无序描述文献案例3

DJ_Tokyo

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无序描述文献案例3

案例来源：CCDC [1]: 2534227. DOI [2]: 10.5517/ccdc.csd.cc2r2286.(Acta Cryst. 2026, E82, 331–335. DOI: 10.1107/S2056989026002276.)

案例结构反应式如图1所示（由ChemBioDraw [3]绘制），该化合物反应原料为六水合硝酸镍（Ni(NO3)2·6H2O, Nickel(II) nitratehexahydrate, CAS: 13478-00-7）、噻吩-2,5-二羧酸 [4]（H2TDC, thiophene-2,5-dicarboxylic acid,CAS: 4282-31-9, CCDC: 1400530）和反式-1,2-双(4-吡啶基)乙烯 [5]（bpe,trans-1,2-bis(pyridin-4-yl)ethylene, CAS: 13362-78-2, CCDC: 1104375 [5a], 1828730 [5b], 1843770 [5c], 1956596 [5d]），反应溶剂为N,N-二甲基甲酰胺 [6]（DMF, N,N-dimethylformamide,CAS: 68-12-2, CCDC: 102756 [6a], 1869635–1869638[6b], 1869744–1869752 [6b]）、乙醇 [7]（EtOH, ethanol, CAS: 64-17-5, CCDC: 1150324 [7a], 1150325 [7b]）和水 [8]（H2O, water, CAS: 7732-18-5, CCDC: 2080050–2080051）。

▲图1 案例结构反应式

如图2所示（由Olex2 [9]呈现），bpe配体中的一个吡啶环和乙烯的一个碳做了二组分无序（普通无序，使用第二个自由变量，参阅推文“使用自由变量和限制(目录+链接)”），精修后占有率为0.54353和0.45647（1 – 0.54353），第一组分原子为N2和C13-C18（PART1分组，SHELXL [10]指令PART，参阅推文“SHELXL指令之PART”），第二组分原子为N12和C113-C118（PART2分组），并使用SHELXL指令DFIX（参阅推文“SHELXL指令之DFIX”）对第二组分吡啶环的键长做了限制。

▲图2 bpe配体无序

游离的DMF溶剂做了特殊无序处理，使用PART -1分组，使用第三个自由变量，精修后占有率为0.20491，并使用SHELXL指令FLAT（参阅推文“SHELXL指令之FLAT”）、DFIX、RIGU [11]（参阅推文“SHELXL指令之RIGU”）和ISOR（参阅推文“SHELXL指令之ISOR”）等对其几何结构和原子位移参数做了限制和约束，如图3所示。

▲图3 游离DMF溶剂无序

论文中对这部分无序的描述如图4所示。

▲图4 无序描述

原文	大意
Part of trans-1,2-bis(pyridyl)ethylene  (atoms N2, C13-C18) was disordered over two positions with occupancies of  0.544 (17) and 0.456 (17). The DMF molecule with refined occupancy 0.205 (7)  was subject to DFIX, FLAT, RIGU and ISOR restraints to maintain the expected  geometry.	反式-1,2-双(4-吡啶基)乙烯部分结构（原子N2、C13至C18）在两个位置上无序，占有率分别为0.544(17)和0.456(17)。DMF分子占有率精修为0.205(7)，并受到DFIX、FLAT、RIGU和ISOR限制以保持预期几何结构

上述描述中的占有率为小数点后三位，且具有标准偏差，其值可从CIF [12]文件中获取，以记事本方式打开CIF文件，在原子列表中读取即可，如图5所示。

▲图5 无序原子的占有率获取

相关视频：

单晶结构解析练习785(MOF-无序处理)：https://www.bilibili.com/video/BV1Co3k6WExz

数据下载：

链接: https://pan.baidu.com/s/1lfpZ50caXNzQgpZPmYismg?pwd=c6rj

提取码: c6rj

相关阅读：

无序描述文献案例1

无序描述文献案例2

参考文献

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