Cs3V4Mn3O16 crystallizes in the triclinic P-1 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 9-coordinate geometry to one O(2), two equivalent O(5), three equivalent O(3), and three equivalent O(6) atoms. In the second Cs site, Cs(2) is bonded in a 10-coordinate geometry to two equivalent O(1), two equivalent O(4), two equivalent O(8), and four equivalent O(7) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(5), and one O(7) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, and  a cornercorner with one V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-58°. In the second V site, V(2) is bonded to one O(2), one O(4), one O(6), and one O(7) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, and  a cornercorner with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-58°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(8) atoms to form MnO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(8) atoms to form MnO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, and edges with four equivalent Mn(1)O6 octahedra. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Cs(2), one V(1), one Mn(1), and one Mn(2) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Cs(1), one V(2), and one Mn(1) atom. In the third O site, O(3) is bonded in a single-bond geometry to three equivalent Cs(1) and one V(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Cs(2), one V(2), one Mn(1), and one Mn(2) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to two equivalent Cs(1), one V(1), and one Mn(1) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to three equivalent Cs(1) and one V(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to two equivalent Cs(2), one V(1), and one V(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Cs(2), one Mn(2), and two equivalent Mn(1) atoms.
Cs3V4Mn3O16 crystallizes in the triclinic P-1 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 9-coordinate geometry to one O(2), two equivalent O(5), three equivalent O(3), and three equivalent O(6) atoms. The Cs(1)-O(2) bond length is 2.99 Å. There is one shorter (3.30 Å) and one longer (3.64 Å) Cs(1)-O(5) bond length. There are a spread of Cs(1)-O(3) bond distances ranging from 3.24-3.42 Å. There are a spread of Cs(1)-O(6) bond distances ranging from 3.05-3.34 Å. In the second Cs site, Cs(2) is bonded in a 10-coordinate geometry to two equivalent O(1), two equivalent O(4), two equivalent O(8), and four equivalent O(7) atoms. Both Cs(2)-O(1) bond lengths are 3.37 Å. Both Cs(2)-O(4) bond lengths are 3.11 Å. Both Cs(2)-O(8) bond lengths are 3.23 Å. There are two shorter (3.28 Å) and two longer (3.54 Å) Cs(2)-O(7) bond lengths. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(5), and one O(7) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, and  a cornercorner with one V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-58°. The V(1)-O(1) bond length is 1.79 Å. The V(1)-O(3) bond length is 1.66 Å. The V(1)-O(5) bond length is 1.75 Å. The V(1)-O(7) bond length is 1.83 Å. In the second V site, V(2) is bonded to one O(2), one O(4), one O(6), and one O(7) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, and  a cornercorner with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-58°. The V(2)-O(2) bond length is 1.75 Å. The V(2)-O(4) bond length is 1.75 Å. The V(2)-O(6) bond length is 1.67 Å. The V(2)-O(7) bond length is 1.84 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(8) atoms to form MnO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The Mn(1)-O(1) bond length is 2.28 Å. The Mn(1)-O(2) bond length is 1.95 Å. The Mn(1)-O(4) bond length is 2.22 Å. The Mn(1)-O(5) bond length is 1.98 Å. There is one shorter (1.96 Å) and one longer (1.99 Å) Mn(1)-O(8) bond length. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(8) atoms to form MnO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, and edges with four equivalent Mn(1)O6 octahedra. Both Mn(2)-O(1) bond lengths are 2.01 Å. Both Mn(2)-O(4) bond lengths are 2.18 Å. Both Mn(2)-O(8) bond lengths are 1.93 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Cs(2), one V(1), one Mn(1), and one Mn(2) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Cs(1), one V(2), and one Mn(1) atom. In the third O site, O(3) is bonded in a single-bond geometry to three equivalent Cs(1) and one V(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Cs(2), one V(2), one Mn(1), and one Mn(2) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to two equivalent Cs(1), one V(1), and one Mn(1) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to three equivalent Cs(1) and one V(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to two equivalent Cs(2), one V(1), and one V(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Cs(2), one Mn(2), and two equivalent Mn(1) atoms.