Materials Data on Zr(TlS)4 by Materials Project

Zr(TlS)4 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. there are three inequivalent Zr4+ sites. In the first Zr4+ site, Zr4+ is bonded to six S2- atoms to form ZrS6 octahedra that share corners with three TlS5 square pyramids, edges with two ZrS6 octahedra, and edges with six TlS5 square pyramids. There are a spread of Zr–S bond distances ranging from 2.54–2.68 Å. In the second Zr4+ site, Zr4+ is bonded to six S2- atoms to form ZrS6 octahedra that share corners with four TlS5 square pyramids, edges with two ZrS6 octahedra, and edges with four TlS5 square pyramids. There are a spread of Zr–S bond distances ranging from 2.54–2.70 Å. In the third Zr4+ site, Zr4+ is bonded to six S2- atoms to form ZrS6 octahedra that share corners with two equivalent TlS5 square pyramids, edges with two equivalent ZrS6 octahedra, and edges with four TlS5 square pyramids. There are a spread of Zr–S bond distances ranging from 2.59–2.63 Å. There are ten inequivalent Tl1+ sites. In the first Tl1+ site, Tl1+ is bonded to five S2- atoms to form distorted TlS5 square pyramids that share corners with two equivalent ZrS6 octahedra, corners with two equivalent TlS5 square pyramids, edges with three ZrS6 octahedra, and an edgeedge with one TlS5 square pyramid. The corner-sharing octahedra tilt angles range from 15–18°. There are a spread of Tl–S bond distances ranging from 2.88–3.40 Å. In the second Tl1+ site, Tl1+ is bonded to five S2- atoms to form distorted TlS5 square pyramids that share corners with two ZrS6 octahedra, corners with two equivalent TlS5 square pyramids, edges with three ZrS6 octahedra, and edges with three TlS5 square pyramids. The corner-sharing octahedral tilt angles are 7°. There are a spread of Tl–S bond distances ranging from 2.94–3.43 Å. In the third Tl1+ site, Tl1+ is bonded in a distorted rectangular see-saw-like geometry to four S2- atoms. There are a spread of Tl–S bond distances ranging from 2.88–3.24 Å. In the fourth Tl1+ site, Tl1+ is bonded to five S2- atoms to form distorted TlS5 square pyramids that share corners with two ZrS6 octahedra, corners with two equivalent TlS5 square pyramids, edges with three ZrS6 octahedra, and edges with two TlS5 square pyramids. The corner-sharing octahedra tilt angles range from 9–10°. There are a spread of Tl–S bond distances ranging from 2.92–3.48 Å. In the fifth Tl1+ site, Tl1+ is bonded in a distorted rectangular see-saw-like geometry to four S2- atoms. There are a spread of Tl–S bond distances ranging from 2.92–3.42 Å. In the sixth Tl1+ site, Tl1+ is bonded in a distorted rectangular see-saw-like geometry to four S2- atoms. There are a spread of Tl–S bond distances ranging from 2.90–3.46 Å. In the seventh Tl1+ site, Tl1+ is bonded to five S2- atoms to form distorted TlS5 square pyramids that share corners with two ZrS6 octahedra, corners with two equivalent TlS5 square pyramids, edges with three ZrS6 octahedra, and edges with three TlS5 square pyramids. The corner-sharing octahedra tilt angles range from 11–15°. There are a spread of Tl–S bond distances ranging from 2.89–3.37 Å. In the eighth Tl1+ site, Tl1+ is bonded in a distorted rectangular see-saw-like geometry to four S2- atoms. There are a spread of Tl–S bond distances ranging from 2.88–3.26 Å. In the ninth Tl1+ site, Tl1+ is bonded in a distorted rectangular see-saw-like geometry to four S2- atoms. There are a spread of Tl–S bond distances ranging from 2.89–3.43 Å. In the tenth Tl1+ site, Tl1+ is bonded in a 5-coordinate geometry to five S2- atoms. There are a spread of Tl–S bond distances ranging from 2.91–3.41 Å. There are ten inequivalent S2- sites. In the first S2- site, S2- is bonded in a 6-coordinate geometry to one Zr4+ and five Tl1+ atoms. In the second S2- site, S2- is bonded to two equivalent Zr4+ and four Tl1+ atoms to form distorted SZr2Tl4 octahedra that share a cornercorner with one SZrTl5 octahedra and edges with two SZr2Tl4 octahedra. The corner-sharing octahedral tilt angles are 19°. In the third S2- site, S2- is bonded in a 6-coordinate geometry to two Zr4+ and four Tl1+ atoms. In the fourth S2- site, S2- is bonded to two Zr4+ and four Tl1+ atoms to form distorted SZr2Tl4 octahedra that share a cornercorner with one SZr2Tl4 octahedra and edges with three SZrTl5 octahedra. The corner-sharing octahedral tilt angles are 0°. In the fifth S2- site, S2- is bonded in a 6-coordinate geometry to one Zr4+ and five Tl1+ atoms. In the sixth S2- site, S2- is bonded in a 6-coordinate geometry to two Zr4+ and four Tl1+ atoms. In the seventh S2- site, S2- is bonded in a 6-coordinate geometry to one Zr4+ and five Tl1+ atoms. In the eighth S2- site, S2- is bonded in a 6-coordinate geometry to one Zr4+ and five Tl1+ atoms. In the ninth S2- site, S2- is bonded to one Zr4+ and five Tl1+ atoms to form a mixture of distorted corner and edge-sharing SZrTl5 octahedra. The corner-sharing octahedra tilt angles range from 0–19°. In the tenth S2- site, S2- is bonded in a 6-coordinate geometry to two Zr4+ and four Tl1+ atoms.

