Abstract
The structures of the solvated zinc ion and the solvated zinc–iodide complexes in methanol solution have been determined by EXAFS. The zinc ion is six-coordinated in an octahedral fashion with a mean Zn–O bond distance of 2.071(4) Å. According to the stability constants of the zinc–iodide system in methanol solution the first complex, ZnI+, is suppressed, which may indicate that a coordination change takes place at this step. On the other hand, the second complex, ZnI2, predominates at excess of iodide. The methanol solvated ZnI2 complex has a tetrahedral structure with mean Zn–I and Zn–O bond distances of 2.55(1) and 1.99(1) Å, respectively. The mean Zn–I bond distance in a solution containing a maximal content of ZnI+, ca. 12%, strongly indicates that the first complex also has a tetrahedral structure.
Similar content being viewed by others
1 Introduction
The stability of zinc(II)–iodide complexes varies very much with the solvent used. In some solvents only very weak complex formation is observed, as in water, dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF), while in others it can be very strong, as in acetonitrile; the stability constants of the zinc(II)–iodide system in various solvents are summarized in Table 1. A major reason for these large differences in stability of zinc–iodide complexes is the strength of the solvation of the zinc and iodide ions in different solvents. The iodide ion is more strongly hydrated in water than solvated in any of the other solvents where the complex formation of the zinc–iodide system has been studied [10, 11] (Table S1). The zinc ion, on the other hand, is more strongly solvated in solvents such as DMSO, DMF and HMPA (hexamethylphosphoric triamide) than in water, while in solvents such as methanol and especially acetonitrile the opposite is found [12, 13] (Table S1). The strongest complex formation is observed in acetonitrile [9], where the zinc and iodide ions both are weakly solvated [10,11,12]. The stability of iodozinc complexes in methanol is medium strong as the zinc and iodide ions are both more weakly solvated than in water but more strongly than in acetonitrile.
The complex distribution of the zinc–iodide systems in the solvents studied show two principal patterns with the first complex dominant over a wide range of free iodide concentration or almost completely suppressed (Figs. S1 and S2); the complex formation function of the zinc–iodide system in methanol is given in Fig. S3. The common property of the solvents where the monoiodozinc complex disproportionates into the solvated zinc ion and the solvated diiodozinc complex, is that the solvated zinc ion is six-coordinate in an octahedral fashion (Table S2). The solvents where the monoiodozinc complex has a wide range of existence, HMPA and ethylene glycol, are both space-demanding upon coordination. The HMPA solvated zinc ion is four-coordinate in solution [7], while the ethylene glycol solvated zinc ion has neither been studied in solution nor in the solid state. This strongly indicates that complex formation between hexasolvated zinc ions and iodide causes a coordination change, from octahedral to tetrahedral structure, and at the step of the coordination change, in this case at the formation of the first complex, this particular complex will be suppressed (Figs. S1 and S2). On the other hand, when the solvated zinc ion already has a tetrahedral structure a substitution reaction takes place and the first complex will get a well-defined dominance region (Fig. S2). The stability of the solvated diiodozinc complex in solvents where the zinc ion has octahedral structure is also shown by the presence of reported solid state structures, [ZnI2(solv)2] for solv = water, DMSO, DMF, DMA, acetonitrile and pyridine (Table S3) among the solvents where complex formation data are available for the zinc iodide system; the structures of triiodo- and tetraiodozincate(II) ions in the solid state are summarized in Table S4. Furthermore, no ZnI(solv) n ]+ complexes have been reported in the solid state with solvents forming octahedral zinc solvates. However, three solid state structures with a complex with the composition [ZnI(solv)3]+ have been reported [14,15,16]. For only one of these solvents, 1-methyl-2(3H)-imidazolinethione, the zinc solvate has been characterized to be four-coordinated in a tetrahedral fashion [17]. For the other two solvents, 3{5}-tert-butylpyrazole and piperidine, one may assume that they are sufficiently space demanding to have a coordination number lower than six or form sufficiently covalent interactions, also promoting low coordination numbers, to form solvated zinc ions with a lower coordination number than six (Fig. 1).
