Oxidative Addition vs. Ligand-Exchange: Fe(II)-Mixed-Phenylchalcogenolate Complexes fac-[PPN][Fe(CO)3(TePh)n(SePh)3-N] (n = 1, 2)

Diphenyldichalcogenides (PhE)₂ (E = Te, Se) react with Fe(0)-phenylchalcogenolate [PPN] [PhEFe(CO)₄] to yield the products of oxidative addition, Fe(II)-mixed-phenylchalcogenolate fac- [PPN][Fe(CO)₃(TePh)_n(ScPh)_3-n] (n = 1, 2). Reactions of [PPN][REFe(CO)₄] (E=Se, R=Me; E=S, R=Et) and diphenyldichalcogenides yielded ligand-exchange products [PPN][PhEFe(CO)₄] (E=Te, Se, S). The compounds [Fe(CO)₃(TePh)(ScPh)₂]^? (l) and [Fe(CO)₃(TePh)₂ (2) crystallize in the isomorphous monoclinic space group C_2/e, with a = 32.035(8), b = 11.708(6), c = 28.909(6) Å, Z = 8, R = 0.048, and R_w = 0.044 (1); with a = 32.089(5), b= 11.745(2), c = 28.990(8) Å, Z = 8, R = 0.048, and R_w = 0.048 (2). The complexes 1 and 2 crystallize as discrete cations of PPN⁺ and anions of [Fe(CO)₃(TcPh)_u(ScPh)_3-n] (n=1, 2), and one half solvent molecule THF. The geometry around Fe(II) is a distorted octahedron with three carbonyl groups and three phenylchalcogenolate ligands occupying facial positions.     

Reactivity of fac-[PPN][Fe(CO)3(TePh)3]: Structure of Fe2(μTePh)2(NO)4

Addition of NOBF₄ to fac-[PPN][Fe(CO)₃(TePh)₃] in THF at ambient temperature results in formation of Fe₂(μ-TePh)₂(NO)_4l Fe₂(?TePh)₂(CO)₆ and organic products. Methylation of fac-[PPN][Fe(CO)₃- (TePh)₃] by Mel or [Me₃O][BF₄] leads to the known dimer Fe₂(μ.-TePh)₂(CO)₆ and organic products. Fe₂(μ-TePh)₂(NO)₄ crystallizes in the orthorhombic space group P bca, with a = 12.701(5) Å, b = 6.7935(16) Å, c = 21.299(9) Å, V = 1837.8(11) ų, and Z = 4. The core geometry of Fe₂(μ-TePh)₂(NO)₄ is best described as a Fe₂Te₂ planar rhombus with Te-Fe-Te bond angle 112.09(4)°. A Fe-Fe bond (length 2.827(2) Å) is proposed for Fe₂(μ-TePh)₂(NO)₄ on the basis of the 18-electron rule. The iron atom adopts a distorted tetrahedral geometry with acute bridge Fe-Te-Fe angles 67.91(3)°, and bridging Fe-Te bond of length 2.53(1) Å.     

Oxidative Addition of Diphenyl Disulfide/Thiophenol to [Mn(CO)5]−: Crystal Structure of cis-[Mn(CO)4(SPh)2]−

Oxidative addition of diphenyl disulfide to the coordinatively unsaturated [Mn(CO)₅]^? led to the formation of low-spin, six-coordinate cis-[Mn(CO)₄(SPh)₂]^?. The complex cis-[PPN][Mn(CO)₄(SPh)₂] crystallized in monoclinic space group P2₁/c with a = 9.965(2) Å, b = 24.604(5) Å, c = 19.291(4) Å, β = 100.05(2)°, V = 4657(2)ų, and Z = 4; final R = 0.036 and R_w = 0.039. Thermal transformation of cis-[Mn(CO)₄(SPh)₂]^? to [(CO)₃Mn(μ-SPh)₃Mn(CO)₃]^? was completed overnight in THF at room temperature. Additionally, reaction of [Mn(CO)₅]^? and PhSH in 1:2 mole ratio also led to cis-[PPN](Mn(CO)₄(SPh)₂]. Presumably, oxidative addition of PhSH to [Mn(CO)₄]^? was followed by a Lewis acid-base reaction to form cis-[Mn(CO)₄(SPh)₂]^? with evolution of H₂.     

