Won't the ambient light from the long exposure infect the flash exposure?
Well, yeah, to some extent. If there's a significant amount of ambient light falling on the subject, then it can certainly add to the flash's exposure of the subject. I alluded to this a little bit in my next-to-last paragraph, and it's certainly different for every situation, and may take some trial-and-error to get right. If the subject is standing under a streetlight, you wouldn't use the exact same settings as if the subject is standing in an unlit area. But if the background is very dim, you wouldn't put the subject under a streetlight anyway.
From the original description, with a cityscape in the background, I would think that the city lights and the sky would probably be much brighter than the subject.
And it depends on how long the "long" exposure is. Relative to most of the photography that I do, 1/2 or even 1/5 second is a "long" exposure. But it's not like a 30-second long exposure.

