European Journal of Chemistry

In an attempt to add ligands to the sixth (axial) position of vanadyl bis-acetylacetonate: A unique tetranuclear vanadyl species


Main Article Content

Roger Lalancette
Ivan Bernal


We have explored the interaction of [(acac)2V=O] (acac = acetylacetone) with a series of potential ligands which were chosen because of their expected ability to attach themselves onto its sixth (axial) position. Furthermore, some of the species chosen were expected to have the capability of linking pairs of [(acac)2V=O] molecules, thus creating magnetically coupled substances whose behavior would be interesting to document by magnetic as well as structural methods. Some of the synthetic results were surprising in that unexpected products were obtained which we had not envisioned; specifically, herein we describe a tetranuclear vanadyl cluster (Crystal data for C38H51N4O17ClV4: orthorhombic, space group Pca21 (no. 29), a = 26.4698(3) Å, b = 13.5167(2) Å, c = 12.7659(2) Å, = 4567.44(11) Å3, Z = 4, μ(CuKα) = 7.842 mm-1, Dcalc = 1.53 g/cm3, 41277 reflections measured (6.538° ≤ 2Θ ≤ 137.892°), 7841 unique (Rint = 0.0428, Rsigma = 0.0421) which were used in all calculations; the final R1 was 0.0675 (I > 2σ(I)) and wR2 was 0.1641 (all data)), which is unusual in several aspects of its composition as well as its stereochemistry.

icon graph This Abstract was viewed 128 times | icon graph Article PDF downloaded 55 times icon graph Article CIF FILE downloaded 0 times

How to Cite
Lalancette, R.; Bernal, I. In an Attempt to Add Ligands to the Sixth (axial) Position of Vanadyl Bis-Acetylacetonate: A Unique Tetranuclear Vanadyl Species. Eur. J. Chem. 2023, 14, 494-498.

Article Details

Crossref - Scopus - Google - European PMC

[1]. Bernal, I.; Rieger, P. H. Solvent effects on the optical and electron spin resonance spectra of vanadyl acetylacetonate. Inorg. Chem. 1963, 2, 256-260.

[2]. Arslan, E.; Lalancette, R. A.; Bernal, I. An unexpected and unusual V(5+)10 cluster containing oxygen bridges as well as six bidentate acetylacetonates. Struct. Chem. 2020, 31, 1217-1222.

[3]. Arslan, E.; Bernal, I.; Lalancette, R. Vanadyl(acetylacetonate)2 mediated hydrolytic splitting of 1,3,5-triazine in a solution of toluene at 130 °C: The crystal structure of its axial formamide adduct. Eur. J. Chem. 2022, 13, 168-171.

[4]. Bruker (2009). SAINT, Version 7.23a. Bruker AXS Inc., Madison, Wisconsin, USA.

[5]. Bruker (2009). APEX2, Version 2.0-2. Bruker AXS Inc., Madison, Wisconsin, USA.

[6]. Bruker (2009). SADABS, Version 2.0-2. Bruker AXS Inc., Madison, Wisconsin, USA.

[7]. Sheldrick, G. M. SHELXT- Integrated space-group and crystal-structure determination. Acta Crystallogr. A Found. Adv. 2015, 71, 3-8.

[8]. Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Crystallogr. C Struct. Chem. 2015, 71, 3-8.

[9]. Sheldrick, G. M. A short history of SHELX. Acta Crystallogr. A 2008, 64, 112-122.

[10]. Groom, C. R.; Bruno, I. J.; Lightfoot, M. P.; Ward, S. C. The Cambridge Structural Database. Acta Crystallogr. B Struct. Sci. Cryst. Eng. Mater. 2016, 72, 171-179.

[11]. Putz, H.; Brandenburg, K. (2019). DIAMOND Version 8.5.10, GbR Kreuzherrenstr. 102, 53227 Bonn, Germany.

[12]. Khan, M. I.; Chang, Y.-D.; Chen, Q.; Salta, J.; Lee, Y.-S.; O'Connor, C. J.; Zubieta, J. Synthesis and characterization of binuclear oxo-vanadium complexes of carbon oxoanion ligands. Crystal structures of the binuclear vanadium(IV) complex (NH4)[V2O2(OH)(C4O4)2 (H2O)3]. Cntdot.H2O, of the mixed-valence vanadium(V)/vanadium (IV)-squarate species [(n-C4H9)4N][V2O3(C4O4)2(H2O)3].Cntdot. 3H2O and [(C4H9)4N]4[V4O6(C4O4)5(H2O)4].Cntdot.6H2O, and of the binuclear vanadium(IV)-oxalate species [V2O2Cl2(C2O4)(CH3OH)4]. Cntdot.2Ph4PCl. Inorg. Chem. 1994, 33, 6340-6350.

