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What I have seen for this is that the Charge Account usually has to be drawn from two areas, the natural account is generated from the category code which has to be defined in the expense account rule for each operating unit. The rest of the default coa is generally brought over from the HR record or Employee record, you would want to check both to make sure they are setup in that OU.
The charge account will default from the following places :
1. Item level, expense account
2. Organization level expense account
3. Employee HR data
4. iProcurement preferences
and the natural account segment is overridden by the expense account rules defined.
Thanks & Regards