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★声明：本文仅代表个人观点，笔者学识有限，资料整理过程中难免存在疏漏谬误，请不吝指正。 跟着审稿意见学习无序细节描述 最近，有小伙伴遇到晶体数据方面的审稿意见找笔者帮忙处理，其中有一条总的审稿意见如下： General: Any restraints applied to a structure should be explainedand justified in the _refine_special_details section of the CIF. If disorder ispresent in a structure this should be explained in the _refine_special_detailssection as well. For example: "Phenylgroup C1 to C7 is disordered over two orientations. The occupancies of the twocomponents were refined competitively, converging to a ratio of 0.58:0.42.Chemically equivalent bonds of the disordered components were restrained beapproximately equal (SADI). The anisotropic thermal parameters of thedisordered atoms were significantly overlapped, and to correctly model themenhanced rigid bond (RIGU) and similarity restraints (SIMU) were applied tothese atoms and the bridgehead atom (C8) linking them." 大意如下： 概述： 应用于结构的任何限制都应在CIF[1]的_refine_special_details（参阅推文“CIF核心词典-REFINE”）部分进行解释和论证。如果结构中存在无序，也应在_refine_special_details部分进行解释。例如： “苯基C1至C7在两个方向上是无序的。这两个组分的占有率经过竞争性精修，收敛至0.58:0.42的比率。无序组分的化学等价键被限制（SADI，参阅推文“SHELXL指令之SADI”）在近似相等。无序原子的各向异性热参数明显重叠，为了正确模拟它们，对这些原子和连接它们的桥头原子（C8）应用了增强刚性键（RIGU [2]，参阅推文“SHELXL指令之RIGU”）和相似性限制（SIMU，参阅推文“SHELXL指令之SIMU”）。” 下面举个具体例子，以结构(S)-2-chloro-6-tosyl-7-vinyl-6,7-dihydro-5H-benzo[5,6]azepino[4,3-b]indolizine[3]（CCDC[4]: 2475440）为例，其结构如图1所示（由ChemBioDraw[5]绘制） ▲图1 CCDC 2475440结构 该结构中乙烯基存在两个方向的无序，C11-C12为其中一个方向，C11A-C12A为另一个方向，如图2所示（由Olex2 [6]呈现）。 ▲图2 乙烯基无序示意图 其精修结果如图3所示，其原子位移参数（ADPs, atomic displacement parameters）用SIMU和RIGU指令进行了限制，几何结构用SAME指令（参阅推文“SHELXL指令之SAME”）进行了限制，两个无序组分占比由自由变量精修，收敛至0.87852:(1 – 0.87852) = 0.87852:0.12148，保留两位小数即为0.88:0.12，桥头原子为C9。 ▲图3 无序精修结果 根据上述情况，可整理如下描述： Vinyl group C11 to C12 is disordered over twoorientations. The occupancies of the two components were refined competitively,converging to a ratio of 0.88:0.12. Chemically equivalent bonds of thedisordered components were restrained be approximately equal (SAME). Theanisotropic thermal parameters of the disordered atoms were significantlyoverlapped, and to correctly model them enhanced rigid bond (RIGU) andsimilarity restraints (SIMU) were applied to these atoms and the bridgeheadatom (C9) linking them. 将上诉内容复制粘贴到Olex2右侧Work选项卡下Report展开栏Diffraction子栏下Refine Special Details后面的输入框中，如图4红色箭头所指。 ▲图4 Olex2中精修特殊细节输入框 精修后，该部分内容由Olex2写入CIF文件_refine_special_details条目下，如图5所示，如果不是使用Olex2作为精修用户图形界面（GUI, Graphical User Interface），则可以手动在CIF文件_refine_special_details条目填入描述内容，注意每行不好超过80字符即可，参阅推文“晶体数据审稿意见-CIF中吸收校正详情文本行超过80字符”。 ▲图5 CIF中记录精修特殊细节的条目 通常情况下，精修人员可能不会主动去填写精修特殊细节，因此CIF中_refine_special_details条目值为问号，如图6所示。 ▲图6 值为问号的精修特殊细节条目 相关视频： 跟着审稿意见学习无序细节描述：https://www.bilibili.com/video/BV1mxeK6EEs6 参考文献 [1] (a)Hall, S. R.; Allen, F. H. Brown, I. D. 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