Materials Data on Tb9Ga5S21 by Materials Project

Tb9Ga5S21 crystallizes in the trigonal R3 space group. The structure is three-dimensional. there are six inequivalent Tb3+ sites. In the first Tb3+ site, Tb3+ is bonded to seven S2- atoms to form distorted TbS7 pentagonal bipyramids that share corners with three TbS7 pentagonal bipyramids, corners with two GaS4 tetrahedra, edges with two TbS7 pentagonal bipyramids, an edgeedge with one GaS4 tetrahedra, and a faceface with one GaS6 octahedra. There are a spread of Tb–S bond distances ranging from 2.79–2.92 Å. In the second Tb3+ site, Tb3+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Tb–S bond distances ranging from 2.75–3.28 Å. In the third Tb3+ site, Tb3+ is bonded to seven S2- atoms to form distorted TbS7 pentagonal bipyramids that share a cornercorner with one GaS6 octahedra, corners with three TbS7 pentagonal bipyramids, corners with two GaS4 tetrahedra, an edgeedge with one TbS7 pentagonal bipyramid, and an edgeedge with one GaS4 tetrahedra. The corner-sharing octahedral tilt angles are 39°. There are a spread of Tb–S bond distances ranging from 2.76–2.94 Å. In the fourth Tb3+ site, Tb3+ is bonded in a 7-coordinate geometry to seven S2- atoms. There are a spread of Tb–S bond distances ranging from 2.75–2.97 Å. In the fifth Tb3+ site, Tb3+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Tb–S bond distances ranging from 2.76–3.28 Å. In the sixth Tb3+ site, Tb3+ is bonded to seven S2- atoms to form distorted TbS7 pentagonal bipyramids that share a cornercorner with one GaS6 octahedra, corners with four TbS7 pentagonal bipyramids, corners with two GaS4 tetrahedra, an edgeedge with one TbS7 pentagonal bipyramid, and an edgeedge with one GaS4 tetrahedra. The corner-sharing octahedral tilt angles are 39°. There are a spread of Tb–S bond distances ranging from 2.77–2.95 Å. There are six inequivalent Ga3+ sites. In the first Ga3+ site, Ga3+ is bonded to four S2- atoms to form GaS4 tetrahedra that share corners with three TbS7 pentagonal bipyramids and edges with two TbS7 pentagonal bipyramids. There are a spread of Ga–S bond distances ranging from 2.25–2.30 Å. In the second Ga3+ site, Ga3+ is bonded to four S2- atoms to form GaS4 tetrahedra that share corners with three TbS7 pentagonal bipyramids and an edgeedge with one TbS7 pentagonal bipyramid. There are a spread of Ga–S bond distances ranging from 2.25–2.29 Å. In the third Ga3+ site, Ga3+ is bonded to six S2- atoms to form GaS6 octahedra that share corners with three equivalent TbS7 pentagonal bipyramids and faces with three equivalent TbS7 pentagonal bipyramids. There are three shorter (2.47 