CaTm4Sm4O12 crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 4-coordinate geometry to one O(12), one O(3), one O(5), and one O(6) atom. There are four inequivalent Tm sites. In the first Tm site, Tm(1) is bonded in a 5-coordinate geometry to one O(1), one O(10), one O(12), one O(3), and one O(8) atom. In the second Tm site, Tm(2) is bonded to one O(1), one O(11), one O(2), one O(4), and one O(9) atom to form distorted TmO5 trigonal bipyramids that share corners with four equivalent Tm(4)O6 octahedra and  a cornercorner with one Sm(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 24-58°. In the third Tm site, Tm(3) is bonded to one O(10), one O(3), one O(5), one O(7), and one O(8) atom to form distorted TmO5 trigonal bipyramids that share  a cornercorner with one Tm(4)O6 octahedra,  a cornercorner with one Sm(1)O5 trigonal bipyramid, and  an edgeedge with one Sm(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 52°. 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 Tm(3)O5 trigonal bipyramid,  a cornercorner with one Sm(1)O5 trigonal bipyramid, and corners with four equivalent Tm(2)O5 trigonal bipyramids. There are four inequivalent Sm sites. In the first Sm site, Sm(1) is bonded to one O(10), one O(11), one O(12), one O(3), and one O(5) atom to form distorted SmO5 trigonal bipyramids that share  a cornercorner with one Tm(4)O6 octahedra,  a cornercorner with one Tm(2)O5 trigonal bipyramid,  a cornercorner with one Tm(3)O5 trigonal bipyramid, and  an edgeedge with one Tm(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 65°. In the second Sm site, Sm(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(7), one O(8), and one O(9) atom. In the third Sm site, Sm(3) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(12), one O(4), one O(5), one O(6), and one O(9) atom. In the fourth Sm site, Sm(4) 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. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Tm(1), one Tm(2), one Sm(2), and one Sm(4) atom to form distorted OSm2Tm2 tetrahedra that share corners with three equivalent O(9)Sm3Tm2 trigonal bipyramids,  a cornercorner with one O(12)CaSm2Tm trigonal pyramid,  a cornercorner with one O(11)Sm2Tm2 trigonal pyramid,  a cornercorner with one O(2)Sm2Tm2 trigonal pyramid,  an edgeedge with one O(4)Sm2Tm2 tetrahedra, and  an edgeedge with one O(2)Sm2Tm2 trigonal pyramid. In the second O site, O(2) is bonded to one Tm(2), one Tm(4), one Sm(2), and one Sm(4) atom to form distorted OSm2Tm2 trigonal pyramids that share  a cornercorner with one O(1)Sm2Tm2 tetrahedra,  a cornercorner with one O(4)Sm2Tm2 tetrahedra, corners with two equivalent O(11)Sm2Tm2 trigonal pyramids,  an edgeedge with one O(1)Sm2Tm2 tetrahedra,  an edgeedge with one O(4)Sm2Tm2 tetrahedra, and edges with two equivalent O(9)Sm3Tm2 trigonal bipyramids. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Ca(1), one Tm(1), one Tm(3), one Sm(1), one Sm(2), and one Sm(4) atom. In the fourth O site, O(4) is bonded to one Tm(2), one Tm(4), one Sm(2), and one Sm(3) atom to form distorted OSm2Tm2 tetrahedra that share corners with two equivalent O(9)Sm3Tm2 trigonal bipyramids,  a cornercorner with one O(12)CaSm2Tm trigonal pyramid,  a cornercorner with one O(5)CaSm2Tm trigonal pyramid,  a cornercorner with one O(11)Sm2Tm2 trigonal pyramid,  a cornercorner with one O(2)Sm2Tm2 trigonal pyramid,  