The structure of the laser-light-induced metastable state MS(1) of the [Ru(NO2)(4)(OH)(NO)](2-) anion in K-2[Ru(NO2)(4)(OH)(NO)] was determined by X-ray analysis at 50 K of a crystal with a 16% excited-state population. Results of an independent determination of the ground-state structure were used in the analysis. The most pronounced geometrical change upon excitation was an increase of the Ru-(NO) distance by 0.097(11) Angstrom, significantly larger than the change of the corresponding distance in sodium nitroprusside (Pressprich, M. R.; White, M. A.; Vekhter, Y.; Coppens, P. J. Am. Chem. Soc. 1994, 116, 5233-5238). A decrease in the angle Ru-(N-O) angle from 174.0(2) to 169(1)degrees was observed. The diffraction results provide evidence that the photoinduced state MS(1) of the transition metal nitrosyl complexes is a linkage isomer in which the NO group is attached to the metal atom through the oxygen, instead of through the nitrogen atom, rather than an electronic excited state as reported previously.