MgCo5(P2O7)4 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a 5-coordinate geometry to one O(17), one O(21), one O(23), one O(24), and one O(3) atom. There are five inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(10), one O(27), one O(7), and one O(8) atom to form CoO4 tetrahedra that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(7)O4 tetrahedra. In the second Co site, Co(2) is bonded to one O(1), one O(11), one O(12), one O(13), and one O(9) atom to form distorted CoO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(8)O4 tetrahedra, and  an edgeedge with one Co(3)O6 octahedra. In the third Co site, Co(3) is bonded to one O(12), one O(17), one O(20), one O(24), one O(5), and one O(9) atom to form CoO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra,  a cornercorner with one P(8)O4 tetrahedra,  an edgeedge with one Co(4)O5 square pyramid, and  an edgeedge with one Co(2)O5 trigonal bipyramid. In the fourth Co site, Co(4) is bonded to one O(16), one O(17), one O(18), one O(20), and one O(28) atom to form distorted CoO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra,  a cornercorner with one P(7)O4 tetrahedra,  a cornercorner with one P(8)O4 tetrahedra, and  an edgeedge with one Co(3)O6 octahedra. In the fifth Co site, Co(5) is bonded to one O(19), one O(2), one O(21), and one O(22) atom to form CoO4 tetrahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. There are eight inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(28), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one Co(4)O5 square pyramid,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one Co(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 18°. 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(5)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one Co(2)O5 trigonal bipyramid. 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(3)O6 octahedra,  a cornercorner with one Co(1)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one Co(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 57°. In the fourth P site, P(4) is bonded to one O(12), one O(15), one O(19), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one Co(1)O4 tetrahedra,  a cornercorner with one Co(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, and  a cornercorner with one Co(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 54°. In the fifth P site, P(5) is bonded to one O(10), one O(14), one O(17), and one O(21) atom to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one Co(4)O5 square pyramid,  a cornercorner with one Co(1)O4 tetrahedra,  a cornercorner with one Co(5)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. In the sixth P site, P(6) is bonded to one O(15), one O(20), one O(22), and one O(26) atom to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one Co(4)O5 square pyramid,  a cornercorner with one Co(5)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. In the seventh P site, P(7) is bonded to one O(16), one O(23), one O(25), and one O(27) atom to form PO4 tetrahedra that share  a cornercorner with one Co(4)O5 square pyramid,  a cornercorner with one Co(1)O4 tetrahedra, and  a cornercorner with one P(8)O4 tetrahedra. In the eighth P site, P(8) is bonded to one O(1), one O(18), one O(24), and one O(25) atom to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one Co(4)O5 square pyramid,  a cornercorner with one P(7)O4 tetrahedra, and  a cornercorner with one Co(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 42°. There are twenty-eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Co(2) and one P(8) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Co(5) and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mg(1) and one P(3) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 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 distorted bent 150 degrees 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 linear geometry to one Co(1) and one P(5) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one 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 bent 120 degrees geometry to one Co(2) and one P(2) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one P(3) and one P(5) atom. In the fifteenth O site, O(15) is bonded in a distorted bent 120 degrees geometry to one P(4) and one P(6) atom. In the sixteenth O site, O(16) is bonded in a bent 120 degrees geometry to one Co(4) and one P(7) atom. In the seventeenth O site, O(17) is bonded in a 4-coordinate geometry to one Mg(1), one Co(3), one Co(4), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a