The aim of the present study is to determine the structures of the methanol solvated zinc ion and iodozinc complexes in solution using EXAFS spectroscopy. These results will validate the assumptions made from the complex formation studies, whether the structure changes from the octahedral structure of methanol solvated zinc ion to tetrahedral iodozinc complexes takes place at the formation of the first complex or not (Fig. 2).
2 Experimental
2.1 Preparation of Salts and Solutions
Zinc trifluoromethanesulfonate was prepared by slurrying zinc oxide (Merck), ZnO, in distilled water, and trifluoromethanesulfonic acid (Fluka), CF3SO3H, was added dropwise until the zinc oxide was dissolved. The solution was filtered and the excess of acid and water were boiled off in an oven at ca. 450 K, and Zn(CF3SO3)2 was obtained as a white powder. It was carefully grained and stored in oven at ca. 450 K.
The methanol solutions were prepared by dissolving weighed amounts of anhydrous zinc trifluoromethanesulfonate, Zn(CF3SO3)2, and zinc iodide (Merck), ZnI2, in freshly distilled methanol. The composition of the studied solutions, and their abbreviations are summarized in Table 2.
2.2 EXAFS Data Collection and Treatment
X-ray absorption data were collected at the Stanford Synchrotron Radiation Lightsource (SSRL), using the unfocussed 8-pole wiggler beam line 4–1 (old station). SSRL was operated at 3.0 GeV and a ring current of 30–100 mA. The radiation was monochromatized by a Si[220] double crystal monochromator. The monochromator was detuned to 50% of maximum intensity to reduce higher order harmonics. The data were collected in the transmission mode using ion chambers with a gentle flow of nitrogen. For each sample 5 scans were collected and averaged.
The EXAFS oscillations were extracted from averaged raw data using standard procedures for pre-edge subtraction, spline removal and data normalization. In order to obtain quantitative information of the coordination structure of the zinc complexes, the experimental k3-weighted EXAFS oscillations were analyzed by linear least-squares fits of the data to the EXAFS equation, refining the model parameters: number of backscattering atoms, N, mean interatomic distances R, Debye–Waller factor coefficients, σ2, and relative ionization energy, ΔEo. Data treatment was performed using the EXAFSPAK program package [18]. The energy scale of the X-ray absorption spectra were calibrated by assigning the first inflection point of a metallic zinc foil as 9659 eV [19]. The sample cells were made of 1.5 mm Teflon spacers and with 6 μm polyprolyene X-ray film windows held together with titanium frames. The refinements of the structure parameters were performed with the EXAFSPAK [18] and FEFF7 [20] software packages allowing the determination of the parameters of the local structure around zinc.
The standard deviations reported for the obtained refined parameters listed in Table 3 are those related to the least-squares refinements and do not include any systematic errors. Variations in the refined parameters obtained using different models and data ranges indicate that the accuracy of the distances given for the separate complexes is within ± 0.005–0.02 Å, which is typical for well-defined interactions.
3 Results and Discussion
The Zn–O bond distance in the methanol solvated zinc ion in solution, solution Zn_0, has been determined to be 2.071(2) Å, which is in reasonable agreement with the distance in solid hexakis(methanol)zinc hexafluorosilcate, [Zn(OHCH3)6]SiF6, 2.086 Å [21]. A similar distance has been reported in the hexakis(ethanol)zinc ion in the solid state, 2.079 Å [21]. The obtained Zn–O bond distance in the methanol solvated zinc(II) ion shows that it is six-coordinated, and the multiple scattering pattern confirms an octahedral configuration.
The methanol solvated diiodozinc complex is the dominant species in solutions Zn_2 and Zn_4 (Fig. S1). The Zn–I and Zn–O bond distances have been refined to 2.545(2) and 1.984(4) Å, and 2.556(2) and 1.991(3) Å in solutions Zn_2 and Zn_4, respectively. This strongly indicates that the methanol solvated diiodozinc(II) complex is basically tetrahedral as also found for the hydrated, DMSO, DMA, acetonitrile and pyridine solvated diiodozinc complexes in the solid state (Table S3).
