It doesn't matter, if you run a 4S and a 2S even if they are both the same brand, same age, same mah, same C rating everything else the same the 4S will completely drain down to 2.2V/C by the time the 2S reaches 3.3V/C. I have my LVC set to 3.2V/C and I've ruined one 4S lipo and slightly damaged another one buy running them in series on my LST2-E. The first time I thought it was a fluke the second time I was keeping an eye on it more closely and caught it before I completely ruined it. That pack has just the slightest puff now but I think its ok. The IR of the cells went up from about 1.3milliohms to about 2.1 so I think it may have damaged it a wee bit but I think its still usable.
I think since the 4S has twice as much voltage it pushes out its power faster than the 2S pack making it drain much more quickly than the 2S pack. So one feel free to correct me if I'm missing something here but thats been my experience.