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(NH4)4[SO4][CB11H12]2: a new double salt with carbaborate anions crystallizing in a monoclinic variant of the anti-K2NiF4-type structure

  • Alexandra Friedly and Thomas Schleid EMAIL logo
Published/Copyright: January 24, 2025
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Zeitschrift für Naturforschung B
From the journal Zeitschrift für Naturforschung B Volume 80 Issue 1-2

Abstract

The new double salt with the empirical formula (NH4)4[SO4][CB11H12]2 can be obtained by the reaction between an aqueous solution of the free acid of the closo-carbaborate (H3O)[CB11H12] and aqueous ammonia (NH3), when the incorporated sulfate anions are introduced by a cation exchanger due to its regeneration with sulfuric acid (H2SO4). (NH4)4[SO4][CB11H12]2 is yielded as colorless, prismatically shaped crystals with a considerable size up to 1 mm. This ammonium sulfate carbaborate crystallizes in the monoclinic space group C2/c with the lattice parameters a = 2715.32(9), b = 713.91(2), c = 1391.24(5) pm and β = 109.203(2)° with four formula units per unit cell. Due to the formation of bridging hydrogen bonds, the [SO4]2− anions and the (NH4)+ cations form ∞ 2 {([(N1)H4]2/2[(N2)H4]2/2[(N3)H4]2/1[SO4])2+} layers parallel to the bc plane. Between these positively charged layers, the [CB11H12]− anions are placed in fashion of the anti-K2NiF4-type structure, where K+ is replaced with [CB11H12]− and [SO4]2−-centered [(NH4)+]6 octahedra, which share four coplanar corners, arrange to the above-mentioned layers. In the Raman spectra of (NH4)4[SO4][CB11H12]2, the dominating bands correspond to the well-known vibration modes of the closo-carbaborate cage. The bands resulting from the (NH4)+ and [SO4]2− ions are visible, but significantly less intense as compared to the vibrations of [CB11H12]−, which can be explained by the formation of hydrogen bonds.

Keywords: double salts; closo-carbaborates; sulfates; crystal structures; Raman spectrum
Corresponding author: Thomas Schleid, Institute for Inorganic Chemistry, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany, E-mail:
Dedicated to Professor Arndt Simon of the Max Planck Institute for Solid State Research, Stuttgart, on the Occasion of his 85th Birthday.

Acknowledgment

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

  1. Research ethics: Not applicable.

  2. Informed consent: Not applicable.

  3. Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  4. Use of Large Language Models, AI and Machine Learning Tools: None declared.

  5. Conflict of interest: The authors state no conflict of interest.

  6. Research funding: None declared.

  7. Data availability: Not applicable.

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Received: 2024-10-22
Accepted: 2024-11-22
Published Online: 2025-01-24
Published in Print: 2025-01-29

© 2024 Walter de Gruyter GmbH, Berlin/Boston

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  7. (NH4)4[SO4][CB11H12]2: a new double salt with carbaborate anions crystallizing in a monoclinic variant of the anti-K2NiF4-type structure
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https://doi.org/10.1515/znb-2024-0096
Keywords for this article
double salts; closo-carbaborates; sulfates; crystal structures; Raman spectrum

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Research Articles
  4. Polyphosphoric acid (PPA): a new, highly efficient catalyst for the synthesis of functionalized azepino phthalazine hybrids
  5. State-dependent gas chromatography based on flexible and tunable porous coordination polymers
  6. A novel samarium(III) orotate complex [NaSm(orotate)4(H2O)10]·3H2O – crystal structure and vibrational spectra
  7. (NH4)4[SO4][CB11H12]2: a new double salt with carbaborate anions crystallizing in a monoclinic variant of the anti-K2NiF4-type structure
  8. K[Hg(CN)2][H3CCOO]: a pseudo-double salt with mercury(II)-cyanide molecules imbedded into an ionic matrix of potassium acetate
  9. An aminosilyl-functionalized zincocene
  10. The stannide SrPd2.23Sn1.73 with CaBe2Ge2-type structure
  11. Note
  12. Revisiting Na[C(CN)3] – refinement of the crystal structure from X-ray powder diffraction data, the Raman and IR spectra
  13. Corrigendum
  14. Corrigendum zu: Die Serie caesiumhaltiger Thioarsenate(V) der Lanthanoide vom Formeltyp Cs3 Ln[AsS4]2 mit Ln = La–Nd und Sm
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