Syntheses and Characterization of Manganese-Tellurolate Complexes by Using Chelating Metalloligand cis-[Mn(Co)4(TePh)2]− and Potential Electrophilic TeMe+ Reagent

The cis-[Mn(CO)₄(TePh)₂]^?, similar to bidentate ligand PhTe(CH₂)₃TePh, acts as a “chelating metalloligand” for the synthesis of metallic tellurolate compounds. The reaction of cis[Mn(CO)₄(TePh)₂]^? with BrMn(CO)₅ in THF leads to a mixture of products[(CO)₃,BrMn(μ-TePh)₂Mn(CO)₄]^? (1) and Mn₂(μ-TePh)₂(CO)_g (2). Complex 1 crystallizes in the triclinic space group Pl? with a = 11.309(3) Å, b = 14.780(5) Å, c = 19.212(6) Å, a = 76.05(3)° β = 72.31(3)°, γ = 70.41(3)° V = 2848(2) Å₃, Z = 2. Final R = 0.034 and R_w = 0.035 resulting from refinement of 10021 total reflections with 677 parameters, Dropwise addition of (MeTe)₂ to a solution of [Me₃O][BF₄] in CH₃CN leads to formation of [Me₂TeTeMe][BF₄], a potential MeTe⁺ donor ligand. In contrast to oxidative addition of diphenyl ditelluride to [Mn(CO)s]^? to give cis-[Mn(CO)₄(TePh)₂]^? which was thermally transformed into [(CO)₃Mn(μ-TePh)₃Mn(CO)₃]^?, reaction of [Mn(CO)₅]^?with [Me₂TeTeMe]⁺ proceeded to give the monomeric species MeTeMn(CO)₅ as initial product which was then dimerized into Mn₂(μ-TeMe)₂(CO)_g (4).     

Physical properties of a new iron(III) complex, [3-pmH · 3-pm][Fe(NCS)4(3-pm)2]

The iron(III) compound of formula [3-pmH · 3-pm][Fe(NCS)₄(3-pm)₂] (3-pm = 3-(hydroxymethyl)pyridine) has been prepared by reaction between iron(III) thiocyanate and 3-(hydroxymethyl)pyridine in ethanol. The characterization was based on elemental analysis, infrared spectra and magnetic measurements. Single crystal X-ray diffraction methods show the monoclinic P2(1)/c space group with unit cell parameters: a = 12.295(3) Å, b = 15.854(3) Å, c = 16.880(3) Å, β = 100.12(3)° and Z = 4. The asymmetric unit of the title compound consists of [3-pmH · 3-pm]⁺ and [Fe(NCS)₄(3-pm)₂]^? held together by ionic interaction and a hydrogen bond interaction (O(68)–H(68) ··· O(78)). The central metal ion is octahedrally coordinated by six nitrogens, four from NCS^? form the equatorial plane and two from two 3-(hydroxymethyl)pyridines occupy axial positions. Magnetic susceptibility data in the temperature range 1.8–300 K show that iron(III) is high-spin S = 5/2(⁵ T _2g). Structural parameters and IR spectra of similar complexes are compared and discussed.     

SYNTHESIS OF A DINUCLEAR YLID COMPLEX DERIVED FROM P(OPh)3: CRYSTAL STRUCTURES OF [Cp2Fe2(CO)2(μ-CO) (μ-CHP(OPh)3)+][BF4 −] AND [Cp2Fe2(CO)2 (μ-CO)(μ-CHPPh3)+][BF4 −]

