A New Family of Trinuclear Complexes (CH3)4N[M3(µ3-F)(TFA)6(py)3] (M = Mn, Co, Ni, Cu, Zn): Synthesis, Crystal Structure, and Thermal Stability

D. S. Tereshchenko; Терещенко Д. С.; M. E. Buzoverov; Бузоверов М. Е.; T. Yu. Glazunova; Глазунова Т. Ю.; E. Kh. Lermontova; Лермонтова Э. Х.; V. E. Goncharenko; Гончаренко В. Е.; T. B. Shatalova; Шаталова Т. Б.; E. V. Khlopkina; Хлопкина Е. В.; I. V. Morozov; Морозов И. В.

doi:10.31857/S0044457X23601190

A New Family of Trinuclear Complexes (CH3)4N[M3(µ3-F)(TFA)6(py)3] (M = Mn, Co, Ni, Cu, Zn): Synthesis, Crystal Structure, and Thermal Stability

Authors: Tereshchenko D.S.¹, Buzoverov M.E.¹, Glazunova T.Y.¹, Lermontova E.K.², Goncharenko V.E.³^,4, Shatalova T.B.¹, Khlopkina E.V.¹, Morozov I.V.¹
Affiliations:
1. Moscow State University
2. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences
3. Lebedev Physical Institute, Russian Academy of Sciences
4. Higher School of Economics
Issue: Vol 68, No 9 (2023)
Pages: 1312-1323
Section: КООРДИНАЦИОННЫЕ СОЕДИНЕНИЯ
URL: https://journals.rcsi.science/0044-457X/article/view/136500
DOI: https://doi.org/10.31857/S0044457X23601190
EDN: https://elibrary.ru/WLAQTQ
ID: 136500

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Abstract
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Abstract

Trinuclear complexes Me4N[Ni3(µ3-F)(TFA)6(MeOH)2(H2O)] (1) and Me4N[M3(μ3-F)(TFA)6(py)3] (M = Mn (2), Co (3), Ni (4), Cu (5), Zn (6)) have been synthesized by crystallization from methanol solutions. Single-crystal X-ray diffraction shows that compounds 1–6 are composed of tetramethylammonium cations Me4N+ and trinuclear triangular anions [Ni3(µ3-F)(TFA)6(MeOH)2(H2O)]– (1) or [M3(μ3-F)(TFA)6(py)3]– (2–6) centered by the μ3-F atom. The bridging trifluoroacetate anions (TFA–) located along the triangle edges link pairs of M2+ cations, and the axial positions are occupied by MeOH, H2O, or pyridine (py) molecules. In 2, the pyridine molecules are nearly coplanar with the [M3F] triangle, while in the other structures they are turned almost perpendicularly. The different orientations of py molecules lead to different packing motifs: columns of alternating trinuclear anions and Me4N+ cations are formed in 2, while in 3–6 anions and cations form neutral layers. A significant role in the organization of structures 1–6 is played by non-covalent interactions, such as hydrogen bonds and stacking and CH···π interactions. Heating complexes 2–4 above 200°С turns out to lead to a stepwise thermal decomposition, which begins with the elimination of py and ends with the formation of d-metal fluoride above 300°С.

