When I first saw this thread the couple that came to mind was Fred/Angel . I know they didn't exactly get together in the show but they did share that one kiss.
I won't deny that i'm a Fred fan. I loved the quirkiness of her character as she tried to adjust to being back in her own dimension and her crush on Angel was understandable.
He saved her from the damnation of being a slave to demons so of course she would have a crush on him.
And then over the seasons she grew as a character to s4 "Magic Bullet" where she was the one to save the day. She knew that the bullet wouldn't kill Angel and I think in that alleyway when they were hiding Angel could see that Fred wasn't that girl he first knew anymore.
And while they kissed to avoid being seen, Fred asks Angel if they bought it and he says "I did" I think the kiss was something more. They were supposed to act as a couple and by Angel saying he bought it the kiss must have been something special like a boyfriend/girlfriend passionate kiss.
Sadly we had no more frangel kiss scenes but when Fred was dying Angel was determined to save her. He cared about her and he knew that Fred wouldn't want to infect everyone else in the world if they did that spell just to save her.
Poor Angel keeps losing the ones he loves.
Runner Ups are Remus/Sirius and Willow/Tara
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