Here, we report the magnetic properties of a metal doubleperovskite framework, Cr[Bi(SCN) 6 ] • xH 2 O, using a combination of bulk magnetometry and neutron powder diffraction. We show that despite the large distances (>8 Å) between paramagnetic ions, there is significant superexchange coupling between these ions: indeed, we find that it has long-range magnetic order below 4.0(2) K. We then go on to solve the magnetic structure of Cr[Bi(SCN) 6 ] • xH 2 O, demonstrating that it orders with ferromagnetically correlated close-packed {111} cubic type planes, antiferromagnetically coupled, like MnO. This finding suggests that by using the extensive range of chemistry available in perovskite analogue metal thiocyanates we could tune the magnetic interactions to realise exotic quantum states.