[MII(H2dapsc)]-[Cr(CN)6] (M = Mn,Co) Chain and Trimer Complexes: Synthesis,Crystal Structure,Non-Covalent Interactions and Magnetic Properties

Four new heterometallic complexes combining [M^II(H₂dapsc)]²⁺ cations with the chelating H₂dapsc {2,6-diacetylpyridine-bis(semicarbazone)} Schiff base ligand and [Cr(CN)₆]³⁻ anion were synthesized: {[M^II(H₂dapsc)]Cr^III(CN)₆K(H₂O)_2.5(EtOH)_0.5}_n·1.2n(H₂O), M = Mn (1) and Co (2), {[Mn(H₂dapsc)]₂Cr(CN)₆(H₂O)₂}Cl·H₂O (3) and {[Co(H₂dapsc)]₂Cr(CN)₆(H₂O)₂}Cl·2EtOH·3H₂O (4). In all the compounds, M(II) centers are seven-coordinated by N₃O₂ atoms of H₂dapsc in the equatorial plane and N or O atoms of two apical –CN/water ligands. Crystals 1 and 2 are isostructural and contain infinite negatively charged chains of alternating [M^II(H₂dapsc)]²⁺ and [Cr^III(CN)₆]³⁻ units linked by CN-bridges. Compounds 3 and 4 consist of centrosymmetric positively charged trimers in which two [M^II(H₂dapsc)]²⁺ cations are bound through one [Cr^III(CN)₆]³⁻ anion. All structures are regulated by π-stacking of coplanar H₂dapsc moieties as well as by an extensive net of hydrogen bonding. Adjacent chains in 1 and 2 interact also by coordination bonds via a pair of K⁺ ions. The compounds containing Mn^II (1, 3) and Co^II (2, 4) show a significant difference in magnetic properties. The ac magnetic measurements revealed that complexes 1 and 3 behave as a spin glass and a field-induced single-molecule magnet, respectively, while 2 and 4 do not exhibit slow magnetic relaxation in zero and non-zero dc fields. The relationship between magnetic properties and non-covalent interactions in the structures 1–4 was traced.     

Cyano‐Bridged MnIII?MIII Single‐Chain Magnets with MIII=CoIII,FeIII, MnIII,and CrIII

A series of isostructural cyano‐bridged Mn^III(h.s.)–M^III(l.s.) alternating chains, [Mn^III(5‐TMAMsalen)M^III(CN)₆] ? 4H₂O (5‐TMAMsalen^2?=N,N′‐ethylenebis(5‐trimethylammoniomethylsalicylideneiminate), Mn^III(h.s.)=high‐spin Mn^III, M^III(l.s.)=low‐spin Co^III, Mn? Co ; Fe^III, Mn? Fe ; Mn^III, Mn? Mn ; Cr^III, Mn? Cr ) was synthesized by assembling [Mn^III(5‐TMAMsalen)]³⁺ and [M^III(CN)₆]^3?. The chains present in the four compounds, which crystallize in the monoclinic space group C2/c, are composed of an [‐Mn^III‐NC‐M^III‐CN‐] repeating motif, for which the ‐NC‐M^III‐CN‐ motif is provided by the [M^III(CN)₆]^3? moiety adopting a trans bridging mode between [Mn^III(5‐TMAMsalen)]³⁺ cations. The Mn^III and M^III ions occupy special crystallographic positions: a C₂ axis and an inversion center, respectively, forming a highly symmetrical chain with only one kind of cyano bridge. The Jahn–Teller axis of the Mn^III(h.s.) ion is perpendicular to the N₂O₂ plane formed by the 5‐TMAMsalen tetradentate ligand. These Jahn–Teller axes are all perfectly aligned along the unique chain direction without a bending angle, although the chains are corrugated with an Mn‐N_axis‐C angle of about 144°. In the crystal structures, the chains are well separated with the nearest inter‐chain M???M distance being relatively large at 9 Å due to steric hindrance of the bulky trimethylammoniomethyl groups of the 5‐TMAMsalen ligand. The magnetic properties of these compounds have been thoroughly studied. Mn? Fe and Mn? Mn display intra‐chain ferromagnetic interactions, whereas Mn? Cr is characterized by an antiferromagnetic exchange that induces a ferrimagnetic spin arrangement along the chain. Detailed analyses of both static and dynamic magnetic properties have demonstrated without ambiguity the single‐chain magnet (SCM) behavior of these three systems, whereas Mn? Co is merely paramagnetic with S_Mn=2 and D/k_B=?5.3 K (D being a zero‐field splitting parameter). At low temperatures, the Mn? M compounds with M=Fe, Mn, and Cr display remarkably large M versus H hysteresis loops for applied magnetic fields along the easy magnetic direction that corresponds to the chain direction. The temperature dependence of the associated relaxation time for this series of compounds systematically exhibits a crossover between two Arrhenius laws corresponding to infinite‐chain and finite‐chain regimes for the SCM behavior. These isostructural hetero‐spin SCMs offer a unique series of alternating [‐Mn‐NC‐M‐CN‐] chains, enabling physicists to test theoretical SCM models between the Ising and Heisenberg limits.     

