1) If the hot water is pressurized beyond 1 atm, then the water can be >100°C. I am aware of a system that typically operates at supply = 125°C, increasing thermal capacity (but still less than that of steam).
2) Some jurisdictions treat hot water systems more leniently than steam systems. For example, the aforementioned system does not require continuous monitoring by a stationary engineer, and the municipal approvals for 'hot water' were easier than they would have been for steam.
3) It is easier at the loads to use water/water heat exchangers rather than steam/water, if the loads include domestic hot water and hot water heating.
4) Sometimes, there is more potential useful waste heat available to a system that only requires 100-125°C of supply temperature than to a system that is looking for steam as source.