I am not gas qualified, so won’t comment on anything gas.
The unvented cylinder will be to regs if heated by a controlled heat source of oil or gas boiler and the 2 port valve supplied with the unvented unit to be in operation, controlled by uv stat.
A combi used with extra zone, or solely a zone for unvented or vented cylinder hot water I would have thought was fine and to MIS.
The space heating main body part of a combi boiler is just the same as a heat only system boiler anyhow, - isn’t it?
But sure it only takes a phone call or email to the boiler manufacturer to confirm.
I know combi boilers are installed on homes where there is some sort of hot water cylinder (vented or not) so to give option of mains pressure hot water at some outlets, or to provide instant hot water at a supply close to where the gas boiler is sited, - like a kitchen tap.