K[Hg(CN)2][H3CCOO]: a pseudo-double salt with mercury(II)-cyanide molecules imbedded into an ionic matrix of potassium acetate

Alexandra Friedly; Thomas Schleid

doi:10.1515/znb-2024-0106

Article

K[Hg(CN)₂][H₃CCOO]: a pseudo-double salt with mercury(II)-cyanide molecules imbedded into an ionic matrix of potassium acetate

Alexandra Friedly and Thomas Schleid

Published/Copyright: February 14, 2025

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From the journal Zeitschrift für Naturforschung B Volume 80 Issue 1-2

Abstract

By dissolving triethylammonium dodecahydro-carba-closo-dodecaborate, mercury(II) acetate and potassium cyanide in an equimolar ratio in acetonitrile and subsequent isothermal evaporation of this solution, the new pseudo-double salt K[Hg(CN)₂][H₃CCOO] could be obtained. K[Hg(CN)₂][H₃CCOO] crystallizes monoclinically in the space group P2₁/c with the lattice parameters a = 954.25(6), b = 905.46(5), c = 904.12(5) pm and β = 90.697(3)° for Z = 4. The Hg²⁺ cations and the (CN)⁻ anions are arranged in the crystal structure as quasi-linear molecular N≡C–Hg–C≡N units. The C≡N distances of the cyanide ligands are shorter as compared to the C≡N contacts in the pseudo-binary compound Hg(CN)₂. These molecules reside between layers of K⁺ cations and [H₃CCOO]⁻ anions, in each of which every acetate group bridges three potassium atoms. This is achieved by both the bidentate coordination of each [H₃CCOO]⁻ anion to one K⁺ cation and the monodentate coordination to two further potassium ions. The coordination environment of K⁺ is complemented by one K–N contact to an end-on coordinated cyanide anion. In the second coordination sphere, there are additionally two side-on coordinated (C≡N)⁻ units. The Raman spectrum of K[Hg(CN)₂][H₃CCOO] shows the three expected, well-known vibrations of the N≡C–Hg–C≡N molecule. These are the valence vibrations of the C≡N and the Hg–C bonds at 2171 and 383 cm⁻¹ and the Hg–C≡N deformation vibration at 261 cm⁻¹. From the valence vibrations of the [H₃CCOO]⁻ anion, the ν(C–H) vibration can be found at 2937 cm⁻¹. In the range between 1300 and 1500 cm⁻¹ both C–O/C=O valence vibrations and the H–C–H deformation vibration are visible. The intensity maximum at 904 cm⁻¹ can be assigned to the C–C valence vibration of the acetate anion.

Keywords: cyanides; acetates; potassium; mercury; crystal structures; Raman spectra

Corresponding author: Thomas Schleid, Institute for Inorganic Chemistry, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany, E-mail: schleid@iac.uni-stuttgart.de

Dedicated to Professor Hans-Jörg Deiseroth on the Occasion of his 80th Birthday.

Acknowledgment

We like to thank Dr. Falk Lissner for the single-crystal X-ray diffraction measurement.

Research ethics: Not applicable.
Informed consent: Not applicable.
Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.
Use of Large Language Models, AI and Machine Learning Tools: None declared.
Conflict of interest: The authors state no conflict of interest.
Research funding: None declared.
Data availability: Not applicable.

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Received: 2024-11-29

Accepted: 2024-12-09

Published Online: 2025-02-14

Published in Print: 2025-01-29

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Articles in the same Issue

https://doi.org/10.1515/znb-2024-0106

Keywords for this article

cyanides; acetates; potassium; mercury; crystal structures; Raman spectra