Bis­(μ-pyridine-2,3-dicarboxyl­ato)bis­[aqua­(3-carb­oxy­pyridine-2-carboxyl­ato)indium(III)] tetra­hydrate

H Eshtiagh-Hosseini; M Mirzaei; A Mousavinezhad; M Necas; J T Mague

doi:10.1107/S1600536811053566

. 2011 Dec 21;68(Pt 1):m71–m72. doi: 10.1107/S1600536811053566

Bis(μ-pyridine-2,3-dicarboxylato)bis[aqua(3-carboxypyridine-2-carboxylato)indium(III)] tetrahydrate

H Eshtiagh-Hosseini ^a, M Mirzaei ^a, A Mousavinezhad ^a, M Necas ^b, J T Mague ^c,^*

PMCID: PMC3254334 PMID: 22259367

Abstract

In the binuclear centrosymmetric title compound, [In₂(C₇H₃NO₄)₂(C₇H₄NO₄)₂(H₂O)₂]·4H₂O, which contains both pyridine-2,3-dicarboxylate and 3-carboxypyridine-2-carboxylate ligands, the In^III atom is six-coordinated in a distorted octahedral geometry. One pyridine ligand is N,O-chelated while the other is N,O-chelated and at the same time bridging to the other via the second carboxyl group. In the crystal, an extensive O—H⋯O hydrogen-bonding network, involving the coordinated and lattice water molecules and the carboxyl groups of the ligands, together with C—H⋯O and π–π interactions [centroid–centroid distance = 3.793 (1) Å], leads to the formation of a three-dimensional structure.

Related literature

For metal complexes with polycarboxylate ligands, see: Aghabozorg, Daneshvar et al. (2007 ▶); Aghabozorg, Khadivi et al. (2008 ▶); Aghabozorg, Ramezanipour et al. (2006 ▶); Eshtiagh-Hosseini et al. (2010 ▶); Mirzaei et al. (2011 ▶). For examples of self-assembly, see: Kondo et al. (1999 ▶); Beobide et al. (2006 ▶). For a discussion of hard–soft acid base concepts, see: Schlemper et al. (1967 ▶). For examples of π–π stacking, see: Janiak (2000 ▶). For three-dimensional network structures, see: Krygowski et al. (1998 ▶).

Experimental

Crystal data

[In₂(C₇H₃NO₄)₂(C₇H₄NO₄)₂(H₂O)₂]·4H₂O
M _r = 1000.17
Triclinic,
a = 8.0166 (3) Å
b = 10.0890 (4) Å
c = 11.9838 (5) Å
α = 110.069 (4)°
β = 96.236 (3)°
γ = 109.076 (3)°
V = 833.36 (6) Å³
Z = 1
Mo Kα radiation
μ = 1.49 mm⁻¹
T = 120 K
0.40 × 0.30 × 0.30 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire2 detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.588, T _max = 0.664
10774 measured reflections
3373 independent reflections
3168 reflections with I > 2σ(I)
R _int = 0.013

Refinement

R[F ² > 2σ(F ²)] = 0.016
wR(F ²) = 0.039
S = 1.10
3373 reflections
254 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.31 e Å⁻³

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

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811053566/su2349sup1.cif

e-68-00m71-sup1.cif^{(27.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811053566/su2349Isup2.hkl

e-68-00m71-Isup2.hkl^{(165.4KB, 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
O9—H91⋯O11ⁱ	0.84	1.75	2.5938 (19)	178
O9—H92⋯O3ⁱ	0.84	1.80	2.6402 (17)	175
O11—H112⋯O7ⁱⁱ	0.84	1.95	2.7595 (18)	162
O10—H101⋯O5ⁱⁱⁱ	0.84	1.97	2.8065 (18)	175
O10—H102⋯O7^iv	0.84	1.88	2.7237 (19)	178
O4—H4O⋯O10	0.84	1.67	2.5124 (17)	178
C4—H4⋯O1^v	0.95	2.35	3.231 (2)	154
C5—H5⋯O6^vi	0.95	2.36	3.293 (2)	168
C11—H11⋯O3^vii	0.95	2.61	3.495 (2)	156
C12—H12⋯O2^vii	0.95	2.33	2.993 (2)	126

