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Single crystals of Bi$_{2} $Rh$ _{3}$S$ _{2}$ and Bi$_{2} $Rh$ _{3.5}$S$_{2}$ were synthesized by solution growth and the crystal structures,thermodynamic and transport properties of both compounds were studied. In thecase of Bi$_{2} $Rh$ _{3}$S$ _{2}$, a structural first-order transition ataround 165 K is identified by single crystal diffraction experiments, withclear signatures visible in resistivity, magnetization and specific heat data.No superconducting transition for Bi$_{2} $Rh$ _{3}$S$ _{2}$ was observed downto 0.5 K. In contrast, no structural phase transition at high temperature wasobserved for Bi$_{2} $Rh$ _{3.5}$S$ _{2}$, however bulk superconductivity witha critical temperature, $T_{c}\approx$ 1.7 K was observed. The Sommerfeldcoefficient $\gamma$\ and the Debye temperature($\varTheta_{\textrm{D}}$) werefound to be 9.4 mJ mol$^{-1}$ K$^{-2}$ and 209 K respectively for Bi$_{2} $Rh$_{3}$S$ _{2}$, and 22 mJ mol$^{-1}$ K$^{-2}$ and 196 K respectively for Bi$_{2}$Rh$ _{3.5}$S$ _{2}$. Study of the specific heat in the superconducting stateof Bi$_{2} $Rh$ _{3.5}$S$ _{2}$ suggests that Bi$_{2} $Rh$ _{3.5}$S$ _{2}$ is aweakly coupled, BCS superconductor.

Superconductivity versus structural phase transition in the closely related Bi$_{2} $Rh$ _{3.5}$S$ _{2}$ and Bi$_{2} $Rh$ _{3}$S$ _{2}$