bent 120 degrees geometry to one Co(4) and one P(8) atom. In the nineteenth O site, O(19) is bonded in a bent 150 degrees geometry to one Co(5) and one P(4) atom. In the twentieth O site, O(20) is bonded in a trigonal planar geometry to one Co(3), one Co(4), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Mg(1), one Co(5), and one P(5) atom. In the twenty-second O site, O(22) is bonded in a bent 150 degrees geometry to one Co(5) and one P(6) atom. In the twenty-third O site, O(23) is bonded in a bent 120 degrees geometry to one Mg(1) and one P(7) atom. In the twenty-fourth O site, O(24) is bonded in a distorted trigonal planar geometry to one Mg(1), one Co(3), and one P(8) atom. In the twenty-fifth O site, O(25) is bonded in a bent 120 degrees geometry to one P(7) and one P(8) atom. In the twenty-sixth O site, O(26) is bonded in a single-bond geometry to one P(6) atom. In the twenty-seventh O site, O(27) is bonded in a distorted bent 150 degrees geometry to one Co(1) and one P(7) atom. In the twenty-eighth O site, O(28) is bonded in a bent 150 degrees geometry to one Co(4) and one P(1) atom.
MgCo5(P2O7)4 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a 5-coordinate geometry to one O(17), one O(21), one O(23), one O(24), and one O(3) atom. The Mg(1)-O(17) bond length is 2.38 Å. The Mg(1)-O(21) bond length is 2.16 Å. The Mg(1)-O(23) bond length is 1.98 Å. The Mg(1)-O(24) bond length is 2.21 Å. The Mg(1)-O(3) bond length is 1.93 Å. There are five inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(10), one O(27), one O(7), and one O(8) atom to form CoO4 tetrahedra that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(7)O4 tetrahedra. The Co(1)-O(10) bond length is 1.92 Å. The Co(1)-O(27) bond length is 1.83 Å. The Co(1)-O(7) bond length is 1.86 Å. The Co(1)-O(8) bond length is 1.84 Å. In the second Co site, Co(2) is bonded to one O(1), one O(11), one O(12), one O(13), and one O(9) atom to form distorted CoO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(8)O4 tetrahedra, and  an edgeedge with one Co(3)O6 octahedra. The Co(2)-O(1) bond length is 1.86 Å. The Co(2)-O(11) bond length is 1.94 Å. The Co(2)-O(12) bond length is 2.06 Å. The Co(2)-O(13) bond length is 1.93 Å. The Co(2)-O(9) bond length is 2.11 Å. In the third Co site, Co(3) is bonded to one O(12), one O(17), one O(20), one O(24), one O(5), and one O(9) atom to form CoO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra,  a cornercorner with one P(8)O4 tetrahedra,  an edgeedge with one Co(4)O5 square pyramid, and  an edgeedge with one Co(2)O5 trigonal bipyramid. The Co(3)-O(12) bond length is 2.04 Å. The Co(3)-O(17) bond length is 2.09 Å. The Co(3)-O(20) bond length is 2.04 Å. The Co(3)-O(24) bond length is 2.07 Å. The Co(3)-O(5) bond length is 1.84 Å. The Co(3)-O(9) bond length is 2.11 Å. In the fourth Co site, Co(4) is bonded to one O(16), one O(17), one O(18), one O(20), and one O(28) atom to form distorted CoO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra,  a cornercorner with one P(7)O4 tetrahedra,  a cornercorner with one P(8)O4 tetrahedra, and  an edgeedge with one Co(3)O6 octahedra. The Co(4)-O(16) bond length is 2.02 Å. The Co(4)-O(17) bond length is 2.31 Å. The Co(4)-O(18) bond length is 2.06 Å. The Co(4)-O(20) bond length is 2.04 Å. The Co(4)-O(28) bond length is 2.00 Å. In the fifth Co site, Co(5) is bonded to one O(19), one O(2), one O(21), and one O(22) atom to form CoO4 tetrahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The Co(5)-O(19) bond length is 1.91 Å. The Co(5)-O(2) bond length is 1.82 Å. The Co(5)-O(21) bond length is 2.01 Å. The Co(5)-O(22) bond length is 1.82 Å. There are eight inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(28), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one Co(4)O5 square pyramid,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one Co(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 18°. The P(1)-O(11) bond length is 1.55 Å. The P(1)-O(28) bond length is 1.51 Å. The P(1)-O(4) bond length is 1.60 Å. The P(1)-O(5) bond length is 1.54 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(5)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one Co(2)O5 trigonal bipyramid. The P(2)-O(13) bond length is 1.54 Å. The P(2)-O(2) bond length is 1.57 Å. The P(2)-O(4) bond length is 1.63 Å. The P(2)-O(6) bond length is 1.48 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(3)O6 octahedra,  a cornercorner with one Co(1)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one Co(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 