Ba3Cu2Al2F16 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 12-coordinate geometry to one F(1), one F(10), one F(12), one F(14), one F(16), one F(4), one F(5), one F(6), one F(8), one F(9), and two equivalent F(7) atoms. In the second Ba site, Ba(2) is bonded in a 11-coordinate geometry to one F(1), one F(10), one F(14), one F(5), one F(7), two equivalent F(16), two equivalent F(6), and two equivalent F(8) atoms. In the third Ba site, Ba(3) is bonded in a 11-coordinate geometry to one F(11), one F(12), one F(3), one F(4), two equivalent F(13), two equivalent F(15), and three equivalent F(2) atoms. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(1), one F(10), one F(11), one F(15), one F(3), and one F(5) atom to form distorted CuF6 octahedra that share corners with two equivalent Al(1)F6 octahedra and edges with two equivalent Cu(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 53-55°. In the second Cu site, Cu(2) is bonded to one F(1), one F(12), one F(13), one F(15), one F(3), and one F(5) atom to form distorted CuF6 octahedra that share corners with two equivalent Al(1)F6 octahedra and edges with two equivalent Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 51-59°. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one F(11), one F(12), one F(14), one F(2), one F(3), and one F(4) atom to form AlF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra and corners with two equivalent Cu(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 51-59°. In the second Al site, Al(2) is bonded to one F(16), one F(6), one F(7), one F(8), and two equivalent F(9) atoms to form corner-sharing AlF6 octahedra. The corner-sharing octahedral tilt angles are 19°. There are sixteen inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(2), one Cu(1), and one Cu(2) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to three equivalent Ba(3) and one Al(1) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Ba(3), one Cu(1), one Cu(2), and one Al(1) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(3), and one Al(1) atom. In the fifth F site, F(5) is bonded in a distorted water-like geometry to one Ba(1), one Ba(2), one Cu(1), and one Cu(2) atom. In the sixth F site, F(6) is bonded in a distorted single-bond geometry to one Ba(1), two equivalent Ba(2), and one Al(2) atom. In the seventh F site, F(7) is bonded in a distorted single-bond geometry to one Ba(2), two equivalent Ba(1), and one Al(2) atom. In the eighth F site, F(8) is bonded in a single-bond geometry to one Ba(1), two equivalent Ba(2), and one Al(2) atom. In the ninth F site, F(9) is bonded in a distorted bent 150 degrees geometry to one Ba(1) and two equivalent Al(2) atoms. In the tenth F site, F(10) is bonded in a distorted trigonal planar geometry to one Ba(1), one Ba(2), and one Cu(1) atom. In the eleventh F site, F(11) is bonded in a distorted bent 120 degrees geometry to one Ba(3), one Cu(1), and one Al(1) atom. In the twelfth F site, F(12) is bonded in a distorted tetrahedral geometry to one Ba(1), one Ba(3), one Cu(2), and one Al(1) atom. In the thirteenth F site, F(13) is bonded in a distorted trigonal planar geometry to two equivalent Ba(3) and one Cu(2) atom. In the fourteenth F site, F(14) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), and one Al(1) atom. In the fifteenth F site, F(15) is bonded in a distorted water-like geometry to two equivalent Ba(3), one Cu(1), and one Cu(2) atom. In the sixteenth F site, F(16) is bonded in a distorted single-bond geometry to one Ba(1), two equivalent Ba(2), and one Al(2) atom.
Ba3Cu2Al2F16 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 12-coordinate geometry to one F(1), one F(10), one F(12), one F(14), one F(16), one F(4), one F(5), one F(6), one F(8), one F(9), and two equivalent F(7) atoms. The Ba(1)-F(1) bond length is 3.00 Å. The Ba(1)-F(10) bond length is 2.76 Å. The Ba(1)-F(12) bond length is 2.71 Å. The Ba(1)-F(14) bond length is 2.86 Å. The Ba(1)-F(16) bond length is 2.99 Å. The Ba(1)-F(4) bond length is 2.74 Å. The Ba(1)-F(5) bond length is 2.93 Å. The Ba(1)-F(6) bond length is 3.19 Å. The Ba(1)-F(8) bond length is 2.88 Å. The Ba(1)-F(9) bond length is 3.18 Å. There is one shorter (2.88 Å) and one longer (2.94 Å) Ba(1)-F(7) bond length. In the second Ba site, Ba(2) is bonded in a 11-coordinate geometry to one F(1), one F(10), one F(14), one F(5), one F(7), two equivalent F(16), two equivalent F(6), and two equivalent F(8) atoms. The Ba(2)-F(1) bond length is 2.65 Å. The Ba(2)-F(10) bond length is 2.70 Å. The Ba(2)-F(14) bond length is 2.76 Å. The Ba(2)-F(5) bond length is 3.15 Å. The Ba(2)-F(7) bond length is 3.27 Å. There is one shorter (2.72 Å) and one longer (3.07 Å) Ba(2)-F(16) bond length. There is one shorter (2.77 Å) and one longer (3.15 Å) Ba(2)-F(6) bond length. There is one shorter (2.96 Å) and one longer (3.00 Å) Ba(2)-F(8) bond length. In the third Ba site, Ba(3) is bonded in a 11-coordinate geometry to one F(11), one F(12), one F(3), one F(4), two equivalent F(13), two equivalent F(15), and three equivalent F(2) atoms. The Ba(3)-F(11) bond length is 3.07 Å. The Ba(3)-F(12) bond length is 2.81 Å. The Ba(3)-F(3) bond length is 2.87 Å. The Ba(3)-F(4) bond length is 2.74 Å. There is one shorter (2.66 Å) and one longer (2.69 Å) Ba(3)-F(13) bond length. There is one shorter (3.00 Å) and one longer (3.14 Å) Ba(3)-F(15) bond length. There are a spread of Ba(3)-F(2) bond distances ranging from 2.79-3.01 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(1), one F(10), one F(11), one F(15), one F(3), and one F(5) atom to form distorted CuF6 octahedra that share corners with two equivalent Al(1)F6 octahedra and edges with two equivalent Cu(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 53-55°. The Cu(1)-F(1) bond length is 2.38 Å. The Cu(1)-F(10) bond length is 1.91 Å. The Cu(1)-F(11) bond length is 1.97 Å. The Cu(1)-F(15) bond length is 1.97 Å. The Cu(1)-F(3) bond length is 2.36 Å. The Cu(1)-F(5) bond length is 1.99 Å. In the second Cu site, Cu(2) is bonded to one F(1), one F(12), one F(13), one F(15), one F(3), and one F(5) atom to form distorted CuF6 octahedra that share corners with two equivalent Al(1)F6 octahedra and edges with two equivalent Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 51-59°. The Cu(2)-F(1) bond length is 1.89 Å. The Cu(2)-F(12) bond length is 2.30 Å. The Cu(2)-F(13) bond length is 1.89 Å. The Cu(2)-F(15) bond length is 2.03 Å. The Cu(2)-F(3) bond length is 2.49 Å. The Cu(2)-F(5) bond length is 1.99 Å. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one F(11), one F(12), one F(14), one F(2), one F(3), and one F(4) atom to form AlF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra and corners with two equivalent Cu(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 51-59°. The Al(1)-F(11) bond length is 1.88 Å. The Al(1)-F(12) bond length is 1.85 Å. The Al(1)-F(14) bond length is 1.80 Å. The Al(1)-F(2) bond length is 1.86 Å. The Al(1)-F(3) bond length is 1.81 Å. The Al(1)-F(4) bond length is 1.80 Å. In the second Al site, Al(2) is bonded to one F(16), one F(6), one F(7), one F(8), and two equivalent F(9) atoms to form corner-sharing AlF6 octahedra. The corner-sharing octahedral tilt angles are 19°. The Al(2)-F(16) bond length is 1.81 Å. The Al(2)-F(6) bond length is 1.79 Å. The Al(2)-F(7) bond length is 1.80 Å. The Al(2)-F(8) bond length is 1.80 Å. There is one shorter (1.88 Å) and one longer (1.90 Å) Al(2)-F(9) bond length. There are sixteen inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(2), one Cu(1), and one Cu(2) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to three equivalent Ba(3) and one Al(1) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Ba(3), one Cu(1), one Cu(2), and one Al(1) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(3), and one Al(1) atom. In the fifth F site, F(5) is bonded in a distorted water-like geometry to one Ba(1), one Ba(2), one Cu(1), and one Cu(2) atom. In the sixth F site, F(6) is bonded in a distorted single-bond geometry to one Ba(1), two equivalent Ba(2), and one Al(2) atom. In the seventh F site, F(7) is bonded in a distorted single-bond geometry to one Ba(2), two equivalent Ba(1), and one Al(2) atom. In the eighth F site, F(8) is bonded in a single-bond geometry to one Ba(1), two equivalent Ba(2), and one Al(2) atom. In the ninth F site, F(9) is bonded in a distorted bent 150 degrees geometry to one Ba(1) and two equivalent Al(2) atoms. In the tenth F site, F(10) is bonded in a distorted trigonal planar geometry to one Ba(1), one Ba(2), and one Cu(1) atom. In the eleventh F site, F(11) is bonded in a distorted bent 120 degrees geometry to one Ba(3), one Cu(1), and one Al(1) atom. In the twelfth F site, F(12) is bonded in a distorted tetrahedral geometry to one Ba(1), one Ba(3), one Cu(2), and one Al(1) atom. In the thirteenth F site, F(13) is bonded in a distorted trigonal planar geometry to two equivalent Ba(3) and one Cu(2) atom. In the fourteenth F site, F(14) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), and one Al(1) atom. In the fifteenth F site, F(15) is bonded in a distorted water-like geometry to two equivalent Ba(3), one Cu(1), and one Cu(2) atom. In the sixteenth F site, F(16) is bonded in a distorted single-bond geometry to one Ba(1), two equivalent Ba(2), and one Al(2) atom.