Kobalt-Komplexe mit O2-Brücken: Die Struktur der Kationen μ-Hydroxo-μ-peroxo-bis[bis(äthylendiamin) kobalt(III)]3+ und μ-Hydroxo-μ-superoxo-bis[bis (äthylendiamin)kobalt(III)]4+

Cobalt Complexes with O₂ Bridges: The Structure of the Cations μ-Hydroxo-μ-peroxo-bis[bis(ethylenediamine) cobalt (III)]³⁺and μ-Hydroxo-μ-superoxo-bis [bis (ethylenediamine) cobalt (III)]⁴⁺ X-ray structure determinations of one salt of each of the two chemically and structurally closely related dinuclear cobalt cations [(en)₂Co · μ(OH, O₂) · Co(en)₂]³⁺ 1a and [(en)₂Co · μ(OH, O₂) · Co(en)₂]⁴⁺ 1b have been performed. In both cases the cations exist as racemic mixtures of ΔΔ and ΔΔ isomers. The O–O distance in the μ-peroxo cation 1a is 1.465 Å and the Co–O–O–Co torsion angle is 60.7°. The corresponding values for the μ-superoxo cation 1b are 1.339 Å and 22.0°.     

Mehrkernige Kobaltkomplexe. V. Präparative Herstellung von Tetrakis (äthylendiamin)-μ-peroxo-μ-amido- und μ-peroxo-μ-thiocyanatodikobalt (III)-Komplexen ausgehend von Tetrakis (äthylendiamin)bis-(ammin)-μ-peroxo-dikobalt (III)-tetraperchlorat

Polynuclear Cobalt Complexes. V. Preparation of tetrakis (ethylenediamine)-μ-peroxo-μ-amido and μ-peroxo-μ-thiocyanato-dicobalt (III) complexes starting from tetrakis (ethylenediamine)bis-(ammine)-μ-peroxo-dicobalt (III)-tetraperchlorate Racemic tetrakis (ethylenediamine)-μ-peroxo-μ-amido-dicobalt (III) thiocyanate and its corresponding hydroperoxo- and superoxo-complexes have been isolated from [(en)₂(NH₃)Co(O₂)(NH₃)(en)₂](ClO₄)₄. A new binuclear peroxo complex containing thiocyanate as bridging ligand was prepared by the same method. The stretching frequencies of the CN- and CS-group as well as the NCS-bending frequence in the IR. spectrum of [(en)₂Co(O₂, SCN)Co(en)₂](NO₃)₃ suggest that the μ-thiocyanato group is N-bonded (2050, 750, 475 cm^?1). A comparison of IR. spectra of known singly and doubly bridged μ-peroxo complexes is made. Characteristic absorption bands, assignable to ν(O? O) and ν(Co? O) are given.     

Synthesis,Crystal Structure,and Hydrogen Bonding of μ‐Hydroxo‐μ‐peroxo‐bis[bis(ethylenediamine)cobalt(III)] Squarate

Black‐brown needle‐shaped single crystals of [Co₂(en)₄(O₂)(OH)][C₄O₄]_1.5 · 4H₂O (en = ethylenediamine) were prepared in aqueous solution at room temperature [space group P$\bar{1}$ (no.2) with a = 800.20(8), b = 1225.48(7), c = 1403.84(9) pm, α = 100.282(5), β = 94.515(7), and γ = 95.596(6)°]. The Co³⁺ cations [Co(1), Co(2)] are coordinated in an octahedral manner by four nitrogen atoms stemming from the ethylenediamine molecules and two oxygen atoms each from a hydroxo group and a peroxo group, respectively. Both Co³⁺ coordination polyhedra are connected by a common corner and by the peroxo group leading to the dinuclear [(en)₂Co(O₂)(OH)Co(en)₂]³⁺ cation. The squarate dianions, not bonded to Co³⁺, and the [(en)₂Co(O₂)(OH)Co(en)₂]³⁺ cations are linked by hydrogen bonds forming a three‐dimensional supramolecular network containing water molecules. Magnetic measurements revealed a diamagnetic behavior indicating a low‐spin electron configuration of Co³⁺. The UV/Vis spectra show two LMCT bands [π*(O₂^2–) → d_σ*(Co³⁺)] at 274 and 368 nm and the d–d transition (¹A_1g → ¹T_1g) at 542 nm. Thermoanalytical investigations in air show that the compound is stable up to 120 °C. Subsequent decomposition processes to cobalt oxide are finished at 460 °C.     

