Magnetostructural correlations in antiperovskite manganese nitrides were investigated systematically for stoichiometric and solid solution Mn₃Cu_1-x A _x N (A = Co, Ni, Zn, Ga, Ge, Rh, Pd, Ag, In, Sn or Sb). This class of nitrides is attracting great attention because of their giant negative thermal expansion, which is achieved by doping Ge or Sn into the A site as a relaxant of the sharp volume contraction on heating (spontaneous volume magnetostriction ω_s) because of the magnetovolume effects. The physical background of large ω_s and mechanism of how the volume contraction becomes gradual with temperature are central concerns for the physics and applications of these nitrides. An entire dataset of thermal expansion, crystal structure and magnetization demonstrates that the cubic triangular antiferromagnetic state is crucial for large ω_s. The intimate relationship between ω_s and the magnetic structure is discussed in terms of geometrical frustration related to the Mn₆N octahedron and magnetic stress concept. The results presented herein also show that ω_s depends on the number of d electrons in the A atom, suggesting the important role of the d orbitals of the A atom. Not all the dopants in the A site, but the elements that disturb the cubic triangular antiferromagnetic state, are effective in broadening the volume change. This fact suggests that instability neighboring the phase boundary is related to the broadening. The relation between the gradual volume change and the local structure anomaly is suggested by recent microprobe studies.

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