晶体结构分子式非整数文献案例2

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晶体结构分子式非整数文献案例2

案例来源：CCDC [1]: 2166315. Nat.Chem. 2023, 15, 200–205. DOI [2]: 10.1038/s41557-022-01081-1.

其反应如图1所示（由ChemBioDraw [3]绘制），利用MsFluid*-Ge（CCDC: ）与碘单质（I2, iodine,CAS: 12190-71-5）在氮气（N2, nitrogen, CAS: 7727-37-9）氛围下以正己烷 [4]（C6H14, n-hexane,CAS: 110-54-3, CCDC: 103189）为溶剂于室温下反应4小时合成目标产物MsFluid*-GeI3。

▲图1 案例结构合成反应式

用Olex2 [5]打开CIF[6]文件2166315.cif，如图2所示，查看Ge上所连的I和OH原子信息，可知I1为全占位（11.00000），I2和I2A以第三个自由变量（31.00000和-31.00000）做二组分无序，占有率之和为1.00000，占有率精修为0.96158，即I2为0.96158，I2A为(1 – 0.96158) = 0.03842；I3和O1-H1以第二个自由变量（21.00000和-21.00000）做二组分无序，占有率之和为1.00000，占有率精修为0.61742，即I3为0.61742，O1-H1为(1 – 0.61742) = 0.38258。

▲图2 无序情况

该无序代表的含义是，这个晶体结构为MsFluid*-GeI3和MsFluid*-GeI2OH（氧原子的来源可能来自于手套箱中的含氧物质）的混合物，二者比例为0.61742:0.38258，晶体结构中含有一个游离的正己烷，其成分和比例如图3所示，因此其分子式为0.61742 × (C72H89I3Ge) + 0.38258 × (C72H90I2OGe) + 1.00000 × (C6H14) =C72H103.38258GeI2.61742O0.38258，保留两位小数即为C72H103.39GeI2.62O0.38，与CIF中一致，如图4所示，其两个结构如图5–6所示。

▲图3 CCDC 2166315结构成分

▲图4 CIF中的分子式

▲图5 MsFluid*-GeI3·C6H14结构

▲图6 MsFluid*-GeI2OH·C6H14结构

视频讲解请参阅：

晶体结构分子式非整数文献案例2：https://www.bilibili.com/video/BV1WNoBBXEgh

如需论文PDF和晶体数据CIF文件，请从以下链接下载：

链接:https://pan.baidu.com/s/1mHjH6jUsDxWFqsMqG8nnNQ?pwd=h39j

提取码: h39j

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