LiTm4Sm4O12 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(1), one O(3), one O(5), and one O(7) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Tm(1)O6 octahedra,  a cornercorner with one Tm(2)O6 octahedra,  a cornercorner with one Tm(4)O6 octahedra, and  an edgeedge with one Tm(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-77°. 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), one O(5), and one O(8) atom to form TmO6 octahedra that share corners with two equivalent Tm(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-50°. In the second Tm site, Tm(2) is bonded to one O(1), one O(11), one O(12), one O(2), one O(4), and one O(9) atom to form TmO6 octahedra that share corners with two equivalent Tm(1)O6 octahedra, corners with four equivalent Tm(4)O6 octahedra, and  a cornercorner with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-50°. In the third Tm site, Tm(3) is bonded in a 6-coordinate geometry to one O(10), one O(3), one O(5), one O(6), one O(7), 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 corners with four equivalent Tm(2)O6 octahedra and  a cornercorner with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-46°. 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(2), one O(4), one O(5), and one O(6) atom. 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(5), 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(11), one O(2), 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 in a 5-coordinate geometry to one Li(1), one Tm(1), one Tm(2), one Sm(2), and one Sm(4) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Tm(2), one Tm(4), one Sm(1), one Sm(2), and one Sm(4) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Tm(1), one Tm(3), 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(6)Sm2Tm2 tetrahedra, corners with two equivalent O(10)Sm2Tm2 tetrahedra,  an edgeedge with one O(6)Sm2Tm2 tetrahedra, and edges with two equivalent O(11)Sm3Tm2 trigonal bipyramids. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Li(1), one Tm(1), one Tm(3), one Sm(1), one Sm(2), and one Sm(3) atom. In the sixth O site, O(6) is bonded to one Tm(3), one Tm(4), one Sm(1), and one Sm(3) atom to form distorted OSm2Tm2 tetrahedra that share corners with three equivalent O(10)Sm2Tm2 tetrahedra, corners with three equivalent O(11)Sm3Tm2 trigonal bipyramids,  a cornercorner with one O(4)Sm2Tm2 trigonal pyramid,  a cornercorner with one O(8)Sm2Tm2 trigonal pyramid, and  an edgeedge with one O(4)Sm2Tm2 trigonal pyramid. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Li(1), one Tm(3), one Tm(4), one Sm(2), and one Sm(4) atom. In the eighth O site, O(8) is bonded to one Tm(1), one Tm(3), one Sm(2), and one Sm(4) atom to form distorted OSm2Tm2 trigonal pyramids that share  a cornercorner with one O(6)Sm2Tm2 tetrahedra, corners with two equivalent O(10)Sm2Tm2 tetrahedra, and  a cornercorner with one O(11)Sm3Tm2 trigonal bipyramid. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Tm(2), one Tm(4), one Sm(2), one Sm(3), and one Sm(4) atom. In the tenth O site, O(10) is bonded to one Tm(1), one Tm(3), one Sm(1), and one Sm(3) atom to form distorted OSm2Tm2 tetrahedra that share corners with three equivalent O(6)Sm2Tm2 tetrahedra, corners with two equivalent O(4)Sm2Tm2 trigonal pyramids, corners with two equivalent O(8)Sm2Tm2 trigonal pyramids, and  an edgeedge with one O(11)Sm3Tm2 trigonal bipyramid. In the eleventh O site, O(11) is bonded to one Tm(2), one Tm(4), one Sm(1), one Sm(3), and one Sm(4) atom to form a mixture of distorted edge and corner-sharing OSm3Tm2 trigonal bipyramids. In the twelfth O site, O(12) is bonded in a distorted see-saw-like geometry to one Tm(1), one Tm(2), one Sm(1), and one Sm(3) atom.
LiTm4Sm4O12 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(1), one O(3), one O(5), and one O(7) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Tm(1)O6 octahedra,  a cornercorner with one Tm(2)O6 octahedra,  a cornercorner with one Tm(4)O6 octahedra, and  an edgeedge with one Tm(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-77°. The Li(1)-O(1) bond length is 1.84 Å. The Li(1)-O(3) bond length is 1.91 Å. The Li(1)-O(5) bond length is 2.06 Å. The Li(1)-O(7) bond length is 1.92 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), one O(5), and one O(8) atom to form TmO6 octahedra that share corners with two equivalent Tm(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-50°. The Tm(1)-O(1) bond length is 2.33 Å. The Tm(1)-O(10) bond length is 2.27 Å. The Tm(1)-O(12) bond length is 2.24 Å. The Tm(1)-O(3) bond length is 2.24 Å. The Tm(1)-O(5) bond length is 2.28 Å. The Tm(1)-O(8) bond length is 2.21 Å. In the second Tm site, Tm(2) is bonded to one O(1), one O(11), one O(12), one O(2), one O(4), and one O(9) atom to form TmO6 octahedra that share corners