ZnBi6P2(O7F)2 crystallizes in the monoclinic C2/c space group. Zn(1) is bonded in a distorted square co-planar geometry to two equivalent O(5) and two equivalent O(8) atoms. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one O(5), one O(7), two equivalent O(3), and two equivalent O(4) atoms. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. In the third Bi site, Bi(3) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom. P(1) is bonded in a tetrahedral geometry to one O(6), one O(7), one O(8), and one F(1) atom. There are eight inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Bi(2) and two equivalent Bi(3) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the second O site, O(2) is bonded to two equivalent Bi(2) and two equivalent Bi(3) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the third O site, O(3) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the fourth O site, O(4) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the fifth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Zn(1) and one P(1) atom. In the sixth O site, O(5) is bonded in a distorted trigonal planar geometry to one Zn(1), one Bi(1), and one Bi(2) atom. In the seventh O site, O(6) is bonded in a single-bond geometry to one Bi(2), one Bi(3), and one P(1) atom. In the eighth O site, O(7) is bonded in a distorted single-bond geometry to one Bi(1), one Bi(3), and one P(1) atom. F(1) is bonded in a single-bond geometry to one P(1) atom.
ZnBi6P2(O7F)2 crystallizes in the monoclinic C2/c space group. Zn(1) is bonded in a distorted square co-planar geometry to two equivalent O(5) and two equivalent O(8) atoms. Both Zn(1)-O(5) bond lengths are 1.87 Å. Both Zn(1)-O(8) bond lengths are 2.34 Å. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one O(5), one O(7), two equivalent O(3), and two equivalent O(4) atoms. The Bi(1)-O(5) bond length is 2.26 Å. The Bi(1)-O(7) bond length is 2.52 Å. There is one shorter (2.35 Å) and one longer (2.55 Å) Bi(1)-O(3) bond length. There is one shorter (2.24 Å) and one longer (2.63 Å) Bi(1)-O(4) bond length. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The Bi(2)-O(1) bond length is 2.24 Å. The Bi(2)-O(2) bond length is 2.52 Å. The Bi(2)-O(3) bond length is 2.41 Å. The Bi(2)-O(4) bond length is 2.28 Å. The Bi(2)-O(5) bond length is 2.35 Å. The Bi(2)-O(6) bond length is 2.81 Å. In the third Bi site, Bi(3) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom. The Bi(3)-O(1) bond length is 2.48 Å. The Bi(3)-O(2) bond length is 2.23 Å. The Bi(3)-O(3) bond length is 2.20 Å. The Bi(3)-O(4) bond length is 2.31 Å. The Bi(3)-O(6) bond length is 2.74 Å. The Bi(3)-O(7) bond length is 2.82 Å. P(1) is bonded in a tetrahedral geometry to one O(6), one O(7), one O(8), and one F(1) atom. The P(1)-O(6) bond length is 1.53 Å. The P(1)-O(7) bond length is 1.53 Å. The P(1)-O(8) bond length is 1.52 Å. The P(1)-F(1) bond length is 1.63 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Bi(2) and two equivalent Bi(3) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the second O site, O(2) is bonded to two equivalent Bi(2) and two equivalent Bi(3) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the third O site, O(3) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the fourth O site, O(4) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the fifth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Zn(1) and one P(1) atom. In the sixth O site, O(5) is bonded in a distorted trigonal planar geometry to one Zn(1), one Bi(1), and one Bi(2) atom. In the seventh O site, O(6) is bonded in a single-bond geometry to one Bi(2), one Bi(3), and one P(1) atom. In the eighth O site, O(7) is bonded in a distorted single-bond geometry to one Bi(1), one Bi(3), and one P(1) atom. F(1) is bonded in a single-bond geometry to one P(1) atom.