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      Synthesis, Structure and Hirshfeld Surface Analysis of A New Decavanadate Compound: Na 2[H 4V 10O 28]·14H 2O




            The synthesis and structural study of a new acid decavanadate compound with a monovalent inorganic cation. This compound makes a contribution to inorganic decavanadate family.


            The synthesis of the compound was carried out by evaporation at room temperature. Good quality crystals were chosen for single crystal x-ray diffraction using a polarizing microscope. Hirshfeld surface analysis, in particular dnorm surface and fingerprint plots, is used to decode intermolecular interactions in the structure of the studied decavanadate compound.


            A new acid decavanadate compound, Na2[H4V10O28]·14H2O, was synthesized and characterized by single crystal X-ray diffraction. The decavanadate compound crystallizes in the triclinic system and the cell parameters are: a=11.282(5) Å, b=10.424(3) Å, c=8.502(1) Å, α=112.81(2)°, β=87.25(2)°, γ=111.49(5)°, V=852.4(5) Å3 and Z=2. The formula unit of Na2[H4V10O28]·14H2O compound is formed by an acidic decavanadate group [H4V10O28]2-, a Na2(H2O)102+ dimer and four molecules of water. The decavanadate group is formed by ten distorted VO6 octahedra interconnected by edge sharing. Decavanadate groups [H4V10O28]2-, the Na2(H2O)102+ dimers and the water molecules stack in layers parallel to the (010) plane. The cohesion of the structure is ensured by hydrogen bonds and van der Waals interactions. The study of the Hirshfeld surface shows that O…H/H…O and H…H interactions dominate the structure.


            A novel synthesized decavanadate compound decorated by inorganic cations is reported and studied by X-ray diffraction. The cohesion is assured by: O-H…O hydrogen bonds and van der Waals interactions. The Hirshfeld surface analysis confirms the presence of O…H/H…O and H…H contacts in the structure.

            Main article text

            1 INTRODUCTION

            Polyoxometalates (POM) are oxo clusters of transition metal ions, such as Mo, W, V, Nb, and Ta, forming a variety of structures. POMs have different sizes and shapes which may allow for the inclusion of other anions. In the structure of POMs, one or more of the metal oxoanions can be substituted[13].

            Polyoxometalates (POM) have potential applications in various fields of science and technology, catalytic, magnetic, and electrochemical, in light of their properties such as thermal stability, redox activity, solubility in polar and non-polar solvents[4,5]. POMs have dominated medicinal chemistry for their intriguing antiviral and anti-tumor activities. Among the POMs, polyoxovanadate compounds (POVs) are known for their extensive applications in several fields such as chemical, physical and biological sciences. Vanadium plays an important role in biological systems and biochemistry[6,7]. Although POVs generally contain vanadium in the +5 oxidation state, recent reports have described POVs with two oxidation states, V(IV) and V(V). Several decavanadate compounds are stable under physiological conditions. The stability of POV under the given experimental conditions requires due consideration in the research on the effects of POV[1,8].

            Decavanadate compounds are formed in the pH range 6-8 and show a potential interest in several fields such as catalysis, nanotechnology, electrochemistry, materials science, anticancer, antibacterial and antiviral activity[1,810]. In the present work, we will focus on the synthesis, structure and Hirshfeld surface analysis of a new decavanadate compound: Na2[H4V10O28]·14H2O.

            2 EXPERIMENTAL

            2.1 Materials and Measurements

            All solvents and reagents were obtained from commercial sources and used without further purification.

            2.2 Synthesis of Na2[H4V10O28]·14H2O Compound

            The compound Na2[H4V10O28]·14H2O was obtained from a mixture of 0.6 g of V2O5 (99.99%, FLUKA) and 0.5 g of NaVO3 (Prolabo, 98%) in 100 mL of pure water. The mixture obtained was placed under magnetic stirring and heating for approximately 2 hours. After five days of slow evaporation at room temperature, orange good quality crystals were obtained.

            2.3 Hirshfeld Surface Study

            Hirshfeld surfaces (HS) were constructed to represent the asymmetric unit of the compound and the analysis was performed using the Crystal-Explorer program[11].