Anomalous Stoichiometry and Antiferromagnetic Ordering for the Extended Hydroxymanganese(II) Cubes/Hexacyanometalate-Based 3D-Structured [MnII4(OH)4][MnII(CN)6](OH2)6⋅H2O

The reaction of Mn^II(O₂CMe)₂ and NaCN or LiCN in water forms a light green insoluble material. Structural solution and Rietveld refinement of high-resolution synchrotron powder diffraction data for this unprecedented, complicated compound of previously unknown composition revealed a new alkali-free ordered structural motif with [Mn^II₄(μ₃-OH)₄]⁴⁺ cubes and octahedral [Mn^II(CN)₆]⁴⁻ ions interconnected in 3D by Mn^II-N≡C-Mn^II linkages. The composition is {[Mn^II(OH₂)₃][Mn^II(OH₂)]₃}(μ₃-OH)₄][Mn^II(μ-CN)₂(CN)₄] ⋅ H₂O=[Mn^II₄(μ₃-OH)₄(OH₂)₆][Mn^II(μ-CN)₂(CN)₄] ⋅ H₂O, which is further simplified to [Mn₄(OH)₄][Mn(CN)₆](OH₂)₇ ( 1 ). 1 has four high-spin (S=5/2) Mn^II sites that are antiferromagnetically coupled within the cube and are antiferromagnetically coupled to six low-spin (S=1/2) octahedral [Mn^II(CN)₆]⁴⁻ ions. Above 40 K the magnetic susceptibility, χ(T), can be fitted to the Curie–Weiss expression, χ ∝(T−θ)⁻¹, with θ=−13.4 K, indicative of significant antiferromagnetic coupling and 1 orders as an antiferromagnet at T_c=7.8 K.     

Front Cover: Water-Solvation-Dependent Spin Transitions in Cobalt(II)-Octacyanidometallate Complexes (Eur. J. Inorg. Chem. 30/2023)

