1. Statue of Liberty, without question.
2. Twin Towers - showed up in just about shot of NYC put into mainstream media from the date of inception until destruction.
3. Empire State Building - Yes it is really recognizable but never got the media exposure of the WTC.
After that things get a little muddier. If I'm doing a top-5 I probably do something Times Square and Rockefeller Center to round out the big-5 pre-9/11.