Pentabismuth(3+) tetrachlorogallate(III), (Bi-5(3+))(GaCL(4)(-))(3), has been synthesized by reducing a BiCl3-GaCl3 melt with bismuth metal and the crystal structure refined from X-ray (Cu K alpha(1)) powder diffraction data. The structure was found to belong to space group R-3c, with the lattice parameters a = 11:871(2) Angstrom and c = 30.101(3) Angstrom (Z 6). It is isostructural with the previously characterized Bi-5(AlCl4)(3). An attempt to synthesise the antimony analogue Sb-5(GaCl4)(3) by reducing a SbCl3-GaCl3 mixture with gallium metal produced a black solid phase. The gallium content of this phase is consistent with the stoichiometry Sb-5(GaCl4)3, and the Raman spectrum of the phase dissolved in SbCl3-GaCl3 comprises strong, low-frequency bands attributable to Sb-Sb stretch vibrations in Sb-5(3+) or another reduced antimony species. Quantum chemical analyses have been performed for the isoelectronic, trigonal pyramidal close-clusters Sn-5(2-), Sb-5(3+), Tl-5(7-), Pb-5(2-), and Bi-5(3+), bath with extended Huckel (eH) and Hartree-Fock (I IF) methods. The HF calculations were performed with and without corrections for the local electron-electron correlation using second-order Moller-Plesset perturbation theory (MP2). All theoretical results are compared and evaluted with respect to experimental cluster structures and vibrational frequencies. The results from the calculations agree well with available experimental data for the solid-state structures and vibrational spectra of these cluster ions, except for the Tl-5(7-) ion. Isolated Tl-5(7-) is suggested to be electronically unstable because of the high charge density. The Sb-5(3+) cluster ion is indicated to be stable. According to the calculations, Sn-5(2-) and Pb-5(2-) may be described in terms of edge-localized bonds without substantial electron density between the equatorial atoms, whereas Sb-5(3+) and Bi-5(3+) have electron density evenly distributed over all M-M vectors. Furthermore, the theoretical results give no support for a D-3h --> C-4v fluxionality of these clusters.