@mporter1744,
Not necessarily. Is there a reason to be suspicious? Do you know this man? How does he know your wife? How did you discover this? Do you share passwords or anything - if so then your wife certainly isn't hiding anything.
To me the time should not be a factor - it could be he is in a different time zone, could be he had difficulty sleeping so was looking up old friends.
Facebook (I personally do not use it), but it is used frequently simply to keep in touch with family and friends - it isn't really a tool for affairs. Usually you are just sharing pictures and keeping up to date.
So unless you actually have a reason to be concerned besides this invite, I wouldn't worry.