Captain Kirk calls Smith "Mr. Smith". First off she is a woman not a man. In the original series a woman never would never have the title of a man. Secondly he would have referred to her as Ensign Smith, which is her title on the ship, not Mr Smith.
The Romulan should not have been able to be transported out of the brig as the security around the cells prevents this, as stated in other ST TOS episodes.