Ca5Bi6(O2Cl3)4 is Esseneite-like structured and crystallizes in the orthorhombic Immm space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to four equivalent O(1), two equivalent Cl(2), and two equivalent Cl(3) atoms. In the second Ca site, Ca(2) is bonded to one Cl(5), one Cl(6), two equivalent Cl(2), and two equivalent Cl(4) atoms to form a mixture of edge and corner-sharing CaCl6 octahedra. The corner-sharing octahedral tilt angles range from 0-14°. In the third Ca site, Ca(3) is bonded to two equivalent Cl(3), two equivalent Cl(4), and two equivalent Cl(6) atoms to form a mixture of edge and corner-sharing CaCl6 octahedra. The corner-sharing octahedra are not tilted. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to four equivalent O(1) and one Cl(1) atom. In the second Bi site, Bi(2) is bonded in a 4-coordinate geometry to four equivalent O(1) and two equivalent Cl(1) atoms. O(1) is bonded to one Ca(1), one Bi(2), and two equivalent Bi(1) atoms to form a mixture of edge and corner-sharing OCaBi3 tetrahedra. There are six inequivalent Cl sites. In the first Cl site, Cl(6) is bonded in a square co-planar geometry to two equivalent Ca(2) and two equivalent Ca(3) atoms. In the second Cl site, Cl(1) is bonded in a 4-coordinate geometry to two equivalent Bi(1) and two equivalent Bi(2) atoms. In the third Cl site, Cl(2) is bonded in a 2-coordinate geometry to one Ca(1) and one Ca(2) atom. In the fourth Cl site, Cl(3) is bonded in a distorted trigonal planar geometry to one Ca(3) and two equivalent Ca(1) atoms. In the fifth Cl site, Cl(4) is bonded in a T-shaped geometry to one Ca(3) and two equivalent Ca(2) atoms. In the sixth Cl site, Cl(5) is bonded in a linear geometry to two equivalent Ca(2) atoms.
Ca5Bi6(O2Cl3)4 is Esseneite-like structured and crystallizes in the orthorhombic Immm space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to four equivalent O(1), two equivalent Cl(2), and two equivalent Cl(3) atoms. All Ca(1)-O(1) bond lengths are 2.39 Å. Both Ca(1)-Cl(2) bond lengths are 3.05 Å. Both Ca(1)-Cl(3) bond lengths are 3.16 Å. In the second Ca site, Ca(2) is bonded to one Cl(5), one Cl(6), two equivalent Cl(2), and two equivalent Cl(4) atoms to form a mixture of edge and corner-sharing CaCl6 octahedra. The corner-sharing octahedral tilt angles range from 0-14°. The Ca(2)-Cl(5) bond length is 2.59 Å. The Ca(2)-Cl(6) bond length is 3.02 Å. Both Ca(2)-Cl(2) bond lengths are 2.74 Å. Both Ca(2)-Cl(4) bond lengths are 2.81 Å. In the third Ca site, Ca(3) is bonded to two equivalent Cl(3), two equivalent Cl(4), and two equivalent Cl(6) atoms to form a mixture of edge and corner-sharing CaCl6 octahedra. The corner-sharing octahedra are not tilted. Both Ca(3)-Cl(3) bond lengths are 2.76 Å. Both Ca(3)-Cl(4) bond lengths are 2.67 Å. Both Ca(3)-Cl(6) bond lengths are 2.79 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to four equivalent O(1) and one Cl(1) atom. There are two shorter (2.28 Å) and two longer (2.30 Å) Bi(1)-O(1) bond lengths. The Bi(1)-Cl(1) bond length is 3.09 Å. In the second Bi site, Bi(2) is bonded in a 4-coordinate geometry to four equivalent O(1) and two equivalent Cl(1) atoms. All Bi(2)-O(1) bond lengths are 2.30 Å. Both Bi(2)-Cl(1) bond lengths are 3.15 Å. O(1) is bonded to one Ca(1), one Bi(2), and two equivalent Bi(1) atoms to form a mixture of edge and corner-sharing OCaBi3 tetrahedra. There are six inequivalent Cl sites. In the first Cl site, Cl(6) is bonded in a square co-planar geometry to two equivalent Ca(2) and two equivalent Ca(3) atoms. In the second Cl site, Cl(1) is bonded in a 4-coordinate geometry to two equivalent Bi(1) and two equivalent Bi(2) atoms. In the third Cl site, Cl(2) is bonded in a 2-coordinate geometry to one Ca(1) and one Ca(2) atom. In the fourth Cl site, Cl(3) is bonded in a distorted trigonal planar geometry to one Ca(3) and two equivalent Ca(1) atoms. In the fifth Cl site, Cl(4) is bonded in a T-shaped geometry to one Ca(3) and two equivalent Ca(2) atoms. In the sixth Cl site, Cl(5) is bonded in a linear geometry to two equivalent Ca(2) atoms.