There were two -- Lewis Cass and Jeremiah Black -- plus one who was an "acting" secretary, William Hunter. Lewis Cass of Michigan. For the last three months of Buchanan's term Cass was replaced by Jeremiah S Black of Pennsylvania.
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No ex-president has later become a Secretary of State- six have moved up from Secretary of State to president, however.
The first cabinet officer in line for the presidency is the Secretary of state, who is behind the vice-president, the Speaker of the House and president pro tempore of the Senate.
Congress approves Secretary of State.
The Secretary of State is fourth in line following the Vice President, the Speaker of the House, and the President Pro Tempore of the Senate.
Webster :)