CaTm4Sm4O12 crystallizes in the monoclinic Pm space group. Ca(1) is bonded to one O(4), one O(8), two equivalent O(3), and two equivalent O(7) atoms to form distorted CaO6 octahedra that share  a cornercorner with one Sm(3)O6 pentagonal pyramid, corners with two equivalent Sm(1)O6 pentagonal pyramids, corners with two equivalent Tm(1)O5 square pyramids,  an edgeedge with one Sm(1)O6 pentagonal pyramid, edges with two equivalent Tm(1)O5 square pyramids, and  a faceface with one Sm(3)O6 pentagonal pyramid. There are two inequivalent Tm sites. In the first Tm site, Tm(1) is bonded to one O(1), one O(2), one O(3), one O(7), and one O(8) atom to form distorted TmO5 square pyramids that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Sm(1)O6 pentagonal pyramid, corners with two equivalent Sm(3)O6 pentagonal pyramids, corners with two equivalent Tm(1)O5 square pyramids,  an edgeedge with one Ca(1)O6 octahedra, and  an edgeedge with one Sm(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles are 35°. In the second Tm site, Tm(2) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), one O(5), and one O(6) atom. There are four inequivalent Sm sites. In the first Sm site, Sm(1) is bonded to one O(4), one O(8), two equivalent O(2), and two equivalent O(7) atoms to form distorted SmO6 pentagonal pyramids that share corners with two equivalent Ca(1)O6 octahedra, corners with two equivalent Sm(3)O6 pentagonal pyramids, corners with two equivalent Tm(1)O5 square pyramids,  an edgeedge with one Ca(1)O6 octahedra, and edges with two equivalent Tm(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 7-29°. In the second Sm site, Sm(2) is bonded in a 6-coordinate geometry to one O(1), one O(5), two equivalent O(3), and two equivalent O(6) atoms. In the third Sm site, Sm(3) is bonded to one O(4), one O(8), two equivalent O(3), and two equivalent O(6) atoms to form distorted SmO6 pentagonal pyramids that share  a cornercorner with one Ca(1)O6 octahedra, corners with two equivalent Sm(1)O6 pentagonal pyramids, corners with four equivalent Tm(1)O5 square pyramids, and  a faceface with one Ca(1)O6 octahedra. The corner-sharing octahedral tilt angles are 70°. In the fourth Sm site, Sm(4) is bonded in a 8-coordinate geometry to one O(1), one O(5), two equivalent O(2), two equivalent O(6), and two equivalent O(7) atoms. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to two equivalent Tm(1), one Sm(2), and one Sm(4) atom. In the second O site, O(2) is bonded to one Tm(1), one Tm(2), one Sm(1), and one Sm(4) atom to form distorted OSm2Tm2 trigonal pyramids that share corners with two equivalent O(3)CaSm2Tm2 square pyramids, corners with three equivalent O(6)Sm3Tm tetrahedra, corners with two equivalent O(2)Sm2Tm2 trigonal pyramids, corners with two equivalent O(5)Sm2Tm2 trigonal pyramids,  an edgeedge with one O(4)CaSm2Tm2 trigonal bipyramid, and  an edgeedge with one O(8)CaSm2Tm2 trigonal bipyramid. In the third O site, O(3) is bonded to one Ca(1), one Tm(1), one Tm(2), one Sm(2), and one Sm(3) atom to form distorted OCaSm2Tm2 square pyramids that share  a cornercorner with one O(3)CaSm2Tm2 square pyramid, corners