Bi12O16F5 crystallizes in the monoclinic C2 space group. There are six inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 5-coordinate geometry to one O(2), one O(4), two equivalent O(1), and one F(1) atom. In the second Bi site, Bi(2) is bonded in a body-centered cubic geometry to one O(1), one O(6), two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. In the third Bi site, Bi(3) is bonded in a 6-coordinate geometry to one O(2), one O(5), two equivalent O(3), and two equivalent F(2) atoms. In the fourth Bi site, Bi(4) is bonded in a 7-coordinate geometry to one O(1), one O(6), one O(8), two equivalent O(4), and two equivalent O(7) atoms. In the fifth Bi site, Bi(5) is bonded in a 6-coordinate geometry to one O(5), one O(7), two equivalent O(6), and two equivalent F(3) atoms. In the sixth Bi site, Bi(6) is bonded in a 5-coordinate geometry to one O(7), three equivalent O(8), and one F(1) atom. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Bi(2), one Bi(4), and two equivalent Bi(1) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the second O site, O(2) is bonded to one Bi(1), one Bi(3), and two equivalent Bi(2) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the third O site, O(3) is bonded to two equivalent Bi(2) and two equivalent Bi(3) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Bi(1) and two equivalent Bi(4) atoms. In the fifth O site, O(5) is bonded to one Bi(3), one Bi(5), and two equivalent Bi(2) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the sixth O site, O(6) is bonded to one Bi(2), one Bi(4), and two equivalent Bi(5) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the seventh O site, O(7) is bonded to one Bi(5), one Bi(6), and two equivalent Bi(4) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the eighth O site, O(8) is bonded to one Bi(4) and three equivalent Bi(6) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 2-coordinate geometry to one Bi(1) and one Bi(6) atom. In the second F site, F(3) is bonded in a square co-planar geometry to four equivalent Bi(5) atoms. In the third F site, F(2) is bonded in a distorted single-bond geometry to two equivalent Bi(3) atoms.
Bi12O16F5 crystallizes in the monoclinic C2 space group. There are six inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 5-coordinate geometry to one O(2), one O(4), two equivalent O(1), and one F(1) atom. The Bi(1)-O(2) bond length is 2.38 Å. The Bi(1)-O(4) bond length is 2.27 Å. Both Bi(1)-O(1) bond lengths are 2.26 Å. The Bi(1)-F(1) bond length is 2.74 Å. In the second Bi site, Bi(2) is bonded in a body-centered cubic geometry to one O(1), one O(6), two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. The Bi(2)-O(1) bond length is 2.45 Å. The Bi(2)-O(6) bond length is 2.61 Å. There is one shorter (2.48 Å) and one longer (2.49 Å) Bi(2)-O(2) bond length. Both Bi(2)-O(3) bond lengths are 2.48 Å. There is one shorter (2.46 Å) and one longer (2.47 Å) Bi(2)-O(5) bond length. In the third Bi site, Bi(3) is bonded in a 6-coordinate geometry to one O(2), one O(5), two equivalent O(3), and two equivalent F(2) atoms. The Bi(3)-O(2) bond length is 2.24 Å. The Bi(3)-O(5) bond length is 2.41 Å. There is one shorter (2.24 Å) and one longer (2.30 Å) Bi(3)-O(3) bond length. There is one shorter (2.52 Å) and one longer (2.79 Å) Bi(3)-F(2) bond length. In the fourth Bi site, Bi(4) is bonded in a 7-coordinate geometry to one O(1), one O(6), one O(8), two equivalent O(4), and two equivalent O(7) atoms. The Bi(4)-O(1) bond length is 2.45 Å. The Bi(4)-O(6) bond length is 2.29 Å. The Bi(4)-O(8) bond length is 2.53 Å. There is one shorter (2.38 Å) and one longer (2.40 Å) Bi(4)-O(4) bond length. There is one shorter (2.40 Å) and one longer (2.41 Å) Bi(4)-O(7) bond length. In the fifth Bi site, Bi(5) is bonded in a 6-coordinate geometry to one O(5), one O(7), two equivalent O(6), and two equivalent F(3) atoms. The Bi(5)-O(5) bond length is 2.23 Å. The Bi(5)-O(7) bond length is 2.31 Å. There is one shorter (2.25 Å) and one longer (2.27 Å) Bi(5)-O(6) bond length. There is one shorter (2.74 Å) and one longer (2.79 Å) Bi(5)-F(3) bond length. In the sixth Bi site, Bi(6) is bonded in a 5-coordinate geometry to one O(7), three equivalent O(8), and one F(1) atom. The Bi(6)-O(7) bond length is 2.32 Å. There are a spread of Bi(6)-O(8) bond distances ranging from 2.22-2.39 Å. The Bi(6)-F(1) bond length is 2.47 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Bi(2), one Bi(4), and two equivalent Bi(1) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the second O site, O(2) is bonded to one Bi(1), one Bi(3), and two equivalent Bi(2) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the third O site, O(3) is bonded to two equivalent Bi(2) and two equivalent Bi(3) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Bi(1) and two equivalent Bi(4) atoms. In the fifth O site, O(5) is bonded to one Bi(3), one Bi(5), and two equivalent Bi(2) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the sixth O site, O(6) is bonded to one Bi(2), one Bi(4), and two equivalent Bi(5) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the seventh O site, O(7) is bonded to one Bi(5), one Bi(6), and two equivalent Bi(4) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the eighth O site, O(8) is bonded to one Bi(4) and three equivalent Bi(6) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 2-coordinate geometry to one Bi(1) and one Bi(6) atom. In the second F site, F(3) is bonded in a square co-planar geometry to four equivalent Bi(5) atoms. In the third F site, F(2) is bonded in a distorted single-bond geometry to two equivalent Bi(3) atoms.