N:N relationships are not possible with Appointment. You can create a custom entity (for example called Attendees) and you will create a 1:N relationship with Appointment (practically you will have a lookup pointing to this custom entity inside the appointment form) after you can create a N:N relationship between accounts and this custom entity. You can also create a quick view form of this custom entity with a subgrid inside in order to show the lists of the accounts inside the appointment form. hope it helps
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