NaAlGeO4 crystallizes in the orthorhombic Pmc2_1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(4), two equivalent O(5), and two equivalent O(8) atoms. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(3), two equivalent O(6), and two equivalent O(7) atoms. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(3), one O(5), two equivalent O(4), and two equivalent O(8) atoms to form AlO6 octahedra that share corners with four equivalent Ge(2)O6 octahedra, edges with two equivalent Al(1)O6 octahedra, and edges with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. In the second Al site, Al(2) is bonded to one O(1), one O(7), two equivalent O(2), and two equivalent O(6) atoms to form AlO6 octahedra that share corners with four equivalent Ge(1)O6 octahedra, edges with two equivalent Al(2)O6 octahedra, and edges with two equivalent Ge(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(4), one O(6), two equivalent O(3), and two equivalent O(7) atoms to form GeO6 octahedra that share corners with four equivalent Al(2)O6 octahedra, edges with two equivalent Al(1)O6 octahedra, and edges with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. In the second Ge site, Ge(2) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(5) atoms to form GeO6 octahedra that share corners with four equivalent Al(1)O6 octahedra, edges with two equivalent Al(2)O6 octahedra, and edges with two equivalent Ge(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(2), one Al(2), and two equivalent Ge(2) atoms to form ONa2AlGe2 square pyramids that share corners with two equivalent O(6)Na2Al2Ge trigonal bipyramids, corners with two equivalent O(3)Na2AlGe2 trigonal bipyramids, corners with two equivalent O(5)Na2AlGe2 trigonal bipyramids, edges with two equivalent O(2)Na2Al2Ge square pyramids, edges with two equivalent O(1)Na2AlGe2 square pyramids,  an edgeedge with one O(3)Na2AlGe2 trigonal bipyramid,  an edgeedge with one O(5)Na2AlGe2 trigonal bipyramid, and edges with two equivalent O(6)Na2Al2Ge trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Na(1), two equivalent Al(2), and one Ge(2) atom to form distorted ONa2Al2Ge square pyramids that share corners with two equivalent O(4)Na2Al2Ge trigonal bipyramids, corners with two equivalent O(6)Na2Al2Ge trigonal bipyramids, corners with two equivalent O(5)Na2AlGe2 trigonal bipyramids, edges with two equivalent O(2)Na2Al2Ge square pyramids, edges with two equivalent O(1)Na2AlGe2 square pyramids,  an edgeedge with one O(4)Na2Al2Ge trigonal bipyramid,  an edgeedge with one O(6)Na2Al2Ge trigonal bipyramid, and edges with two equivalent O(5)Na2AlGe2 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Na(2), one Al(1), and two equivalent Ge(1) atoms to form distorted ONa2AlGe2 trigonal bipyramids that share corners with two equivalent O(1)Na2AlGe2 square pyramids,  a cornercorner with one O(5)Na2AlGe2 trigonal bipyramid, corners with two equivalent O(6)Na2Al2Ge trigonal bipyramids,  an edgeedge with one O(1)Na2AlGe2 square pyramid, edges with two equivalent O(4)Na2Al2Ge trigonal bipyramids, edges with two equivalent O(6)Na2Al2Ge trigonal bipyramids, and edges with two equivalent O(3)Na2AlGe2 trigonal bipyramids. In the fourth O site, O(4) is bonded to two equivalent Na(1), two equivalent Al(1), and one Ge(1) atom to form distorted ONa2Al2Ge trigonal bipyramids that share corners with two equivalent O(2)Na2Al2Ge square pyramids,  a cornercorner with one O(6)Na2Al2Ge trigonal bipyramid, corners with two equivalent O(5)Na2AlGe2 trigonal bipyramids,  an edgeedge with one O(2)Na2Al2Ge square pyramid, edges with two equivalent O(4)Na2Al2Ge trigonal bipyramids, edges with two equivalent O(3)Na2AlGe2 trigonal bipyramids, and edges with two equivalent O(5)Na2AlGe2 trigonal bipyramids. In the fifth O site, O(5) is bonded to two equivalent Na(1), one Al(1), and two equivalent