What is the nature of binding of BF4¯, NO3¯ and ClO4¯ to Cu(II) complexes with Girard's T hydrazine? When can binuclear complexes be formed?
Kakva je priroda vezivanja BF4-, NO3- i ClO4- za komplekse Cu(II) sa Žirarovim T hidrazidom? Kada mogu nastati binuklearni kompleksi?
Abstract
Four complexes, [CuLCl]BF4, [CuLCl]NO3, [Cu2L2Cl2](BF4)2 and [CuLCl]ClO4 having the same [CuLCl]+ moiety, (L=(E)-N,N,N-trimethyl-2-oxo-2-(2-(1-(pyridin-2-yl)ethylidene) hydrazi-nyl)ethan-1-amin), were characterized by single crystal X-ray diffraction methods. According to the bond distances, the formulas have been written such that [CuLCl]+ is the inner sphere, while BF4¯, NO3¯ and ClO4¯ belong to the outer sphere. Non-local density-dependent dispersion corrected Density functional theory (DFT) calculations on the X-ray structures have been performed to rationalize interactions of anions to the Cu(II) ion. Results of analysis based on energy decomposition, Non-Covalent Interactions Index, Independent Gradient Model analysis, and Quantum Theory of Atoms in Molecules revealed that in mononuclear complexes, anions are weakly coordinated, while in binuclear complex, BF4¯ is counter-anion, electrostatically bonded to the inner sphere. Furthermore, DFT calculations rationalized the fact that... only complex [Cu2L2Cl2](BF4)2 is binuclear with bridging Cl¯ ions. The present study shows that ambiguity about actual coordination number in the real crystal structures of coordination compounds can be solved with thorough analysis of the electron density.
Četiri kompleksa, [CuLCl]BF4, [CuLCl]NO3, [Cu2L2Cl2](BF4)2 i [CuLCl]ClO4, sa istim [CuLCl]+ fragmentom (L=(E)-N,N,N-trimethyl-2-oxo-2-(2-(1-(pyridin-2-yl)ethylidene) hydrazinyl)eth-an-1-amin) su okarakterisani metodom difrakcije X-zraka. Na osnovu dužina veza, formule kompleksa su napisane tako da je [CuLCl]+ unutrašnja sfera kompleksa, a BF4¯, NO3¯ i ClO4¯ pripadaju spoljašnjoj sferi. Proračuni zasnovani na Teoriji funkcionala gustine, u kojoj je disperzija korigovana na ne-lokalan način, na strukturama dobijenim difrakcijom X-zraka, su izvedeni u cilju razjašnjavanja prirode interakcija anjona sa Cu(II) jonom. Rezultati različitih analiza, kao što su dekompozicija interakcione energije, indeks nekovalentnih interakcija, model nezavisnog gradijenta i kvantna teorija atoma u molekulima, pokazuju da su anjoni u mononuklearnim kompleksima slabo koordinovani, dok je BF4¯ u binuklearnom kompleksu kontra jon, elektrostatički vezan za unutrašnju sferu. Takođe, proračuni objašnjavaju činjenic...u da je samo kompleks [Cu2L2Cl2](BF4)2 binuklearni sa mostnim Cl¯ jonima. Ova studija pokazuje da se nedoumice oko koordinacionog broja u realnim kristalnim strukturama kompleksa mogu otkloniti detaljnom analizom elektronske gustine.
