BaVZnF7 crystallizes in the monoclinic P2_1/c space group. Ba(1) is bonded to one F(1), one F(2), two equivalent F(3), two equivalent F(4), two equivalent F(5), two equivalent F(6), and two equivalent F(7) atoms to form distorted BaF12 cuboctahedra that share corners with two equivalent Ba(1)F12 cuboctahedra, corners with three equivalent V(1)F6 octahedra, corners with three equivalent Zn(1)F6 octahedra, edges with four equivalent Ba(1)F12 cuboctahedra, edges with two equivalent V(1)F6 octahedra, edges with two equivalent Zn(1)F6 octahedra,  a faceface with one V(1)F6 octahedra, and  a faceface with one Zn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 40-54°. V(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form VF6 octahedra that share corners with three equivalent Ba(1)F12 cuboctahedra, corners with three equivalent Zn(1)F6 octahedra, edges with two equivalent Ba(1)F12 cuboctahedra,  an edgeedge with one Zn(1)F6 octahedra, and  a faceface with one Ba(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 50-57°. Zn(1) is bonded to one F(1), one F(2), one F(3), one F(5), one F(6), and one F(7) atom to form ZnF6 octahedra that share corners with three equivalent Ba(1)F12 cuboctahedra, corners with three equivalent V(1)F6 octahedra, edges with two equivalent Ba(1)F12 cuboctahedra,  an edgeedge with one V(1)F6 octahedra, and  a faceface with one Ba(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 50-57°. There are seven inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 120 degrees geometry to one Ba(1), one V(1), and one Zn(1) atom. In the second F site, F(2) is bonded in a distorted bent 120 degrees geometry to one Ba(1), one V(1), and one Zn(1) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to two equivalent Ba(1), one V(1), and one Zn(1) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to two equivalent Ba(1) and one V(1) atom. In the fifth F site, F(5) is bonded in a distorted bent 120 degrees geometry to two equivalent Ba(1), one V(1), and one Zn(1) atom. In the sixth F site, F(6) is bonded in a distorted water-like geometry to two equivalent Ba(1), one V(1), and one Zn(1) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to two equivalent Ba(1) and one Zn(1) atom.
BaVZnF7 crystallizes in the monoclinic P2_1/c space group. Ba(1) is bonded to one F(1), one F(2), two equivalent F(3), two equivalent F(4), two equivalent F(5), two equivalent F(6), and two equivalent F(7) atoms to form distorted BaF12 cuboctahedra that share corners with two equivalent Ba(1)F12 cuboctahedra, corners with three equivalent V(1)F6 octahedra, corners with three equivalent Zn(1)F6 octahedra, edges with four equivalent Ba(1)F12 cuboctahedra, edges with two equivalent V(1)F6 octahedra, edges with two equivalent Zn(1)F6 octahedra,  a faceface with one V(1)F6 octahedra, and  a faceface with one Zn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 40-54°. The Ba(1)-F(1) bond length is 3.03 Å. The Ba(1)-F(2) bond length is 3.01 Å. There is one shorter (2.93 Å) and one longer (2.97 Å) Ba(1)-F(3) bond length. There is one shorter (2.75 Å) and one longer (2.80 Å) Ba(1)-F(4) bond length. There is one shorter (3.00 Å) and one longer (3.22 Å) Ba(1)-F(5) bond length. Both Ba(1)-F(6) bond lengths are 3.00 Å. There is one shorter (2.67 Å) and one longer (2.68 Å) Ba(1)-F(7) bond length. V(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form VF6 octahedra that share corners with three equivalent Ba(1)F12 cuboctahedra, corners with three equivalent Zn(1)F6 octahedra, edges with two equivalent Ba(1)F12 cuboctahedra,  an edgeedge with one Zn(1)F6 octahedra, and  a faceface with one Ba(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 50-57°. The V(1)-F(1) bond length is 1.97 Å. The V(1)-F(2) bond length is 2.00 Å. The V(1)-F(3) bond length is 1.98 Å. The V(1)-F(4) bond length is 1.91 Å. The V(1)-F(5) bond length is 2.00 Å. The V(1)-F(6) bond length is 2.03 Å. Zn(1) is bonded to one F(1), one F(2), one F(3), one F(5), one F(6), and one F(7) atom to form ZnF6 octahedra that share corners with three equivalent Ba(1)F12 cuboctahedra, corners with three equivalent V(1)F6 octahedra, edges with two equivalent Ba(1)F12 cuboctahedra,  an edgeedge with one V(1)F6 octahedra, and  a faceface with one Ba(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 50-57°. The Zn(1)-F(1) bond length is 2.03 Å. The Zn(1)-F(2) bond length is 2.06 Å. The Zn(1)-F(3) bond length is 2.25 Å. The Zn(1)-F(5) bond length is 2.08 Å. The Zn(1)-F(6) bond length is 2.12 Å. The Zn(1)-F(7) bond length is 1.94 Å. There are seven inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 120 degrees geometry to one Ba(1), one V(1), and one Zn(1) atom. In the second F site, F(2) is bonded in a distorted bent 120 degrees geometry to one Ba(1), one V(1), and one Zn(1) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to two equivalent Ba(1), one V(1), and one Zn(1) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to two equivalent Ba(1) and one V(1) atom. In the fifth F site, F(5) is bonded in a distorted bent 120 degrees geometry to two equivalent Ba(1), one V(1), and one Zn(1) atom. In the sixth F site, F(6) is bonded in a distorted water-like geometry to two equivalent Ba(1), one V(1), and one Zn(1) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to two equivalent Ba(1) and one Zn(1) atom.