Conformations of Cycloalkylammonoium Ions in Crystal

制备了A_2MCl_6配合物（A=C_4H_8NH_2, C_5H_< 10bbb_nh_2, C_6H_< 12bbb_nh_2； M=Sn, Te, Pt），用单晶x射线衍射测定了它们在室温下的晶体结构。对（C_4H_8NH_2）_2MCl_6进行了^1H NMR、^<35>Cl NQR和热分析（DTA和DSC）。研究了C_4H_8NH_2^+离子的构象、正离子和阴离子的运动以及固-固相变的机理。热分析发现（C_5H_<10 bbb_nh_2）_2MCl_6和（C_6H_<12 bbb_nh_2）_2MCl_6存在固固转变，并对其温度和焓变进行了计算。对分离的C_4H_8NH_2^+、C_5H_<10>NH_2^+和C_6H_<12>NH_2^+离子进行了分子轨道计算（从头算和DFT-HF法）。测定了阳离子在稳定态和过渡态的构象及其电能。制备了（C_5H_<10>NH_2） PF_6、（C_4H_8NH_2） PF_6和（C_4H_8NH_2） ClO_4，并进行了^1H、^2H、^<19>F、^<31>P和^<35>Cl的NMR、x射线粉末衍射和热分析（DTA和DSC）。发现了固-固转变，并对其温度和焓变进行了计算。测定了C_5H_<10>NH_2^+和C_4H_8NH_2^+离子在固相中的运动态。制备了（C_4H_8NH_2O）（C_6HCl_2O_4），并在室温下用单晶x射线衍射测定了其晶体结构。C_4H_8NH_2O^+离子的构象和涉及N-H的氢键构型。O和O- h…测定了晶体中的O型氢键。

A_2MCl_6 complexes (A=C_4H_8NH_2, C_5H_<10>NH_2, C_6H_<12>NH_2 ; M=Sn, Te, Pt) were prepared and their crystal structures at room temperature were determined by single crystal X-ray diffraction. Measurements of ^1H NMR, ^<35>Cl NQR and thermal analysis (DTA and DSC) were made for (C_4H_8NH_2)_2MCl_6. The conformation of C_4H_8NH_2^+ ion, the motions of the cation and the anion, and the mechanism of the solid-solid phase transition were investigated. Solid-solid transitions were found in (C_5H_<10>NH_2)_2MCl_6 and (C_6H_<12>NH_2)_2MCl_6 from thermal analysis and their temperatures and enthalpy changes were evaluated.Molecular orbital calculations (ab initio and DFT-HF methods) were carried out for isolated C_4H_8NH_2^+, C_5H_<10>NH_2^+, and C_6H_<12>NH_2^+ ions. Conformations in stable and transition state and their electric energies were determined for the cations.(C_5H_<10>NH_2) PF_6, (C_4H_8NH_2) PF_6, and (C_4H_8NH_2) ClO_4 were prepared and measurements of ^1H, ^2H, ^<19>F, ^<31>P, and ^<35>Cl NMR, X-ray powder diffraction, and thermal analysis (DTA and DSC) were carried out. Solid-solid transitions were found and their temperatures and enthalpy changes were evaluated. Motional states of C_5H_<10>NH_2^+ and C_4H_8NH_2^+ ions in the solid phases were determined.(C_4H_8NH_2O)(C_6HCl_2O_4) was prepared and the crystal structure was determined at room temperature by single crystal X-ray diffraction. The conformation of C_4H_8NH_2O^+ ion and the hydrogen-bond scheme involving N-H...O and O-H...O type hydrogen bonds in the crystal were determined.