Keywords

triangular fluorocarboxylates, transition metal trifluoroacetate complexes

References

Никифорова М.Е., Луценко И.А., Кискин М.А. и др. // Журн. неорган. химии. 2021. Т. 66. № 9. С. 1247. Nikiforova M.E., Lutsenko I.A., Kiskin M.A. et al. // Russ. J. Inorg. Chem. 2021. V. 66. № 9. P. 1343. https://doi.org/10.1134/S0036023621090102
Шарутин В.В., Шарутина О.К. // Журн. неорган. химии. 2021. Т. 66. № 3. С. 358. Sharutin. V.V., Sharutina O.K. // Russ. J. Inorg. Chem. 2021. V. 66. P. 361. https://doi.org/10.1134/S0036023621030153
Сережкина Л.Б., Митина Д.С., Вологжанина А.В. и др. // Журн. неорган. химии. 2022. Т. 67. № 11. С. 1581. https://doi.org/ Serezhkina L.B., Mitina D.S., Vologzhanina A.V. et al. // Russ. J. Inorg. Chem. 2022. V. 67. № 11. P. 1769. https://doi.org/10.1134/S003602362260091510.1134/S0036023622600915https://doi.org/10.31857/S0044457X22100427
Чикинева Т.Ю., Кошелев Д.С., Медведько А.В. и др. // Журн. неорган. химии. 2021. Т. 66. № 2. С. 168 Chikineva T.Y., Koshelev D.S., Medved’ko A.V. et al. // Russ. J. Inorg. Chem. 2021. V. 66. № 2. P. 170. https://doi.org/10.1134/S0036023621020054
Tereshchenko D.S., Morozov I.V., Boltalin A.I. et al. // Russ. J. Inorg. Chem. 2004. V. 49. № 6. P. 836.
Tereshchenko D.S., Morozov I.V., Boltalin A.I. et al. // Crystallogr. Rep. 2013. V. 58. № 1. P. 68. https://doi.org/10.1134/S106377451206017X
Morozov I.V., Karpova E.V., Glazunova T.Yu. et al. // Russ. J. Coord. Chem. 2016. V. 42. № 10. P. 647. https://doi.org/10.1134/S107032841610002X
Xie Z.-L., Feng M.-L., Tan B., Huang X.-Y. // CrystEngComm. 2012. V. 14. P. 4894. https://doi.org/10.1039/C2CE25169H
Noack J., Fritz C., Flügel C. et al. // Dalton Trans. 2013. V. 42. P. 5706. https://doi.org/10.1039/c3dt32652g
Walsh J.P.S., Meadows S.B., Ghirri A. et al. // Inorg. Chem. 2015. V. 54. № 24. P. 12019. https://doi.org/10.1021/acs.inorgchem.5b01898
Reynolds J.III, Walsh K.M., Li B. et al. // Chem. Commun. 2018. V. 54. P. 9937. https://doi.org/10.1039/C8CC05402A
Aulakh D., Islamoglu T., Bagundeset V.F. et al. // Chem. Mater. 2018. V. 30. № 22. P. 8332. https://doi.org/10.1021/acs.chemmater.8b03885
STOE WinXPOW, version 2.25 (05-Oct-2009) © STOE & Cie GmbH.
Jana2008. Version 25/10/2015. By Vaclav Petricek, Michal Dusek & Lukas Palatinus. Instirute of Physics, Academy of Sciences of the Czech Republic. Praha.
PCPDFWIN. Version 2.2. June 2001. JCPDS-ICDD.
Sheldrick G.M. // Acta Cryst. 2015. V. A71. P. 3. https://doi.org/10.1107/S2053273314026370
Sheldrick G.M. // Acta Cryst. 2015. V. C71. P. 3. https://doi.org/10.1107/S2053229614024218
Dolomanov O.V., Bourhis, L.J., Gildea R.J. et al. // J. Appl. Cryst. 2009. V. 42. P. 339. https://doi.org/10.1107/S0021889808042726
Shannon R.D. // Acta Cryst. 1976. V. A32. P. 751. https://doi.org/10.1107/S0567739476001551
Кембриджский банк структурных данных органических соединений Cambridge Structural Database System (версия 2019 г).
Irving H., Williams R.J.P. // J. Chem. Soc. 1953. P. 3192. https://doi.org/10.1039/JR9530003192
Glazunova T.Yu., Tereschenko D.S., Buzoverov M.E. et al. // Russ. J. Coord. Chem. 2021. V. 47. № 5. P. 347 https://doi.org/10.1134/S1070328421040023
Armanasco N.L., Baker M.V., Brown D.H. et al. // Inorg. Chim. Acta. 2004. V. 357. P. 4562. https://doi.org/10.1016/j.ica.2004.07.012
Steiner T. // Angew. Chem. Int. Ed. 2002. V. 41. P. 48. https://doi.org/10.1002/1521-3773(20020104)41:1%3-C48::AID-ANIE48%3E3.0.CO;2-U
Howard J.A.K., Hoy V.J., O’Hagan D., Smith G.T. // Tetrahedron. 1996. V. 52. № 38. P. 12613. https://doi.org/10.1016/0040-4020(96)00749-1
Sierański T. // J. Mol. Model. 2017. V. 23. P. 338. https://doi.org/10.1007/s00894-017-3496-4
Umezawa Y., Tsuboyama S., Honda K. et al. // Bull. Chem. Soc. Jpn. 1998. V. 71. P. 1207. https://doi.org/10.1246/bcsj.71.1207
Shibasaki K., Fujii A., Mikami N., Tsuzuki S. // J. Phys. Chem. A. 2006. V. 110. P. 4397. https://doi.org/10.1021/jp0605909
Kayumova D.B., Tereschenko D.S., Shatalova T.B. et al. // Russ. J. Coord. Chem. 2022. V. 48. № 12. P. 870. https://doi.org/10.1134/S1070328422700026