Na4Zr2(GeO4)3 crystallizes in the trigonal R-3 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to six equivalent O(3) atoms. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to six equivalent O(2) atoms. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form ZrO6 octahedra that share corners with six equivalent Ge(1)O4 tetrahedra. In the second Zr site, Zr(2) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form ZrO6 octahedra that share corners with six equivalent Ge(1)O4 tetrahedra. Ge(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form GeO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-43°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one Ge(1) atom. In the second O site, O(3) is bonded to one Na(2), two equivalent Na(1), one Zr(1), and one Ge(1) atom to form a mixture of distorted edge, face, and corner-sharing ONa3ZrGe trigonal bipyramids. In the third O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Zr(2), and one Ge(1) atom. In the fourth O site, O(2) is bonded to one Na(3), two equivalent Na(1), one Zr(2), and one Ge(1) atom to form a mixture of distorted edge, face, and corner-sharing ONa3ZrGe trigonal bipyramids.
Na4Zr2(GeO4)3 crystallizes in the trigonal R-3 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms. The Na(1)-O(1) bond length is 2.67 Å. The Na(1)-O(4) bond length is 2.61 Å. There is one shorter (2.61 Å) and one longer (2.64 Å) Na(1)-O(2) bond length. There is one shorter (2.51 Å) and one longer (2.68 Å) Na(1)-O(3) bond length. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to six equivalent O(3) atoms. All Na(2)-O(3) bond lengths are 2.46 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to six equivalent O(2) atoms. All Na(3)-O(2) bond lengths are 2.48 Å. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form ZrO6 octahedra that share corners with six equivalent Ge(1)O4 tetrahedra. All Zr(1)-O(1) bond lengths are 2.06 Å. All Zr(1)-O(3) bond lengths are 2.18 Å. In the second Zr site, Zr(2) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form ZrO6 octahedra that share corners with six equivalent Ge(1)O4 tetrahedra. All Zr(2)-O(2) bond lengths are 2.17 Å. All Zr(2)-O(4) bond lengths are 2.06 Å. Ge(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form GeO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-43°. The Ge(1)-O(1) bond length is 1.76 Å. The Ge(1)-O(2) bond length is 1.77 Å. The Ge(1)-O(3) bond length is 1.77 Å. The Ge(1)-O(4) bond length is 1.77 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one Ge(1) atom. In the second O site, O(3) is bonded to one Na(2), two equivalent Na(1), one Zr(1), and one Ge(1) atom to form a mixture of distorted edge, face, and corner-sharing ONa3ZrGe trigonal bipyramids. In the third O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Zr(2), and one Ge(1) atom. In the fourth O site, O(2) is bonded to one Na(3), two equivalent Na(1), one Zr(2), and one Ge(1) atom to form a mixture of distorted edge, face, and corner-sharing ONa3ZrGe trigonal bipyramids.