The spin-crossover (SCO) and charge-transfer (CT) phenomena, the switching processes between two distinguishable magnetic states, are promising for developing materials capable of sophisticated memory and sensing functionalities. The majority of SCO systems are based on iron(II) complexes. However, cobalt(II)-2,2′:6′,2′′-terpyridine (terpy) systems emerge as a promising alternative. In this work, new complex salts [Co^II(terpy)₂]₂[Mo^IV(CN)₈] ⋅ 15H₂O, Co₂Mo (H₂O), and [Co^II(terpy)₂]₃[W^V(CN)₈]₂ ⋅ 12H₂O, Co₃W₂ (H₂O) were synthesized and physiochemically characterized. Structural studies for both compounds revealed [Co(terpy)₂]²⁺ layers pillared by octacyanidometallate anions and completed with water molecules between them. Magnetic studies confirmed that the (de)solvated phases of both complexes exhibit partial SCO on the cobalt(II) centers: Co^II−LS (S_Co(II)-LS=¹/₂)↔Co^II−HS (S_Co(II)-HS=³/₂). Moreover, handling dehydrated samples in a high-humidity environment leads to partial recovery of previous magnetic properties via humidity-induced SCO for Co₂Mo : Co^II−HS→Co^II−LS, and the new phenomenon of isothermal humidity-activated charge-transfer-induced spin transition, which we define here as HACTIST, for Co₃W₂ : Co^II−HS⋅⋅⋅W^V (S_Co(II)-HS=³/₂ and S_W(V)=¹/₂)→Co^III−LS⋅⋅⋅W^IV (S_W(IV)=0 and S_Co(III)-LS=0). These comprehensive studies shed light on the water-solvation-dependent spin transitions in Co(II)-octacyanidometallate(IV/V) complexes.     

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).     

Reactions of chromium(III) complexes with ferricyanide. Magnetism of K2[Cr(salen)(H2O)][Fe(CN)6]·H2O and the crystal structure of [trans-Cr(tn)2Cl2]3[Fe(CN)6]·6H2O [salen2− = N,N′-ethylenebis(salicylideneaminato) dianion,tn = 1,3-diaminopropane]

Two Cr^III–Fe^III complexes, K₂[Cr(salen)(H₂O)][Fe(CN)₆]·H₂O (1) and [trans-Cr(tn)₂Cl₂]₃[Fe(CN)₆]·6H₂O (2), have been prepared. Crystal structure determination shows that complex (2) possesses an ionic salt structure. General physical measurements and magnetic studies indicate that (1) assumes a cyanide-bridged dinuclear structure, and that the Cr^III–Fe^III magnetic coupling through the cyanide bridge is antiferromagnetic, which can be rationalized by the overlap of magnetic orbitals of the same symmetry.     

Cyanide-bridged complexes based on dinuclear Cu(II)-M(II) [M = Pb and Cu] building blocks: Synthesis, crystal structures and magnetic properties

Four cyanide-bridged heterometallic complexes {[CuPb(L 1 )][Fe III (bpb)(CN) 2 ]} 2 ·(ClO 4 ) 2 ·2H 2 O·2CH 3 CN (1), {[CuPb(L 1 )] 2 [Fe II (CN) 6 ](H 2 O) 2 }·10H 2 O (2), {[Cu 2 (L 2 )][Fe III (bpb)(CN) 2 ] 2 }·2H 2 O·2CH 3 OH (3) and {[Cu 2 (L 2 )] 3 [Fe III (CN) 6 ] 2 (H 2 O) 2 }·10H 2 O (4) have been synthesized by treating K[Fe III (bpb)(CN) 2 ] [bpb 2-=1,2-bis(pyridine-2-carboxamido)benzenate] and K 3 [Fe III (CN)] 6 with dinuclear compartmental macrocyclic Schiff-base complexes [CuPb(L 1 )] (ClO 4 ) 2 or [Cu 2 (L 2 )]·(ClO 4 ) 2 , in which H 2 L 1 was derived from 2,6-diformyl-4-methyl-phenol, ethylenediamine, and diethylenetriamine in the molar ratio of 2:1:1 and H 2 L 2 from 2,6-diformyl-4-methyl-phenol and propylenediamine in the molar ratio of 1:1. Single crystal X-ray diffraction analysis reveals that compound 1 displays a cyclic hexanuclear heterotrimetallic molecular structure with alternating [FeⅢ (bpb)(CN) 2 ]- and [CuPb(L 1 )] 2+ units. Complex 2 is of a neutral dumb-bell-type pentanuclear molecular configuration consisting of one [Fe(CN)6] 4- anion sandwiched in two [CuPu(L 1 )] 2+ cations, and the pentanuclear moieties are further connected by the hydrogen bonding to give a 2D supramolecular framework. Heterobimetallic complex 3 is a tetranuclear molecule composed of a centrosymmetric [Cu 2 (L2)] 2+ segment and two terminal cyanide-containing blocks [FeⅢ (bpb)(CN)2 ]- . Octanuclear compound 4 is built from two [Fe(CN)6]3- anions sandwiched in the three [Cu 2 L 2 ] 2+ cations. Investigation of their magnetic properties reveals the overall antiferromagnetic behavior in the series of complexes except 2.     

