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  Crystal Structures of Homoleptic Propynyloargentates AI[Ag(C3H3)2] with AI = Ag, Li, Na Solved and Refined from X-ray Powder Diffraction Data

Pak, L., Zibrowius, B., Lumeij, M.-W., Dronskowski, R., & Ruschewitz, U. (2014). Crystal Structures of Homoleptic Propynyloargentates AI[Ag(C3H3)2] with AI = Ag, Li, Na Solved and Refined from X-ray Powder Diffraction Data. Zeitschrift für anorganische und allgemeine Chemie, 640(15), 3127-3134. doi:10.1002/zaac.201400420.

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 Creators:
Pak, L.1, Author
Zibrowius, B.2, Author              
Lumeij, M.-W.3, Author
Dronskowski, R.3, Author
Ruschewitz, U.3, Author
Affiliations:
1Department für Chemie, Universität zu Köln, Greinstraße 6, 50939 Köln, Germany, ou_persistent22              
2Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445623              
3Institut für Anorganische Chemie and JARA-HPC, RWTH Aachen University, 52056 Aachen, Germany, ou_persistent22              

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Free keywords: Alkali metals; Alkyne ligands; Band-structure calculations; Silver; Solid-state NMR spectroscopy; X-ray powder diffraction
 Abstract: The crystal structures of three isostructural homoleptic propynyloargentates, namely Ag[Ag(C3H3)2], Li[Ag(C3H3)2], and Na[Ag(C3H3)2] were solved and refined from laboratory X-ray powder diffraction data (Iba2, Z = 4). Almost linear [H3C–C≡C···Ag···C≡C–CH3]– anions are found: The alkali metal cations or the second silver cation coordinate side-on to the C≡C triple bond of the alkyne ligand (CN = 8) so that layer-like structural fragments are formed, which are stacked in an AB fashion along [100]. These crystal structures are corroborated by IR and solid-state NMR spectra. Powder SHG measurements confirm the acentric space group Iba2. On the other hand, these methods also supported a first structural model obtained earlier, in which very unusual bent [Ag(CCCH3)2]– units were found in a smaller unit cell (Amm2, Z = 2). Bond-analytical COHP calculations clearly indicate that this structural motif cannot be stable. A close re-inspection of the diffraction data, now also including high-resolution synchrotron powder diffraction data (HASYLAB, beamline B2), reveal the existence of one weak additional reflection indicating a larger unit cell. Hence, this investigation clearly shows that under very specific circumstances – e.g. ligands with a weak scattering power compared to the central metal ion – wrong structural models can be obtained from X-ray powder diffraction data, even when additional information from complementary spectroscopic methods is taken into account. Additional electronic-structure calculations are therefore needed to elucidate the correct structural arrangement.

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Language(s): eng - English
 Dates: 2014-10-232014-12
 Publication Status: Published in print
 Pages: -
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/zaac.201400420
 Degree: -

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Title: Zeitschrift für anorganische und allgemeine Chemie
  Other : Journal of Inorganic and General Chemistry
  Other : J. Inorg. Gen Chem.
  Abbreviation : Z. Anorg. Allg. Chem.
Source Genre: Journal
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Publ. Info: Weinheim : Wiley-VCH
Pages: - Volume / Issue: 640 (15) Sequence Number: - Start / End Page: 3127 - 3134 Identifier: ISSN: 0044-2313
CoNE: https://pure.mpg.de/cone/journals/resource/954925453895