Ba2VCu2F12 crystallizes in the triclinic P-1 space group. Ba(1) is bonded to one F(3), two equivalent F(1), two equivalent F(2), two equivalent F(4), two equivalent F(6), and three equivalent F(5) atoms to form distorted BaF12 cuboctahedra that share corners with two equivalent Ba(1)F12 cuboctahedra, corners with two equivalent Cu(1)F6 octahedra, corners with three equivalent V(1)F6 octahedra, edges with four equivalent Ba(1)F12 cuboctahedra,  an edgeedge with one V(1)F6 octahedra, edges with two equivalent Cu(1)F6 octahedra,  a faceface with one Ba(1)F12 cuboctahedra, and faces with two equivalent Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-50°. V(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form VF6 octahedra that share corners with six equivalent Ba(1)F12 cuboctahedra, corners with four equivalent Cu(1)F6 octahedra, and edges with two equivalent Ba(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 48-53°. Cu(1) is bonded to one F(2), one F(3), one F(5), one F(6), and two equivalent F(4) atoms to form CuF6 octahedra that share corners with two equivalent Ba(1)F12 cuboctahedra, corners with two equivalent V(1)F6 octahedra, edges with two equivalent Ba(1)F12 cuboctahedra,  an edgeedge with one Cu(1)F6 octahedra, and faces with two equivalent Ba(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 48-53°. There are six inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to two equivalent Ba(1) and one V(1) atom. In the second F site, F(2) is bonded in a distorted bent 120 degrees geometry to two equivalent Ba(1), one V(1), and one Cu(1) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Ba(1), one V(1), and one Cu(1) atom. In the fourth F site, F(4) is bonded to two equivalent Ba(1) and two equivalent Cu(1) atoms to form distorted edge-sharing FBa2Cu2 trigonal pyramids. In the fifth F site, F(5) is bonded in a distorted single-bond geometry to three equivalent Ba(1) and one Cu(1) atom. In the sixth F site, F(6) is bonded in a distorted single-bond geometry to two equivalent Ba(1) and one Cu(1) atom.
Ba2VCu2F12 crystallizes in the triclinic P-1 space group. Ba(1) is bonded to one F(3), two equivalent F(1), two equivalent F(2), two equivalent F(4), two equivalent F(6), and three equivalent F(5) atoms to form distorted BaF12 cuboctahedra that share corners with two equivalent Ba(1)F12 cuboctahedra, corners with two equivalent Cu(1)F6 octahedra, corners with three equivalent V(1)F6 octahedra, edges with four equivalent Ba(1)F12 cuboctahedra,  an edgeedge with one V(1)F6 octahedra, edges with two equivalent Cu(1)F6 octahedra,  a faceface with one Ba(1)F12 cuboctahedra, and faces with two equivalent Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-50°. The Ba(1)-F(3) bond length is 2.75 Å. There is one shorter (2.97 Å) and one longer (3.06 Å) Ba(1)-F(1) bond length. There is one shorter (3.18 Å) and one longer (3.23 Å) Ba(1)-F(2) bond length. There is one shorter (2.74 Å) and one longer (2.78 Å) Ba(1)-F(4) bond length. There is one shorter (2.75 Å) and one longer (2.80 Å) Ba(1)-F(6) bond length. There are a spread of Ba(1)-F(5) bond distances ranging from 2.92-3.11 Å. V(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form VF6 octahedra that share corners with six equivalent Ba(1)F12 cuboctahedra, corners with four equivalent Cu(1)F6 octahedra, and edges with two equivalent Ba(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 48-53°. Both V(1)-F(1) bond lengths are 1.83 Å. Both V(1)-F(2) bond lengths are 1.93 Å. Both V(1)-F(3) bond lengths are 1.89 Å. Cu(1) is bonded to one F(2), one F(3), one F(5), one F(6), and two equivalent F(4) atoms to form CuF6 octahedra that share corners with two equivalent Ba(1)F12 cuboctahedra, corners with two equivalent V(1)F6 octahedra, edges with two equivalent Ba(1)F12 cuboctahedra,  an edgeedge with one Cu(1)F6 octahedra, and faces with two equivalent Ba(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 48-53°. The Cu(1)-F(2) bond length is 2.05 Å. The Cu(1)-F(3) bond length is 2.27 Å. The Cu(1)-F(5) bond length is 1.89 Å. The Cu(1)-F(6) bond length is 1.88 Å. There is one shorter (1.97 Å) and one longer (2.30 Å) Cu(1)-F(4) bond length. There are six inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to two equivalent Ba(1) and one V(1) atom. In the second F site, F(2) is bonded in a distorted bent 120 degrees geometry to two equivalent Ba(1), one V(1), and one Cu(1) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Ba(1), one V(1), and one Cu(1) atom. In the fourth F site, F(4) is bonded to two equivalent Ba(1) and two equivalent Cu(1) atoms to form distorted edge-sharing FBa2Cu2 trigonal pyramids. In the fifth F site, F(5) is bonded in a distorted single-bond geometry to three equivalent Ba(1) and one Cu(1) atom. In the sixth F site, F(6) is bonded in a distorted single-bond geometry to two equivalent Ba(1) and one Cu(1) atom.