You can do that by creating a group for that couple, naming it accordingly (so that you can recognize it, e.g.: "Smith couple"), and assigning the two people to that group (from CONTACTS TAB > Contact Name > Profile tab > "Groups Information" section > check the group name and save). Then, when you schedule the appointment, you schedule it as an appointment "with a group" and select their group from the drop-down list in the scheduling pop-up window.
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