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The reaction in water of Cu(OH)2 with 2,2′-bipyridine (bipy) and (NH4)2HPO4 in a 4 : 4 : 2 molar ratio under an inert atmosphere leads to the formation of a tetranuclear copper(ii) complex of formula {[(H2O)2Cu4(bipy)4(μ4–PO4)2(μ2–OH)]·0.5HPO4·15.5H2O}, 1, with butterfly topology. The structure of the tetranuclear core in 1 consists of four crystallographically unique copper(ii) ions in approximate square-pyramidal geometry with each coordinated to a bipy ligand and interacting through two μ4–O,O′,O″-phosphate bridges. Additional bridging between Cu(3) and Cu(4) is provided by a hydroxide ligand, whereas two water molecules cap the Cu(1) and Cu(2) square pyramids to yield a N2O3 chromophore at each copper atom. Adjacent tetranuclear units align in anti-parallel fashion where proximate metal-bound water molecules interact with each other through both intra- and inter-molecular H-bonding to link two such clusters. These pairs then further associate through π⋯π interactions between bipy ligands to form a 2D sheet with neighbouring sheets separated by H-bonded lattice water molecules, which form a 2D H-bonded network. Variable-temperature magnetic susceptibility measurements performed upon 1 reveal net intramolecular ferromagnetic coupling between the copper(ii) ions and this is supported and rationalized by a DFT study. [ABSTRACT FROM AUTHOR]