NaCaVO4 crystallizes in the orthorhombic Cmcm space group. Na(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form NaO6 octahedra that share corners with six equivalent Ca(1)O4 tetrahedra, corners with six equivalent V(1)O4 tetrahedra, and edges with two equivalent Na(1)O6 octahedra. Ca(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted CaO4 tetrahedra that share corners with six equivalent Na(1)O6 octahedra, corners with two equivalent V(1)O4 tetrahedra, and  an edgeedge with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 73-79°. V(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form VO4 tetrahedra that share corners with six equivalent Na(1)O6 octahedra, corners with two equivalent Ca(1)O4 tetrahedra, and  an edgeedge with one Ca(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-52°. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), one Ca(1), and one V(1) atom to form a mixture of distorted edge and corner-sharing ONa2CaV tetrahedra. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Ca(1), and one V(1) atom.
NaCaVO4 crystallizes in the orthorhombic Cmcm space group. Na(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form NaO6 octahedra that share corners with six equivalent Ca(1)O4 tetrahedra, corners with six equivalent V(1)O4 tetrahedra, and edges with two equivalent Na(1)O6 octahedra. Both Na(1)-O(2) bond lengths are 2.37 Å. All Na(1)-O(1) bond lengths are 2.47 Å. Ca(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted CaO4 tetrahedra that share corners with six equivalent Na(1)O6 octahedra, corners with two equivalent V(1)O4 tetrahedra, and  an edgeedge with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 73-79°. Both Ca(1)-O(1) bond lengths are 2.38 Å. Both Ca(1)-O(2) bond lengths are 2.27 Å. V(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form VO4 tetrahedra that share corners with six equivalent Na(1)O6 octahedra, corners with two equivalent Ca(1)O4 tetrahedra, and  an edgeedge with one Ca(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-52°. Both V(1)-O(1) bond lengths are 1.75 Å. Both V(1)-O(2) bond lengths are 1.74 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), one Ca(1), and one V(1) atom to form a mixture of distorted edge and corner-sharing ONa2CaV tetrahedra. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Ca(1), and one V(1) atom.