Na3VCPO7 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(6), and two equivalent O(4) atoms. V(1) is bonded to one O(1), one O(3), one O(5), one O(6), and two equivalent O(4) atoms to form VO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra. C(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. P(1) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-53°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), two equivalent Na(2), one V(1), and one C(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Na(1), two equivalent Na(2), and one C(1) atom. In the third O site, O(3) is bonded to one Na(1), two equivalent Na(2), one V(1), and one C(1) atom to form distorted corner-sharing ONa3VC trigonal bipyramids. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(2), one V(1), and one P(1) atom. In the sixth O site, O(6) is bonded to two equivalent Na(2), one V(1), and one P(1) atom to form distorted corner-sharing ONa2VP tetrahedra.
Na3VCPO7 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms. The Na(1)-O(1) bond length is 2.30 Å. The Na(1)-O(3) bond length is 2.66 Å. There is one shorter (2.40 Å) and one longer (2.90 Å) Na(1)-O(2) bond length. Both Na(1)-O(4) bond lengths are 2.44 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(6), and two equivalent O(4) atoms. The Na(2)-O(1) bond length is 2.91 Å. The Na(2)-O(2) bond length is 2.38 Å. The Na(2)-O(3) bond length is 2.47 Å. The Na(2)-O(5) bond length is 2.35 Å. The Na(2)-O(6) bond length is 2.41 Å. There is one shorter (2.50 Å) and one longer (2.90 Å) Na(2)-O(4) bond length. V(1) is bonded to one O(1), one O(3), one O(5), one O(6), and two equivalent O(4) atoms to form VO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra. The V(1)-O(1) bond length is 2.20 Å. The V(1)-O(3) bond length is 2.26 Å. The V(1)-O(5) bond length is 2.16 Å. The V(1)-O(6) bond length is 2.17 Å. Both V(1)-O(4) bond lengths are 2.19 Å. C(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. The C(1)-O(1) bond length is 1.31 Å. The C(1)-O(2) bond length is 1.29 Å. The C(1)-O(3) bond length is 1.31 Å. P(1) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-53°. The P(1)-O(5) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.56 Å. Both P(1)-O(4) bond lengths are 1.56 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), two equivalent Na(2), one V(1), and one C(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Na(1), two equivalent Na(2), and one C(1) atom. In the third O site, O(3) is bonded to one Na(1), two equivalent Na(2), one V(1), and one C(1) atom to form distorted corner-sharing ONa3VC trigonal bipyramids. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(2), one V(1), and one P(1) atom. In the sixth O site, O(6) is bonded to two equivalent Na(2), one V(1), and one P(1) atom to form distorted corner-sharing ONa2VP tetrahedra.