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The inventory, aaset items would always be evaluated and set at Inventory org level or can be tracked at subinventory level and therefore can be setup or modified only at the options available at those level. This is because these accounts affects inventory valuation. While you can create inventory expense items for which account generator can be customized to default an account you wish.
To resolve this issue there are 2 options.
1> Specific item you want to charge could be type INVNTORY.
In this case you need to create PR/PO as destination inventory system will charge it to Masterial Inventory accuont.
Receive PO in Asset type of subinventory . and Now Transfer this Received item to User's department ( defnied user Dept as Expense type of subinventory) for transfering material you can use Subinventory transfer or Move order tranasation form.
2> create This specific item as Expense Item
If you have clear rule than you cna automate change a/c generation through modifing a/c generator for expense type
Or optionally Requester manually go to PR Destribution and change charge a/c to cirrect department code of requester.
Hope one of above option will solve your issue
In oracle purchasing PO Account Generator workflow can be customised to build the charge account for each Purchase order, Release and Requisition distribution based on distrubution's Expense, Inventory, or Shop floor destination type.