catena-Poly[[[bis(1,10-phenanthroline-κ2 N,N′)manganese(II)]-μ-9,10-dioxoanthracene-1,5-disulfonato-κ2 O 1:O 5] tetrahydrate]

The title complex, {[Mn(C14H6O8S2)(C12H8N2)2]·4H2O}n, exhibits a chain-like polymeric structure with 9,10-dioxoanthracene-1,5-disulfonate anions bridging MnII atoms in a bis-monodentate mode. The unique MnII atom is located on a crystallographic centre of inversion. Four N atoms from two chelating 1,10-phenanthroline ligands and two sulfonate O atoms from two symmetry-related 9,10-dioxoanthracene-1,5-disulfonate anions give rise to a slightly distorted octahedral coordination environment around the MnII centre. The centroid of the central ring of the anthraquinone ligand represents another crystallographic centre of inversion. In the crystal structure, interligand π–π stacking [centroid-to-centroid distances 3.532 (1) and 3.497 (3) Å] and intermolecular O—H⋯O hydrogen-bonding interactions assemble the chains into a three-dimensional supramolecular network.

The title complex, {[Mn(C 14 H 6 O 8 S 2 )(C 12 H 8 N 2 ) 2 ]Á4H 2 O} n , exhibits a chain-like polymeric structure with 9,10-dioxoanthracene-1,5-disulfonate anions bridging Mn II atoms in a bis-monodentate mode. The unique Mn II atom is located on a crystallographic centre of inversion. Four N atoms from two chelating 1,10-phenanthroline ligands and two sulfonate O atoms from two symmetry-related 9,10-dioxoanthracene-1,5disulfonate anions give rise to a slightly distorted octahedral coordination environment around the Mn II centre. The centroid of the central ring of the anthraquinone ligand represents another crystallographic centre of inversion. In the crystal structure, interligandstacking [centroid-tocentroid distances 3.532 (1) and 3.497 (3) Å ] and intermolecular O-HÁ Á ÁO hydrogen-bonding interactions assemble the chains into a three-dimensional supramolecular network.

S1. Comment
Recently, organosulfonate-based metal complexes have drawn intense interest due to their adjustable coordination ability and interesting applications as functional materials [Cai, 2004;Côté & Shimizu, 2003;Zhao et al., 2007]. By introducing popular nitrogen-containing functional organic molecules as coligands, a series of sulfonate-based complexes have successfully been synthesized, which exhibit diverse structures ranging from discrete zero-dimensional (0D) to infinite high-dimensional structures [Cai et al., 2001;Gándara et al., 2006;Du et al., 2006]. As part of our continuous investigation on the coordination chemistry of mixed-ligand systems [Dai et al., 2006;Cui et al., 2007;Wu et al., 2007], we herein report the crystal structure of a Mn II complex with 1,10-phenanthroline and 9,10-dioxoanthracene-1,5-disulfonate ligands (I).
The local coordination environment of Mn II atom in I is shown in Fig. 1. The unique Mn II atom is situated on a crystallodraphic centre of inversion and is six-coordinated by four N atoms from two chelating 1,10-phenanthroline ligands and two sulfonate O atoms from two independent 9,10-dioxoanthracene-1,5-disulfonate anions, exhibiting a slightly distorted octahedral coordination mode. The centrosymmetric 9,10-dioxoanthracene-1,5-disulfonate anion adopts a bis-monodentate mode, linking the adjacent Mn II atoms into a one-dimensional infinite chain along the c-axis (Fig. 2).
Additionally, the adjacent two-dimensional planes are extended into a three-dimensional supramolecular network by fourfold O-H···O hydrogen-bonding interactions between the sulfonate O atoms and the lattice water molecules (Table 1 and Fig. 2).

S3. Refinement
H atoms were located from difference Fourier maps, but were subsequently placed in calculated positions and treated as riding, with C-H = 0.93 Å and O-H = 0.85 Å. All H atoms were allocated displacement parameters related to those of their parent atoms [U iso (H) = 1.2Ueq(C,O)].

Figure 1
The local coordination environment of Mn II in I) drawn with 30% probability displacement ellipsoids. H atoms were omitted for clarity. The short dashed lines indicate interligand π-π stacking interactions [Symmetry code: (A) 1 -x, 1 -y,

Figure 2
The three-dimensional supramolecular network of (I) produced by hydrogen-bonding and π-π stacking interactions.

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.