There is absolutely something wrong here. You should not be sitting idle at those temps. Did you plug the cpu fan into the cpu header? The h100i comes with pre-applied thermal paste and usually it is applied perfectly across the mount. However, you can try re-mounting your cooler, do not install it too tight just tight enough with your fingers so it does not move. Otherwise, remove the thermal paste from the cooler and re apply with new paste. Make sure you check your cpu usage and confirm that nothing is running in the background to make your cpu under load. My 6700k with the h100i GTX is 23C, under 100% load only reaches 58C.
Edit: first try using a different software for temp monitoring like real temp or core temp or hwinfo or...