with three equivalent O(6)Sm3Tm tetrahedra,  a cornercorner with one O(4)CaSm2Tm2 trigonal bipyramid,  a cornercorner with one O(8)CaSm2Tm2 trigonal bipyramid, corners with two equivalent O(2)Sm2Tm2 trigonal pyramids,  an edgeedge with one O(3)CaSm2Tm2 square pyramid,  an edgeedge with one O(6)Sm3Tm tetrahedra,  an edgeedge with one O(4)CaSm2Tm2 trigonal bipyramid,  an edgeedge with one O(8)CaSm2Tm2 trigonal bipyramid, and  an edgeedge with one O(5)Sm2Tm2 trigonal pyramid. In the fourth O site, O(4) is bonded to one Ca(1), two equivalent Tm(2), one Sm(1), and one Sm(3) atom to form OCaSm2Tm2 trigonal bipyramids that share corners with two equivalent O(3)CaSm2Tm2 square pyramids, corners with three equivalent O(8)CaSm2Tm2 trigonal bipyramids, corners with two equivalent O(5)Sm2Tm2 trigonal pyramids, edges with two equivalent O(3)CaSm2Tm2 square pyramids, edges with two equivalent O(6)Sm3Tm tetrahedra, and edges with two equivalent O(2)Sm2Tm2 trigonal pyramids. In the fifth O site, O(5) is bonded to two equivalent Tm(2), one Sm(2), and one Sm(4) atom to form distorted OSm2Tm2 trigonal pyramids that share corners with two equivalent O(6)Sm3Tm tetrahedra, corners with two equivalent O(4)CaSm2Tm2 trigonal bipyramids, corners with four equivalent O(2)Sm2Tm2 trigonal pyramids, edges with two equivalent O(3)CaSm2Tm2 square pyramids, and edges with two equivalent O(6)Sm3Tm tetrahedra. In the sixth O site, O(6) is bonded to one Tm(2), one Sm(2), one Sm(3), and one Sm(4) atom to form distorted OSm3Tm tetrahedra that share corners with three equivalent O(3)CaSm2Tm2 square pyramids,  a cornercorner with one O(6)Sm3Tm tetrahedra,  a cornercorner with one O(8)CaSm2Tm2 trigonal bipyramid,  a cornercorner with one O(5)Sm2Tm2 trigonal pyramid, corners with three equivalent O(2)Sm2Tm2 trigonal pyramids,  an edgeedge with one O(3)CaSm2Tm2 square pyramid,  an edgeedge with one O(6)Sm3Tm tetrahedra,  an edgeedge with one O(4)CaSm2Tm2 trigonal bipyramid, and  an edgeedge with one O(5)Sm2Tm2 trigonal pyramid. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Ca(1), one Tm(1), one Sm(1), and one Sm(4) atom. In the eighth O site, O(8) is bonded to one Ca(1), two equivalent Tm(1), one Sm(1), and one Sm(3) atom to form OCaSm2Tm2 trigonal bipyramids that share corners with two equivalent O(3)CaSm2Tm2 square pyramids, corners with two equivalent O(6)Sm3Tm tetrahedra, corners with three equivalent O(4)CaSm2Tm2 trigonal bipyramids, edges with two equivalent O(3)CaSm2Tm2 square pyramids, and edges with two equivalent O(2)Sm2Tm2 trigonal pyramids.
CaTm4Sm4O12 crystallizes in the monoclinic Pm space group. Ca(1) is bonded to one O(4), one O(8), two equivalent O(3), and two equivalent O(7) atoms to form distorted CaO6 octahedra that share  a cornercorner with one Sm(3)O6 pentagonal pyramid, corners with two equivalent Sm(1)O6 pentagonal pyramids, corners with two equivalent Tm(1)O5 square pyramids,  an edgeedge with one Sm(1)O6 pentagonal pyramid, edges with two equivalent Tm(1)O5 square pyramids, and  a faceface with one Sm(3)O6 pentagonal pyramid. The Ca(1)-O(4) bond length is 2.46 Å. The Ca(1)-O(8) bond length is 2.27 Å. Both