I had an exchange with G.SKILL's tech-support, who are always good with their e-mail responses. I'll take a step backward to explain.
In the last DDR3 generation of RAM, you could, if you wished, fill your motherboard with 4x8GB of their "OC" XMP RAM with 2x 2-module kits and get the full XMP spec performance. I think this may have worked with lower-tier motherboards like the ASUS "-A" model-line. We have a Z77-A motherboard, and you could mix the size of the two kits, so we put in a 2x4 and a 2x2 kit for a total of 12 GB.
So I was fishing for a similar way to add RAM to my Skylake, which as a 2x8GB set of DDR4-3200 XMP TridentZ 14-14-14. I couldn't find anything like a 2x2GB kit or a 2x4 kit, and I put in a tech-support query asking for a recommendation. My past history with G.SKILL leaves me trusting that they're not just "trying to sell more stuff," and their recommendations have always been spot-on.
They said that adding a second 2x8GB DDR4 kit might make it difficult to run at the XMP spec, and they'd have to be set lower -- either by reducing the speed, or loosening the timings from 14 to 16. So they recommended simply replacing the 2x8 kit with the identical 2x16GB=32GB kit.
I can't speak to the Gigabyte Z170X, but you can cross-reference the board's QVL list and a RAM-manufacturer's "configurator" link. As for Corsair, I've got a set of 4x4GB DDR3-1600 which are stellar. I picked them up as part of someone's used bundle. I'd used prior-gen Corsair at least a couple times.
However, this is the way you do it. The board will, by default, choose 2133Mhz as the speed for a set of DDR4-[higher speed]. You should overclock your processor at that speed first, then choose the XMP RAM profile for the spec. There shouldn't be a problem with it proving stable right away, as far as my G.SKILL experience goes. Of course, you'd have to stress-test again. If there is any problem with the stressing, it's more likely that it needs more VCORE. Upping the VCCIO (IMC) wasn't necessary for me with my 2x8 kit.
Personally, I don't think it's worth the trouble "OC'ing" the RAM beyond its "OC-XMP-spec." Just buy the speed you want and run them at their XMP specification.
PS . . . If you purchased RAM at a spec higher than 2133, they should run at the spec (3,000 for instance) out of the box at stock CPU setting using the RAM XMP profile. And as I said, I only had to bump up my VCORE a tad to get complete stability with the RAM XMP profile while OC'ing the CPU.
There are a lot of different views concerning the CPU OC voltage. I see people who say they run their Skylake at 1.38V to get 4.7 or 4.8. I have a different view, based on an engineering white-paper I found about the processor. For an i7-6700K (not sure about 6600K) you should be able to find the perfectly-stable setting by starting with these numbers for each OC going up the scale:
4300 . . . 1.20V
4400 . . . 1.232V
4500 . . . 1.280V
4600 . . . 1.344V
4700 . . . 1.408V
You could either start at numbers close to but below these and test with possibility of bumping up the voltage, or you could start with the numbers and test by lowering the voltage.
if it's a 6700K, the processor will either run at 4600 or 4700 with stellar cooling -- or it won't. Luck of the draw. Another member got his 6600K to 4.5 Ghz, and I'm not sure about his voltage, but I think it was around 1.28. He was rocking a Hyper 212 EVO cooler, and his temperatures reached 80C.
If you reach that temperature with a stable overclock, you may not get much further unless you can improve the cooling. Heat causes electrical noise. And the Skylakes are more sensitive to temperature than earlier models. But they're supposed to be more resilient to voltage degradation -- how much, I cannot be sure. It could be around 1.4V, though.