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TmS2 is Cubic Laves structured and crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. Tm3+ is bonded in a 12-coordinate geometry to twelve equivalent S+1.50- atoms. All Tm–S bond lengths are 3.22 Å. S+1.50- is bonded to six equivalent Tm3+ and six equivalent S+1.50- atoms to form a mixture of corner, edge, and face-sharing STm6S6 cuboctahedra. All S–S bond lengths are 2.74 Å.
Sm4(TmS2)11 crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. there are six inequivalent Tm3+ sites. In the first Tm3+ site, Tm3+ is bonded to six S2- atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedra tilt angles range from 48–59°. There are a spread of Tm–S bond distances ranging from 2.61–2.75 Å. In the second Tm3+ site, Tm3+ is bonded to six S2- atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedra tilt angles range from 48–59°. There are a spread of Tm–S bond distances ranging from 2.63–2.74 Å. In the third Tm3+ site, Tm3+ is bonded to six S2- atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, a cornercorner with one TmS7 pentagonal bipyramid, edges with four equivalent TmS6 octahedra, and edges with two equivalent TmS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 51–63°. There are a spread of Tm–S bond distances ranging from 2.64–2.74 Å. In the fourth Tm3+ site, Tm3+ is bonded to seven S2- atoms to form distorted TmS7 pentagonal bipyramids that share corners with three TmS6 octahedra, edges with two equivalent TmS6 octahedra, and edges with four equivalent TmS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 39–50°. There are a spread of Tm–S bond distances ranging from 2.67–2.86 Å. In the fifth Tm3+ site, Tm3+ is bonded to six S2- atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedral tilt angles are 55°. All Tm–S bond lengths are 2.71 Å. In the sixth Tm3+ site, Tm3+ is bonded to six S2- atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, corners with two equivalent TmS7 pentagonal bipyramids, and edges with four TmS6 octahedra. The corner-sharing octahedra tilt angles range from 51–63°. There are a spread of Tm–S bond distances ranging from 2.64–2.76 Å. There are two inequivalent Sm+2.75+ sites. In the first Sm+2.75+ site, Sm+2.75+ is bonded in a 7-coordinate geometry to eight S2- atoms. There are a spread of Sm–S bond distances ranging from 2.87–3.39 Å. In the second Sm+2.75+ site, Sm+2.75+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Sm–S bond distances ranging from 2.87–3.02 Å. There are eleven inequivalent S2- sites. In the first S2- site, S2- is bonded to two equivalent Tm3+ and three Sm+2.75+ atoms to form distorted SSm3Tm2 trigonal bipyramids that share corners with four SSm2Tm3 square pyramids, corners with two equivalent SSm2Tm3 trigonal bipyramids, a cornercorner with one SSmTm3 trigonal pyramid, edges with three SSm2Tm3 square pyramids, and edges with five SSm3Tm2 trigonal bipyramids. In the second S2- site, S2- is bonded in a rectangular see-saw-like geometry to four Tm3+ atoms. In the third S2- site, S2- is bonded to two equivalent Tm3+ and three Sm+2.75+ atoms to form distorted SSm3Tm2 trigonal bipyramids that share corners with six SSm2Tm3 square pyramids, corners with four equivalent STm4 trigonal pyramids, edges with two SSm2Tm3 square pyramids, edges with six SSm3Tm2 trigonal bipyramids, and edges with three SSmTm3 trigonal pyramids. In the fourth S2- site, S2- is bonded to three Tm3+ and two equivalent Sm+2.75+ atoms to form distorted SSm2Tm3 square pyramids that share corners with four SSm2Tm3 square pyramids, corners with two equivalent SSm3Tm2 trigonal bipyramids, corners with two equivalent SSmTm3 trigonal pyramids, edges with four SSm2Tm3 square pyramids, and edges with three SSm3Tm2 trigonal bipyramids. In the fifth S2- site, S2- is bonded to three Tm3+ and one Sm+2.75+ atom to form distorted SSmTm3 trigonal pyramids that share corners with four SSm2Tm3 square pyramids, corners with two SSm3Tm2 trigonal bipyramids, corners with five SSmTm3 trigonal pyramids, edges with three SSm2Tm3 square pyramids, and edges with two equivalent SSm3Tm2 trigonal bipyramids. In the sixth S2- site, S2- is bonded to four Tm3+ atoms to form distorted STm4 trigonal pyramids that share corners with five SSm3Tm2 trigonal bipyramids, corners with five SSmTm3 trigonal pyramids, edges with three SSm2Tm3 trigonal bipyramids, and edges with two equivalent STm4 trigonal pyramids. In the seventh S2- site, S2- is bonded to three Tm3+ and two equivalent Sm+2.75+ atoms to form distorted SSm2Tm3 trigonal bipyramids that share corners with two equivalent SSm2Tm3 square pyramids, corners with two equivalent SSm3Tm2 trigonal bipyramids, corners with two SSmTm3 trigonal pyramids, an edgeedge with one SSm2Tm3 square pyramid, edges with five SSm3Tm2 trigonal bipyramids, and edges with two equivalent STm4 trigonal pyramids. In the eighth S2- site, S2- is bonded in a 4-coordinate geometry to three Tm3+ and one Sm+2.75+ atom. In the ninth S2- site, S2- is bonded to three Tm3+ and two equivalent Sm+2.75+ atoms to form distorted SSm2Tm3 square pyramids that share corners with six SSm3Tm2 trigonal bipyramids, corners with two equivalent SSmTm3 trigonal pyramids, edges with four SSm2Tm3 square pyramids, edges with two SSm3Tm2 trigonal bipyramids, and an edgeedge with one SSmTm3 trigonal pyramid. In the tenth S2- site, S2- is bonded in a rectangular see-saw-like geometry to four Tm3+ atoms. In the eleventh S2- site, S2- is bonded to three Tm3+ and two equivalent Sm+2.75+ atoms to form distorted SSm2Tm3 square pyramids that share corners with two equivalent SSm2Tm3 square pyramids, corners with four SSm3Tm2 trigonal bipyramids, edges with five SSm2Tm3 square pyramids, an edgeedge with one SSm3Tm2 trigonal bipyramid, and edges with two equivalent SSmTm3 trigonal pyramids.
