晶体结构分子式非整数文献案例3

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晶体结构分子式非整数文献案例3

案例来源：CCDC [1]: 2203584. Chem2023, 9, 2573–2584. DOI [2]: 10.1016/j.chempr.2023.05.005.

其反应如图1所示（由ChemBioDraw [3]绘制），利用MsFluid*-Sb（CCDC: 2203582）与九羰基二铁（Fe2(CO)9, nonacarbonyldiiron, CAS: 15321-51-4）以正己烷[4]（C6H14,n-hexane, CAS: 110-54-3, CCDC: 103189）作溶剂于室温下反应12小时合成目标产物MsFluid*-SbFe(CO)4。

▲图1 案例结构合成反应式

用Olex2 [5]打开CIF[6]文件2203584.cif，如图2所示，查看SbFe(CO)4和Br原子信息，可知SbFe(CO)4和Br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0.91681，即SbFe(CO)4为0.91681，Br为(1 – 0.91681) = 0.08319。

▲图2 无序情况

该无序代表的含义是，这个晶体结构为MsFluid*-SbFe(CO)4和MsFluid*-Br的混合物，二者比例为0.91681:0.08319，其中溴的来源很可能是通过MsFluid*-SbBr2所合成的MsFluid*-Sb并不纯，导致其与九羰基二铁反应时，生成了部分MsFluid*-Br，其成分和比例如图3所示，因此其分子式为0.91681 × (C76H89FeO4Sb) + 0.08319 × (C72H89Br) = C75.66724H89Br0.08319Fe0.91681O3.66724Sb0.91681，保留三位小数即为C75.667H89Br0.083Fe0.917O3.667Sb0.917，与CIF中_chemical_formula_moiety（参阅推文“CIF核心词典-CHEMICAL_FORMULA”）一致，保留两位小数即为C75.67H89Br0.09Fe0.91O3.67Sb0.91，与CIF中_chemical_formula_sum（参阅推文“CIF核心词典-CHEMICAL_FORMULA”）一致，如图4所示，其两个结构如图5–6所示。

▲图3 CCDC 2203584结构成分

▲图4 CIF中的分子式

▲图5 MsFluid*-SbFe(CO)4结构

▲图6 MsFluid*-Br结构

视频讲解请参阅：

晶体结构分子式非整数文献案例3：https://www.bilibili.com/video/BV1KaLm6DEzn

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/1BKSQtdkKdSrAOiXXI4R28A?pwd=3rxm

提取码: 3rxm

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