[13]. Blackburn, B. J.; Crane, J. H.; Knapp, C. E.; Powell, M. J.; Marchand, P.; Pugh, D.; Bear, J. C.; Parkin, I. P.; Carmalt, C. J. Reactivity of vanadium oxytrichloride with β-diketones and diesters as precursors for vanadium nitride and carbide. Mater. Des. 2016, 108, 780-790.

[14]. Bouma, R. J.; Teuben, J. H.; Beukema, W. R.; Bansemer, R. L.; Huffman, J. C.; Caulton, K. G. Identification of the zinc reduction product of VCl3.3THF as [V2Cl3(THF)6]2[Zn2Cl6]. Inorg. Chem. 1984, 23, 2715-2718.

[15]. Ishida, T.; Mitsubori, S.-I.; Nogami, T.; Takeda, N.; Ishikawa, M.; Iwamura, H. Ferromagnetic exchange coupling of vanadium(IV) dπ spins across pyrimidine rings: Dinuclear complexes of oxovanadium(IV) bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionate) bridged by pyrimidine derivatives. Inorg. Chem. 2001, 40, 7059-7064.

[16]. Brouca-Cabarrecq, C.; Mohanu, A.; Millet, P.; Trombe, J. C. New binuclear vanadium(III) and (IV) squarate species: synthesis, structure and characterization of [V(OH)(H2O)2(C4O4)]2·2H2O and (NH4)[(VO)2(OH)(C4O4)2(H2O)3]·3H2O. J. Solid State Chem. 2004, 177, 2575-2583.

[17]. Ma, J.; Zhao, K.-Q.; Walton, M. J.; Wright, J. A.; Frese, J. W. A.; Elsegood, M. R. J.; Xing, Q.; Sun, W.-H.; Redshaw, C. Vanadyl complexes bearing bi-dentate phenoxyimine ligands: synthesis, structural studies and ethylene polymerization capability. Dalton Trans. 2014, 43, 8300-8310.

[18]. Crans, D. C.; Marshman, R. W.; Gottlieb, M. S.; Anderson, O. P.; Miller, M. M. Oxovanadium(V) 1,3-propanediolate chloride complexes: tetrameric clusters. Inorg. Chem. 1992, 31, 4939-4949.

[19]. Sohail, K.; Lalancette, R. A.; Bernal, I.; Guo, X.; Zhao, L. Revisiting the structure of (±)-[Co(en)3]I3·H2O - X-ray crystallographic and second-Harmonic results. Z. Kristallogr. Cryst. Mater. 2022, 237, 393-402.

[20]. Whuler, A.; Spinat, P.; Brouty, C. Structure de l'iodure de tris(éthylènediamine)cobalt(III) monohydraté. Acta Crystallogr. B 1980, 36, 1086-1091.

[21]. Spek, A. L. Structure validation in chemical crystallography. Acta Crystallogr. D Biol. Crystallogr. 2009, 65, 148-155.

[22]. Bernal, I.; Lalancette, R. A. Unbalanced racemates: solid state solutions containing enantiomeric pairs crystallizing in Sohncke space groups with (L:D) ratios other than (1:1) - illustrated with crystals of a Co(III) coordination compound. Z. Kristallogr. Cryst. Mater. 2022, 237, 311-316.


Dimensions - Altmetric - scite_ - PlumX

Downloads and views


Download data is not yet available.


Metrics Loading ...
License Terms

License Terms


Copyright © 2024 by Authors. This work is published and licensed by Atlanta Publishing House LLC, Atlanta, GA, USA. The full terms of this license are available at and incorporate the Creative Commons Attribution-Non Commercial (CC BY NC) (International, v4.0) License ( By accessing the work, you hereby accept the Terms. This is an open access article distributed under the terms and conditions of the CC BY NC License, which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited without any further permission from Atlanta Publishing House LLC (European Journal of Chemistry). No use, distribution, or reproduction is permitted which does not comply with these terms. Permissions for commercial use of this work beyond the scope of the License ( are administered by Atlanta Publishing House LLC (European Journal of Chemistry).