Structural classification of metal complexes with three-coordinate centresElectronic supplementary information (ESI) available: Experimental procedures, crystal data, other characterization data, details of CSD search, further discussion of triangle and pyramid metrics, interactive spreadsheet with classification system. CCDC 1400747 for 1 and 1400748 for 2. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5dt02773j

• Main Authors: Davis, Timothy L, Watts, Joshua L, Brown, Kenneth J, Hewage, Jeewantha S, Treleven, Alexander R, Lindeman, Sergey V, Gardinier, James R
• Format: Article
• Language: English
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c5dt02773j

Attempts to describe the geometry about three-coordinate silver( i ) complexes have proven difficult because interatomic angles generally vary wildly and there is no adequate or readily available classification system found in the literature. A search of the Cambridge Structural Database shows that complexes formed between any metal centre and three non-metal donors (18 001 examples) usually adopt geometries that are quite different than ideal 'textbook' extremes of either trigonal planar (∼4% with α = β = γ = 120 ± 2°), T-shaped (∼0.05% with α = 180 ± 2°, β = γ = 90 ± 2°), or trigonal pyramidal (∼0.3% with α = β = γ = 110 ± 2°). Moreover, there are multiple variations of "Y-type" and "other" shapes that require elaboration. Thus, to assist in future structural descriptions, we developed a classification system that spans all known and yet-to-be-discovered three-coordinate geometries. A spreadsheet has also been constructed that utilizes the "shape-space" approach to extract the structural description from a user input of three angles about a tri-coordinate centre and the number of atoms in a plane. The structures of two silver( i ) complexes of new N-donor ligands p -NH 2 C 6 H 4 C 6 H 4 CH(pz = pyrazol-1-yl) 2 , L1 , and 2-ferrocenyl-4,5-di(2-pyridyl)imidazole, L2 , illustrate the utility of this classification system. A classification system was developed to account for all known and yet-to-be-discovered three-coordinate geometries.