Intramolecular Antiferromagnetism in μ-Oxo-bis[(5,15-dimethyl-2,3,7,8,12,13,17,18-octaethylporphyrinato)iron(III)]

The magnetism of μ-oxo-bis[(5,15-dimethyl-2,3,7,8,12,13,17,18-octaethylporphyrinato)iron(III)] with bridge geometry d(Fe? O) = 1.752 Å and ?(Fe? O? Fe) = 178.6° can be explained in terms of antiferromagnetically exchange coupled iron(III)-3d⁵ pairs. The magnetochemical analysis in the temperature range 6K–295K on the basis of the isotropic Heisenberg model (spin Hamiltonian: ? = ?2J?₁ · ?₂ S₁ = S₂ = 5/2) leads to the exchange parameter J = ?125 cm^?1. With regard to the Fe? O bond length the J value corresponds to the series of data observed for other μ-oxodiiron-porphyrins and -porphycenes. Compared to the spin-spin coupling in [Fe₂Cl₆O]^2?, |J| is enhanced by ≈ 10%.     

Synthesis and Structure of a New Vanadium(IV)‐Cadmium(II) Compound with the Nitrilotriacetate Ligand: {(NH4)2[(VIVO)2(μ2‐O)(nta)2Cd(H2O)2]·H2O}n

A polymeric V^IV‐Cd compound, {(NH₄)₂[(V^IVO)₂(μ₂‐O)(nta)₂Cd(H₂O)₂]·H₂O}_n (H₃nta = nitrilotriacetic acid), has been prepared and characterized by single‐crystal X‐ray diffraction. The compound crystallizes in the monoclinic space group C2/c with a = 17.3760(2) Å, b = 8.0488(1) Å, c = 17.3380(2) Å, β = 107.9690(10)°, V = 2306.55(5) ų, Z = 4, and R₁ = 0.0303 for 1958 observed reflections. The structure exhibits a heterometallic three‐dimensional network formed by polymeric [(V^IVO)₂(μ₂‐O)(nta)₂Cd(H₂O)₂]^2? anions.     

Orthomanganated arenes in synthesis VII. Transition-metal mediated formation of a P?P bond; the X-ray crystal structure of Mn2(μ-η1, η1-Ph2PPPh2)(μ-Cl)2(CO)6

The reaction of PPh₂Cl with orthomanganated acetophenone, 2′-CH₃C(O)C₆H₄Mn(CO)₄, gives Mn₂(μ-η₁,η¹-Ph₂PPPh₂)(μ-Cl)₂(CO)₆. An X-ray structure determination [triclinic, space group P1 , a = 10.908(4) Å, b = 11.756(3) Å, c = 12.186(3) Å, α = 96.20(2)°, β = 99.51(2)°, γ = 96.52(2)°] shows two Mn(CO)₃ groups held together by two bridging Cl ligands, and further bridged by a Ph₂P? PPh₂ group prepared in situ.     

