The coordination geometry of the tetrapyridine-copper(II) complex in frozen solution is investigated by proton and deuterium two-dimensional hyperfine sublevel correlation spectroscopy (HYSCORE) electron spin resonance experiments. In particular, the deuterium experiment demonstrates the potential of this method, which lies in the superior spectral resolution of the two-dimensional spectra. This allows us to resolve deuterium nuclear quadrupole splittings of the cross peak ridges even in orientationally disordered systems, which in turn yield structural information about the overall complex symmetry. Proton and deuterium experiments show pronounced cross peak ridges from protons and deuteriums at the C2 and C6 carbon atoms of the pyridine molecule. The coordination geometry within the complexes could be deduced from orientation-selective deuterium spectra. Severe deviations from the D-4h complex symmetry were found in such a way that the pyridine molecules are arranged with their molecular mirror plane perpendicular to the complex plane. The complex geometry experiences a significant variance with respect to the Cu-N bond directions due to random spatial constraints induced by solvent molecules.