A-site vacancy ordered molecular perovskites are rare, as the additional structural degrees of freedom often mean other structure types are favoured for high vacancy concentrations: for example AM II M III (HCO 2 ) 6 compounds adopt niccolite type structures . The Prussian Blue analogue cyanides can accommodate the complete range of A-site compositions, which has been exploited for their potential as battery electrode materials , but the A-sites are typically disordered. Some degree of rocksalt A-site cation order has been observed in a number of frameworks of approximate composition AM II M III (CN) 6 but this is typically incomplete, perhaps due to the high symmetry of these phases . Perhaps the best described example of A-site order in a vacancy perovskite is the recent report of 2 0.5 H 2 DABCO 0.5 {Mn(H 2 PO 2 ) 3 }, H 2 DABCO 2+ = 1,4-diazabicyclo[2.2.2]octane-1,4-diium, where vacancies order into {111} cubic layers presumably, as in A-site vacancy oxides, to minimise strain. It is therefore noteworthy that A-site vacancy order appears to be the rule in NCS-perovskites, rather than the exception. 1-4 all possess complete A-site order and these orderings are unusual for perovskites molecular otherwise: in 1 and 2 the cations have columnar order; in 3 the MeNH + 3 order into 3 × 2 × 1 blocks and in 4 the cations are present in one quarter of the cages with Cu 3 Au order. The block-order of cations in MeNH 3 {Ni[Bi(SCN) 6 ]} is to the best of our knowledge unknown in any other perovskite. It can be related to the nanochequerboard/nanochessboard phases observed in compositionally complex analogues of the rare-earth vacancy perovskites, such as 2 1 3 +4x Nd 2 3 -x Li 3x {TiO 3 }, x ≈ 0.1 57 and 2 0.2 Nd 0.6 Ca 0.1 {TiO 3 } 58 . These phases have a modulation in the occupancy of the A-site on a ca. 5 nm lengthscale. In addition the combination of M-site rocksalt and A-site columnar order found in 1 and 2 has only been reported previously for the high-pressure oxides MnLnMnSbO 6 , Ln=La,Pr,Nd,Sm, and CaMM ReO 6 , M=Mn or (Mn 0.5 Cu 0.5 ) and M'= Mn or Fe .