It remains a challenge to establish structural models of multicomponent oxide glass systems. In this study, we have investigated 68.3SiO(2)-16.1B(2)O(3)-4.2Al(2)O(3)-11.4Na(2)O glass and melt structures by abinitio molecular dynamics (AIMD) simulations. The atomic configurations obtained from AIMD simulations were validated against O-17 solid-state NMR spectrum under 24.0 T and neutron diffraction data, and excellent agreement was achieved. The bond lengths, angles, and coordination geometries were statistically analyzed for each atomic species. Here we particularly address the role of minor atomic species such as five-coordinate Si (Si-V) and Al (Al-V). The Si-V-O bond lengths and O-Si-V-O angle distribution in the glass indicated 1.718 angstrom and three peaks at 90 degrees, 120 degrees, and 175 degrees, which are assigned to a coordination geometry of the trigonal bipyramidal structure. Ring statistic analysis revealed that Si-V and Al-V were found to preferentially contribute to the formation of small ring sizes.