Rb12Li(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 4-coordinate geometry to one O(1), one O(2), one Cl(1), and one Cl(2) atom. In the second Rb site, Rb(2) is bonded in a 1-coordinate geometry to one O(2), 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(1), and one Cl(2) atom. In the fourth Rb site, Rb(4) is bonded to one O(1), one O(3), one Cl(3), and one Cl(4) atom to form distorted edge-sharing RbCl2O2 tetrahedra. In the fifth Rb site, Rb(5) is bonded to one O(2), one O(4), one Cl(1), one Cl(3), and one Cl(4) atom to form distorted edge-sharing RbCl3O2 square pyramids. In the sixth Rb site, Rb(6) is bonded in a 1-coordinate geometry to one O(3) and one Cl(2) atom. In the seventh Rb site, Rb(7) is bonded in a 4-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 3-coordinate geometry to one O(1), one O(3), and one Cl(2) atom. In the ninth Rb site, Rb(9) is bonded in a 4-coordinate geometry to one O(2), one O(4), one Cl(2), and one Cl(3) atom. In the tenth Rb site, Rb(10) is bonded in a distorted T-shaped geometry to one O(1), one O(3), and one Cl(4) atom. In the eleventh Rb site, Rb(11) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(4), one Cl(1), and one Cl(4) 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. Li(1) is bonded in a 3-coordinate 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 corner-sharing ORb6 octahedra. The corner-sharing octahedral tilt angles range from 11-36°. In the second O site, O(2) is bonded to one Rb(1), one Rb(11), one Rb(12), one Rb(2), one Rb(5), and one Rb(9) atom to form corner-sharing ORb6 octahedra. The corner-sharing octahedral tilt angles range from 18-28°. 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 11-36°. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Rb(11), one Rb(5), one Rb(7), one Rb(9), and one Li(1) atom. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(11), one Rb(3), one Rb(5), and one Li(1) atom. In the second Cl site, Cl(2) is bonded in a 6-coordinate geometry to one Rb(1), one Rb(3), one Rb(6), one Rb(8), one Rb(9), and one Li(1) atom. In the third Cl site, Cl(3) is bonded in a 6-coordinate geometry to one Rb(12), one Rb(2), one Rb(4), one Rb(5), one Rb(7), and one Rb(9) atom. In the fourth Cl site, Cl(4) is bonded in a 7-coordinate geometry to one Rb(10), one Rb(11), one Rb(12), one Rb(2), one Rb(4), one Rb(5), and one Rb(7) atom.
Rb12Li(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 4-coordinate geometry to one O(1), one O(2), one Cl(1), and one Cl(2) atom. The Rb(1)-O(1) bond length is 2.97 Å. The Rb(1)-O(2) bond length is 3.02 Å. The Rb(1)-Cl(1) bond length is 3.40 Å. The Rb(1)-Cl(2) bond length is 3.37 Å. In the second Rb site, Rb(2) is bonded in a 1-coordinate geometry to one O(2), one Cl(3), and one Cl(4) atom. The Rb(2)-O(2) bond length is 2.68 Å. The Rb(2)-Cl(3) bond length is 3.47 Å. The Rb(2)-Cl(4) bond length is 3.31 Å. In the third Rb site, Rb(3) is bonded in a 4-coordinate geometry to one O(1), one O(3), one Cl(1), and one Cl(2) atom. The Rb(3)-O(1) bond length is 2.82 Å. The Rb(3)-O(3) bond length is 2.97 Å. The Rb(3)-Cl(1) bond length is 3.64 Å. The Rb(3)-Cl(2) bond length is 3.74 Å. In the fourth Rb site, Rb(4) is bonded to one O(1), one O(3), one Cl(3), and one Cl(4) atom to form distorted edge-sharing RbCl2O2 tetrahedra. The Rb(4)-O(1) bond length is 