In that case, you DEFINITELY want to make sure you have good air-flow through the case. A decent way to test (if your case has a window) is to hang short lengths of string from different parts of the case (but not close to fans - haha), and see where you have solid or little flow, too much turbulence, etc. Your case model looks like it should be capable of decent air-flow, but I don't know anything specific about that model.
What is the temperature of the air inside the case while your machine is under a normal load? The cooler is always trying to bring the CPU temperature down to that level, and not necessarily the ambient air temperature. If the house is 75, then the case will be hotter, and the CPU hotter still.
Nonetheless, 45 degrees under load on that CPU is far from poor, and you probably won't gain more than a few degrees with the NH-D14 or the H100i.
Edit: I just recalled that you're not over-clocked at all. Check for good air-flow, and also look online to see what temps other people are getting with your cooler (keep an eye also on their ambient air temperatures).
Z