Both prepositions are correct.
Many prepositions would be correct. In addition to "in" and "at" you could also use: "during", "before", "after", "within", "around", "with", "near", "on", "until", "over", "through".
Each preposition has its own meaning. Use the one that has the meaning you want to express.
"In" connotes containment in the hour.
"At" connotes a location in time.