Md. Carducci et al., DIFFRACTION STUDIES OF PHOTOEXCITED CRYSTALS - METASTABLE NITROSYL-LINKAGE ISOMERS OF SODIUM-NITROPRUSSIDE, Journal of the American Chemical Society, 119(11), 1997, pp. 2669-2678
The geometries of two known metastable states of sodium nitroprusside
dihydrate, Na-2[Fe(CN)(5)NO]. 2H(2)O and that of the ground state have
been analyzed by X-ray diffraction at 50 K, a temperature at which no
decay of metastable-state concentration with time is observed. Data w
ere collected on two laser-excited crystals containing populations of
similar to 37% of metastable state I (MS(1)) and similar to 10% of met
astable state II (MS(2)), respectively, using imaging plates and a rot
ating anode source. For MS(1) the apparent geometry changes upon excit
ation, determined earlier at 138 K (Pressprich, M. R.; White, M. A.; V
ekhter, Y.; Coppens, P. J. Am. Chem. Sec. 1994, 116, 5233-5238), are c
onfirmed. However, reinterpretation of the diffraction data points to
a linear, oxygen-bound isonitrosyl geometry of this species with Fe-O
and N-O distances of 1.715(5) and 1.140(7) Angstrom, respectively. The
diffraction evidence points to a geometry for the MS(2) species in wh
ich NO is sideways bound (eta(2)), with Fe-N, Fe-O, and N-O distances
of 1.89(2), 2.07(2), and 1.14(2) Angstrom, respectively, compared with
1.6656(7) and 1.133(1) Angstrom for Fe-N and N-O in the ground state.
The three geometries correspond to minima in the nondissociative end-
over-end linkage isomerization pathway of a diatomic molecule proposed
by Armour and Taube for N-2 (Armor, J. N.; Taube, H. J. Am. Chem. Sec
. 1970, 92, 2560-2561).