Na3Ga2(PO4)3 crystallizes in the monoclinic Cc space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted hexagonal planar geometry to one O(1), one O(11), one O(12), one O(2), one O(5), and one O(6) atom. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(11), one O(12), one O(2), one O(7), one O(8), and one O(9) atom. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(1), one O(12), one O(5), one O(6), one O(8), and two equivalent O(3) atoms. There are two inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to one O(1), one O(11), one O(4), one O(5), one O(8), and one O(9) atom to form GaO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. In the second Ga site, Ga(2) is bonded to one O(10), one O(12), one O(2), one O(3), one O(6), and one O(7) atom to form GaO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(12), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Ga(1)O6 octahedra and corners with two equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-40°. In the second P site, P(2) is bonded to one O(2), one O(5), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Ga(1)O6 octahedra and corners with two equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-38°. In the third P site, P(3) is bonded to one O(1), one O(10), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Ga(1)O6 octahedra and corners with two equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-38°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), one Na(3), one Ga(1), and one P(3) atom to form distorted ONa3GaP trigonal bipyramids that share corners with three equivalent O(12)Na3GaP trigonal bipyramids and  a faceface with one O(5)Na2GaP trigonal pyramid. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(2), one Ga(2), and one P(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to two equivalent Na(3), one Ga(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Ga(1) and one P(1) atom. In the fifth O site, O(5) is bonded to one Na(1), one Na(3), one Ga(1), and one P(2) atom to form a mixture of distorted face and corner-sharing ONa2GaP trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one Ga(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Na(2), one Ga(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Ga(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(2), one Ga(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(2), one Ga(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Ga(1), and one P(1) atom. In the twelfth O site, O(12) is bonded to one Na(1), one Na(2), one Na(3), one Ga(2), and one P(1) atom to form distorted ONa3GaP trigonal bipyramids that share corners with three equivalent O(1)Na3GaP trigonal bipyramids and corners with two equivalent O(5)Na2GaP trigonal pyramids.
Na3Ga2(PO4)3 crystallizes in the monoclinic Cc space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted hexagonal planar geometry to one O(1), one O(11), one O(12), one O(2), one O(5), and one O(6) atom. The Na(1)-O(1) bond length is 2.56 Å. The Na(1)-O(11) bond length is 2.32 Å. The Na(1)-O(12) bond length is 2.53 Å. The Na(1)-O(2) bond length is 2.35 Å. The Na(1)-O(5) bond length is 2.41 Å. The Na(1)-O(6) bond length is 2.42 Å. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(11), one O(12), one O(2), one O(7), one O(8), and one O(9) atom. The Na(2)-O(1) bond length is 2.41 Å. The Na(2)-O(10) bond length is 2.51 Å. The Na(2)-O(11) bond length is 2.41 Å. The Na(2)-O(12) bond length is 2.46 Å. The Na(2)-O(2) bond length is 2.39 Å. The Na(2)-O(7) bond length is 2.84 Å. The Na(2)-O(8) bond length is 2.84 Å. The Na(2)-O(9) bond length is 2.46 Å. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(1), one O(12), one O(5), one O(6), one O(8), and two equivalent O(3) atoms. The Na(3)-O(1) bond length is 2.46 Å. The Na(3)-O(12) bond length is 2.38 Å. The Na(3)-O(5) bond length is 2.40 Å. The Na(3)-O(6) bond length is 2.42 Å. The Na(3)-O(8) bond length is 2.43 Å. There is one shorter (2.71 Å) and one longer (2.75 Å) Na(3)-O(3) bond length. There are two inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to one O(1), one O(11), one O(4), one O(5), one O(8), and one O(9) atom to form GaO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The Ga(1)-O(1) bond length is 2.11 Å. The Ga(1)-O(11) bond length is 2.00 Å. The Ga(1)-O(4) bond length is 1.90 Å. The Ga(1)-O(5) bond length is 2.02 Å. The Ga(1)-O(8) bond length is 1.98 Å. The Ga(1)-O(9) bond length is 1.99 Å. In the second Ga site, Ga(2) is bonded to one O(10), one O(12), one O(2), one O(3), one O(6), and one O(7) atom to form GaO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The Ga(2)-O(10) bond length is 1.97 Å. The Ga(2)-O(12) bond length is 2.05 Å. The Ga(2)-O(2) bond length is 2.03 Å. The Ga(2)-O(3) bond length is 1.97 Å. The Ga(2)-O(6) bond length is 2.03 Å. The Ga(2)-O(7) bond length is 1.92 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(12), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Ga(1)O6 octahedra and corners with two equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-40°. The P(1)-O(11) bond length is 1.55 Å. The P(1)-O(12) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(2), one O(5), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Ga(1)O6 octahedra and corners with two equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-38°. The P(2)-O(2) bond length is 1.55 Å. The P(2)-O(5) bond length is 1.55 Å. The P(2)-O(7) bond length is 1.54 Å. The P(2)-O(9) bond length is 1.56 Å. In the third P site, P(3) is bonded to one O(1), one O(10), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Ga(1)O6 octahedra and corners with two equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-38°. The P(3)-O(1) bond length is 1.57 Å. The P(3)-O(10) bond length is 1.54 Å. The P(3)-O(6) bond length is 1.55 Å. The P(3)-O(8) bond length is 1.56 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), one Na(3), one Ga(1), and one P(3) atom to form distorted ONa3GaP trigonal bipyramids that share corners with three equivalent O(12)Na3GaP trigonal bipyramids and  a faceface with one O(5)Na2GaP trigonal pyramid. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(2), one Ga(2), and one P(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to two equivalent Na(3), one Ga(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Ga(1) and one P(1) atom. In the fifth O site, O(5) is bonded to one Na(1), one Na(3), one Ga(1), and one P(2) atom to form a mixture of distorted face and corner-sharing ONa2GaP trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one Ga(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Na(2), one Ga(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Ga(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(2), one Ga(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(2), one Ga(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Ga(1), and one P(1) atom. In the twelfth O site, O(12) is bonded to one Na(1), one Na(2), one Na(3), one Ga(2), and one P(1) atom to form distorted ONa3GaP trigonal bipyramids that share corners with three equivalent O(1)Na3GaP trigonal bipyramids and corners with two equivalent O(5)Na2GaP trigonal pyramids.