K6Bi6O19 crystallizes in the monoclinic C2 space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(3), one O(4), one O(5), one O(6), and one O(8) atom. In the second K site, K(2) is bonded in a 10-coordinate geometry to one O(1), one O(10), one O(11), one O(2), one O(4), one O(5), one O(8), one O(9), and two equivalent O(7) atoms. In the third K site, K(3) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(2), one O(4), one O(5), one O(6), and one O(9) atom. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to two equivalent O(10), two equivalent O(5), and two equivalent O(8) atoms to form a mixture of edge and corner-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles are 54°. In the second Bi site, Bi(2) is bonded to two equivalent O(11), two equivalent O(5), and two equivalent O(9) atoms to form a mixture of edge and corner-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. In the third Bi site, Bi(3) is bonded to one O(10), one O(11), one O(2), one O(3), one O(6), and one O(7) atom to form a mixture of edge and corner-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 52-55°. In the fourth Bi site, Bi(4) is bonded to one O(6), one O(7), one O(8), one O(9), and two equivalent O(4) atoms to form a mixture of edge and corner-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 52-55°. There are eleven inequivalent O sites. In the first O site, O(7) is bonded in a 4-coordinate geometry to two equivalent K(2), one Bi(3), and one Bi(4) atom. In the second O site, O(8) is bonded in a 3-coordinate geometry to one K(1), one K(2), one Bi(1), and one Bi(4) atom. In the third O site, O(9) is bonded to one K(2), one K(3), one Bi(2), and one Bi(4) atom to form distorted corner-sharing OK2Bi2 trigonal pyramids. In the fourth O site, O(10) is bonded to one K(2), one K(3), one Bi(1), and one Bi(3) atom to form distorted corner-sharing OK2Bi2 tetrahedra. In the fifth O site, O(11) is bonded in a 4-coordinate geometry to one K(1), one K(2), one Bi(2), and one Bi(3) atom. In the sixth O site, O(1) is bonded in a 6-coordinate geometry to two equivalent K(1), two equivalent K(2), and two equivalent K(3) atoms. In the seventh O site, O(2) is bonded in a distorted water-like geometry to two equivalent K(2), two equivalent K(3), and two equivalent Bi(3) atoms. In the eighth O site, O(3) is bonded in a 4-coordinate geometry to two equivalent K(1) and two equivalent Bi(3) atoms. In the ninth O site, O(4) is bonded in a 2-coordinate geometry to one K(1), one K(2), one K(3), and two equivalent Bi(4) atoms. In the tenth O site, O(5) is bonded in a distorted water-like geometry to one K(1), one K(2), one K(3), one Bi(1), and one Bi(2) atom. In the eleventh O site, O(6) is bonded in a 4-coordinate geometry to one K(1), one K(3), one Bi(3), and one Bi(4) atom.
K6Bi6O19 crystallizes in the monoclinic C2 space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(3), one O(4), one O(5), one O(6), and one O(8) atom. The K(1)-O(1) bond length is 2.82 Å. The K(1)-O(11) bond length is 2.77 Å. The K(1)-O(3) bond length is 2.86 Å. The K(1)-O(4) bond length is 3.12 Å. The K(1)-O(5) bond length is 3.11 Å. The K(1)-O(6) bond length is 3.10 Å. The K(1)-O(8) bond length is 2.77 Å. In the second K site, K(2) is bonded in a 10-coordinate geometry to one O(1), one O(10), one O(11), one O(2), one O(4), one O(5), one O(8), one O(9), and two equivalent O(7) atoms. The K(2)-O(1) bond length is 3.05 Å. The K(2)-O(10) bond length is 2.75 Å. The K(2)-O(11) bond length is 3.11 Å. The K(2)-O(2) bond length is 3.26 Å. The K(2)-O(4) bond length is 3.27 Å. The K(2)-O(5) bond