Keywords:
Cu(II) complexes / X-ray diffraction / DFT / Energy Decomposition Analysis / Non-Covalent Interactions Index / Independent Gradient Model analysis / Quantum Theory of Atoms in Molecule / counter-anionsSource:
56th Meeting of the Serbian chemical Society - Book of Abstracts / 56. Savetovanje Srpskog hemijskog društva - Kratki izvodi radova Niš 7-8.9. 2019., 2019, 8-Publisher:
- Serbian Chemical Society, Belgrade / Srpsko hemijsko društvo, Beograd
Funding / projects:
Note:
- Related to Crystal Growth & Design, 2019, 19, 4810-4821 https://dx.doi.org/10.1021/acs.cgd.9b00760
- Related to: http://cer.ihtm.bg.ac.rs/handle/123456789/3051
Collections
Institution/Community
IHTMTY - CONF AU - Zlatar, Matija AU - Čobeljić, Božidar AU - Gruden, Maja AU - Anđelković, Katarina PY - 2019 UR - https://www.shd.org.rs/index.php/abstracts-56 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/3284 AB - Four complexes, [CuLCl]BF4, [CuLCl]NO3, [Cu2L2Cl2](BF4)2 and [CuLCl]ClO4 having the same [CuLCl]+ moiety, (L=(E)-N,N,N-trimethyl-2-oxo-2-(2-(1-(pyridin-2-yl)ethylidene) hydrazi-nyl)ethan-1-amin), were characterized by single crystal X-ray diffraction methods. According to the bond distances, the formulas have been written such that [CuLCl]+ is the inner sphere, while BF4¯, NO3¯ and ClO4¯ belong to the outer sphere. Non-local density-dependent dispersion corrected Density functional theory (DFT) calculations on the X-ray structures have been performed to rationalize interactions of anions to the Cu(II) ion. Results of analysis based on energy decomposition, Non-Covalent Interactions Index, Independent Gradient Model analysis, and Quantum Theory of Atoms in Molecules revealed that in mononuclear complexes, anions are weakly coordinated, while in binuclear complex, BF4¯ is counter-anion, electrostatically bonded to the inner sphere. Furthermore, DFT calculations rationalized the fact that only complex [Cu2L2Cl2](BF4)2 is binuclear with bridging Cl¯ ions. The present study shows that ambiguity about actual coordination number in the real crystal structures of coordination compounds can be solved with thorough analysis of the electron density. AB - Četiri kompleksa, [CuLCl]BF4, [CuLCl]NO3, [Cu2L2Cl2](BF4)2 i [CuLCl]ClO4, sa istim [CuLCl]+ fragmentom (L=(E)-N,N,N-trimethyl-2-oxo-2-(2-(1-(pyridin-2-yl)ethylidene) hydrazinyl)eth-an-1-amin) su okarakterisani metodom difrakcije X-zraka. Na osnovu dužina veza, formule kompleksa su napisane tako da je [CuLCl]+ unutrašnja sfera kompleksa, a BF4¯, NO3¯ i ClO4¯ pripadaju spoljašnjoj sferi. Proračuni zasnovani na Teoriji funkcionala gustine, u kojoj je disperzija korigovana na ne-lokalan način, na strukturama dobijenim difrakcijom X-zraka, su izvedeni u cilju razjašnjavanja prirode interakcija anjona sa Cu(II) jonom. Rezultati različitih analiza, kao što su dekompozicija interakcione energije, indeks nekovalentnih interakcija, model nezavisnog gradijenta i kvantna teorija atoma u molekulima, pokazuju da su anjoni u mononuklearnim kompleksima slabo koordinovani, dok je BF4¯ u binuklearnom kompleksu kontra jon, elektrostatički vezan za unutrašnju sferu. Takođe, proračuni objašnjavaju činjenicu da je samo kompleks [Cu2L2Cl2](BF4)2 binuklearni sa mostnim Cl¯ jonima. Ova studija pokazuje da se nedoumice oko koordinacionog broja u realnim kristalnim strukturama kompleksa mogu otkloniti detaljnom analizom elektronske gustine. PB - Serbian Chemical Society, Belgrade / Srpsko hemijsko društvo, Beograd C3 - 56th Meeting of the Serbian chemical Society - Book of Abstracts / 56. Savetovanje Srpskog hemijskog društva - Kratki izvodi radova Niš 7-8.9. 2019. T1 - What is the nature of binding of BF4¯, NO3¯ and ClO4¯ to Cu(II) complexes with Girard's T hydrazine? When can binuclear complexes be formed? T1 - Kakva je priroda vezivanja BF4-, NO3- i ClO4- za komplekse Cu(II) sa Žirarovim T hidrazidom? Kada mogu nastati binuklearni kompleksi? SP - 8 UR - https://hdl.handle.net/21.15107/rcub_cer_3284 ER -
