If you mean the 6th clue in the list then yes, it could go in the place you say, but it is one of the thematic entries and it can also be placed at the bottom of the first column(the lyrics to the song mention two distinct groups and where they are positioned). The top row can only be decided at the end of the grid fill.
I found two members of each group to place. Each thematic answer is 'paired' with a non-thematic answer (their letters correspond in checked squares) and these eight answers can occupy positions on either side of the grid.
The long word at the end of row 2 is not thematic and is a good place to start (it starts with F). Hope it's not more complicated now.