Synthesis and Crystal Structure of an Unprecedented Supramolecular Complex [Co(µ2-ClO4)2(H2O)2]·2MA

A new supramolecular framework [Co(µ2‐ClO4)2(H2O)2]·2MA (1) [MA=melamine (C3H6N6)] has been synthesized by a hydrothermal method. Interestingly, there are inorganic and organic building blocks with two different supramolecular synthons: (a) 2D (4,4) network constructed by infinite inorganic 1D chains through interchain hydrogen bonding interactions; (b) 1D zigzag organic chains formed by hydrogen bonds, which further stack up through π‐π interactions between the two adjacent MA molecules. The entire structure of 1 is a 3D supramolecular framework resulting from the presence of abundant hydrogen bonds between infinite [Co(µ2‐ClO4)2(H2O)2]n chains and zigzag MA chains in different sheets. 1 gives a nice example of supramolecular framework based on non‐covalent interactions including hydrogen bonding and π‐π interactions. A new 3D supramolecular framework [Co(µ2‐ClO4)2(H2O)2]·2MA linked by hydrogen bonding and π‐π interactions is reported.