Hybrid Chlorides with Methylhydrazinium Cation: [CH3NH2NH2]CdCl3 and Jahn-Teller Distorted [CH3NH2NH2]CuCl3.

The synthesis, structural, phonon, optical, and magnetic properties of two hybrid organic-inorganic chlorides with monoprotonated methylhydrazinium cations (CH3NH2NH2+, MHy+), [CH3NH2NH2]CdCl3 (MHyCdCl3), and [CH3NH2NH2]CuCl3 (MHyCuCl3), are reported. In contrast to previously reported MHyMIICl3 (MII = Mn2+, Ni2+, and Co2+) analogues, neither compound undergoes phase transitions. The MHyCuCl3 has a crystal structure familiar to previous crystals composed of edge-shared 1D chains of the [CuCl5N] octahedra. MHyCuCl3 crystallizes in monoclinic P21/c symmetry with MHy+ cations directly linked to the Cu2+ ions. The MHyCdCl3 analogue crystallizes in lower triclinic symmetry with zig-zag chains of the edge-shared [CdCl6] octahedra. The absence of phase transitions is investigated and discussed. It is connected with slightly stronger hydrogen bonding between cations and the copper-chloride chains in MHyCuCl3 due to the strong Jahn-Teller effect causing the octahedra to elongate, resulting in a better fit of cations in the accessible space between chains. The absence of structural transformation in MHyCdCl3 is due to intermolecular hydrogen bonding between two neighboring MHy+ cations, which has never been reported for MHy+-based hybrid halides. Optical investigations revealed that the bandgaps in Cu2+ and Cd2+ analogues are 2.62 and 5.57 eV, respectively. Magnetic tests indicated that MHyCuCl3 has smeared antiferromagnetic ordering at 4.8 K.