Manzano sent off Clement Lenglet midway through the first-half.
Movistar captured Pique speaking to Manzano in the tunnel at halftime about the decision.
"It is very clear, do you really believe that there was intention..? " queried Piqué, referring to Lenglet's elbow.
The ref replied: "It is not that the elbow is like that but that he moves it..."
Pique was unconvinced and is quoted: "It's true the record already speaks for itself."