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 F&uuml ; glein ; Enrique J. Baran ; Julia Vannahme ; Hans J. Jakobsen ; Jg src="http ; //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) &Aring;, b = 5.5854(5) &Aring;, c = 14.7840(13)&Aring;, and ges/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 90.178(2)ges/entities/deg.gif">. The crystal structure of 1 [R(F² &gt; 2ges/gifchars/sigma.gif" BORDER=0 >(F²) = 0.0268, wR(F² all) = 0.0665] is composed ofthree crystallographically independent Ag⁺ cations and PO₃F^2- anions as single building units. The oxygen environmentaround each of the Ag⁺ cations is different, with one Ag⁺ in distorted octahedral (ges/entities/dmacr.gif">(Ag-O) = 2.553 &Aring;), one innearly rectangular (ges/entities/dmacr.gif">(Ag-O) = 2.445 &Aring;), and one in distorted tetrahedral (ges/entities/dmacr.gif">(Ag-O) = 2.399 &Aring;) coordination.Additional Ag-F contacts to more remote F atoms located at distances &gt;2.80 &Aring; augment the coordination polyhedrafor the two latter Ag⁺ cations. The monofluorophosphate anion deviates slightly from C_3v symmetry and exhibits thecharacteristic differences in bond lengths, with a mean of 1.510 &Aring; for the P-O bonds and one considerably longerP-F bond of 1.575(2) &Aring;. 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 ¹J_PF = -1045 Hz. Thermal analysis (TG, DSC) revealed a reversible phase transition at 308 ges/entities/deg.gif">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 ges/entities/deg.gif">C.