Having read all the Asimov novels when I was younger....
spoiler
The Caves of Steel: human killed because he was mistaken for the android that he built in his own image.
The Robots of Dawn: robot killed (positronic brain essentially bricked) to prevent it from revealing the secrets of how to build robots that can pass for human. It had been a human's sex partner, but that wasn't the motive. No one thought banging a robot was that strange; the only thing that perturbed them was the human getting emotional fulfillment from it (the planet Aurora is a decadent world where sex is for entertainment and fashion, not relationships).
The Naked Sun: the villain manipulates robots to commit crimes by having multiple robots each do a part of the task, so that the "a robot shall not harm a human being" software directive is never activated. He tries to poison a man by having one robot dose a water carafe and another unknowingly pour from it, but being a poisoning noob, he screws up the dosage and the victim lives. His only successful murder involves a human as well; he programs a robot to hand a blunt object to a human during a violent quarrel with the intended victim.
As a wise friend of mine said years ago, when hipsters drinking PBR were having a cultural moment, "You can say you're drinking piss beer 'ironically', but at the end of the day, you're still drinking piss beer."