Abstract

[Cp₂Fe₂(CO)₂(μ-CO)(μ-CHP(OPh)₃)⁺][BF^? ₄] crystallizes in the centrosymmetric monoclinic space group P2₁/n with a = 12.553(7) Å, b = 16.572(11) Å, c = 15.112(8) Å, β = 100.00(4)°, V = 3096(3) ų and D(calcd.) = 1.579 g/cm³ for Z = 4. The structure was refined to R(F) = 5.83% for 1972 reflections above 4σ(F). The cation contains two CpFe(CO) fragments linked via an iron—iron bond (Fe(1)—Fe(2) = 2.544(3)Å), a bridging carbonyl ligand (Fe(1)—C(4) = 1.918(1) Å, Fe(2)—C(4) = 1.946(12)Å) and a bridging CHP(OPh)₃ ligand (Fe(1)—C(1) = 1.980(9)Å, Fe(2)—C(1) = 1.989(8)Å). Distances within the μ-CHP(OPh)₃ moiety include a rather short carbon—phosphorus bond [C(1)—P(1) = 1.680(10)Å] and P—O bond lengths of 1.550(7)–1.579(6)Å. The crystal is stabilized by a network of F…H—C interactions involving the BF^? ₄ anion.

[Cp₂Fe₂(CO)₂(μ-CO)(μ-CHPPh₃)⁺][BF^? ₄], which differs from the previous compound only in having a μ-CHPPh₃ (rather than μ-CHP(OPh)₃) ligand, crystallizes in the centrosymmetric monoclinic space group P2₁/c with a = 11.248(5)Å, b = 13.855(5)Å, c = 18.920(7)Å, β = 96.25(3)°, V = 2931(2)ų and D(calcd.) = 1.559 g/cm³ for Z = 4. This structure was refined to R(F) = 4.66% for 1985 reflections above 4σ(F). Bond lengths within the dinuclear cation here include Fe(1)-Fe(2) = 2.529(2)Å, Fe(1)—C(3) = 1.904(9) Å and Fe(2)—C(3) = 1.911(8) Å (for the bridging CO ligand) and Fe(1)—C(1P) = 1.995(6) Å and Fe(2)—C(1P) = 1.981(7) Å (for the bridging CHPPh₃ ligand). Distances within the μ-CHPPh₃ ligand include a longer carbon—phosphorus bond [C(1P)—P(1) = 1.768(6)Å] and P(1)—C(phenyl) = 1.797(7)–1.815(8) Å.     

Rhenium(I) Tellurolate,Telluroether and Bidentate-Telluroether Complexes: Crystal Structures of Re(CO)3Br(PhTe(CH2)3TePh), PhTeRe(CO)5 Re2(μ-SePh)2(CO)8 and [(PhTeMe)Re(CO)5][BF4]

The monomeric rhenium(I) complex with bidentate telluroether ligand Re(CO)₃Br(PhTe(CH₂)₃TePh) (1) was accessible via reaction of the PhTe(CH₂)₃TePh with Re(CO)₅Br. This chelate complex crystallized in triclinic space group $ {\rm P}\bar 1 $ with a = 9.390(5) Å, b = 10.961(3) Å, c = 11.849(4) Å a = 63.30(3)°, β = 87.49(4)° γ = 69.31(4)°, V = 1009.5(7) ų Z = 2, R = 0.033, and R_w = 0.034. Reaction of Re(CO)₅Cl with NaTePh yielded the Re(I) specics PhTeRe(CO)₅ (2). This complex crystallized in triclinic space group $ {\rm P}\bar 1 $ with a = 7.085(1) Å, b = 9.203(1) Å, c = 11.341(1) Å, α = 107.24(1)°, β = 100.56(1)°, γ = 96.47(1)°, V = 683.2(2) ų, Z = 2, R = 0.027, R_w = 0.022. Reaction of PhTeRe(CO)₅ and (PhSe)₂ in THF at 65 °C yielded a product that was confirmed crystallographically to be the known species Re₂(μ-SePh)₂(CO)₈ (3), in which two phenylselenolate ligands bridge the two Re(I). Compound 3 crystallized in monoclinic space group P2₁/n with a = 7.210(2) Å, b = 18.862(6) Å, c = 9.083(3) Å, β = 107.48(3)° V = 1178.2(7) ų, Z = 2, R = 0.046, and R_w = 0.051. Methylation of PhTeRe(CO)₅ with [Me₃O][BF₄] afforded Re(I) product [(PhTeMe)Re(CO)₅][BF₄] (4). This monodentate telluroether species crystallized in monoclinic space group P2₁/n with a = 8.405(1) Å, b = 13.438(3) Å, c = 15.560(2) Å, β = 92.59(1)° V = 1755.5(5) ų, Z = 4, R = 0.035, and R_w = 0.035.     