            2.4 X-ray Crystallography

            An Enraf-Nonius CAD4[12] 4-circle diffractometer was used to collect the diffracted intensities (λ = 0.71067 Å). The resolution of the structure was performed by the direct method using the SHELXS-97[13] program and the refinement was performed by the least-squares method using SHELXL-2014[14]. Hydrogen atoms were attached using the HFIX instruction. The absorption correction was performed by psi-scan[15]. All the figures of the structure have been represented by the DIAMOND software[16].

            Crystal data, data collection, and structural refinement details are summarized in Table 1.

            Table 1.

            Crystallographic Characteristics, X-ray Data Collection, and Structure-Refinement Parameters of Na2[H4V10O28]·14H2O Compound

            Crystal Data
            Chemical formulaNa2[H4V10O28]·14H2O
            Formula weight (g;mol−1)1263.67
            Crystal system, space groupTriclinic, P-1
            T (K)298(2)
            a b c (Å)11.282(5), 10.424(3), 8.502(1)
            α, β, γ (°)112.81(2), 87.25(2), 111.49(5)
            Radiation λ (Å)MoKα 0.71073
            Crystal size (mm3)0.68×0.54×0.39
            μ (mm−1)2.771
            Data Collection
            DiffractometerEnraf-Nonius CAD4
            Absorption correctionΨ-scan
            Tmin,Tmax 0.181,0.339
            Range for data collection (°)2.3≤θ≤ 27
            h, k, l ranges-14≤ h ≤14, -12≤ k ≤13, -10≤ l ≤1
            Scan modeω/2θ
            No. of measured, independent, and observed4205, 3713, 3304
            [I >2σ(I)] reflections
            Rint 0.016
            R1 [F2 > 2 σ (F2)]0.033
            No. of parameters301
            Maximum residual electron density
            Δρmax (e.Å−3)
            Minimum residual electron density
            Δρmin (e.Å−3)


            3.1 Crystal Structure

            The formula unit of Na2[H4V10O28]·14H2O compound was formed by an acidic decavanadate group [H4V10O28]2-, a Na2(H2O)10 2+ dimer, and four molecules of water. The structure of the decavanadate group [V10O28]6- is formed by ten VO6 octahedra interconnected by sharing of edges[17,18](Figure 1).

            Figure 1.

            Formula unit of Na2[H4V10O28]·14H2O compound.

            The projection, according to c, of the structure of the compound Na2[H4V10O28]·14H2O shows that the decavanadate groups [H4V10O28]2-, the Na2(H2O)10 2+ dimers, and the water molecules stack in layers parallel to the (010) plane (Figure 2).

            Figure 2.

            (A) Projection of the structure of Na2[H4V10O28]·14H2O compound according to the caxis, (B) Decavanadate group, (C) Na2(H2O)10 2+dimer.

            The cohesion of the structure is ensured by O-H…O hydrogen bonds and van der Waals interactions (Figure 3). These bonds are weak according to Brown’s criterion[19] (Table 2). The comparison of the studied structure with the two structures (NH4)4Li2[V10O28]·10H2O and Na5.22Li0.78[V10O28]·20H2O: studied by KSIKSI et al.[18,20], shows that sodium and lithium form dimers in the structure studied and the compound (NH4)4Li2[V10O28]·10H2O. The cohesion in these two structures is ensured only by hydrogen bonds and van der Waals interactions. In the structure of Na5.22Li0.78[V10O28]·20H2O, sodium forms infinite chains. The cohesion of the decavanadate structure Na5.22Li0.78[V10O28]·20H2O is ensured by the pooling of oxygen vertices, ridges and vertices, and by van der Waals interactions. Sodium forms chains, interconnected by the pooling of vertices, edges and faces. These strong bonds can provide better stability to decavanadates compounds, which encourages the synthesis of decavanadates compounds containing sodium.

            Figure 3.

            Cohesion of the structure by O-H…Ohydrogen bonds.

            Table 2.

