The clock in the picture is a Randall 102 clock. It has 3 settings
Hot water which will fire the boiler and run the pump.
Off.
Water and heating which as well as firing the boiler, running the pump would also open the valve for heating.
As has been said it would be better to upgrade to a S plan by adding a valve to the hot water circuit and installing a cylinder thermostat.
However, the Nest can be used on the system as it is by a slight change to the wiring to it.
Hot water which will fire the boiler and run the pump.
Off.
Water and heating which as well as firing the boiler, running the pump would also open the valve for heating.
As has been said it would be better to upgrade to a S plan by adding a valve to the hot water circuit and installing a cylinder thermostat.
However, the Nest can be used on the system as it is by a slight change to the wiring to it.