M + 2 irreps), which is the same as the parent M[Bi(SCN) 6 ] phases and the related M-site defect-ordered NCS-frameworks {M[Bi(SCN) 6 ] 2+x 3 } x-{guest} x+ (M=Mn, Co, Ni, Zn). The combination of octahedral tilting and rocksalt Msite order leaves all pseudocubic Ni 4 Bi 4 (SCN) 12 cages still equivalent by symmetry, meaning that the A-site cation ordering may not be viewed being drive by these three distortions alone. The A-site cation ordering therefore lowers the space-group symmetry further, from P2 1 /n to P 1, and in addition produces a large shear strain compared to the M[Bi(SCN) 6 ] structures (α ≈ 97 • vs α = 90 • ).