Na2ZrGe2O7 crystallizes in the triclinic P-1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to one O(1), one O(5), one O(6), two equivalent O(3), and three equivalent O(4) atoms. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(3), one O(5), one O(7), and two equivalent O(2) atoms. Zr(1) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form ZrO6 octahedra that share corners with three equivalent Ge(1)O4 tetrahedra and corners with three equivalent Ge(2)O4 tetrahedra. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form GeO4 tetrahedra that share corners with three equivalent Zr(1)O6 octahedra and  a cornercorner with one Ge(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 29-58°. In the second Ge site, Ge(2) is bonded to one O(1), one O(2), one O(3), and one O(7) atom to form GeO4 tetrahedra that share corners with three equivalent Zr(1)O6 octahedra and  a cornercorner with one Ge(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 14-54°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Na(1), one Zr(1), and one Ge(2) atom. In the second O site, O(2) is bonded to two equivalent Na(2), one Ge(1), and one Ge(2) atom to form distorted ONa2Ge2 trigonal pyramids that share  a cornercorner with one O(5)Na2ZrGe trigonal pyramid,  an edgeedge with one O(2)Na2Ge2 trigonal pyramid, and  an edgeedge with one O(5)Na2ZrGe trigonal pyramid. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Na(1), one Zr(1), and one Ge(2) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to three equivalent Na(1), one Zr(1), and one Ge(1) atom. In the fifth O site, O(5) is bonded to one Na(1), one Na(2), one Zr(1), and one Ge(1) atom to form a mixture of corner and edge-sharing ONa2ZrGe trigonal pyramids. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one Ge(1) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Na(2), one Zr(1), and one Ge(2) atom.
Na2ZrGe2O7 crystallizes in the triclinic P-1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to one O(1), one O(5), one O(6), two equivalent O(3), and three equivalent O(4) atoms. The Na(1)-O(1) bond length is 2.56 Å. The Na(1)-O(5) bond length is 2.49 Å. The Na(1)-O(6) bond length is 2.48 Å. There is one shorter (2.85 Å) and one longer (2.89 Å) Na(1)-O(3) bond length. There are a spread of Na(1)-O(4) bond distances ranging from 2.46-2.91 Å. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(3), one O(5), one O(7), and two equivalent O(2) atoms. The Na(2)-O(3) bond length is 2.36 Å. The Na(2)-O(5) bond length is 2.44 Å. The Na(2)-O(7) bond length is 2.58 Å. There is one shorter (2.38 Å) and one longer (2.56 Å) Na(2)-O(2) bond length. Zr(1) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form ZrO6 octahedra that share corners with three equivalent Ge(1)O4 tetrahedra and corners with three equivalent Ge(2)O4 tetrahedra. The Zr(1)-O(1) bond length is 2.08 Å. The Zr(1)-O(3) bond length is 2.16 Å. The Zr(1)-O(4) bond length is 2.18 Å. The Zr(1)-O(5) bond length is 2.15 Å. The Zr(1)-O(6) bond length is 2.08 Å. The Zr(1)-O(7) bond length is 2.07 Å. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form GeO4 tetrahedra that share corners with three equivalent Zr(1)O6 octahedra and  a cornercorner with one Ge(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 29-58°. The Ge(1)-O(2) bond length is 1.83 Å. The Ge(1)-O(4) bond length is 1.76 Å. The Ge(1)-O(5) bond length is 1.78 Å. The Ge(1)-O(6) bond length is 1.74 Å. In the second Ge site, Ge(2) is bonded to one O(1), one O(2), one O(3), and one O(7) atom to form GeO4 tetrahedra that share corners with three equivalent Zr(1)O6 octahedra and  a cornercorner with one Ge(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 14-54°. The Ge(2)-O(1) bond length is 1.74 Å. The Ge(2)-O(2) bond length is 1.83 Å. The Ge(2)-O(3) bond length is 1.76 Å. The Ge(2)-O(7) bond length is 1.75 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Na(1), one Zr(1), and one Ge(2) atom. In the second O site, O(2) is bonded to two equivalent Na(2), one Ge(1), and one Ge(2) atom to form distorted ONa2Ge2 trigonal pyramids that share  a cornercorner with one O(5)Na2ZrGe trigonal pyramid,  an edgeedge with one O(2)Na2Ge2 trigonal pyramid, and  an edgeedge with one O(5)Na2ZrGe trigonal pyramid. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Na(1), one Zr(1), and one Ge(2) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to three equivalent Na(1), one Zr(1), and one Ge(1) atom. In the fifth O site, O(5) is bonded to one Na(1), one Na(2), one Zr(1), and one Ge(1) atom to form a mixture of corner and edge-sharing ONa2ZrGe trigonal pyramids. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one Ge(1) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Na(2), one Zr(1), and one Ge(2) atom.