Using glass crystallization and solid-state
techniques, we were
able to complete the family of salt-inclusion silver halide borates,
Ag4B7O12X, by the X = Cl and I members.
The new compounds are characterized by differential scanning calorimetry,
single-crystal and high-temperature powder X-ray diffraction, optical
spectroscopy, and density functional theory calculations. In all structures,
the silver atoms exhibit strong anharmonicity of thermal vibrations,
which could be modeled using Gram-Charlier expansion, and its asymmetry
was characterized by the skewness vector. The topology of the silver
halide and borate sublattices has been analyzed separately for the
first time. Along the I → Br → Cl series, we observe
a decrease of the melting point and configuration entropy and an increase
of thermal expansion and its anisotropy and thermal vibration anharmonicity,
which indicates decreasing stability.