If we just read this sentence, "a man who is complaining all the time that he doesn’t want to be in relationships with the woman he is living with", we should ask ourselves, without a horoscope, So why hasn't he simply left the woman he is not happy with instead of complaining to others about it?". Does his current partner think he is happy with her, has she any idea he wants out? If your sister enters a relationship with him, where he casually slip slides from the old to the new (she being the new), would he then treat her in the future in the same way?
His qualities, mars in pisces in his 12th, don't promise very much of a character as a man.
You say your sister's 7th is ruled by Neptune, so maybe this is the type of man and relationship she dreams about. But there are many ways it can manifest itself (pairing off with a poet or a musician or a religious man, for example).
They say, be careful about what you wish for, you may get it.
Your sister isn't in a strong position right now, approaching illusive Neptune, and also she is opposite the part of fortune, so her judgement is off.
She has nothing to lose by waiting it out, to see how he acts with his current partner, and decide from there.