Na2GeCPO7 crystallizes in the monoclinic P2_1/m space group. Na(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted NaO6 octahedra that share corners with two equivalent Ge(1)O6 octahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one Na(1)O6 octahedra,  a faceface with one Na(1)O6 octahedra, and  a faceface with one Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 65-80°. Ge(1) is bonded to one O(2), one O(3), one O(5), one O(6), and two equivalent O(4) atoms to form GeO6 octahedra that share corners with four equivalent Na(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and faces with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 65-80°. 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 Ge(1)O6 octahedra and corners with six equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-70°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one C(1) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to two equivalent Na(1), one Ge(1), and one C(1) atom. In the third O site, O(3) is bonded to two equivalent Na(1), one Ge(1), and one C(1) atom to form distorted corner-sharing ONa2GeC trigonal pyramids. 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(1), one Ge(1), and one P(1) atom. In the sixth O site, O(6) is bonded to two equivalent Na(1), one Ge(1), and one P(1) atom to form distorted corner-sharing ONa2GeP tetrahedra.
Na2GeCPO7 crystallizes in the monoclinic P2_1/m space group. Na(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted NaO6 octahedra that share corners with two equivalent Ge(1)O6 octahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one Na(1)O6 octahedra,  a faceface with one Na(1)O6 octahedra, and  a faceface with one Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 65-80°. The Na(1)-O(1) bond length is 2.24 Å. The Na(1)-O(2) bond length is 2.38 Å. The Na(1)-O(3) bond length is 2.39 Å. The Na(1)-O(4) bond length is 2.53 Å. The Na(1)-O(5) bond length is 2.44 Å. The Na(1)-O(6) bond length is 2.55 Å. Ge(1) is bonded to one O(2), one O(3), one O(5), one O(6), and two equivalent O(4) atoms to form GeO6 octahedra that share corners with four equivalent Na(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and faces with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 65-80°. The Ge(1)-O(2) bond length is 2.03 Å. The Ge(1)-O(3) bond length is 2.19 Å. The Ge(1)-O(5) bond length is 2.09 Å. The Ge(1)-O(6) bond length is 2.37 Å. Both Ge(1)-O(4) bond lengths are 2.07 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 1.25 Å. The C(1)-O(2) bond length is 1.33 Å. The C(1)-O(3) bond length is 1.32 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 Ge(1)O6 octahedra and corners with six equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-70°. The P(1)-O(5) bond length is 1.57 Å. The P(1)-O(6) bond length is 1.55 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 two equivalent Na(1) and one C(1) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to two equivalent Na(1), one Ge(1), and one C(1) atom. In the third O site, O(3) is bonded to two equivalent Na(1), one Ge(1), and one C(1) atom to form distorted corner-sharing ONa2GeC trigonal pyramids. 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(1), one Ge(1), and one P(1) atom. In the sixth O site, O(6) is bonded to two equivalent Na(1), one Ge(1), and one P(1) atom to form distorted corner-sharing ONa2GeP tetrahedra.