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Each single bond a central atom has attaches to it is a sigma bond, every additional bond added to the initial single bond (double or triple bond) is a pi bond. So in the case of SF6, S has 6 single bonded F's, so it has 6 sigma bonds and no pi bonds. NO3- on the other hand has 2 single bonds and 1 double bond, so it has 3 sigma bonds and 1 pi bond.
A central atom can have multiple sigma bonds as long as they are all single bonds connecting the central atom to different atoms. Any double or triple bonds that are added in addition to those single bonds become pi bonds.
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