Reactions of RSe− (R = Me,Ph) Groups in [RSeFe(CO)4I and [RSeCr(CO)5−]

The anionic [MeSeFe(CO)₄] and [MeSeCr(CO)₅] complexes were synthesized by reaction of [PPN][HFe(CO)₄] and [PPN][HCr(CO)₅] with MeSeSeMe respectively via nucleophilic cleavage of the Se-Se bond. The ease of cleavage of the Se-Se bond follows the nucleophilic strength of metal-hydride complexes. Methylation of [RSeCr(CO)₅^?] by the soft alkylating agent MeI resulted in the formation of neutral (MeSeMe)Cr(CO)₅ in THF at 0°C. In contrast, the [ICr(CO)₅^?] was isolated at ambient temperature. Reaction of [MeSeFe(CO)₄^?] or [MeSeCr(CO)₅^?] with HBF₄ yielded (CO)₃Fc(μ-SeMe)₂Fe(CO)₃ dimer and anionic [(CO )₅Cr (μ-SeMe)Cr(CO)₅^?] respectively, and no neutral (HSeMe)Fe(CO)₄ and (HSeMe)Cr(CO)₅ were detected spectrally (IR) even at low temperature. Reaction of NOBF₄ or [Ph₃C][BF₄] and [MeSeCr(CO)₅^?] resulted in the neutral monodentate (MeSeSeMe)Cr(CO)₅ complex. Addition of 1 equiv CpFe(CO)₂I to 2 equiv [MeSeCr(CO)₅^?] gave CpFe(CO)₂(SeMe) and the anionic [(CO)₅Cr(μ-SeMe)Cr(CO)₅^?] in THF at ambient temperature.     

Reaction Behavior of Decacarbonyldimetalates(2‐) (M = Cr and Mo) towards the Nitrosyl Carbonyls of Iron and Cobalt

The reaction of the nitrosyl carbonyl complexes [Fe(NO)₂(CO)₂] and [Co(NO)(CO)₃] with the decacarbonyldimetalates [M₂(CO)₁₀]^2– (M = Cr and Mo) in THF as the solvent at room temperature was investigated. Thereby a substitution of one nitrosyl ligand towards carbon monoxide was observed in each case. Both reactions afforded the known metalate complexes [Fe(NO)(CO)₃]^– and [Co(CO)₄]^–, respectively. These species were isolated as their corresponding PPN salts [PPN⁺ = bis(triphenylphosphane)iminium cation] in nearly quantitative yields. The products were unambiguously identified by their IR spectroscopic and elemental analytic data as well as by their characteristic colors and melting points.     

Synthesis,electrochemical and antimicrobial studies of mono and binuclear iron(III) and oxovanadium(IV) complexes of [ONO] donor tridentate Schiff-base ligands

Tridentate Schiff bases (H₂L¹ or H₂L²) were derived from condensation of acetylacetone and 2-aminophenol or 2-aminobenzoic acid. Binuclear square pyramidal complexes of the type [M₂(L¹)₂]?·?nH₂O (M?=?Fe–Cl, n?=?0; M?=?VO, n?=?1) were accessed from interaction of H₂L¹ with anhydrous FeCl₃ and VOSO₄?·?5H₂O, respectively. A similar reaction with H₂L², however, produced mononuclear complexes [ML²(H₂O) _x ]?·?nH₂O (M=Fe–Cl, x?=?0, n?=?0; M=VO, x?=?1, n?=?1). The compounds were characterized using elemental analysis, FT-IR, UV-Vis, and NMR (for ligand only), and mass spectroscopies and solution electrical conductivity studies. Magnetic susceptibility measurements suggest antiferromagnetic exchange in binuclear Fe(III) and VO(IV) complexes. Thermo gravimetric analysis (TGA) provided unambiguous evidence for the presence of coordinated as well as lattice water in [VOL²(H₂O)]?·?H₂O. Cyclic voltammetric studies showed well-defined redox processes corresponding to Fe(III)/Fe(II) and VO(V)/VO(IV). In vitro antimicrobial activities of the compounds were investigated against Klebsiella pneumoniae, Staphylococcus aureus, Pseudomonas aeroginosa, Escherichia coli, Bacillus subtilis, and Proteus vulgaris. H₂L¹ and its binuclear complexes exhibited pronounced activity against all the microorganisms tested.     

