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

ABSTRACT: 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 MHyM^IICl₃ (M^II = 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.

SUBMITTER: Zienkiewicz JA 

PROVIDER: S-EPMC9865361 | biostudies-literature | 2023 Jan

REPOSITORIES: biostudies-literature