Molecular Magnetic Materials Based on {CoIII(Tp*)(CN)3}− Cyanidometallate: Combined Magnetic,Structural and 59Co NMR Study

The cyanidocobaltate of formula fac-PPh₄[Co^III(^Me2Tp)(CN)₃] ⋅ CH₃CN ( 1 ) has been used as a metalloligand to prepare polynuclear magnetic complexes (^Me2Tp=hydrotris(3,5-dimethylpyrazol-1-yl)borate). The association of 1 with in situ prepared [Fe^II(bik)₂(MeCN)₂](OTf)₂ (bik=bis(1-methylimidazol-2-yl)ketone) leads to a molecular square of formula {[Co^III{(^Me2Tp)}(CN)₃]₂[Fe^II(bik)₂]₂}(OTf)₂ ⋅ 4MeCN ⋅ 2H₂O ( 2 ), whereas the self-assembly of 1 with preformed cluster [Co^II₂(OH₂)(piv)₄(Hpiv)₄] in MeCN leads to the two-dimensional network of formula {[Co^II₂(piv)₃]₂[Co^III(^Me2Tp)(CN)₃]₂ ⋅ 2CH₃CN}_∞ ( 3 ). These compounds were structurally characterized via single crystal X-ray analysis and their spectroscopic (FTIR, UV-Vis and ⁵⁹Co NMR) properties and magnetic behaviours were also investigated. Bulk magnetic susceptibility measurements reveal that 1 is diamagnetic and 3 is paramagnetic throughout the explored temperature range, whereas 2 exhibits sharp spin transition centered at ca. 292 K. Compound 2 also exhibits photomagnetic effects at low temperature, selective light irradiations allowing to promote reversibly and repeatedly low-spin⇔high-spin conversion. Besides, the diamagnetic nature of the Co(III) building block allows us studying these compounds by means of ⁵⁹Co NMR spectroscopy. Herein, a ⁵⁹Co chemical shift has been used as a magnetic probe to corroborate experimental magnetic data obtained from bulk magnetic susceptibility measurements. An influence of the magnetic state of the neighbouring atoms is observed on the ⁵⁹Co NMR signals. Moreover, for the very first time, ⁵⁹Co NMR technique has been successfully introduced to investigate molecular materials with distinct magnetic properties.     

Diamond‐ and Graphite‐Like Octacyanometalate‐Based Polymers Induced by Metal Ions

