very good question
🙂
I don't know how we know it.
But with my experience, I just know how to draw XeF4. I know that this is not a good answer.
I think there are list of 'unusual' atom that forms more than octet.
I think Xe is one of them and then I think S or Se is another unusual exception.
http://www.saskschools.ca/curr_content/chem20/covmolec/movies/expand.html
This link teaches about expanded octets.
how about this.
Just write XeF4. total valance electrons are 36
Draw Xe surroudned by 4F with single bond = 36-8 = 28
Then make F octet = 28-24 = 4
put these 4 around Xe.
Usually, if we don't have enough electrons to satisfy every thing octet, we move 2 electrons and make it into double bond thus two atoms can share them and overcome the problem. But in this case, we made both Xe and F octet and still have extras, so I think the only thing we can do is putting 4 electrons to the Xe.
Try this one, PCl5.
total valence is 40
P surrounded by 5 Cl and linked with 1 bond each = 30 left
make Cl octet = used all~
🙂
now look at P, it's more than octet~