Metal-oxo clusters can serve as directional and rigid building units of coordination and noncovalent supramolecular assemblies. Therefore, an in-depth understanding of their multi-faceted chemistry is vital for the development of self-assembled solid-state structures of desired properties. Here we present a comprehensive comparative structural analysis of isostructural benzoate, benzamidate, and new benzamidinate zinc-oxo clusters incorporating the [O,O]-, [O,NH]- and [NH,NH]-anchoring donor centers, respectively. We demonstrated that the NH groups in the proximal secondary coordination sphere are prone to the formation of intermolecular hydrogen bonds, which affects the packing of clusters in the crystal structure. Coordination sphere engineering can lead to the rational design of new catalytic sites and novel molecular building units of supramolecular assemblies.

金属-氧簇可以作为配位和非共价超分子组装的定向和刚性构建单元。因此，深入了解它们的多方面化学对于开发具有所需特性的自组装固态结构至关重要。在这里，我们对分别包含 [O,O]-、[O,NH]- 和 [NH,NH]-锚定供体中心的同构苯甲酸盐、苯甲酰胺酸盐和新的苯甲脒锌氧簇进行了全面的比较结构分析。我们证明了近端二级配位球中的 NH 基团易于形成分子间氢键，这会影响晶体结构中簇的堆积。