Diamondoid framework solid with Sn(OCH₃)₂-tetrapyridylporphyrin linkers, Cu^I nodes and [Cu^ICl₂]^- counter-ions

We report on the synthesis of a new metal-organic framework (MOF) composed of Sn(OCH₃)₂-tetrakis(pyridin-4-yl)porphyrin linkers, Cu⁺ connecting nodes and [CuCl₂]^- counter-ions, namely poly[[bis(methanolato-κO)[μ₅-5,10,15,20-tetrakis(pyridin-4-yl)porphyrin-κ⁸1κN ⁵:1′κN ¹⁰:1′′κN ¹⁵:1′′′κN ²⁰:2κ⁴ N ²¹,N ²²,N ²³,N ²⁴]copper(I)tin(II)] dichloridocuprate(I)], [CuSn(C₄₀H₂₄N₈)(CH₃O)₂][CuCl₂]. Its crystal structure consists of a single-framework coordination polymer of the organic ligand and the Cu^I ions. The latter are characterized by a tetrahedral coordination geometry [with CN (coordination number) = 4], linking to the pyridyl N-atom sites of four different ligands and imparting to the positively charged polymeric assembly a diamondoid PtS-type topology. Correspondingly, every porphyrin unit is coordinated to four different Cu^I connectors. The [CuCl₂]^- anions occupy the intra-lattice voids, along with disordered molecules of the water crystallization solvent. The asymmetric unit of this structure consists of two halves of the porphyrin scaffold, located on centres of crystallographic inversion, and the Cu⁺ and [CuCl₂]^- ions. This report provides unique structural evidence for the formation of tetrapyridylporphyrin-based three-dimensional MOFs with a diamondoid architecture that have been observed earlier only on rare occasions.