晶体结构不是预期结构案例29

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晶体结构不是预期结构案例29

案例85：

本来是按照如图85所示（由ChemBioDraw [1]绘制），利用三苯基丙基溴化膦 [2]（Triphenyl(propyl)phosphoniumbromide, CAS: 6228-47-3; CCDC: 248856 [2a], 1977045[2b], 2587082 [2c]）和某金属醋酸盐水合物在一定条件下进行反应，以期得到含该金属的配合物，然而所得产物结晶后，经单晶X射线衍射（SC-XRD,single-crystal X-ray diffraction）实验得到晶体数据，经结构解析发现产物结构为[Ph3nPrP+][Br–]0.675[AcO–]0.325，可能在该条件下二者未能反应得到预期结构，也可能是后处理过程中分解，并且过程中阴离子发生了交换。

                              

▲图85 案例85反应示意图

相关视频：

单晶结构解析练习787(非预期结构-溴和乙酸根混占无序处理)：https://www.bilibili.com/video/BV1pHYq6bEjp

案例86：

本来是按照如图86所示，利用配体1（L1）二苯基甲基膦、配体2（L2）和碘化亚铜 [3]（CuI, Copper(I) iodide,CAS: 7681-65-4; CCDC: 1594151 [3a], 1600048 [3b], 1600783–1600784 [3c], 1602525 [3d], 1604540–1604544 [3e], 1604707 [3f], 1606466–1606471 [3g], 1608909 [3h], 1624288 [3i], 1637167 [3j], 1638550–1638554 [3k], 1640440–1640481 [3l], 1644229 [3m], 1673978–1673979 [3n], 1679593–1679618 [3o], 1679963–1679964 [3p], 1713334–1713337 [3q], 2149217 [3r]）在一定条件下反应，以期得到含L1和L2的铜配合物，然而所得产物结晶后，经SC-XRD实验得到晶体数据，经结构解析发现产物结构为只含L1的[Ph2MePCuI]4[4]（CCDC: 1214058 [4a],1835363 [4b], 2587083 [4c]），显然，在该反应条件下，L2未参与构建结构。

▲图86 案例86反应示意图

相关视频：

单晶结构解析练习788(非预期结构-无序处理-残余峰-PLAT097)：https://www.bilibili.com/video/BV1fHYy6rERz

案例87：

本来是按照如图87所示，利用三苯基丙基溴化膦 [2]与某金属醋酸盐水合物和溴化锰在一定条件下反应，以期获得含该金属与锰的杂双金属配合物，然而所得产物结晶后，经SC-XRD实验得到晶体数据，经结构解析发现产物结构为只含金属锰的离子型盐的乙醇溶剂化物[Ph3PPr]2[MnBr4]·1/3EtOH [5]（CCDC: 2210616 [5a], 2380213 [5b],2587150 [5c]）。

▲图87 案例87反应示意图

相关视频：

单晶结构解析练习789(非预期结构-SHELXT解不出结构)：https://www.bilibili.com/video/BV1cbep6HEEr

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