For my geared hub motor systems powered by LiPoly, I've settled on 14S, which makes a nominal 51 Volt pack and the Volts value does matter.
It matters because this range is the highest one can go without paying much attention to:
1) Wire gauge, easy to work with 12 and 14 awg can be used.
2) Cheap and easy to use low capacity connectors like 6 m/m bullets can be used with no anti-spark consideration.
3) Budget controllers can be used without concern of blowing capacitors.
4) If a mistake is made, there is no perm. damage to one's fingers and eyesight
Con:
1) Not much available in the way of 7S LiPoly bricks. I make my own.
More important than the ultimate Volts value settled on, is matching the motor speed range to achieve the desired top speed.
I am most comfortable in the mid 20's MPH range and that means for a bike w/ 26" whl.s, motor speeds in the 240 RPM to 260RPM rated @ 36 Volts.
IMO, matching these values, whl. size, motor speed and system Voltage is key to building a happy rider/ebike relationship.