N₂)₃](C₁₀H₅O₈)₂.H₂O, (I) was obtained unintentionally during an attempt to synthesize a mixed-ligand complex of Ni^II with Phen and 1,2,4,5-benzenetetracarboxylate ligand via a hydrothermal (solvothermal) reaction. The crystal structure of (I), has not hitherto been reported.

X-ray diffraction indicated that the title compound, (I), has the Ni²⁺ metal ion in a slightly distorted octahedral coordination geometry. The Ni^II atom is bonded by six N atoms of the three bidentate chelating 1,10-phenanthroline ligands. In the cation of [Ni(phen)₃]²⁺, the Ni—N bond distances range from 2.074 (2) Å to 2.094 (2) Å and the N—Ni—N bite angles [80.02 (7)–79.49 (9)°] (see Table 1), which are similar to the reported literature values (Zhong et al., 2009; Ni et al., 2010). The dihedral angles between the neighbor two chelating NCCN groups is 85.71 (3)°, 73.75 (2)° and 85.71 (3)°, respectively. A twofold rotation axis (symmetry code: -x + 2, y, -z + 3/2) passes through the Ni atom and the phenyl ring of 1,10-phenanthroline. In the crystal structure, the uncoordinated trihydrogen-1,2,4,5-benzenetetracarboxylate anions (C₁₀H₅O₈^-) connected to each other by intermolecular O—H···O H-bonds through carboxylic acid to form a two-dimensional hydrogen-bonded layer structure along bc plane. The adjacent layers are further linked via additional water O–H···O carboxyl hydrogen interactions, forming a three-dimensional supramolecular network structure.

Experimental

0.1 mmol NiSO₄^.7H₂O, 0.1 mmol phen, 0.1 mmol 1,2,4,5-Benzenetetracarboxylic acid and 3.0 ml water were mixed and placed in a thick Pyrex tube, which was sealed and heated to 423 K for 96 h, whereupon orange block-shaped crystals of (I) were obtained.