She was killing the man who had ignored Angel's pardon; thereby, he'd had a part in Angel's death at the front lines. She killed him for vengeance; I'm guessing she wanted to make his death as painful as possible, though you're right -- it's kind of a weird way to kill someone.
Jeunet explains that he likes this scene because Marion Cotillard is acting perfectly as 20's sexually attractive woman, and also because the wounded belly special effect is quite good.
Maybe the symbolism is that the officer can see his death irrevocably coming in the mirror above him, just as the 5 condemned men could see their death coming in No-man's land ... a sort of tit for tat.
Only the officer didn't have to suffer for as long as the condemned did.