Just been playing around with it. What I had done is adjusted the b-screw so that the dérailleur cleared the biggest cog, before fitting the chain. Which was actually far more than required when the chain was fitted.
Normally I would fit the chain and adjust the b-screw according to the noise when going up to the largest cog, I always assumed that this meant the dérailleur would clear the cogs anyhow. I just fiddled around more than usual, with it not being a supported configuration, and the 42 cog being so bloody huge, rather than just doing it my usual way.
So, lesson learned.