By using cyclohexane‐1,2‐diamine (chxn), Ni(ClO₄)₂ ? 6H₂O and Na₃[Mo(CN)₈] ? 4H₂O, a 3D diamond‐like polymer {[Ni^II(chxn)₂]₂[Mo^IV(CN)₈] ? 8H₂O}_n ( 1 ) was synthesised, whereas the reaction of chxn and Cu(ClO₄)₂ ? 6H₂O with Na₃[M^V(CN)₈] ? 4H₂O (M=Mo, W) afforded two isomorphous graphite‐like complexes {[Cu^II(chxn)₂]₃[Mo^V(CN)₈]₂ ? 2H₂O}_n ( 2 ) and {[Cu^II(chxn)₂]₃[W^V(CN)₈]₂ ? 2H₂O}_n ( 3 ). When the same synthetic procedure was employed, but replacing Na₃[Mo(CN)₈] ? 4H₂O by (Bu₃NH)₃[Mo(CN)₈] ? 4H₂O (Bu₃N=tributylamine), {[Cu^II(chxn)₂Mo^IV(CN)₈][Cu^II(chxn)₂] ? 2H₂O}_n ( 4 ) was obtained. Single‐crystal X‐ray diffraction analyses showed that the framework of 4 is similar to 2 and 3 , except that a discrete [Cu(chxn)₂]²⁺ moiety in 4 possesses large channels of parallel adjacent layers. The experimental results showed that in this system, the diamond‐ or graphite‐like framework was strongly influenced by the inducement of metal ions. The magnetic properties illustrate that the diamagnetic [Mo^IV(CN)₈] bridges mediate very weak antiferromagnetic coupling between the Ni^II ions in 1 , but lead to the paramagnetic behaviour in 4 because [Mo^IV(CN)₈] weakly coordinates to the Cu^II ions. The magnetic investigations of 2 and 3 indicate the presence of ferromagnetic coupling between the Cu^II and W^V/Mo^V ions, and the more diffuse 5d orbitals lead to a stronger magnetic coupling interaction between the W^V and Cu^II ions than between the Mo^V and Cu^II ions.     

The synthesis,crystal structure and magnetic properties of a one‐dimensional terbium(III)–octacyanidomolybdate(V) assembly

A one‐dimensional cyanide‐bridged coordination polymer, poly[[aquadi‐μ‐cyanido‐κ⁴C:N‐hexacyanido‐κ⁶C‐(dimethylformamide‐κO)bis(3,4,7,8‐tetramethyl‐1,10‐phenanthroline‐κ²N,N′)terbium(III)molybdate(V)] 4.5‐hydrate], [MoTb(CN)₈(C₁₆H₁₆N₂)₂(C₃H₇NO)(H₂O)]·4.5H₂O}_n, has been prepared and characterized through IR spectroscopy, elemental analysis and single‐crystal X‐ray diffraction. The compound consists of one‐dimensional chains in which cationic [Tb(tmphen)₂(DMF)(H₂O)]³⁺ (tmphen is 3,4,7,8‐tetramethyl‐1,10‐phenanthroline) and anionic [Mo^V(CN)₈]³⁻ units are linked in an alternating fashion through bridging cyanide ligands. Neighbouring chains are connected by three types of hydrogen bonds (O—H...O, O—H...N and C—H...O) and by π–π interactions to form a three‐dimensional supramolecular structure. In addition, magnetic investigations show that ferromagnetic interactions exist in the compound.     

Synthesis, crystal structures and magnetic properties of cyanide-bridged macrocyclic complexes

Three cyanide-bridged dodecanuclear macrocyclic wheel-like complexes [Cr(bpmb)(CN)₂]₆[Mn(5-Brsalpn)]₆·12H₂O (1), [Co(bpmb)(CN)₂]₆[Mn(5-Brsalpn)]₆·12H₂O (2) and [Co(bpmb)(CN)₂]₆[Mn(5-Clsalpn)]₆·24H₂O·8CH₃CN (3) [bpmb²⁻= 1,2-bis(pyridine-2-carboxamido)-4-methylbenzenate dianion; 5-Brsalpn²⁻ = N,N′-propylenebis(5-bromosalicylideneaminato) dianion; 5-Clsalpn²⁻ = N,N′-propylenebis(5-chlorosalicylideneaminato) dianion] have been synthesized and their crystal structures and magnetic properties have been investigated. The three compounds are structurally isomorphous and consist of alternating Mn(III)-Schiff base cations and [M(bpmb)(CN)₂]⁻ anions, generating cyanide-bridged nanosized dodecanuclear macrocyclic structures with an approximate diameter of 2 nm. The study of the magnetic properties of complex 1 reveals an antiferromagnetic interaction between the Cr(III) and Mn(III) ions through the cyanide bridges. A best-fit to the magnetic susceptibility of the complex leads to a magnetic coupling constant of J _CrMn = −2.65(6) cm⁻¹ on the basis of a one-dimensional alternating chain model with the Hamiltonian $ H = - J_{CrMn} \sum\limits_{i = 0}^N {S_i \cdot S_{i + 1} } $ H = - J_{CrMn} \sum\limits_{i = 0}^N {S_i \cdot S_{i + 1} } .     

