The reaction of [ReBr3(CO)3][NEt4]2 with 3‐hydroxy‐1,2,3‐benzotriazine‐4(3H)‐one in the presence of base gave the ionic rhenium complex [ReBr(C7H4N3O2)(CO)3][NEt4] (2) which was crystallographically characterized. A neutral metallamacrocycle 3 was obtained upon abstraction of [NEt4]Br from complex 2. This complex cocrystallizes with an unusual C3‐symmetric [Ag(η2‐benzene)3(OH2)][BF4] complex as evidenced by single‐crystal X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)