I think it's episode 132, because it's called "Hitsugaya, Karin, and The Soccer Ball".
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Season 13: Zanpakutō: The Alternate Tale (2009-2010) Episode 239-Toward the middle of the episode.
She appears in the magna and in the anime sometime around Pervy sage's death
It will never come out beacus Koge-Donbo doesn't want Kamichama Karin Chu to be made into an anime and Kamichama Karin is finished.
They haven't met in the manga. At least, not yet, but as of chapter 460, there is a chance. Hitsugaya meets Karin only in the anime (episode 132), and there's a later episode with them, 316, as well.
No, she does not. Because Toshiro is very young than Rangiku.