CaCo2(P2O7)2 crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 7-coordinate geometry to one O(10), one O(12), one O(14), one O(3), one O(6), one O(7), and one O(9) atom. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(11), one O(12), one O(14), one O(3), one O(5), and one O(8) atom to form CoO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  an edgeedge with one Co(2)O6 octahedra. In the second Co site, Co(2) is bonded to one O(11), one O(13), one O(14), one O(4), one O(6), and one O(7) atom to form CoO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one Co(1)O6 octahedra. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(14), one O(2), and one O(3) atom to form PO4 tetrahedra that share  a cornercorner with one Co(2)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-62°. In the second P site, P(2) is bonded to one O(1), one O(11), one O(4), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-58°. In the third P site, P(3) is bonded to one O(13), one O(2), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-48°. In the fourth P site, P(4) is bonded to one O(1), one O(12), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Co(2)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 39-54°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one P(2) and one P(4) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one P(1) and one P(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ca(1), one Co(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Co(2) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Co(1) and one P(3) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Ca(1), one Co(2), and one P(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Ca(1), one Co(2), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted bent 120 degrees geometry to one Co(1) and one P(4) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one Ca(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one Ca(1) and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Ca(1), one Co(1), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Co(2) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Ca(1), one Co(1), one Co(2), and one P(1) atom.
CaCo2(P2O7)2 crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 7-coordinate geometry to one O(10), one O(12), one O(14), one O(3), one O(6), one O(7), and one O(9) atom. The Ca(1)-O(10) bond length is 2.17 Å. The Ca(1)-O(12) bond length is 2.67 Å. The Ca(1)-O(14) bond length is 2.72 Å. The Ca(1)-O(3) bond length is 2.34 Å. The Ca(1)-O(6) bond length is 2.45 Å. The Ca(1)-O(7) bond length is 2.77 Å. The Ca(1)-O(9) bond length is 2.24 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(11), one O(12), one O(14), one O(3), one O(5), and one O(8) atom to form CoO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  an edgeedge with one Co(2)O6 octahedra. The Co(1)-O(11) bond length is 2.05 Å. The Co(1)-O(12) bond length is 2.10 Å. The Co(1)-O(14) bond length is 2.19 Å. The Co(1)-O(3) bond length is 1.99 Å. The Co(1)-O(5) bond length is 1.89 Å. The Co(1)-O(8) bond length is 2.03 Å. In the second Co site, Co(2) is bonded to one O(11), one O(13), one O(14), one O(4), one O(6), and one O(7) atom to form CoO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one Co(1)O6 octahedra. The Co(2)-O(11) bond length is 2.18 Å. The Co(2)-O(13) bond length is 1.94 Å. The Co(2)-O(14) bond length is 2.16 Å. The Co(2)-O(4) bond length is 1.98 Å. The Co(2)-O(6) bond length is 2.03 Å. The Co(2)-O(7) bond length is 2.09 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(14), one O(2), and one O(3) atom to form PO4 tetrahedra that share  a cornercorner with one Co(2)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-62°. The P(1)-O(10) bond length is 1.48 Å. The P(1)-O(14) bond length is 1.58 Å. The P(1)-O(2) bond length is 1.60 Å. The P(1)-O(3) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(1), one O(11), one O(4), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-58°. The P(2)-O(1) bond length is 1.60 Å. The P(2)-O(11) bond length is 1.58 Å. The P(2)-O(4) bond length is 1.54 Å. The P(2)-O(9) bond length is 1.49 Å. In the third P site, P(3) is bonded to one O(13), one O(2), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-48°. The P(3)-O(13) bond length is 1.52 Å. The P(3)-O(2) bond length is 1.61 Å. The P(3)-O(5) bond length is 1.54 Å. The P(3)-O(7) bond length is 1.54 Å. In the fourth P site, P(4) is bonded to one O(1), one O(12), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Co(2)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 39-54°. The P(4)-O(1) bond length is 1.60 Å. The P(4)-O(12) bond length is 1.53 Å. The P(4)-O(6) bond length is 1.56 Å. The P(4)-O(8) bond length is 1.53 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one P(2) and one P(4) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one P(1) and one P(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ca(1), one Co(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Co(2) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Co(1) and one P(3) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Ca(1), one Co(2), and one P(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Ca(1), one Co(2), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted bent 120 degrees geometry to one Co(1) and one P(4) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one Ca(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one Ca(1) and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Ca(1), one Co(1), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Co(2) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Ca(1), one Co(1), one Co(2), and one P(1) atom.