(VCo2(PO6)2)2N2 crystallizes in the triclinic P1 space group. The structure consists of two ammonia atoms inside a VCo2(PO6)2 framework. In the VCo2(PO6)2 framework, there are two inequivalent V sites. In the first V site, V(1) is bonded to one O(13), one O(15), one O(17), one O(19), one O(20), and one O(24) atom to form distorted VO6 octahedra that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one Co(4)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-59°. In the second V site, V(2) is bonded to one O(14), one O(16), one O(18), one O(21), one O(22), and one O(23) atom to form VO6 octahedra that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one Co(4)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 41-53°. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(14), one O(15), one O(5), one O(8), and one O(9) atom to form distorted CoO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and edges with two equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. In the second Co site, Co(2) is bonded to one O(10), one O(14), one O(15), one O(2), one O(5), and one O(8) atom to form distorted CoO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-51°. In the third Co site, Co(3) is bonded to one O(11), one O(13), one O(16), one O(3), one O(6), and one O(7) atom to form distorted CoO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and edges with two equivalent Co(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-59°. In the fourth Co site, Co(4) is bonded to one O(12), one O(13), one O(16), one O(4), one O(6), and one O(7) atom to form CoO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and edges with two equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-52°. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(19), one O(20), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one Co(4)O6 octahedra, and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-58°. In the second P site, P(2) is bonded to one O(21), one O(22), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one Co(4)O6 octahedra, and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-57°. In the third P site, P(3) is bonded to one O(1), one O(17), one O(2), and one O(23) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra, and  a cornercorner with one Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-59°. In the fourth P site, P(4) is bonded to one O(18), one O(24), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra, and  a cornercorner with one Co(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-60°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Co(1) and one P(3) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Co(2) and one P(3) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Co(3) and one P(4) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Co(4) and one P(4) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Co(3), one Co(4), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Co(3), one Co(4), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a single-bond geometry to one Co(1) atom. In the tenth O site, O(10) is bonded in a single-bond geometry to one Co(2) atom. In the eleventh O site, O(11) is bonded in a single-bond geometry to one Co(3) atom. In the twelfth O site, O(12) is bonded in a single-bond geometry to one Co(4) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one V(1), one Co(3), and one Co(4) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one V(2), one Co(1), and one Co(2) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one V(1), one Co(1), and one Co(2) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one V(2), one Co(3), and one Co(4) atom. In the seventeenth O site, O(17) is bonded in a bent 150 degrees geometry to one V(1) and one P(3) atom. In the eighteenth O site, O(18) is bonded in a bent 150 degrees geometry to one V(2) and one P(4) atom. In the nineteenth O site, O(19) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the twentieth O site, O(20) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the twenty-first O site, O(21) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the twenty-second O site, O(22) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(2) atom. In the twenty-third O site, O(23) is bonded in a bent 120 degrees geometry to one V(2) and one P(3) atom. In the twenty-fourth O site, O(24) is bonded in a bent 120 degrees geometry to one V(1) and one P(4) atom.
(VCo2(PO6)2)2N2 crystallizes in the triclinic P1 space group. The structure consists of two ammonia atoms inside a VCo2(PO6)2 framework. In the VCo2(PO6)2 framework, there are two inequivalent V sites. In the first V site, V(1) is bonded to one O(13), one O(15), one O(17), one O(19), one O(20), and one O(24) atom to form distorted VO6 octahedra that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one Co(4)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-59°. The V(1)-O(13) bond length is 2.21 Å. The V(1)-O(15) bond length is 1.74 Å. The V(1)-O(17) bond length is 1.83 Å. The V(1)-O(19) bond length is 1.89 Å. The V(1)-O(20) bond length is 1.90 Å. The V(1)-O(24) bond length is 1.95 Å. In the second V site, V(2) is bonded to one O(14), one O(16), one O(18), one O(21), one O(22), and one O(23) atom to form VO6 octahedra that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one Co(4)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 41-53°. The V(2)-O(14) bond length is 1.83 Å. The V(2)-O(16) bond length is 1.83 Å. The V(2)-O(18) bond length is 1.97 Å. The V(2)-O(21) bond length is 1.89 Å. The V(2)-O(22) bond length is 1.90 Å. The V(2)-O(23) bond length is 1.99 Å. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(14), one O(15), one O(5), one O(8), and one O(9) atom to form distorted CoO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and edges with two equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. The Co(1)-O(1) bond length is 1.93 Å. The Co(1)-O(14) bond length is 2.08 Å. The Co(1)-O(15) bond length is 2.14 Å. The Co(1)-O(5) bond length is 2.08 Å. The Co(1)-O(8) bond length is 2.06 Å. The Co(1)-O(9) bond length is 1.61 Å. In the second Co site, Co(2) is bonded to one O(10), one O(14), one O(15), one O(2), one O(5), and one O(8) atom to form distorted CoO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-51°. The Co(2)-O(10) bond length is 1.61 Å. The Co(2)-O(14) bond length is 2.07 Å. The Co(2)-O(15) bond length is 2.14 Å. The Co(2)-O(2) bond length is 1.94 Å. The Co(2)-O(5) bond length is 2.09 Å. The Co(2)-O(8) bond length is 2.06 Å. In the third Co site, Co(3) is bonded to one O(11), one O(13), one O(16), one O(3), one O(6), and one O(7) atom to form distorted CoO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and edges with two equivalent Co(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-59°. The Co(3)-O(11) bond length is 1.62 Å. The Co(3)-O(13) bond length is 1.99 Å. The Co(3)-O(16) bond length is 2.13 Å. The Co(3)-O(3) bond length is 1.92 Å. The Co(3)-O(6) bond length is 2.11 Å. The Co(3)-O(7) bond length is 2.20 Å. In the fourth Co site, Co(4) is bonded to one O(12), one O(13), one O(16), one O(4), one O(6), and one O(7) atom to form CoO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and edges with two equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-52°. The Co(4)-O(12) bond length is 1.64 Å. The Co(4)-O(13) bond length is 1.86 Å. The Co(4)-O(16) bond length is 1.92 Å. The Co(4)-O(4) bond length is 1.97 Å. The Co(4)-O(6) bond length is 2.09 Å. The Co(4)-O(7) bond length is 1.97 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(19), one O(20), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one Co(4)O6 octahedra, and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-58°. The P(1)-O(19) bond length is 1.54 Å. The P(1)-O(20) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.54 Å. The P(1)-O(7) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(21), one O(22), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one Co(4)O6 octahedra, and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-57°. The P(2)-O(21) bond length is 1.54 Å. The P(2)-O(22) bond length is 1.53 Å. The P(2)-O(6) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.54 Å. In the third P site, P(3) is bonded to one O(1), one O(17), one O(2), and one O(23) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra, and  a cornercorner with one Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-59°. The P(3)-O(1) bond length is 1.55 Å. The P(3)-O(17) bond length is 1.56 Å. The P(3)-O(2) bond length is 1.55 Å. The P(3)-O(23) bond length is 1.54 Å. In the fourth P site, P(4) is bonded to one O(18), one O(24), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra, and  a cornercorner with one Co(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-60°. The P(4)-O(18) bond length is 1.52 Å. The P(4)-O(24) bond length is 1.55 Å. The P(4)-O(3) bond length is 1.56 Å. The P(4)-O(4) bond length is 1.57 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Co(1) and one P(3) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Co(2) and one P(3) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Co(3) and one P(4) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Co(4) and one P(4) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Co(3), one Co(4), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Co(3), one Co(4), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a single-bond geometry to one Co(1) atom. In the tenth O site, O(10) is bonded in a single-bond geometry to one Co(2) atom. In the eleventh O site, O(11) is bonded in a single-bond geometry to one Co(3) atom. In the twelfth O site, O(12) is bonded in a single-bond geometry to one Co(4) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one V(1), one Co(3), and one Co(4) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one V(2), one Co(1), and one Co(2) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one V(1), one Co(1), and one Co(2) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one V(2), one Co(3), and one Co(4) atom. In the seventeenth O site, O(17) is bonded in a bent 150 degrees geometry to one V(1) and one P(3) atom. In the eighteenth O site, O(18) is bonded in a bent 150 degrees geometry to one V(2) and one P(4) atom. In the nineteenth O site, O(19) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the twentieth O site, O(20) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the twenty-first O site, O(21) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the twenty-second O site, O(22) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(2) atom. In the twenty-third O site, O(23) is bonded in a bent 120 degrees geometry to one V(2) and one P(3) atom. In the twenty-fourth O site, O(24) is bonded in a bent 120 degrees geometry to one V(1) and one P(4) atom.