Controlling the dimensionality in H bonded systems involving octahedral [Re6Q8(CN)6]4– and trans-[Re6S8(CN)4(H2O)2]2– anions

[Display omitted] •[Re6Q8(CN)6]4– (Q = S, Se) or [Re6S8(CN)4(OH)2]4– octahedral clusters.•H bonded molecular networks.•Charge Assisted H-Bonding. The combination of 1,4-diamidiniumbenzene cation of H2DAB with [Re6Q8(CN)6]4– (Q = S, Se) or [Re6S8(CN)4(OH)2]4– leads to solid-state compounds of formula (H2DAB)2[Re6Q8(CN)6]∙nH2O (Q = S, n = 2.5 (1) or Q = Se, n = 2 (2)), and (HDAB)2[Re6S8(CN)4(H2O)2]∙7H2O (3). Two isostructural compounds are formed through the monohapto recognition mode between H bond donors (H2DAB2+) and H bond acceptors (the –CN moieties of the cluster anions). A 2D system involving water molecules was formed, whereas with the disordered [Re6S8(CN)4(H2O)2]2– anion, a deformed diamondoid porous compound was obtained. Moreover, amidinium cation becomes partially deprotonated (HDAB+). These are rare examples of reliable charge assisted H bonded network involving Re cyanide clusters.