It sure burnt up like a RIFA though!
The capacitor that burnt up was identical to the one immediately to the left of it. EPOC E68 polyester metallized film capacitor, 250V 2.2uF.
It's not clear in the picture but the capacitor that is not burnt does have visible signs of stress, the ends have cracks and a bit of melted plastic "oozing" out, so it obviously got very hot.
I haven't yet determined if this was just a result of heat from the adjacent capacitor on fire, or from electrical over-stress.
This is a power supply with a half-bridge converter topology where one end of the single primary winding is capacitively coupled between the positive and negative high voltage rail. The capacitors in the picture are the transformer coupling ones (these caps are not across AC mains).
Interestingly, neither of the switching MOSFETs have failed.
I'll update this once I've done more troubleshooting, but this is definitely unlike any SMPS failure mode I've ever come across to date.