The crystalline sponge method updated.
The crystalline sponge method updated.
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DOI：
10.1107/s2052252515024379
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发表时间：
2016-03-01
期刊：
影响因子：
3.9
通讯作者：
Fujita M
中科院分区：
文献类型：
--
作者：
Hoshino M;Khutia A;Xing H;Inokuma Y;Fujita M
结晶海绵方法的协议，特别是那些在浸泡，数据收集和细化过程中，大大改善，以提供可靠的结构信息。结晶海绵是多孔金属复合物，可以在其孔隙中吸收和定向常见的有机分子，并使其通过常规X射线结构分析（结晶海绵法）可观察到。在这项研究中，结晶海绵方法中的所有步骤，包括海绵晶体制备，孔-溶剂交换，客体浸泡，数据收集和晶体学分析，都经过仔细检查和彻底优化，以提供可靠和有意义的化学信息作为化学晶体学。主要改进的方法已在客人浸泡和数据收集步骤。在浸泡步骤中，获得客体的高占位率是特别重要的，因此必须针对每种样品化合物优化客体浸泡的主要参数（例如温度、时间、浓度、溶剂）。当标准条件不起作用时，高通量方法可用于有效优化浸泡条件。X射线实验也被仔细地重新检查。通过在高角度区域进行完整的数据收集，实现了客户数据质量的显著提高。对主体框架中最灵活的ZnI 2部分进行适当的无序处理以及填充剩余空隙的溶剂的细化对于获得更好的数据质量也特别重要。一个基准测试的结晶海绵方法对非手性分子提出了一个愈创木蓝客体，其中的客体结构（与100%的网站占有率）进行了改进，而不施加任何约束或限制。 得到的数据质量与Rint = 0.0279和R1 = 0.0379是目前的常规晶体分析的小分子。另一个基准测试，这种方法对手性分子也提出了与山道宁客人。获得的晶体学数据[R int = 0.0421，R 1 = 0.0312，Flack（Parsons）= −0.0071（11）]代表了该方法用于可靠的绝对结构测定的潜在能力。
The protocols of the crystalline sponge method, particularly those in the soaking, data collection and refinement processes, are considerably improved to give reliable structural information. Crystalline sponges are porous metal complexes that can absorb and orient common organic molecules in their pores and make them observable by conventional X-ray structure analysis (crystalline sponge method). In this study, all of the steps in the crystalline sponge method, including sponge crystal preparation, pore–solvent exchange, guest soaking, data collection and crystallographic analysis, are carefully examined and thoroughly optimized to provide reliable and meaningful chemical information as chemical crystallography. Major improvements in the method have been made in the guest-soaking and data-collection steps. In the soaking step, obtaining a high site occupancy of the guest is particularly important, and dominant parameters for guest soaking (e.g. temperature, time, concentration, solvents) therefore have to be optimized for every sample compound. When standard conditions do not work, a high-throughput method is useful for efficiently optimizing the soaking conditions. The X-ray experiments are also carefully re-examined. Significant improvement of the guest data quality is achieved by complete data collection at high angle regions. The appropriate disorder treatment of the most flexible ZnI2 portions of the host framework and refinement of the solvents filling the remaining void are also particularly important for obtaining better data quality. A benchmark test for the crystalline sponge method toward an achiral molecule is proposed with a guaiazulene guest, in which the guest structure (with ∼ 100% site occupancy) is refined without applying any restraints or constraints. The obtained data quality with R int = 0.0279 and R 1 = 0.0379 is comparable with that of current conventional crystallographic analysis for small molecules. Another benchmark test for this method toward a chiral molecule is also proposed with a santonin guest. The crystallographic data obtained [R int = 0.0421, R 1 = 0.0312, Flack (Parsons) = −0.0071 (11)] represents the potential ability of this method for reliable absolute structure determination.