Na2Al2(GeO4)3 crystallizes in the orthorhombic Fdd2 space group. Na(1) is bonded to one O(5), one O(6), two equivalent O(1), and two equivalent O(2) atoms to form distorted NaO6 pentagonal pyramids that share corners with two equivalent Al(1)O4 tetrahedra, corners with two equivalent Ge(1)O4 tetrahedra, edges with two equivalent Na(1)O6 pentagonal pyramids,  an edgeedge with one Al(1)O4 tetrahedra, and  an edgeedge with one Ge(1)O4 tetrahedra. Al(1) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form AlO4 tetrahedra that share corners with two equivalent Na(1)O6 pentagonal pyramids,  a cornercorner with one Ge(2)O4 tetrahedra, corners with three equivalent Ge(1)O4 tetrahedra, and  an edgeedge with one Na(1)O6 pentagonal pyramid. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form GeO4 tetrahedra that share corners with two equivalent Na(1)O6 pentagonal pyramids,  a cornercorner with one Ge(2)O4 tetrahedra, corners with three equivalent Al(1)O4 tetrahedra, and  an edgeedge with one Na(1)O6 pentagonal pyramid. In the second Ge site, Ge(2) is bonded to two equivalent O(3) and two equivalent O(4) atoms to form GeO4 tetrahedra that share corners with two equivalent Al(1)O4 tetrahedra and corners with two equivalent Ge(1)O4 tetrahedra. There are six inequivalent O sites. In the first O site, O(3) is bonded in a bent 150 degrees geometry to one Al(1) and one Ge(2) atom. In the second O site, O(4) is bonded in a bent 150 degrees geometry to one Ge(1) and one Ge(2) atom. In the third O site, O(5) is bonded in a distorted trigonal planar geometry to one Na(1), one Al(1), and one Ge(1) atom. In the fourth O site, O(6) is bonded in a distorted trigonal planar geometry to one Na(1), one Al(1), and one Ge(1) atom. In the fifth O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Al(1), and one Ge(1) atom. In the sixth O site, O(2) is bonded in a water-like geometry to two equivalent Na(1) atoms.
Na2Al2(GeO4)3 crystallizes in the orthorhombic Fdd2 space group. Na(1) is bonded to one O(5), one O(6), two equivalent O(1), and two equivalent O(2) atoms to form distorted NaO6 pentagonal pyramids that share corners with two equivalent Al(1)O4 tetrahedra, corners with two equivalent Ge(1)O4 tetrahedra, edges with two equivalent Na(1)O6 pentagonal pyramids,  an edgeedge with one Al(1)O4 tetrahedra, and  an edgeedge with one Ge(1)O4 tetrahedra. The Na(1)-O(5) bond length is 2.34 Å. The Na(1)-O(6) bond length is 2.36 Å. There is one shorter (2.53 Å) and one longer (2.55 Å) Na(1)-O(1) bond length. There is one shorter (2.44 Å) and one longer (2.46 Å) Na(1)-O(2) bond length. Al(1) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form AlO4 tetrahedra that share corners with two equivalent Na(1)O6 pentagonal pyramids,  a cornercorner with one Ge(2)O4 tetrahedra, corners with three equivalent Ge(1)O4 tetrahedra, and  an edgeedge with one Na(1)O6 pentagonal pyramid. The Al(1)-O(1) bond length is 1.78 Å. The Al(1)-O(3) bond length is 1.76 Å. The Al(1)-O(5) bond length is 1.77 Å. The Al(1)-O(6) bond length is 1.76 Å. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form GeO4 tetrahedra that share corners with two equivalent Na(1)O6 pentagonal pyramids,  a cornercorner with one Ge(2)O4 tetrahedra, corners with three equivalent Al(1)O4 tetrahedra, and  an edgeedge with one Na(1)O6 pentagonal pyramid. The Ge(1)-O(1) bond length is 1.77 Å. The Ge(1)-O(4) bond length is 1.78 Å. The Ge(1)-O(5) bond length is 1.75 Å. The Ge(1)-O(6) bond length is 1.76 Å. In the second Ge site, Ge(2) is bonded to two equivalent O(3) and two equivalent O(4) atoms to form GeO4 tetrahedra that share corners with two equivalent Al(1)O4 tetrahedra and corners with two equivalent Ge(1)O4 tetrahedra. Both Ge(2)-O(3) bond lengths are 1.75 Å. Both Ge(2)-O(4) bond lengths are 1.78 Å. There are six inequivalent O sites. In the first O site, O(3) is bonded in a bent 150 degrees geometry to one Al(1) and one Ge(2) atom. In the second O site, O(4) is bonded in a bent 150 degrees geometry to one Ge(1) and one Ge(2) atom. In the third O site, O(5) is bonded in a distorted trigonal planar geometry to one Na(1), one Al(1), and one Ge(1) atom. In the fourth O site, O(6) is bonded in a distorted trigonal planar geometry to one Na(1), one Al(1), and one Ge(1) atom. In the fifth O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Al(1), and one Ge(1) atom. In the sixth O site, O(2) is bonded in a water-like geometry to two equivalent Na(1) atoms.