Ca(1)-O(3) bond lengths are 2.50 Å. Both Ca(1)-O(7) bond lengths are 2.31 Å. There are two inequivalent Tm sites. In the first Tm site, Tm(1) is bonded to one O(1), one O(2), one O(3), one O(7), and one O(8) atom to form distorted TmO5 square pyramids that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Sm(1)O6 pentagonal pyramid, corners with two equivalent Sm(3)O6 pentagonal pyramids, corners with two equivalent Tm(1)O5 square pyramids,  an edgeedge with one Ca(1)O6 octahedra, and  an edgeedge with one Sm(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles are 35°. The Tm(1)-O(1) bond length is 2.14 Å. The Tm(1)-O(2) bond length is 2.21 Å. The Tm(1)-O(3) bond length is 2.21 Å. The Tm(1)-O(7) bond length is 2.18 Å. The Tm(1)-O(8) bond length is 2.35 Å. In the second Tm site, Tm(2) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The Tm(2)-O(2) bond length is 2.23 Å. The Tm(2)-O(3) bond length is 2.37 Å. The Tm(2)-O(4) bond length is 2.24 Å. The Tm(2)-O(5) bond length is 2.22 Å. The Tm(2)-O(6) bond length is 2.20 Å. There are four inequivalent Sm sites. In the first Sm site, Sm(1) is bonded to one O(4), one O(8), two equivalent O(2), and two equivalent O(7) atoms to form distorted SmO6 pentagonal pyramids that share corners with two equivalent Ca(1)O6 octahedra, corners with two equivalent Sm(3)O6 pentagonal pyramids, corners with two equivalent Tm(1)O5 square pyramids,  an edgeedge with one Ca(1)O6 octahedra, and edges with two equivalent Tm(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 7-29°. The Sm(1)-O(4) bond length is 2.41 Å. The Sm(1)-O(8) bond length is 2.39 Å. Both Sm(1)-O(2) bond lengths are 2.38 Å. Both Sm(1)-O(7) bond lengths are 2.39 Å. In the second Sm site, Sm(2) is bonded in a 6-coordinate geometry to one O(1), one O(5), two equivalent O(3), and two equivalent O(6) atoms. The Sm(2)-O(1) bond length is 2.32 Å. The Sm(2)-O(5) bond length is 2.33 Å. Both Sm(2)-O(3) bond lengths are 2.49 Å. Both Sm(2)-O(6) bond lengths are 2.45 Å. In the third Sm site, Sm(3) is bonded to one O(4), one O(8), two equivalent O(3), and two equivalent O(6) atoms to form distorted SmO6 pentagonal pyramids that share  a cornercorner with one Ca(1)O6 octahedra, corners with two equivalent Sm(1)O6 pentagonal pyramids, corners with four equivalent Tm(1)O5 square pyramids, and  a faceface with one Ca(1)O6 octahedra. The corner-sharing octahedral tilt angles are 70°. The Sm(3)-O(4) bond length is 2.30 Å. The Sm(3)-O(8) bond length is 2.39 Å. Both Sm(3)-O(3) bond lengths are 2.46 Å. Both Sm(3)-O(6) bond lengths are 2.52 Å. In the fourth Sm site, Sm(4) is bonded in a 8-coordinate geometry to one O(1), one O(5), two equivalent O(2), two equivalent O(6), and two equivalent O(7) atoms. The Sm(4)-O(1) bond length is 3.13 Å. The Sm(4)-O(5) bond length is 2.37 Å. Both Sm(4)-O(2) bond lengths are 2.67 Å. Both Sm(4)-O(6) bond lengths are 2.53 Å. Both Sm(4)-O(7) bond lengths are 2.56 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to two equivalent Tm(1), one Sm(2), and one Sm(4) atom. In the second O site, O(2) is bonded to one Tm(1), one Tm(2), one Sm(1), and one Sm(4) atom to form distorted