CaTm4Sm4O12 crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(2), one O(3), one O(5), and one O(7) atom. There are four inequivalent Tm sites. In the first Tm site, Tm(1) is bonded to one O(1), one O(10), one O(12), one O(3), and one O(8) atom to form TmO5 trigonal bipyramids that share  a cornercorner with one Sm(3)O6 octahedra,  a cornercorner with one Tm(2)O6 pentagonal pyramid,  a cornercorner with one Sm(4)O6 pentagonal pyramid, and  an edgeedge with one Sm(4)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles are 67°. In the second Tm site, Tm(2) is bonded to one O(1), one O(11), one O(2), one O(4), one O(7), and one O(9) atom to form distorted TmO6 pentagonal pyramids that share  a cornercorner with one Sm(3)O6 octahedra, corners with three equivalent Tm(4)O6 octahedra,  a cornercorner with one Tm(1)O5 trigonal bipyramid,  an edgeedge with one Tm(4)O6 octahedra,  an edgeedge with one Sm(3)O6 octahedra, and edges with two equivalent Sm(4)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 6-58°. In the third Tm site, Tm(3) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(3), one O(5), one O(6), and one O(8) atom. In the fourth Tm site, Tm(4) is bonded to one O(11), one O(2), one O(4), one O(6), one O(7), and one O(9) atom to form TmO6 octahedra that share  a cornercorner with one Sm(4)O6 pentagonal pyramid, corners with three equivalent Tm(2)O6 pentagonal pyramids, edges with two equivalent Sm(3)O6 octahedra,  an edgeedge with one Tm(2)O6 pentagonal pyramid, and  an edgeedge with one Sm(4)O6 pentagonal pyramid. There are four inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(12), one O(3), one O(4), one O(5), and one O(6) atom. In the second Sm site, Sm(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(7), one O(8), and one O(9) atom. In the third Sm site, Sm(3) is bonded to one O(11), one O(12), one O(4), one O(5), one O(6), and one O(9) atom to form SmO6 octahedra that share  a cornercorner with one Tm(2)O6 pentagonal pyramid,  a cornercorner with one Sm(4)O6 pentagonal pyramid,  a cornercorner with one Tm(1)O5 trigonal bipyramid, edges with two equivalent Tm(4)O6 octahedra, and  an edgeedge with one Tm(2)O6 pentagonal pyramid. In the fourth Sm site, Sm(4) is bonded to one O(1), one O(10), one O(2), one O(7), one O(8), and one O(9) atom to form distorted SmO6 pentagonal pyramids that share  a cornercorner with one Tm(4)O6 octahedra,  a cornercorner with one Sm(3)O6 octahedra,  a cornercorner with one Tm(1)O5 trigonal bipyramid,  an edgeedge with one Tm(4)O6 octahedra, edges with two equivalent Tm(2)O6 pentagonal pyramids, and  an edgeedge with one Tm(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 9-62°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), one Tm(1), one Tm(2), one Sm(2), and one Sm(4) atom to form OCaSm2Tm2 square pyramids that share corners with three equivalent O(9)Sm3Tm2 square pyramids,  a cornercorner with one O(12)Sm2Tm2 trigonal pyramid,  a cornercorner with one O(4)Sm2Tm2 trigonal pyramid, and  a faceface with one O(10)CaSm2Tm2 trigonal bipyramid. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Ca(1), one Tm(2), one Tm(4), one Sm(2), and one Sm(4) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Ca(1), one Tm(1), one Tm(3), one Sm(1), and one Sm(2) atom. In the fourth O site, O(4) is bonded to one Tm(2), one Tm(4), one Sm(1), and one Sm(3) atom to form distorted OSm2Tm2 trigonal pyramids that share  a cornercorner with one O(1)CaSm2Tm2 square pyramid, corners with three equivalent O(9)Sm3Tm2 square pyramids,  a cornercorner with one O(10)CaSm2Tm2 trigonal bipyramid, and corners with two equivalent O(12)Sm2Tm2 trigonal pyramids. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Tm(3), one Sm(1), and one Sm(3) atom. In the sixth O site, O(6) is bonded in a see-saw-like geometry to one Tm(3), one Tm(4), one Sm(1), and one Sm(3) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Ca(1), one Tm(2), one Tm(4), one Sm(2), and one Sm(4) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Tm(1), one Tm(3), one Sm(2), and one Sm(4) atom. In the ninth O site, O(9) is bonded to one Tm(2), one Tm(4), one Sm(2), one Sm(3), and one Sm(4) atom to form OSm3Tm2 square pyramids that share corners with three equivalent O(1)CaSm2Tm2 square pyramids,  a cornercorner with one O(10)CaSm2Tm2 trigonal bipyramid,  a cornercorner with one O(12)Sm2Tm2 trigonal pyramid, and corners with three equivalent O(4)Sm2Tm2 trigonal pyramids. In the tenth O site, O(10) is bonded to one Ca(1), one Tm(1), one Tm(3), one Sm(1), and one Sm(4) atom to form distorted OCaSm2Tm2 trigonal bipyramids that share  a cornercorner with one O(9)Sm3Tm2 square pyramid,  a cornercorner with one O(12)Sm2Tm2 trigonal pyramid,  a cornercorner with one O(4)Sm2Tm2 trigonal pyramid,  an edgeedge with one O(12)Sm2Tm2 trigonal pyramid, and  a faceface with one O(1)CaSm2Tm2 square pyramid. