I'll assume you're talking about cigarettes. I don't know how that's a sign that you're clicking with them. When I'm smoking, I'll chit chat with anyone outside. That doesn't mean I want these people to be my fraternity brothers.
Every time I have ever heard someone say they were invited to go smoke with people somewhere, it means that they were smoking weed. I think that's what he is talking about. I could be wrong though.
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