Wow, I thought at least Pym Particles debuted in the Avengers, but it looks like Tales to Astonish takes that honor.
According to the Comic Vine wiki the Marvel Multiverse first appeared in The Avengers issue 23.
There at least has to be some alien races or locations introduced in the Avengers. The X-Men had the Savage Land, Genosha, Krakoa, Asteroid M, Otherplace (Limbo), Muir Island, Madripoor, Phalanx, Brood, and Shi'ar.
I think a major difference when comparing the the contributions of other stories to that of the Avengers is mainly that the X-men (or the Fantastic Four or whoever) represent their own mythology in and of themselves, whereas the Avengers is sort of where all those mythologies come together. Most marvel comics take place within this shared universe, but it's really only in the Avengers that it's actually integral to most of the stories. The Avengers actually represent that shared universe, and couldn't exist without it.
That's not to say that I think the mythos of the Avengers has added less to that shared reality than the other corners though. Take your Pym particles there as an example; yes, Hank Pym and his amazing particles did debut outside of the Avengers, but would he or they have had any impact on the MU if he hadn't been one of the original Avengers? Would anyone even know who he was? I think if you look at most of the classic Avengers (outside of the big 4, and maybe Black Panther), characters like the Pyms, Hawkeye, Black Widow, the Vision, and probably even Iron-man, would probably not even be remembered, let alone central characters within the MU, had they not been Avengers.
The Avengers, more than any other marvel mythology simply, can't exist off in it's own little corner of the MU because it's basis really is that it's the center of that world.
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