Sn5P6O25 crystallizes in the trigonal R-3 space group. There are three inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form SnO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. In the second Sn site, Sn(2) is bonded to one O(5) and three equivalent O(3) atoms to form SnO4 tetrahedra that share  a cornercorner with one Sn(2)O4 tetrahedra and corners with three equivalent P(1)O4 tetrahedra. In the third Sn site, Sn(3) is bonded to six equivalent O(1) atoms to form SnO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. 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 Sn(3)O6 octahedra, corners with two equivalent Sn(1)O6 octahedra, and  a cornercorner with one Sn(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 28-53°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Sn(3) and one P(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Sn(1) and one P(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Sn(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Sn(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to two equivalent Sn(2) atoms.
Sn5P6O25 crystallizes in the trigonal R-3 space group. There are three inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form SnO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. All Sn(1)-O(2) bond lengths are 2.09 Å. All Sn(1)-O(4) bond lengths are 2.04 Å. In the second Sn site, Sn(2) is bonded to one O(5) and three equivalent O(3) atoms to form SnO4 tetrahedra that share  a cornercorner with one Sn(2)O4 tetrahedra and corners with three equivalent P(1)O4 tetrahedra. The Sn(2)-O(5) bond length is 1.90 Å. All Sn(2)-O(3) bond lengths are 1.97 Å. In the third Sn site, Sn(3) is bonded to six equivalent O(1) atoms to form SnO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. All Sn(3)-O(1) bond lengths are 2.06 Å. 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 Sn(3)O6 octahedra, corners with two equivalent Sn(1)O6 octahedra, and  a cornercorner with one Sn(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 28-53°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.59 Å. The P(1)-O(4) bond length is 1.52 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Sn(3) and one P(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Sn(1) and one P(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Sn(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Sn(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to two equivalent Sn(2) atoms.