Pentacyanido(L)ferrate(III) complexes: Crystal structures, electrochemical and DFT studies (L = pyrazine, 4,4′-bipyridine, azide)

The crystal structures of two pentacyanido(L) ferrate(III) complexes, [P(C₆H₅)₄]₂[Fe(CN)₅(prz)]·4H₂O 1, [P(C₆H₅)₄]₂[Fe(CN)₅(4,4′-bipy)]·3H₂O 2, have been solved. Within the two complex anions the iron atoms are hexacoordinated by five cyanido ligands, the sixth position being occupied by the nitrogen atom arising from pyrazine and, respectively, 4,4′-bipyridine. The electrochemical properties of compounds 1, 2 and of the azido derivative, (Ph₄As)₂[Na(H₂O)₄][Fe(CN)₅(N₃)] 3, have been investigated by cyclic voltammetry. A relatively complicated redox behavior of these complexes was found, due especially to the electron transfer involving the central metallic ion that changes reversibly its oxidation state (Fe^III/Fe^II redox site) and also to the coligand (4,4′-bipyridine, pyrazine or azide) which intervenes in a distinct electron transfer. The experimental data have been rationalized through DFT calculations.     

Supramolecular framework adducts constructed of hexamethylenetetramine,aquated alkali metal cationic clusters,and hexacyanoferrates(II/III)

The reaction of alkali metal hexacyanoferrate(II/III) with (CH₂)₆N₄ (hexamethylenetetramine, abbreviated HMT) in an acidic medium yielded crystalline compounds of stoichiometries HK₂[Fe¹¹¹(CN)₆]·2HMT·4H₂O, H₂K₂[Fe¹¹(CN)₆]·2HMT·4H₂O, and HNa₂[Fe¹¹¹(CN)₆]· 2HMT·5H₂O. Their crystal structures are based on a packing of three molecular components: neutral and/orprotonated HMT, hexacyanoferrate, and an alkali metal ion-water cluster. The resulting three-dimensional supramolecular framework is constructed from the coordination of the alkali metal ion by aqua ligands as well as [Fe(CN)₆]{n–} and HMT units, and further stabilization is achieved by hydrogen bonding between water molecules and the noncoordinated nitrogen atoms of HMT and hexacyanoferrate.     

Syntheses,crystal structures and magnetic properties of two cyano-bridged two-dimensional assemblies [Fe(salpn)]2 [Fe(CN)5NO] and [Fe(salpn)]2[Ni(CN)4]

Two cyano-bridged assemblies, [Fe^III(salpn)]₂[Fe^II(CN)₅NO] (1) and [Fe^III (salpn)]₂[Ni^II(CN)₄] (2) [salpn = N, N-1,2-propylenebis(salicylideneiminato)dianion], have been prepared and structurally and magnetically characterized. In each complex, [Fe(CN)₅NO]^2– or [Ni(CN)₄]^2– coordinates with four [Fe(salpn)]⁺ cations using four co-planar CN^– ligands, whereas each [Fe(salpn)]⁺ links two [Fe(CN)₅NO]^2– or [Ni(CN)₄]^2– ions in the trans form, which results in a two-dimensional (2D) network consisting of pillow-like octanuclear [—M^II—CN—Fe^III—NC—]₄ units (M = Fe or Ni). In complex (1), the NO group of [Fe(CN)₅NO]^2– remains monodentate and the bond angle of Fe^II—N—O is 180.0°. The variable temperature magnetic susceptibilities, measured in the 5–300 K range, show weak intralayer antiferromagnetic interactions in both complexes with the intramolecular iron(III)iron(III) exchange integrals of –0.017 cm^–1 for (1) and –0.020 cm^–1 for (2), respectively.     

