Single-Crystal Growth and Characterization of Disilver(I) Monofluorophosphate(V), Ag2PO3F: Crystal Structure, Thermal Behavior, Vibrational Spectroscopy, and Solid-State 19<
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- 作者：Matthias Weil ; Michael Puchberger ; Ekkehard Fü ; glein ; Enrique J. Baran ; Julia Vannahme ; Hans J. Jakobsen ; J
//pubs.acs.org/images/gifchars/oslash.gif" border="0">rgen Skibsted
- 刊名：Inorganic Chemistry
- 出版年：2007
- 出版时间：February 5, 2007
- 年：2007
- 卷：46
- 期：3
- 页码：801 - 808
- 全文大小：189K
- 年卷期：v.46,no.3(February 5, 2007)
- ISSN：1520-510X
文摘
Single crystals of disilver(I) monofluorophosphate(V), Ag2PO3F (1), were obtained by slow evaporation of a dilutedaqueous Ag2PO3F solution. Compound 1 adopts a new structure type and crystallizes in the monoclinic spacegroup C2/c with eight formula units and lattice parameters of a = 9.2456(8) Å, b = 5.5854(5) Å, c = 14.7840(13)Å, and 
= 90.178(2)
. The crystal structure of 1 [R(F2 > 2
(F2) = 0.0268, wR(F2 all) = 0.0665] is composed ofthree crystallographically independent Ag+ cations and PO3F2- anions as single building units. The oxygen environmentaround each of the Ag+ cations is different, with one Ag+ in distorted octahedral (
(Ag-O) = 2.553 Å), one innearly rectangular ((Ag-O) = 2.445 Å), and one in distorted tetrahedral ((Ag-O) = 2.399 Å) coordination.Additional Ag-F contacts to more remote F atoms located at distances >2.80 Å augment the coordination polyhedrafor the two latter Ag+ cations. The monofluorophosphate anion deviates slightly from C3v symmetry and exhibits thecharacteristic differences in bond lengths, with a mean of 1.510 Å for the P-O bonds and one considerably longerP-F bond of 1.575(2) Å. Compound 1 was further characterized by vibrational spectroscopy (Raman and IR) andsolid-state 19F, 31P, and 109Ag MAS NMR spectroscopy. The value for the isotropic one-bond P-F coupling constantin 1 is 1JPF = -1045 Hz. Thermal analysis (TG, DSC) revealed a reversible phase transition at 308 C, which isvery close to the decomposition range of 1. Under release of POF3, Ag4P2O7 and Ag3PO4 are the thermaldecomposition products at temperatures above 450 C.
= 90.178(2). The crystal structure of 1 [R(F2 > 2(F2) = 0.0268, wR(F2 all) = 0.0665] is composed ofthree crystallographically independent Ag+ cations and PO3F2- anions as single building units. The oxygen environmentaround each of the Ag+ cations is different, with one Ag+ in distorted octahedral ((Ag-O) = 2.553 Å), one innearly rectangular ((Ag-O) = 2.445 Å), and one in distorted tetrahedral ((Ag-O) = 2.399 Å) coordination.Additional Ag-F contacts to more remote F atoms located at distances >2.80 Å augment the coordination polyhedrafor the two latter Ag+ cations. The monofluorophosphate anion deviates slightly from C3v symmetry and exhibits thecharacteristic differences in bond lengths, with a mean of 1.510 Å for the P-O bonds and one considerably longerP-F bond of 1.575(2) Å. Compound 1 was further characterized by vibrational spectroscopy (Raman and IR) andsolid-state 19F, 31P, and 109Ag MAS NMR spectroscopy. The value for the isotropic one-bond P-F coupling constantin 1 is 1JPF = -1045 Hz. Thermal analysis (TG, DSC) revealed a reversible phase transition at 308 C, which isvery close to the decomposition range of 1. Under release of POF3, Ag4P2O7 and Ag3PO4 are the thermaldecomposition products at temperatures above 450 C.