We are using OpenLDAP 2.4 and currently we use the following LDIF to load the unique module and assure that the mail attribute is unique:
dn: cn=module,cn=config
cn: module
objectclass: olcModuleList
objectclass: top
olcmoduleload: unique
olcmodulepath: /usr/lib/ldap
dn: olcOverlay=unique,olcDatabase={1}hdb,cn=config
objectClass: olcOverlayConfig
objectClass: olcUniqueConfig
olcOverlay: {0}unique
olcUniqueAttribute: mail