Tolerance Groups are used to define different control amounts which apply to maximum amount of the document, maximum amount of the line item, maximum cash discount to customers and vendors. Those could be defined globally for every company code or per group of employees.
IMG Path: Financial Accounting (New) -> Financial Accounting Global Settings (New) -> Document -> Tolerance Groups -> Define Tolerance Groups for Employees
When you open the transaction, you could either edit an already existing Tolerance Group or Create a new with New Entries button.
Fill the options as you required and save your customization. Following is a global group defined per company code.
Following is a screenshot from IDES group samples.