CaSm4(HO2)4 crystallizes in the monoclinic Pm space group. Ca(1) is bonded in a 9-coordinate geometry to one H(2), two equivalent H(3), one O(1), one O(6), two equivalent O(3), and two equivalent O(8) atoms. There are four inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 6-coordinate geometry to one O(1), one O(7), two equivalent O(3), and two equivalent O(8) atoms. In the second Sm site, Sm(2) is bonded in a 7-coordinate geometry to one H(2), one O(4), one O(6), two equivalent O(2), and two equivalent O(5) atoms. In the third Sm site, Sm(3) is bonded in a 7-coordinate geometry to one H(3), one O(3), one O(5), two equivalent O(4), and two equivalent O(7) atoms. In the fourth Sm site, Sm(4) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form distorted edge-sharing SmO6 octahedra. There are four inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(4) atom. In the second H site, H(2) is bonded in a single-bond geometry to one Ca(1), one Sm(2), and one O(1) atom. In the third H site, H(3) is bonded in a distorted linear geometry to two equivalent Ca(1), one Sm(3), one O(3), and one O(8) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(5) atom. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Ca(1), one Sm(1), two equivalent Sm(4), and one H(2) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Sm(4) and two equivalent Sm(2) atoms. In the third O site, O(3) is bonded in a distorted single-bond geometry to two equivalent Ca(1), one Sm(3), two equivalent Sm(1), and one H(3) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Sm(2), two equivalent Sm(3), and one H(1) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Sm(3), two equivalent Sm(2), and one H(4) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Ca(1), one Sm(2), and two equivalent Sm(4) atoms. In the seventh O site, O(7) is bonded in a trigonal non-coplanar geometry to one Sm(1) and two equivalent Sm(3) atoms. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to two equivalent Ca(1), one Sm(4), two equivalent Sm(1), and one H(3) atom.
CaSm4(HO2)4 crystallizes in the monoclinic Pm space group. Ca(1) is bonded in a 9-coordinate geometry to one H(2), two equivalent H(3), one O(1), one O(6), two equivalent O(3), and two equivalent O(8) atoms. The Ca(1)-H(2) bond length is 2.13 Å. Both Ca(1)-H(3) bond lengths are 2.18 Å. The Ca(1)-O(1) bond length is 2.34 Å. The Ca(1)-O(6) bond length is 2.43 Å. Both Ca(1)-O(3) bond lengths are 2.57 Å. Both Ca(1)-O(8) bond lengths are 2.38 Å. There are four inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 6-coordinate geometry to one O(1), one O(7), two equivalent O(3), and two equivalent O(8) atoms. The Sm(1)-O(1) bond length is 2.64 Å. The Sm(1)-O(7) bond length is 2.31 Å. Both Sm(1)-O(3) bond lengths are 2.53 Å. Both Sm(1)-O(8) bond lengths are 2.46 Å. In the second Sm site, Sm(2) is bonded in a 7-coordinate geometry to one H(2), one O(4), one O(6), two equivalent O(2), and two equivalent O(5) atoms. The Sm(2)-H(2) bond length is 2.54 Å. The Sm(2)-O(4) bond length is 2.43 Å. The Sm(2)-O(6) bond length is 2.31 Å. Both Sm(2)-O(2) bond lengths are 2.29 Å. Both Sm(2)-O(5) bond lengths are 2.51 Å. In the third Sm site, Sm(3) is bonded in a 7-coordinate geometry to one H(3), one O(3), one O(5), two equivalent O(4), and two equivalent O(7) atoms. The Sm(3)-H(3) bond length is 2.53 Å. The Sm(3)-O(3) bond length is 2.41 Å. The Sm(3)-O(5) bond length is 2.41 Å. Both Sm(3)-O(4) bond lengths are 2.51 Å. Both Sm(3)-O(7) bond lengths are 2.30 Å. In the fourth Sm site, Sm(4) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form distorted edge-sharing SmO6 octahedra. The Sm(4)-O(2) bond length is 2.33 Å. The Sm(4)-O(8) bond length is 2.68 Å. Both Sm(4)-O(1) bond lengths are 2.49 Å. Both Sm(4)-O(6) bond lengths are 2.39 Å. There are four inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(4) atom. The H(1)-O(4) bond length is 1.00 Å. In the second H site, H(2) is bonded in a single-bond geometry to one Ca(1), one Sm(2), and one O(1) atom. The H(2)-O(1) bond length is 1.00 Å. In the third H site, H(3) is bonded in a distorted linear geometry to two equivalent Ca(1), one Sm(3), one O(3), and one O(8) atom. The H(3)-O(3) bond length is 1.42 Å. The H(3)-O(8) bond length is 1.08 Å. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(5) atom. The H(4)-O(5) bond length is 0.99 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Ca(1), one Sm(1), two equivalent Sm(4), and one H(2) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Sm(4) and two equivalent Sm(2) atoms. In the third O site, O(3) is bonded in a distorted single-bond geometry to two equivalent Ca(1), one Sm(3), two equivalent Sm(1), and one H(3) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Sm(2), two equivalent Sm(3), and one H(1) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Sm(3), two equivalent Sm(2), and one H(4) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Ca(1), one Sm(2), and two equivalent Sm(4) atoms. In the seventh O site, O(7) is bonded in a trigonal non-coplanar geometry to one Sm(1) and two equivalent Sm(3) atoms. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to two equivalent Ca(1), one Sm(4), two equivalent Sm(1), and one H(3) atom.