@conference{ author = "Zlatar, Matija and Čobeljić, Božidar and Gruden, Maja and Anđelković, Katarina", year = "2019", abstract = "Four complexes, [CuLCl]BF4, [CuLCl]NO3, [Cu2L2Cl2](BF4)2 and [CuLCl]ClO4 having the same [CuLCl]+ moiety, (L=(E)-N,N,N-trimethyl-2-oxo-2-(2-(1-(pyridin-2-yl)ethylidene) hydrazi-nyl)ethan-1-amin), were characterized by single crystal X-ray diffraction methods. According to the bond distances, the formulas have been written such that [CuLCl]+ is the inner sphere, while BF4¯, NO3¯ and ClO4¯ belong to the outer sphere. Non-local density-dependent dispersion corrected Density functional theory (DFT) calculations on the X-ray structures have been performed to rationalize interactions of anions to the Cu(II) ion. Results of analysis based on energy decomposition, Non-Covalent Interactions Index, Independent Gradient Model analysis, and Quantum Theory of Atoms in Molecules revealed that in mononuclear complexes, anions are weakly coordinated, while in binuclear complex, BF4¯ is counter-anion, electrostatically bonded to the inner sphere. Furthermore, DFT calculations rationalized the fact that only complex [Cu2L2Cl2](BF4)2 is binuclear with bridging Cl¯ ions. The present study shows that ambiguity about actual coordination number in the real crystal structures of coordination compounds can be solved with thorough analysis of the electron density., Četiri kompleksa, [CuLCl]BF4, [CuLCl]NO3, [Cu2L2Cl2](BF4)2 i [CuLCl]ClO4, sa istim [CuLCl]+ fragmentom (L=(E)-N,N,N-trimethyl-2-oxo-2-(2-(1-(pyridin-2-yl)ethylidene) hydrazinyl)eth-an-1-amin) su okarakterisani metodom difrakcije X-zraka. Na osnovu dužina veza, formule kompleksa su napisane tako da je [CuLCl]+ unutrašnja sfera kompleksa, a BF4¯, NO3¯ i ClO4¯ pripadaju spoljašnjoj sferi. Proračuni zasnovani na Teoriji funkcionala gustine, u kojoj je disperzija korigovana na ne-lokalan način, na strukturama dobijenim difrakcijom X-zraka, su izvedeni u cilju razjašnjavanja prirode interakcija anjona sa Cu(II) jonom. Rezultati različitih analiza, kao što su dekompozicija interakcione energije, indeks nekovalentnih interakcija, model nezavisnog gradijenta i kvantna teorija atoma u molekulima, pokazuju da su anjoni u mononuklearnim kompleksima slabo koordinovani, dok je BF4¯ u binuklearnom kompleksu kontra jon, elektrostatički vezan za unutrašnju sferu. Takođe, proračuni objašnjavaju činjenicu da je samo kompleks [Cu2L2Cl2](BF4)2 binuklearni sa mostnim Cl¯ jonima. Ova studija pokazuje da se nedoumice oko koordinacionog broja u realnim kristalnim strukturama kompleksa mogu otkloniti detaljnom analizom elektronske gustine.", publisher = "Serbian Chemical Society, Belgrade / Srpsko hemijsko društvo, Beograd", journal = "56th Meeting of the Serbian chemical Society - Book of Abstracts / 56. Savetovanje Srpskog hemijskog društva - Kratki izvodi radova Niš 7-8.9. 2019.", title = "What is the nature of binding of BF4¯, NO3¯ and ClO4¯ to Cu(II) complexes with Girard's T hydrazine? When can binuclear complexes be formed?, Kakva je priroda vezivanja BF4-, NO3- i ClO4- za komplekse Cu(II) sa Žirarovim T hidrazidom? Kada mogu nastati binuklearni kompleksi?", pages = "8", url = "https://hdl.handle.net/21.15107/rcub_cer_3284" }
Zlatar, M., Čobeljić, B., Gruden, M.,& Anđelković, K.. (2019). What is the nature of binding of BF4¯, NO3¯ and ClO4¯ to Cu(II) complexes with Girard's T hydrazine? When can binuclear complexes be formed?. in 56th Meeting of the Serbian chemical Society - Book of Abstracts / 56. Savetovanje Srpskog hemijskog društva - Kratki izvodi radova Niš 7-8.9. 2019. Serbian Chemical Society, Belgrade / Srpsko hemijsko društvo, Beograd., 8. https://hdl.handle.net/21.15107/rcub_cer_3284
Zlatar M, Čobeljić B, Gruden M, Anđelković K. What is the nature of binding of BF4¯, NO3¯ and ClO4¯ to Cu(II) complexes with Girard's T hydrazine? When can binuclear complexes be formed?. in 56th Meeting of the Serbian chemical Society - Book of Abstracts / 56. Savetovanje Srpskog hemijskog društva - Kratki izvodi radova Niš 7-8.9. 2019.. 2019;:8. https://hdl.handle.net/21.15107/rcub_cer_3284 .
Zlatar, Matija, Čobeljić, Božidar, Gruden, Maja, Anđelković, Katarina, "What is the nature of binding of BF4¯, NO3¯ and ClO4¯ to Cu(II) complexes with Girard's T hydrazine? When can binuclear complexes be formed?" in 56th Meeting of the Serbian chemical Society - Book of Abstracts / 56. Savetovanje Srpskog hemijskog društva - Kratki izvodi radova Niš 7-8.9. 2019. (2019):8, https://hdl.handle.net/21.15107/rcub_cer_3284 .