catena-Poly[[[aqua(formato-κO)(1,10-phenanthroline-κ2 N,N′)manganese(II)]-μ-formato-κ2 O:O′] monohydrate]

The title compound, {[Mn(HCOO)2(C12H8N2)(H2O)]·H2O}n, consists of polymeric chains of the complex [Mn(HCOO)2(phen)(H2O)]∞ (phen is 1,10-phenanthroline) with solvent water molecules. The chains contain six-coordinate MnII ions bridged by formate anions. They are further extended into a three-dimensional network via O—H⋯O hydrogen-bonding interactions and interchain π–π stacking interactions, with a centroid–centroid distance of 3.679 (4) Å.


Experimental
Crystal data  Table 1 Hydrogen-bond geometry (Å , ). catena-Poly [[[aqua(formato-O) (1,10-phenanthroline-2 In recent years, extensive efforts have been dedicated to the design and construction of coordination polymers because their supramolecular architectures with specific topologies may endow them with promising properties for material chemistry, such as gas sorption, storage and separations, molecular recognition, heterogeneous catalysis, nonlinear optics and magnetic properties (Robin & Fromm, 2006;Farrusseng, et al., 2008;Chen, et al., 2010). Investigations on a series of transition metal formate anions showed that it tend to function as a bidentate ligand to bridge metal atoms into one-dimensional chains, two-dimensional layers and three-dimensional networks (Hagen, et al., 2009;Hu, et al., 2009;Paredes-Gaecía, 2009 (Yuan, et al., 2008). The coordinated water molecule forms a strong intra-chain hydrogen bond to the carboxyl O2 with d(O···O) = 2.713 (5) Å and <O-H···O = 150°. There are three kinds of independent inter-chain hydrogen bonds responsible for the two-dimensional layers assembly (Fig. 3, Table 1). One kind of the inter-chain O-H···O hydrogen bonds is formed between the O-H group of coordinated water molecules acting as acceptors (the O···O distance is 2.601 (6) Å with a O-H···O angle of 177°). The other two kinds are formed between the O-H groups of uncoordinated water molecules and the uncoordinated oxygen atoms of the carboxyl groups from the coordianted terminal formate anions in two adjacent chains, with the different O···O distances of 2.693 (8) and 2.864 (9) Å, and two different O-H···O angles of 166° and 145°, respectively. The phen ligands chelating Mn atoms exhibit nearly perfect coplanarity. Two neighboring phen ligands of different chains parallelly face opposite directions at an interplanar centroid to centroid distance of 3.679 (4) Å, with the quinoline fragments partially covered, which suggests significant inter-chain π-π stacking interactions (Janiak, 2000). Acoording to the above description, it is clear that the π-π interactions and inter-chain hydrogen bonding interactions are responsible for the supramolecular assembly of the three-dimensional network.
supplementary materials sup-2 Experimental Addition of 2.0 mL (1.0 M) NaOH to a stirred aqueous of 0.201 g (1.0 mmol) MnCl 2 .4H 2 O in 5.0 mL H 2 O yield yellowish precipitate, which was then separated by centrifugation, followed by washing with double-distilled water until no detectable Clanions in supernatant. The precipitate was added to a stirred ethanolic aqueous solution of 0.198 g (1.0 mmol) 1,10phenanthroline monohydrate in 20 mL EtOH/H 2 O (v:v = 1: 1). To the mixture was added 2.0 mL (1.0 M) HCOOH and the yellowish suspension was further stirred for ca. 30 min. After filtration, the solution (pH = 6.58) was allowed to stand at room temperature. Slow evaporation for two weeks affored yellowish crystals (yield 62% based on the initial MnCl 2 .4H 2 O input).

Refinement
All H atoms bound to C were position geometrically and refined as riding, with C-H = 0.93 Å and U iso (H) = 1.2U eq (C). H atoms attached to O were located in difference Fourier maps and placed at fixed positions with U iso (H) = 1.5U eq (O). catena-Poly [[[aqua(formato-κO) (1,10-phenanthrolineκ 2 N,N')

Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2σ(F 2 ) is used only for calculating R-supplementary materials sup-4 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.