Reaktionsprodukte von S7NH mit Nickel- und Kupfersalzen Darstellung und Struktur der Komplexe [(CH3)4N][Ni(S3N)(CN)2], [(C6H5)4As][Cu(S3N)2] und [(C6H5)4As][Cu(S3N)CI]

Metal Sulfur Nitrogen Compounds 18. Reaction Products of S₇NH with Nickel and Copper Salts. Preparation and Structures of the Complexes [Ch₃₄N][Ni(S₃N)(CN)₂], [(C₆H₅)₄As][Cu(S₃N)₂], and [(C₆H₅)₄AS][Cu(S₃N)Cl]. In the presence of MOH (M = K, [(CH₃)₄N]), S₇NH reacts with Ni(CN)₂ to yield, besides the three-nuclear complex M[(S₃NNi)₃S₂], the new mononuclear complex M[Ni(S₃N)(CN)₂]. The [(CH₃)₄N]⁺ salt is monoclinic, C2/m, a = 19.303(9), b =6.941(3), c=16.309(10) Å, β = 144.51⁰(2), Z = 4. The [Ni(S₃N)(CN)₂]- anion is planar, Ni being coordinated by one S₃N^? chelate ligand and by two CN^? ions. From the reaction of CuCI₂, S₇NH, and [Ph₄As]OH result the salts [Ph₄As][Cu(S₃N)₂] or [Ph₄As][Cu(S₃N)Cl], depending on the reaction conditions. [Ph₄As][Cu(S₃N)₂] is triclinic, P&1macr;, a = 7.073(3), b = 11.742(4), c = 16.439(6) Å α = 91.08°(3), β = 99.01°(3), γ = 91.58°(3), Z = 2. Two S₃N^? chelate ligands coordinate to Cu^I in a distorted tetrahedral arrangement. [Ph₄As][Cu(S₃N)Cl] is monoclinic, C2/c, a = 17.174(6), b = 13.650(5), c = 21.783(5) Å β = 100.45°(2), Z = 8. Cu^I is coordinated by one S₃N^? chelate ligand and one C1^?, resulting in a trigonal planar environment.     

Kinetic Study of the Reduction of Bromate Ion by Tris(1,10-Phenanthroline)Iron(II) and Aquoiron(II) Ions — Implication for the Bromate-Gallic Acid Oscillating Reaction

The kinetics of the bromate oxidation of tris(1,10-phenanthroline)iron(II) (Fe(phen)₃²⁺) and aquoiron(II) (Fe²⁺ (aq)) have been studied in aqueous sulfuric acid solutions at μ = 1.0M and with Fe(II) complexes in great excess. The rate laws for both reactions generally can be described as -d [Fe(II)]/6dt = d[Br^?]/dt = k[Fe(II)] [BrO^?₃] for [H⁺]₀ = 0.428–1.00M. For [BrO^?₃]₀ = 1.00 × 10^?4M. [Fe²⁺]₀ = (0.724–1.45)x 10^?2 M, and [H⁺]₀ = 1.00M, k = 3.34 ± 0.37 M^?1s^?1 at 25°. For [BrO^?₃]₀ = (1.00–1.50) × 10^?4M, [Fe²⁺]₀ = 7.24 × 10^?3M ([phen]₀ = 0.0353M), and [H⁺]₀ = 1.00M, k = (4.40 ± 0.16) × 10^?2 M^?1s^?1 at 25°. Kinetic results suggest that the BrO^?₃-Fe²⁺ reaction proceeds by an inner-sphere mechanism while the BrO^?₃-Fe(phen)₃²⁺ reaction by a dissociative mechanism. The implication of these results for the bromate-gallic acid and other bromate oscillators is also presented.     