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Tm(2), one Tm(4), one Sm(1), and one Sm(3) atom. In the twelfth O site, O(12) is bonded to one Tm(1), one Tm(3), one Sm(1), and one Sm(3) atom to form OSm2Tm2 trigonal pyramids that share  a cornercorner with one O(1)CaSm2Tm2 square pyramid,  a cornercorner with one O(9)Sm3Tm2 square pyramid,  a cornercorner with one O(10)CaSm2Tm2 trigonal bipyramid, corners with two equivalent O(4)Sm2Tm2 trigonal pyramids, and  an edgeedge with one O(10)CaSm2Tm2 trigonal bipyramid.
CaTm4Sm4O12 crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(2), one O(3), one O(5), and one O(7) atom. The Ca(1)-O(1) bond length is 2.42 Å. The Ca(1)-O(10) bond length is 2.55 Å. The Ca(1)-O(2) bond length is 2.94 Å. The Ca(1)-O(3) bond length is 2.45 Å. The Ca(1)-O(5) bond length is 2.24 Å. The Ca(1)-O(7) bond length is 2.87 Å. There are four inequivalent Tm sites. In the first Tm site, Tm(1) is bonded to one O(1), one O(10), one O(12), one O(3), and one O(8) atom to form TmO5 trigonal bipyramids that share  a cornercorner with one Sm(3)O6 octahedra,  a cornercorner with one Tm(2)O6 pentagonal pyramid,  a cornercorner with one Sm(4)O6 pentagonal pyramid, and  an edgeedge with one Sm(4)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles are 67°. The Tm(1)-O(1) bond length is 2.26 Å. The Tm(1)-O(10) bond length is 2.26 Å. The Tm(1)-O(12) bond length is 2.18 Å. The Tm(1)-O(3) bond length is 2.15 Å. The Tm(1)-O(8) bond length is 2.11 Å. In the second Tm site, Tm(2) is bonded to one O(1), one O(11), one O(2), one O(4), one O(7), and one O(9) atom to form distorted TmO6 pentagonal pyramids that share  a cornercorner with one Sm(3)O6 octahedra, corners with three equivalent Tm(4)O6 octahedra,  a cornercorner with one Tm(1)O5 trigonal bipyramid,  an edgeedge with one Tm(4)O6 octahedra,  an edgeedge with one Sm(3)O6 octahedra, and edges with two equivalent Sm(4)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 6-58°. The Tm(2)-O(1) bond length is 2.35 Å. The Tm(2)-O(11) bond length is 2.25 Å. The Tm(2)-O(2) bond length is 2.33 Å. The Tm(2)-O(4) bond length is 2.27 Å. The Tm(2)-O(7) bond length is 2.25 Å. The Tm(2)-O(9) bond length is 2.40 Å. In the third Tm site, Tm(3) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(3), one O(5), one O(6), and one O(8) atom. The Tm(3)-O(10) bond length is 2.37 Å. The Tm(3)-O(12) bond length is 2.26 Å. The Tm(3)-O(3) bond length is 2.26 Å. The Tm(3)-O(5) bond length is 2.27 Å. The Tm(3)-O(6) bond length is 2.31 Å. The Tm(3)-O(8) bond length is 2.25 Å. In the fourth Tm site, Tm(4) is bonded to one O(11), one O(2), one O(4), one O(6), one O(7), and one O(9) atom to form TmO6 octahedra that share  a cornercorner with one Sm(4)O6 pentagonal pyramid, corners with three equivalent Tm(2)O6 pentagonal pyramids, edges with two equivalent Sm(3)O6 octahedra,  an edgeedge with one Tm(2)O6 pentagonal pyramid, and  an edgeedge with one Sm(4)O6 pentagonal pyramid. The Tm(4)-O(11) bond length is 2.58 Å. The Tm(4)-O(2) bond length is 2.29 Å. The Tm(4)-O(4) bond length is 2.30 Å. The Tm(4)-O(6) bond length is 2.21 Å. The Tm(4)-O(7) bond length is 2.22 Å. The Tm(4)-O(9) bond length is 2.41 Å. There are four inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(12), one O(3), one O(4), one O(5), and one O(6) atom. The Sm(1)-O(10) bond length is 2.57 Å. The Sm(1)-O(11) bond length is 2.38 Å. The Sm(1)-O(12) bond length is 2.36 Å. The Sm(1)-O(3) bond length is 2.92 Å. The Sm(1)-O(4) bond length is 2.43 Å. The Sm(1)-O(5) bond length is 2.36 Å. The Sm(1)-O(6) bond length is 2.41 Å. In the second Sm site, Sm(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(7), one O(8), and one O(9) atom. The