Å) and three longer (2.51 Å) Ga–S bond lengths. In the fourth Ga3+ site, Ga3+ is bonded in a 6-coordinate geometry to six S2- atoms. There are three shorter (2.29 Å) and three longer (2.86 Å) Ga–S bond lengths. In the fifth Ga3+ site, Ga3+ is bonded in a 6-coordinate geometry to six S2- atoms. There are three shorter (2.28 Å) and three longer (2.88 Å) Ga–S bond lengths. In the sixth Ga3+ site, Ga3+ is bonded to six S2- atoms to form GaS6 octahedra that share corners with three equivalent TbS7 pentagonal bipyramids. There are three shorter (2.47 Å) and three longer (2.51 Å) Ga–S bond lengths. There are fourteen inequivalent S2- sites. In the first S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to three Tb3+ and one Ga3+ atom. In the second S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to three Tb3+ and one Ga3+ atom. In the third S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to three Tb3+ and one Ga3+ atom. In the fourth S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to three Tb3+ and one Ga3+ atom. In the fifth S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to three Tb3+ and one Ga3+ atom. In the sixth S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to three Tb3+ and one Ga3+ atom. In the seventh S2- site, S2- is bonded to three Tb3+ and one Ga3+ atom to form distorted STb3Ga tetrahedra that share corners with three STb3Ga2 square pyramids and corners with three STb3Ga trigonal pyramids. In the eighth S2- site, S2- is bonded to three Tb3+ and one Ga3+ atom to form distorted STb3Ga tetrahedra that share corners with three STb3Ga2 square pyramids and corners with three STb3Ga trigonal pyramids. In the ninth S2- site, S2- is bonded in a 5-coordinate geometry to four Tb3+ and one Ga3+ atom. In the tenth S2- site, S2- is bonded to three Tb3+ and two Ga3+ atoms to form distorted STb3Ga2 square pyramids that share corners with three STb3Ga tetrahedra, a cornercorner with one STb3Ga trigonal pyramid, edges with two equivalent STb3Ga trigonal pyramids, and faces with two equivalent STb3Ga2 square pyramids. In the eleventh S2- site, S2- is bonded to three Tb3+ and one Ga3+ atom to form distorted STb3Ga trigonal pyramids that share a cornercorner with one STb3Ga2 square pyramid, corners with three STb3Ga tetrahedra, edges with two equivalent STb3Ga2 square pyramids, and edges with two equivalent STb3Ga trigonal pyramids. In the twelfth S2- site, S2- is bonded to three Tb3+ and two Ga3+ atoms to form distorted STb3Ga2 square pyramids that share corners with three STb3Ga tetrahedra, a cornercorner with one STb3Ga trigonal pyramid, edges with two equivalent STb3Ga trigonal