Ce(TmS2)3 crystallizes in the monoclinic P2_1/m space group. The structure is three-dimensional. there are three inequivalent Tm3+ sites. In the first Tm3+ site, Tm3+ is bonded to seven S2- atoms to form distorted TmS7 pentagonal bipyramids that share corners with three TmS6 octahedra, edges with two equivalent TmS6 octahedra, and edges with four equivalent TmS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 39–50°. There are a spread of Tm–S bond distances ranging from 2.67–2.90 Å. In the second Tm3+ site, Tm3+ is bonded to six S2- atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, a cornercorner with one TmS7 pentagonal bipyramid, edges with four equivalent TmS6 octahedra, and edges with two equivalent TmS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 54–62°. There are a spread of Tm–S bond distances ranging from 2.65–2.75 Å. In the third Tm3+ site, Tm3+ is bonded to six S2- atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, corners with two equivalent TmS7 pentagonal bipyramids, and edges with four equivalent TmS6 octahedra. The corner-sharing octahedra tilt angles range from 54–62°. There are a spread of Tm–S bond distances ranging from 2.64–2.77 Å. Ce3+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Ce–S bond distances ranging from 2.90–3.04 Å. There are six inequivalent S2- sites. In the first S2- site, S2- is bonded in a 4-coordinate geometry to four Tm3+ atoms. In the second S2- site, S2- is bonded to three Tm3+ and one Ce3+ atom to form distorted SCeTm3 trigonal pyramids that share corners with two equivalent SCe2Tm3 square pyramids, corners with four SCe2Tm3 trigonal bipyramids, corners with two equivalent SCeTm3 trigonal pyramids, edges with three equivalent SCe2Tm3 square pyramids, and edges with two equivalent SCe3Tm2 trigonal bipyramids. In the third S2- site, S2- is bonded in a rectangular see-saw-like geometry to four Tm3+ atoms. In the fourth S2- site, S2- is bonded to three equivalent Tm3+ and two equivalent Ce3+ atoms to form distorted SCe2Tm3 square pyramids that share corners with six SCe2Tm3 trigonal bipyramids, corners with two equivalent SCeTm3 trigonal pyramids, edges with four equivalent SCe2Tm3 square pyramids, edges with two SCe2Tm3 trigonal bipyramids, and edges with three equivalent SCeTm3 trigonal pyramids. In the fifth S2- site, S2- is bonded to three Tm3+ and two equivalent Ce3+ atoms to form distorted SCe2Tm3 trigonal bipyramids that share corners with two equivalent SCe2Tm3 square pyramids, corners with two equivalent SCe3Tm2 trigonal bipyramids, corners with three equivalent SCeTm3 trigonal pyramids, an edgeedge with one SCe2Tm3 square pyramid, and edges with five SCe2Tm3 trigonal bipyramids. In the sixth S2- site, S2- is bonded to two equivalent Tm3+ and three equivalent Ce3+ atoms to form distorted SCe3Tm2 trigonal bipyramids that share corners with four equivalent SCe2Tm3 square pyramids, corners with two equivalent SCe2Tm3 trigonal bipyramids, a cornercorner with one SCeTm3 trigonal pyramid, an edgeedge with one SCe2Tm3 square pyramid, edges with seven SCe2Tm3 trigonal bipyramids, and edges with two equivalent SCeTm3 trigonal pyramids.
Pr(TmS2)3 crystallizes in the monoclinic P2_1/m space group. The structure is three-dimensional. there are three inequivalent Tm3+ sites. In the first Tm3+ site, Tm3+ is bonded to seven S2- atoms to form distorted TmS7 pentagonal bipyramids that share corners with three TmS6 octahedra, edges with two equivalent TmS6 octahedra, and edges with four equivalent TmS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 39–51°. There are a spread of Tm–S bond distances ranging from 2.67–2.90 Å. In the second Tm3+ site, Tm3+ is bonded to six S2- atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, a cornercorner with one TmS7 pentagonal bipyramid, edges with four equivalent TmS6 octahedra, and edges with two equivalent TmS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 55–61°. There are a spread of Tm–S bond distances ranging from 2.65–2.76 Å. In the third Tm3+ site, Tm3+ is bonded to six S2- atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, corners with two equivalent TmS7 pentagonal bipyramids, and edges with four equivalent TmS6 octahedra. The corner-sharing octahedra tilt angles range from 55–61°. There are a spread of Tm–S bond distances ranging from 2.64–2.77 Å. Pr3+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Pr–S bond distances ranging from 2.91–3.04 Å. There are six inequivalent S2- sites. In the first S2- site, S2- is bonded in a 4-coordinate geometry to four Tm3+ atoms. In the second S2- site, S2- is bonded to three Tm3+ and one Pr3+ atom to form distorted SPrTm3 trigonal pyramids that share corners with two equivalent SPr2Tm3 square pyramids, corners with four SPr2Tm3 trigonal bipyramids, corners with two equivalent SPrTm3 trigonal pyramids, edges with three equivalent SPr2Tm3 square pyramids, and edges with two equivalent SPr3Tm2 trigonal bipyramids. In the third S2- site, S2- is bonded in a rectangular see-saw-like geometry to four Tm3+ atoms. In the fourth S2- site, S2- is bonded to three equivalent Tm3+ and two equivalent Pr3+ atoms to form distorted SPr2Tm3 square pyramids that share corners with six SPr2Tm3 trigonal bipyramids, corners with two equivalent SPrTm3 trigonal pyramids, edges with four equivalent SPr2Tm3 square pyramids, edges with two SPr2Tm3 trigonal bipyramids, and edges with three equivalent SPrTm3 trigonal pyramids. In the fifth S2- site, S2- is bonded to three Tm3+ and two equivalent Pr3+ atoms to form distorted SPr2Tm3 trigonal bipyramids that share corners with two equivalent SPr2Tm3 square pyramids, corners with two equivalent SPr3Tm2 trigonal bipyramids, corners with three equivalent SPrTm3 trigonal pyramids, an edgeedge with one SPr2Tm3 square pyramid, and edges with five SPr2Tm3 trigonal bipyramids. In the sixth S2- site, S2- is bonded to two equivalent Tm3+ and three equivalent Pr3+ atoms to form distorted SPr3Tm2 trigonal bipyramids that share corners with four equivalent SPr2Tm3 square pyramids, corners with two equivalent SPr2Tm3 trigonal bipyramids, a cornercorner with one SPrTm3 trigonal pyramid, an edgeedge with one SPr2Tm3 square pyramid, edges with seven SPr2Tm3 trigonal bipyramids, and edges with two equivalent SPrTm3 trigonal pyramids.
