Single crystals of disilver(I) monofluorophosphate(V), Ag
2PO
3F (
1), were obtained by slow evaporation of a dilutedaqueous Ag
2PO
3F 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 PO
3F
2- 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 POF
3, Ag
4P
2O
7 and Ag
3PO
4 are the thermaldecomposition products at temperatures above 450
C.