Crystallization method controlled trinuclear or ion-pair Manganese(III)-porphyrin-based heterobimetallic complexes: Synthesis,spectra characterization,and crystal structure

Cyanide-bridged trinuclear heterometallic Ag(I)-Mn(III) complex {[Mn(TClPP)(H₂O)]₂[Ag(CN)₂]}₂ · 2Br · 2C₃H₆O · 3H₂O (I) and ion-pair complex {[Mn(TClPP)(CH₃OH)₂][Ag(CN)₂]} · 0.5H₂O (II) have been synthesized with [Mn(TClTPP)(H₂O)₂]Br (H₂TClTPP = meso-tetra(4-chlorophenyl)porphyrin) as assembling segment and K[Ag(CN)₂] as building block by using different crystallization method. These two complexes have been characterized by elemental analysis, IR spectroscopy and X-ray structure determination. In the trinuclear complex I, [Ag(CN)₂]^? as bidentate ligand coordinates with the two central Mn(III) atom of [Mn(TClPP)(H₂O)₂]⁺ through its two trans cyanide groups to form the complex cation of [Mn(TClPP)(H₂O)]₂[Ag(CN)₂]⁺, which further constructs the neutral complexes with the help of one Br^? as balanced anion. For the ion-pair complex II composed by free [Mn(TClPP)(CH₃OH)₂]⁺ cation and free [Ag(CN)2]^? anion, it can be linked into one-dimensional supramolecular structure with the dependence of the intermolecular O-H...N and O-H...O hydrogen bond interactions.     

Double complexes [Co(NH3)5(H2O)]2[Zr3F18]·6H2O and [Co(NH3)6]2[Zr3F18]·6H2O

The structures of orthorhombic bis[pentaammineaquacobalt(III)] tetra‐μ₂‐fluorido‐tetradecafluoridotrizirconium(IV) hexahydrate (space group Ibam), [Co(NH₃)₅(H₂O)]₂[Zr₃F₁₈]·6H₂O, (I), and bis[hexaamminecobalt(III)] tetra‐μ₂‐fluorido‐tetradecafluoridotrizirconium(IV) hexahydrate (space group Pnna), [Co(NH₃)₆]₂[Zr₃F₁₈]·6H₂O, (II), consist of complex [Co(NH₃)_x(H₂O)_y]³⁺ cations with either m [in (I)] or and 2 [in (II)] symmetry, [Zr₃F₁₈]⁶⁻ anionic chains located on sites with 222 [in (I)] or 2 [in (II)] symmetry, and water molecules.     

Die Kristallstruktur der hydratisierten Cyanokomplexe NMe4MnII[(Mn, Cr)III(CN)6] · 3 H2O und NMe4Cd[MIII(CN)6] · 3 H2O (MIII = Fe,Co): Verwandte des Berliner Blaus

The Crystal Structure of the Hydrated Cyano Complexes NMe₄Mn^II[(Mn, Cr)^III(CN)₆] · 3 H₂O and NMe₄Cd[M^III(CN)₆] · 3 H₂O (M^III = Fe, Co): Compounds Related to Prussian Blue The crystal structures of the isotypic tetragonal compounds (space group I4, Z = 10) NMe₄Mn^II · [(Mn, Cr)^III(CN)₆] · 3 H₂O (a = 1653.2(4), c = 1728.8(6) pm), NMe₄Cd[Fe(CN)₆] · 3 H₂O (a = 1642.7(1), c = 1733.1(1) pm) and NMe₄Cd[Co(CN)₆] · 3 H₂O (a = 1632.1(2), c = 1722.4(3) pm) were determined by X‐rays. They exhibit ⊥ c cyanobridged layers of octahedra [M^III(CN)₆] and [M^IIN₄(OH₂)₂], which punctually are interconnected also || c to yield altogether a spaceous framework. The M^II atoms at the positions linking into the third dimension are only five‐coordinated and form square pyramids [M^IIN₅] with angles N–M^II–N near 104° and distances of Mn–N: 1 × 214, 4 × 219 pm; Cd–N: 1 × 220 resp. 222, 4 × 226 resp. 228 pm. Further details and structural relations within the family of Prussian Blue are reported and discussed.     