an edgeedge with one O(1)Sm2Tm2 tetrahedra,  an edgeedge with one O(9)Sm3Tm2 trigonal bipyramid,  an edgeedge with one O(11)Sm2Tm2 trigonal pyramid, and  an edgeedge with one O(2)Sm2Tm2 trigonal pyramid. In the fifth O site, O(5) is bonded to one Ca(1), one Tm(3), one Sm(1), and one Sm(3) atom to form distorted OCaSm2Tm trigonal pyramids that share  a cornercorner with one O(4)Sm2Tm2 tetrahedra,  a cornercorner with one O(9)Sm3Tm2 trigonal bipyramid, corners with two equivalent O(11)Sm2Tm2 trigonal pyramids, and corners with three equivalent O(12)CaSm2Tm trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Ca(1), one Tm(4), and one Sm(3) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Tm(3), one Tm(4), one Sm(2), and one Sm(4) atom. In the eighth O site, O(8) is bonded in a 4-coordinate 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 distorted OSm3Tm2 trigonal bipyramids that share corners with two equivalent O(4)Sm2Tm2 tetrahedra, corners with three equivalent O(1)Sm2Tm2 tetrahedra,  a cornercorner with one O(12)CaSm2Tm trigonal pyramid,  a cornercorner with one O(5)CaSm2Tm trigonal pyramid,  a cornercorner with one O(11)Sm2Tm2 trigonal pyramid,  an edgeedge with one O(4)Sm2Tm2 tetrahedra,  an edgeedge with one O(11)Sm2Tm2 trigonal pyramid, and edges with two equivalent O(2)Sm2Tm2 trigonal pyramids. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Tm(1), one Tm(3), one Sm(1), and one Sm(3) atom. In the eleventh O site, O(11) is bonded to one Tm(2), one Tm(4), one Sm(1), and one Sm(3) atom to form OSm2Tm2 trigonal pyramids that share  a cornercorner with one O(1)Sm2Tm2 tetrahedra,  a cornercorner with one O(4)Sm2Tm2 tetrahedra,  a cornercorner with one O(9)Sm3Tm2 trigonal bipyramid, corners with two equivalent O(12)CaSm2Tm trigonal pyramids, corners with two equivalent O(5)CaSm2Tm trigonal pyramids, corners with two equivalent O(2)Sm2Tm2 trigonal pyramids,  an edgeedge with one O(4)Sm2Tm2 tetrahedra, and  an edgeedge with one O(9)Sm3Tm2 trigonal bipyramid. In the twelfth O site, O(12) is bonded to one Ca(1), one Tm(1), one Sm(1), and one Sm(3) atom to form OCaSm2Tm trigonal pyramids that share  a cornercorner with one O(1)Sm2Tm2 tetrahedra,  a cornercorner with one O(4)Sm2Tm2 tetrahedra,  a cornercorner with one O(9)Sm3Tm2 trigonal bipyramid, corners with two equivalent O(11)Sm2Tm2 trigonal pyramids, and corners with three equivalent O(5)CaSm2Tm trigonal pyramids.
CaTm4Sm4O12 crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 4-coordinate geometry to one O(12), one O(3), one O(5), and one O(6) atom. The Ca(1)-O(12) bond length is 2.26 Å. The Ca(1)-O(3) bond length is 2.49 Å. The Ca(1)-O(5) bond length is 2.34 Å. The Ca(1)-O(6) bond length is 2.22 Å. There are four inequivalent Tm sites. In the first Tm site, Tm(1) is bonded in a 5-coordinate geometry to one O(1), one O(10), one O(12), one O(3), and one O(8) atom. The Tm(1)-O(1) bond length is 2.20 Å. The Tm(1)-O(10) bond length is 2.19 Å. The Tm(1)-O(12) bond length is 2.30 Å. The Tm(1)-O(3) bond length is 2.28 Å. The Tm(1)-O(8) bond length is 2.23 Å. In the second Tm site, Tm(2) is bonded to one O(1), one O(11), one O(2), one O(4), and one O(9) atom to form distorted TmO5 trigonal bipyramids that share corners with four equivalent Tm(4)O6 octahedra and  a cornercorner with one Sm(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 