Cr5Zn2(PO4)6 crystallizes in the triclinic P-1 space group. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(10), one O(11), one O(4), one O(9), and two equivalent O(2) atoms to form CrO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Cr(1)O6 octahedra, and  an edgeedge with one Zn(1)O5 trigonal bipyramid. In the second Cr site, Cr(2) is bonded to two equivalent O(12), two equivalent O(5), and two equivalent O(7) atoms to form CrO6 octahedra that share corners with two equivalent Cr(3)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent Zn(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 65°. In the third Cr site, Cr(3) is bonded to one O(1), one O(6), one O(7), one O(8), and two equivalent O(3) atoms to form CrO6 octahedra that share  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra,  an edgeedge with one Cr(3)O6 octahedra, and  an edgeedge with one Zn(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 65°. Zn(1) is bonded to one O(1), one O(11), one O(12), one O(6), and one O(9) atom to form ZnO5 trigonal bipyramids that share  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Cr(1)O6 octahedra, and  an edgeedge with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles are 63°. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(4), one O(6), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(2)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Cr(3)O6 octahedra, and corners with two equivalent Zn(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 35-60°. In the second P site, P(2) is bonded to one O(10), one O(11), one O(12), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Cr(3)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, and corners with two equivalent Zn(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 26-62°. In the third P site, P(3) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(2)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, corners with three equivalent Cr(3)O6 octahedra, and  a cornercorner with one Zn(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 26-55°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Cr(3), one Zn(1), and one P(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent Cr(1) and one P(3) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent Cr(3) and one P(3) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Cr(2) and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Cr(3), one Zn(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Cr(2), one Cr(3), and one P(1) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Cr(3) and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Cr(1), one Zn(1), and one P(1) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(2) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Cr(1), one Zn(1), and one P(2) atom. In the twelfth O site, O(12) is bonded in a trigonal planar geometry to one Cr(2), one Zn(1), and one P(2) atom.
Cr5Zn2(PO4)6 crystallizes in the triclinic P-1 space group. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(10), one O(11), one O(4), one O(9), and two equivalent O(2) atoms to form CrO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Cr(1)O6 octahedra, and  an edgeedge with one Zn(1)O5 trigonal bipyramid. The Cr(1)-O(10) bond length is 1.94 Å. The Cr(1)-O(11) bond length is 2.06 Å. The Cr(1)-O(4) bond length is 1.96 Å. The Cr(1)-O(9) bond length is 2.00 Å. There is one shorter (2.06 Å) and one longer (2.14 Å) Cr(1)-O(2) bond length. In the second Cr site, Cr(2) is bonded to two equivalent O(12), two equivalent O(5), and two equivalent O(7) atoms to form CrO6 octahedra that share corners with two equivalent Cr(3)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent Zn(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 65°. Both Cr(2)-O(12) bond lengths are 2.33 Å. Both Cr(2)-O(5) bond lengths are 2.04 Å. Both Cr(2)-O(7) bond lengths are 2.26 Å. In the third Cr site, Cr(3) is bonded to one O(1), one O(6), one O(7), one O(8), and two equivalent O(3) atoms to form CrO6 octahedra that share  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra,  an edgeedge with one Cr(3)O6 octahedra, and  an edgeedge with one Zn(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 65°. The Cr(3)-O(1) bond length is 2.03 Å. The Cr(3)-O(6) bond length is 2.07 Å. The Cr(3)-O(7) bond length is 2.05 Å. The Cr(3)-O(8) bond length is 1.94 Å. Both Cr(3)-O(3) bond lengths are 2.04 Å. Zn(1) is bonded to one O(1), one O(11), one O(12), one O(6), and one O(9) atom to form ZnO5 trigonal bipyramids that share  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Cr(1)O6 octahedra, and  an edgeedge with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles are 63°. The Zn(1)-O(1) bond length is 2.12 Å. The Zn(1)-O(11) bond length is 2.09 Å. The Zn(1)-O(12) bond length is 1.97 Å. The Zn(1)-O(6) bond length is 2.05 Å. The Zn(1)-O(9) bond length is 2.14 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(4), one O(6), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(2)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Cr(3)O6 octahedra, and corners with two equivalent Zn(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 35-60°. The P(1)-O(4) bond length is 1.51 Å. The P(1)-O(6) bond length is 1.57 Å. The P(1)-O(7) bond length is 1.57 Å. The P(1)-O(9) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(10), one O(11), one O(12), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(2)O6 octahedra,  a cornercorner with one Cr(3)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, and corners with two equivalent Zn(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 26-62°. The P(2)-O(10) bond length is 1.53 Å. The P(2)-O(11) bond length is 1.58 Å. The P(2)-O(12) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.53 Å. In the third P site, P(3) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(2)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, corners with three equivalent Cr(3)O6 octahedra, and  a cornercorner with one Zn(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 26-55°. The P(3)-O(1) bond length is 1.57 Å. The P(3)-O(2) bond length is 1.57 Å. The P(3)-O(3) bond length is 1.58 Å. The P(3)-O(5) bond length is 1.50 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Cr(3), one Zn(1), and one P(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent Cr(1) and one P(3) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent Cr(3) and one P(3) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Cr(2) and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Cr(3), one Zn(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Cr(2), one Cr(3), and one P(1) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Cr(3) and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Cr(1), one Zn(1), and one P(1) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(2) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Cr(1), one Zn(1), and one P(2) atom. In the twelfth O site, O(12) is bonded in a trigonal planar geometry to one Cr(2), one Zn(1), and one P(2) atom.