Ba2W2F11 crystallizes in the trigonal P3_2 space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one F(11), one F(2), one F(7), one F(8), two equivalent F(4), and two equivalent F(5) atoms. In the second Ba site, Ba(2) is bonded in a 5-coordinate geometry to one F(10), one F(3), one F(5), one F(7), and one F(9) atom. There are two inequivalent W sites. In the first W site, W(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(6), and one F(9) atom to form a mixture of corner and edge-sharing WF6 octahedra. The corner-sharing octahedral tilt angles are 59°. In the second W site, W(2) is bonded to one F(1), one F(10), one F(11), one F(6), one F(8), and one F(9) atom to form a mixture of corner and edge-sharing WF6 octahedra. The corner-sharing octahedral tilt angles are 59°. There are eleven inequivalent F sites. In the first F site, F(11) is bonded in a distorted single-bond geometry to one Ba(1) and one W(2) atom. In the second F site, F(1) is bonded in a water-like geometry to one W(1) and one W(2) atom. In the third F site, F(2) is bonded in a distorted bent 150 degrees geometry to one Ba(1) and one W(1) atom. In the fourth F site, F(3) is bonded in a bent 120 degrees geometry to one Ba(2) and one W(1) atom. In the fifth F site, F(4) is bonded in a distorted trigonal planar geometry to two equivalent Ba(1) and one W(1) atom. In the sixth F site, F(5) is bonded in a distorted trigonal planar geometry to one Ba(2) and two equivalent Ba(1) atoms. In the seventh F site, F(6) is bonded in a bent 120 degrees geometry to one W(1) and one W(2) atom. In the eighth F site, F(7) is bonded in a bent 150 degrees geometry to one Ba(1) and one Ba(2) atom. In the ninth F site, F(8) is bonded in a bent 120 degrees geometry to one Ba(1) and one W(2) atom. In the tenth F site, F(9) is bonded in a distorted trigonal non-coplanar geometry to one Ba(2), one W(1), and one W(2) atom. In the eleventh F site, F(10) is bonded in a distorted bent 150 degrees geometry to one Ba(2) and one W(2) atom.
Ba2W2F11 crystallizes in the trigonal P3_2 space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one F(11), one F(2), one F(7), one F(8), two equivalent F(4), and two equivalent F(5) atoms. The Ba(1)-F(11) bond length is 2.91 Å. The Ba(1)-F(2) bond length is 2.61 Å. The Ba(1)-F(7) bond length is 2.56 Å. The Ba(1)-F(8) bond length is 2.72 Å. There is one shorter (2.75 Å) and one longer (3.00 Å) Ba(1)-F(4) bond length. There is one shorter (2.67 Å) and one longer (3.03 Å) Ba(1)-F(5) bond length. In the second Ba site, Ba(2) is bonded in a 5-coordinate geometry to one F(10), one F(3), one F(5), one F(7), and one F(9) atom. The Ba(2)-F(10) bond length is 2.82 Å. The Ba(2)-F(3) bond length is 2.68 Å. The Ba(2)-F(5) bond length is 2.50 Å. The Ba(2)-F(7) bond length is 2.46 Å. The Ba(2)-F(9) bond length is 3.08 Å. There are two inequivalent W sites. In the first W site, W(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(6), and one F(9) atom to form a mixture of corner and edge-sharing WF6 octahedra. The corner-sharing octahedral tilt angles are 59°. The W(1)-F(1) bond length is 2.19 Å. The W(1)-F(2) bond length is 2.09 Å. The W(1)-F(3) bond length is 2.06 Å. The W(1)-F(4) bond length is 2.09 Å. The W(1)-F(6) bond length is 2.16 Å. The W(1)-F(9) bond length is 2.24 Å. In the second W site, W(2) is bonded to one F(1), one F(10), one F(11), one F(6), one F(8), and one F(9) atom to form a mixture of corner and edge-sharing WF6 octahedra. The corner-sharing octahedral tilt angles are 59°. The W(2)-F(1) bond length is 2.09 Å. The W(2)-F(10) bond length is 1.96 Å. The W(2)-F(11) bond length is 1.96 Å. The W(2)-F(6) bond length is 2.10 Å. The W(2)-F(8) bond length is 1.99 Å. The W(2)-F(9) bond length is 2.08 Å. There are eleven inequivalent F sites. In the first F site, F(11) is bonded in a distorted single-bond geometry to one Ba(1) and one W(2) atom. In the second F site, F(1) is bonded in a water-like geometry to one W(1) and one W(2) atom. In the third F site, F(2) is bonded in a distorted bent 150 degrees geometry to one Ba(1) and one W(1) atom. In the fourth F site, F(3) is bonded in a bent 120 degrees geometry to one Ba(2) and one W(1) atom. In the fifth F site, F(4) is bonded in a distorted trigonal planar geometry to two equivalent Ba(1) and one W(1) atom. In the sixth F site, F(5) is bonded in a distorted trigonal planar geometry to one Ba(2) and two equivalent Ba(1) atoms. In the seventh F site, F(6) is bonded in a bent 120 degrees geometry to one W(1) and one W(2) atom. In the eighth F site, F(7) is bonded in a bent 150 degrees geometry to one Ba(1) and one Ba(2) atom. In the ninth F site, F(8) is bonded in a bent 120 degrees geometry to one Ba(1) and one W(2) atom. In the tenth F site, F(9) is bonded in a distorted trigonal non-coplanar geometry to one Ba(2), one W(1), and one W(2) atom. In the eleventh F site, F(10) is bonded in a distorted bent 150 degrees geometry to one Ba(2) and one W(2) atom.