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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