This article reports on the ground-state spin and moments measured in 72,74 Cu using collinear laser spectroscopy at the CERN On-Line Isotope Mass Separator (ISOLDE) facility. From the measured hyperfine coefficients, the nuclear observables µ( 72 Cu) = −1.3472(10)µ N , µ( 74 Cu) = −1.068(3)µ N , Q( 72 Cu) = +8(2) efm 2 , Q( 74 Cu) = +26(3) efm 2 , I ( 72 Cu) = 2, and I ( 74 Cu) = 2 have been determined. Through a comparison of the measured magnetic moments with different models, the negative moment reveals a strong πf 5/2 ⊗ νg 9/2 component in the ground-state wave function. Consequently, a negative parity has been assigned to the ground states of 72,74 Cu. Large-scale shell-model calculations illustrate the strong sensitivity of the nuclear moments to configuration mixing and to the effective interaction employed. The neutron-rich nuclei surrounding the Z = 28 and N = 50 shell closures have received a great deal of experimental and theoretical attention in the last decade. This region presents a key proving ground for the latest shell-model interactions, since it offers an attractively simple structure of the excited states in terms of particle-particle or particle-hole couplings. A compelling question in this region is related to the rapid reduction in energy of the 5/2 − state as the νg 9/2 orbital is filled in the Cu isotopes [1,2]. Given that this state remains static at approximately 1 MeV as neutrons fill the fp shell, its abrupt change at N = 40 garnered a great deal of interest and motivated further experimental and theoretical attention [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17]. A major step in understanding the evolution of nuclear structure in this region was the suggestion to include the monopole term from the tensor force interaction [18,19]. This work predicted a reduction in energy of the 5/2 − state and an inversion with the 3/2 − state in the mid-shell region, which was recently confirmed to occur at N = 46 in the odd-Cu isotopes [20]. Effective shell-model interactions which include this effect have recently been developed in the fpg model space. Two of these interactions start from a 56 Ni core [21,22], while the most recent one also includes excitations of protons from the πf 7/2 orbit across Z = 28 [23]. The odd-odd Cu isotopes are an ideal testing ground for these models, as their properties are extremely sensitive to the proton-neutron interaction.Recent beta-decay studies of 72 Ni [8] have tentatively assigned a spin I = 2 to the ground state (gs) of 72 Cu. Shell-model calculations, based on effective and realistic interactions, could not reproduce such gs spin [8], but placed the 2 − and 2 + states around 400 keV. A gs spin I = 2 is particularly interesting since the spins of 71,73 Cu now have been measured as I = 3/2, and their magnetic moments are compatible with a leading πp 3/2 configuration [20]. However, a [πp 3/2 ⊗ νg 3 9/2 , σ = 1] cannot couple to spin 2, so this configuration cannot be the leading term in the gs wave function of 72 Cu. Alternatively it could be...