If you'd like to track unpaid time off, you can do so by going to Settings --> Time Off:

On the Time Off page, you can either add a new time off earning code if needed or Edit an existing code:

This is where you can designate what type of time off code you're creating. In this case you'll want to select Unpaid:

Unpaid time off will show up under a new column on an employees time card:

Just as with paid time off, unpaid time off is not included in overtime calculations. 

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