In order to pay part or the whole salary to someone else than the employee, it is necessary to create third-parties.
Go to references / tab banks & third-parties
Click on Add.
Example : debt collection office if you want to pay them along the salaries :
Give the third-party a code, its bank (or postal account in the example).
Check the box Pay the salary to someone else than the employee. Insert full name and address.
The account number will be indicated in the employee management.