The structure of tetramethyl μ-monothiopyrophosphate

The compound tetramethyl μ-monothiopyrophosphate (C₄H₁₂O₆P₂S) crystallizes in the monoclinic space group C 2/c, with (at -130°C) a = 10.322 Å, b = 8.229 Å, c = 12.062 Å, β = 98.44°, and D_calc = 1.639 g/mL³ and Z = 4. The crystal structure has been determined by single crystal X-ray diffraction to give a final R value of 0.0329 for 614 independent observed reflections [F_˚ > 2.5σ(F_˚)]. The sulfur atom resides on a crystallographic two-fold axis. The P S P bond angle is 105.4° and the P S bond lengths are 2.093 Å. The bond angles around phosphorus range from 99.1° to 118.2°. The terminal PO bond is 1.465 Å, and the methoxyl P O bond is about 1.556 Å. The H₃C O P bond angle is about 119.5°. Many structural features are interpreted in terms of π-bonding to phosphorus. Comparisons with the structures of pyrophosphate and related compounds indicate that the combined effects of increased acuteness of the P S P bond and the increased length of the P—S bonds lead to an increase of about 0.4 Å in the separation of phosphorus atoms in the sulfur-bridging compound. These facts, together with the weakness of the P S bond, must be taken into account in the interpretation of kinetic data for enzymatic reactions of phosphorothiolates as substrates in place of phosphates.     

Homo- und heterodinukleare α-Pyridonat-verbrückte Platin- und Palladium-komplexe mit Bis(N-methylimidazol-2-yl)keton (BMIK). Kristallstrukturen von [(BMIK)Pt(α-Pyridonat)2Pt(BMIK)](NO3)2 · 4H2O, [(BMIK)Pd(α-Pyridonat)2Pd(BMIK)](NO3)2 · 4H2O und [(BMIK)Pd(α-Pyridonat)2Pt/Pd(BMIK)](NO3)2 · 4H2O

Homo- and Heterodinuclear α-Pyridonate-bridged Platinum and Palladium Complexes with Bis(N-methylimidazol-2-yl)ketone (BMIK). Crystal Structures of [(BMIK)Pt(α-pyridonate)₂Pt(BMIK)](NO₃)₂ · 4H₂O, [(BMIK)Pd(α-pyridonate)₂Pd(BMIK)](NO₃)₂ · 4H₂O, and [(BMIK)Pd(α-pyridonate)₂Pt/Pd(BMIK)](NO₃)₂ · 4H₂O The isotypic dinuclear complexes [(BMIK)Pt(α-pyridonate)₂Pt(BMIK)](NO₃)₂ · 4H₂O ( 1 ) (P1 ; a = 12.197(5) Å, b = 12.505(5) Å, c = 12.866(5) Å, α = 88.17(3)°, β = 73.55(3)°, γ = 69.84(3)°; Z = 2) and [(BMIK)Pd(α-pyridonate)₂Pd(BMIK)](NO₃)₂ · 4H₂O ( 2 ) (a = 12.408(3) Å, b = 12.660(3) Å, c = 12.913(3) Å, α = 89.55(3)°, β = 74.59(2)°, γ = 68.68(2)°) were prepared by reaction of [Pt(BMIK)(H₂O)₂](NO₃)₂ or [Pd(BMIK)(H₂O)₂](NO₃)₂ with α-pyridone in aqueous solutions at 40°C and were isolated as red air-stable crystals (BMIK = bis(N-methylimidazol-2-yl)ketone). For the synthesis of mixed crystals of 2 with the heterometal complex [(BMIK)Pd(α-pyridonate)₂Pt(BMIK)](NO₃)₂ · 4H₂O ( 3 ) (a = 12.430(4) Å, b = 12.648(3) Å, c = 12.907(4) Å, α = 89.64(2)°, β = 74.57(2)°, γ = 68.65(2)°) α-pyridone was reacted with [Pd(BMIK)(H₂O)₂](NO₃)₂ in a molar ratio of 2 : 1 followed by addition of [Pt(BMIK)(H₂O)₂](NO₃)₂. The dinuclear cations consist of two M(BMIK) moieties (M = Pt, Pd) bridged by the N- and O-atoms of α-pyridonate, forcing the heterocyclic ring into head-head-orientation. Within the dinuclear cation, the two metal atoms are between 2.840 Å and 2.860 Å apart. The intermolecular distances are between 4.762 Å and 4.837 Å. The coordination geometry of both metal atoms is square-planar with the metal atoms being diplaced slightly from their respective coordination planes toward each other. ¹H and ¹⁹⁵Pt NMR spectra are reported for the complexes.     