24-58°. The Tm(2)-O(1) bond length is 2.12 Å. The Tm(2)-O(11) bond length is 2.21 Å. The Tm(2)-O(2) bond length is 2.22 Å. The Tm(2)-O(4) bond length is 2.29 Å. The Tm(2)-O(9) bond length is 2.33 Å. In the third Tm site, Tm(3) is bonded to one O(10), one O(3), one O(5), one O(7), and one O(8) atom to form distorted TmO5 trigonal bipyramids that share  a cornercorner with one Tm(4)O6 octahedra,  a cornercorner with one Sm(1)O5 trigonal bipyramid, and  an edgeedge with one Sm(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 52°. The Tm(3)-O(10) bond length is 2.19 Å. The Tm(3)-O(3) bond length is 2.19 Å. The Tm(3)-O(5) bond length is 2.27 Å. The Tm(3)-O(7) bond length is 2.21 Å. The Tm(3)-O(8) bond length is 2.41 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 Tm(3)O5 trigonal bipyramid,  a cornercorner with one Sm(1)O5 trigonal bipyramid, and corners with four equivalent Tm(2)O5 trigonal bipyramids. The Tm(4)-O(11) bond length is 2.37 Å. The Tm(4)-O(2) bond length is 2.20 Å. The Tm(4)-O(4) bond length is 2.26 Å. The Tm(4)-O(6) bond length is 2.16 Å. The Tm(4)-O(7) bond length is 2.30 Å. The Tm(4)-O(9) bond length is 2.42 Å. There are four inequivalent Sm sites. In the first Sm site, Sm(1) is bonded to one O(10), one O(11), one O(12), one O(3), and one O(5) atom to form distorted SmO5 trigonal bipyramids that share  a cornercorner with one Tm(4)O6 octahedra,  a cornercorner with one Tm(2)O5 trigonal bipyramid,  a cornercorner with one Tm(3)O5 trigonal bipyramid, and  an edgeedge with one Tm(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 65°. The Sm(1)-O(10) bond length is 2.29 Å. The Sm(1)-O(11) bond length is 2.30 Å. The Sm(1)-O(12) bond length is 2.28 Å. The Sm(1)-O(3) bond length is 2.50 Å. The Sm(1)-O(5) bond length is 2.27 Å. In the second Sm site, Sm(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(7), one O(8), and one O(9) atom. The Sm(2)-O(1) bond length is 2.47 Å. The Sm(2)-O(2) bond length is 2.52 Å. The Sm(2)-O(3) bond length is 3.01 Å. The Sm(2)-O(4) bond length is 2.37 Å. The Sm(2)-O(7) bond length is 2.42 Å. The Sm(2)-O(8) bond length is 2.43 Å. The Sm(2)-O(9) bond length is 2.63 Å. In the third Sm site, Sm(3) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(12), one O(4), one O(5), one O(6), and one O(9) atom. The Sm(3)-O(10) bond length is 2.57 Å. The Sm(3)-O(11) bond length is 2.36 Å. The Sm(3)-O(12) bond length is 2.45 Å. The Sm(3)-O(4) bond length is 2.35 Å. The Sm(3)-O(5) bond length is 2.40 Å. The Sm(3)-O(6) bond length is 2.22 Å. The Sm(3)-O(9) bond length is 2.93 Å. In the fourth Sm site, Sm(4) 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(4)-O(1) bond length is 2.37 Å. The Sm(4)-O(2) bond length is 2.31 Å. The Sm(4)-O(3) bond length is 2.75 Å. The Sm(4)-O(7) bond length is 2.51 Å. The Sm(4)-O(8) bond length is 2.38 Å. The Sm(4)-O(9) bond length is 2.39 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Tm(1), one Tm(2), one Sm(2), and one Sm(4) atom to form distorted OSm2Tm2 tetrahedra that share corners with three equivalent O(9)Sm3Tm2 trigonal bipyramids,  a cornercorner with one O(12)CaSm2Tm trigonal pyramid,  a cornercorner with one O(11)Sm2Tm2 trigonal pyramid,  a cornercorner with one O(2)Sm2Tm2 trigonal pyramid,  an edgeedge with one O(4)Sm2Tm2 tetrahedra, and  an edgeedge with one O(2)Sm2Tm2 trigonal pyramid. In the second O site, O(2) is bonded to one Tm(2), one Tm(4), one Sm(2), and one Sm(4) atom to form distorted OSm2Tm2 trigonal pyramids that share  a cornercorner with one O(1)Sm2Tm2 tetrahedra,  a cornercorner with one O(4)Sm2Tm2 tetrahedra, corners with two equivalent O(11)Sm2Tm2 trigonal pyramids,  an edgeedge with one O(1)Sm2Tm2 tetrahedra,  an edgeedge with one O(4)Sm2Tm2 tetrahedra, and edges with two equivalent O(9)Sm3Tm2 trigonal bipyramids. