Preparation and Characterization of Dimercury(I) Monofluorophosphate(V), Hg2PO3F: Crystal Structure, Thermal Behavior, Vibrational Spectra, and Solid-State 31P and
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- 作者：Matthias Weil ; Michael Puchberger ; and Enrique J. Baran
- 刊名：Inorganic Chemistry
- 出版年：2004
- 出版时间：December 27, 2004
- 年：2004
- 卷：43
- 期：26
- 页码：8330 - 8335
- 全文大小：183K
- 年卷期：v.43,no.26(December 27, 2004)
- ISSN：1520-510X
文摘
Single crystals of anhydrous dimercury(I) monofluorophosphate(V), Hg2PO3F (1), were obtained by cooling dilutedaqueous Hg2(NO3)2 and (NH4)2PO3F solutions from 85 
C to room temperature. Compound 1 crystallizes with eightformula units in the orthorhombic space group Ibam (No. 72) and lattice parameters a = 9.406(2) Å, b = 12.145(3) Å, c = 8.567(2) Å. It adopts a new structure type even though a topological relation with dimercury(I) sulfate,Hg2SO4, is established. The crystal structure of 1 (R(F2 > 2
(F2) = 0.0353) exhibits Hg22+ dumbbells and discretePO3F2- anions as single building units which are organized in a layered assembly parallel to (100). The symmetricHg22+ dumbbell shows a typical Hg-Hg distance of 2.5051(9) Å, and for each Hg atom, three Hg-O distances arefound, ranging from 2.327(6) to 2.476(5) Å. No interactions between Hg and F atoms are realized. The latter isexclusively bonded to the phosphorus atom at a distance d(P-F) = 1.568(8) Å which is considerably longer thanthe P-O distances with a mean of 1.515 Å. Compound 1 was further characterized by vibrational spectroscopy(Raman and IR) in the spectral range between 4000 and 50 cm-1, thermal analysis (TG, DSC) up to 650 C whichrevealed Hg2(P2O7) and Hg3(PO4)2 as thermal decomposition products, and 19F and 31P solid-state NMR spectroscopy.The value for the P-F coupling constant in 1 is JPF = -1072 Hz at 20 C. The absolute sign of JPF is negative.
C to room temperature. Compound 1 crystallizes with eightformula units in the orthorhombic space group Ibam (No. 72) and lattice parameters a = 9.406(2) Å, b = 12.145(3) Å, c = 8.567(2) Å. It adopts a new structure type even though a topological relation with dimercury(I) sulfate,Hg2SO4, is established. The crystal structure of 1 (R(F2 > 2(F2) = 0.0353) exhibits Hg22+ dumbbells and discretePO3F2- anions as single building units which are organized in a layered assembly parallel to (100). The symmetricHg22+ dumbbell shows a typical Hg-Hg distance of 2.5051(9) Å, and for each Hg atom, three Hg-O distances arefound, ranging from 2.327(6) to 2.476(5) Å. No interactions between Hg and F atoms are realized. The latter isexclusively bonded to the phosphorus atom at a distance d(P-F) = 1.568(8) Å which is considerably longer thanthe P-O distances with a mean of 1.515 Å. Compound 1 was further characterized by vibrational spectroscopy(Raman and IR) in the spectral range between 4000 and 50 cm-1, thermal analysis (TG, DSC) up to 650 C whichrevealed Hg2(P2O7) and Hg3(PO4)2 as thermal decomposition products, and 19F and 31P solid-state NMR spectroscopy.The value for the P-F coupling constant in 1 is JPF = -1072 Hz at 20 C. The absolute sign of JPF is negative.