Universität zu Köln

Pak, Leo, Zibrowius, Bodo ORCID: 0000-0002-3894-7318, Lumeij, Marck-Willem, Dronskowski, Richard and Ruschewitz, Uwe ORCID: 0000-0002-6511-6894 (2014). Crystal Structures of Homoleptic Propynyloargentates A(I)[Ag(C3H3)(2)] with A(I) = Ag, Li, Na Solved and Refined from X-ray Powder Diffraction Data. Z. Anorg. Allg. Chem., 640 (15). S. 3127 - 3135. WEINHEIM: WILEY-V C H VERLAG GMBH. ISSN 1521-3749

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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 center dot center dot center dot Ag center dot center dot center dot 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.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Pak, Leo UNSPECIFIED UNSPECIFIED UNSPECIFIED Zibrowius, Bodo UNSPECIFIED orcid.org/0000-0002-3894-7318 UNSPECIFIED Lumeij, Marck-Willem UNSPECIFIED UNSPECIFIED UNSPECIFIED Dronskowski, Richard UNSPECIFIED UNSPECIFIED UNSPECIFIED Ruschewitz, Uwe UNSPECIFIED orcid.org/0000-0002-6511-6894 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-421685
DOI:	10.1002/zaac.201400420
Journal or Publication Title:	Z. Anorg. Allg. Chem.
Volume:	640
Number:	15
Page Range:	S. 3127 - 3135
Date:	2014
Publisher:	WILEY-V C H VERLAG GMBH
Place of Publication:	WEINHEIM
ISSN:	1521-3749
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Inorganic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language ALKINYLOVERBINDUNGEN VON UBERGANGSMETALLEN; TRANSITION; ACETYLIDE; COMPLEXES; COPPER; SILVER; STATE; PROGRAM; GOLD(I); METALS Multiple languages Chemistry, Inorganic & Nuclear Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/42168