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★声明：本文仅代表个人观点，笔者学识有限，资料整理过程中可能存在疏漏错误，请不吝指正。 晶体结构不是预期结构案例26 案例76： 本来是按照如图76所示（由ChemBioDraw [1]绘制），以4,4-二溴二苯甲酮[2]（4,4'-dibromobenzophenone, CAS: 3988-03-2, CCDC [3]: 2542222）和二苯基氧膦 [4]（diphenylphosphineoxide, CAS: 4559-70-0, CCDC: 936826）为底物，在催化剂作用下一定条件下反应，以期得到催化产物，然而分离物结晶后，经单晶X射线衍射实验（SC-XRD,single-crystal X-ray diffraction）得到晶体数据，经结构解析发现为原料4,4-二溴二苯甲酮，显然，要么在该催化剂和反应条件下二者未发生反应，或者分离纯化未收集到催化产物，或者后处理时催化产物分解。
▲图76 案例76反应示意图 相关视频： 单晶结构解析练习760(数据还原-非预期结构-空间群)：https://www.bilibili.com/video/BV1UN9cB7EpJ 案例77： 本来是按照如图77所示，利用含羧基的醇和某二溴化合物以化学计量比2:1反应，以期得到两个醚基连接的而羧酸钠产物，然而经后处理，结晶，SC-XRD得到晶体数据，经结构解析发现是碳酸钠一水合物（Na2CO3·H2O,CAS: 5968-11-6, CCDC: 2542403），可能是**（NaOH, Sodiumhydroxide, CAS: 1310-73-2）和二氧化碳（CO2,Carbon dioxide, CAS: 124-38-9）反应得到的。
▲图77 案例77反应示意图 相关视频： 单晶结构解析练习761(数据还原-非预期结构)：https://www.bilibili.com/video/BV1vUSDBxEF4 案例78： 本来是按照如图78所示，利用醋酸镍（Ni(OAc)2,Nickelous acetate, CAS: 373-02-4）和某配体在N,N-二甲基甲酰胺[5]（DMF, N,N-dimethylformamide, CAS: 68-12-2,CCDC: 102756 [5a], 1869635–1869638 [5b], 1869744–1869752[5b]）、水 [6]（H2O,water, CAS: 7732-18-5, CCDC: 2080050–2080051）和盐酸作反应溶剂在一定条件下反应，以期得到含该配体的镍配合物，然而经后处理，结晶，SC-XRD得到晶体数据，经结构解析发现得到的晶体结构为[Ni(HCO2)3]n·n(CH3NH2CH3)，显然，结构中的甲酸根阴离子和二甲胺阳离子来自于DMF的分解（参阅推文“DMF和DEF会为晶体结构带来什么”）。
▲图78 案例78反应示意图 相关视频： 单晶结构解析练习774(非预期结构-特殊无序)：https://www.bilibili.com/video/BV1sCLQ6fEA4 参考文献 [1] (a)Klein, F. M. CS ChemDraw Pro,1 Version 3.1 for Windows. J. Chem. Inf. Comput. Sci. 1995, 35, 166–167. DOI: 10.1021/ci00023a026. (b)Cousins, K. R. ChemDraw 6.0 Ultra CambridgeSoft Corporation, 100 Cambridge ParkDrive, Cambridge, MA 02140. http://www.camsoft.com. Commercial Price: $1395.Academic Price: $699. J. Am. Chem. Soc. 2000, 122, 10257–10258. DOI: 10.1021/ja0047572.(c) Buntrock, R. E. ChemOffice Ultra 7.0. J. Chem. Inf. Comput. Sci. 2002, 42, 1505–1506. DOI: 10.1021/ci025575p. (d) Li, Z.; Wan, H.; Shi, Y.;Ouyang, P. Personal Experience with Four Kinds of Chemical Structure DrawingSoftware: Review on ChemDraw, ChemWindow, ISIS/Draw, and ChemSketch. J. Chem. Inf. Comput. Sci. 2004, 44, 1886–1890. DOI: 10.1021/ci049794h.(e) Mendelsohn, L. D. ChemDraw8 Ultra, Windows and Macintosh Versions. J. Chem. Inf. Comput. Sci. 2004, 44, 2225–2226. DOI: 10.1021/ci040123t. (f) Cousins, K. R. ChemDrawUltra 9.0. CambridgeSoft, 100 CambridgePark Drive, Cambridge, MA 02140. www.cambridgesoft.com. See Web site for pricing options. J. Am. Chem. Soc. 2005, 127, 4115–4116. DOI:10.1021/ja0410237. (g) Zielesny, A. Chemistry Software PackageChemOffice Ultra 2005. J. Chem. Inf.Model. 