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What about 5 cylinder engine (or other odd cylinder engine ) I could see that the math for calculating VE would be the the same however do they not have a paired cylinder? Are the all offset by a certain angle?
I don't quite follow your question - it's very late/early here.
With an in-line engine, it's simply dividing 720 degrees by the number of cylinders to get an even firing order.
With a normal flat, or 120, or 60 degree "V" configuration, the same principle applies.
There are 90 degree "V" engines, and they have three basic variations, "odd-fire" when a common journal is used for paired cylinders, and this results in a, IIRC, 90-150-90-150-90-150... firing angle timing. The second, 'Even Fire" type has the big end journals "split ground" so rather than have the paired pistons on the 'same'journal, they're separated by, IIRC, 30 degrees, but as this is difficult to design with adequate strength, there is a compromise. Can't recall the term - semi-odd fire? - where the crank pins are ground with a small split, which is a compromise between the two - it's a bit smoother but still has a relatively strong crankshaft.
The 90 degree V6 can work well, though - GM had different versions of them, and for some years now the F1 engines have been of that configuration.
There is a narrow angle "V" five cylinder engine made by VAG, that uses the split journal design as well.
More later, if interested, my bed is calling me now.