Rb12Ca(OCl)4 is Pb (Zr_0.50 Ti_0.48) O_3-derived structured and crystallizes in the triclinic P1 space group. There are twelve inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a distorted bent 150 degrees geometry to one O(1) and one Cl(1) atom. In the second Rb site, Rb(2) is bonded in a 4-coordinate geometry to one O(2), one O(4), one Cl(1), one Cl(3), and one Cl(4) atom. In the third Rb site, Rb(3) is bonded in a 4-coordinate geometry to one O(1), one O(3), one Cl(3), and one Cl(4) atom. In the fourth Rb site, Rb(4) is bonded in a 4-coordinate geometry to one O(1), one O(3), one Cl(3), and one Cl(4) atom. In the fifth Rb site, Rb(5) is bonded in a distorted square pyramidal geometry to one O(2), one O(4), one Cl(1), one Cl(2), and one Cl(3) atom. In the sixth Rb site, Rb(6) is bonded in a 3-coordinate geometry to one O(3), one Cl(1), and one Cl(2) atom. In the seventh Rb site, Rb(7) is bonded in a 3-coordinate geometry to one O(3), one O(4), one Cl(3), and one Cl(4) atom. In the eighth Rb site, Rb(8) is bonded in a distorted T-shaped geometry to one O(1), one O(3), and one Cl(3) atom. In the ninth Rb site, Rb(9) is bonded in a 5-coordinate geometry to one O(2), one O(4), one Cl(1), one Cl(2), and one Cl(4) atom. In the tenth Rb site, Rb(10) is bonded in a distorted bent 150 degrees geometry to one O(1), one O(3), and one Cl(4) atom. In the eleventh Rb site, Rb(11) is bonded in a 4-coordinate geometry to one O(2), one O(4), one Cl(1), and one Cl(2) atom. In the twelfth Rb site, Rb(12) is bonded in a 4-coordinate geometry to one O(1), one O(2), one Cl(3), and one Cl(4) atom. Ca(1) is bonded in a distorted trigonal non-coplanar geometry to one O(4), one Cl(1), and one Cl(2) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Rb(1), one Rb(10), one Rb(12), one Rb(3), one Rb(4), and one Rb(8) atom to form ORb6 octahedra that share corners with four equivalent O(3)Rb6 octahedra and  a cornercorner with one O(2)Rb5 square pyramid. The corner-sharing octahedral tilt angles range from 19-30°. In the second O site, O(2) is bonded to one Rb(11), one Rb(12), one Rb(2), one Rb(5), and one Rb(9) atom to form corner-sharing ORb5 square pyramids. The corner-sharing octahedral tilt angles are 40°. In the third O site, O(3) is bonded to one Rb(10), one Rb(3), one Rb(4), one Rb(6), one Rb(7), and one Rb(8) atom to form corner-sharing ORb6 octahedra. The corner-sharing octahedral tilt angles range from 19-30°. In the fourth O site, O(4) is bonded in a 1-coordinate geometry to one Rb(11), one Rb(2), one Rb(5), one Rb(7), one Rb(9), and one Ca(1) atom. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 7-coordinate geometry to one Rb(1), one Rb(11), one Rb(2), one Rb(5), one Rb(6), one Rb(9), and one Ca(1) atom. In the second Cl site, Cl(2) is bonded in a 5-coordinate geometry to one Rb(11), one Rb(5), one Rb(6), one Rb(9), and one Ca(1) atom. In the third Cl site, Cl(3) is bonded in a 7-coordinate geometry to one Rb(12), one Rb(2), one Rb(3), one Rb(4), one Rb(5), one Rb(7), and one Rb(8) atom. In the fourth Cl site, Cl(4) is bonded in a 7-coordinate geometry to one Rb(10), one Rb(12), one Rb(2), one Rb(3), one Rb(4), one Rb(7), and one Rb(9) atom.
