From Amateur_Ninja on Reddit:

Sky is an instantly likeable character. I think it's because she was designed to be the character that the audience can relate to. She was meant to be the "average joe" among highly trained professionals, in terms of personality. Right before this particular scene, there's a dramatic, somewhat cliche scene where Sky is told, "You have the gun- but can you pull the trigger?" The cliche response would be a extended pause, holding the gun to the antagonist's head, hand shaking wildly, perhaps a few tears from the stress.

Sky acts as the audience's relief from "traditional" action movie scenes. After pausing for a half second, she looks him in the eye and calmly says "Nope," then proceeds to jump out the window. No cliche "hero-with-too-good-morals" reaction. Her character is that of a normal girl in an abnormal situation.

Run, Skye, run! Yes, I misspelled the name Skye in the title...

Every Day in Between by Chloé Wang aka Chloe Bennett aka Skye:

Uh oh:

Skye in Agents of SHIELD episode 1x04 "Eye Spy":

http://pandawhale.com/post/29763/chloe-bennet-skye-appreciation-gifs-agents-of-shield-1x04-eye-spy