I don't understand what Mep means about leaving the 3rd slot blocked in the new sub panel either? If the new panel will be single phase, wouldn't you pull (2) of the 120v leads off the three phase panel to make single phase 220v in your sub panel???
My ER is set up the same way. I have a 3 phase panel that supplies my pump stand. I also have a single phase 220v panel that supplies either 220v or 120v to everything else. Just make sure you don't use the "High" leg to power your sub-panel...
At my wash, Only 3 phase comes to the building from the transformer. It splits to 2 seperate meters then into the ER to the two seperate panels. If you power a single phase sub panel from the three phase panel, you might check to make sure you're not violating any codes.