Two octacyanomolybdate(IV)-M(II) (M = Mn,Co) bimetallic assemblies: Crystal structures and magnetic properties

Two cyano-bridged bimetallic complexes {[M₂(H₂O)₄Mo(CN)₈] · 4H₂O} _n [M = Mn (I) and Co (II)] have been synthesized and structurally characterized. The single-crystal X-ray analyses reveal that these two compounds have three-dimensional structures, and cell parameters are similar in a tetragonal system with space group I $ \bar 4 $ \bar 4 . In the both complexes, each [Mo(CN)₈]⁴⁻ building block is linked with M²⁺ [M = Mn and Co] ions through its eight CN ligands. Each M²⁺ center is connected to four Mo units forming a three-dimensional framework. In addition, magnetic studies of these complexes have been presented.     

Dinuclear complexes with a μ-cyano ligand. Part XI(1). Synthesis and characterization of several derivatives ofcis-[Co(NH3)(en)2(H2O)]3+

Summary The new complex double saltscw-[Co(NH₃)(en)₂(H₂O)]₂ [M(CN)₄]₃ (en = ethylenediamine; M = Ni, Pd or Pt),cis-[Co(NH₃(en)₂(H₂O)]₂[FeNO(CN)₅]₃ andcis-[Co(NH₃)(en)₂(H₂O)][Co(CN)₆] have been synthesized and by anation in the solid state the corresponding new dinuclear complexes with a cyano bridgecis- ortrans-[(NH₃)(en)₂Co-NC-M(CN)₃]₂ [M(CN)₄] (M = Ni, Pd or Pt);cis-, trans-[(NH₃)(en)₂Co-NC-FeNO(CN)₄]₂[FeNO(CN)₅] andcis-[(NH₃)(en)₂Co-NC-Co(CN)₅ have been prepared. The complexes have been characterized by chemical analysis, t.g. measurements, and by i.r. and electronic spectroscopy. With [Ni(CN)₄][^2– and [Co(CN)in]₆ ^3– only thecis-isomer is produced; with [Pd(CN)₄]^2–, [Pt(CN)₄]^2– and [FeNO(CN)₅]^2– thetrans- isomer is the dominant species. The dinuclear complex derived from [Pt(CN)₄]^2– shows strong Pt-Pt interactions both in the solid state and in solution.     

Crystal structure and magnetic properties of a three-dimensional complex constructed from [CuL]2+ and [Fe(CN)6]3− precursors

Self-assembly of the precursor [Cu(L)]²⁺ (L = 3,10-dipropyl-1,3,5,8,10,12-hexaazacyclotetradecane) with hexacyanometalate [Fe(CN)₆]³⁻ produces a 3-D cyano-bridged Cu(II)–Fe(III) bimetallic assembly, [CuL]₂[Fe(CN)₆]ClO₄ · H₂O (1), characterized by single-crystal X-ray diffraction studies, and magnetic measurements. The crystallographic determination reveals that each hexacyanoferromate(III) ion connects four copper(II) ions using four co-planar CN⁻ groups which axially coordinate to the copper ion in a trans fashion forming trans-CuL(N≡C)₂ moieties in (1). Magnetic studies reveal that (1) displays a ferromagnetic interaction between Cu(II) and Fe(III) through the CN linkage.