四(一硫化铊)合锆（Zr(TlS)₄）结晶于三斜晶系P-1空间群，其晶体结构为三维框架。体系中存在三个非等价的四价锆（Zr⁴+）配位位点：在第一个Zr⁴+配位位点中，四价锆与六个二价硫（S²-）离子配位形成ZrS₆八面体，该八面体与三个TlS₅四方锥共享顶角、与两个ZrS₆八面体共享边，同时与六个TlS₅四方锥共享边。Zr-S键的键长分布范围为2.54~2.68埃（Å）。在第二个Zr⁴+配位位点中，四价锆与六个S²-离子配位形成ZrS₆八面体，该八面体与四个TlS₅四方锥共享顶角、与两个ZrS₆八面体共享边，同时与四个TlS₅四方锥共享边。Zr-S键的键长分布范围为2.54~2.70埃。在第三个Zr⁴+配位位点中，四价锆与六个S²-离子配位形成ZrS₆八面体，该八面体与两个等价的TlS₅四方锥共享顶角、与两个等价的ZrS₆八面体共享边，同时与四个TlS₅四方锥共享边。Zr-S键的键长分布范围为2.59~2.63埃。
体系中同时存在十个非等价的一价铊（Tl⁺）配位位点：在第一个Tl⁺配位位点中，一价铊与五个S²-离子配位形成畸变的TlS₅四方锥，该四方锥与两个等价的ZrS₆八面体共享顶角、与两个等价的TlS₅四方锥共享顶角，与三个ZrS₆八面体共享边，同时与一个TlS₅四方锥共享边。共顶角八面体的倾斜角范围为15°~18°，Tl-S键的键长分布范围为2.88~3.40埃。在第二个Tl⁺配位位点中，一价铊与五个S²-离子配位形成畸变的TlS₅四方锥，该四方锥与两个ZrS₆八面体共享顶角、与两个等价的TlS₅四方锥共享顶角，与三个ZrS₆八面体共享边，同时与三个TlS₅四方锥共享边。共顶角八面体的倾斜角为7°，Tl-S键的键长分布范围为2.94~3.43埃。在第三个Tl⁺配位位点中，一价铊以畸变的矩形跷跷板型配位几何与四个S²-离子配位，Tl-S键的键长分布范围为2.88~3.24埃。在第四个Tl⁺配位位点中，一价铊与五个S²-离子配位形成畸变的TlS₅四方锥，该四方锥与两个ZrS₆八面体共享顶角、与两个等价的TlS₅四方锥共享顶角，与三个ZrS₆八面体共享边，同时与两个TlS₅四方锥共享边。共顶角八面体的倾斜角范围为9°~10°，Tl-S键的键长分布范围为2.92~3.48埃。在第五个Tl⁺配位位点中，一价铊以畸变的矩形跷跷板型配位几何与四个S²-离子配位，Tl-S键的键长分布范围为2.92~3.42埃。在第六个Tl⁺配位位点中，一价铊以畸变的矩形跷跷板型配位几何与四个S²-离子配位，Tl-S键的键长分布范围为2.90~3.46埃。在第七个Tl⁺配位位点中，一价铊与五个S²-离子配位形成畸变的TlS₅四方锥，该四方锥与两个ZrS₆八面体共享顶角、与两个等价的TlS₅四方锥共享顶角，与三个ZrS₆八面体共享边，同时与三个TlS₅四方锥共享边。共顶角八面体的倾斜角范围为11°~15°，Tl-S键的键长分布范围为2.89~3.37埃。在第八个Tl⁺配位位点中，一价铊以畸变的矩形跷跷板型配位几何与四个S²-离子配位，Tl-S键的键长分布范围为2.88~3.26埃。在第九个Tl⁺配位位点中，一价铊以畸变的矩形跷跷板型配位几何与四个S²-离子配位，Tl-S键的键长分布范围为2.89~3.43埃。在第十个Tl⁺配位位点中，一价铊以五配位几何与五个S²-离子配位，Tl-S键的键长分布范围为2.91~3.41埃。
体系中还存在十个非等价的二价硫（S²-）配位位点：在第一个S²-配位位点中，二价硫以六配位几何与1个Zr⁴+和5个Tl⁺离子配位。在第二个S²-配位位点中，二价硫与2个等价的Zr⁴+和4个Tl⁺离子配位，形成畸变的SZr₂Tl₄八面体，该八面体与1个SZrTl₅八面体共享顶角，同时与两个SZr₂Tl₄八面体共享边。共顶角八面体的倾斜角为19°。在第三个S²-配位位点中，二价硫以六配位几何与2个Zr⁴+和4个Tl⁺离子配位。在第四个S²-配位位点中，二价硫与2个Zr⁴+和4个Tl⁺离子配位，形成畸变的SZr₂Tl₄八面体，该八面体与1个SZr₂Tl₄八面体共享顶角，同时与三个SZrTl₅八面体共享边。共顶角八面体的倾斜角为0°。在第五个S²-配位位点中，二价硫以六配位几何与1个Zr⁴+和5个Tl⁺离子配位。在第六个S²-配位位点中，二价硫以六配位几何与2个Zr⁴+和4个Tl⁺离子配位。在第七个S²-配位位点中，二价硫以六配位几何与1个Zr⁴+和5个Tl⁺离子配位。在第八个S²-配位位点中，二价硫以六配位几何与1个Zr⁴+和5个Tl⁺离子配位。在第九个S²-配位位点中，二价硫与1个Zr⁴+和5个Tl⁺离子配位，形成兼具畸变共顶角与共边模式的SZrTl₅八面体混合结构。共顶角八面体的倾斜角范围为0°~19°。在第十个S²-配位位点中，二价硫以六配位几何与2个Zr⁴+和4个Tl⁺离子配位。