Na4Ge5O12 crystallizes in the trigonal P-3 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(2) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to six equivalent O(1) atoms. There are three inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(2) atoms. In the second Ge site, Ge(2) is bonded to six equivalent O(2) atoms to form distorted edge-sharing GeO6 pentagonal pyramids. In the third Ge site, Ge(3) is bonded in an octahedral geometry to six equivalent O(1) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Na(1), two equivalent Na(2), one Ge(1), and one Ge(3) atom. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Na(1), one Ge(1), and two equivalent Ge(2) atoms.
Na4Ge5O12 crystallizes in the trigonal P-3 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(2) atoms. All Na(1)-O(1) bond lengths are 2.35 Å. All Na(1)-O(2) bond lengths are 2.27 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to six equivalent O(1) atoms. There are three shorter (2.21 Å) and three longer (2.62 Å) Na(2)-O(1) bond lengths. There are three inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(2) atoms. All Ge(1)-O(1) bond lengths are 1.81 Å. All Ge(1)-O(2) bond lengths are 2.21 Å. In the second Ge site, Ge(2) is bonded to six equivalent O(2) atoms to form distorted edge-sharing GeO6 pentagonal pyramids. There are three shorter (1.90 Å) and three longer (1.98 Å) Ge(2)-O(2) bond lengths. In the third Ge site, Ge(3) is bonded in an octahedral geometry to six equivalent O(1) atoms. All Ge(3)-O(1) bond lengths are 1.95 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Na(1), two equivalent Na(2), one Ge(1), and one Ge(3) atom. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Na(1), one Ge(1), and two equivalent Ge(2) atoms.