with two equivalent Tm(1)O6 octahedra, corners with four equivalent Tm(4)O6 octahedra, and  a cornercorner with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-50°. The Tm(2)-O(1) bond length is 2.30 Å. The Tm(2)-O(11) bond length is 2.26 Å. The Tm(2)-O(12) bond length is 2.36 Å. The Tm(2)-O(2) bond length is 2.21 Å. The Tm(2)-O(4) bond length is 2.20 Å. The Tm(2)-O(9) bond length is 2.25 Å. In the third Tm site, Tm(3) is bonded in a 6-coordinate geometry to one O(10), one O(3), one O(5), one O(6), one O(7), and one O(8) atom. The Tm(3)-O(10) bond length is 2.17 Å. The Tm(3)-O(3) bond length is 2.44 Å. The Tm(3)-O(5) bond length is 2.24 Å. The Tm(3)-O(6) bond length is 2.15 Å. The Tm(3)-O(7) bond length is 2.44 Å. The Tm(3)-O(8) bond length is 2.16 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 corners with four equivalent Tm(2)O6 octahedra and  a cornercorner with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-46°. The Tm(4)-O(11) bond length is 2.27 Å. The Tm(4)-O(2) bond length is 2.22 Å. The Tm(4)-O(4) bond length is 2.20 Å. The Tm(4)-O(6) bond length is 2.26 Å. The Tm(4)-O(7) bond length is 2.33 Å. The Tm(4)-O(9) bond length is 2.23 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(2), one O(4), one O(5), and one O(6) atom. The Sm(1)-O(10) bond length is 2.39 Å. The Sm(1)-O(11) bond length is 2.39 Å. The Sm(1)-O(12) bond length is 2.30 Å. The Sm(1)-O(2) bond length is 2.66 Å. The Sm(1)-O(4) bond length is 2.52 Å. The Sm(1)-O(5) bond length is 2.83 Å. The Sm(1)-O(6) bond length is 2.43 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(5), one O(7), one O(8), and one O(9) atom. The Sm(2)-O(1) bond length is 2.53 Å. The Sm(2)-O(2) bond length is 2.94 Å. The Sm(2)-O(3) bond length is 2.45 Å. The Sm(2)-O(5) bond length is 2.95 Å. The Sm(2)-O(7) bond length is 2.35 Å. The Sm(2)-O(8) bond length is 2.33 Å. The Sm(2)-O(9) bond length is 2.29 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 2.51 Å. The Sm(3)-O(11) bond length is 2.66 Å. The Sm(3)-O(12) bond length is 2.45 Å. The Sm(3)-O(4) bond length is 2.31 Å. The Sm(3)-O(5) bond length is 2.50 Å. The Sm(3)-O(6) bond length is 2.31 Å. The Sm(3)-O(9) bond length is 2.91 Å. In the fourth Sm site, Sm(4) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(2), one O(7), one O(8), and one O(9) atom. The Sm(4)-O(1) bond length is 2.42 Å. The Sm(4)-O(11) bond length is 2.54 Å. The Sm(4)-O(2) bond length is 2.31 Å. The Sm(4)-O(7) bond length is 2.37 Å. The Sm(4)-O(8) bond length is 2.53 Å. The Sm(4)-O(9) bond length is 2.60 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Li(1), one Tm(1), one Tm(2), one Sm(2), and one Sm(4) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Tm(2), one Tm(4), one Sm(1), one Sm(2), and one Sm(4) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Tm(1), one Tm(3), 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(6)Sm2Tm2 tetrahedra, corners with two equivalent O(10)Sm2Tm2 tetrahedra,  an edgeedge with one O(6)Sm2Tm2 tetrahedra, and edges with two equivalent O(11)Sm3Tm2 trigonal bipyramids. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Li(1), one Tm(1), one Tm(3), one Sm(1), one Sm(2), and one Sm(3) atom. In the sixth O site, O(6) is bonded to one Tm(3), one Tm(4), one Sm(1), and one Sm(3) atom to form distorted OSm2Tm2 tetrahedra that share corners with three equivalent O(10)Sm2Tm2 tetrahedra, corners with three equivalent O(11)Sm3Tm2 trigonal bipyramids,  a cornercorner with one O(4)Sm2Tm2 trigonal pyramid,  a cornercorner with one O(8)Sm2Tm2 trigonal pyramid, and  an edgeedge with one O(4)Sm2Tm2 trigonal pyramid. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Li(1), one Tm(3), one Tm(4), one Sm(2), and one Sm(4) atom. In the eighth O site, O(8) is bonded to one Tm(1), one Tm(3), one Sm(2), and one Sm(4) atom to form distorted OSm2Tm2 trigonal pyramids that share  a cornercorner with one O(6)Sm2Tm2 tetrahedra, corners with two equivalent O(10)Sm2Tm2 tetrahedra, and  a cornercorner with one O(11)Sm3Tm2 trigonal bipyramid. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Tm(2), one Tm(4), one Sm(2), one Sm(3), and one Sm(4) atom. In the tenth O site, O(10) is bonded to one Tm(1), one Tm(3), one Sm(1), and one Sm(3) atom to form distorted OSm2Tm2 tetrahedra that share corners with three equivalent O(6)Sm2Tm2 tetrahedra, corners with two equivalent O(4)Sm2Tm2 trigonal pyramids, corners with two equivalent O(8)Sm2Tm2 trigonal pyramids, and  an edgeedge with one O(11)Sm3Tm2 trigonal bipyramid. In the eleventh O site, O(11) is bonded to one Tm(2), one Tm(4), one Sm(1), one Sm(3), and one Sm(4) atom to form a mixture of distorted edge and corner-sharing OSm3Tm2 trigonal bipyramids. In the twelfth O site, O(12) is bonded in a distorted see-saw-like geometry to one Tm(1), one Tm(2), one Sm(1), and one Sm(3) atom.