The application of a new solid-state NMR technique, total through-bond correlation spectroscopy, and of an improved scheme for total through-space correlation spectroscopy to structure determination in organic solids is explored. Both experimental techniques are employed under high-resolution conditions using magic-angle sample spinning (MAS). The results from a test sample (calcium acetate monohydrate) show that through-space and through-bond connectivities can be probed separately. The information contained in the two experiments is complementary and the combination of both results can lead to improved structure determination schemes in biomolecular and material-science applications.