LiAlGe2O6 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a distorted pentagonal planar geometry to one O(1), one O(2), one O(3), one O(4), and one O(5) atom. Al(1) is bonded to one O(3), one O(6), two equivalent O(1), and two equivalent O(5) atoms to form AlO6 octahedra that share corners with three equivalent Ge(2)O4 tetrahedra, corners with two equivalent Ge(1)O5 trigonal bipyramids, edges with two equivalent Al(1)O6 octahedra, and  an edgeedge with one Ge(1)O5 trigonal bipyramid. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(6) atom to form distorted GeO5 trigonal bipyramids that share corners with two equivalent Al(1)O6 octahedra, corners with three equivalent Ge(2)O4 tetrahedra, and  an edgeedge with one Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-51°. In the second Ge site, Ge(2) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form GeO4 tetrahedra that share corners with three equivalent Al(1)O6 octahedra and corners with three equivalent Ge(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 46-67°. There are six inequivalent O sites. In the first O site, O(5) is bonded to one Li(1), two equivalent Al(1), and one Ge(2) atom to form a mixture of corner and edge-sharing OLiAl2Ge tetrahedra. In the second O site, O(6) is bonded in a 3-coordinate geometry to one Al(1), one Ge(1), and one Ge(2) atom. In the third O site, O(1) is bonded to one Li(1), two equivalent Al(1), and one Ge(1) atom to form a mixture of distorted corner and edge-sharing OLiAl2Ge tetrahedra. In the fourth O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Ge(1), and one Ge(2) atom. In the fifth O site, O(3) is bonded in a T-shaped geometry to one Li(1), one Al(1), and one Ge(1) atom. In the sixth O site, O(4) is bonded in a trigonal planar geometry to one Li(1), one Ge(1), and one Ge(2) atom.
LiAlGe2O6 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a distorted pentagonal planar geometry to one O(1), one O(2), one O(3), one O(4), and one O(5) atom. The Li(1)-O(1) bond length is 2.18 Å. The Li(1)-O(2) bond length is 2.17 Å. The Li(1)-O(3) bond length is 2.07 Å. The Li(1)-O(4) bond length is 2.05 Å. The Li(1)-O(5) bond length is 2.16 Å. Al(1) is bonded to one O(3), one O(6), two equivalent O(1), and two equivalent O(5) atoms to form AlO6 octahedra that share corners with three equivalent Ge(2)O4 tetrahedra, corners with two equivalent Ge(1)O5 trigonal bipyramids, edges with two equivalent Al(1)O6 octahedra, and  an edgeedge with one Ge(1)O5 trigonal bipyramid. The Al(1)-O(3) bond length is 1.84 Å. The Al(1)-O(6) bond length is 1.87 Å. There is one shorter (1.93 Å) and one longer (2.01 Å) Al(1)-O(1) bond length. There is one shorter (1.95 Å) and one longer (2.03 Å) Al(1)-O(5) bond length. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(6) atom to form distorted GeO5 trigonal bipyramids that share corners with two equivalent Al(1)O6 octahedra, corners with three equivalent Ge(2)O4 tetrahedra, and  an edgeedge with one Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-51°. The Ge(1)-O(1) bond length is 1.79 Å. The Ge(1)-O(2) bond length is 1.82 Å. The Ge(1)-O(3) bond length is 1.74 Å. The Ge(1)-O(4) bond length is 1.80 Å. The Ge(1)-O(6) bond length is 2.39 Å. In the second Ge site, Ge(2) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form GeO4 tetrahedra that share corners with three equivalent Al(1)O6 octahedra and corners with three equivalent Ge(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 46-67°. The Ge(2)-O(2) bond length is 1.77 Å. The Ge(2)-O(4) bond length is 1.78 Å. The Ge(2)-O(5) bond length is 1.79 Å. The Ge(2)-O(6) bond length is 1.75 Å. There are six inequivalent O sites. In the first O site, O(5) is bonded to one Li(1), two equivalent Al(1), and one Ge(2) atom to form a mixture of corner and edge-sharing OLiAl2Ge tetrahedra. In the second O site, O(6) is bonded in a 3-coordinate geometry to one Al(1), one Ge(1), and one Ge(2) atom. In the third O site, O(1) is bonded to one Li(1), two equivalent Al(1), and one Ge(1) atom to form a mixture of distorted corner and edge-sharing OLiAl2Ge tetrahedra. In the fourth O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Ge(1), and one Ge(2) atom. In the fifth O site, O(3) is bonded in a T-shaped geometry to one Li(1), one Al(1), and one Ge(1) atom. In the sixth O site, O(4) is bonded in a trigonal planar geometry to one Li(1), one Ge(1), and one Ge(2) atom.