V4(AgO4)3 crystallizes in the triclinic P1 space group. There are eight inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(1), one O(18), one O(21), one O(23), one O(24), and one O(3) atom. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(17), one O(2), one O(22), one O(23), one O(24), and one O(4) atom. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(13), one O(14), one O(16), one O(20), one O(7), and one O(9) atom. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to one O(10), one O(13), one O(14), one O(15), one O(19), and one O(8) atom. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(12), one O(14), one O(15), one O(16), one O(17), and one O(22) atom. In the sixth V site, V(6) is bonded in a 6-coordinate geometry to one O(11), one O(13), one O(15), one O(16), one O(18), and one O(21) atom. In the seventh V site, V(7) is bonded in a 6-coordinate geometry to one O(16), one O(20), one O(21), one O(22), one O(24), and one O(5) atom. In the eighth V site, V(8) is bonded in a 6-coordinate geometry to one O(15), one O(19), one O(21), one O(22), one O(23), and one O(6) atom. There are six inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to one O(1), one O(10), one O(2), one O(5), and one O(9) atom to form distorted AgO5 square pyramids that share  an edgeedge with one Ag(3)O6 octahedra,  an edgeedge with one Ag(4)O6 octahedra, and edges with two equivalent Ag(2)O5 square pyramids. In the second Ag site, Ag(2) is bonded to one O(1), one O(10), one O(2), one O(6), and one O(9) atom to form distorted AgO5 square pyramids that share  an edgeedge with one Ag(3)O6 octahedra,  an edgeedge with one Ag(4)O6 octahedra, and edges with two equivalent Ag(1)O5 square pyramids. In the third Ag site, Ag(3) is bonded to one O(10), one O(11), one O(12), one O(4), one O(5), and one O(6) atom to form AgO6 octahedra that share edges with two equivalent Ag(4)O6 octahedra,  an edgeedge with one Ag(1)O5 square pyramid,  an edgeedge with one Ag(2)O5 square pyramid, and  an edgeedge with one Ag(5)O5 square pyramid. In the fourth Ag site, Ag(4) is bonded to one O(11), one O(12), one O(3), one O(5), one O(6), and one O(9) atom to form AgO6 octahedra that share edges with two equivalent Ag(3)O6 octahedra,  an edgeedge with one Ag(1)O5 square pyramid,  an edgeedge with one Ag(2)O5 square pyramid, and  an edgeedge with one Ag(5)O5 square pyramid. In the fifth Ag site, Ag(5) is bonded to one O(12), one O(3), one O(4), one O(7), and one O(8) atom to form distorted edge-sharing AgO5 square pyramids. In the sixth Ag site, Ag(6) is bonded in a 4-coordinate geometry to one O(17), one O(18), one O(20), and one O(7) atom. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(1), one Ag(1), and one Ag(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one V(2), one Ag(1), and one Ag(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(1), one Ag(4), and one Ag(5) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(2), one Ag(3), and one Ag(5) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one V(7), one Ag(1), one Ag(3), and one Ag(4) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one V(8), one Ag(2), one Ag(3), and one Ag(4) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one V(3), one Ag(5), and one Ag(6) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one V(4) and one Ag(5) atom. In the ninth O site, O(9) is bonded to one V(3), one Ag(1), one Ag(2), and one Ag(4) atom to form distorted corner-sharing OVAg3 tetrahedra. In the tenth O site, O(10) is bonded to one V(4), one Ag(1), one Ag(2), and one Ag(3) atom to form distorted corner-sharing OVAg3 tetrahedra. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one V(6), one Ag(3), and one Ag(4) atom. In the twelfth O site, O(12) is bonded in a distorted single-bond geometry to one V(5), one Ag(3), one Ag(4), and one Ag(5) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal non-coplanar geometry to one V(3), one V(4), and one V(6) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one V(3), one V(4), and one V(5) atom. