三核钼－硫簇合物的低热固相合成及其晶体结构

三核钼－硫配合物Ｍｏ_３Ｓ_７（ｄｔｃ）_３Ｉ·Ｓ_８·２ＣＨ_２Ｃｌ_２（ｄｔｃ＝Ｃ_４Ｈ_８ＮＣＳ_２~－）是由低热固相合成得到的。晶体属单斜晶系，Ｍ_ｒ＝１５００．１９，空间群Ｐ２_１／ｎ，ａ＝１１．８８１（３），ｂ＝１５．５５９（４），ｃ＝２６．１９７（７），β＝９８．５３（２）°，Ｖ＝４７８９Ａ~３，Ｚ＝４，Ｄ_ｃ＝２．０８ｇ／ｃｍ~３，Ｆ（０００）＝２９２０，μ（ＭｏＫα）＝２５．２４ｃｍ~（－１），对于２３９７个Ｉ≥３σ（Ｉ）的独立衍射点，最终偏离因子Ｒ＝０．０６０，Ｒ＝０．０６６。该配合物的基本骨架是［Ｍｏ_３Ｓ_７（ｄｔｃ）_３］~＋，其簇芯为［Ｍｏ_３Ｓ_７］~（４＋）单元，３中Ｍｏ原子组成正三角形平面，Ｍｏ－Ｍｏ的平均键长力２．７２３，Ｍｏ原子平面上的硫原子形成盖帽的μ_３－Ｓ，其Ｍｏ－Ｓ平均键长为２．３８３Ａ，３个Ｓ_２基团分别位于三角形３个棱的外侧，并分别与邻近的两个Ｍｏ原子结合形成１２中Ｍｏ－Ｓ键。与μ_３－Ｓ相对而位于平面另一侧的Ⅰ原子与３个μ_２－Ｓ连结，平均距离为３．２５７Ａ，成键作用较弱。

Synthesis and Crystal Structure of Trinuclear Molybdenum-Sulfur Cluster by Solid State Reaction at Low Heating Temperature

The trinuclear molybdenum-sulfur cluster Mo_3S_7 (dtc)_3I·S_8·2CH_2Cl_2(dtc=C_4H_8NCS_2￣-) was synthesized by solid state reaction at low temperature.It crystallizes in the monoclinic space group P2_1/n with a=11.881(2),b=15. 559(4),c=26.197(7),β=98.53(2)°V=4789;Z=4;D_c=2.08 g/cm￣3;F(000)=2920;μ=25.24 cm￣(-1)(MoKα).The final R=0.060,Rw=0.066 for 2397 independent reflections with I≥3σ(I).The essential skeleton structure of the title compound isMo_3S_7(dtc)_3]￣+ with a cluster core Mo_3S_7]￣(4+) unit.The three Mo atoms form an equilateral triangle with an average distance of 2.723.The average distance from these three Mo atoms to the triple bridging S atom is 2.383.Each pair of Mo atoms is bridged by a S_2 group.In addition,the I atom located on the side of the plane opposite to the μ_3-S atom connects with three S atoms with an average distance of 3.257,showing weak bonding interaction.