What structure should there be for nlogn solution to be applicable?
The issue isn't structure but rather density. If you have N values ranging from -M to M, the "obvious" solution is O(N^2) and the convolution us O(M log M). So if you have lots of values within a narrow range the convolution wins.
I wasn't silent for half an hour, just for the first couple minutes; but I didn't write any code (which is what the interviewer was pressing me to do).
(Speaking of entirely new algorithms though, there was an interview question which was a thinly disguised 3SUM, and they expected the very obvious N^2 solution; my interviewers were shocked when I pointed out that the way they had structured the problem, the density was high enough to use a convolution and solve it in N log N time.)