Die Kristall- und Molekülstruktur von Dicäsium- μ-Oxodekafluorodiarsenat

Crystal and Molecular Structure of Dicaesium-μ-Oxodecafluorodiarsenate, Cs₂(As₂F₁₀O) The crystal structure of Cs₂(As₂F₁₀O) has been determined from three-dimensional data. The compound crystallizes in the monoclinic space group P2₁/m, the lattice constants being a = 9.175(4), b = 10.690(5), c = 5.619(3)(Å); β = 105,50(5)°. The anion (As₂F₁₀O)^2– with the point symmetry C_s contains a As? O? As-bridge, whose partial π-bonding is to be discussed. The bond lengths and angles are: As? O: 1.77(2) and 1.68(2) Å, resp., As? O? As: 139(1)°; As…As: 3.225(4) Å, the numbers in parantheses being the standard deviation of the last figure.     

A Novel Adipate Bridged Supramolecular Layer: Crystal Structure of the Cobalt(II) Complex [(μ‐C6H8O4)4/2Co(μ‐H2O)2Co(H2O)4] · 4 H2O

The pale‐rose compound [(μ‐C₆H₈O₄)_4/2Co(μ‐H₂O)₂Co(H₂O)₄] · 4 H₂O was prepared from adipic acid and CoCO₃ in aqueous solution. The crystal structure (monoclinic, P2₁/n (no. 14), a = 8.061(1), b = 15.160(2), c = 9.708(2) Å, β = 90.939(7)°, Z = 2, R = 0.0405, wR² = 0.0971) consists of adipate bridged supramolecular [(μ‐C₆H₈O₄)_4/2Co(μ‐H₂O)₂Co(H₂O)₄] layers and hydrogen bonded H₂O molecules. The cobalt atoms Co1 and Co2 are distorted octahedrally coordinated by the O atoms of two bridging trans‐H₂O molecules and four bidentate adipate anions (Co1) and by the O atoms of two bridging trans‐H₂O molecules and four monodentate H₂O molecules (Co2), respectively. Equatorial bonds: d(Co1–O) = 2.048 Å (2 × ), 2.060 Å (2 × ); d(Co2–O) = 2.057 Å (2 × ), 2.072 Å (2 × ). Axial bonds: d(Co1–O) = 2.235 Å (2 × ); d(Co2–O) = 2.156 Å (2 × ).     

Two New Polyoxovanadate‐supported Transition Metal Complexes: [Zn(en)2][Zn(en)2(H2O)2][{Zn(en)(enMe)}As6V15O42(H2O)]·4H2O and [Zn2(enMe)2(en)3][{Zn(enMe)2}As6V15O42(H2O)]·4H2O

Two novel As‐V‐O cluster supported transition metal complexes, [Zn(en)₂][Zn(en)₂(H₂O)₂][{Zn(en)(enMe)}As₆V₁₅O₄₂(H₂O)]·4H₂O ( 1 ) and [Zn₂(enMe)₂(en)₃][{Zn(enMe)₂}As₆V₁₅O₄₂(H₂O)]·4H₂O ( 2 ), have been hydrothermally synthesized. The single X‐ray diffraction studies reveal that both compounds consist of discrete noncentral polyoxoanions [{Zn(en)(enMe)}As₆V₁₅O₄₂(H₂O)]^4? or [{Zn(enMe)₂}As₆V₁₅O₄₂(H₂O)]^4? cocrystallized with respective zinc coordination complexes. Interestingly, compounds 1 and 2 exhibit the first two polyoxovanadates containing As₈V₁₅O₄₂‐(H₂O)]^6? cluster decorated by only one transition metal complex. Crystal data: 1 , monoclinic, P2₁/n, a = 14.9037(4) Å, b = 18.1243(5) Å, c = 27.6103(7) Å, β = 105.376(6)°, Z = 4; 2 monoclinic, P2₁/n, a = 14.9786(7) Å, b = 33.0534(16) Å, c = 14.9811(5) Å, Z = 4.     

