You should take a look at the documentation of atan2 (here).
What you're looking of is finding the difference between B (your upper left vector) and A (your bottom right vector), then pass this as a parameter to atan2
return Math.Atan2(b.Y - a.Y, b.X - a.X);
What your code currently does is find the angle of the vector b in reference to 0,0 and subtract the angle of the vector a in reference to 0,0.
The reason you always get 0 is because 1,1 and 50,50 are on the same line that crosses 0,0 (both calls return something approx. 0.785398), so subtracting them will result in 0