Communications
P1 (No. 2), Z = 2, 1calcd = 1.878 gcmꢀ3, m = 6.904 mmꢀ1; data collec-
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¯
tion: Oxford-Diffraction Xcalibur3 Diffractometer,Mo
radiation,
Ka
qmax = 20.868,29141 measured reflections,14346 independent reflec-
tions, Rint = 0.031, R1 = 0.053 and wR2 = 0.121 for reflections with I >
2s(I), R1 = 0.096 und wR2 = 0.130 for all data. CCDC-606528 (1)
contains the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cambridge
cif.
Calculations: Single-point DFT calculations with the LanL2DZ
basis set and B3LYP functional were performed on the cluster 1a by
using the atomic positions deduced from the single-crystal X-ray
analysis. Full structure optimization was run for [Au(PH3)Cl],leading
[17] For 1a to have a net charge of ꢀ5,clusters A and B must
formally be fourfold negatively charged. Indeed,the shape of
cluster A is very similar to a number of Ge nido clusters,as in
(Cs+)4[Ge94ꢀ].[33] Cluster B with three nearly equal prism heights
compares well to the 22-electron nido cluster ([Bi9]5+)2-
([BiX5]2ꢀ)8([Bi2X8]2ꢀ)2.[34] A similar distortion of a 22-skeletal-
electron cluster with the same h/e ratio of 1.14 is also found in the
fourfold negatively charged tin cluster in [K+([18]crown-
6)]3(K+)[Sn9]4ꢀ [35]
.
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ꢀ
ꢀ
to a P-Au-Cl angle of 180.08 as well as Au P and Au Cl bond lengths
of 2.389 and 2.373 ,respectively,and is in agreement with earlier
studies.[31] Computations were executed with the Gaussian03 pack-
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Received: May 19,2006
Revised: October 2,2006
Published online: January 18,2007
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[28] X-ray diffraction structure analysis of crystals from subsequent
reactions which were different in shape and appearance
contained [K([2.2.2]crypt)]8K[Ge45Au3] and led to the ortho-
rhombic space group Pna21 with a = 69.30, b = 25.07, c =
31.61 . A. Spiekermann,S. D. Hoffmann,T. F. Fꢀssler,I.
Krossing,U. Preiss,unpublished results.
Keywords: cluster compounds · germanides · gold ·
structure elucidation · Zintl ions
.
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ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2007, 46, 1638 –1640