The aim of this paper is to characterise the abundance patterns of five iron-peak elements (Mn, Fe, Ni, Cu, and Zn) for which the stellar origin and chemical evolution are still debated. We automatically derived iron peak (Mn, Fe, Ni, Cu, and Zn) and alpha element (Mg) chemical abundances for 4666 stars. We used the bimodal distribution of [Mg/Fe] to chemically classify sample stars into different Galactic substructures: thin disc, metal-poor and high-alpha metal rich, high-alpha and low-alpha metal-poor populations. High-alpha and low-alpha metal-poor populations are fully distinct in Mg, Cu, and Zn. Thin disc trends of [Ni/Fe] and [Cu/Fe] are very similar and show a small increase at supersolar metallicities. Thin and thick disc trends of Ni and Cu are very similar and indistinguishable. Mn looks different from Ni and Cu. [Mn/Fe] trends of thin and thick discs actually have noticeable differences: the thin disc is slightly Mn richer than the thick disc. [Zn/Fe] trends look very similar to those of [alpha/Fe] trends. The dispersion of results in both discs is low (approx 0.05 dex for [Mg, Mn, and Cu/Fe]) and is even much lower for [Ni/Fe] (approx 0.035 dex). Zn is an alpha-like element and could be used to separate thin and thick disc stars. [Mn/Mg] ratio could also be a very good tool for tagging Galactic substructures. Some models can partially reproduce the observed Mg, Zn, and, Cu behaviours. Models mostly fail to reproduce Mn and Ni in all metallicity domains, however, models adopting yields normalised from solar chemical properties reproduce Mn and Ni better, suggesting that there is still a lack of realistic theoretical yields of some iron-peak elements. Very low scatter (approx 0.05 dex) in thin and thick disc sequences could provide an observational constrain for Galactic evolutionary models that study the efficiency of stellar radial migration. ; Comment: 21 pages, 20 figures