Is he set up as a *system* admin, or just a project admin? (A project admin does not get "login" rights, unless they are a normal user or a system admin as well)
The error says the account is "not yet available" - how long ago did you add it?
Hmm, that implies someone has disabled his account. I am sort of assuming you are an admin in the system - can you go into his profile and check? If not, then you'll need to find an admin for your system (if you don't know any in your organisation, you'll need to talk to Atlassian OnDemand support directly)
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