OSm2Tm2 trigonal pyramids that share corners with two equivalent O(3)CaSm2Tm2 square pyramids, corners with three equivalent O(6)Sm3Tm tetrahedra, corners with two equivalent O(2)Sm2Tm2 trigonal pyramids, corners with two equivalent O(5)Sm2Tm2 trigonal pyramids,  an edgeedge with one O(4)CaSm2Tm2 trigonal bipyramid, and  an edgeedge with one O(8)CaSm2Tm2 trigonal bipyramid. In the third O site, O(3) is bonded to one Ca(1), one Tm(1), one Tm(2), one Sm(2), and one Sm(3) atom to form distorted OCaSm2Tm2 square pyramids that share  a cornercorner with one O(3)CaSm2Tm2 square pyramid, corners with three equivalent O(6)Sm3Tm tetrahedra,  a cornercorner with one O(4)CaSm2Tm2 trigonal bipyramid,  a cornercorner with one O(8)CaSm2Tm2 trigonal bipyramid, corners with two equivalent O(2)Sm2Tm2 trigonal pyramids,  an edgeedge with one O(3)CaSm2Tm2 square pyramid,  an edgeedge with one O(6)Sm3Tm tetrahedra,  an edgeedge with one O(4)CaSm2Tm2 trigonal bipyramid,  an edgeedge with one O(8)CaSm2Tm2 trigonal bipyramid, and  an edgeedge with one O(5)Sm2Tm2 trigonal pyramid. In the fourth O site, O(4) is bonded to one Ca(1), two equivalent Tm(2), one Sm(1), and one Sm(3) atom to form OCaSm2Tm2 trigonal bipyramids that share corners with two equivalent O(3)CaSm2Tm2 square pyramids, corners with three equivalent O(8)CaSm2Tm2 trigonal bipyramids, corners with two equivalent O(5)Sm2Tm2 trigonal pyramids, edges with two equivalent O(3)CaSm2Tm2 square pyramids, edges with two equivalent O(6)Sm3Tm tetrahedra, and edges with two equivalent O(2)Sm2Tm2 trigonal pyramids. In the fifth O site, O(5) is bonded to two equivalent Tm(2), one Sm(2), and one Sm(4) atom to form distorted OSm2Tm2 trigonal pyramids that share corners with two equivalent O(6)Sm3Tm tetrahedra, corners with two equivalent O(4)CaSm2Tm2 trigonal bipyramids, corners with four equivalent O(2)Sm2Tm2 trigonal pyramids, edges with two equivalent O(3)CaSm2Tm2 square pyramids, and edges with two equivalent O(6)Sm3Tm tetrahedra. In the sixth O site, O(6) is bonded to one Tm(2), one Sm(2), one Sm(3), and one Sm(4) atom to form distorted OSm3Tm tetrahedra that share corners with three equivalent O(3)CaSm2Tm2 square pyramids,  a cornercorner with one O(6)Sm3Tm tetrahedra,  a cornercorner with one O(8)CaSm2Tm2 trigonal bipyramid,  a cornercorner with one O(5)Sm2Tm2 trigonal pyramid, corners with three equivalent O(2)Sm2Tm2 trigonal pyramids,  an edgeedge with one O(3)CaSm2Tm2 square pyramid,  an edgeedge with one O(6)Sm3Tm tetrahedra,  an edgeedge with one O(4)CaSm2Tm2 trigonal bipyramid, and  an edgeedge with one O(5)Sm2Tm2 trigonal pyramid. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Ca(1), one Tm(1), one Sm(1), and one Sm(4) atom. In the eighth O site, O(8) is bonded to one Ca(1), two equivalent Tm(1), one Sm(1), and one Sm(3) atom to form OCaSm2Tm2 trigonal bipyramids that share corners with two equivalent O(3)CaSm2Tm2 square pyramids, corners with two equivalent O(6)Sm3Tm tetrahedra, corners with three equivalent O(4)CaSm2Tm2 trigonal bipyramids, edges with two equivalent O(3)CaSm2Tm2 square pyramids, and edges with two equivalent O(2)Sm2Tm2 trigonal pyramids.