Two-dimensional materials offer a unique range of magnetic, electronic, and mechanical properties which
can be controlled by external stimuli. Pressure is a particularly important stimulus, as it can be achieved readily
and can produce large responses, especially in low-dimensional materials. In this paper, we explore the pressure
dependence of the structural and magnetic properties of a two-dimensional van der Waals (vdW) molecular
framework antiferromagnet with ferromagnetic layers, Ni(NCS)2, up to 8.4 kbar. Through a combination of
x-ray and neutron diffraction analysis, we find that Ni(NCS)2 is significantly more compressible than comparable
vdW metal halides, and its response is anisotropic not only out of the plane, but also within the layers. Using
bulk magnetization and neutron diffraction data, we show that the ambient layered antiferromagnetic phase
is maintained up to the largest investigated pressure, but with an enhanced Néel temperature, TN (TN/TN =
+19%), and a large pressure sensitivity (Q = 1
TN
dTN
dP = +2.3% kbar−1
), one of the larger values of magnetic
pressure responsiveness for a vdW material. Density functional theory calculations suggest that this is due to
increasing three dimensionality. These results provide insights into the pressure response of molecular framework
vdW magnets and suggest that the investigation of other molecular framework vdW magnets might uncover
contenders for future pressure-switchable devices.