In Google's latest Webmaster Help video, Matt Cutts discusses location and ccTLDs. Specifically, he responds to the following user-submitted question:
We have a vanity domain (http://ran.ge) that unfortunately isn't one of the generic TLDs, which means we can't set our geographic target in Webmaster Tools. Is there any way to still target our proper location?
"We've seen this trend - as the domain name space gets a little more exhausted in .com, people get creative, and so Matt Mullenweg at WordPress grabbed ma.tt, for example, which is a really creative URL, but something that people don't think about is: what is .tt? Or what is .ge?" says Cutts. "It's Georgia, you know, there's a lot of startups that have been using .io, which is the TLD for the Indian Ocean, I believe. So you have to think hard about is it the case that this is going to be known as an international area? If your'e just using .es because you can find some cool word that ends in .es, most people using that domain are targeting Spain. So that is our assumption - that you're targeting Spain."
He says that some people want .li to be associated with Long Island, but it's really associated with Lichtenstein, and that's how Google views it.
"In some sense, it comes down to a little bit of a call about when a domain becomes truly generic. When it becomes appropriate for the entire world. So .co, which used to be, I think, Columbia, might be more generic now, where everybody's using it as if it is another .com, but some domains, I would put some thought into. Just because it's a cool URL, a lot of the times we're going to be looking at it and thinking, 'Hmm, this is actually related more to Lichtenstein that it is to Long Island, and so even though people want to do a Long Island business, we're more likely to think that it's in Lichtenstein."
He goes on to suggest that you post on Webmaster forums and "rally your case," and do a blog post that says, ".iO is mostly startups, and this should not be related to this country..." Still, he says, Google has to look at the data and look at the domains that are in use, and make a judgment call.