Barry fights the Reverse-Flash outside the building in episode 1x09 "The Man in the Yellow Suit". The crew loads up their prisoners into the transport truck, and later Barry and others battle Wells outside the building in episode 1x22 "Rogue Air". Caitlin and Ronnie get married by Dr. Stein outside the building in episode 1x23 "Fast Enough". Appears in 9 more episodes.
Oliver and Laurel watch Lance's press conference about the new low level of crime in Starling City in episode 3x01 "The Calm".
Oliver and Felicity talk after leaving the board meeting at Queen Consolidated in episode 3x01 "The Calm".
Etta and Simon sneak Walter into Manhattan through this mass transit station in episode #419 "Letters of Transit".