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one V(4), one V(5), one V(6), and one V(8) atom. In the sixteenth O site, O(16) is bonded in a 4-coordinate geometry to one V(3), one V(5), one V(6), and one V(7) atom. In the seventeenth O site, O(17) is bonded in a distorted single-bond geometry to one V(2), one V(5), and one Ag(6) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one V(1), one V(6), and one Ag(6) atom. In the nineteenth O site, O(19) is bonded in a bent 120 degrees geometry to one V(4) and one V(8) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one V(3), one V(7), and one Ag(6) atom. In the twenty-first O site, O(21) is bonded in a 4-coordinate geometry to one V(1), one V(6), one V(7), and one V(8) atom. In the twenty-second O site, O(22) is bonded in a 4-coordinate geometry to one V(2), one V(5), one V(7), and one V(8) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one V(8) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one V(7) atom.
V4(AgO4)3 crystallizes in the triclinic P1 space group. There are eight inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(1), one O(18), one O(21), one O(23), one O(24), and one O(3) atom. The V(1)-O(1) bond length is 1.73 Å. The V(1)-O(18) bond length is 2.27 Å. The V(1)-O(21) bond length is 2.21 Å. The V(1)-O(23) bond length is 1.89 Å. The V(1)-O(24) bond length is 1.89 Å. The V(1)-O(3) bond length is 1.74 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(17), one O(2), one O(22), one O(23), one O(24), and one O(4) atom. The V(2)-O(17) bond length is 2.32 Å. The V(2)-O(2) bond length is 1.72 Å. The V(2)-O(22) bond length is 2.21 Å. The V(2)-O(23) bond length is 1.89 Å. The V(2)-O(24) bond length is 1.87 Å. The V(2)-O(4) bond length is 1.74 Å. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(13), one O(14), one O(16), one O(20), one O(7), and one O(9) atom. The V(3)-O(13) bond length is 1.89 Å. The V(3)-O(14) bond length is 1.86 Å. The V(3)-O(16) bond length is 2.23 Å. The V(3)-O(20) bond length is 2.25 Å. The V(3)-O(7) bond length is 1.70 Å. The V(3)-O(9) bond length is 1.79 Å. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to one O(10), one O(13), one O(14), one O(15), one O(19), and one O(8) atom. The V(4)-O(10) bond length is 1.84 Å. The V(4)-O(13) bond length is 1.89 Å. The V(4)-O(14) bond length is 1.89 Å. The V(4)-O(15) bond length is 2.29 Å. The V(4)-O(19) bond length is 2.12 Å. The V(4)-O(8) bond length is 1.66 Å. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(12), one O(14), one O(15), one O(16), one O(17), and one O(22) atom. The V(5)-O(12) bond length is 1.70 Å. The V(5)-O(14) bond length is 2.28 Å. The V(5)-O(15) bond length is 1.89 Å. The V(5)-O(16) bond length is 1.91 Å. The V(5)-O(17) bond length is 1.70 Å. The V(5)-O(22) bond length is 2.42 Å. In the sixth V site, V(6) is bonded in a 6-coordinate geometry to one O(11), one O(13), one O(15), one O(16), one O(18), and one O(21) atom. The V(6)-O(11) bond length is 1.68 Å. The V(6)-O(13) bond length is 2.16 Å. The V(6)-O(15) bond length is 1.91 Å. The V(6)-O(16) bond length is 1.92 Å. The V(6)-O(18) bond length is 1.72 Å. The V(6)-O(21) bond length is 2.44 Å. In the seventh V site, V(7) is bonded in a 6-coordinate geometry to one O(16), one O(20), one O(21), one O(22), one O(24), and one O(5) atom. The V(7)-O(16) bond length is 2.42 Å. The V(7)-O(20) bond length is 1.71 Å. The V(7)-O(21) bond length is 1.90 Å. The V(7)-O(22) bond length is 1.90 Å. The V(7)-O(24) bond length is 2.22 Å. The V(7)-O(5) bond length is 1.69 Å. In the eighth V site, V(8) is bonded in a 6-coordinate geometry to one O(15), one O(19), one O(21), one O(22), one O(23), and one O(6) atom. The V(8)-O(15) bond length is 2.40 Å. The V(8)-O(19) bond length is 1.69 Å. The V(8)-O(21) bond length is 1.91 Å. The V(8)-O(22) bond length is 1.91 Å. The V(8)-O(23) bond length is 2.18 Å. The V(8)-O(6) bond length is 1.71 Å. There are six inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to one O(1), one O(10), one O(2), one O(5), and one O(9) atom to form distorted AgO5 square pyramids that share  an edgeedge with one Ag(3)O6 octahedra,  an edgeedge with one Ag(4)O6 octahedra, and edges with two equivalent Ag(2)O5 square pyramids. The Ag(1)-O(1) bond length is 2.30 Å. The Ag(1)-O(10) bond length is 2.27 Å. The Ag(1)-O(2) bond length is 2.29 Å. The Ag(1)-O(5) bond length is 2.70 Å. The Ag(1)-O(9) bond length is 2.30 Å. In the second Ag site, Ag(2) is bonded to one O(1), one O(10), one O(2), one O(6), and one O(9) atom to form distorted AgO5 square pyramids that share  an edgeedge with one Ag(3)O6 octahedra,  an edgeedge with one Ag(4)O6 octahedra, and edges with