2-(吡啶-2-氨基)吡啶三氟甲磺酸盐的晶体结构

IF 0.1 Q4 CRYSTALLOGRAPHY
Mari Toyama, Noriharu Nagao
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引用次数: 0

摘要

化合物2-(吡啶-2-基氨基)吡啶,称为二-2吡啶胺(Hdpa),已被广泛用作与各种过渡金属离子的双齿配体。J.E.Jonson、T.a.Beineke和R.a.Jacobson于1971.1报道了与Hdpa配体的配合物的第一个晶体结构,即Cu(II)-Hdpa配合物[Cu(Hdpa)2](ClO4)2。然后,他们还确定了未配位的Hdpa的晶体结构。2到目前为止,许多化学家已经揭示了与Hdpa的过渡金属配合物的许多晶体结构,1,3,4和一些不配位Hdpa的晶体多态性。5,6此外,据报道,含有质子化Hdpa阳离子H2dpa,2-(吡啶-2-基氨基)吡啶鎓的化合物的晶体结构约为80种,如F.a.Cotton及其同事1998年的(H2dpa)2[CoCl4]和B.Schmitt及其同事2011年的(H2dpa)(NCS)·CH3CN,7以及我们所知。我们测定了2-(吡啶-2-基氨基)吡啶鎓三氟甲磺酸盐H2dpa(OTf)(OTf–=CF3O3,图1)的晶体结构。H2dpa(OTf)的单晶由顺式-[Co(CO3)(Hdpa)2]的水溶液在过量(HOTf)aq存在下的热反应获得。尽管我们预计该反应会产生顺式-[Co(Hdpa)2(OH2)2](OTf)3,但发生了意外的分解反应,产生了游离的Hdpa,其中与过量HOTf的反应产生了H2dpa(OTf)。通过使反应混合物在减压下蒸发,获得了适用于X射线晶体学的H2dpa(OTf)的无色晶体。H2dpa(OTf)的晶体也由Hdpa的乙醇溶液与HOTf在278K下的混合物在不搅拌几天的情况下获得。在Rigaku Mercury70衍射仪上使用石墨单色MoKα辐射在173K下进行X射线晶体学。该结构通过直接方法(SIR2014)求解,并通过全矩阵最小二乘法对所有非氢原子的各向异性热参数进行细化。氨基的C–H氢原子和N–H氢分子位于差分傅立叶图中,并对它们的坐标和各向同性热参数进行了细化。与N2和N3相关的H7a和H7b氢原子,2021©日本分析化学学会
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Crystal Structure of 2-(Pyridin-2-ylamino)pyridinium Trifluoromethanesulfonate
The compound 2-(pyridin-2-ylamino)pyridine, known as di-2pyridylamine (Hdpa), has been widely used as a bidentate ligand with various transition metal ions. The first crystal structure of a complex with the Hdpa ligand, which was a Cu(II)-Hdpa complex, [Cu(Hdpa)2](ClO4)2, was reported by J. E. Jonson, T. A. Beineke, and R. A. Jacobson in 1971.1 They then also determined the crystal structure of uncoordinated Hdpa.2 Up to now many chemists have revealed many crystal structures of transition metal complexes with Hdpa,1,3,4 and a few crystal polymorphisms of uncoordinated Hdpa.5,6 Moreover, about eighty crystal structures of compounds containing a protonated Hdpa cation, H2dpa, 2-(pyridin-2-ylamino)pyridinium, are reported, such as (H2dpa)2[CoCl4] by F. A. Cotton and co-workers in 1998,3 and (H2dpa)(NCS)·CH3CN by B. Schmitt and co-workers in 2011,7 as well as we know. We determined the crystal structure of a 2-(pyridin-2-ylamino)pyridinium trifluoromethanesulfonate, H2dpa(OTf ) (OTf– = CF3SO3, Fig. 1). Single crystals of H2dpa(OTf ) were obtained from a thermal reaction of an aqueous solution of cis-[Co(CO3)(Hdpa)2](OTf ) in the presence of an excess amount of (HOTf )aq. Although we expected the reaction to afford cis-[Co(Hdpa)2(OH2)2](OTf )3, an unexpected decomposition reaction occurred to afford free Hdpa, of which the reaction with excess HOTf afforded H2dpa(OTf ). Colorless crystals of H2dpa(OTf ) suitable for X-ray crystallography were obtained by allowing the reaction mixture to evaporate under reduce pressure. The crystals of H2dpa(OTf ) were also obtained from the mixture of an ethanol solution of Hdpa with HOTf at 278 K without stirring for several days. X-ray crystallography was performed at 173 K on a Rigaku Mercury70 diffractometer using graphite-monochromated MoKα radiation. The structure was solved by direct methods (SIR2014), and refined by full-matrix least-squares techniques with anisotropic thermal parameters for all non-hydrogen atoms. The C–H hydrogen atoms and the N–H hydrogen atom of an amino group were located in the difference Fourier map, and their coordinate and isotropic thermal parameters were refined. The H7a and H7b hydrogen atoms associated with N2 and N3, 2021 © The Japan Society for Analytical Chemistry
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