ZnBi6P2(O7F)2 crystallizes in the monoclinic C2/c space group. Zn(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form distorted ZnO6 octahedra that share corners with four equivalent P(1)O3F tetrahedra. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one O(4), one O(5), two equivalent O(2), and two equivalent O(7) atoms. In the second Bi site, Bi(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(4), one O(5), one O(6), one O(7), and one O(8) atom. In the third Bi site, Bi(3) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(6), one O(7), and one O(8) atom. P(1) is bonded to one O(1), one O(3), one O(4), and one F(1) atom to form PO3F tetrahedra that share corners with two equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-55°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Zn(1), one Bi(2), and one P(1) atom. In the second O site, O(2) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(1) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Zn(1), one Bi(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Bi(1), one Bi(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Zn(1), one Bi(1), and one Bi(2) atom. In the sixth O site, O(6) 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 seventh O site, O(7) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(1) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the eighth O site, O(8) is bonded to two equivalent Bi(2) and two equivalent Bi(3) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra. 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 to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form distorted ZnO6 octahedra that share corners with four equivalent P(1)O3F tetrahedra. Both Zn(1)-O(1) bond lengths are 2.44 Å. Both Zn(1)-O(3) bond lengths are 2.40 Å. Both Zn(1)-O(5) bond lengths are 1.89 Å. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one O(4), one O(5), two equivalent O(2), and two equivalent O(7) atoms. The Bi(1)-O(4) bond length is 2.71 Å. The Bi(1)-O(5) bond length is 2.27 Å. There is one shorter (2.19 Å) and one longer (2.56 Å) Bi(1)-O(2) bond length. There is one shorter (2.30 Å) and one longer (2.52 Å) Bi(1)-O(7) bond length. In the second Bi site, Bi(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(4), one O(5), one O(6), one O(7), and one O(8) atom. The Bi(2)-O(1) bond length is 2.82 Å. The Bi(2)-O(2) bond length is 2.61 Å. The Bi(2)-O(4) bond length is 2.62 Å. The Bi(2)-O(5) bond length is 2.26 Å. The Bi(2)-O(6) bond length is 2.32 Å. The Bi(2)-O(7) bond length is 2.24 Å. The Bi(2)-O(8) bond length is 2.66 Å. In the third Bi site, Bi(3) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(6), one O(7), and one O(8) atom. The Bi(3)-O(2) bond length is 2.28 Å. The Bi(3)-O(3) bond length is 2.72 Å. The Bi(3)-O(6) bond length is 2.33 Å. The Bi(3)-O(7) bond length is 2.36 Å. The Bi(3)-O(8) bond length is 2.20 Å. P(1) is bonded to one O(1), one O(3), one O(4), and one F(1) atom to form PO3F tetrahedra that share corners with two equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-55°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.54 Å. The P(1)-F(1) bond length is 1.62 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Zn(1), one Bi(2), and one P(1) atom. In the second O site, O(2) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(1) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Zn(1), one Bi(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Bi(1), one Bi(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Zn(1), one Bi(1), and one Bi(2) atom. In the sixth O site, O(6) 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 seventh O site, O(7) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(1) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the eighth O site, O(8) is bonded to two equivalent Bi(2) and two equivalent Bi(3) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra. F(1) is bonded in a single-bond geometry to one P(1) atom.