Solution Zn_1 contains ca. 44% of Zn2+ and ZnI2 each and 12% ZnI+ complexes. The observed Zn–I bond distance, 2.538 Å, is in agreement the ones found in solutions Zn_2 and Zn_4, which are dominated by the tetrahedral [ZnI2(CH3OH)2] complex. If the methanol solvated ZnI+ complex had remained octahedral a longer Zn–I bond distance should be expected in the order of 2.8 Å, based on the ionic radii given by Shannon [22]. Even though the fraction of the ZnI+ complex in solution is expected to be low, ca. 12%, the expected mean Zn–I bond distance should be in the order of 2.58 Å. The observed mean Zn–I bond distance, 2.538 Å, in solution Zn_1, indicates, on the other hand, that the Zn–I bond distance in the [ZnI(CH3OH)3]+ complex is slightly shorter than in [ZnI2(CH3OH)2].
4 Conclusions
The methanol solvated zinc ion is six-coordinate in octahedral fashion with a mean Zn–O bond distance of 2.071(2) Å. The methanol solvated ZnI2 complex has tetrahedral configuration with mean Zn-I and Zn–O bond distances of 2.55(1) and 1.99(1) Å, respectively. The mean Zn-I bond distance in a solution containing a maximal content of ZnI+, ca. 12%, strongly indicates that the first complex also has tetrahedral structure as indicated by the suppressed dominance of the first complex.
References
Gerding, P.: Thermochemical studies on metal complexes. IX. Free energy, enthalpy, and entropy changes for stepwise formation of zinc(II) halide complexes in aqueous solution. Acta Chem. Scand. Ser. A 23, 1695–1703 (1969)
Doe, H., Shibagaki, A., Kitagawa, T.: Studies of formation of zinc(II) bromide, iodide, and thiocyanate complexes in methanol using the respective ion-selective electrodes. Inorg. Chem. 22, 1639–1643 (1983)
Ishiguro, S.-I., Miyauchi, M., Ozutsumi, K.: Thermodynamics of formation of binary and ternary complexes of zinc(II) with halide and thiocyanate ions and 2,2′-bipyridine in dimethylformamide. J. Chem. Soc. Dalton Trans. 7, 2035–2041 (1990)
Suzuki, H., Koide, M., Ishiguro, S.-I.: Solution equilibria of binary and ternary zinc(II) halogeno complexes in N,N-dimethylacetamide. Bull. Chem. Soc. Jpn. 67, 1320–1326 (1994)
Ahrland, S., Björk, N.-O.: Metal halide and pseudohalide complexes in dimethyl sulfoxide solution. V. Equilibrium measurements on the zinc(II) chloride, bromide, iodide and thiocyanate systems. Acta Chem. Scand. Ser. A 30, 265–269 (1976)
Ahrland, S., Björk, N.-O., Portanova, R.: Metal halide and pseudohalide complexes in dimethyl sulfoxide solution. VI. Enthalpy measurements on the zinc(II) chloride, bromide, iodide, and thiocyanate systems. Acta Chem. Scand. Ser. A 30, 270–276 (1976)
Abe, Y., Ishiguro, S.-I.: Thermodynamics of complexation of zinc(II) with chloride, bromide and iodide ions in hexamethylphosphoric triamide. J. Solution Chem. 20, 793–803 (1991)
Kumagai, T.: Ion exchange from a nonaqueous solution. zinc(II) bromide and iodide in ethylene glycol. Bull. Chem. Soc. Jpn. 57, 2738–2740 (1984)
Dash, K.C., Kinjo, Y., Persson, I.: Equilibrium and enthalpy measurements on the zinc(II) chloride, bromide and iodide systems in acetonitrile and pyridine, and on the mercury(II) chloride, bromide and iodide systems in acetonitrile. Acta Chem. Scand. 44, 433–442 (1990)
Johnsson, M., Persson, I.: Determination of Gibbs free energy of transfer for some univalent ions from water to methanol, acetonitrile, dimethyl sulfoxide, pyridine, tetrahydrothiophene and liquid ammonia; standard electrode potentials of some couples in these solvents. Inorg. Chim. Acta 127, 15–24 (1987)