TmS2 crystallizes in the tetragonal P4/nmm space group. The structure is three-dimensional. Tm3+ is bonded in a 9-coordinate geometry to nine S+1.50- atoms. There are five shorter (2.80 Å) and four longer (2.88 Å) Tm–S bond lengths. There are two inequivalent S+1.50- sites. In the first S+1.50- site, S+1.50- is bonded in a 8-coordinate geometry to four equivalent Tm3+ and four equivalent S+1.50- atoms. All S–S bond lengths are 2.70 Å. In the second S+1.50- site, S+1.50- is bonded to five equivalent Tm3+ atoms to form a mixture of distorted edge and corner-sharing STm5 trigonal bipyramids.
Ca(TmS2)2 crystallizes in the orthorhombic Cmc2_1 space group. The structure is three-dimensional. Ca2+ is bonded in a 7-coordinate geometry to seven S2- atoms. There are a spread of Ca–S bond distances ranging from 2.77–3.22 Å. There are two inequivalent Tm3+ sites. In the first Tm3+ site, Tm3+ is bonded to six S2- atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedra tilt angles range from 8–54°. There are a spread of Tm–S bond distances ranging from 2.63–2.76 Å. In the second Tm3+ site, Tm3+ is bonded to six S2- atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedra tilt angles range from 8–54°. There are a spread of Tm–S bond distances ranging from 2.64–2.77 Å. There are four inequivalent S2- sites. In the first S2- site, S2- is bonded to two equivalent Ca2+ and two Tm3+ atoms to form distorted SCa2Tm2 tetrahedra that share corners with two equivalent SCaTm4 square pyramids, corners with two equivalent SCa2Tm2 tetrahedra, corners with ten SCa2Tm3 trigonal bipyramids, edges with two equivalent SCaTm4 square pyramids, and edges with two SCa2Tm3 trigonal bipyramids. In the second S2- site, S2- is bonded to two equivalent Ca2+ and three Tm3+ atoms to form distorted SCa2Tm3 trigonal bipyramids that share corners with two equivalent SCaTm4 square pyramids, corners with five equivalent SCa2Tm2 tetrahedra, corners with two equivalent SCa2Tm3 trigonal bipyramids, edges with three equivalent SCaTm4 square pyramids, an edgeedge with one SCa2Tm2 tetrahedra, and edges with five SCa2Tm3 trigonal bipyramids. In the third S2- site, S2- is bonded to two equivalent Ca2+ and three Tm3+ atoms to form distorted SCa2Tm3 trigonal bipyramids that share corners with six equivalent SCaTm4 square pyramids, corners with five equivalent SCa2Tm2 tetrahedra, corners with two equivalent SCa2Tm3 trigonal bipyramids, an edgeedge with one SCaTm4 square pyramid, an edgeedge with one SCa2Tm2 tetrahedra, and edges with five SCa2Tm3 trigonal bipyramids. In the fourth S2- site, S2- is bonded to one Ca2+ and four Tm3+ atoms to form distorted SCaTm4 square pyramids that share corners with two equivalent SCa2Tm2 tetrahedra, corners with eight SCa2Tm3 trigonal bipyramids, edges with two equivalent SCaTm4 square pyramids, edges with two equivalent SCa2Tm2 tetrahedra, and edges with four SCa2Tm3 trigonal bipyramids.
La(TmS2)3 crystallizes in the monoclinic P2_1/m space group. The structure is three-dimensional. there are three inequivalent Tm3+ sites. In the first Tm3+ site, Tm3+ is bonded to seven S2- atoms to form distorted TmS7 pentagonal bipyramids that share corners with three TmS6 octahedra, edges with two equivalent TmS6 octahedra, and edges with four equivalent TmS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 39–51°. There are a spread of Tm–S bond distances ranging from 2.67–2.90 Å. In the second Tm3+ site, Tm3+ is bonded to six S2- atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, a cornercorner with one TmS7 pentagonal bipyramid, edges with four equivalent TmS6 octahedra, and edges with two equivalent TmS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 53–62°. There are a spread of Tm–S bond distances ranging from 2.65–2.76 Å. In the third Tm3+ site, Tm3+ is bonded to six S2- atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, corners with two equivalent TmS7 pentagonal bipyramids, and edges with four equivalent TmS6 octahedra. The corner-sharing octahedra tilt angles range from 53–62°. There are a spread of Tm–S bond distances ranging from 2.63–2.77 Å. La3+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of La–S bond distances ranging from 2.93–3.06 Å. There are six inequivalent S2- sites. In the first S2- site, S2- is bonded in a 4-coordinate geometry to four Tm3+ atoms. In the second S2- site, S2- is bonded to three Tm3+ and one La3+ atom to form distorted SLaTm3 trigonal pyramids that share corners with two equivalent SLa2Tm3 square pyramids, corners with four SLa2Tm3 trigonal bipyramids, corners with two equivalent SLaTm3 trigonal pyramids, edges with three equivalent SLa2Tm3 square pyramids, and edges with two equivalent SLa3Tm2 trigonal bipyramids. In the third S2- site, S2- is bonded in a rectangular see-saw-like geometry to four Tm3+ atoms. In the fourth S2- site, S2- is bonded to three equivalent Tm3+ and two equivalent La3+ atoms to form distorted SLa2Tm3 square pyramids that share corners with six SLa2Tm3 trigonal bipyramids, corners with two equivalent SLaTm3 trigonal pyramids, edges with four equivalent SLa2Tm3 square pyramids, edges with two SLa2Tm3 trigonal bipyramids, and edges with three equivalent SLaTm3 trigonal pyramids. In the fifth S2- site, S2- is bonded to three Tm3+ and two equivalent La3+ atoms to form distorted SLa2Tm3 trigonal bipyramids that share corners with two equivalent SLa2Tm3 square pyramids, corners with two equivalent SLa3Tm2 trigonal bipyramids, corners with three equivalent SLaTm3 trigonal pyramids, an edgeedge with one SLa2Tm3 square pyramid, and edges with five SLa2Tm3 trigonal bipyramids. In the sixth S2- site, S2- is bonded to two equivalent Tm3+ and three equivalent La3+ atoms to form distorted SLa3Tm2 trigonal bipyramids that share corners with four equivalent SLa2Tm3 square pyramids, corners with two equivalent SLa2Tm3 trigonal bipyramids, a cornercorner with one SLaTm3 trigonal pyramid, an edgeedge with one SLa2Tm3 square pyramid, edges with seven SLa2Tm3 trigonal bipyramids, and edges with two equivalent SLaTm3 trigonal pyramids.
