NaGe4(PO4)3 crystallizes in the trigonal R3c space group. Na(1) is bonded in a 9-coordinate geometry to three equivalent O(1), three equivalent O(2), and three equivalent O(4) atoms. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a distorted T-shaped geometry to three equivalent O(2) atoms. In the second Ge site, Ge(2) is bonded in a distorted T-shaped geometry to one O(1), one O(3), and one O(4) atom. P(1) is bonded in a tetrahedral geometry to one O(1), one O(2), one O(3), and one O(4) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(1), one Ge(2), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Ge(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Ge(2) 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(2), and one P(1) atom.
NaGe4(PO4)3 crystallizes in the trigonal R3c space group. Na(1) is bonded in a 9-coordinate geometry to three equivalent O(1), three equivalent O(2), and three equivalent O(4) atoms. All Na(1)-O(1) bond lengths are 2.54 Å. All Na(1)-O(2) bond lengths are 2.75 Å. All Na(1)-O(4) bond lengths are 2.70 Å. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a distorted T-shaped geometry to three equivalent O(2) atoms. All Ge(1)-O(2) bond lengths are 1.96 Å. In the second Ge site, Ge(2) is bonded in a distorted T-shaped geometry to one O(1), one O(3), and one O(4) atom. The Ge(2)-O(1) bond length is 1.99 Å. The Ge(2)-O(3) bond length is 1.95 Å. The Ge(2)-O(4) bond length is 1.96 Å. P(1) is bonded in a tetrahedral geometry to one O(1), one O(2), one O(3), and one O(4) atom. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.56 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(1), one Ge(2), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Ge(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Ge(2) 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(2), and one P(1) atom.