The first phospho­ramide-mercury(II) complex with a Cl₂Hg-OP[N(C)(C)]₃ segment

Mercury(II) exhibits a strong preference for linear coordination which has been attributed to relativistic effects splitting the 6p orbitals and promoting sp hybridization. If the two ligands attached to the mercury(II) ion are weak donors, the metal ion can act as a good Lewis acid and expand its coordination number. Moreover, mercury has a special affinity for softer bases, such as S and N atoms, and has much less affinity for hard bases, such as those including an O atom. The asymmetric unit of di­chlorido­[tris­(piperidin-1-yl)phos­phane oxide- ΚO]mercury(II)-di­chlorido­ mercury(II) (2/1), [HgCl₂{(C₅H₁₀N)₃PO}]₂·[HgCl₂], is composed of one HgCl₂{(C₅H₁₀N)₃PO} complex and one half of a discrete HgCl₂ entity located on an inversion centre. The coordination environment around the HgII centre in the complex component is a distorted T-shape. Bond- valence-sum calculations confirm the three-coordination mode of the HgII atom of the complex mol­ ecule. The noncovalent nature of the Hg...Cl and Hg...O inter­actions in the structure are discussed

The non-coordinating anion 1,1,3,3-tetracyano-2-propoxy-propenide as an anion-pi donor in cis-diaquabis(2,2 '-dipyridylamine)zinc and its cadmium analog: Luminescence properties, Hirshfeld analysis and central-atom induced polymorphism

Metals in Catalysis, Biomimetics & Inorganic Material

The synergistic cooperation of NH⋯O and CH⋯O hydrogen bonds in the structures of three new phosphoric triamides

<p>The supramolecular assemblies of three new phosphoric triamides, {(C₆H₅CH₂)(CH₃)N}₂(4-CH₃-C₆H₄C(O)NH)P(O) (<b>1</b>), {(C₆H₁₁)(CH₃)N}₂(4-CH₃-C₆H₄C(O)NH)P(O) (<b>2</b>) and {(C₂H₅)₂N}₂(4-CH₃-C₆H₄C(O)NH)P(O) (<b>3</b>) were studied by single crystal X-ray diffraction as well as by Hirshfeld surface analysis. It was found that a synergistic cooperation of NH⋯O and CH⋯O hydrogen bonds occurs in all three structures, but forming unique supramolecular architectures individually. Along with the presence of centrosymmetric dimers in <b>1, 2</b> and <b>3</b>, based on a classical NH⋯O hydrogen bond, the presence of weak CH⋯O interactions play an additional and vital role in crystal architecture and construction of the final assemblies, collectively identified as a centrosymmetric dimer (0D), a 1-D array and a 3-D network, respectively. These differences in superstructures are related to the effect of aromatic, bulk and flexible groups used in the molecules designed, with a similar C(O)NHP(O) backbone. The NH⋯O contacts in <b>1, 2</b> and <b>3</b> are of the “resonance-assisted hydrogen bond” types and also the <i>anti</i>-cooperativity effect can be considered in the multi-acceptor sites P═O in <b>1</b> and <b>2</b> and C═O in <b>3</b>. All three compounds were further studied by 1D NMR experiments, 2D NMR techniques (HMQC and HMBC (H–C correlation)), high resolution ESI–MS, EI–MS spectrometry and IR spectroscopy methods.</p

Puckering behavior in six new phosphoric triamides containing aliphatic six- and seven-membered ring groups and a database survey of analogous ring-containing structures

The influence of a N heteroatom on the ring conformations of six- and seven- membered aliphatic rings in six new C(O)NHP(O)-based phosphoric triamide structures (analysed by X-ray crystallography) is investigated. Additionally the influence of steric and crystal packing effects is also studied by the analysis of Hirshfeld surfaces. The results are compared to analogous structures with three- to seven- aliphatic membered rings deposited in the Cambridge Structural Database. In the newly determined structures, the six-membered rings only show the near-chair conformation with a maximum deviation of the θ puckering parameter of 4.4° from the ideal chair value of 0°/180°, while the seven-membered rings are found in different conformations such as near-chair, twist chair and twist sofa