Water heaters are for hot water in you're whole house boiler is for the heat
Unless the boiler has a hot water coil built into it which many still have. Than it serves a dual purpose of providing heat for your heating system and hot water for bathing etc.
Everything strgazr has posted is correct. Even the link shows copper has 200 times greater heat transfer than SS.
Jameson if your looking to do something like this the second RC thread posted with the water heater is done well but I think you would be better off with the boiler the high temp would give you a better heat transfer. Someone touched on something you should know about though. If the return water to the boiler is to cool (under 140) on a cast iron boiler the flue gases will condense and will clog the boiler flue passages over time. To avoid this a heat exchanger between would solve that problem. You could also then regulate the water temp of the coil in the sump just incase you need to lower it. This of course would not be cheap and none of these are a free way to heat your tank your still using gas or oil but in a large tank may work better than a heater for you but im not sure its worth the effort.
Off topic but you may want to rethink that on demand. The cost is high depending on the home. The savings is actually extremely low. If you even read the fine print from the manufactures the average savings from a gas water heater is 30 dollars a year and that's not for the north east. Your indirect heater is actually the better choice an indirect water heater losses 2 degrees a day a standard gas water heater looses 2 degrees an hour. On demand water heaters need annual service to keep the warranties and the do not last very long like this old house keeps saying on there shows there average life is the same as a gas water heater.