catena-Poly[[[triaqua[3-(4-carboxyphenoxy)phthalato-κO 2]manganese(II)]-μ-4,4′-bipyridine-κ2 N:N′] 4,4′-bipyridine monosolvate dihydrate]

In the title compound, {[Mn(C15H8O7)(C10H8N2)(H2O)3]·C10H8N2·2H2O}n, the bridging mode of the coordinating 4,4′-bipyridine ligands leads to the formation of polymeric zigzag chains parallel to [0-11]. The chains are separated by 4,4′-bipyridine and water solvent molecules. Within a chain, the MnII atom is six-coordinated by two N atoms of the bridging 4,4′-bipyridine ligands, three water O atoms and one carboxylate O atom of a single deprotonated 3-(4-carboxyphenoxy)phthalic acid ligand. Both coordinating and solvent 4,4′-bipyridine molecules are situated on centres of inversion. An intricate network of O—H⋯O and O—H⋯N hydrogen bonds involving the carboxy group, the coordinating water molecules and the two types of solvent molecules leads to the formation of a three-dimensional network.

In the title compound, {[Mn(C 15 H 8 O 7 )(C 10 H 8 N 2 )(H 2 O) 3 ]Á-C 10 H 8 N 2 Á2H 2 O} n , the bridging mode of the coordinating 4,4 0bipyridine ligands leads to the formation of polymeric zigzag chains parallel to [011]. The chains are separated by 4,4 0bipyridine and water solvent molecules. Within a chain, the Mn II atom is six-coordinated by two N atoms of the bridging 4,4 0 -bipyridine ligands, three water O atoms and one carboxylate O atom of a single deprotonated 3-(4-carboxyphenoxy)phthalic acid ligand. Both coordinating and solvent 4,4 0bipyridine molecules are situated on centres of inversion. An intricate network of O-HÁ Á ÁO and O-HÁ Á ÁN hydrogen bonds involving the carboxy group, the coordinating water molecules and the two types of solvent molecules leads to the formation of a three-dimensional network.

Related literature
For applications of metal-organic coordination polymers, see: Leininger et al. (2000). For a related structure, see: Wang et al.

Experimental
Crystal data [Mn(C 15 Table 1 Hydrogen-bond geometry (Å , ). has been prepared hydrothermally, and its structure is described here.
The asymmetric unit of compound (I) is composed of a 3-(4-carboxyphenoxy) phthalate ligand (L), two halves of two 4,4′-bipyridine ligands, a divalent manganese ion, three coordinating water molecules, two halves of 4,4′-bipyridine solvent molecules and two solvent water molecules. The ligand L is in a single deprotonated form. The Mn II atom is octahedrally coordinated by two N atoms of two bridging 4,4′-bipyridine ligands, three water O atoms and one O atom of a carboxylate function of L (Fig. 1). The bridging mode of the 4,4′-bipyridine ligands leads to the formation of zig-zag chains extending parallel to [011].
Extensive O-H···O and O-H···N hydrogen bonding between water molecules and the carboxy function as donors and 4,4′-bipyridine molecules, carboxyate groups, and water molecules as acceptors (Table 1) leads to the construction of a three-dimensional supramolecular structure (Fig. 2). The hydrogen-bonding scheme resembles that of a related structure discussed by Wang et al. (2009).

Refinement
All C-bound H atoms were placed in geometrically idealized positions and treated as riding on their parent atoms with C -H = 0.93 Å and U iso = 1.2U eq (C). The H atoms associated with the carboxyl group and the water molecules were clearly discernible from difference maps. They were refined with distance restraints (O-H and H-H) by using the DFIX command in SHELXTL, and with U iso (H) = 1.5U eq (O).

Figure 1
The coordination of Mn II in the structure of (I). Displacement ellipsoids are drawn at the 30% probability level. The solvent 4,4′-bipyridine as well as the two solvent water molecules are also shown. All H atoms were omitted for clarity.

Figure 2
A view of three-dimensional supramolecular structure of (I) resulting from the hydrogen bonding (dashed lines represent donor···acceptor interactions).

catena-Poly[[[triaqua[3-(4-carboxyphenoxy)phthalato-κO 2 ]manganese(II)]-µ-4,4′-bipyridine
Special details Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > σ(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.