pyramids, and faces with two equivalent STb3Ga2 square pyramids. In the thirteenth S2- site, S2- is bonded to three Tb3+ and one Ga3+ atom to form distorted STb3Ga trigonal pyramids that share a cornercorner with one STb3Ga2 square pyramid, corners with three STb3Ga tetrahedra, edges with two equivalent STb3Ga2 square pyramids, and edges with two equivalent STb3Ga trigonal pyramids. In the fourteenth S2- site, S2- is bonded in a 5-coordinate geometry to four Tb3+ and one Ga3+ atom.

Tb9Ga5S21晶体属于三方晶系R3空间群（trigonal R3 space group），其结构为三维骨架结构。存在6个不等价的铽(III)（Tb³+）离子位点。
在第一个Tb³+位点中，Tb³+与7个硫离子（S²-）配位，形成畸变的TbS7五角双锥（pentagonal bipyramids）配位多面体；该多面体通过共角与3个TbS7五角双锥、2个GaS4四面体（tetrahedra）相连，通过共边与2个TbS7五角双锥、1个GaS4四面体相连，同时通过共面与1个GaS6八面体（octahedra）相连。Tb–S键的键长分布范围为2.79~2.92 Å。
在第二个Tb³+位点中，Tb³+为8配位几何，与8个S²-配位，Tb–S键长分布范围为2.75~3.28 Å。
在第三个Tb³+位点中，Tb³+与7个S²-配位，形成畸变的TbS7五角双锥；该多面体通过共角与1个GaS6八面体、3个TbS7五角双锥、2个GaS4四面体相连，通过共边分别与1个TbS7五角双锥和1个GaS4四面体相连。共角八面体的倾斜角为39°，Tb–S键长分布范围为2.76~2.94 Å。
在第四个Tb³+位点中，Tb³+为7配位几何，与7个S²-配位，Tb–S键长分布范围为2.75~2.97 Å。
在第五个Tb³+位点中，Tb³+为8配位几何，与8个S²-配位，Tb–S键长分布范围为2.76~3.28 Å。
在第六个Tb³+位点中，Tb³+与7个S²-配位，形成畸变的TbS7五角双锥；该多面体通过共角与1个GaS6八面体、4个TbS7五角双锥、2个GaS4四面体相连，通过共边分别与1个TbS7五角双锥和1个GaS4四面体相连。共角八面体的倾斜角为39°，Tb–S键长分布范围为2.77~2.95 Å。
存在6个不等价的镓(III)（Ga³+）离子位点。
在第一个Ga³+位点中，Ga³+与4个S²-配位，形成GaS4四面体配位多面体；该多面体通过共角与3个TbS7五角双锥相连，通过共边与2个TbS7五角双锥相连。Ga–S键长分布范围为2.25~2.30 Å。
在第二个Ga³+位点中，Ga³+与4个S²-配位，形成GaS4四面体配位多面体；该多面体通过共角与3个TbS7五角双锥相连，通过共边与1个TbS7五角双锥相连。Ga–S键长分布范围为2.25~2.29 Å。
在第三个Ga³+位点中，Ga³+与6个S²-配位，形成GaS6八面体配位多面体；该多面体通过共角与3个等价的TbS7五角双锥相连，通过共面与3个等价的TbS7五角双锥相连。其Ga–S键长分为两组：3个较短键长为2.47 Å，3个较长键长为2.51 Å。
在第四个Ga³+位点中，Ga³+为6配位几何，与6个S²-配位。其Ga–S键长分为两组：3个较短键长为2.29 Å，3个较长键长为2.86 Å。
在第五个Ga³+位点中，Ga³+为6配位几何，与6个S²-配位。其Ga–S键长分为两组：3个较短键长为2.28 Å，3个较长键长为2.88 Å。
在第六个Ga³+位点中，Ga³+与6个S²-配位，形成GaS6八面体配位多面体；该多面体通过共角与3个等价的TbS7五角双锥相连。其Ga–S键长分为两组：3个较短键长为2.47 Å，3个较长键长为2.51 Å。
存在14个不等价的硫离子（S²-）位点。
在第1至第6个S²-位点中，S²-均为畸变的矩形跷跷板型配位几何，分别与3个Tb³+和1个Ga³+配位。
在第7和第8个S²-位点中，S²-与3个Tb³+和1个Ga³+配位，形成畸变的STb3Ga四面体配位多面体；该多面体通过共角分别与3个STb3Ga2四方锥（square pyramids）和3个STb3Ga三角锥（trigonal pyramids）相连。
在第9和第14个S²-位点中，S²-为5配位几何，分别与4个Tb³+和1个Ga³+配位。
在第10个S²-位点中，S²-与3个Tb³+和2个Ga³+配位，形成畸变的STb3Ga2四方锥配位多面体；该多面体通过共角与3个STb3Ga四面体相连，通过共角与1个STb3Ga三角锥相连，通过共边与2个等价的STb3Ga三角锥相连，同时通过共面与2个等价的STb3Ga2四方锥相连。
在第11个S²-位点中，S²-与3个Tb³+和1个Ga³+配位，形成畸变的STb3Ga三角锥配位多面体；该多面体通过共角与1个STb3Ga2四方锥相连，通过共角与3个STb3Ga四面体相连，通过共边与2个等价的STb3Ga2四方锥和2个等价的STb3Ga三角锥相连。
在第12个S²-位点中，S²-与3个Tb³+和2个Ga³+配位，形成畸变的STb3Ga2四方锥配位多面体；该多面体通过共角与3个STb3Ga四面体相连，通过共角与1个STb3Ga三角锥相连，通过共边与2个等价的STb3Ga三角锥相连，同时通过共面与2个等价的STb3Ga2四方锥相连。
在第13个S²-位点中，S²-与3个Tb³+和1个Ga³+配位，形成畸变的STb3Ga三角锥配位多面体；该多面体通过共角与1个STb3Ga2四方锥相连，通过共角与3个STb3Ga四面体相连，通过共边与2个等价的STb3Ga2四方锥和2个等价的STb3Ga三角锥相连。