57°. The P(3)-O(14) bond length is 1.61 Å. The P(3)-O(3) bond length is 1.50 Å. The P(3)-O(7) bond length is 1.52 Å. The P(3)-O(9) bond length is 1.57 Å. In the fourth P site, P(4) is bonded to one O(12), one O(15), one O(19), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one Co(1)O4 tetrahedra,  a cornercorner with one Co(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, and  a cornercorner with one Co(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 54°. The P(4)-O(12) bond length is 1.57 Å. The P(4)-O(15) bond length is 1.58 Å. The P(4)-O(19) bond length is 1.51 Å. The P(4)-O(8) bond length is 1.54 Å. In the fifth P site, P(5) is bonded to one O(10), one O(14), one O(17), and one O(21) atom to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one Co(4)O5 square pyramid,  a cornercorner with one Co(1)O4 tetrahedra,  a cornercorner with one Co(5)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. The P(5)-O(10) bond length is 1.50 Å. The P(5)-O(14) bond length is 1.59 Å. The P(5)-O(17) bond length is 1.56 Å. The P(5)-O(21) bond length is 1.55 Å. In the sixth P site, P(6) is bonded to one O(15), one O(20), one O(22), and one O(26) atom to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one Co(4)O5 square pyramid,  a cornercorner with one Co(5)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. The P(6)-O(15) bond length is 1.63 Å. The P(6)-O(20) bond length is 1.59 Å. The P(6)-O(22) bond length is 1.55 Å. The P(6)-O(26) bond length is 1.47 Å. In the seventh P site, P(7) is bonded to one O(16), one O(23), one O(25), and one O(27) atom to form PO4 tetrahedra that share  a cornercorner with one Co(4)O5 square pyramid,  a cornercorner with one Co(1)O4 tetrahedra, and  a cornercorner with one P(8)O4 tetrahedra. The P(7)-O(16) bond length is 1.52 Å. The P(7)-O(23) bond length is 1.51 Å. The P(7)-O(25) bond length is 1.65 Å. The P(7)-O(27) bond length is 1.55 Å. In the eighth P site, P(8) is bonded to one O(1), one O(18), one O(24), and one O(25) atom to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one Co(4)O5 square pyramid,  a cornercorner with one P(7)O4 tetrahedra, and  a cornercorner with one Co(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 42°. The P(8)-O(1) bond length is 1.55 Å. The P(8)-O(18) bond length is 1.52 Å. The P(8)-O(24) bond length is 1.55 Å. The P(8)-O(25) bond length is 1.61 Å. There are twenty-eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Co(2) and one P(8) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Co(5) and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mg(1) and one P(3) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 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 distorted bent 150 degrees 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 linear geometry to one Co(1) and one P(5) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one 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 bent 120 degrees geometry to one Co(2) and one P(2) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one P(3) and one P(5) atom. In the fifteenth O site, O(15) is bonded in a distorted bent 120 degrees geometry to one P(4) and one P(6) atom. In the sixteenth O site, O(16) is bonded in a bent 120 degrees geometry to one Co(4) and one P(7) atom. In the seventeenth O site, O(17) is bonded in a 4-coordinate geometry to one Mg(1), one Co(3), one Co(4), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a bent 120 degrees geometry to one Co(4) and one P(8) atom. In the nineteenth O site, O(19) is bonded in a bent 150 degrees geometry to one Co(5) and one P(4) atom. In the twentieth O site, O(20) is bonded in a trigonal planar geometry to one Co(3), one Co(4), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Mg(1), one Co(5), and one P(5) atom. In the twenty-second O site, O(22) is bonded in a bent 150 degrees geometry to one Co(5) and one P(6) atom. In the twenty-third O site, O(23) is bonded in a bent 120 degrees geometry to one Mg(1) and one P(7) atom. In the twenty-fourth O site, O(24) is bonded in a distorted trigonal planar geometry to one Mg(1), one Co(3), and one P(8) atom. In the twenty-fifth O site, O(25) is bonded in a bent 120 degrees geometry to one P(7) and one P(8) atom. In the twenty-sixth O site, O(26) is bonded in a single-bond geometry to one P(6) atom. In the twenty-seventh O site, O(27) is bonded in a distorted bent 150 degrees geometry to one Co(1) and one P(7) atom. In the twenty-eighth O site, O(28) is bonded in a bent 150 degrees geometry to one Co(4) and one P(1) atom.