Xenon trioxide (XeO₃), a highly shock-sensitive detonator, forms adducts with the N-bases, pyridine and 4-dimethylaminopyridine (4-DMAP). The reactions of pyridine and 4-DMAP with XeO₃ in rigorously dried CH₃CN and in CH₃CN that had not been dried yielded (C₅H₅N)₃XeO₃ (1) and (4-(CH₃)₂NC₅H₅N)₃ XeO₃·H₂O (3), respectively, whereas their reactions in HF-acidified CH₃CN yielded [C₅H₅NH]₄[HF₂]₂[F]₂(XeO₃)₂ (2) and [4-(CH₃)₂NC₅H₄NH][HF₂]XeO₃ (4). Crystalline (1), (2), and (4) failed to detonate when subjected to mechanical shock; however, (3) was significantly more sensitive to mechanical or thermal shock than XeO₃. The adducts and their pyridinium salts were structurally characterized by low-temperature, single-crystal X-ray diffraction, and Raman spectroscopy. The crystal structures of (1) and (3) consist of XeO₃ molecules that are N-coordinated to three pyridine and 4-DMAP ligands, respectively. A water molecule is also H-bonded to two oxygen atoms of two adjacent XeO₃ molecules of (3). The pyridinium cations of (2) and (4) are H-bonded to [F]⁻ and/or [HF₂]⁻ ions which are, in turn, F-coordinated to XeO₃. Both [F]⁻ ions of (2) bridge two XeO₃ molecules to form Xe₂F₂-rings. Each [HF₂]⁻ anion of (4) bridges two cations and two XeO₃ molecules by means of Xe⋯F secondary bonds and N(H)⋯F H-bonds. Quantum-chemical calculations for (1) and (2) provided energy-minimized geometries and calculated vibrational frequencies and intensities which were used to aid in the assignments of their Raman spectra. The NBO analyses showed the Xe⋯N, Xe⋯O, and Xe⋯F secondary bonding interactions are electrostatic in nature and may be described as σ-hole bonds.

高度震动敏感的雷管三氧化氙（XeO ₃）与N基，吡啶和4-二甲基氨基吡啶（4-DMAP）形成加合物。吡啶和4-DMAP与XEO的反应₃中严格干燥CH ₃ CN和CH中₃ CN尚未被干燥，得到（C ₅ H ^ ₅ N）₃ XEO ₃ （1）和（4-（CH ₃）₂ NC ₅ H ₅ N）₃ XeO ₃ ·H ₂ O （3），而它们在HF酸化的CH _3中的反应CN生成[C ₅ H ₅ NH] ₄ [HF ₂ ] ₂ [F] ₂（XeO ₃）₂ （2）和[4-（CH ₃）₂ NC ₅ H ₄ NH] [HF ₂ ] XeO ₃ （4 ）。晶体（1），（2）和（4）在遭受机械冲击时无法引爆；但是，（3）比XeO ₃对机械或热冲击的敏感性要高得多。。通过低温，单晶X射线衍射和拉曼光谱对加合物及其吡啶鎓盐进行结构表征。（1）和（3）的晶体结构由分别与三个吡啶和4-DMAP配体N配位的XeO ₃分子组成。水分子还与（3）的两个相邻XeO ₃分子的两个氧原子H键合。（2）和（4）的吡啶鎓阳离子H键合至[F] ^-和/或[HF ₂ ] ^-离子，这些离子又F-配位至XeO ₃。两者[F] ^-（2）的离子桥接两个XeO ₃分子以形成Xe ₂ F _2-环。（4）的每个[HF ₂ ] ^-阴离子通过Xe⋯F次级键和N（H）⋯F H键桥接两个阳离子和两个XeO ₃分子。（1）和（2）的量子化学计算提供了能量最小的几何形状，并计算了振动频率和强度，以帮助分配其拉曼光谱。NBO分析表明，Xe⋯N，Xe⋯O和Xe⋯F二级键相互作用本质上是静电的，可以描述为σ-空穴键。