Na3GeCPO7 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(4), two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(6) atom. In the third Na site, Na(3) is bonded to two equivalent O(5), two equivalent O(6), and two equivalent O(7) atoms to form distorted NaO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra and faces with two equivalent Na(3)O6 octahedra. Ge(1) is bonded in a 3-coordinate geometry to one O(4), one O(5), and one O(7) atom. C(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(5) atom. P(1) is bonded to one O(3), one O(4), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-71°. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), two equivalent Na(1), and one C(1) atom to form distorted corner-sharing ONa3C trigonal pyramids. In the second O site, O(2) is bonded in a 1-coordinate geometry to one Na(2), two equivalent Na(1), and one C(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(2), two equivalent Na(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Ge(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(3), one Ge(1), and one C(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(3), and one P(1) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to two equivalent Na(3), one Ge(1), and one P(1) atom.
Na3GeCPO7 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(4), two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. The Na(1)-O(4) bond length is 2.53 Å. There is one shorter (2.41 Å) and one longer (2.46 Å) Na(1)-O(1) bond length. There is one shorter (2.36 Å) and one longer (2.60 Å) Na(1)-O(2) bond length. There is one shorter (2.34 Å) and one longer (2.82 Å) Na(1)-O(3) bond length. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(6) atom. The Na(2)-O(1) bond length is 2.49 Å. The Na(2)-O(2) bond length is 2.34 Å. The Na(2)-O(3) bond length is 2.30 Å. The Na(2)-O(6) bond length is 2.32 Å. In the third Na site, Na(3) is bonded to two equivalent O(5), two equivalent O(6), and two equivalent O(7) atoms to form distorted NaO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra and faces with two equivalent Na(3)O6 octahedra. There is one shorter (2.68 Å) and one longer (2.69 Å) Na(3)-O(5) bond length. There is one shorter (2.38 Å) and one longer (2.67 Å) Na(3)-O(6) bond length. There is one shorter (2.42 Å) and one longer (2.44 Å) Na(3)-O(7) bond length. Ge(1) is bonded in a 3-coordinate geometry to one O(4), one O(5), and one O(7) atom. The Ge(1)-O(4) bond length is 1.95 Å. The Ge(1)-O(5) bond length is 2.07 Å. The Ge(1)-O(7) bond length is 2.08 Å. C(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(5) atom. The C(1)-O(1) bond length is 1.27 Å. The C(1)-O(2) bond length is 1.30 Å. The C(1)-O(5) bond length is 1.34 Å. P(1) is bonded to one O(3), one O(4), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-71°. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.58 Å. The P(1)-O(6) bond length is 1.54 Å. The P(1)-O(7) bond length is 1.58 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), two equivalent Na(1), and one C(1) atom to form distorted corner-sharing ONa3C trigonal pyramids. In the second O site, O(2) is bonded in a 1-coordinate geometry to one Na(2), two equivalent Na(1), and one C(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(2), two equivalent Na(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Ge(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(3), one Ge(1), and one C(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(3), and one P(1) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to two equivalent Na(3), one Ge(1), and one P(1) atom.