Despite buhockey21 using the term "similar situation", I suspect, as KrisD15 did, that he's really asking about the more common situation: he got $5250 of tax free tuition assistance and some additional assistance that was included as taxable income on his W-2.
His question is can he use the "excess" assistance to claim a tuition credit or deduction. The answer is yes. Because he has paid tax on that money, it is treated as "his" money not the employer's money.
He may actually come out ahead. The LLC is worth 20% of the amount claimed.