Silicone caulk is fine, but get the GE Silicone II, or whichever brand/model is labelled as paintable. Cut the nozzle only a short way back, to dispense a fine bead, perhaps 1/8 inch or less, so it is not noticeable, and makes it easier to razor blade the excess off, where it smears or drips. I hope you intend to caulk at the pane edges and casing/trim; not between the moving part and the sill. Unopenable windows are draftproof, but dangerous, should you have a fire.