Anionische Nickel-Pseudohalogenid-Komplexe der Typen [Ni{N(CN)2}3]− und [Ni{N(CN)2}2(NCS)2]2−

Anionie Nickel Pseudohalide Complexes of the Types [Ni{N(CN)₂}₃]^? and [Ni{N(CN)₂}₂(NCS)₂]^2? The preparation of a new type of anionic pseudohalide complexes of nickel [Ni{N(CN)₂}₃]^? and of mixed thiocyanate-dicyanamide complexes [Ni{N(CN)₂}₂(NCS)₂]^2? is reported. The structures of the complexes are discussed on the basis of IR- and magnetic measurements. The new compounds are representing polymer octahedral complexes with a bridging function of the dicyanamide ligands.     

Kristallstrukturen der Terpyridin-Komplexe [Cd(terpy)Cl2], [Cu(terpy)(CN)Cl] und [Cu(terpy)][Cu(CN)3] · H2O

Crystal Structures of the Terpyridine Complexes [Cd(terpy)Cl₂], [Cu(terpy)(CN)Cl], and [Cu(terpy)][Cu(CN)₃] · H₂O By reaction of cadmium chloride with 2,2′ : 6′,2″-terpyridine (“terpy”) in water/acetone crystals of [Cd(terpy)Cl₂] ( 1) were formed. The compound crystallizes monoclinic, space group P2₁/c, a = 1111.70(10), b = 823.10(7), c = 1643.00(14) pm, β = 93.913(1)°, Z = 4. Starting from mixtures of different molar ratios of copper(II) chloride, terpyridine, and KCN in water/methanole, two complexes of different composition were obtained. At the molar ratio of 1 : 1 : 2 a copper(II) coordination compound with both halide and pseudohalide ligands, [Cu(terpy)(CN)Cl] ( 2 ), was formed which also crystallizes monoclinic, P2₁/c, a = 1065.6(3), b = 824.6(2), c = 1644.5(7) pm, β = 98.214(3)°, Z = 4. At a molar ratio of 1 : 1 : 10 a partial reduction of copper(II) occured with formation of a mixed valency compound [Cu(terpy)][Cu(CN)₃] · H₂O ( 3 ) which crystallizes in the hexagonal space group P6₅22, with a = b = 800.29(1), c = 4771.05(7) pm, Z = 6. Compounds 1 and 2 are structurally similar, the coordination of the metal atoms is square pyramidal. Networks are formed by hydrogen bridges. In 3 the copper(II) ions show a distorted square planar coordination by the three N atoms of the terpy ligand and one N atom of a bridging CN^– group, the copper(I) atoms, however, show trigonal planar coordination by three CN^– ligands to which the water molecules are bonded by hydrogen bridges. Thus helical chains are formed which stretch in the direction of the screw axes. The EPR spectrum of 3 was measured.     

[Ni(terpy)(H2O)]‐trans‐[Ni‐(μ‐CN)2‐(CN)2]n,a one‐dimensional linear tetra­cyano­nickelate chain

The one‐dimensional chain catena‐poly­[[aqua(2,2′:6′,2′′‐terpyridyl‐κ³N)­nickel(II)]‐μ‐cyano‐κ²N:C‐[bis­(cyano‐κC)nickelate(II)]‐μ‐cyano‐κ²C:N], [Ni(terpy)(H₂O)]‐trans‐[Ni‐μ‐(CN)₂‐(CN)₂]_n or [Ni₂­(CN)₄­(C₁₅H₁₁N₃)(H₂O)], consists of infinite linear chains along the crystallographic [10] direction. The chains are composed of two distinct types of nickel ions, paramagnetic octahedral [Ni(terpy)(H₂O)]²⁺ cations (with twofold crystallographic symmetry) and diamagnetic planar [Ni(CN)₄]^2? anions (with the Ni atom on an inversion center). The [Ni(CN)₄]^2? units act as bidentate ligands bridging through two trans cyano groups thus giving rise to a new example of a trans–trans chain among planar tetra­cyano­nickelate complexes. The coordination geometry of the planar nickel unit is typical of slightly distorted octahedral nickel(II) complexes, but for the [Ni(CN)₄]^2? units, the geometry deviates from a planar configuration due to steric interactions with the ter­pyridine ligands.     

Synthese und spektroskopische Charakterisierung von [Rh(SeCN)6]3– und trans‐[Rh(CN)2(SeCN)4]3–, Kristallstruktur von (Me4N)3[Rh(SeCN)6]

Synthesis and Spectroscopic Characterization of [Rh(SeCN)₆]^3– and trans ‐[Rh(CN)₂(SeCN)₄]^3–, Crystal Structure of (Me₄N)₃[Rh(SeCN)₆] Treatment of RhCl₃ with KSeCN in acetone yields a mixture of selenocyanato‐rhodates(III), from which [Rh(SeCN)₆]^3– and trans‐[Rh(CN)₂(SeCN)₄]^3– have been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The X‐ray structure determination on a single crystal of (Me₄N)₃[Rh(SeCN)₆] (trigonal, space group R3, a = 14.997(2), c = 24.437(3) Å, Z = 6) reveals, that the compound crystallizes isotypically to (Me₄N)₃[Ir(SCN)₆]. The exclusively via Se coordinated selenocyanato ligands are bonded with the average Rh–Se distance of 2.490 Å and the Rh–Se–C angle of 104.6°. In the low temperature IR and Raman spectra the metal ligand stretching modes ν(RhSe) of (n‐Bu₄N)₃[Rh(SeCN)₆] ( 1 ) and trans‐(n‐Bu₄N)₃[Rh(CN)₂(SeCN)₄] ( 2 ) are in the range of 170–250 cm^–1. In 2 ν_as(CRhC) is observed at 479 cm^–1. The vibrational spectra are assigned by normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constants are f_d(RhSe) = 1.08 ( 1 ), 1.10 ( 2 ) and f_d(RhC) = 3.14 mdyn/Å ( 2 ). f_d(RhS) = 1.32 mdyn/Å is determined for [Rh(SCN)₆]^3–, which has not been calculated so far. The ¹⁰³Rh NMR resonances are 2287 ( 1 ), 1680 ppm ( 2 ) and the ⁷⁷Se NMR resonances are –32.7 ( 1 ) and –110.7 ppm ( 2 ). The Rh–C bonding of the cyano ligand in 2 is confirmed by a dublett in the ¹³C NMR spectrum at 136.3 ppm.     

Structural organization and thermal behavior of the heteropolynuclear complex [Au2{S2CN(CH3)2}4][ZnCl4] and the heterovalent complex ([Au{S2CN(CH3)2}2][AuCl2]) n obtained in the chemisorption system [Zn2{S2CN(CH3)2}4]-Au3+/2 M HCl

Reactions of freshly precipitated binuclear zinc dimethyldithiocarbamate with [AuCl₄]^? anions in 2 M HCl were studied. The heteropolynuclear complex [Au₂{S₂CN(CH₃)₂}₄][ZnCl₄] (I) and the polymeric heterovalent complex ([Au{S₂CN(CH₃)₂}₂][AuCl₂]) _n (II) were preparatively isolated from the chemisorption system [Zn₂{S₂CN(CH₃)₂}₄]-Au³⁺/2 M HCl. The products were characterized by ¹³C MAS NMR data and by X-ray diffraction determination of crystal and molecular structures. The principal structural units of compounds I and II are the tetragonal planar complex cations [Au{S₂CN(CH₃)₂}₂]⁺ (in which the complex-forming ion coordinates two MDtc ligands in the S,S′-bidentate mode) and the anions, namely, the distorted tetrahedral anion [ZnCl₄]^2? in I and the linear [AuCl₂]^? anion in II. The further structural self-organization of complexes at the supramoleular level occurs through relatively weak secondary bonds Au?S and Au?Cl. The chemisorption capacities of zinc dimethyldithiocarbamate calculated from gold(III)-binding reactions are 644.1 and 1288.2 mg of gold per gram of the sorbent. Simultaneous thermal analysis studies of the thermal behavior of I and II were used to elucidate the conditions of gold recovery.     

Synthesis,structure and magnetic properties of 2-D and 3-D [cation]{M[Au(CN)2]3} (M = Ni, Co) coordination polymers

In order to study the templating effect of the cation and the resulting impact on the magnetic properties, reactions of M(II) salts with [cation][Au(CN)₂] were conducted, yielding a series of coordination polymers of the form [cation]{M[Au(CN)₂]₃} (cation = ⁿBu₄N⁺, PPN⁺ (bis(triphenylphosphoranylidene)ammonium); M = Ni(II) and Co(II)). The structures of ⁿBu₄N{M[Au(CN)₂]₃} and PPN{M[Au(CN)₂]₃} (M = Ni and Co) contain two distinct 3-D anionic frameworks of {M[Au(CN)₂]₃}⁻, hence the framework was sensitive to the cation, but not to the identity of the metal center. In ⁿBu₄N{M[Au(CN)₂]₃}, the metal centers are connected by [Au(CN)₂] units to form six 2-D (4, 4) rectangular grids that are fused through the M centers to yield a complex three-dimensional framework which accommodates the ⁿBu₄N⁺ cations. In PPN{M[Au(CN)₂]₃}, the framework adopts a simpler non-interpenetrated Prussian-blue-type pseudo-cubic array, with the PPN⁺ cations occupying each cavity; no reduction in dimensionality occurs despite the large cation size. In the presence of water, {Co(H₂O)₂[Au(CN)₂]₂} · ⁿBu₄N[Au(CN)₂] was obtained, a 2-D layered polymer that contains neutral sheets of {Co(H₂O)₂[Au(CN)₂]₂} which are separated by ⁿBu₄N[Au(CN)₂] layers; aurophilic interactions of 3.4250(13) Å and hydrogen-bonding connect the layers. The magnetic properties of all compounds were investigated by SQUID magnetometry. The Ni(II) polymers have similar magnetic behaviour, which are dominated by zero-field splitting with very weak antiferromagnetic interactions at low temperature (D ∼ 2–3 cm⁻¹, zJ < 1 cm⁻¹). The magnetic behaviour of all of the Co(II) polymers were found to be very similar, and dominated by single-ion effects (i.e. a large first-order orbital contribution). No significant magnetic coupling is observed in any of these coordination polymers, suggesting that the [Au(CN)₂] bridging unit behaves as a poor mediator of magnetic exchange in these high-dimensionality systems.     

Salts of HCN‐Cyanide Aggregates: [CN(HCN)2]− and [CN(HCN)3]−

Although pure hydrogen cyanide can spontaneously polymerize or even explode, when initiated by small amounts of bases (e.g. CN^?), the reaction of liquid HCN with [WCC]CN (WCC=weakly coordinating cation=Ph₄P, Ph₃PNPPh₃=PNP) was investigated. Depending on the cation, it was possible to extract salts containing the formal dihydrogen tricyanide [CN(HCN)₂]^? and trihydrogen tetracyanide ions [CN(HCN)₃]^? from liquid HCN when a fast crystallization was carried out at low temperatures. X‐ray structure elucidation revealed hydrogen‐bridged linear [CN(HCN)₂]^? and Y‐shaped [CN(HCN)₃]^? molecular ions in the crystal. Both anions can be considered members of highly labile cyanide‐HCN solvates of the type [CN(HCN)_n]^? (n=1, 2, 3 …) as well as formal polypseudohalide ions.     

Hydrate isomerism in [Cu(en)2(H2O)1.935]2[Fe(CN)6]·4H2O

The title compound, bis[di­aqua­bis­(ethyl­enedi­amine‐κ²N,N′)copper(II)­] hexa­cyano­iron(II) tetrahydrate, [Cu(C₂H₈N₂)₂(H₂O)_1.935]₂[Fe(CN)₆]·4H₂O, was crystallized from an aqueous reaction mixture initially containing CuSO₄, K₃[Fe(CN)₆] and ethyl­enedi­amine (en) in a 3:2:6 molar ratio. Its structure is ionic and is built up of two crystallographically different cations, viz. [Cu(en)₂(H₂O)₂]²⁺ and [Cu(en)₂(H₂O)_1.87]²⁺, there being a deficiency of aqua ligands in the latter, [Fe(CN)₆]⁴⁻ anions and disordered solvent water mol­ecules. All the metal atoms lie on centres of inversion. The Cu atom is octahedrally coordinated by two chelate‐bonded en mol­ecules [mean Cu—N = 2.016 (2) Å] in the equatorial plane, and by axial aqua ligands, showing very long distances due to the Jahn–Teller effect [mean Cu—O = 2.611 (2) Å]. In one of the cations, significant underoccupation of the O‐atom site is observed, correlated with the appearance of a non‐coordinated water mol­ecule. This is interpreted as the partial contribution of a hydrate isomer. The [Fe(CN)₆]⁴⁻ anions form quite regular octahedra, with a mean Fe—C distance of 1.913 (2) Å. The dominant intermolecular interactions are cation–anion O—H⋯N hydrogen bonds and these inter­actions form layers parallel to (001).     

Poly[tetraamminecopper(II) bis[tris(μ2‐cyanido‐κ2C,N)dicuprate(I)]]: a unique CuI–CuII mixed‐valence complex containing anionic cuprous cyanide layers and [Cu(NH3)4]2+ cations

The title compound, {[Cu(NH₃)₄][Cu(CN)₃]₂}_n, features a Cu^I–Cu^II mixed‐valence CuCN framework based on {[Cu₂(CN)₃]⁻}_n anionic layers and [Cu(NH₃)₄]²⁺ cations. The asymmetric unit contains two different Cu^I ions and one Cu^II ion which lies on a centre of inversion. Each Cu^I ion is coordinated to three cyanide ligands with a distorted trigonal–planar geometry, while the Cu^II ion is ligated by four ammine ligands, with a distorted square‐planar coordination geometry. The interlinkage between Cu^I ions and cyanide bridges produces a honeycomb‐like {[Cu₂(CN)₃]⁻}_n anionic layer containing 18‐membered planar [Cu(CN)]₆ metallocycles. A [Cu(NH₃)₄]²⁺ cation fills each metallocyclic cavity within pairs of exactly superimposed {[Cu₂(CN)₃]⁻}_n anionic layers, but there are no cations between the layers of adjacent pairs, which are offset. Pairs of N—H...N hydrogen‐bonding interactions link the N—H groups of the ammine ligands to the N atoms of cyanide ligands.     

Tetracyanometallates with Complex Dien Cations: [Ni(dien)2][Ni(CN)4]·2H2O and [Ni(dien)2][Pd(CN)4]

The crystal structures of two square tetracyanocomplexes were determined. [Ni(dien)₂][Ni(CN)₄]·2H₂O (NDNCH) and [Ni‐(dien)₂][Pd(CN)₄] (NDPC) (dien = diethylene triamine) exhibit ionic structures consisting of mer‐[Ni(dien)₂]²⁺ cations and [Ni(CN)₄]^2‐ or [Pd(CN)₄]^2‐ anions, respectively. Moreover, the structure of NDNCH is completed by two water molecules of crystallisation. In both compounds hydrogen bonds contribute to the stabilisation of the structure. NDNCH dehydrates on air quickly yielding anhydrous [Ni(dien)₂][Ni(CN)₄] (NDNC). Its thermal decomposition proceeds in a complicated process followed by aerial oxidation of metallic nickel to NiO.     

Darstellung und spektroskopische Charakterisierung von Kupfer(II)- und Nickel(II)-tricyanmethanid-Komplexen mit Imidazol-Derivaten – Kristallstruktur von [Cu{C(CN)3}2(2-meiz)2]

Synthesis and Spectroscopic Characterization of Copper(II) and Nickel(II) Tricyanomethanide Complexes with Imidazoles – Crystal Structure of [Cu{C(CN)₃}₂(2-meiz)₂] The copper(II) and nickel(II) tricyanomethanide complexes with imidazoles of the type [Cu{C(CN)₃}₂L₄], [L = 2- or 4-methylimidazole (meiz)] and [M{C(CN)₃}₂L₂] [M = Cu, L = imidazole (iz), 2- or 4-meiz; M = Ni, L = iz, 2- or 4-meiz] were prepared and characterized by electronic, infrared, and – some of them – by ESR spectroscopy. The structure [Cu{C(CN)₃}₂(2-meiz)₂], solved by X-ray crystallographic analysis, shows a two-dimensional network with unsymmetric C(CN)₃-bridges between the Cu^II atoms. Polymeric structures with bridging C(CN)₃-groups were identified by means of spectroscopic methods also for the other [M{C(CN)₃}₂L₂] complexes. On the other hand, for the complexes [M{C(CN)₃}₂L₄] follow molecular structures, in which monodentate C(CN)₃ ligands are present. All compounds under investigation show a tetragonal-bipyramidal geometry with various degree of tetragonal distortion.     

Crystal Structure and Structural Transformation of [(CH3)3NH]2[CuZn(CN)5]

A newly synthesized coordination polymer, [(CH₃)₃NH]₂[CuZn(CN)₅], was investigated using ¹³C and ⁶³Cu solid‐state NMR techniques and single‐crystal X‐ray diffractometry. It consists of a three‐dimensional (3D) net composed of tetrahedral Cu^I and Zn^II ions and CN^– ligands bridging between the two metal ions. (CH₃)₃NH⁺ ions are trapped in the inner space of the 3D net. Three coordination sites of each metal ion are used for the formation of the 3D net and the remaining site is occupied by a unidentate CN^– ligand. The structure of the 3D net is chiral and categorized as srs in the notation of the Reticular Chemistry Structure Resource (RCSR). In water vapor or open air at room temperature under ambient pressure, a powder of [(CH₃)₃NH]₂[CuZn(CN)₅] showed a structural transformation to [(CH₃)₃NH][CuZn(CN)₄] · 1.5H₂O, which is a known compound with a diamond‐like 3D net of [CuZn(CN)₄]^– composed of tetrahedral Cu^I and Zn^II ions and bridging CN^– ligands. ⁶³Cu solid‐state NMR spectroscopy revealed that the Cu‐CN‐Zn orientation of the bridging CN^– ligands was conserved after the structural transformation.     

Attempted Abstraction of the Halogenides in (HNEt3)[Re(CH3CN)2Cl4] and Crystal Structures of cis‐[Re(CH3CN)2Cl4]·CH3CN and cis‐[Re(NHC(OCH3)CH3)2Cl4]

The abstraction of the halogenide ligands in [Re(CH₃CN)₂Cl₄]^? should result in a solvent‐only stabilized Re^III complex. The reactions of salts of [Re(CH₃CN)₂Cl₄]^? with silver(I) and thallium(I) salts were investigated and the solid‐state structures of cis‐[Re(CH₃CN)₂Cl₄]·CH₃CN and cis‐[Re(NHC(OCH₃)CH₃)₂Cl₄] are described.     

A Novel 3‐D Heterobimetallic Cyano‐bridged Coordination Polymer Incorporating Ag···Ag Interaction: [Cu(dien)Ag(CN)2]2[Ag2(CN)3][Ag(CN)2]

A three‐dimensional cyano‐bridged copper(II) complex, [Cu(dien)Ag(CN)₂]₂[Ag₂(CN)₃][Ag(CN)₂] ( 1 ) (dien = diethylenetriamine), has been prepared and characterized by X‐ray crystallography. Complex 1 crystallized in the monoclinic space group P2₁/n with a = 6.988(2), b = 17.615(6), c = 12.564(4) Å, β = 90.790(5)°. The crystal consists of cis‐[Cu(dien)]²⁺ units bridged by [Ag(CN)₂]^— to form a zig‐zag chain. The Ag atoms of the free and bridging [Ag(CN)₂]^— link together to form additional infinite zig‐zag chains with short Ag···Ag distances. The presence of Ag···Ag interactions effectively increases the dimensionality from a 1‐D chain to a 3‐D coordination polymer.     

Molecular and Crystal Structures of Mononuclear trans‐[Fe(CN)2(tOcNC)4] and trans‐[Mn(CN)(CO)(tOcNC)4] as well as of Cyanide Bridged Coordination Polymers Derived from trans‐[M(CN)2(tOcNC)4] (M = Fe,Ru)

The octahedral complexes trans‐[Fe(CN)₂(^tOcNC)₄] and trans‐[Mn(CN)(CO)(^tOcNC)₄] are produced by the reaction of 2‐isocyano‐2,4,4‐trimethyl‐pentane (tert. octyl‐isocyanide) with the corresponding transition metal carbonyls Fe₂(CO)₉ and Mn₂(CO)₁₀. In contrast to isostructural compounds with less bulky tert.‐butylisocyanide ligands the cyanide groups in trans‐[Fe(CN)₂(^tOcNC)₄] and trans‐[Mn(CN)(CO)(^tOcNC)₄] do not act as hydrogen bond acceptors towards solvent molecules in the crystal structures. In addition, the corresponding cis‐isomers are configurationally unstable. The reaction of trans‐[Fe(CN)₂(^tOcNC)₄] and trans‐[Ru(CN)₂(^tOcNC)₄] with MnCl₂, NiCl₂ and Co(NO₃)₂ ends up in the formation of cyanide bridged coordination polymers. X‐ray structure determinations of the cobalt compounds reveal different molecular structures. Whereas the former produces highly distorted infinite polymeric chains with the nitrate anions still coordinated to the cobalt centers, the latter forms polymers with the cobalt atoms being coordinated by four ethanol molecules to which the anions are bound via hydrogen bond interactions. The coordination geometries around ruthenium and cobalt in this coordination polymer are therefore nearly perfectly octahedral and tetrahedral, respectively. Measurements of the magnetic susceptibility of the coordination polymers at different temperatures are indicative of weak antiferromagnetic coupling of the paramagnetic centers along the polymeric chains.     

KCd2[N(CN)2]5(H2O)4: an enmeshed honeycomb grid

The title compound, poly[potassium [diaquapenta‐μ₂‐dicyanamido‐dicadmium(II)] dihydrate], {K[Cd₂(C₂N₃)₅(H₂O)₂]·2H₂O}_n, contains two‐dimensional anionic sheets of {[Cd₂{N(CN)₂}(H₂O)₂]⁻}_n with a modified (6,3)‐net (layer group , No. 35). Two sets of equivalent sheets interpenetrate orthogonally to form a tetragonal enmeshed grid.     

Cu2(dien)2Ag5(CN)9 containing the one‐dimensional polymeric cation [Cu(dien)Ag(CN)2]nn+ and the unusual [Ag2(CN)3]− anion (dien is diethylenetriamine)

From the 1:1 system of [Cu(dien)₂](NO₃)₂ and K[Ag(CN)₂] in water (dien is diethyl­enetri­amine, C₄H₁₃N₃), the novel compound catena‐poly­[bis­[[μ‐cyano‐1:2κ²C:N‐diethyl­enetri­amine‐2κ³N‐copper(II)silver(I)]‐μ‐cyano‐1:2′κ²C:N] di­cyano­silver(I) tri­cyanodisilver(I)], [CuAg(CN)₂(dien)]₂[Ag(CN)₂][Ag₂(CN)₃], has been isolated. The structure is formed from positively charged [–Cu(dien)–NC–Ag–CN–]_nⁿ⁺ chains and two isolated centrosymmetric [Ag(CN)₂]^? and [Ag₂(CN)₃]^? anions. In the cationic chains, the Cu atoms are linked by bridging di­cyano­argentate groups, and the deformed square‐pyramidal coordination polyhedron of the Cu^II cation is formed from a tridentate chelate‐like bonded dien ligand and two N‐bonded bridging cyano groups. One of the bridging cyano groups occupies the apical (ap) position [mean Cu—­N_eq = 2.02 (2) Å, and Cu—N_ap = 2.170 (3) Å; eq is equatorial]. Short argentophilic interactions in the range 3.16–­3.30 Å are present in the crystal structure.     

Sorption of [Au(CN)2]- Ions from Cyanide Solutions with Activated Carbon Fiber

Sorption of [Au(CN)₂]^- ions from cyanide aqueous solutions with activated carbon fiber was studied, and the effect of the gas phase composition and additives (phenol, hydroquinone, ethanol, Na₂SO₃, Na₂S₂O₃) on sorption was considered. The results are compared with data on interaction of C_{6 0} with [Au(CN)₂]^-.     

Synthesis and structure of a new rhodium(I) complex [Rh{P(OPh)3}3CN]

Summary The [Rh(acac){P(OPh)₃)}₂] complex (Hacac = 2,4-pentadione) reacts in solution with gaseous HCN in the presence of P(OPh)₃ to give [Rh{P(OPh)₃}₃CN]. Structural investigations of this complex including its³¹P n.m.r. spectra are reported.     

Syntheses and Characterization of Cyanide‐Bridged Bimetallic Compounds Zn(terpy)(H2O)M(CN)4 (terpy = 2,2′:6′,2′′‐ter­pyridine; M = Ni,Pd, Pt) with Linear Chains

The self‐assembly reaction of zinc ions with tetracyanometalates in the presence of the tridentate chelated ligand 2,2′:6′,2′′‐terpyridine (terpy) yielded three cyanide‐bridged bimetallic compounds of general formula Zn(terpy)(H₂O)M(CN)₄ [M = Ni ( 1 ), Pd ( 2 ), Pt ( 3 )]. Compounds 1 – 3 were characterized by X‐ray diffraction (XRD), infrared spectroscopy (IR), and thermogravimetric (TG) analysis. Single‐crystal XRD analysis revealed that compounds 1 – 3 are isostructural and the structure consists of [Zn(terpy)(H₂O)]²⁺ moieties and [M(CN)₄]^2– units linked alternatively to generate a one‐dimensional (1D) linear chain. The chains are further connected together through hydrogen bonding and π–π stacking interactions, forming a 3D supramolecular network. IR spectroscopic analysis indicated the presence of cyanide groups and terpy ligands in the structure. TG and powder XRD results showed that compounds 1 – 3 have higher thermal stabilities and exhibited irreversible for desorption/resorption of one coordinated water molecule.