Ce4(TmS2)11 crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. there are six inequivalent Tm sites. In the first Tm site, Tm is bonded to seven S atoms to form distorted TmS7 pentagonal bipyramids that share corners with three TmS6 octahedra, edges with two equivalent TmS6 octahedra, and edges with four equivalent TmS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 39–50°. There are a spread of Tm–S bond distances ranging from 2.68–2.87 Å. In the second Tm site, Tm is bonded to six S atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedra tilt angles range from 49–59°. There are a spread of Tm–S bond distances ranging from 2.63–2.76 Å. In the third Tm site, Tm is bonded to six S atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, corners with two equivalent TmS7 pentagonal bipyramids, and edges with four TmS6 octahedra. The corner-sharing octahedra tilt angles range from 52–62°. There are a spread of Tm–S bond distances ranging from 2.64–2.77 Å. In the fourth Tm site, Tm is bonded to six S atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, a cornercorner with one TmS7 pentagonal bipyramid, edges with four equivalent TmS6 octahedra, and edges with two equivalent TmS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 52–62°. There are a spread of Tm–S bond distances ranging from 2.65–2.75 Å. In the fifth Tm site, Tm is bonded to six S atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedra tilt angles range from 49–59°. There are a spread of Tm–S bond distances ranging from 2.64–2.76 Å. In the sixth Tm site, Tm is bonded to six S atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedral tilt angles are 55°. All Tm–S bond lengths are 2.72 Å. There are two inequivalent Ce sites. In the first Ce site, Ce is bonded in a 8-coordinate geometry to eight S atoms. There are a spread of Ce–S bond distances ranging from 2.90–3.03 Å. In the second Ce site, Ce is bonded in a 7-coordinate geometry to eight S atoms. There are a spread of Ce–S bond distances ranging from 2.88–3.45 Å. There are eleven inequivalent S sites. In the first S site, S is bonded to three Tm and two equivalent Ce atoms to form SCe2Tm3 trigonal bipyramids that share corners with two equivalent SCe2Tm3 square pyramids, corners with two equivalent SCe3Tm2 trigonal bipyramids, corners with two SCeTm3 trigonal pyramids, an edgeedge with one SCe2Tm3 square pyramid, edges with five SCe2Tm3 trigonal bipyramids, and edges with two equivalent STm4 trigonal pyramids. In the second S site, S is bonded in a rectangular see-saw-like geometry to four Tm atoms. In the third S site, S is bonded in a 4-coordinate geometry to three Tm and one Ce atom. In the fourth S site, S is bonded to three Tm and two equivalent Ce atoms to form SCe2Tm3 square pyramids that share corners with six SCe2Tm3 trigonal bipyramids, corners with two equivalent SCeTm3 trigonal pyramids, edges with four SCe2Tm3 square pyramids, edges with two SCe2Tm3 trigonal bipyramids, and an edgeedge with one SCeTm3 trigonal pyramid. In the fifth S site, S is bonded to three Tm and two equivalent Ce atoms to form SCe2Tm3 square pyramids that share corners with two equivalent SCe2Tm3 square pyramids, corners with four SCe3Tm2 trigonal bipyramids, edges with five SCe2Tm3 square pyramids, an edgeedge with one SCe3Tm2 trigonal bipyramid, and edges with two equivalent SCeTm3 trigonal pyramids. In the sixth S site, S is bonded to three Tm and two equivalent Ce atoms to form SCe2Tm3 square pyramids that share corners with four SCe2Tm3 square pyramids, corners with two equivalent SCe3Tm2 trigonal bipyramids, corners with two equivalent SCeTm3 trigonal pyramids, edges with four SCe2Tm3 square pyramids, and edges with three SCe3Tm2 trigonal bipyramids. In the seventh S site, S is bonded to two equivalent Tm and three Ce atoms to form distorted SCe3Tm2 trigonal bipyramids that share corners with six SCe2Tm3 square pyramids, corners with four equivalent STm4 trigonal pyramids, edges with two SCe2Tm3 square pyramids, edges with six SCe2Tm3 trigonal bipyramids, and edges with three SCeTm3 trigonal pyramids. In the eighth S site, S is bonded to three Tm and one Ce atom to form distorted SCeTm3 trigonal pyramids that share corners with four SCe2Tm3 square pyramids, corners with two SCe2Tm3 trigonal bipyramids, corners with five SCeTm3 trigonal pyramids, edges with three SCe2Tm3 square pyramids, and edges with two equivalent SCe3Tm2 trigonal bipyramids. In the ninth S site, S is bonded in a rectangular see-saw-like geometry to four Tm atoms. In the tenth S site, S is bonded to four Tm atoms to form distorted STm4 trigonal pyramids that share corners with five SCe2Tm3 trigonal bipyramids, corners with five SCeTm3 trigonal pyramids, edges with three SCe2Tm3 trigonal bipyramids, and edges with two equivalent STm4 trigonal pyramids. In the eleventh S site, S is bonded to two equivalent Tm and three Ce atoms to form distorted SCe3Tm2 trigonal bipyramids that share corners with four SCe2Tm3 square pyramids, corners with two equivalent SCe2Tm3 trigonal bipyramids, a cornercorner with one SCeTm3 trigonal pyramid, edges with three SCe2Tm3 square pyramids, and edges with five SCe2Tm3 trigonal bipyramids.