length is 3.24 Å. The K(2)-O(8) bond length is 3.27 Å. The K(2)-O(9) bond length is 2.75 Å. There is one shorter (2.66 Å) and one longer (3.17 Å) K(2)-O(7) bond length. In the third K site, K(3) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(2), one O(4), one O(5), one O(6), and one O(9) atom. The K(3)-O(1) bond length is 2.77 Å. The K(3)-O(10) bond length is 2.67 Å. The K(3)-O(2) bond length is 3.14 Å. The K(3)-O(4) bond length is 3.03 Å. The K(3)-O(5) bond length is 3.09 Å. The K(3)-O(6) bond length is 2.76 Å. The K(3)-O(9) bond length is 2.68 Å. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to two equivalent O(10), two equivalent O(5), and two equivalent O(8) atoms to form a mixture of edge and corner-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles are 54°. Both Bi(1)-O(10) bond lengths are 2.17 Å. Both Bi(1)-O(5) bond lengths are 2.18 Å. Both Bi(1)-O(8) bond lengths are 2.14 Å. In the second Bi site, Bi(2) is bonded to two equivalent O(11), two equivalent O(5), and two equivalent O(9) atoms to form a mixture of edge and corner-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. Both Bi(2)-O(11) bond lengths are 2.19 Å. Both Bi(2)-O(5) bond lengths are 2.16 Å. Both Bi(2)-O(9) bond lengths are 2.12 Å. In the third Bi site, Bi(3) is bonded to one O(10), one O(11), one O(2), one O(3), one O(6), and one O(7) atom to form a mixture of edge and corner-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 52-55°. The Bi(3)-O(10) bond length is 2.13 Å. The Bi(3)-O(11) bond length is 2.13 Å. The Bi(3)-O(2) bond length is 2.18 Å. The Bi(3)-O(3) bond length is 2.16 Å. The Bi(3)-O(6) bond length is 2.18 Å. The Bi(3)-O(7) bond length is 2.17 Å. In the fourth Bi site, Bi(4) is bonded to one O(6), one O(7), one O(8), one O(9), and two equivalent O(4) atoms to form a mixture of edge and corner-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 52-55°. The Bi(4)-O(6) bond length is 2.14 Å. The Bi(4)-O(7) bond length is 2.13 Å. The Bi(4)-O(8) bond length is 2.18 Å. The Bi(4)-O(9) bond length is 2.17 Å. There is one shorter (2.16 Å) and one longer (2.17 Å) Bi(4)-O(4) bond length. There are eleven inequivalent O sites. In the first O site, O(7) is bonded in a 4-coordinate geometry to two equivalent K(2), one Bi(3), and one Bi(4) atom. In the second O site, O(8) is bonded in a 3-coordinate geometry to one K(1), one K(2), one Bi(1), and one Bi(4) atom. In the third O site, O(9) is bonded to one K(2), one K(3), one Bi(2), and one Bi(4) atom to form distorted corner-sharing OK2Bi2 trigonal pyramids. In the fourth O site, O(10) is bonded to one K(2), one K(3), one Bi(1), and one Bi(3) atom to form distorted corner-sharing OK2Bi2 tetrahedra. In the fifth O site, O(11) is bonded in a 4-coordinate geometry to one K(1), one K(2), one Bi(2), and one Bi(3) atom. In the sixth O site, O(1) is bonded in a 6-coordinate geometry to two equivalent K(1), two equivalent K(2), and two equivalent K(3) atoms. In the seventh O site, O(2) is bonded in a distorted water-like geometry to two equivalent K(2), two equivalent K(3), and two equivalent Bi(3) atoms. In the eighth O site, O(3) is bonded in a 4-coordinate geometry to two equivalent K(1) and two equivalent Bi(3) atoms. In the ninth O site, O(4) is bonded in a 2-coordinate geometry to one K(1), one K(2), one K(3), and two equivalent Bi(4) atoms. In the tenth O site, O(5) is bonded in a distorted water-like geometry to one K(1), one K(2), one K(3), one Bi(1), and one Bi(2) atom. In the eleventh O site, O(6) is bonded in a 4-coordinate geometry to one K(1), one K(3), one Bi(3), and one Bi(4) atom.