two equivalent Ag(1)O5 square pyramids. The Ag(2)-O(1) bond length is 2.37 Å. The Ag(2)-O(10) bond length is 2.42 Å. The Ag(2)-O(2) bond length is 2.43 Å. The Ag(2)-O(6) bond length is 2.46 Å. The Ag(2)-O(9) bond length is 2.39 Å. In the third Ag site, Ag(3) is bonded to one O(10), one O(11), one O(12), one O(4), one O(5), and one O(6) atom to form AgO6 octahedra that share edges with two equivalent Ag(4)O6 octahedra,  an edgeedge with one Ag(1)O5 square pyramid,  an edgeedge with one Ag(2)O5 square pyramid, and  an edgeedge with one Ag(5)O5 square pyramid. The Ag(3)-O(10) bond length is 2.27 Å. The Ag(3)-O(11) bond length is 2.36 Å. The Ag(3)-O(12) bond length is 2.42 Å. The Ag(3)-O(4) bond length is 2.25 Å. The Ag(3)-O(5) bond length is 2.46 Å. The Ag(3)-O(6) bond length is 2.44 Å. In the fourth Ag site, Ag(4) is bonded to one O(11), one O(12), one O(3), one O(5), one O(6), and one O(9) atom to form AgO6 octahedra that share edges with two equivalent Ag(3)O6 octahedra,  an edgeedge with one Ag(1)O5 square pyramid,  an edgeedge with one Ag(2)O5 square pyramid, and  an edgeedge with one Ag(5)O5 square pyramid. The Ag(4)-O(11) bond length is 2.38 Å. The Ag(4)-O(12) bond length is 2.43 Å. The Ag(4)-O(3) bond length is 2.26 Å. The Ag(4)-O(5) bond length is 2.46 Å. The Ag(4)-O(6) bond length is 2.44 Å. The Ag(4)-O(9) bond length is 2.31 Å. In the fifth Ag site, Ag(5) is bonded to one O(12), one O(3), one O(4), one O(7), and one O(8) atom to form distorted edge-sharing AgO5 square pyramids. The Ag(5)-O(12) bond length is 2.54 Å. The Ag(5)-O(3) bond length is 2.29 Å. The Ag(5)-O(4) bond length is 2.29 Å. The Ag(5)-O(7) bond length is 2.26 Å. The Ag(5)-O(8) bond length is 2.25 Å. In the sixth Ag site, Ag(6) is bonded in a 4-coordinate geometry to one O(17), one O(18), one O(20), and one O(7) atom. The Ag(6)-O(17) bond length is 2.37 Å. The Ag(6)-O(18) bond length is 2.30 Å. The Ag(6)-O(20) bond length is 2.26 Å. The Ag(6)-O(7) bond length is 2.46 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(1), one Ag(1), and one Ag(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one V(2), one Ag(1), and one Ag(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(1), one Ag(4), and one Ag(5) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(2), one Ag(3), and one Ag(5) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one V(7), one Ag(1), one Ag(3), and one Ag(4) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one V(8), one Ag(2), one Ag(3), and one Ag(4) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one V(3), one Ag(5), and one Ag(6) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one V(4) and one Ag(5) atom. In the ninth O site, O(9) is bonded to one V(3), one Ag(1), one Ag(2), and one Ag(4) atom to form distorted corner-sharing OVAg3 tetrahedra. In the tenth O site, O(10) is bonded to one V(4), one Ag(1), one Ag(2), and one Ag(3) atom to form distorted corner-sharing OVAg3 tetrahedra. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one V(6), one Ag(3), and one Ag(4) atom. In the twelfth O site, O(12) is bonded in a distorted single-bond geometry to one V(5), one Ag(3), one Ag(4), and one Ag(5) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal non-coplanar geometry to one V(3), one V(4), and one V(6) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one V(3), one V(4), and one V(5) atom. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one V(4), one V(5), one V(6), and one V(8) atom. In the sixteenth O site, O(16) is bonded in a 4-coordinate geometry to one V(3), one V(5), one V(6), and one V(7) atom. In the seventeenth O site, O(17) is bonded in a distorted single-bond geometry to one V(2), one V(5), and one Ag(6) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one V(1), one V(6), and one Ag(6) atom. In the nineteenth O site, O(19) is bonded in a bent 120 degrees geometry to one V(4) and one V(8) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one V(3), one V(7), and one Ag(6) atom. In the twenty-first O site, O(21) is bonded in a 4-coordinate geometry to one V(1), one V(6), one V(7), and one V(8) atom. In the twenty-second O site, O(22) is bonded in a 4-coordinate geometry to one V(2), one V(5), one V(7), and one V(8) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one V(8) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one V(7) atom.