Create part with 45 degree pins
For SCH:
A possible solution is to draw the symbol as you want to see it.  Include lines to mimic the position of pins (at any angle).  

Make sure the pin 'lines' end on-grid.  Then place zero-length pins at the end of the graphical lines.  Be aware that any text associated with the pins will remain orthogonal.

You can add zero-length pins in the SCHLIB editor in pin-properties.

-Chris