James Buchanan never married. His niece Harriet Lane acted as Whitehouse hostess during his presidency.
In addition to Buchanan, a few presidents' wives died young and their other female relatives served as hostess. Chester Arthur's sister Mary Arthur McElroy, Thomas Jefferson's daughter Martha Jefferson Randolph, Martin Van Buren's daughter in law Angelica Singleton Van Buren, etc all served as First Lady. After Margaret Woodrow Wilson's very brief tenure all First Ladies are the president's wife.