Conformations of Cycloalkylammonoium Ions in Crystal

合成了A_2MCl6配合物(A=C_4H_8NH_2，C_5H_&lt；10&gt；NH_2，C_6H_&lt；12&gt；NH_2；M=锡，Te，铂)，并用单晶X射线衍射法测定了它们的室温晶体结构。对(C_4H_8NH_2)_2MCl6进行了~1H核磁共振、~(35&t；35)&gt；Cl~(NQR)和热分析(DTA和DSC)测定，研究了C_4H_8NH_2~+离子的构象、阳离子和阴离子的运动以及固-固相变机理。用热分析方法研究了(C5H&lt；10&gt；NH_2)_2MCl6和(C6H_&lt；12&gt；NH_2)_2MCl6的固-固相变，计算了它们的温度和热变。测定了(C_5H_&lt；10&gt；NH_2)PF_6、(C_4H_8NH_2)PF_6和(C_4H_8NH_2)ClO_4的稳定和过渡态构象及其电能量，并测定了它们的^1H，^2H，^&lt；19&gt；F，^&lt；31&gt；P和^&lt；35&gt；Cl的核磁共振、X-射线粉末衍射和热分析(DTA和DSC)。发现了固-固相变，并估算了它们的温度和热焓变化。测定了C5H&lt；10&Gt，NH_2~+和C_4H_8NH_2~+离子在固相中的运动状态，制备了(C_4H_8NH_2O)(C_6HCl_2O_4)，并用单晶X射线衍射法测定了其室温晶体结构。确定了C_4H_8NH_2O~+离子的构象和晶体中N-H…O和O-H…O型氢键的氢键方案。

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.