Co5(P2O7)4 crystallizes in the triclinic P-1 space group. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(10), one O(2), one O(7), and one O(8) atom to form distorted CoO4 trigonal pyramids that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. In the second Co site, Co(2) is bonded to one O(1), one O(12), one O(13), one O(9), and two equivalent O(11) atoms to form CoO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one Co(2)O6 octahedra, and  an edgeedge with one Co(3)O6 octahedra. In the third Co site, Co(3) is bonded to two equivalent O(12), two equivalent O(5), and two equivalent O(9) atoms to form CoO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and edges with two equivalent Co(2)O6 octahedra. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(11), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra, corners with three equivalent Co(2)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-60°. In the second P site, P(2) is bonded to one O(13), one O(2), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one Co(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles are 60°. In the third P site, P(3) is bonded to one O(14), one O(3), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one P(4)O4 tetrahedra, and  a cornercorner with one Co(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 39-60°. In the fourth P site, P(4) is bonded to one O(10), one O(12), one O(14), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent Co(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 52-54°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Co(2) and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Co(1) and one P(2) atom. In the third O site, O(3) is bonded in a single-bond geometry to one P(3) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Co(3) and one P(1) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one P(2) atom. In the seventh O site, O(7) is bonded in a linear geometry to one Co(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Co(1) and one P(4) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Co(2), one Co(3), and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Co(1) and one P(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to two equivalent Co(2) and one P(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Co(2), one Co(3), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a distorted bent 120 degrees geometry to one Co(2) and one P(2) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 120 degrees geometry to one P(3) and one P(4) atom.
Co5(P2O7)4 crystallizes in the triclinic P-1 space group. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(10), one O(2), one O(7), and one O(8) atom to form distorted CoO4 trigonal pyramids that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The Co(1)-O(10) bond length is 1.85 Å. The Co(1)-O(2) bond length is 1.92 Å. The Co(1)-O(7) bond length is 1.82 Å. The Co(1)-O(8) bond length is 1.91 Å. In the second Co site, Co(2) is bonded to one O(1), one O(12), one O(13), one O(9), and two equivalent O(11) atoms to form CoO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one Co(2)O6 octahedra, and  an edgeedge with one Co(3)O6 octahedra. The Co(2)-O(1) bond length is 2.00 Å. The Co(2)-O(12) bond length is 2.05 Å. The Co(2)-O(13) bond length is 2.07 Å. The Co(2)-O(9) bond length is 2.12 Å. There is one shorter (2.09 Å) and one longer (2.22 Å) Co(2)-O(11) bond length. In the third Co site, Co(3) is bonded to two equivalent O(12), two equivalent O(5), and two equivalent O(9) atoms to form CoO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and edges with two equivalent Co(2)O6 octahedra. Both Co(3)-O(12) bond lengths are 2.08 Å. Both Co(3)-O(5) bond lengths are 1.87 Å. Both Co(3)-O(9) bond lengths are 2.10 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(11), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra, corners with three equivalent Co(2)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-60°. The P(1)-O(1) bond length is 1.51 Å. The P(1)-O(11) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.61 Å. The P(1)-O(5) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(13), one O(2), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one Co(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles are 60°. The P(2)-O(13) bond length is 1.53 Å. The P(2)-O(2) bond length is 1.54 Å. The P(2)-O(4) bond length is 1.61 Å. The P(2)-O(6) bond length is 1.51 Å. In the third P site, P(3) is bonded to one O(14), one O(3), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one P(4)O4 tetrahedra, and  a cornercorner with one Co(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 39-60°. The P(3)-O(14) bond length is 1.62 Å. The P(3)-O(3) bond length is 1.49 Å. The P(3)-O(7) bond length is 1.54 Å. The P(3)-O(9) bond length is 1.57 Å. In the fourth P site, P(4) is bonded to one O(10), one O(12), one O(14), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent Co(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 52-54°. The P(4)-O(10) bond length is 1.54 Å. The P(4)-O(12) bond length is 1.55 Å. The P(4)-O(14) bond length is 1.59 Å. The P(4)-O(8) bond length is 1.52 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Co(2) and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Co(1) and one P(2) atom. In the third O site, O(3) is bonded in a single-bond geometry to one P(3) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Co(3) and one P(1) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one P(2) atom. In the seventh O site, O(7) is bonded in a linear geometry to one Co(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Co(1) and one P(4) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Co(2), one Co(3), and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Co(1) and one P(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to two equivalent Co(2) and one P(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Co(2), one Co(3), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a distorted bent 120 degrees geometry to one Co(2) and one P(2) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 120 degrees geometry to one P(3) and one P(4) atom.