La4(TmS2)11 crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. there are six inequivalent Tm3+ sites. In the first Tm3+ site, Tm3+ is bonded to seven S2- atoms to form distorted TmS7 pentagonal bipyramids that share corners with three TmS6 octahedra, edges with two equivalent TmS6 octahedra, and edges with four equivalent TmS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 40–50°. There are a spread of Tm–S bond distances ranging from 2.68–2.87 Å. In the second Tm3+ site, Tm3+ is bonded to six S2- atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedra tilt angles range from 49–59°. There are a spread of Tm–S bond distances ranging from 2.64–2.76 Å. In the third Tm3+ site, Tm3+ is bonded to six S2- atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, corners with two equivalent TmS7 pentagonal bipyramids, and edges with four TmS6 octahedra. The corner-sharing octahedra tilt angles range from 51–63°. There are a spread of Tm–S bond distances ranging from 2.64–2.78 Å. In the fourth Tm3+ site, Tm3+ is bonded to six S2- atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, a cornercorner with one TmS7 pentagonal bipyramid, edges with four equivalent TmS6 octahedra, and edges with two equivalent TmS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 51–63°. There are a spread of Tm–S bond distances ranging from 2.65–2.76 Å. In the fifth Tm3+ site, Tm3+ is bonded to six S2- atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedra tilt angles range from 49–59°. There are a spread of Tm–S bond distances ranging from 2.64–2.76 Å. In the sixth Tm3+ site, Tm3+ is bonded to six S2- atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedral tilt angles are 55°. There are four shorter (2.71 Å) and two longer (2.72 Å) Tm–S bond lengths. There are two inequivalent La+2.75+ sites. In the first La+2.75+ site, La+2.75+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of La–S bond distances ranging from 2.94–3.06 Å. In the second La+2.75+ site, La+2.75+ is bonded in a 7-coordinate geometry to eight S2- atoms. There are a spread of La–S bond distances ranging from 2.92–3.47 Å. There are eleven inequivalent S2- sites. In the first S2- site, S2- is bonded to three Tm3+ and two equivalent La+2.75+ atoms to form distorted SLa2Tm3 trigonal bipyramids that share corners with two equivalent SLa2Tm3 square pyramids, corners with two equivalent SLa3Tm2 trigonal bipyramids, a cornercorner with one SLaTm3 trigonal pyramid, an edgeedge with one SLa2Tm3 square pyramid, and edges with five SLa2Tm3 trigonal bipyramids. In the second S2- site, S2- is bonded in a rectangular see-saw-like geometry to four Tm3+ atoms. In the third S2- site, S2- is bonded in a 3-coordinate geometry to three Tm3+ and one La+2.75+ atom. In the fourth S2- site, S2- is bonded to three Tm3+ and two equivalent La+2.75+ atoms to form distorted SLa2Tm3 square pyramids that share corners with six SLa2Tm3 trigonal bipyramids, corners with two equivalent SLaTm3 trigonal pyramids, edges with four SLa2Tm3 square pyramids, edges with two SLa2Tm3 trigonal bipyramids, and an edgeedge with one SLaTm3 trigonal pyramid. In the fifth S2- site, S2- is bonded to three Tm3+ and two equivalent La+2.75+ atoms to form distorted SLa2Tm3 square pyramids that share corners with two equivalent SLa2Tm3 square pyramids, corners with four SLa3Tm2 trigonal bipyramids, edges with five SLa2Tm3 square pyramids, an edgeedge with one SLa3Tm2 trigonal bipyramid, and edges with two equivalent SLaTm3 trigonal pyramids. In the sixth S2- site, S2- is bonded to three Tm3+ and two equivalent La+2.75+ atoms to form distorted SLa2Tm3 square pyramids that share corners with four SLa2Tm3 square pyramids, corners with two equivalent SLa3Tm2 trigonal bipyramids, corners with two equivalent SLaTm3 trigonal pyramids, edges with four SLa2Tm3 square pyramids, and edges with three SLa3Tm2 trigonal bipyramids. In the seventh S2- site, S2- is bonded to two equivalent Tm3+ and three La+2.75+ atoms to form distorted SLa3Tm2 trigonal bipyramids that share corners with six SLa2Tm3 square pyramids, edges with two SLa2Tm3 square pyramids, edges with six SLa2Tm3 trigonal bipyramids, and edges with two equivalent SLaTm3 trigonal pyramids. In the eighth S2- site, S2- is bonded to three Tm3+ and one La+2.75+ atom to form distorted SLaTm3 trigonal pyramids that share corners with four SLa2Tm3 square pyramids, corners with two SLa2Tm3 trigonal bipyramids, corners with two equivalent SLaTm3 trigonal pyramids, edges with three SLa2Tm3 square pyramids, and edges with two equivalent SLa3Tm2 trigonal bipyramids. In the ninth S2- site, S2- is bonded in a rectangular see-saw-like geometry to four Tm3+ atoms. In the tenth S2- site, S2- is bonded in a 4-coordinate geometry to four Tm3+ atoms. In the eleventh S2- site, S2- is bonded to two equivalent Tm3+ and three La+2.75+ atoms to form distorted SLa3Tm2 trigonal bipyramids that share corners with four SLa2Tm3 square pyramids, corners with two equivalent SLa2Tm3 trigonal bipyramids, a cornercorner with one SLaTm3 trigonal pyramid, edges with three SLa2Tm3 square pyramids, and edges with five SLa2Tm3 trigonal bipyramids.
