That may be an indicator of your problem. The the grey wire is only made live when hot water is not required.Got up and observed no hot water so:
Progammer shows heating constant (but up to temperature on stat)
Water constant. Felt pipes around MPV, hot to heating, cool to water cylinder
Voltage at MPV white 0 grey 250
The hot water not required signal comes from either the hot water 'off' connection at the programmer, or the changeover contact on the hot water cylinder thermostat which is energised when it switches over from 'call' to 'satisfied'
Looking at the test you describe above where you got up and there was no hot water, assuming it was selected 'on' at the programmer and the hot water cylinder thermostat was calling for heat, the grey wire should not be 'live'
There it is again, the 250V hot water not required signal present when actually hot water is required.Thanks again.
I observed the water didnt seem to be heating again so re-metered it:
White 0 Grey 250