Dataset Information

The importance of tetrel bonding interactions with carbon in two arrestive iso-structural Cd(ii)-Salen coordination complexes: a comprehensive DFT overview in crystal engineering.

ABSTRACT: In this article, we describe the serendipitous synthesis of two remarkable iso-structural Cd(ii)-Salen complexes [L₂Cd₄(OAc)₂(NCS)₂] in the presence of H₂L and NaSCN {where L = L¹ (N,N'-bis(3-methoxysalicylidene)-1,2-diaminopropane) and L = L² (N,N'-bis(3-methoxysalicylidene)-ethylenediamine) in 1 and 2, respectively}. The complexes were characterized by using elemental analysis, SEM-EDX, PXRD, spectroscopy, and X-ray crystallography. The X-ray crystal structure revealed that both complexes crystallize in the orthorhombic space group Pbcn, with unit cell parameters: a = 20.758(6), b = 11.022(3), c = 21.396(6) Å, V = 4895(2) Å³, and Z = 4. The inner N₂O₂ and outer O₄ compartments are essentially occupied by two different Cd(ii) metal ions resulting from the de-protonated form of the ligand (L^2-) with the Cd(1) metal ions adopting a capped octahedral geometry. At the same time, Cd(2) assumes a distorted trigonal prismatic geometry. The solid-state crystal structure involves various non-covalent supramolecular interactions delineated by Hirshfeld Surface and 2D fingerprint plot analysis. Noteworthily, interesting S⋯H, O⋯H, and N⋯H contacts were observed, which have identical percentages in both complexes. The sparse tetrel bonding interactions in the complex, involving the CH₃ group, were evaluated in a new dimension of DFT. We observed this privileged bonding landscape that leads to the formation of self-assembled dimers in the crystal complexes. DFT-based MEP, RDG surface, NBO, and QTAIM/NCI plot investigation quantified such unique tetrel bonding interactions.

SUBMITTER: Majumdar D

PROVIDER: S-EPMC9753102 | biostudies-literature | 2022 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

The importance of tetrel bonding interactions with carbon in two arrestive iso-structural Cd(ii)-Salen coordination complexes: a comprehensive DFT overview in crystal engineering.

Majumdar Dhrubajyoti D Roy Sourav S Frontera Antonio A

RSC advances 20221215 55

In this article, we describe the serendipitous synthesis of two remarkable iso-structural Cd(ii)-Salen complexes [L2Cd4(OAc)2(NCS)2] in the presence of H2L and NaSCN {where L = L1 (N,N'-bis(3-methoxysalicylidene)-1,2-diaminopropane) and L = L2 (N,N'-bis(3-methoxysalicylidene)-ethylenediamine) in 1 and 2, respectively}. The complexes were characterized by using elemental analysis, SEM-EDX, PXR ...[more]

PMID: 36545098

Similar Datasets

Project description:Spontaneous self-assembly is one of the available synthetic routes to achieve structurally versatile and unique crystal complexes with selected metal-ligand combinations in the spirit of pseudohalides. In this endeavour, we designed a novel 1D coordination polymer (CP), [(Cd)(Pb)(L)(η1-NCS)(η1-SCN)] n (1), using a compartmental Salen ligand (H3L) in the presence of NaSCN. The characterization of the CP was accomplished using several spectroscopic techniques: MALDI-TOF, PXRD, SEM, EDX mapping, and single-crystal X-ray crystallography. The CP crystallizes in the monoclinic space group P21/c with Z = 4. SCXRD reveals Cd(ii) and Pb(ii) metal ions fulfilled distorted square pyramidal and hemi-directed coordination spheres. Cd(ii) is placed in the inner N2O2 and heavier Pb(ii) in the outer O4 compartments of the de-protonated form of the ligand [L]2-. Supramolecular interactions in the intricate crystal structure produced attractive molecular architectures of the compound. The flexible aliphatic -OH pendent group coordinates with the Pb(ii) ions. This unique binding further elevates the supramolecular crystal topographies. The supramolecular interactions were authenticated by Hirshfeld surface analysis (HSA). The observation of the recurring unconventional tetrel bonds was rationalized by DFT calculations and surface plots of molecular electrostatic potential (MEP). In the 1D polymeric chain in the complex, the O-atom of the -OH groups shows a tetrel bonding interaction with the Pb atom. We have found that the combination of QTAIM/NCI and QTAIM/ELF plots helps reveal the nature of these contacts. Moreover, the QTAIM/ELF plot determines the donor-acceptor interaction between the O-atom and the Pb atom, establishing the σ-hole. Agreeably, the σ-hole interaction also helps Pb(ii) serve as a Lewis acid in the complex. Finally, spodium and tetrel bonds are formed, possible thanks to a hemi-directional coordination sphere of the Pb atoms in the polymer described.

Project description:The structural stability of the extensively studied organic-inorganic hybrid methylammonium tetrel halide perovskite semiconductors, MATtX3 (MA = CH3NH3+; Tt = Ge, Sn, Pb; X = Cl, Br, I), arises as a result of non-covalent interactions between an organic cation (CH3NH3+) and an inorganic anion (TtX3-). However, the basic understanding of the underlying chemical bonding interactions in these systems that link the ionic moieties together in complex configurations is still limited. In this study, ion pair models constituting the organic and inorganic ions were regarded as the repeating units of periodic crystal systems and density functional theory simulations were performed to elucidate the nature of the non-covalent interactions between them. It is demonstrated that not only the charge-assisted N-H···X and C-H···X hydrogen bonds but also the C-N···X pnictogen bonds interact to stabilize the ion pairs and to define their geometries in the gas phase. Similar interactions are also responsible for the formation of crystalline MATtX3 in the low-temperature phase, some of which have been delineated in previous studies. In contrast, the Tt···X tetrel bonding interactions, which are hidden as coordinate bonds in the crystals, play a vital role in holding the inorganic anionic moieties (TtX3-) together. We have demonstrated that each Tt in each [CH3NH3+•TtX3-] ion pair has the capacity to donate three tetrel (σ-hole) bonds to the halides of three nearest neighbor TtX3- units, thus causing the emergence of an infinite array of 3D TtX64- octahedra in the crystalline phase. The TtX44- octahedra are corner-shared to form cage-like inorganic frameworks that host the organic cation, leading to the formation of functional tetrel halide perovskite materials that have outstanding optoelectronic properties in the solid state. We harnessed the results using the quantum theory of atoms in molecules, natural bond orbital, molecular electrostatic surface potential and independent gradient models to validate these conclusions.

Dataset Information

The importance of tetrel bonding interactions with carbon in two arrestive iso-structural Cd(ii)-Salen coordination complexes: a comprehensive DFT overview in crystal engineering.

Publications

The importance of tetrel bonding interactions with carbon in two arrestive iso-structural Cd(ii)-Salen coordination complexes: a comprehensive DFT overview in crystal engineering.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets