Synthesis and Crystal Structure of a Two‐dimensional Silver(I)‐Iron(III) Heteronuclear Coordination Polymer: {[Ag,Fe 2 (SCN) 12 (H 2 O) 2 ] [(inaH) 2 (H 2 O) 2 ]} n

The 2‐D heteronuclear coordination polymer {[Ag 4 Fe2(SCN) 12 (H 2 O) 2 ] (inaH) 2 (H 2 O) 2 } n (1) (inaH is the abbreviation of protonated isonicotinic acid) with chemical formula C 24 Ag 4 Fe 2 N 14 O 8 S 12 has been synthesized and characterized by single crystal X‐ray diffraction, elemental analysis and IR spectroscopy. The Ag 2 S 2 rings connect two kinds of octahedral geometries of Fe(III) ions, [Fe(NCS) 6 ] 3– and Fe(H 2 O) 2 (NCS) 4 ] − units with bridging thiocyanate ions leading to 2‐D [Ag 4 Fe 2 (SCN) 12 (H 2 O) 2 2– anion framework. Four kinds of rings including the unprecedented thirty‐two membered Ag 4 Fe 4 (SCN) 8 rings share comers or edges in the 2‐D anion layer structure. All thiocyanates coordinate to the metal ions according to the HSAB principle with N atoms binding to the Fe(III) ions and with S atoms binding to Ag(I) ions. Pronoated ina cations stabilize the layer structure as counter ions and hydrogen bonds were formed within the pronoated in a cations dimer and between the dimers and the lattice waters. Crystal data: M r = 1560.44, triclinic, P 1, a =0.76082(1) nm, b=0.9234 nm, c= 1.85611(4) nm, a= 103.0170(10)°, β=93.7780(10)°, y =97.4080(10)°, V = 1.25385(3) nm 3 , Z=1, μ(Mo Kα)=2.650 mm −1 , D c ,=2.067 g · cm −3 , F (000)=758, R 1 =0.0412. wR 2 =0.1003.