If you have the time to deliberately aim down the barrel, placing the front sight in the direct center of the rear sight, and even horizontally, then slowly squeeze one off between the perps eyeballs, then by all means, go for it. I'm certain the bad guy will pose, standing perfectly motionless, while you line him up. ;)
It takes a lot longer to even say that than it takes to do it. The guy with the .44 was firing from some distance, and partially from behind cover and concealment. Probably had a rest available as well, but it's hard to tell that from the description. Besides, I'd never aim for anything other than center of mass, or whatever was showing. (The bad guy was partially behind concealment as well.) In this case there was obviously a lot of missing going on. Doesn't matter how quickly you shoot, if you miss, other than its value in keeping the other guys head down and forcing him to rush his shots. Of course an aimed shot that merely hits near his position behind cover and or concealment does that as well. With the .44 you could probably shoot through many types of concealment, if you still had a good notion of where the bad guy was behind it.