A New Type of Anionic Framework in Microporous Potassium Iron(II) Phosphate K[Fe(PO4)]

A new iron(II) orthophosphate K[Fe(PO₄)] has been obtained by hydrothermal synthesis and its crystal structure was determined by single‐crystal X‐ray diffraction: space group P2₁/n, Z = 8, a = 9.6199(10), b = 8.6756(8), c = 10.8996(13) Å, β = 115.577(8)° at 193 K, R = 0.023. Fe^II shows coordination numbers (CN) 4 (distorted tetrahedral) and CN 5 (distorted trigonal bipyramidal). The [FeO₄] and [FeO₅] units form together with the [PO₄] tetrahedra a microporous 3D para‐framework with open channels along the a and b directions. The potassium ions positioned in the channels show CN 7 and 8. The structural relations within the morphotropic row of non‐isotypic K[M(PO₄)] structures (M = Zn, Ni, Mn, Fe) are discussed on the basis of common basic structural units.     

Crystal Structure of μ‐Oxo‐bis[9,22‐(bisbutyloxy)hemiporphyrazinato]iron(III)

The crystal structure of the title compound, C₆₈H₆₀N₁₆O₅Fe₂, shows a dinuclear complex of two crystallographically independent, distorted hemiporphrazinato iron complexes with five‐coordinate iron and oxygen as bridging ligand. The Fe1‐O1‐Fe2 angle is 151.16°, the Fe‐O bond lengths are Fe1‐O1 [1.771(2) Å] and Fe2‐O1 [1.773(2) Å]. The dinuclear complexes have a staggered conformation with a dihedral angle of 26.2°, but coaxially to form tetrameric units is not observed. The molecule is characterized by short Fe‐N (isoindole) bonds [1.998(3) Å] and long Fe‐N (pyridine) bonds, values range from [2.175(3) Å] to [2.245(3) Å].     

Reaction of the unsaturated anion [Re3H4(CO)10]− with mercaptans. Synthesis and X-ray Characterization of the anion [ Re3H3 (CO)9(μ3-SBut)]−

The novel anion [Re₃H₃(CO)₉(μ₃-SBu^t)]^?, obtained by reaction of [Re₃H₄(CO)₁₀]^? with t-butyl mercaptan, has been characterized by IR, NMR and X-ray diffraction studies. It contains an equilateral Re₃ triangle (mean ReRe 3.091 Å), with nine terminal carbonyl groups, three for each metal atom, and a triply-bridging thiolate ligand (mean ReS 2.393 Å). The three hydrides are bridging on the edges of the triangle of metal atoms.     

Reactivity of [Te6Fe8(CO)24]2− and Its Conversion to [Te4Fe5(CO)14]2−

Whereas reaction of [PhCH₂NMe₃]₂|Te₆Fe₈(CO)₂₄] (1) in refluxing CH₂CI₂ forms Fe₂(CO)₆(μ0-) TeCH₂Te), treatment of 1 with Ph₂SnCl ₂ or Mel gave the oxidation product Te₂Fe₃(CO)₉. Oxidation of 1 with [Cu(CH₃CN)₄]BF₄ afforded Te₂Fe₃(CO)₉ in good yield. Cluster 1 was converted to [PhCH₂NMe₃][Te₄Fe₅(CO)₁₄] (2) in MeOH/CH₂Cl₂ solution. Cluster 2 was structurally characterized by single-crystal X-ray diffraction and spectral methods. Complex 2 is composed of two Te₂Fe₂(CO)₆ fragments linked by one Fe(CO)₂ group. 2 crystallizes in the orthorhombic space group Pbcn with a = 13.351 (4) Å, b = 13.417 (4) Å, c = 26.077 (3) Å, V = 4671 (2) Å ₃, Z = 4.     

Double deoxygenation of PPN(NO2) using metal carbonyl clusters of cobalt,rhodium, and iridium

