CaBi6(PO5)4 crystallizes in the triclinic P-1 space group. Ca(1) is bonded in a distorted body-centered cubic geometry to two equivalent O(10), two equivalent O(3), two equivalent O(6), and two equivalent O(9) atoms. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(10), one O(2), one O(5), and one O(9) atom to form distorted BiO5 square pyramids that share  a cornercorner with one P(2)O4 tetrahedra and corners with two equivalent P(1)O4 tetrahedra. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to one O(4), one O(5), one O(7), one O(8), and two equivalent O(1) atoms. In the third Bi site, Bi(3) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(6), one O(8), and two equivalent O(10) atoms. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(5), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Bi(1)O5 square pyramids. In the second P site, P(2) is bonded to one O(2), one O(4), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Bi(1)O5 square pyramid. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one Bi(1), one Bi(3), and two equivalent Bi(2) atoms to form distorted OBi4 tetrahedra that share  a cornercorner with one O(10)CaBi3 tetrahedra,  an edgeedge with one O(1)Bi4 tetrahedra, and  an edgeedge with one O(10)CaBi3 tetrahedra. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Bi(1), one Bi(3), and one P(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Ca(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(2), one Bi(3), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Bi(1), one Bi(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Ca(1), one Bi(3), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Bi(2) and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one Bi(2), one Bi(3), and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Ca(1), one Bi(1), and one P(1) atom. In the tenth O site, O(10) is bonded to one Ca(1), one Bi(1), and two equivalent Bi(3) atoms to form OCaBi3 tetrahedra that share  a cornercorner with one O(1)Bi4 tetrahedra,  a cornercorner with one O(10)CaBi3 tetrahedra,  an edgeedge with one O(1)Bi4 tetrahedra, and  an edgeedge with one O(10)CaBi3 tetrahedra.
CaBi6(PO5)4 crystallizes in the triclinic P-1 space group. Ca(1) is bonded in a distorted body-centered cubic geometry to two equivalent O(10), two equivalent O(3), two equivalent O(6), and two equivalent O(9) atoms. Both Ca(1)-O(10) bond lengths are 2.70 Å. Both Ca(1)-O(3) bond lengths are 2.54 Å. Both Ca(1)-O(6) bond lengths are 2.42 Å. Both Ca(1)-O(9) bond lengths are 2.53 Å. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(10), one O(2), one O(5), and one O(9) atom to form distorted BiO5 square pyramids that share  a cornercorner with one P(2)O4 tetrahedra and corners with two equivalent P(1)O4 tetrahedra. The Bi(1)-O(1) bond length is 2.35 Å. The Bi(1)-O(10) bond length is 2.14 Å. The Bi(1)-O(2) bond length is 2.34 Å. The Bi(1)-O(5) bond length is 2.32 Å. The Bi(1)-O(9) bond length is 2.42 Å. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to one O(4), one O(5), one O(7), one O(8), and two equivalent O(1) atoms. The Bi(2)-O(4) bond length is 2.44 Å. The Bi(2)-O(5) bond length is 2.73 Å. The Bi(2)-O(7) bond length is 2.42 Å. The Bi(2)-O(8) bond length is 2.37 Å. There is one shorter (2.22 Å) and one longer (2.33 Å) Bi(2)-O(1) bond length. In the third Bi site, Bi(3) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(6), one O(8), and two equivalent O(10) atoms. The Bi(3)-O(1) bond length is 2.56 Å. The Bi(3)-O(2) bond length is 2.73 Å. The Bi(3)-O(3) bond length is 2.42 Å. The Bi(3)-O(4) bond length is 2.63 Å. The Bi(3)-O(6) bond length is 2.47 Å. The Bi(3)-O(8) bond length is 2.78 Å. There is one shorter (2.27 Å) and one longer (2.37 Å) Bi(3)-O(10) bond length. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(5), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Bi(1)O5 square pyramids. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.56 Å. The P(1)-O(8) bond length is 1.55 Å. The P(1)-O(9) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(2), one O(4), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Bi(1)O5 square pyramid. The P(2)-O(2) bond length is 1.56 Å. The P(2)-O(4) bond length is 1.56 Å. The P(2)-O(6) bond length is 1.55 Å. The P(2)-O(7) bond length is 1.56 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one Bi(1), one Bi(3), and two equivalent Bi(2) atoms to form distorted OBi4 tetrahedra that share  a cornercorner with one O(10)CaBi3 tetrahedra,  an edgeedge with one O(1)Bi4 tetrahedra, and  an edgeedge with one O(10)CaBi3 tetrahedra. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Bi(1), one Bi(3), and one P(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Ca(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(2), one Bi(3), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Bi(1), one Bi(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Ca(1), one Bi(3), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Bi(2) and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one Bi(2), one Bi(3), and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Ca(1), one Bi(1), and one P(1) atom. In the tenth O site, O(10) is bonded to one Ca(1), one Bi(1), and two equivalent Bi(3) atoms to form OCaBi3 tetrahedra that share  a cornercorner with one O(1)Bi4 tetrahedra,  a cornercorner with one O(10)CaBi3 tetrahedra,  an edgeedge with one O(1)Bi4 tetrahedra, and  an edgeedge with one O(10)CaBi3 tetrahedra.