Rb12Ca(OCl)4 is Pb (Zr_0.50 Ti_0.48) O_3-derived structured and crystallizes in the triclinic P1 space group. There are twelve inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a distorted bent 150 degrees geometry to one O(1) and one Cl(1) atom. The Rb(1)-O(1) bond length is 2.65 Å. The Rb(1)-Cl(1) bond length is 3.36 Å. In the second Rb site, Rb(2) is bonded in a 4-coordinate geometry to one O(2), one O(4), one Cl(1), one Cl(3), and one Cl(4) atom. The Rb(2)-O(2) bond length is 2.66 Å. The Rb(2)-O(4) bond length is 3.04 Å. The Rb(2)-Cl(1) bond length is 3.82 Å. The Rb(2)-Cl(3) bond length is 3.37 Å. The Rb(2)-Cl(4) bond length is 3.43 Å. In the third Rb site, Rb(3) is bonded in a 4-coordinate geometry to one O(1), one O(3), one Cl(3), and one Cl(4) atom. The Rb(3)-O(1) bond length is 2.82 Å. The Rb(3)-O(3) bond length is 2.88 Å. The Rb(3)-Cl(3) bond length is 3.52 Å. The Rb(3)-Cl(4) bond length is 3.43 Å. In the fourth Rb site, Rb(4) is bonded in a 4-coordinate geometry to one O(1), one O(3), one Cl(3), and one Cl(4) atom. The Rb(4)-O(1) bond length is 2.87 Å. The Rb(4)-O(3) bond length is 2.84 Å. The Rb(4)-Cl(3) bond length is 3.36 Å. The Rb(4)-Cl(4) bond length is 3.48 Å. In the fifth Rb site, Rb(5) is bonded in a distorted square pyramidal geometry to one O(2), one O(4), one Cl(1), one Cl(2), and one Cl(3) atom. The Rb(5)-O(2) bond length is 2.78 Å. The Rb(5)-O(4) bond length is 3.05 Å. The Rb(5)-Cl(1) bond length is 3.38 Å. The Rb(5)-Cl(2) bond length is 3.50 Å. The Rb(5)-Cl(3) bond length is 3.59 Å. In the sixth Rb site, Rb(6) is bonded in a 3-coordinate geometry to one O(3), one Cl(1), and one Cl(2) atom. The Rb(6)-O(3) bond length is 2.72 Å. The Rb(6)-Cl(1) bond length is 3.75 Å. The Rb(6)-Cl(2) bond length is 3.56 Å. In the seventh Rb site, Rb(7) is bonded in a 3-coordinate geometry to one O(3), one O(4), one Cl(3), and one Cl(4) atom. The Rb(7)-O(3) bond length is 2.84 Å. The Rb(7)-O(4) bond length is 2.91 Å. The Rb(7)-Cl(3) bond length is 3.82 Å. The Rb(7)-Cl(4) bond length is 3.31 Å. In the eighth Rb site, Rb(8) is bonded in a distorted T-shaped geometry to one O(1), one O(3), and one Cl(3) atom. The Rb(8)-O(1) bond length is 2.88 Å. The Rb(8)-O(3) bond length is 2.98 Å. The Rb(8)-Cl(3) bond length is 3.54 Å. In the ninth Rb site, Rb(9) is bonded in a 5-coordinate geometry to one O(2), one O(4), one Cl(1), one Cl(2), and one Cl(4) atom. The Rb(9)-O(2) bond length is 2.72 Å. The Rb(9)-O(4) bond length is 2.99 Å. The Rb(9)-Cl(1) bond length is 3.47 Å. The Rb(9)-Cl(2) bond length is 3.43 Å. The Rb(9)-Cl(4) bond length is 3.74 Å. In the tenth Rb site, Rb(10) is bonded in a distorted bent 150 degrees geometry to one O(1), one O(3), and one Cl(4) atom. The Rb(10)-O(1) bond length is 2.80 Å. The Rb(10)-O(3) bond length is 2.79 Å. The Rb(10)-Cl(4) bond length is 3.75 Å. In the eleventh Rb site, Rb(11) is bonded in a 4-coordinate geometry to one O(2), one O(4), one Cl(1), and one Cl(2) atom. The Rb(11)-O(2) bond length is 2.69 Å. The Rb(11)-O(4) bond length is 3.48 Å. The Rb(11)-Cl(1) bond length is 3.39 Å. The Rb(11)-Cl(2) bond length is 3.40 Å. In the twelfth Rb site, Rb(12) is bonded in a 4-coordinate geometry to one O(1), one O(2), one Cl(3), and one Cl(4) atom. The Rb(12)-O(1) bond length is 2.91 Å. The Rb(12)-O(2) bond length is 2.65 Å. The Rb(12)-Cl(3) bond length is 3.37 Å. The Rb(12)-Cl(4) bond length is 3.49 Å. Ca(1) is bonded in a distorted trigonal non-coplanar geometry to one O(4), one Cl(1), and one Cl(2) atom. The Ca(1)-O(4) bond length is 2.04 Å. The Ca(1)-Cl(1) bond length is 2.76 Å. The Ca(1)-Cl(2) bond length is 2.75 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Rb(1), one Rb(10), one Rb(12), one Rb(3), one Rb(4), and one Rb(8) atom to form ORb6 octahedra that share corners with four equivalent O(3)Rb6 octahedra and  a cornercorner with one O(2)Rb5 square pyramid. The corner-sharing octahedral tilt angles range from 19-30°. In the second O site, O(2) is bonded to one Rb(11), one Rb(12), one Rb(2), one Rb(5), and one Rb(9) atom to form corner-sharing ORb5 square pyramids. The corner-sharing octahedral tilt angles are 40°. In the third O site, O(3) is bonded to one Rb(10), one Rb(3), one Rb(4), one Rb(6), one Rb(7), and one Rb(8) atom to form corner-sharing ORb6 octahedra. The corner-sharing octahedral tilt angles range from 19-30°. In the fourth O site, O(4) is bonded in a 1-coordinate geometry to one Rb(11), one Rb(2), one Rb(5), one Rb(7), one Rb(9), and one Ca(1) atom. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 7-coordinate geometry to one Rb(1), one Rb(11), one Rb(2), one Rb(5), one Rb(6), one Rb(9), and one Ca(1) atom. In the second Cl site, Cl(2) is bonded in a 5-coordinate geometry to one Rb(11), one Rb(5), one Rb(6), one Rb(9), and one Ca(1) atom. In the third Cl site, Cl(3) is bonded in a 7-coordinate geometry to one Rb(12), one Rb(2), one Rb(3), one Rb(4), one Rb(5), one Rb(7), and one Rb(8) atom. In the fourth Cl site, Cl(4) is bonded in a 7-coordinate geometry to one Rb(10), one Rb(12), one Rb(2), one Rb(3), one Rb(4), one Rb(7), and one Rb(9) atom.