What the heck is that chimney for, a blast furnace? Why not cast the whole thing, and just put a brick veneer outer layer, on a cast conc. brick ledge and up under a 7-8" overhanging, conc. outer lip at the cap. Cast a water drip reglet 3/4" back from the outer edge of the cap, all around, on the underside of the overhanging conc. outer lip.
Brick tends to expand, while conc. tends to contract with time, so all-in-all keying them together may not be a real good idea. Maybe a case could be made for putting a through wall flashing on top of the brick, with a drip edge, and casting the cap on top of that flashing. Where is that cap going to go? Cast a retainer ring on the inside of the conc. cap. Put a 1x2 strippable form board against the brick on the inside of the chimney and cast the cap 2" lower than the top of the brick on the inside. Then, pull the form board, just a retaining ring is left.
You could also have some problems with that 4 wythe brick wall and moisture and heat on the inside and cold on the outer surface.