I would like a report showing the structure of departments as well as which people have been assigned which roles per department. Do you have this?

In the deviation module itself, we do not have such a report. You need to go to "Organization" to see the structure and click on each department to see who is assigned there. If you have Simployer Portal, you can go to "Reports → My Organization → Roles" and generate a report specifically for deviations. This report will show the individuals and their roles in the deviation module.