Several U.S. presidents had military service in war time and would have killed men in battle, other than that the answer is no.
President Andrew Jackson, Duel with Charles Dickinson 1806 Andrew Jackson challenged Charles Dickinson, a lawyer, to a duel for having maligned the character of Mrs. Jackson and for a misunderstanding following cancellation of an important horse race. The two squared off with pistols at the customary eight paces in a popular forest clearing in Harrison's Mill, Kentucky in 1806. Dickinson got off the first shot...a direct hit into Jackson's breast that raised dust from his coat as the bullet entered. Andrew Jackson remained so stiff that Dickinson stumbled back in sheer disbelief. At the angry shouts of Jackson's second.... demanding to return to his mark, Dickinson complied and returned to his position. Although it was commonplace for a man in Jackson's position to spare the life of his opponent by firing into the air, Jackson chose otherwise. Jackson fired his pistol. The ball penetrated Dickinson's abdomen and exited the other side... killing him instantly. The future president simply walked off the field... feet sloshing in blood that drained from his chest. Dickinson's bullet had lodged too close to Jackson's heart to be removed safely. Jackson would carry it to his grave.(S.Menzel)
Jefferson's VP (does this count?) Dueling was a common way to kill someone in the 1800s. Another famous duel, perhaps more famous than Jackson's, happened in 1804 between Jefferson's Vice President Aaron Burr and former Secretary of the Treasury Alexander Hamilton. Burr was angry at Hamilton for standing in the way of the advancement of his career, and challenged him to a duel. People still argue about exactly what happened, but Burr shot Hamilton, and his bullet killed him. Because Hamilton died in New York, but the duel was in New Jersey, the charges were dropped. Later, however, Burr would be tried for treason.