We perform an optical pump ‒ X-ray probe experiment to track optically excited structural dynamics of [Ir2 (dimen)4 ] 2+ (dimen=1,8-diisocyano-p-menthane) molecules in solution. We determine angular correlations in the scattered X-rays, which comprise a complex fingerprint of the ultrafast dynamics in the system. Model-assisted analysis of the experimental correlation data allows us to elucidate various aspects of the photoinduced changes in the excited molecular ensembles.