Cr3Co(PO4)4 crystallizes in the monoclinic Pm space group. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(3), one O(7), two equivalent O(11), and two equivalent O(5) atoms to form CrO6 octahedra that share corners with four equivalent Cr(3)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. In the second Cr site, Cr(2) is bonded to one O(10), one O(6), two equivalent O(2), and two equivalent O(8) atoms to form CrO6 octahedra that share corners with four equivalent Co(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. In the third Cr site, Cr(3) is bonded to one O(1), one O(9), two equivalent O(11), and two equivalent O(5) atoms to form CrO6 octahedra that share corners with four equivalent Cr(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. Co(1) is bonded to one O(12), one O(4), two equivalent O(2), and two equivalent O(8) atoms to form distorted CoO6 octahedra that share corners with four equivalent Cr(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), and two equivalent O(2) atoms 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 Co(1)O6 octahedra, and  an edgeedge with one Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. In the second P site, P(2) is bonded to one O(6), one O(9), and two equivalent O(5) atoms 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  an edgeedge with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-57°. In the third P site, P(3) is bonded to one O(4), one O(7), and two equivalent O(8) atoms to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Cr(2)O6 octahedra, and  an edgeedge with one Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-56°. In the fourth P site, P(4) is bonded to one O(12), one O(3), and two equivalent O(11) atoms to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Cr(3)O6 octahedra, and  an edgeedge with one Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-57°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Cr(3) and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Cr(2), one Co(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Cr(1) and one P(4) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Co(1) and one P(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Cr(1), one Cr(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Cr(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Cr(2), one Co(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted bent 120 degrees geometry to one Cr(3) and one P(2) atom. In the tenth O site, O(10) is bonded in a bent 120 degrees geometry to one Cr(2) and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Cr(1), one Cr(3), and one P(4) atom. In the twelfth O site, O(12) is bonded in a distorted bent 120 degrees geometry to one Co(1) and one P(4) atom.
Cr3Co(PO4)4 crystallizes in the monoclinic Pm space group. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(3), one O(7), two equivalent O(11), and two equivalent O(5) atoms to form CrO6 octahedra that share corners with four equivalent Cr(3)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. The Cr(1)-O(3) bond length is 1.97 Å. The Cr(1)-O(7) bond length is 1.97 Å. Both Cr(1)-O(11) bond lengths are 2.08 Å. Both Cr(1)-O(5) bond lengths are 2.05 Å. In the second Cr site, Cr(2) is bonded to one O(10), one O(6), two equivalent O(2), and two equivalent O(8) atoms to form CrO6 octahedra that share corners with four equivalent Co(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. The Cr(2)-O(10) bond length is 1.98 Å. The Cr(2)-O(6) bond length is 1.97 Å. Both Cr(2)-O(2) bond lengths are 2.09 Å. Both Cr(2)-O(8) bond lengths are 2.02 Å. In the third Cr site, Cr(3) is bonded to one O(1), one O(9), two equivalent O(11), and two equivalent O(5) atoms to form CrO6 octahedra that share corners with four equivalent Cr(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. The Cr(3)-O(1) bond length is 1.97 Å. The Cr(3)-O(9) bond length is 1.96 Å. Both Cr(3)-O(11) bond lengths are 2.05 Å. Both Cr(3)-O(5) bond lengths are 2.08 Å. Co(1) is bonded to one O(12), one O(4), two equivalent O(2), and two equivalent O(8) atoms to form distorted CoO6 octahedra that share corners with four equivalent Cr(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. The Co(1)-O(12) bond length is 1.95 Å. The Co(1)-O(4) bond length is 1.93 Å. Both Co(1)-O(2) bond lengths are 1.96 Å. Both Co(1)-O(8) bond lengths are 2.22 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), and two equivalent O(2) atoms 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 Co(1)O6 octahedra, and  an edgeedge with one Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(10) bond length is 1.51 Å. Both P(1)-O(2) bond lengths are 1.60 Å. In the second P site, P(2) is bonded to one O(6), one O(9), and two equivalent O(5) atoms 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  an edgeedge with one Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-57°. The P(2)-O(6) bond length is 1.51 Å. The P(2)-O(9) bond length is 1.52 Å. Both P(2)-O(5) bond lengths are 1.60 Å. In the third P site, P(3) is bonded to one O(4), one O(7), and two equivalent O(8) atoms to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Cr(2)O6 octahedra, and  an edgeedge with one Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-56°. The P(3)-O(4) bond length is 1.55 Å. The P(3)-O(7) bond length is 1.53 Å. Both P(3)-O(8) bond lengths are 1.57 Å. In the fourth P site, P(4) is bonded to one O(12), one O(3), and two equivalent O(11) atoms to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Cr(3)O6 octahedra, and  an edgeedge with one Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-57°. The P(4)-O(12) bond length is 1.52 Å. The P(4)-O(3) bond length is 1.52 Å. Both P(4)-O(11) bond lengths are 1.59 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Cr(3) and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Cr(2), one Co(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Cr(1) and one P(4) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Co(1) and one P(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Cr(1), one Cr(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Cr(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Cr(2), one Co(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted bent 120 degrees geometry to one Cr(3) and one P(2) atom. In the tenth O site, O(10) is bonded in a bent 120 degrees geometry to one Cr(2) and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Cr(1), one Cr(3), and one P(4) atom. In the twelfth O site, O(12) is bonded in a distorted bent 120 degrees geometry to one Co(1) and one P(4) atom.