There's a couple of ways, but the easiest is to remember that the exterior angles of any polygon add up to 360.
360/16 = 22.5 degrees.
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180 - interior angle = exterior angle
No, you cannot find the exterior angle before the interior because the interior angles can vary in many ways.
By dividing number of its sides into 360 will give you the exterior angle.
Subtract it from 180
The interior angle and the exterior angle are supplementary. That's why you learned about supplementary angles ... or at least they were presented in class ... before polygons.