Sm(2)-O(1) bond length is 2.36 Å. The Sm(2)-O(2) bond length is 2.47 Å. The Sm(2)-O(3) bond length is 2.44 Å. The Sm(2)-O(7) bond length is 2.43 Å. The Sm(2)-O(8) bond length is 2.34 Å. The Sm(2)-O(9) bond length is 2.40 Å. In the third Sm site, Sm(3) is bonded to one O(11), one O(12), one O(4), one O(5), one O(6), and one O(9) atom to form SmO6 octahedra that share  a cornercorner with one Tm(2)O6 pentagonal pyramid,  a cornercorner with one Sm(4)O6 pentagonal pyramid,  a cornercorner with one Tm(1)O5 trigonal bipyramid, edges with two equivalent Tm(4)O6 octahedra, and  an edgeedge with one Tm(2)O6 pentagonal pyramid. The Sm(3)-O(11) bond length is 2.36 Å. The Sm(3)-O(12) bond length is 2.34 Å. The Sm(3)-O(4) bond length is 2.41 Å. The Sm(3)-O(5) bond length is 2.30 Å. The Sm(3)-O(6) bond length is 2.39 Å. The Sm(3)-O(9) bond length is 2.45 Å. In the fourth Sm site, Sm(4) is bonded to one O(1), one O(10), one O(2), one O(7), one O(8), and one O(9) atom to form distorted SmO6 pentagonal pyramids that share  a cornercorner with one Tm(4)O6 octahedra,  a cornercorner with one Sm(3)O6 octahedra,  a cornercorner with one Tm(1)O5 trigonal bipyramid,  an edgeedge with one Tm(4)O6 octahedra, edges with two equivalent Tm(2)O6 pentagonal pyramids, and  an edgeedge with one Tm(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 9-62°. The Sm(4)-O(1) bond length is 2.38 Å. The Sm(4)-O(10) bond length is 2.51 Å. The Sm(4)-O(2) bond length is 2.42 Å. The Sm(4)-O(7) bond length is 2.40 Å. The Sm(4)-O(8) bond length is 2.39 Å. The Sm(4)-O(9) bond length is 2.53 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), one Tm(1), one Tm(2), one Sm(2), and one Sm(4) atom to form OCaSm2Tm2 square pyramids that share corners with three equivalent O(9)Sm3Tm2 square pyramids,  a cornercorner with one O(12)Sm2Tm2 trigonal pyramid,  a cornercorner with one O(4)Sm2Tm2 trigonal pyramid, and  a faceface with one O(10)CaSm2Tm2 trigonal bipyramid. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Ca(1), one Tm(2), one Tm(4), one Sm(2), and one Sm(4) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Ca(1), one Tm(1), one Tm(3), one Sm(1), and one Sm(2) atom. In the fourth O site, O(4) is bonded to one Tm(2), one Tm(4), one Sm(1), and one Sm(3) atom to form distorted OSm2Tm2 trigonal pyramids that share  a cornercorner with one O(1)CaSm2Tm2 square pyramid, corners with three equivalent O(9)Sm3Tm2 square pyramids,  a cornercorner with one O(10)CaSm2Tm2 trigonal bipyramid, and corners with two equivalent O(12)Sm2Tm2 trigonal pyramids. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Tm(3), one Sm(1), and one Sm(3) atom. In the sixth O site, O(6) is bonded in a see-saw-like geometry to one Tm(3), one Tm(4), one Sm(1), and one Sm(3) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Ca(1), one Tm(2), one Tm(4), one Sm(2), and one Sm(4) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Tm(1), one Tm(3), one Sm(2), and one Sm(4) atom. In the ninth O site, O(9) is bonded to one Tm(2), one Tm(4), one Sm(2), one Sm(3), and one Sm(4) atom to form OSm3Tm2 square pyramids that share corners with three equivalent O(1)CaSm2Tm2 square pyramids,  a cornercorner with one O(10)CaSm2Tm2 trigonal bipyramid,  a cornercorner with one O(12)Sm2Tm2 trigonal pyramid, and corners with three equivalent O(4)Sm2Tm2 trigonal pyramids. In the tenth O site, O(10) is bonded to one Ca(1), one Tm(1), one Tm(3), one Sm(1), and one Sm(4) atom to form distorted OCaSm2Tm2 trigonal bipyramids that share  a cornercorner with one O(9)Sm3Tm2 square pyramid,  a cornercorner with one O(12)Sm2Tm2 trigonal pyramid,  a cornercorner with one O(4)Sm2Tm2 trigonal pyramid,  an edgeedge with one O(12)Sm2Tm2 trigonal pyramid, and  a faceface with one O(1)CaSm2Tm2 square pyramid. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Tm(2), one Tm(4), one Sm(1), and one Sm(3) atom. In the twelfth O site, O(12) is bonded to one Tm(1), one Tm(3), one Sm(1), and one Sm(3) atom to form OSm2Tm2 trigonal pyramids that share  a cornercorner with one O(1)CaSm2Tm2 square pyramid,  a cornercorner with one O(9)Sm3Tm2 square pyramid,  a cornercorner with one O(10)CaSm2Tm2 trigonal bipyramid, corners with two equivalent O(4)Sm2Tm2 trigonal pyramids, and  an edgeedge with one O(10)CaSm2Tm2 trigonal bipyramid.