CaBi3P3O13 crystallizes in the monoclinic P2_1/m space group. Ca(1) is bonded in a 7-coordinate geometry to one O(9), two equivalent O(2), two equivalent O(4), and two equivalent O(8) atoms. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(5), one O(6), one O(9), and two equivalent O(8) atoms to form distorted BiO6 octahedra that share corners with two equivalent Bi(3)O6 octahedra,  a cornercorner with one Bi(2)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. In the second Bi site, Bi(2) is bonded to one O(1), one O(3), one O(7), and two equivalent O(2) atoms to form distorted BiO5 square pyramids that share  a cornercorner with one Bi(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with three equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 62°. In the third Bi site, Bi(3) is bonded to two equivalent O(10), two equivalent O(4), and two equivalent O(6) atoms to form BiO6 octahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and edges with two equivalent Bi(3)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(5), one O(7), and two equivalent O(2) atoms to form PO4 tetrahedra that share  a cornercorner with one Bi(1)O6 octahedra and corners with three equivalent Bi(2)O5 square pyramids. The corner-sharing octahedral tilt angles are 41°. In the second P site, P(2) is bonded to one O(10), one O(3), and two equivalent O(8) atoms to form PO4 tetrahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with two equivalent Bi(3)O6 octahedra, and  a cornercorner with one Bi(2)O5 square pyramid. The corner-sharing octahedral tilt angles range from 45-51°. In the third P site, P(3) is bonded to one O(1), one O(9), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent Bi(3)O6 octahedra,  a cornercorner with one Bi(2)O5 square pyramid, and  an edgeedge with one Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles are 48°. There are ten inequivalent O sites. In the first O site, O(10) is bonded in a distorted single-bond geometry to two equivalent Bi(3) and one P(2) atom. In the second O site, O(1) is bonded in a 3-coordinate geometry to one Bi(1), one Bi(2), and one P(3) atom. In the third O site, O(2) is bonded in a distorted single-bond geometry to one Ca(1), one Bi(2), and one P(1) atom. In the fourth O site, O(3) is bonded in a distorted linear geometry to one Bi(2) and one P(2) atom. In the fifth O site, O(4) is bonded in a distorted single-bond geometry to one Ca(1), one Bi(3), and one P(3) atom. In the sixth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Bi(1) and one P(1) atom. In the seventh O site, O(6) is bonded in a trigonal planar geometry to one Bi(1) and two equivalent Bi(3) atoms. In the eighth O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Bi(2) and one P(1) atom. In the ninth O site, O(8) is bonded in a 3-coordinate geometry to one Ca(1), one Bi(1), and one P(2) atom. In the tenth O site, O(9) is bonded in a 3-coordinate geometry to one Ca(1), one Bi(1), and one P(3) atom.
CaBi3P3O13 crystallizes in the monoclinic P2_1/m space group. Ca(1) is bonded in a 7-coordinate geometry to one O(9), two equivalent O(2), two equivalent O(4), and two equivalent O(8) atoms. The Ca(1)-O(9) bond length is 2.44 Å. Both Ca(1)-O(2) bond lengths are 2.75 Å. Both Ca(1)-O(4) bond lengths are 2.85 Å. Both Ca(1)-O(8) bond lengths are 2.43 Å. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(5), one O(6), one O(9), and two equivalent O(8) atoms to form distorted BiO6 octahedra that share corners with two equivalent Bi(3)O6 octahedra,  a cornercorner with one Bi(2)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. The Bi(1)-O(1) bond length is 2.45 Å. The Bi(1)-O(5) bond length is 2.31 Å. The Bi(1)-O(6) bond length is 2.17 Å. The Bi(1)-O(9) bond length is 2.64 Å. Both Bi(1)-O(8) bond lengths are 2.37 Å. In the second Bi site, Bi(2) is bonded to one O(1), one O(3), one O(7), and two equivalent O(2) atoms to form distorted BiO5 square pyramids that share  a cornercorner with one Bi(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with three equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 62°. The Bi(2)-O(1) bond length is 2.30 Å. The Bi(2)-O(3) bond length is 2.26 Å. The Bi(2)-O(7) bond length is 2.20 Å. Both Bi(2)-O(2) bond lengths are 2.40 Å. In the third Bi site, Bi(3) is bonded to two equivalent O(10), two equivalent O(4), and two equivalent O(6) atoms to form BiO6 octahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and edges with two equivalent Bi(3)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. Both Bi(3)-O(10) bond lengths are 2.42 Å. Both Bi(3)-O(4) bond lengths are 2.41 Å. Both Bi(3)-O(6) bond lengths are 2.28 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(5), one O(7), and two equivalent O(2) atoms to form PO4 tetrahedra that share  a cornercorner with one Bi(1)O6 octahedra and corners with three equivalent Bi(2)O5 square pyramids. The corner-sharing octahedral tilt angles are 41°. The P(1)-O(5) bond length is 1.54 Å. The P(1)-O(7) bond length is 1.57 Å. Both P(1)-O(2) bond lengths are 1.56 Å. In the second P site, P(2) is bonded to one O(10), one O(3), and two equivalent O(8) atoms to form PO4 tetrahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with two equivalent Bi(3)O6 octahedra, and  a cornercorner with one Bi(2)O5 square pyramid. The corner-sharing octahedral tilt angles range from 45-51°. The P(2)-O(10) bond length is 1.57 Å. The P(2)-O(3) bond length is 1.53 Å. Both P(2)-O(8) bond lengths are 1.56 Å. In the third P site, P(3) is bonded to one O(1), one O(9), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent Bi(3)O6 octahedra,  a cornercorner with one Bi(2)O5 square pyramid, and  an edgeedge with one Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles are 48°. The P(3)-O(1) bond length is 1.58 Å. The P(3)-O(9) bond length is 1.55 Å. Both P(3)-O(4) bond lengths are 1.56 Å. There are ten inequivalent O sites. In the first O site, O(10) is bonded in a distorted single-bond geometry to two equivalent Bi(3) and one P(2) atom. In the second O site, O(1) is bonded in a 3-coordinate geometry to one Bi(1), one Bi(2), and one P(3) atom. In the third O site, O(2) is bonded in a distorted single-bond geometry to one Ca(1), one Bi(2), and one P(1) atom. In the fourth O site, O(3) is bonded in a distorted linear geometry to one Bi(2) and one P(2) atom. In the fifth O site, O(4) is bonded in a distorted single-bond geometry to one Ca(1), one Bi(3), and one P(3) atom. In the sixth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Bi(1) and one P(1) atom. In the seventh O site, O(6) is bonded in a trigonal planar geometry to one Bi(1) and two equivalent Bi(3) atoms. In the eighth O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Bi(2) and one P(1) atom. In the ninth O site, O(8) is bonded in a 3-coordinate geometry to one Ca(1), one Bi(1), and one P(2) atom. In the tenth O site, O(9) is bonded in a 3-coordinate geometry to one Ca(1), one Bi(1), and one P(3) atom.