TY - JOUR

T1 - An extended supramolecular coordination compound produced from PbCl2 and N′-isonicotinoylpicolinohydrazonamide

AU - Garcia-Santos, Isabel

AU - Iglesias-Pereiro, Tamara

AU - Labisbal, Elena

AU - Castiñeiras, Alfonso

AU - Eftekhari-Sis, Bagher

AU - Mahmoudi, Ghodrat

AU - Sagan, Filip

AU - Mitoraj, Mariusz P.

AU - Safin, Damir A.

N1 - M. P. Mitoraj and F. Sagan acknowledge Poland's high-performance Infrastructure PLGrid (HPC Centers: ACK Cyfronet AGH, PCSS, CI TASK, WCSS) for providing computer facilities. M. P. Mitoraj also acknowledges financial support from the Polish National Science Center within the Sonata Bis Project 2017/26/E/ST4/00104.

PY - 2024

Y1 - 2024

N2 - We report a heteroleptic complex [PbCl2(HL′)]·MeOH (1·MeOH), obtained from N′-isonicotinoylpicolinohydrazonamide (HL) and PbCl2, where HL′ is a zwitterionic form of HL with the protonated 4-pyridyl and deprotonated amide nitrogen atoms. All the coordination bonds around the Pb2+ cation are collected in one hemisphere, yielding a large space gap, which allows two molecules of 1 to come into close proximity to each other and linked through two Pb⋯Cl tetrel bonds of ∼3.41 Å. As a result, a supramolecular dimeric species [PbCl2(HL′)]2 is formed, which is stabilized by two C-H⋯Pb anagostic and two C-H⋯Cl interactions. The coordination sphere of the Pb2+ cation is completed by the formation of the Pb⋯O tetrel bond with the methanolic oxygen atom. The supramolecular dimeric species are linked through π⋯π(chelate ring) and π⋯π interactions, yielding a 1D supramolecular chain, which is strengthened by N-H⋯Cl hydrogen bonds. These chains are interlinked through a set of hydrogen bonds and weaker interactions. Extensive computational analyses by charge and energy decomposition scheme ETS-NOCV as well as interacting quantum atoms (IQA) allowed us to conclude that most electrostatically dominated noncovalent interactions follow the strength order: Pb⋯O > Pb⋯Cl > N-H⋯Cl > C-H⋯Pb > C-H⋯Cl. Cooperative action of π⋯π and N-H⋯Cl provides an extraordinary dimeric stabilization energy of about −75 kcal mol−1. Finally, an unusual C-H⋯Pb interaction was identified to be attractive despite its long distance (>3.7 Å). Methanol species is found to be engaged not only in Pb⋯O tetrel bonds, but also in hydrogen N-H⋯O bonds and untypical homopolar dihydrogen interactions C-H⋯H-C.

AB - We report a heteroleptic complex [PbCl2(HL′)]·MeOH (1·MeOH), obtained from N′-isonicotinoylpicolinohydrazonamide (HL) and PbCl2, where HL′ is a zwitterionic form of HL with the protonated 4-pyridyl and deprotonated amide nitrogen atoms. All the coordination bonds around the Pb2+ cation are collected in one hemisphere, yielding a large space gap, which allows two molecules of 1 to come into close proximity to each other and linked through two Pb⋯Cl tetrel bonds of ∼3.41 Å. As a result, a supramolecular dimeric species [PbCl2(HL′)]2 is formed, which is stabilized by two C-H⋯Pb anagostic and two C-H⋯Cl interactions. The coordination sphere of the Pb2+ cation is completed by the formation of the Pb⋯O tetrel bond with the methanolic oxygen atom. The supramolecular dimeric species are linked through π⋯π(chelate ring) and π⋯π interactions, yielding a 1D supramolecular chain, which is strengthened by N-H⋯Cl hydrogen bonds. These chains are interlinked through a set of hydrogen bonds and weaker interactions. Extensive computational analyses by charge and energy decomposition scheme ETS-NOCV as well as interacting quantum atoms (IQA) allowed us to conclude that most electrostatically dominated noncovalent interactions follow the strength order: Pb⋯O > Pb⋯Cl > N-H⋯Cl > C-H⋯Pb > C-H⋯Cl. Cooperative action of π⋯π and N-H⋯Cl provides an extraordinary dimeric stabilization energy of about −75 kcal mol−1. Finally, an unusual C-H⋯Pb interaction was identified to be attractive despite its long distance (>3.7 Å). Methanol species is found to be engaged not only in Pb⋯O tetrel bonds, but also in hydrogen N-H⋯O bonds and untypical homopolar dihydrogen interactions C-H⋯H-C.

UR - http://www.scopus.com/inward/record.url?partnerID=8YFLogxK&scp=85184013143

UR - https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=tsmetrics&SrcApp=tsm_test&DestApp=WOS_CPL&DestLinkType=FullRecord&KeyUT=001158212200001

U2 - 10.1039/D3CE01066J

DO - 10.1039/D3CE01066J

M3 - Article

VL - 26

SP - 1252

EP - 1260

JO - CrystEngComm

JF - CrystEngComm

SN - 1466-8033

IS - 9

ER -