New Ni(II) 1,2-bis(diphenylphosphino)ethane dithiolates: crystallographic, computational and Hirshfeld surface analyses

Reena Yadav, Manoj Trivedi, Gabriele Kociok-Kohn, Rajendra Prasad, Abhinav Kumar

Research output: Contribution to journalArticle

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Abstract

Three new nickel(ii) 1,2-bis(diphenylphosphino)ethane dithiolate complexes viz. [Ni(dppe)(benzylcyanidedithiolate)] (1), [Ni(dppe)(2-cyanobenzylcyanidedithiolate)] (2) and [Ni(dppe)(pyridine-2-cyanidedithiolate)] (3) have been synthesized and characterized spectroscopically and by single-crystal X-ray analysis. The X-ray analyses of 2 and 3 reveal a distorted square planar geometry around Ni(ii) satisfied by the two sulfur atoms of the dithiolate and two phosphorus atoms of the dppe ligands. Both 2 and 3 display intermolecular C-N⋯H, π⋯π and C-H⋯π and C-S⋯H interactions which generate a supramolecular framework. Additionally, both 2 and 3 show intramolecular C-H⋯Ni anagostic interactions. These interactions have been addressed by ab initio, AIM and Hirshfeld surface analyses. The anagostic interactions are verified using bond order and natural charge calculations which indicated depletion of electron density on the ortho-hydrogen atoms undergoing the anagostic interactions. All three compounds exhibit photoluminescence in dichloromethane solution as well as in the solid state. The solid-state emissions are red-shifted in comparison to the solution-phase emissions which may be attributed to the existence of intermolecular interactions in the solid state.

Original languageEnglish
Pages (from-to)9175-9184
Number of pages10
JournalCrystEngComm
Volume17
Issue number47
DOIs
Publication statusPublished - 21 Dec 2015

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Ethane
ethane
Atoms
Methylene Chloride
X ray analysis
Dichloromethane
interactions
Nickel
solid state
Sulfur
Pyridine
Phosphorus
Carrier concentration
Hydrogen
Photoluminescence
Ligands
ortho hydrogen
Single crystals
X rays
Geometry

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New Ni(II) 1,2-bis(diphenylphosphino)ethane dithiolates : crystallographic, computational and Hirshfeld surface analyses. / Yadav, Reena; Trivedi, Manoj; Kociok-Kohn, Gabriele; Prasad, Rajendra; Kumar, Abhinav.

In: CrystEngComm, Vol. 17, No. 47, 21.12.2015, p. 9175-9184.

Research output: Contribution to journalArticle

Yadav, Reena ; Trivedi, Manoj ; Kociok-Kohn, Gabriele ; Prasad, Rajendra ; Kumar, Abhinav. / New Ni(II) 1,2-bis(diphenylphosphino)ethane dithiolates : crystallographic, computational and Hirshfeld surface analyses. In: CrystEngComm. 2015 ; Vol. 17, No. 47. pp. 9175-9184.
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