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

Acknowledgments

The authors wish to thank to the Ferdowsi University of Mashhad for financial support (grant No. P/2098).

supplementary crystallographic information

Comment

For several years our research group, among others, has been interested in the synthesis of new coordination compounds from polycarboxylic acids and amines using a proton transfer methodology (Aghabozorg, Daneshvar, et al., 2007; Aghabozorg, Khadivi, et al., 2008; Aghabozorg, Ramezanipour, et al., 2006; Eshtiagh-Hosseini et al., 2010; Mirzaei et al., 2011). Polycarboxylate ligands are versatile because of their diversity of coordination modes and also because of their ability to initiate self assembly processes by supramolecular interactions (Kondo et al., 1999; Beobide et al., 2006). In the majority of the complexes obtained by proton-transfer methods the metal complex is anionic with the cation derived from the amine used in the synthesis. Among these multicarboxylate ligands, pyridine-2,3-dicarboxylic acid (py-2,3dcH₂) has rarely been used under the conditions generally employed in our studies. In the course of this work we prepared the title binuclear indium(II) compound, whose crystal structure we report on herein.

In addition to being a neutral complex, the title compound (Fig. 1) appears to be the first indium^III complex N,O chelated by one py-2,3-dcH^- ion and one py-2,3-dc^2-ion, with the latter using the carboxyl group in the 3-position to bridge to a second metal. In the resulting centrosymmetric dimer, the coordination sphere of each metal is completed by a water molecule. The O₄N₂ coordination sphere adopts a distorted octahedral geometry with the largest departure being the 75.30 (5)° angles subtended by the chelating ligands (Fig. 1). The average In—O distance of 2.1253 (14) Å is slightly shorter than the average In—N of 2.2478 (17) Å. This can be explained by Pearson's hard and soft acid-base concept (Schlemper et al., 1967).

The solid state structure can be described as chains of dimers associated via hydrogen bonding interactions between the coordinated water molecule, the monoprotonated carboxyl group and oxygen atoms in the pyridine dicarboxylate ligand as well as C—H···O interactons between ring hydrogen atoms and carboxylate oxygen atoms (Table 1). Additionally there is a slipped π-π stacking interaction (Fig. 2) between the (N1,C1-C5) ring and its counterpart in the dimer at -x+1, -y+2, -z+1 [perpendicular separation = 3.107 (1) Å, centroid-to-centroid distance = 3.793 (1) Å, slippage = 1.37 Å, angle between planes = 11.28 (8)° (Janiak, 2000)]. The chains are associated via hydrogen bonding interactions between the lattice water molecules, the coordinated water molecule and oxygen atoms of the carboxylate ligands (Table 1, Fig. 3) to complete the three-dimensional network structure (Krygowski et al., 1998).

A final interaction of significance is a complementary π-π stacking interaction (Fig. 2) between the C13═O6 moiety in one half of the dimer and the (N2,C8-C12) ring in the other half (centroid-to-centroid distance = 3.347 (2) Å, angle of the line joining the centroids to the plane of the ring = 74.7 (1)°).

Experimental

A solution of In₂(SO₄)₃.xH₂O (34 mg, 0.06 mmol) in water (5 ml) was added dropwise to an aqueous solution of pyridine-2,3-dicarboxylic acid (10 mg, 0.06 mmol) and 2-amino-6-methyl pyridine (13 mg, 0.12 mmol) in a 1:1:2 molar ratio at reflux. The solution was cooled to room temperature and upon slow evaporation, X-ray quality crystals were formed which were collected and washed with distilled water.