晶体数据审稿意见-分辨率和溶剂遮掩(ChemCommun)

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晶体数据审稿意见-分辨率和溶剂遮掩(ChemCommun)

案例来源：CCDC[1] 2377155. Chem. Commun. 2024, 60, 15051–15054. DOI[2]: 10.1039/d4cc04194a.

审稿意见：

- I note that the content of the squeezed solvent has still notbeen added to the formula quoted. This must be estimated and added as itaffects follow on quantities e.g. density, molecular mass, F000, absorptioncoefficient etc.

- I appreciate this type of structure often requires restraints.However, the structure is still very heavily over restrained, with 1483restraints, many of which are very strong restraints and some are essentiallydoing similar things so both probably aren't needed. Please look at these togive more reasonable restraints.

- The I/sigma drops below 3 at around 2 theta = 42 degrees. Thisis not surprising given the type of structure, however, the data should ideallybe cut around this point. A vrf response will need to be added for theresultant CheckCif alert.

大意：

- 我注意到，挤掉的溶剂的含量尚未添加到引用的分子式中。这必须进行估算和添加，因为它会影响诸如密度、分子量、F000、吸收系数等后续量。

- 我理解这种结构通常需要限制。然而，该结构仍然严重过度限制，有1483个限制，其中许多是非常强的限制，有些基本上是在做相似的事情，所以可能不都需要。请检查这些，以提供更合理的限制。

- 信噪比在2θ = 42°左右降至3以下。对于此类结构这并不奇怪，但理想情况下该数据应将分辨率截断在此处。需要添加验证答复表来回应由此产生的CheckCIF警报。

该数据还原的时候分辨率截断在0.68Å（2θ = 63.4°），如图1所示（由Olex2[3]呈现），查看信噪比与分辨率之间的关系图（I/σ(I) vs. Resolution），确如审稿人所说，信噪比在2θ = 42°左右降至3以下。

▲图1 CCDC 2377155初始分辨率

该数据用SHELXL[4]指令SHEL（参阅推文“SHELXL指令之SHEL”）将分辨率截断在0.854 Å（2θ = 49.2°），另外用PLATON[5]程序SQUEEZE[6]做了溶剂挤出，但没有向CIF[7]中添加挤出的溶剂细节，如图2所示。

▲图2 分辨率截断和溶剂挤出

后经重新还原，将分辨率截断在0.99Å（2θ = 42.0°）（参阅推文“晶体数据审稿意见-分辨率应在何时截断”），如图3所示。

▲图3 重新还原截断分辨率结果

分辨率低触发了A级警报THETM01（参阅推文“CheckCIF-THETM01”），另外还有一个B级警报PLAT342（参阅推文“CheckCIF-PLAT342”），对于AB级警报，在CIF中添加验证回复表进行解释，如图4所示。

▲图4 对AB级警报的解释说明

重新处理的数据用Olex2中的Solvent Mask[8]做了溶剂遮掩，并在分子式中添加了遮掩的内容，如图5右侧所示。

▲图5 向分子中添加溶剂遮掩的内容

审稿意见回复如下：

Comments:

There is 1Structure in this paper. We examined this file: 2377155 Thank you for yourcomments and corrections. The recollected data look much better.

There are a fewmore minor issues to address with the refinement prior to publication.

Our answer: Thank you verymuch for your kind and insightful suggestions. We are truly grateful to thereferee for their thoughtful comments, which have significantly contributed toimproving the quality of our manuscript. We have carefully addressed all the refinementissues as recommended by the referee and therevised CIF file has been updated accordingly.

**Ti12TPA**(CCDC 2377155)

- I note thatthe content of the squeezed solvent has still not been added to the formulaquoted. This must be estimated and added as it affects follow on quantitiese.g. density, molecular mass, F000, absorption coefficient etc.

Our answer: Thanks a lotfor the valuable suggestion. We have now included the content of the squeezedsolvent, and the related crystallographic data andrefinement parameters have been updated in the revised Table S1.

- I appreciatethis type of structure often requires restraints. However, the structure isstill very heavily over restrained, with 1483 restraints, many of which arevery strong restraints and some are essentially doing similar things so bothprobably aren't needed. Please look at these to give more reasonablerestraints.

Our answer: Thanks a lotfor the valuable suggestion. Followingyour comments, we have reviewed and adjusted the restraints, removing some unnecessaryrefinements.

- The I/sigmadrops below 3 at around 2 theta = 42 degrees. This is not surprising given thetype of structure, however, the data should ideally be cut around this point. Avrf response will need to be added for the resultant CheckCif alert.

Our answer: Thanks a lotfor the valuable suggestion. As recommended, we have cut the data below anI/sigma of 3 and added a vrf response for the resulting CheckCif alert.

视频讲解请参阅：

晶体数据审稿意见-分辨率和溶剂遮掩(ChemCommun)：https://www.bilibili.com/video/BV1PR6bYcEtW

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参考文献

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[3]    Dolomanov, O. V.;Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H. OLEX2: A Complete Structure Solution,Refinement and Analysis Program. J. Appl. Cryst. 2009, 42, 339–341. DOI: 10.1107/S0021889808042726.

[4]    (a) Sheldrick, G. M. SHELXL-2019/3, Program for Crystal Structure Refinement, University of Göttingen,Germany, 2019. (b)Sheldrick, G. M. A Short History of SHELX.Acta Cryst. 2008, A64, 112–122. DOI:10.1107/S0108767307043930. (c) Sheldrick, G. M. Crystal Structure Refinement with SHELXL. Acta Cryst. 2015, C71, 3–8. DOI: 10.1107/S2053229614024218.(d) Lübben, J.; Wandtke, C. M.;Hübschle, C. B.; Ruf, M.; Sheldrick, G. M.; Dittrich, B. Aspherical ScatteringFactors for SHELXL – Model,Implementation and Application. ActaCryst. 2019, A75, 50–62. DOI:10.1107/S2053273318013840.

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[6]    Spek, A. L. PLATON SQUEEZE: A Tool for theCalculation of the Disordered Solvent Contribution to the Calculated StructureFactors. Acta Cryst. 2015, C71, 9–18. DOI:10.1107/S2053229614024929.

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