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We present Fe K$β$ X-ray emission (XES) and Fe K X-ray absorption spectra (XAS) of Iron(II)sulfide (FeS) and Iron(II)disulfide (FeS$_2$). While XES and XAS offer different discrimination capabilities for chemical speciation, depending on the valence states of the compounds probed, XES allows for using different excitation sources. The XES data was measured using polychromatic X-ray radiation with a full-cylinder von Hamos spectrometer being characterized by an energy window of up to 700 eV and a spectral resolving power of $E/ ΔE = 800$. The large energy window at a single position of the spectrometer components is made profit of to circumvent the instrumental sensitivity of wavelength-dispersive spectrometers to sample positioning. This results in a robust energy scale which is used to compare experimental data with ab initio valence-to-core calculations, which are carried out using the OCEAN package. To validate the reliability of the OCEAN package for the two sample systems, near edge X-ray absorption fine structure measurements of the Fe K absorption edge are compared to theory using the same input parameters as in the case of the X-ray emission calculations. Based on the example of iron sulfide compounds, the combination of XES experiments and OCEAN calculations allows unravelling the electronic structure of different transition metal sulfides and qualifying XES investigations for the speciation of different compounds.