2.92 Å. The Rb(4)-O(3) bond length is 2.86 Å. The Rb(4)-Cl(3) bond length is 3.37 Å. The Rb(4)-Cl(4) bond length is 3.48 Å. In the fifth Rb site, Rb(5) is bonded to one O(2), one O(4), one Cl(1), one Cl(3), and one Cl(4) atom to form distorted edge-sharing RbCl3O2 square pyramids. The Rb(5)-O(2) bond length is 2.92 Å. The Rb(5)-O(4) bond length is 2.90 Å. The Rb(5)-Cl(1) bond length is 3.40 Å. The Rb(5)-Cl(3) bond length is 3.53 Å. The Rb(5)-Cl(4) bond length is 3.65 Å. In the sixth Rb site, Rb(6) is bonded in a 1-coordinate geometry to one O(3) and one Cl(2) atom. The Rb(6)-O(3) bond length is 2.60 Å. The Rb(6)-Cl(2) bond length is 3.39 Å. In the seventh Rb site, Rb(7) is bonded in a 4-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 2.78 Å. The Rb(7)-O(4) bond length is 2.82 Å. The Rb(7)-Cl(3) bond length is 3.41 Å. The Rb(7)-Cl(4) bond length is 3.47 Å. In the eighth Rb site, Rb(8) is bonded in a 3-coordinate geometry to one O(1), one O(3), and one Cl(2) atom. The Rb(8)-O(1) bond length is 2.84 Å. The Rb(8)-O(3) bond length is 3.12 Å. The Rb(8)-Cl(2) bond length is 3.33 Å. In the ninth Rb site, Rb(9) is bonded in a 4-coordinate geometry to one O(2), one O(4), one Cl(2), and one Cl(3) atom. The Rb(9)-O(2) bond length is 2.76 Å. The Rb(9)-O(4) bond length is 2.91 Å. The Rb(9)-Cl(2) bond length is 3.33 Å. The Rb(9)-Cl(3) bond length is 3.55 Å. In the tenth Rb site, Rb(10) is bonded in a distorted T-shaped geometry to one O(1), one O(3), and one Cl(4) atom. The Rb(10)-O(1) bond length is 2.78 Å. The Rb(10)-O(3) bond length is 2.84 Å. The Rb(10)-Cl(4) bond length is 3.42 Å. In the eleventh Rb site, Rb(11) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(4), one Cl(1), and one Cl(4) atom. The Rb(11)-O(2) bond length is 2.85 Å. The Rb(11)-O(4) bond length is 2.85 Å. The Rb(11)-Cl(1) bond length is 3.41 Å. The Rb(11)-Cl(4) bond length is 3.65 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 2.85 Å. The Rb(12)-O(2) bond length is 2.82 Å. The Rb(12)-Cl(3) bond length is 3.42 Å. The Rb(12)-Cl(4) bond length is 3.45 Å. Li(1) is bonded in a 3-coordinate geometry to one O(4), one Cl(1), and one Cl(2) atom. The Li(1)-O(4) bond length is 1.78 Å. The Li(1)-Cl(1) bond length is 2.40 Å. The Li(1)-Cl(2) bond length is 2.44 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 corner-sharing ORb6 octahedra. The corner-sharing octahedral tilt angles range from 11-36°. In the second O site, O(2) is bonded to one Rb(1), one Rb(11), one Rb(12), one Rb(2), one Rb(5), and one Rb(9) atom to form corner-sharing ORb6 octahedra. The corner-sharing octahedral tilt angles range from 18-28°. 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 11-36°. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Rb(11), one Rb(5), one Rb(7), one Rb(9), and one Li(1) atom. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(11), one Rb(3), one Rb(5), and one Li(1) atom. In the second Cl site, Cl(2) is bonded in a 6-coordinate geometry to one Rb(1), one Rb(3), one Rb(6), one Rb(8), one Rb(9), and one Li(1) atom. In the third Cl site, Cl(3) is bonded in a 6-coordinate geometry to one Rb(12), one Rb(2), one Rb(4), one Rb(5), one Rb(7), and one Rb(9) atom. In the fourth Cl site, Cl(4) is bonded in a 7-coordinate geometry to one Rb(10), one Rb(11), one Rb(12), one Rb(2), one Rb(4), one Rb(5), and one Rb(7) atom.