2005, 45, 1474–1477. DOI:10.1021/ci050273j. (h) Mills, N. ChemDraw Ultra 10.0 CambridgeSoft, 100CambridgePark Drive, Cambridge, MA 02140. www.cambridgesoft.com. CommercialPrice: $1910 for download, $2150 for CD-ROM; Academic Price: $710 fordownload, $800 for CD-ROM. J. Am. Chem. Soc. 2006, 128, 13649–13650. DOI: 10.1021/ja0697875. (i) Kerwin, S. M.ChemBioOffice Ultra 2010 Suite. J. Am. Chem. Soc. 2010, 132, 2466–2467. DOI: 10.1021/ja1005306. (j) Milne, G. W. A. SoftwareReview of ChemBioDraw 12.0. J. Chem. Inf.Model. 2010, 50, 2053. DOI:10.1021/ci100385n. (k) Narayanaswamy, V. K.; Rissdörfer, M.; Odhav, B.Review on CambridgeSoft ChemBioDraw Ultra 13.0v. Int. J. Theor. Appl. Sci. 2013, 5, 43–49. [2] Peric, B.; Kojic-Prodic, B. 4,4'-Dibromobenzophenoneat 293 and 103 K. ActaCryst. 2000, C56, 211–212. DOI: 10.1107/S0108270199013839. [3] (a)Allen, F. H. The Cambridge Structural Database: A Quarter of a Million CrystalStructures and Rising. Acta Cryst. 2002, B58, 380–388. DOI:10.1107/S0108768102003890. (b) Groom, C. R.; Bruno, I. J.; Lightfoot, M.P.; Ward, S. C. The Cambridge Structural Database. Acta Cryst. 2016, B72, 171–179. DOI:10.1107/S2052520616003954. (c) Mitchell, J.; Robertson, J. H.; Raithby,P. R. Cambridge Crystallographic Data Centre (CCDC). Comprehensive Coordination Chemistry III 2021, 413–437. DOI: 10.1016/B978-0-12-409547-2.14829-2. [4] Härling, S.; Greiser, J.; Al-Shboul, T. M. A.;Görls, H.; Krieck, S.; Westerhausen, M. Calcium-Mediated Hydrophosphorylationof Organic Isocyanates with Diphenylphosphane Oxide. Aust. J. Chem. 2013, 66, 1264–1273. DOI: 10.1071/CH13259. [5] (a) Borrmann, H.; Persson, I.;Sandström, M.; Stålhandske, C. M. V. The Crystal and Liquid Structures of N,N-Dimethylthioformamideand N,N-Dimethylformamide Showing a Stronger Hydrogen BondingEffect for C–H⋯S than of C–H⋯O. J. Chem. Soc. Perkin Trans. 2 2000,393–402. DOI: 10.1039/a904531g. (b) Ratajczyk, P.; Sobczak, S.;Katrusiak, A. High-Pressure Structure and Properties of N,N-Dimethylformamide(DMF). Cryst. Growth Des. 2019, 19, 896–901. DOI: 10.1021/acs.cgd.8b01452. [6] Salzmann, C. G., Loveday, J. S., Rosu-Finsen, A.;Bull, C. L. Structure and nature of ice XIX. Nat. Commun. 2021, 12, 3162. DOI: 10.1038/s41467-021-23399-z.
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