            Hydrogen Bonds of Na2[H4V10O28]·14H2O Compound

            O15-H15A…O6i 0.7762.1682.665122.37
            O15-H15A…O8i 0.7762.2682.682114.28
            O16-H16A…O8ii 0.8732.2033.040160.52
            O16-H16B…O15iii 0.8112.0482.853172.50
            O18-H18A…O1iii 0.7692.2522.954152.11
            O18-H18A…O10iv 0.7692.5393.110132.27
            O19-H19B…O8iv 0.8712.3062.979134.05
            O19-H19B…O10iv 0.8712.3103.054143.32
            O20-H20A…O12v 0.8602.2482.982143.22
            O21-H21A…O14vi 1.0632.1873.222164.03
            O21-H21B…O13I 0.9092.3363.093140.60
            O21-H21B…O15i 0.9092.3413.161150.04
            O22-H22A…O7vii 0.8552.1262.863144.07
            O22-H22B…O10iv 0.8842.2552.924132.32

            Symmetry codes : i: -x+1, -y+1, -z+1, ii: x+1, y+1, z+1, iii: x, y+1, z+1, iv: -x+1, -y+2, -z+1, v: -x+2, -y+2, -z+2, vi: x-1, y-1, z, vii: -x+1, -y+1, -z.

            3.2 Hirshfeld Surface Analysis of Na2[H4V10O28]·14H2O

            The Hirshfeld surface of the decavanadate compound studied in normal mode dnorm is shown in Figure 4A. This figure shows that the main interactions are between the surfaces H…H and O…H/H…O[21,22]. The structure of the compound Na2[H4V10O28]·14H2O is dominated by the interactions O…H/H…O (59.5 ℅), H…H (14.9 ℅), and V…O/O…V contacts (11.8 ℅) (Figures 4 A, B and C). The O…O contacts represent 9.3 ℅.

            Figure 4.

            Hirshfeld surface and fingerprint plot of Na2[H4V10O28]·14H2O compound

            4 CONCLUSION

            A new compound decavanadate, Na2[H4V10O28]·14H2O, was synthesized by slow evaporation at room temperature. The structure is formed by the decavanadate groups, Na2(H2O)10 2+ dimers, and water molecules. The cohesion of the structure is ensured by hydrogen bonds and van der Waals interactions. The study of the HS surface shows that the structure is dominated by O…H/H…O, H…H and V…O/O…V contacts.


            Financial support from the Ministry of Higher Education and Scientific Research of Tunisia is gratefully acknowledged. This work is done as part of a federated research project under the code PRF2019-D3P2.

            Conflicts of Interest

            There is no conflict of interest between the authors of this article.

            Author Contribution

            Ksiksi R wrote the manuscript; Ksiksi R and Nasri R performed the data curation; Graia M reviewed the article, and Zid MF supervised the project.

            Abbreviation List

            T, Temperature

            A, b, c, α, β, γ, Cells

            V, Volume

            Μ, Absorption coefficient

            T, Absorption transmission factor

            R, Reliability factors

            F(000), Structure factor

            Dnorm, Normalized contact distance


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            Author and article information

            Journal of Modern Nanotechnology
            Innovation Forever Publishing Group (China )
            25 December 2021
            : 1
            : 1
            [1 ]Faculty of Scieces of Tunis, University of Tunis El Manar, Tunis, Tunisia
            [2 ]High Institute of Preparatory Studies in Biology and Geology (ISEP-BG) of Soukra, University of Carthage, Tunis, Tunisia
            [3 ]Faculty of Sciences, University of Sfax, Sfax, Tunisia
            Author notes
            *Correspondence to: Regaya Ksiksi; Email: rksiksi@ 123456gmail.com
            Copyright 2021, Regaya Ksiksi, Rawia Nasri, Mohsen Graia and Mohamed Faouzi Zid

            This is an open-access article distributed under the terms of the Creative Commons Attribution Licence (CC BY) 4.0 https://creativecommons.org/licenses/by/4.0/, which permits unrestricted use, distribution and reproduction in any medium, provided the original author and source are credited.

            Page count
            Figures: 4, Tables: 2, References: 22, Pages: 6
            Research Article

            Clinical chemistry,Chemistry,Physical chemistry,Batteries & Fuel cells,Polymer chemistry
            decavanadate,hirshfeld surface analysis,structure,synthesis


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