Nd4(TmS2)11 crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. there are six inequivalent Tm3+ sites. In the first Tm3+ site, Tm3+ is bonded to seven S2- atoms to form distorted TmS7 pentagonal bipyramids that share corners with three TmS6 octahedra, edges with two equivalent TmS6 octahedra, and edges with four equivalent TmS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 39–50°. There are a spread of Tm–S bond distances ranging from 2.67–2.86 Å. In the second Tm3+ site, Tm3+ is bonded to six S2- atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedra tilt angles range from 48–59°. There are a spread of Tm–S bond distances ranging from 2.62–2.75 Å. In the third Tm3+ site, Tm3+ is bonded to six S2- atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, corners with two equivalent TmS7 pentagonal bipyramids, and edges with four TmS6 octahedra. The corner-sharing octahedra tilt angles range from 50–63°. There are a spread of Tm–S bond distances ranging from 2.63–2.76 Å. In the fourth Tm3+ site, Tm3+ is bonded to six S2- atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, a cornercorner with one TmS7 pentagonal bipyramid, edges with four equivalent TmS6 octahedra, and edges with two equivalent TmS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 50–63°. There are a spread of Tm–S bond distances ranging from 2.64–2.74 Å. In the fifth Tm3+ site, Tm3+ is bonded to six S2- atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedra tilt angles range from 48–59°. There are a spread of Tm–S bond distances ranging from 2.63–2.74 Å. In the sixth Tm3+ site, Tm3+ is bonded to six S2- atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedral tilt angles are 55°. There are four shorter (2.70 Å) and two longer (2.72 Å) Tm–S bond lengths. There are two inequivalent Nd+2.75+ sites. In the first Nd+2.75+ site, Nd+2.75+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Nd–S bond distances ranging from 2.90–3.03 Å. In the second Nd+2.75+ site, Nd+2.75+ is bonded in a 7-coordinate geometry to eight S2- atoms. There are a spread of Nd–S bond distances ranging from 2.89–3.41 Å. There are eleven inequivalent S2- sites. In the first S2- site, S2- is bonded to three Tm3+ and two equivalent Nd+2.75+ atoms to form distorted SNd2Tm3 trigonal bipyramids that share corners with two equivalent SNd2Tm3 square pyramids, corners with two equivalent SNd3Tm2 trigonal bipyramids, corners with two SNdTm3 trigonal pyramids, an edgeedge with one SNd2Tm3 square pyramid, edges with five SNd2Tm3 trigonal bipyramids, and edges with two equivalent STm4 trigonal pyramids. In the second S2- site, S2- is bonded in a rectangular see-saw-like geometry to four Tm3+ atoms. In the third S2- site, S2- is bonded in a 4-coordinate geometry to three Tm3+ and one Nd+2.75+ atom. In the fourth S2- site, S2- is bonded to three Tm3+ and two equivalent Nd+2.75+ atoms to form distorted SNd2Tm3 square pyramids that share corners with six SNd2Tm3 trigonal bipyramids, corners with two equivalent SNdTm3 trigonal pyramids, edges with four SNd2Tm3 square pyramids, edges with two SNd2Tm3 trigonal bipyramids, and an edgeedge with one SNdTm3 trigonal pyramid. In the fifth S2- site, S2- is bonded to three Tm3+ and two equivalent Nd+2.75+ atoms to form distorted SNd2Tm3 square pyramids that share corners with two equivalent SNd2Tm3 square pyramids, corners with four SNd3Tm2 trigonal bipyramids, edges with five SNd2Tm3 square pyramids, an edgeedge with one SNd3Tm2 trigonal bipyramid, and edges with two equivalent SNdTm3 trigonal pyramids. In the sixth S2- site, S2- is bonded to three Tm3+ and two equivalent Nd+2.75+ atoms to form distorted SNd2Tm3 square pyramids that share corners with four SNd2Tm3 square pyramids, corners with two equivalent SNd3Tm2 trigonal bipyramids, corners with two equivalent SNdTm3 trigonal pyramids, edges with four SNd2Tm3 square pyramids, and edges with three SNd3Tm2 trigonal bipyramids. In the seventh S2- site, S2- is bonded to two equivalent Tm3+ and three Nd+2.75+ atoms to form distorted SNd3Tm2 trigonal bipyramids that share corners with six SNd2Tm3 square pyramids, corners with four equivalent STm4 trigonal pyramids, edges with two SNd2Tm3 square pyramids, edges with six SNd2Tm3 trigonal bipyramids, and edges with three SNdTm3 trigonal pyramids. In the eighth S2- site, S2- is bonded to three Tm3+ and one Nd+2.75+ atom to form distorted SNdTm3 trigonal pyramids that share corners with four SNd2Tm3 square pyramids, corners with two SNd2Tm3 trigonal bipyramids, corners with five SNdTm3 trigonal pyramids, edges with three SNd2Tm3 square pyramids, and edges with two equivalent SNd3Tm2 trigonal bipyramids. In the ninth S2- site, S2- is bonded in a rectangular see-saw-like geometry to four Tm3+ atoms. In the tenth S2- site, S2- is bonded to four Tm3+ atoms to form distorted STm4 trigonal pyramids that share corners with five SNd2Tm3 trigonal bipyramids, corners with five SNdTm3 trigonal pyramids, edges with three SNd2Tm3 trigonal bipyramids, and edges with two equivalent STm4 trigonal pyramids. In the eleventh S2- site, S2- is bonded to two equivalent Tm3+ and three Nd+2.75+ atoms to form distorted SNd3Tm2 trigonal bipyramids that share corners with four SNd2Tm3 square pyramids, corners with two equivalent SNd2Tm3 trigonal bipyramids, a cornercorner with one SNdTm3 trigonal pyramid, edges with three SNd2Tm3 square pyramids, and edges with five SNd2Tm3 trigonal bipyramids.
Yb(TmS2)2 crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. Yb2+ is bonded to seven S2- atoms to form distorted YbS7 pentagonal bipyramids that share corners with eight TmS6 octahedra, edges with five TmS6 octahedra, edges with two equivalent YbS7 pentagonal bipyramids, and faces with two equivalent YbS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 14–67°. There are a spread of Yb–S bond distances ranging from 2.86–2.98 Å. There are two inequivalent Tm3+ sites. In the first Tm3+ site, Tm3+ is bonded to six S2- atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, corners with four equivalent YbS7 pentagonal bipyramids, edges with six TmS6 octahedra, and an edgeedge with one YbS7 pentagonal bipyramid. The corner-sharing octahedra tilt angles range from 52–60°. There are a spread of Tm–S bond distances ranging from 2.68–2.78 Å. In the second Tm3+ site, Tm3+ is bonded to six S2- atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, corners with four equivalent YbS7 pentagonal bipyramids, edges with four TmS6 octahedra, and edges with four equivalent YbS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 52–60°. There are a spread of Tm–S bond distances ranging from 2.67–2.75 Å. There are four inequivalent S2- sites. In the first S2- site, S2- is bonded to two equivalent Yb2+ and three Tm3+ atoms to form a mixture of distorted edge and corner-sharing SYb2Tm3 trigonal bipyramids. In the second S2- site, S2- is bonded to two equivalent Yb2+ and three Tm3+ atoms to form SYb2Tm3 square pyramids that share corners with two equivalent SYb3Tm2 square pyramids, corners with two equivalent SYb2Tm3 trigonal bipyramids, edges with five SYb2Tm3 square pyramids, and edges with three equivalent SYb2Tm3 trigonal bipyramids. In the third S2- site, S2- is bonded to three equivalent Yb2+ and two equivalent Tm3+ atoms to form a mixture of distorted edge and corner-sharing SYb3Tm2 square pyramids. In the fourth S2- site, S2- is bonded in a rectangular see-saw-like geometry to four Tm3+ atoms.