The reaction of PP(NO₂) with M₄(CO)₁₂ (M = Co, Rh) gives the nitrido clusters [M₆N(CO)₁₅]^? in 13 and 21% yields, respectively. A high yield synthesis (77%) of [Rh₆N(CO)₁₅)]^? directly from Rh₆(CO)₁₆ and PPN(NO₂) is also presented. PPN(NO₂) reacts with Ir₄(CO)₁₂ to give the new isocyanato cluster, [Ir₄(NCO)(CO)₁₁]^? in 34% yield, while the direct synthesis of this isocyanate product occurs in 77% yield from PPN(N₃) and Ir₄(CO)₁₂. Modifications of published procedures for the preparation of [N(C₂H₅)₄]₂ [Ir₆(CO)₁₅] and Ir₆(CO)₁₆ are reported that allow shorter reaction times and give higher yields. The reaction of Ir₆(CO)₁₆ with one equivalent of PPN(NO₂) generates a new cluster, PPN[Ir₆(CO)₁₅(NO)], in 57% yield which is proposed to contain a bent nitrosyl ligand. An additional equivalent of PPN(NO₂) gives (PPN)₂[Ir₆(CO)₁₅] in 84% yield with the evolution of N₂O as well as CO₂.     

Synthesis and Crystal Structure of [Cu2(H2O)2(phen)2(OH)2][Cu2(phen)2(OH)2(CO3)2] · 10 H2O with phen = 1,10‐phenanthroline

The blue copper complex [Cu₂(H₂O)₂(phen)₂(OH)₂][Cu₂(phen)₂(OH)₂(CO₃)₂] · 10 H₂O, which was prepared by reaction of 1,10‐phenanthroline monohydrate, CuCl₂ · 2 H₂O and Na₂CO₃ in the presence of succinic acid in CH3OH/H₂O at pH = 13.0, crystallized in the triclinic space group P1 (no. 2) with cell dimensions: a = 9.515(1) Å, b = 12.039(1) Å, c = 12.412(2) Å, α = 70.16(1)°, β = 85.45(1)°, γ = 81.85(1)°, V = 1323.2(2) ų, Z = 1. The crystal structure consists of dinuclear [Cu₂(H₂O)₂(phen)₂(OH)₂]²⁺ complex cations, dinuclear [Cu₂(phen)₂(OH)₂(CO₃)₂]^2– complex anions and hydrogen bonded H₂O molecules. In both the centrosymmetric dinuclear cation and anion, the Cu atoms are coordinated by two N atoms of one phen ligand, three O atoms of two μ‐OH groups and respectively one H₂O molecule or one CO₃^2– anion to complete distorted [CuN₂O₃] square‐pyramids with the H₂O molecule or the CO₃^2– anion at the apical position (equatorial d(Cu–O) = 1.939–1.961 Å, d(Cu–N) = 2.026–2.051 Å and axial d(Cu–O) = 2.194, 2.252 Å). Two adjacent [CuN₂O₃] square pyramids are condensed via two μ‐OH groups. Through the interionic hydrogen bonds, the dinuclear cations and anions are linked into 1D chains with parallel phen ligands on both sides. Interdigitation of phen ligands of neighboring 1D chains generated 2D layers, between which the hydrogen bonded water molecules are sandwiched.     

An Azelaato‐bridged Dinuclear Copper(II) Complex, [Cu2(phen)2(C9H14O4)2] · 6 H2O (phen = 1,10‐phenanthroline)

The title compound [Cu₂(phen)₂(C₉H₁₄O₄)₂] · 6 H₂O was prepared by the reaction of CuCl₂ · 2 H₂O, 1,10‐phenanthroline (phen), azelaic acid and Na₂CO₃ in a CH₃OH/H₂O solution. The crystal structure (monoclinic, C2/c (no. 15), a = 22.346(3), b = 11.862(1), c = 17.989(3) Å, β = 91.71(1)°, Z = 4, R = 0.0473, wR² = 0.1344 for 4279 observed reflections) consists of centrosymmetric dinuclear [Cu₂(phen)₂(C₉H₁₄O₄)₂] complexes and hydrogen bonded H₂O molecules. The Cu atom is square‐planar coordinated by the two N atoms of the chelating phen ligand and two O atoms of different bidentate bridging azelaate groups with d(Cu–N) = 2.053, 2.122(2) Å and d(Cu–O) = 1.948(2), 2.031(2) Å. Two azelaate anions bridge two common Cu atoms via the terminal O atoms (d(C–O) = 1.29(2) Å; d(C–C) = 1.550(4)–1.583(4) Å). Phen ligands of adjacent complexes cover each other at distances of about 3.62 Å, indicating π‐π stacking interaction, by which the complexes are linked to 1 D bands.     

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).