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Ca(1), one Tm(1), one Tm(3), one Sm(1), one Sm(2), and one Sm(4) atom. In the fourth O site, O(4) is bonded to one Tm(2), one Tm(4), one Sm(2), and one Sm(3) atom to form distorted OSm2Tm2 tetrahedra that share corners with two equivalent O(9)Sm3Tm2 trigonal bipyramids,  a cornercorner with one O(12)CaSm2Tm trigonal pyramid,  a cornercorner with one O(5)CaSm2Tm trigonal pyramid,  a cornercorner with one O(11)Sm2Tm2 trigonal pyramid,  a cornercorner with one O(2)Sm2Tm2 trigonal pyramid,  an edgeedge with one O(1)Sm2Tm2 tetrahedra,  an edgeedge with one O(9)Sm3Tm2 trigonal bipyramid,  an edgeedge with one O(11)Sm2Tm2 trigonal pyramid, and  an edgeedge with one O(2)Sm2Tm2 trigonal pyramid. In the fifth O site, O(5) is bonded to one Ca(1), one Tm(3), one Sm(1), and one Sm(3) atom to form distorted OCaSm2Tm trigonal pyramids that share  a cornercorner with one O(4)Sm2Tm2 tetrahedra,  a cornercorner with one O(9)Sm3Tm2 trigonal bipyramid, corners with two equivalent O(11)Sm2Tm2 trigonal pyramids, and corners with three equivalent O(12)CaSm2Tm trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Ca(1), one Tm(4), and one Sm(3) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Tm(3), one Tm(4), one Sm(2), and one Sm(4) atom. In the eighth O site, O(8) is bonded in a 4-coordinate 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 distorted OSm3Tm2 trigonal bipyramids that share corners with two equivalent O(4)Sm2Tm2 tetrahedra, corners with three equivalent O(1)Sm2Tm2 tetrahedra,  a cornercorner with one O(12)CaSm2Tm trigonal pyramid,  a cornercorner with one O(5)CaSm2Tm trigonal pyramid,  a cornercorner with one O(11)Sm2Tm2 trigonal pyramid,  an edgeedge with one O(4)Sm2Tm2 tetrahedra,  an edgeedge with one O(11)Sm2Tm2 trigonal pyramid, and edges with two equivalent O(2)Sm2Tm2 trigonal pyramids. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Tm(1), one Tm(3), one Sm(1), and one Sm(3) atom. In the eleventh O site, O(11) is bonded to one Tm(2), one Tm(4), one Sm(1), and one Sm(3) atom to form OSm2Tm2 trigonal pyramids that share  a cornercorner with one O(1)Sm2Tm2 tetrahedra,  a cornercorner with one O(4)Sm2Tm2 tetrahedra,  a cornercorner with one O(9)Sm3Tm2 trigonal bipyramid, corners with two equivalent O(12)CaSm2Tm trigonal pyramids, corners with two equivalent O(5)CaSm2Tm trigonal pyramids, corners with two equivalent O(2)Sm2Tm2 trigonal pyramids,  an edgeedge with one O(4)Sm2Tm2 tetrahedra, and  an edgeedge with one O(9)Sm3Tm2 trigonal bipyramid. In the twelfth O site, O(12) is bonded to one Ca(1), one Tm(1), one Sm(1), and one Sm(3) atom to form OCaSm2Tm trigonal pyramids that share  a cornercorner with one O(1)Sm2Tm2 tetrahedra,  a cornercorner with one O(4)Sm2Tm2 tetrahedra,  a cornercorner with one O(9)Sm3Tm2 trigonal bipyramid, corners with two equivalent O(11)Sm2Tm2 trigonal pyramids, and corners with three equivalent O(5)CaSm2Tm trigonal pyramids.