Ca(TmS2)2 crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. Ca2+ is bonded to seven S2- atoms to form distorted CaS7 pentagonal bipyramids that share corners with eight TmS6 octahedra, edges with five TmS6 octahedra, edges with two equivalent CaS7 pentagonal bipyramids, and faces with two equivalent CaS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 14–67°. There are a spread of Ca–S bond distances ranging from 2.87–3.00 Å. There are two inequivalent Tm3+ sites. In the first Tm3+ site, Tm3+ is bonded to six S2- atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, corners with four equivalent CaS7 pentagonal bipyramids, edges with six TmS6 octahedra, and an edgeedge with one CaS7 pentagonal bipyramid. The corner-sharing octahedra tilt angles range from 52–60°. There are a spread of Tm–S bond distances ranging from 2.68–2.79 Å. In the second Tm3+ site, Tm3+ is bonded to six S2- atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, corners with four equivalent CaS7 pentagonal bipyramids, edges with four TmS6 octahedra, and edges with four equivalent CaS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 52–60°. There are a spread of Tm–S bond distances ranging from 2.67–2.76 Å. There are four inequivalent S2- sites. In the first S2- site, S2- is bonded to two equivalent Ca2+ and three Tm3+ atoms to form a mixture of distorted edge and corner-sharing SCa2Tm3 trigonal bipyramids. In the second S2- site, S2- is bonded to two equivalent Ca2+ and three Tm3+ atoms to form SCa2Tm3 square pyramids that share corners with two equivalent SCa3Tm2 square pyramids, corners with two equivalent SCa2Tm3 trigonal bipyramids, edges with five SCa2Tm3 square pyramids, and edges with three equivalent SCa2Tm3 trigonal bipyramids. In the third S2- site, S2- is bonded to three equivalent Ca2+ and two equivalent Tm3+ atoms to form a mixture of distorted edge and corner-sharing SCa3Tm2 square pyramids. In the fourth S2- site, S2- is bonded in a rectangular see-saw-like geometry to four Tm3+ atoms.
Nd(TmS2)3 crystallizes in the monoclinic P2_1/m space group. The structure is three-dimensional. there are three inequivalent Tm3+ sites. In the first Tm3+ site, Tm3+ is bonded to six S2- atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, a cornercorner with one TmS7 pentagonal bipyramid, edges with four equivalent TmS6 octahedra, and edges with two equivalent TmS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 53–62°. There are a spread of Tm–S bond distances ranging from 2.65–2.75 Å. In the second Tm3+ site, Tm3+ is bonded to seven S2- atoms to form distorted TmS7 pentagonal bipyramids that share corners with three TmS6 octahedra, edges with two equivalent TmS6 octahedra, and edges with four equivalent TmS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 39–51°. There are a spread of Tm–S bond distances ranging from 2.67–2.89 Å. In the third Tm3+ site, Tm3+ is bonded to six S2- atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, corners with two equivalent TmS7 pentagonal bipyramids, and edges with four equivalent TmS6 octahedra. The corner-sharing octahedra tilt angles range from 53–62°. There are a spread of Tm–S bond distances ranging from 2.63–2.76 Å. Nd3+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Nd–S bond distances ranging from 2.91–3.03 Å. There are six inequivalent S2- sites. In the first S2- site, S2- is bonded in a 4-coordinate geometry to four Tm3+ atoms. In the second S2- site, S2- is bonded to three equivalent Tm3+ and two equivalent Nd3+ atoms to form distorted SNd2Tm3 square pyramids that share corners with six SNd3Tm2 trigonal bipyramids, corners with two equivalent SNdTm3 trigonal pyramids, edges with four equivalent SNd2Tm3 square pyramids, edges with two SNd3Tm2 trigonal bipyramids, and edges with three equivalent SNdTm3 trigonal pyramids. In the third S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to four Tm3+ atoms. In the fourth S2- site, S2- is bonded to three Tm3+ and two equivalent Nd3+ atoms to form distorted SNd2Tm3 trigonal bipyramids that share corners with two equivalent SNd2Tm3 square pyramids, corners with two equivalent SNd3Tm2 trigonal bipyramids, corners with three equivalent SNdTm3 trigonal pyramids, an edgeedge with one SNd2Tm3 square pyramid, and edges with five SNd2Tm3 trigonal bipyramids. In the fifth S2- site, S2- is bonded to two equivalent Tm3+ and three equivalent Nd3+ atoms to form distorted SNd3Tm2 trigonal bipyramids that share corners with four equivalent SNd2Tm3 square pyramids, corners with two equivalent SNd2Tm3 trigonal bipyramids, a cornercorner with one SNdTm3 trigonal pyramid, an edgeedge with one SNd2Tm3 square pyramid, edges with seven SNd2Tm3 trigonal bipyramids, and edges with two equivalent SNdTm3 trigonal pyramids. In the sixth S2- site, S2- is bonded to three Tm3+ and one Nd3+ atom to form distorted SNdTm3 trigonal pyramids that share corners with two equivalent SNd2Tm3 square pyramids, corners with four SNd2Tm3 trigonal bipyramids, corners with two equivalent SNdTm3 trigonal pyramids, edges with three equivalent SNd2Tm3 square pyramids, and edges with two equivalent SNd3Tm2 trigonal bipyramids.
