catena-Poly[[[(2,2′-bipyridine-κ2 N,N′)manganese(II)]-μ-(2,5-dichloro-3,6-dioxocyclohexa-1,4-diene-1,4-diolato)-κ4 O 1,O 6:O 3,O 4] ethanol disolvate]

The asymmetric unit of the title coordination polymer, {[Mn(C6Cl2O4)(C10H8N2)]·2C2H5OH}n, consists of one MnII ion, one 2,2′-bipyridine (bpy) ligand, one chloranilate (CA2−) ligand and two ethanol solvent molecules. The MnII ion is octahedrally coordinated by two N atoms of one bpy ligand and four O atoms of two chloranilate ions. The chloranilate ion serves as a bridging ligand between the MnII ions, leading to an infinite zigzag chain along [101]. π–π stacking interactions [centroid–centroid distance = 4.098 (2) Å] is observed between the pyridine rings of adjacent chains. The ethanol molecules act as accepters as well as donors for O—H⋯O hydrogen bonds, and form a hydrogen-bonded chain along the a axis. The H atoms of the hydroxy groups of the two independent ethanol molecules are each disordered over two sites with equal occupancies.

The asymmetric unit of the title coordination polymer, {[Mn(C 6 Cl 2 O 4 )(C 10 H 8 N 2 )]Á2C 2 H 5 OH} n , consists of one Mn II ion, one 2,2 0 -bipyridine (bpy) ligand, one chloranilate (CA 2À ) ligand and two ethanol solvent molecules. The Mn II ion is octahedrally coordinated by two N atoms of one bpy ligand and four O atoms of two chloranilate ions. The chloranilate ion serves as a bridging ligand between the Mn II ions, leading to an infinite zigzag chain along [101].stacking interactions [centroid-centroid distance = 4.098 (2) Å ] is observed between the pyridine rings of adjacent chains. The ethanol molecules act as accepters as well as donors for O-HÁ Á ÁO hydrogen bonds, and form a hydrogen-bonded chain along the a axis. The H atoms of the hydroxy groups of the two independent ethanol molecules are each disordered over two sites with equal occupancies.
Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: Il Milione (Burla et al., 2007); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Crys-talStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure (Rigaku, 2010 In this paper manganese assembled structures of chloranilic acid (H 2 CA = 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone) are rationally designed by using bpy. Chloranilic acid can coordinate to metal ions in both the bidentate and the bisbidentate fashions (Nagayoshi et al., 2003). The dianion of chloranilic acid consists of two allyl systems connected by C -C single bonds, with four oxygen atoms partially negatively charged. This potentiality allows for the coordination of transition-metal ions through CA 2bridges and permits the probable propagation of magnetic super-exchange interactions between the paramagnetic centers. These kind of complexes using manganese two ions and H 2 CA were reported previously (Kabir et al., 2001). We report here, {[Mn (C 10    [73.67 (7) bridges Mn(II) ions, which leads to infinite chains exhibiting a zig-zag pattern with bipyridine ligands stacking between the chains. The nearest C-C distance of the stacked bipyridine ligands is 3.607 (3) Å. This stacking interaction makes two-dimensional packing structure. This Mn···Mn [8.131 (1) Å] separation is a little smaller than the Mn···Mn [8.170 Å] separation in the chain of 2. The chain complex was assembled in the bc plane to form a one-dimensional channel along the a axis. The crystal structures of 1, 2 and [Mn(CA)(terpy)] n (terpy = 2,2:6,2-terpyridine) are similar. However, only compound 1 contains two ethanol solvents as solvent molecules. Interstitial solvents are introduced to the channel constructed by the assembling of one-dimensional chains to make a clathrate. Two ethanol solvent molecules are connected through hydrogen bonding, and form a one-dimensional chain along the a axis. As a result, voids of compound 1 is expanded by introduction of solvents into the clathrate.

Experimental
A mixture of MnCl 2 .4H 2 O (1 ml, 5 mmolL -1 ) in aqueous solution and 2,2′-bipyridine (1 ml, 5 mmolL -1 ) in ethanol solution was transferred to a glass tube, and then an ethanol solution (10 ml) of H 2 CA (2 ml, 5 mmolL -1 ) was poured into the tube without mixing the two solutions. Dark violet crystals began to form at ambient temperature in a one week. One of these crystals was used for X-ray crystallography.

Refinement
The C-bound H atoms in the bpy and the methyl group of the ethanol molecule were placed at calculated positions with C -H = 0.95 and 0.98 Å, respectively, and were treated as riding on their parent atoms with U iso (H) set to 1.2U eq (C). Both of the hydrogen atoms on the hydroxy groups of the ethanol solvent molecules are disordered over two sites, each with an occupancy of 0.5 and were treated as riding on their parent oxygen atoms, with O-H = 0.84 Å and with U iso (H) set to 1.5U eq (O).

Computing details
Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: Il Milione (Burla et al., 2007); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).    -(2,5-dichloro-3,6-dioxocyclohexa-1,4-diene-1,4- where P = (F o 2 + 2F c 2 )/3 (Δ/σ) max = 0.002 Δρ max = 0.99 e Å −3 Δρ min = −0.57 e Å −3 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.