K2Bi3F11 crystallizes in the triclinic P1 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded to one F(1), one F(4), and three equivalent F(2) atoms to form distorted corner-sharing KF5 trigonal bipyramids. In the second K site, K(2) is bonded in a 7-coordinate geometry to one F(7), three equivalent F(4), and three equivalent F(5) atoms. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 7-coordinate geometry to one F(10), one F(2), one F(6), two equivalent F(1), and two equivalent F(11) atoms. In the second Bi site, Bi(2) is bonded in a 7-coordinate geometry to one F(5), one F(8), one F(9), two equivalent F(3), and two equivalent F(7) atoms. In the third Bi site, Bi(3) is bonded in a 6-coordinate geometry to one F(10), one F(8), two equivalent F(6), and two equivalent F(9) atoms. There are eleven inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one K(1) and two equivalent Bi(1) atoms. In the second F site, F(2) is bonded to three equivalent K(1) and one Bi(1) atom to form FK3Bi tetrahedra that share corners with six equivalent F(2)K3Bi tetrahedra and corners with three equivalent F(4)K4 trigonal pyramids. In the third F site, F(3) is bonded in a distorted bent 150 degrees geometry to two equivalent Bi(2) atoms. In the fourth F site, F(4) is bonded to one K(1) and three equivalent K(2) atoms to form FK4 trigonal pyramids that share corners with three equivalent F(2)K3Bi tetrahedra, corners with three equivalent F(5)K3Bi tetrahedra, corners with six equivalent F(4)K4 trigonal pyramids, and edges with three equivalent F(5)K3Bi tetrahedra. In the fifth F site, F(5) is bonded to three equivalent K(2) and one Bi(2) atom to form distorted FK3Bi tetrahedra that share corners with six equivalent F(5)K3Bi tetrahedra, corners with three equivalent F(4)K4 trigonal pyramids, and edges with three equivalent F(4)K4 trigonal pyramids. In the sixth F site, F(6) is bonded in a 3-coordinate geometry to one Bi(1) and two equivalent Bi(3) atoms. In the seventh F site, F(7) is bonded in a distorted trigonal non-coplanar geometry to one K(2) and two equivalent Bi(2) atoms. In the eighth F site, F(8) is bonded in a bent 120 degrees geometry to one Bi(2) and one Bi(3) atom. In the ninth F site, F(9) is bonded in a 2-coordinate geometry to one Bi(2) and two equivalent Bi(3) atoms. In the tenth F site, F(10) is bonded in a bent 120 degrees geometry to one Bi(1) and one Bi(3) atom. In the eleventh F site, F(11) is bonded in a bent 150 degrees geometry to two equivalent Bi(1) atoms.
K2Bi3F11 crystallizes in the triclinic P1 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded to one F(1), one F(4), and three equivalent F(2) atoms to form distorted corner-sharing KF5 trigonal bipyramids. The K(1)-F(1) bond length is 2.67 Å. The K(1)-F(4) bond length is 2.47 Å. There are a spread of K(1)-F(2) bond distances ranging from 2.75-2.77 Å. In the second K site, K(2) is bonded in a 7-coordinate geometry to one F(7), three equivalent F(4), and three equivalent F(5) atoms. The K(2)-F(7) bond length is 2.90 Å. There are a spread of K(2)-F(4) bond distances ranging from 2.77-2.81 Å. There are a spread of K(2)-F(5) bond distances ranging from 2.86-2.91 Å. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 7-coordinate geometry to one F(10), one F(2), one F(6), two equivalent F(1), and two equivalent F(11) atoms. The Bi(1)-F(10) bond length is 2.36 Å. The Bi(1)-F(2) bond length is 2.24 Å. The Bi(1)-F(6) bond length is 2.68 Å. There is one shorter (2.21 Å) and one longer (2.64 Å) Bi(1)-F(1) bond length. There is one shorter (2.26 Å) and one longer (2.33 Å) Bi(1)-F(11) bond length. In the second Bi site, Bi(2) is bonded in a 7-coordinate geometry to one F(5), one F(8), one F(9), two equivalent F(3), and two equivalent F(7) atoms. The Bi(2)-F(5) bond length is 2.14 Å. The Bi(2)-F(8) bond length is 2.53 Å. The Bi(2)-F(9) bond length is 2.79 Å. There is one shorter (2.28 Å) and one longer (2.33 Å) Bi(2)-F(3) bond length. There is one shorter (2.19 Å) and one longer (2.68 Å) Bi(2)-F(7) bond length. In the third Bi site, Bi(3) is bonded in a 6-coordinate geometry to one F(10), one F(8), two equivalent F(6), and two equivalent F(9) atoms. The Bi(3)-F(10) bond length is 2.24 Å. The Bi(3)-F(8) bond length is 2.20 Å. There is one shorter (2.19 Å) and one longer (2.61 Å) Bi(3)-F(6) bond length. There is one shorter (2.18 Å) and one longer (2.50 Å) Bi(3)-F(9) bond length. There are eleven inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one K(1) and two equivalent Bi(1) atoms. In the second F site, F(2) is bonded to three equivalent K(1) and one Bi(1) atom to form FK3Bi tetrahedra that share corners with six equivalent F(2)K3Bi tetrahedra and corners with three equivalent F(4)K4 trigonal pyramids. In the third F site, F(3) is bonded in a distorted bent 150 degrees geometry to two equivalent Bi(2) atoms. In the fourth F site, F(4) is bonded to one K(1) and three equivalent K(2) atoms to form FK4 trigonal pyramids that share corners with three equivalent F(2)K3Bi tetrahedra, corners with three equivalent F(5)K3Bi tetrahedra, corners with six equivalent F(4)K4 trigonal pyramids, and edges with three equivalent F(5)K3Bi tetrahedra. In the fifth F site, F(5) is bonded to three equivalent K(2) and one Bi(2) atom to form distorted FK3Bi tetrahedra that share corners with six equivalent F(5)K3Bi tetrahedra, corners with three equivalent F(4)K4 trigonal pyramids, and edges with three equivalent F(4)K4 trigonal pyramids. In the sixth F site, F(6) is bonded in a 3-coordinate geometry to one Bi(1) and two equivalent Bi(3) atoms. In the seventh F site, F(7) is bonded in a distorted trigonal non-coplanar geometry to one K(2) and two equivalent Bi(2) atoms. In the eighth F site, F(8) is bonded in a bent 120 degrees geometry to one Bi(2) and one Bi(3) atom. In the ninth F site, F(9) is bonded in a 2-coordinate geometry to one Bi(2) and two equivalent Bi(3) atoms. In the tenth F site, F(10) is bonded in a bent 120 degrees geometry to one Bi(1) and one Bi(3) atom. In the eleventh F site, F(11) is bonded in a bent 150 degrees geometry to two equivalent Bi(1) atoms.