Pr4(TmS2)11 crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. there are six inequivalent Tm sites. In the first Tm site, Tm is bonded to seven S atoms to form distorted TmS7 pentagonal bipyramids that share corners with three TmS6 octahedra, edges with two equivalent TmS6 octahedra, and edges with four equivalent TmS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 39–50°. There are a spread of Tm–S bond distances ranging from 2.67–2.86 Å. In the second Tm site, Tm is bonded to six S atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedra tilt angles range from 48–59°. There are a spread of Tm–S bond distances ranging from 2.62–2.75 Å. In the third Tm site, Tm is bonded to six S atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, corners with two equivalent TmS7 pentagonal bipyramids, and edges with four TmS6 octahedra. The corner-sharing octahedra tilt angles range from 50–63°. There are a spread of Tm–S bond distances ranging from 2.63–2.76 Å. In the fourth Tm site, Tm is bonded to six S atoms to form TmS6 octahedra that share corners with three equivalent TmS6 octahedra, a cornercorner with one TmS7 pentagonal bipyramid, edges with four equivalent TmS6 octahedra, and edges with two equivalent TmS7 pentagonal bipyramids. The corner-sharing octahedra tilt angles range from 50–63°. There are a spread of Tm–S bond distances ranging from 2.64–2.75 Å. In the fifth Tm site, Tm is bonded to six S atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedra tilt angles range from 48–59°. There are a spread of Tm–S bond distances ranging from 2.63–2.74 Å. In the sixth Tm site, Tm is bonded to six S atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedral tilt angles are 55°. There are four shorter (2.70 Å) and two longer (2.72 Å) Tm–S bond lengths. There are two inequivalent Pr sites. In the first Pr site, Pr is bonded in a 8-coordinate geometry to eight S atoms. There are a spread of Pr–S bond distances ranging from 2.92–3.04 Å. In the second Pr site, Pr is bonded in a 7-coordinate geometry to eight S atoms. There are a spread of Pr–S bond distances ranging from 2.91–3.41 Å. There are eleven inequivalent S sites. In the first S site, S is bonded to three Tm and two equivalent Pr atoms to form SPr2Tm3 trigonal bipyramids that share corners with two equivalent SPr2Tm3 square pyramids, corners with two equivalent SPr3Tm2 trigonal bipyramids, corners with two SPrTm3 trigonal pyramids, an edgeedge with one SPr2Tm3 square pyramid, edges with five SPr2Tm3 trigonal bipyramids, and edges with two equivalent STm4 trigonal pyramids. In the second S site, S is bonded in a rectangular see-saw-like geometry to four Tm atoms. In the third S site, S is bonded in a 4-coordinate geometry to three Tm and one Pr atom. In the fourth S site, S is bonded to three Tm and two equivalent Pr atoms to form SPr2Tm3 square pyramids that share corners with six SPr2Tm3 trigonal bipyramids, corners with two equivalent SPrTm3 trigonal pyramids, edges with four SPr2Tm3 square pyramids, edges with two SPr2Tm3 trigonal bipyramids, and an edgeedge with one SPrTm3 trigonal pyramid. In the fifth S site, S is bonded to three Tm and two equivalent Pr atoms to form SPr2Tm3 square pyramids that share corners with two equivalent SPr2Tm3 square pyramids, corners with four SPr3Tm2 trigonal bipyramids, edges with five SPr2Tm3 square pyramids, an edgeedge with one SPr3Tm2 trigonal bipyramid, and edges with two equivalent SPrTm3 trigonal pyramids. In the sixth S site, S is bonded to three Tm and two equivalent Pr atoms to form SPr2Tm3 square pyramids that share corners with four SPr2Tm3 square pyramids, corners with two equivalent SPr3Tm2 trigonal bipyramids, corners with two equivalent SPrTm3 trigonal pyramids, edges with four SPr2Tm3 square pyramids, and edges with three SPr3Tm2 trigonal bipyramids. In the seventh S site, S is bonded to two equivalent Tm and three Pr atoms to form distorted SPr3Tm2 trigonal bipyramids that share corners with six SPr2Tm3 square pyramids, corners with four equivalent STm4 trigonal pyramids, edges with two SPr2Tm3 square pyramids, edges with six SPr2Tm3 trigonal bipyramids, and edges with three SPrTm3 trigonal pyramids. In the eighth S site, S is bonded to three Tm and one Pr atom to form SPrTm3 trigonal pyramids that share corners with four SPr2Tm3 square pyramids, corners with two SPr2Tm3 trigonal bipyramids, corners with five SPrTm3 trigonal pyramids, edges with three SPr2Tm3 square pyramids, and edges with two equivalent SPr3Tm2 trigonal bipyramids. In the ninth S site, S is bonded in a rectangular see-saw-like geometry to four Tm atoms. In the tenth S site, S is bonded to four Tm atoms to form distorted STm4 trigonal pyramids that share corners with five SPr2Tm3 trigonal bipyramids, corners with five SPrTm3 trigonal pyramids, edges with three SPr2Tm3 trigonal bipyramids, and edges with two equivalent STm4 trigonal pyramids. In the eleventh S site, S is bonded to two equivalent Tm and three Pr atoms to form distorted SPr3Tm2 trigonal bipyramids that share corners with four SPr2Tm3 square pyramids, corners with two equivalent SPr2Tm3 trigonal bipyramids, a cornercorner with one SPrTm3 trigonal pyramid, edges with three SPr2Tm3 square pyramids, and edges with five SPr2Tm3 trigonal bipyramids.
BaTm2S4 crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. Ba2+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Ba–S bond distances ranging from 3.19–3.37 Å. There are two inequivalent Tm3+ sites. In the first Tm3+ site, Tm3+ is bonded to six S2- atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedra tilt angles range from 48–59°. There are a spread of Tm–S bond distances ranging from 2.67–2.74 Å. In the second Tm3+ site, Tm3+ is bonded to six S2- atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedra tilt angles range from 48–59°. There are a spread of Tm–S bond distances ranging from 2.69–2.76 Å. There are four inequivalent S2- sites. In the first S2- site, S2- is bonded in a 5-coordinate geometry to two equivalent Ba2+ and three Tm3+ atoms. In the second S2- site, S2- is bonded to two equivalent Ba2+ and three equivalent Tm3+ atoms to form a mixture of distorted edge and corner-sharing SBa2Tm3 square pyramids. In the third S2- site, S2- is bonded to two equivalent Ba2+ and three Tm3+ atoms to form a mixture of distorted edge and corner-sharing SBa2Tm3 trigonal bipyramids. In the fourth S2- site, S2- is bonded to two equivalent Ba2+ and three equivalent Tm3+ atoms to form a mixture of distorted edge and corner-sharing SBa2Tm3 trigonal bipyramids.
SrTm2S4 crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. Sr2+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Sr–S bond distances ranging from 3.08–3.28 Å. There are two inequivalent Tm3+ sites. In the first Tm3+ site, Tm3+ is bonded to six S2- atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedra tilt angles range from 48–61°. There are a spread of Tm–S bond distances ranging from 2.68–2.74 Å. In the second Tm3+ site, Tm3+ is bonded to six S2- atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedra tilt angles range from 48–61°. There are a spread of Tm–S bond distances ranging from 2.66–2.74 Å. There are four inequivalent S2- sites. In the first S2- site, S2- is bonded in a 5-coordinate geometry to two equivalent Sr2+ and three Tm3+ atoms. In the second S2- site, S2- is bonded to two equivalent Sr2+ and three equivalent Tm3+ atoms to form a mixture of distorted edge and corner-sharing SSr2Tm3 square pyramids. In the third S2- site, S2- is bonded to two equivalent Sr2+ and three Tm3+ atoms to form a mixture of distorted edge and corner-sharing SSr2Tm3 trigonal bipyramids. In the fourth S2- site, S2- is bonded to two equivalent Sr2+ and three equivalent Tm3+ atoms to form a mixture of distorted edge and corner-sharing SSr2Tm3 trigonal bipyramids.