KGa(PO3)4 crystallizes in the monoclinic C2/m space group. K(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), and four equivalent O(3) atoms. Ga(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form GaO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with four equivalent P(2)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Ga(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 43°. In the second P site, P(2) is bonded to one O(2), one O(4), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Ga(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-47°. There are seven inequivalent O sites. In the first O site, O(6) is bonded in a distorted bent 120 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(7) is bonded in a bent 150 degrees geometry to two equivalent P(2) atoms. In the third O site, O(1) is bonded in a 2-coordinate geometry to one K(1), one Ga(1), and one P(1) atom. In the fourth O site, O(2) is bonded in a 2-coordinate geometry to one K(1), one Ga(1), and one P(2) atom. In the fifth O site, O(3) is bonded in a distorted single-bond geometry to two equivalent K(1) and one P(1) atom. In the sixth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Ga(1) and one P(2) atom. In the seventh O site, O(5) is bonded in a bent 120 degrees geometry to two equivalent P(1) atoms.
KGa(PO3)4 crystallizes in the monoclinic C2/m space group. K(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), and four equivalent O(3) atoms. Both K(1)-O(1) bond lengths are 2.96 Å. Both K(1)-O(2) bond lengths are 3.29 Å. There are two shorter (2.78 Å) and two longer (2.91 Å) K(1)-O(3) bond lengths. Ga(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form GaO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with four equivalent P(2)O4 tetrahedra. Both Ga(1)-O(1) bond lengths are 1.95 Å. Both Ga(1)-O(2) bond lengths are 2.01 Å. Both Ga(1)-O(4) bond lengths are 1.99 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Ga(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 43°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(3) bond length is 1.48 Å. The P(1)-O(5) bond length is 1.62 Å. The P(1)-O(6) bond length is 1.63 Å. In the second P site, P(2) is bonded to one O(2), one O(4), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Ga(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-47°. The P(2)-O(2) bond length is 1.51 Å. The P(2)-O(4) bond length is 1.50 Å. The P(2)-O(6) bond length is 1.59 Å. The P(2)-O(7) bond length is 1.60 Å. There are seven inequivalent O sites. In the first O site, O(6) is bonded in a distorted bent 120 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(7) is bonded in a bent 150 degrees geometry to two equivalent P(2) atoms. In the third O site, O(1) is bonded in a 2-coordinate geometry to one K(1), one Ga(1), and one P(1) atom. In the fourth O site, O(2) is bonded in a 2-coordinate geometry to one K(1), one Ga(1), and one P(2) atom. In the fifth O site, O(3) is bonded in a distorted single-bond geometry to two equivalent K(1) and one P(1) atom. In the sixth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Ga(1) and one P(2) atom. In the seventh O site, O(5) is bonded in a bent 120 degrees geometry to two equivalent P(1) atoms.