AC Milan - 2-0 victors over the Hoops last midweek - lost 2-1 against Napoli in the San Siro where Mario Balotelli scored, but also missed from the spot.
Ajax were crushed 4-0 at PSV Eindhoven and are four points behind their table-topping rivals in the Dutch title race.
Barcelona continued their superb form with a 4-0 thrashing of Rayo Vallecano and are joint top of the Primera alongside Atletico Madrid, who have also won their opening five games.
Real Madrid moved into third place with a 4-1 win over Getafe last night. Cristiano Ronaldo scored twice as Gareth Bale injured himself in the warm-up and missed out on his Bernabeu debut.