BaZr4P6O24 crystallizes in the trigonal R-3 space group. Ba(1) is bonded in a distorted hexagonal planar geometry to six equivalent O(3) atoms. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to three equivalent O(1) and three equivalent O(4) atoms to form ZrO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. In the second Zr site, Zr(2) is bonded to three equivalent O(2) and three equivalent O(3) atoms to form ZrO6 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 corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-33°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Zr(2) and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ba(1), one Zr(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(1) atom.
BaZr4P6O24 crystallizes in the trigonal R-3 space group. Ba(1) is bonded in a distorted hexagonal planar geometry to six equivalent O(3) atoms. All Ba(1)-O(3) bond lengths are 2.76 Å. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to three equivalent O(1) and three equivalent O(4) atoms to form ZrO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. All Zr(1)-O(1) bond lengths are 2.15 Å. All Zr(1)-O(4) bond lengths are 2.07 Å. In the second Zr site, Zr(2) is bonded to three equivalent O(2) and three equivalent O(3) atoms to form ZrO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. All Zr(2)-O(2) bond lengths are 2.05 Å. All Zr(2)-O(3) bond lengths are 2.16 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 corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-33°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.54 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Zr(2) and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ba(1), one Zr(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(1) atom.