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Melamine diamine 1 is able to displace CB[5] from the CB[10]·CB[5] complex resulting in CB[10]·1₂ and precipitated CB[5]·1. We were able to isolate free CB[10] by treatment of CB[10]·1 with acetic anhydride followed by washing with MeOH, DMSO, and water. The spacious cavity of CB[10] is able to complex large guests, including a cationic calix[4]arene derivative in its 1,3-alternate form (CB[10]·1,3-alt-3). The addition of adamantane carboxylic acid (4) to CB[10]·3 triggers a conformational change during the formation of termolecular complex CB[10]·cone-3·4.