Na3Ga(OH)(HPO4)(PO4) crystallizes in the monoclinic C2/m space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form distorted NaO6 octahedra that share corners with two equivalent Ga(1)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, and edges with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(7), and two equivalent O(4) atoms. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms. Ga(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(7) atoms to form GaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Ga(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-55°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent Ga(1)O6 octahedra and edges with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 46°. In the second P site, P(2) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent Na(1)O6 octahedra and corners with two equivalent Ga(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-65°. There are two inequivalent H sites. In the first H site, H(1) is bonded in a distorted linear geometry to one O(5) and one O(6) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(7) atom. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted see-saw-like geometry to one Na(2), two equivalent Na(1), and one P(1) atom. In the second O site, O(2) is bonded to one Na(2), two equivalent Na(3), and one P(1) atom to form distorted corner-sharing ONa3P tetrahedra. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Ga(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Ga(1), and one P(2) atom. In the fifth O site, O(5) is bonded to two equivalent Na(1), one P(2), and one H(1) atom to form distorted edge-sharing ONa2PH tetrahedra. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to two equivalent Na(3), one P(2), and one H(1) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Na(2), two equivalent Ga(1), and one H(2) atom.
Na3Ga(OH)(HPO4)(PO4) crystallizes in the monoclinic C2/m space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form distorted NaO6 octahedra that share corners with two equivalent Ga(1)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, and edges with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. Both Na(1)-O(1) bond lengths are 2.47 Å. Both Na(1)-O(3) bond lengths are 2.44 Å. Both Na(1)-O(5) bond lengths are 2.48 Å. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(7), and two equivalent O(4) atoms. The Na(2)-O(1) bond length is 2.21 Å. The Na(2)-O(2) bond length is 2.27 Å. The Na(2)-O(7) bond length is 2.49 Å. Both Na(2)-O(4) bond lengths are 2.52 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms. Both Na(3)-O(2) bond lengths are 2.25 Å. Both Na(3)-O(4) bond lengths are 2.46 Å. Both Na(3)-O(6) bond lengths are 2.75 Å. Ga(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(7) atoms to form GaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Ga(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-55°. Both Ga(1)-O(3) bond lengths are 1.96 Å. Both Ga(1)-O(4) bond lengths are 2.05 Å. Both Ga(1)-O(7) bond lengths are 2.01 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent Ga(1)O6 octahedra and edges with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 46°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.53 Å. Both P(1)-O(3) bond lengths are 1.58 Å. In the second P site, P(2) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent Na(1)O6 octahedra and corners with two equivalent Ga(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-65°. The P(2)-O(5) bond length is 1.53 Å. The P(2)-O(6) bond length is 1.61 Å. Both P(2)-O(4) bond lengths are 1.55 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a distorted linear geometry to one O(5) and one O(6) atom. The H(1)-O(5) bond length is 1.64 Å. The H(1)-O(6) bond length is 1.02 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(7) atom. The H(2)-O(7) bond length is 0.97 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted see-saw-like geometry to one Na(2), two equivalent Na(1), and one P(1) atom. In the second O site, O(2) is bonded to one Na(2), two equivalent Na(3), and one P(1) atom to form distorted corner-sharing ONa3P tetrahedra. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Ga(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Ga(1), and one P(2) atom. In the fifth O site, O(5) is bonded to two equivalent Na(1), one P(2), and one H(1) atom to form distorted edge-sharing ONa2PH tetrahedra. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to two equivalent Na(3), one P(2), and one H(1) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Na(2), two equivalent Ga(1), and one H(2) atom.