Johnsson, M., Persson, I.: Determination of heats and entropies of transfer for some univalent ions from water to methanol, acetonitrile, dimethyl sulfoxide, pyridine and tetrahydrothiophene. Inorg. Chim. Acta 127, 25–34 (1987)
Chaudhry, M., Dash, K.C., Kamienska-Piotrowicz, E., Kinjo, Y., Persson, I.: Determination of the transfer thermodynamic functions for the zinc(II), cadmium(II), mercury(II) and mercury(I) ions from water to methanol, dimethyl sulfoxide, acetonitrile, pyridine and N,N-dimethylthioformamide, and of standard electrode potentials of M(s)/M2+ couples in these solvents. J. Chem. Soc. Faraday Trans. I 90, 2235–2242 (1994)
Marcus, Y.: Thermodynamic functions of transfer of single ions from water to nonaqueous and mixed solvents. Part I: Gibbs free energies of transfer to nonaqueous solvents. Pure Appl. Chem. 55, 977–1021 (1983). and references therein
Matsunaga, Y., Fujisawa, K., Amir, N., Mayashita, Y., Okamoto, K.-I.: Group 12 metal(II) complexes with 1-methylimidazoline-2(3H)-thione (mitH): correlation between crystal structure and physicochemical property. J. Coord. Chem. 58, 1047–1061 (2005)
Liu, X., Kilner, C.A., Halcrow, M.A.: 3{5}-tert-Butylpyrazole is a ditopic receptor for zinc(II) halides. Chem. Commun. 7, 704–705 (2002)
Allen, F.H.: The Cambridge Structural Database: a quarter of a million crystal structures and rising. Acta Crystallogr. B 32, 380–388 (2002)
Nowell, I.W., Cox, A.G., Raper, E.S.: Structure of tetrakis[1-methyl-2(3H)-imidazolinethione]zinc(II) nitrate monohydrate. Acta Crystallogr. Sect. B 35, 3047–3050 (1979)
George, G.N., Pickering, I.J.: EXAFSPAK: A Suite of Computer Programs for Analysis of X-Ray Absorption Spectra. Stanford Synchrotron Radiation Laboratory, Stanford (2000)
Thompson, A., Attwood, D., Gullikson, E., Howells, M., Kim, K.-J., Kirz, K., Kortright, J., Lindau, I., Liu, Y., Pianetta, P., Robinson, A., Scofield, J. Underwood, J., Williams, G., Winick, H.: X-ray Data Booklet. Lawrence Berkley National Laboratory (2009)
Zabinsky, S.I., Rehr, J.J., Ankudinov, A., Albers, R.C., Eller, M.J.: Multiple-scattering calculations of x-ray-absorption spectra. Phys. Rev. B 52, 2995–3009 (1995)
Sudbrake, C., Muller, B., Vahrenkamp, H.: Hexakis(alcohol)zinc complexes. Eur. J. Inorg. Chem. 11, 2009–2012 (1999)
Shannon, R.D.: Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr. Sect. A 32, 751–767 (1976)
Acknowledgements
Portions of this research were carried out at the Stanford Synchrotron Radiation Light source (SSRL), which is acknowledged for the allocation of beam time and laboratory facilities. SSRL is a national user facility operated by Stanford University on behalf of the US Department of Energy, Office of Basic Energy Services. The SSRL Structural Molecular Biology Program is supported by the Department of Energy, Office of Biological and Environmental Research, and by the National Institute of Health, National Center for Research Resources, Biomedical Technology Program.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
Open Access This article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.
About this article
Cite this article
Persson, I. Structure of Methanol Solvated Iodozinc(II) Complexes in Solution. J Solution Chem 47, 560–567 (2018). https://doi.org/10.1007/s10953-018-0737-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10953-018-0737-9