Systematics in NH+···N-Bonded Monosalts of 4,4′-Bipyridine (44′biPy) with Mineral Acids
Systematics in NH+···N-Bonded Monosalts of 4,4′-Bipyridine (44′biPy) with Mineral Acids
复制标题
4,4′-联吡啶 (44′biPy) 与矿物酸的 NH+...N-键合单盐的系统学
DOI：
10.1021/cg400752y
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发表时间：
2013
影响因子：
3.8
通讯作者：
Grzegorz Stefański
中科院分区：
文献类型：
--
作者：
M. Ratajczak;A. Katrusiak;Z. Dega‐Szafran;Grzegorz Stefański
尽管4，4 ′-联吡啶（44′biPy）与无机酸HA = HCl、HBr、HI、HClO 4、HBF 4和H2SiF 6的NH+···N氢键盐的晶体对称性和堆积方式有很大不同，但它们的晶体结构在水合、阳离子聚集、扭曲构象和质子无序等方面具有相似性。所有单盐都已合成，在正常条件下，形成通式为[44′biPyH]+A-·xH 2 O（x = 0.5、1或2）和[44′biPyH]+2SiF62-·5 H2O的晶体。在结构中，44′biPyH+阳离子是NH+···N键合成线性链，并且在大多数[44′biPyH]+A-·xH 2 O晶体中质子是无序的，类似于各向异性弛豫剂1，4-二氮双环[2.2.2]辛烷氢碘酸盐和氢溴酸盐（分别为dabcoHI和dabcoHBr）。质子无序意味着中性44′biPy分子和[44′ biPyH 2]2+离子的点缺陷在所有这些结构中产生。在所有的[44′biPyH]+A-结构中，酸阴离子都是通过氢键与水分子结合。
Despite significantly different crystal symmetry and packing, the crystal structures of NH+···N hydrogen-bonded salts of 4,4′-bipyridine (44′biPy) with mineral acids HA = HCl, HBr, HI, HClO4, HBF4 and H2SiF6 exhibit close analogies in the hydration, aggregation of the cations and their twisted conformation, as well as proton disordering. All monosalts have been synthesized and, at normal conditions, form crystals of general formula [44′biPyH]+A–·xH2O (x = 0.5, 1, or 2), and [44′biPyH]+2SiF62–·5H2O. In the structures, the 44′biPyH+ cations are NH+···N bonded into linear chains, and in most [44′biPyH]+A–·xH2O crystals the protons are disordered, similarly as in anisotropic relaxors 1,4-diazabicyclo[2.2.2]octane hydroiodide and hydrobromide (dabcoHI and dabcoHBr, respectively). The proton disorder implies generation of point defects of neutral 44′biPy molecules and [44′biPyH2]2+ dications in all these structures. In all [44′biPyH]+A– structures investigated, the acid anions are hydrogen bonded to water molec...