Ge(2) atoms to form distorted ONa2AlGe2 trigonal bipyramids that share corners with two equivalent O(2)Na2Al2Ge square pyramids, corners with two equivalent O(1)Na2AlGe2 square pyramids,  a cornercorner with one O(3)Na2AlGe2 trigonal bipyramid, corners with two equivalent O(4)Na2Al2Ge trigonal bipyramids, corners with four equivalent O(5)Na2AlGe2 trigonal bipyramids,  an edgeedge with one O(1)Na2AlGe2 square pyramid, edges with two equivalent O(2)Na2Al2Ge square pyramids, and edges with two equivalent O(4)Na2Al2Ge trigonal bipyramids. In the sixth O site, O(6) is bonded to two equivalent Na(2), two equivalent Al(2), and one Ge(1) atom to form distorted ONa2Al2Ge trigonal bipyramids that share corners with two equivalent O(2)Na2Al2Ge square pyramids, corners with two equivalent O(1)Na2AlGe2 square pyramids,  a cornercorner with one O(4)Na2Al2Ge trigonal bipyramid, corners with two equivalent O(3)Na2AlGe2 trigonal bipyramids, corners with four equivalent O(6)Na2Al2Ge trigonal bipyramids,  an edgeedge with one O(2)Na2Al2Ge square pyramid, edges with two equivalent O(1)Na2AlGe2 square pyramids, and edges with two equivalent O(3)Na2AlGe2 trigonal bipyramids. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to two equivalent Na(2), one Al(2), and two equivalent Ge(1) atoms. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Al(1), and one Ge(2) atom.
NaAlGeO4 crystallizes in the orthorhombic Pmc2_1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(4), two equivalent O(5), and two equivalent O(8) atoms. Both Na(1)-O(2) bond lengths are 2.36 Å. Both Na(1)-O(4) bond lengths are 2.36 Å. There is one shorter (2.50 Å) and one longer (2.51 Å) Na(1)-O(5) bond length. Both Na(1)-O(8) bond lengths are 2.56 Å. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(3), two equivalent O(6), and two equivalent O(7) atoms. Both Na(2)-O(1) bond lengths are 2.33 Å. Both Na(2)-O(3) bond lengths are 2.33 Å. There is one shorter (2.42 Å) and one longer (2.52 Å) Na(2)-O(6) bond length. Both Na(2)-O(7) bond lengths are 2.52 Å. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(3), one O(5), two equivalent O(4), and two equivalent O(8) atoms to form AlO6 octahedra that share corners with four equivalent Ge(2)O6 octahedra, edges with two equivalent Al(1)O6 octahedra, and edges with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. The Al(1)-O(3) bond length is 1.97 Å. The Al(1)-O(5) bond length is 2.00 Å. Both Al(1)-O(4) bond lengths are 1.93 Å. Both Al(1)-O(8) bond lengths are 1.95 Å. In the second Al site, Al(2) is bonded to one O(1), one O(7), two equivalent O(2), and two equivalent O(6) atoms to form AlO6 octahedra that share corners with four equivalent Ge(1)O6 octahedra, edges with two equivalent Al(2)O6 octahedra, and edges with two equivalent Ge(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. The Al(2)-O(1) bond length is 1.99 Å. The Al(2)-O(7) bond length is 2.03 Å. Both Al(2)-O(2) bond lengths are 1.91 Å. Both Al(2)-O(6) bond lengths are 1.92 Å. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(4), one O(6), two equivalent O(3), and two equivalent O(7) atoms to form GeO6 octahedra that share corners with four equivalent Al(2)O6 octahedra, edges with two equivalent Al(1)O6 octahedra, and edges with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. The Ge(1)-O(4) bond length is 1.93 Å. The Ge(1)-O(6) bond length is 1.95 Å. Both Ge(1)-O(3) bond lengths are 1.93 Å. Both Ge(1)-O(7) bond lengths are 1.97 Å. In the second Ge site, Ge(2) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(5) atoms to form GeO6 octahedra that share corners with four equivalent Al(1)O6 octahedra, edges with two equivalent Al(2)O6 octahedra, and edges with two equivalent Ge(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. The Ge(2)-O(2) bond length is 1.96 Å. The Ge(2)-O(8) bond length is 1.96 Å. Both Ge(2)-O(1) bond