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The asymmetric unit of the title compound, {[Mn3{W(CN)8}2(C16H16N2)3(C3H7NO)3(CH3OH)3]·2H2O} n , consists of three [Mn(N,N-di-methyl-formamide)(methanol)(3,4,7,8-tetra-methyl-1,10-phenanthroline)](2+) cations, two [W(CN)8](3-) anions and two water mol-ecules. Each water mol-ecule is disordered over three sets of sites, with a refined occupancy ratio of 0.310 (9):0.275 (9):0.415 (9) for one mol-ecule and 0.335 (9):0.288 (9):0.377 (9) for the other mol-ecule. The Mn(II) atoms exhibit a distorted octa-hedral geometry, while the W(V) atoms adopt a distorted square-anti-prismatic geometry. The Mn(II) and W(V) atoms are linked alternatively through cyanide groups, forming a tetra-nuclear 12-atom rhombic metallacycle. Adjacent metallacycles are further connected by μ2-bridging cyanide anions, generating a 3,2-chain structure running parallel to [101]. Inter-chain π-π inter-actions are observed [centroid-centroid distances = 3.763 (3) and 3.620 (2) Å].

acta crystallographica. section e

Poly[[tetra-μ-cyanido-κ8C:N-dodeca-cyanido-κ12C-tris(N,N-dimethylformamide-κO)tris(methanol-κO)tris(3,4,7,8-tetramethyl-1,10-phenanthroline-κ2N,N′)trimanganese(II)ditungstate(V)] dihydrate]