RbNa2P3(HO2)6 crystallizes in the triclinic P-1 space group. Rb(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(6), one O(8), and two equivalent O(9) atoms. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(10), one O(11), one O(12), one O(7), and one O(9) atom to form NaO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(3), one O(8), and two equivalent O(6) atoms. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. In the second P site, P(2) is bonded to one O(3), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. In the third P site, P(3) is bonded to one O(4), one O(5), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Na(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 50°. There are six inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(10) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(10) atom. In the third H site, H(3) is bonded in a single-bond geometry to one O(11) and one O(7) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(11) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one O(12) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one O(12) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to one Rb(1), one Na(1), and one P(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one Rb(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Na(2), one P(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one P(2) and one P(3) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Rb(1), two equivalent Na(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one P(2), and one H(3) atom. In the eighth O site, O(8) is bonded in a 1-coordinate geometry to one Rb(1), one Na(2), and one P(3) atom. In the ninth O site, O(9) is bonded in a 1-coordinate geometry to two equivalent Rb(1), one Na(1), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted water-like geometry to one Na(1), one Na(2), one H(1), and one H(2) atom. In the eleventh O site, O(11) is bonded in a distorted water-like geometry to one Na(1), one H(3), and one H(4) atom. In the twelfth O site, O(12) is bonded in a distorted water-like geometry to one Na(1), one Na(2), one H(5), and one H(6) atom.
RbNa2P3(HO2)6 crystallizes in the triclinic P-1 space group. Rb(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(6), one O(8), and two equivalent O(9) atoms. The Rb(1)-O(1) bond length is 2.96 Å. The Rb(1)-O(2) bond length is 3.01 Å. The Rb(1)-O(6) bond length is 3.15 Å. The Rb(1)-O(8) bond length is 3.25 Å. There is one shorter (2.98 Å) and one longer (3.16 Å) Rb(1)-O(9) bond length. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(10), one O(11), one O(12), one O(7), and one O(9) atom to form NaO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The Na(1)-O(1) bond length is 2.37 Å. The Na(1)-O(10) bond length is 2.45 Å. The Na(1)-O(11) bond length is 2.37 Å. The Na(1)-O(12) bond length is 2.45 Å. The Na(1)-O(7) bond length is 2.52 Å. The Na(1)-O(9) bond length is 2.46 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(3), one O(8), and two equivalent O(6) atoms. The Na(2)-O(10) bond length is 2.41 Å. The Na(2)-O(12) bond length is 2.49 Å. The Na(2)-O(3) bond length is 2.88 Å. The Na(2)-O(8) bond length is 2.45 Å. There is one shorter (2.41 Å) and one longer (2.49 Å) Na(2)-O(6) bond length. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. The P(1)-O(1) bond length is 1.50 Å. The P(1)-O(2) bond length is 1.51 Å. The P(1)-O(3) bond length is 1.62 Å. The P(1)-O(4) bond length is 1.62 Å. In the second P site, P(2) is bonded to one O(3), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. The P(2)-O(3) bond length is 1.62 Å. The P(2)-O(5) bond length is 1.64 Å. The P(2)-O(6) bond length is 1.51 Å. The P(2)-O(7) bond length is 1.50 Å. In the third P site, P(3) is bonded to one O(4), one O(5), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Na(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 50°. The P(3)-O(4) bond length is 1.62 Å. The P(3)-O(5) bond length is 1.64 Å. The P(3)-O(8) bond length is 1.51 Å. The P(3)-O(9) bond length is 1.50 Å. There are six inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(10) atom. The H(1)-O(10) bond length is 0.99 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(10) atom. The H(2)-O(10) bond length is 0.98 Å. In the third H site, H(3) is bonded in a single-bond geometry to one O(11) and one O(7) atom. The H(3)-O(11) bond length is 0.99 Å. The H(3)-O(7) bond length is 1.73 Å. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(11) atom. The H(4)-O(11) bond length is 0.98 Å. In the fifth H site, H(5) is bonded in a single-bond geometry to one O(12) atom. The H(5)-O(12) bond length is 0.98 Å. In the sixth H site, H(6) is bonded in a single-bond geometry to one O(12) atom. The H(6)-O(12) bond length is 0.99 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to one Rb(1), one Na(1), and one P(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one Rb(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Na(2), one P(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one P(2) and one P(3) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Rb(1), two equivalent Na(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one P(2), and one H(3) atom. In the eighth O site, O(8) is bonded in a 1-coordinate geometry to one Rb(1), one Na(2), and one P(3) atom. In the ninth O site, O(9) is bonded in a 1-coordinate geometry to two equivalent Rb(1), one Na(1), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted water-like geometry to one Na(1), one Na(2), one H(1), and one H(2) atom. In the eleventh O site, O(11) is bonded in a distorted water-like geometry to one Na(1), one H(3), and one H(4) atom. In the twelfth O site, O(12) is bonded in a distorted water-like geometry to one Na(1), one Na(2), one H(5), and one H(6) atom.