lengths are 1.93 Å. Both Ge(2)-O(5) bond lengths are 1.94 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(2), one Al(2), and two equivalent Ge(2) atoms to form ONa2AlGe2 square pyramids that share corners with two equivalent O(6)Na2Al2Ge trigonal bipyramids, corners with two equivalent O(3)Na2AlGe2 trigonal bipyramids, corners with two equivalent O(5)Na2AlGe2 trigonal bipyramids, edges with two equivalent O(2)Na2Al2Ge square pyramids, edges with two equivalent O(1)Na2AlGe2 square pyramids,  an edgeedge with one O(3)Na2AlGe2 trigonal bipyramid,  an edgeedge with one O(5)Na2AlGe2 trigonal bipyramid, and edges with two equivalent O(6)Na2Al2Ge trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Na(1), two equivalent Al(2), and one Ge(2) atom to form distorted ONa2Al2Ge square pyramids that share corners with two equivalent O(4)Na2Al2Ge trigonal bipyramids, corners with two equivalent O(6)Na2Al2Ge trigonal bipyramids, corners with two equivalent O(5)Na2AlGe2 trigonal bipyramids, edges with two equivalent O(2)Na2Al2Ge square pyramids, edges with two equivalent O(1)Na2AlGe2 square pyramids,  an edgeedge with one O(4)Na2Al2Ge trigonal bipyramid,  an edgeedge with one O(6)Na2Al2Ge trigonal bipyramid, and edges with two equivalent O(5)Na2AlGe2 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Na(2), one Al(1), and two equivalent Ge(1) atoms to form distorted ONa2AlGe2 trigonal bipyramids that share corners with two equivalent O(1)Na2AlGe2 square pyramids,  a cornercorner with one O(5)Na2AlGe2 trigonal bipyramid, corners with two equivalent O(6)Na2Al2Ge trigonal bipyramids,  an edgeedge with one O(1)Na2AlGe2 square pyramid, edges with two equivalent O(4)Na2Al2Ge trigonal bipyramids, edges with two equivalent O(6)Na2Al2Ge trigonal bipyramids, and edges with two equivalent O(3)Na2AlGe2 trigonal bipyramids. In the fourth O site, O(4) is bonded to two equivalent Na(1), two equivalent Al(1), and one Ge(1) atom to form distorted ONa2Al2Ge trigonal bipyramids that share corners with two equivalent O(2)Na2Al2Ge square pyramids,  a cornercorner with one O(6)Na2Al2Ge trigonal bipyramid, corners with two equivalent O(5)Na2AlGe2 trigonal bipyramids,  an edgeedge with one O(2)Na2Al2Ge square pyramid, edges with two equivalent O(4)Na2Al2Ge trigonal bipyramids, edges with two equivalent O(3)Na2AlGe2 trigonal bipyramids, and edges with two equivalent O(5)Na2AlGe2 trigonal bipyramids. In the fifth O site, O(5) is bonded to two equivalent Na(1), one Al(1), and two equivalent Ge(2) atoms to form distorted ONa2AlGe2 trigonal bipyramids that share corners with two equivalent O(2)Na2Al2Ge square pyramids, corners with two equivalent O(1)Na2AlGe2 square pyramids,  a cornercorner with one O(3)Na2AlGe2 trigonal bipyramid, corners with two equivalent O(4)Na2Al2Ge trigonal bipyramids, corners with four equivalent O(5)Na2AlGe2 trigonal bipyramids,  an edgeedge with one O(1)Na2AlGe2 square pyramid, edges with two equivalent O(2)Na2Al2Ge square pyramids, and edges with two equivalent O(4)Na2Al2Ge trigonal bipyramids. In the sixth O site, O(6) is bonded to two equivalent Na(2), two equivalent Al(2), and one Ge(1) atom to form distorted ONa2Al2Ge trigonal bipyramids that share corners with two equivalent O(2)Na2Al2Ge square pyramids, corners with two equivalent O(1)Na2AlGe2 square pyramids,  a cornercorner with one O(4)Na2Al2Ge trigonal bipyramid, corners with two equivalent O(3)Na2AlGe2 trigonal bipyramids, corners with four equivalent O(6)Na2Al2Ge trigonal bipyramids,  an edgeedge with one O(2)Na2Al2Ge square pyramid, edges with two equivalent O(1)Na2AlGe2 square pyramids, and edges with two equivalent O(3)Na2AlGe2 trigonal bipyramids. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to two equivalent Na(2), one Al(2), and two equivalent Ge(1) atoms. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Al(1), and one Ge(2) atom.