BaZnF4 crystallizes in the monoclinic Pc space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 12-coordinate geometry to one F(2), one F(7), two equivalent F(1), two equivalent F(3), two equivalent F(5), two equivalent F(6), and two equivalent F(8) atoms. In the second Ba site, Ba(2) is bonded to one F(1), one F(8), two equivalent F(2), 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(2)F12 cuboctahedra,  a cornercorner with one Zn(1)F6 octahedra, faces with two equivalent Ba(2)F12 cuboctahedra, faces with two equivalent Zn(1)F6 octahedra, and faces with four equivalent Zn(2)F6 octahedra. The corner-sharing octahedral tilt angles are 50°. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one F(1), one F(3), one F(5), one F(6), and two equivalent F(8) atoms to form ZnF6 octahedra that share  a cornercorner with one Ba(2)F12 cuboctahedra, corners with two equivalent Zn(1)F6 octahedra, corners with two equivalent Zn(2)F6 octahedra, and faces with two equivalent Ba(2)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 6-17°. In the second Zn site, Zn(2) is bonded to one F(2), one F(4), one F(5), one F(6), and two equivalent F(7) atoms to form ZnF6 octahedra that share corners with two equivalent Zn(1)F6 octahedra, corners with two equivalent Zn(2)F6 octahedra, and faces with four equivalent Ba(2)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 6-18°. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Ba(2), two equivalent Ba(1), and one Zn(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Ba(1), two equivalent Ba(2), and one Zn(2) atom. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ba(1) and one Zn(1) atom. In the fourth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ba(2) and one Zn(2) atom. In the fifth F site, F(5) is bonded in a distorted linear geometry to two equivalent Ba(1), two equivalent Ba(2), one Zn(1), and one Zn(2) atom. In the sixth F site, F(6) is bonded in a distorted linear geometry to two equivalent Ba(1), two equivalent Ba(2), one Zn(1), and one Zn(2) atom. In the seventh F site, F(7) is bonded in a 2-coordinate geometry to one Ba(1), two equivalent Ba(2), and two equivalent Zn(2) atoms. In the eighth F site, F(8) is bonded in a 2-coordinate geometry to one Ba(2), two equivalent Ba(1), and two equivalent Zn(1) atoms.
BaZnF4 crystallizes in the monoclinic Pc space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 12-coordinate geometry to one F(2), one F(7), two equivalent F(1), two equivalent F(3), two equivalent F(5), two equivalent F(6), and two equivalent F(8) atoms. The Ba(1)-F(2) bond length is 2.70 Å. The Ba(1)-F(7) bond length is 2.97 Å. There is one shorter (2.75 Å) and one longer (2.77 Å) Ba(1)-F(1) bond length. There is one shorter (2.65 Å) and one longer (2.66 Å) Ba(1)-F(3) bond length. There is one shorter (3.02 Å) and one longer (3.04 Å) Ba(1)-F(5) bond length. There is one shorter (3.27 Å) and one longer (3.29 Å) Ba(1)-F(6) bond length. There is one shorter (2.99 Å) and one longer (3.12 Å) Ba(1)-F(8) bond length. In the second Ba site, Ba(2) is bonded to one F(1), one F(8), two equivalent F(2), 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(2)F12 cuboctahedra,  a cornercorner with one Zn(1)F6 octahedra, faces with two equivalent Ba(2)F12 cuboctahedra, faces with two equivalent Zn(1)F6 octahedra, and faces with four equivalent Zn(2)F6 octahedra. The corner-sharing octahedral tilt angles are 50°. The Ba(2)-F(1) bond length is 2.70 Å. The Ba(2)-F(8) bond length is 2.97 Å. There is one shorter (2.76 Å) and one longer (2.78 Å) Ba(2)-F(2) bond length. There is one shorter (2.66 Å) and one longer (2.67 Å) Ba(2)-F(4) bond length. There is one shorter (3.17 Å) and one longer (3.21 Å) Ba(2)-F(5) bond length. There is one shorter (3.05 Å) and one longer (3.06 Å) Ba(2)-F(6) bond length. There is one shorter (3.01 Å) and one longer (3.10 Å) Ba(2)-F(7) bond length. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one F(1), one F(3), one F(5), one F(6), and two equivalent F(8) atoms to form ZnF6 octahedra that share  a cornercorner with one Ba(2)F12 cuboctahedra, corners with two equivalent Zn(1)F6 octahedra, corners with two equivalent Zn(2)F6 octahedra, and faces with two equivalent Ba(2)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 6-17°. The Zn(1)-F(1) bond length is 1.99 Å. The Zn(1)-F(3) bond length is 1.96 Å. The Zn(1)-F(5) bond length is 2.12 Å. The Zn(1)-F(6) bond length is 2.12 Å. Both Zn(1)-F(8) bond lengths are 2.13 Å. In the second Zn site, Zn(2) is bonded to one F(2), one F(4), one F(5), one F(6), and two equivalent F(7) atoms to form ZnF6 octahedra that share corners with two equivalent Zn(1)F6 octahedra, corners with two equivalent Zn(2)F6 octahedra, and faces with four equivalent Ba(2)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 6-18°. The Zn(2)-F(2) bond length is 2.00 Å. The Zn(2)-F(4) bond length is 1.96 Å. The Zn(2)-F(5) bond length is 2.17 Å. The Zn(2)-F(6) bond length is 2.08 Å. Both Zn(2)-F(7) bond lengths are 2.13 Å. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Ba(2), two equivalent Ba(1), and one Zn(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Ba(1), two equivalent Ba(2), and one Zn(2) atom. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ba(1) and one Zn(1) atom. In the fourth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ba(2) and one Zn(2) atom. In the fifth F site, F(5) is bonded in a distorted linear geometry to two equivalent Ba(1), two equivalent Ba(2), one Zn(1), and one Zn(2) atom. In the sixth F site, F(6) is bonded in a distorted linear geometry to two equivalent Ba(1), two equivalent Ba(2), one Zn(1), and one Zn(2) atom. In the seventh F site, F(7) is bonded in a 2-coordinate geometry to one Ba(1), two equivalent Ba(2), and two equivalent Zn(2) atoms. In the eighth F site, F(8) is bonded in a 2-coordinate geometry to one Ba(2), two equivalent Ba(1), and two equivalent Zn(1) atoms.