CoBi6P2(O7F)2 crystallizes in the monoclinic C2/c space group. Co(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form CoO6 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 4-coordinate geometry to one O(2), one O(3), one O(7), and one O(8) atom. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to one O(1), one O(6), two equivalent O(7), and two equivalent O(8) atoms. 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(5), one O(7), and one O(8) atom. P(1) is bonded to one O(4), one O(5), one O(6), and one F(1) atom to form PO3F tetrahedra that share corners with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-54°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Co(1), one Bi(2), and one Bi(3) atom. In the second O site, O(2) is bonded to two equivalent Bi(1) 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 two equivalent Bi(1) and two equivalent Bi(3) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Co(1) and one P(1) atom. In the fifth O site, O(8) is bonded to one Bi(1), one Bi(3), and two equivalent Bi(2) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the sixth O site, O(5) is bonded in a distorted single-bond geometry to one Co(1), one Bi(3), and one P(1) atom. In the seventh O site, O(6) is bonded in a distorted single-bond geometry to one Bi(2) and one P(1) atom. In the eighth O site, O(7) is bonded to one Bi(1), one Bi(3), and two equivalent Bi(2) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. F(1) is bonded in a single-bond geometry to one P(1) atom.
CoBi6P2(O7F)2 crystallizes in the monoclinic C2/c space group. Co(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form CoO6 octahedra that share corners with four equivalent P(1)O3F tetrahedra. Both Co(1)-O(1) bond lengths are 1.93 Å. Both Co(1)-O(4) bond lengths are 2.22 Å. Both Co(1)-O(5) bond lengths are 2.52 Å. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(7), and one O(8) atom. The Bi(1)-O(2) bond length is 2.22 Å. The Bi(1)-O(3) bond length is 2.45 Å. The Bi(1)-O(7) bond length is 2.20 Å. The Bi(1)-O(8) bond length is 2.30 Å. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to one O(1), one O(6), two equivalent O(7), and two equivalent O(8) atoms. The Bi(2)-O(1) bond length is 2.26 Å. The Bi(2)-O(6) bond length is 2.51 Å. There is one shorter (2.34 Å) and one longer (2.52 Å) Bi(2)-O(7) bond length. There is one shorter (2.24 Å) and one longer (2.61 Å) Bi(2)-O(8) bond length. 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(5), one O(7), and one O(8) atom. The Bi(3)-O(1) bond length is 2.31 Å. The Bi(3)-O(2) bond length is 2.55 Å. The Bi(3)-O(3) bond length is 2.24 Å. The Bi(3)-O(5) bond length is 2.85 Å. The Bi(3)-O(7) bond length is 2.44 Å. The Bi(3)-O(8) bond length is 2.27 Å. P(1) is bonded to one O(4), one O(5), one O(6), and one F(1) atom to form PO3F tetrahedra that share corners with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-54°. The P(1)-O(4) bond length is 1.52 Å. The P(1)-O(5) bond length is 1.53 Å. The P(1)-O(6) bond length is 1.53 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 in a distorted trigonal planar geometry to one Co(1), one Bi(2), and one Bi(3) atom. In the second O site, O(2) is bonded to two equivalent Bi(1) 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 two equivalent Bi(1) and two equivalent Bi(3) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Co(1) and one P(1) atom. In the fifth O site, O(8) is bonded to one Bi(1), one Bi(3), and two equivalent Bi(2) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the sixth O site, O(5) is bonded in a distorted single-bond geometry to one Co(1), one Bi(3), and one P(1) atom. In the seventh O site, O(6) is bonded in a distorted single-bond geometry to one Bi(2) and one P(1) atom. In the eighth O site, O(7) is bonded to one Bi(1), one Bi(3), and two equivalent Bi(2) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. F(1) is bonded in a single-bond geometry to one P(1) atom.