(VP2(HO4)2)6N2(NH4)4 crystallizes in the triclinic P-1 space group. The structure consists of one ammonia atom and two ammonium molecules inside a VP2(HO4)2 framework. In the VP2(HO4)2 framework, there are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(4), two equivalent O(6), and two equivalent O(9) atoms to form VO6 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 V site, V(2) is bonded to one O(1), one O(10), one O(11), one O(3), one O(5), and one O(7) atom to form VO6 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(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-46°. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-54°. In the third P site, P(3) is bonded to one O(10), one O(11), one O(12), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-49°. There are three inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(2) atom. In the second H site, H(2) is bonded in a distorted linear geometry to one O(10) and one O(8) atom. In the third H site, H(3) 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 distorted bent 120 degrees geometry to one V(2) and one P(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one P(1) and one H(1) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one V(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted linear geometry to one V(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one V(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one V(2) and one P(2) atom. In the eighth O site, O(8) is bonded in a water-like geometry to one P(2) and one H(2) atom. In the ninth O site, O(9) is bonded in a 2-coordinate geometry to one V(1) and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(2), one P(3), and one H(2) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one V(2) and one P(3) atom. In the twelfth O site, O(12) is bonded in a water-like geometry to one P(3) and one H(3) atom.
(VP2(HO4)2)6N2(NH4)4 crystallizes in the triclinic P-1 space group. The structure consists of one ammonia atom and two ammonium molecules inside a VP2(HO4)2 framework. In the VP2(HO4)2 framework, there are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(4), two equivalent O(6), and two equivalent O(9) atoms to form VO6 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. Both V(1)-O(4) bond lengths are 2.05 Å. Both V(1)-O(6) bond lengths are 2.04 Å. Both V(1)-O(9) bond lengths are 2.07 Å. In the second V site, V(2) is bonded to one O(1), one O(10), one O(11), one O(3), one O(5), and one O(7) atom to form VO6 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 V(2)-O(1) bond length is 1.94 Å. The V(2)-O(10) bond length is 2.04 Å. The V(2)-O(11) bond length is 2.01 Å. The V(2)-O(3) bond length is 2.03 Å. The V(2)-O(5) bond length is 1.92 Å. The V(2)-O(7) bond length is 2.04 Å. 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 V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-46°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.59 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.52 Å. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-54°. The P(2)-O(5) bond length is 1.55 Å. The P(2)-O(6) bond length is 1.54 Å. The P(2)-O(7) bond length is 1.54 Å. The P(2)-O(8) bond length is 1.59 Å. In the third P site, P(3) is bonded to one O(10), one O(11), one O(12), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-49°. The P(3)-O(10) bond length is 1.55 Å. The P(3)-O(11) bond length is 1.52 Å. The P(3)-O(12) bond length is 1.61 Å. The P(3)-O(9) bond length is 1.55 Å. There are three inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(2) atom. The H(1)-O(2) bond length is 1.00 Å. In the second H site, H(2) is bonded in a distorted linear geometry to one O(10) and one O(8) atom. The H(2)-O(10) bond length is 1.63 Å. The H(2)-O(8) bond length is 1.01 Å. In the third H site, H(3) is bonded in a single-bond geometry to one O(12) atom. The H(3)-O(12) bond length is 1.00 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one V(2) and one P(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one P(1) and one H(1) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one V(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted linear geometry to one V(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one V(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one V(2) and one P(2) atom. In the eighth O site, O(8) is bonded in a water-like geometry to one P(2) and one H(2) atom. In the ninth O site, O(9) is bonded in a 2-coordinate geometry to one V(1) and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(2), one P(3), and one H(2) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one V(2) and one P(3) atom. In the twelfth O site, O(12) is bonded in a water-like geometry to one P(3) and one H(3) atom.