In the title three-dimensional tetrazolate-based coordination polymer, poly[bis(μ(3)-cyanido-κ(3)N:C:C)[μ(5)-5-(pyridin-4-yl)tetrazolato-κ(5)N:N':N'':N''':N'''']tricopper(I)], [Cu(3)(C(6)H(4)N(5))(CN)(2)](n), there are two types of coordinated Cu(I) atoms. One type exhibits a tetrahedral environment and the other, residing on a twofold axis, adopts a trigonal coordination environment. The closest Cu···Cu distance is only 2.531 (2) Å, involving a bridging cyanide C atom. All four tetrazolate and the pyridine N atom of the 4-(pyridin-4-yl)-1H-tetrazolate anion are coordinated to these Cu(I) atoms and exhibit a μ(5)-bridging mode. The three-dimensional coordination network can be topologically simplified as a rarely observed (3,3,4,5)-connected network with the Schläfli symbol (4.6.8(4))(2).(4(2).6.8(7)).(6.8(2))(3).

Key indicators: single-crystal X-ray study; T = 298 K; mean (C-C) = 0.004 Å; R factor = 0.068; wR factor = 0.139; data-to-parameter ratio = 11.2.The asymmetric unit of the title compound, C 6 H 5 N 5 ÁC 9 H 6 O 6 , comprises a full molecule each of neutral trimesic acid (tma) and zwitterionic 5-(pyridin-1-ium-3-yl)-5H-1,2,3,4-tetrazol ExperimentalCrystal data

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