Not an ordinance of the legislature of the state, an act by the people of their state in their sovereign capacity. Again note that the people of the several states are not bound by the Supremacy clause.
It doesn't say how the laws are enacted.
Article I § 7 states 'Every Bill which shall have passed the House of Representatives and the Senate, shall, before it become a Law...'
A state law(ordinance) can not trump the constitution.
The several states ratified unilaterally - no state could ratify for another. Their ratifications were the act of the people of each state - not their legislatures. The act is not their state constitution, or a law passed by a legislature. In Federalist No. 48, James Madison stated that the 'convention which passed the ordinance of government, laid its foundation on this basis, that the legislative, executive, and judiciary departments should be separate and distinct.' It wasn't a law.