LiGaPO5 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form distorted LiO5 square pyramids that share corners with two equivalent Ga(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Ga(2)O6 octahedra,  an edgeedge with one Li(1)O5 square pyramid, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-61°. There are two inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form GaO6 octahedra that share corners with two equivalent Ga(2)O6 octahedra, corners with four equivalent Li(1)O5 square pyramids, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 45°. In the second Ga site, Ga(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form GaO6 octahedra that share corners with two equivalent Ga(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with four equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 45°. P(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Ga(1)O6 octahedra, corners with two equivalent Ga(2)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids, and  an edgeedge with one Li(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 37-55°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Ga(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one Ga(2), and one P(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one Ga(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(1), one Ga(1), and one Ga(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Ga(1), and one P(1) atom.
LiGaPO5 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form distorted LiO5 square pyramids that share corners with two equivalent Ga(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Ga(2)O6 octahedra,  an edgeedge with one Li(1)O5 square pyramid, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-61°. The Li(1)-O(3) bond length is 2.18 Å. The Li(1)-O(4) bond length is 1.98 Å. The Li(1)-O(5) bond length is 2.06 Å. There is one shorter (2.10 Å) and one longer (2.22 Å) Li(1)-O(2) bond length. There are two inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form GaO6 octahedra that share corners with two equivalent Ga(2)O6 octahedra, corners with four equivalent Li(1)O5 square pyramids, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 45°. Both Ga(1)-O(1) bond lengths are 2.03 Å. Both Ga(1)-O(4) bond lengths are 1.94 Å. Both Ga(1)-O(5) bond lengths are 1.97 Å. In the second Ga site, Ga(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form GaO6 octahedra that share corners with two equivalent Ga(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with four equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 45°. Both Ga(2)-O(2) bond lengths are 2.05 Å. Both Ga(2)-O(3) bond lengths are 1.94 Å. Both Ga(2)-O(4) bond lengths are 1.96 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Ga(1)O6 octahedra, corners with two equivalent Ga(2)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids, and  an edgeedge with one Li(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 37-55°. The P(1)-O(1) bond length is 1.53 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(5) bond length is 1.57 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Ga(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one Ga(2), and one P(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one Ga(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(1), one Ga(1), and one Ga(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Ga(1), and one P(1) atom.