| Summary: | A survey of the trends in metal–ligand coordination and hydrogen bonding has been carried out on complexes of singly deprotonated cyanuric acid CY<sup>−</sup> and alkaline earth metals, synthesised from aqueous solution and characterised by X-ray crystallography. The involvement of cyanurate in metal coordination increases from Mg through Ca and Sr to Ba relative to coordination by water, in parallel with increasing ionic radius and coordination number. The incidence of the bridging of metal centres by both water and cyanurate also increases in this series. The Mg complex [Mg(H<sub>2</sub>O)<sub>6</sub>][CY]<sub>2</sub>·2H<sub>2</sub>O contains hexaaqua-coordinated cations, uncoordinated CY<sup>−</sup> anions, and additional water molecules. The Ca and Sr complexes {[Ca(CY)(H<sub>2</sub>O)<sub>3</sub>][CY]}<sub>∞</sub> and {[Sr(CY)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]}<sub>∞</sub> feature polymeric chains of coordinated metal ions, the Ca complex with uncoordinated anions and the Sr complex with all potential ligands coordinated. The Ba complex {[Ba(CY)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]}<sub>∞</sub> has a two-dimensional coordination network. Extensive hydrogen bonding plays a key role in generating a three-dimensional network in all four structures. The competition between cyanurate and water for coordination to the alkaline earth metal cations, and that between coordination and the hydrogen bonding propensities of the cyanurate anion, appear to be finely balanced, with the structural outcomes depending on the relative sizes and degrees of hardness of the four cations of the group.
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