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Single crystals of sodium copper(II) indium bis[phosphate(V)], NaCuIn(PO4)2, were grown from the melt under atmospheric conditions. The title phosphate crystallizes in the space group P21/n and is isotypic with KCuFe(PO4)2. In the crystal, two [CuO5] trigonal bipyramids share an edge to form a dimer [Cu2O8] that is connected to two PO4 tetrahedra. The obtained [Cu2P2O12] units are interconnected through vertices to form sheets that are sandwiched between undulating layers resulting from the junction of PO4 tetrahedra and [InO6] octahedra. The two types of layers are alternately stacked along [101] and are joined into a three-dimensional framework through vertex- and edge-sharing, leaving channels parallel to the stacking direction. The channels host the sodium cations that are surrounded by four oxygen atoms in form of a distorted disphenoid.

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The title transition metal vanadate crystallizes in an alluaudite-type structure. The chains characterizing the alluaudite structure are built up from edge-sharing [FeO6] octa­hedra linked together by VO4 tetra­hedra.

Crystals of the new compound, AgSr4Cu4.5(PO4)6, were grown successfully by the hydrothermal process. The asymmetric unit of the crystal structure of the title compound contains 40 independent atoms (4 Sr, 4.5 Cu, 1 Ag, 6 P and 24 O), which are all in general positions except for one Cu atom, which is located on an inversion centre. The Cu atoms are arranged in CuO n (n = 4 or 5) polyhedra, linked through common oxygen corners to build a rigid three-dimensional motif. The connection of these copper units is assured by PO4 tetrahedra. This arrangement allows the construction of layers extending parallel to the (100) plane and hosts suitable cavities in which Ag+ and Sr2+ cations are located. The crystal-structure cohesion is ensured by ionic bonds between the silver and strontium cations and the oxygen anions belonging to two adjacent sheets. Charge-distribution analysis and bond-valence-sum calculations were used to validate the structural model.