The Real Madrid centre back had a scan at a Madrid clinic that confirmed the fracture and had left the national team’s training camp, Real said in a statement on their website.
The Spanish club did not say how long he might be sidelined.
Spain, the world and European champions, qualified for the Euro 2012 finals in Ukraine and Poland with two games to spare and top Group I with a perfect 21 points from seven matches.
With one game to play, Scotland are second on 11 points and a win in Alicante would secure them a playoff berth. Czech Republic, who play in Lithuania on Tuesday, are third on 10.
Spain midfielder Xabi Alonso is doubtful for the Scotland game after sustaining a gashed shin in Friday’s 2-0 win in Prague. (Reporting by Iain Rogers; Editing by Clare Fallon)