Studies of Organometallic Compounds XV. The Crystal Structure of Bis(tribenzyl-titanium(IV))-μ-oxo

The crystal and molecular structure of bis(tribenzyl-titanium(IV))-μ-oxo, [(PhCH₂)₃-Ti]₂O, has been determined from analysis of X-ray photographic data. The crystal system is rhombohedral, a = 9.58(2) Å, α = 83.6(2)°, space group R3 , Z = 1.     

The synthesis and crystal structure of a trinuclear molybdenum cluster compound [Mo3(μ-O)(μ-S)3(μ(μ-OAc)2(dtp)2·(Py)]·0.5H2O

[Mo₃,OS₃(dtp)₄(H₂O)] reacts with NaOAc·3H₂O in Py to give the title compound. The crystal data are as follows: [Mo₂OS₃)(OAc)₂(dtp)₂·Py]?0.5H,O(dtp = [S₃P(OC₂H₅)₂]^?, Py = C₅H₅N); M = 976.64; triclinic; space group P1 ; a=11.704(5), b=14.169(7), c= 11.688 (5) Å α=109.94(4) β = 91.53(4), γ = 91.93(4)°; V= 1819(1) Ų; Z=2; D_c = 1.78 g·cm^?3 λ(Mo Kα) = 0.71069 Å μ=15.15 cm^?1; F(000) = 970 T=296 K; final R=0.071 for 1652 reflections with I>3σ(I). In the molecule, the [Mo₃OS₃] core is surrounded by two bridging OAc groups and two terminal chelate dtp groups attached to the {Mo₃} triangle in a symmetric style, and the Py ligand is coordinated to the Mo atom at the apex of {Mo₃} triangle with the nitrogen. This novel configuration is obtained for the first time with Mo—N bond length being 2.27 (2) Å and three Mo—Mo bond lengths 2.584 (4), 2.587 (4) and 2.657(4) Å, respectively. As a whole, the molecule has a virtual C₂ symmetry.     

Synthesis and structure of the cluster μ3-sulfido-μ-–(diethylphosphorodithioato-S,S'-)-allylthioureocyclo-tris-[ (μ-sulfido)-χ-(diethylphosphorodithioato-S,S')-molybdenum(IV)], Mo3S4(C4H10O2S2P)4(C4H8N2S)

Title compound, M_r =1273.16, was synthesized by a substitution reaction and its crystal is triclinic belonging to space group P1 with cell parameters: a =13.944(2), b =14.143(7), c =14.233(3) Å, α =77.35(3)°, β =69.94(2)°, γ =63.50(3)°, V=2351(1) ų, Z=2, D_c =1.799g cm^?2. Room temperature, graphite-filtered Mo K_α radiation (λ =0.71073Å) was used for data collection. μ =14.988 cm^?1, F(000) =1280, R=0.051 for 7025 observed reflections. The crystal consists of decrete cluster molecules containing a cluster core [Mo₂(μ₃-S)]¹⁰⁺ with three μ-S, one μ-dtp(dtp =[S₂P(OC₂H₅)]^2-), three χ-dtp and one allylthioureo to form a local six-coordinated sphere around each Mo atom. The bonds of cluster skeleton [Mo₃(μ₃-S)(μ-S)₃]⁴⁺, Mo? Mo 2.744～2.766, Mo—(μ₂-S) 2.340～2.342 and Mo—(μ-S)2.272～2.296 Å, are comparable with those found in the related analogues.     

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.     

Two Succinato‐bridged Zinc(II) Phenanthroline Complexes: [Zn(phen)L2/2](H2L) and [(phen)2Zn(μ‐L)Zn(phen)2]L � 11H2O with H2L = Succinic Acid

Two mixed ligand Zn^II complexes [Zn(phen)L_2/2](H₂L) ( 1 ) and [(phen)₂Zn(μ‐L)Zn(phen)₂]L � 11H₂O ( 2 ) with H₂L = suc‐cinic acid were prepared and crystallographically characterized. Complex 1 crystallizes in the monoclinic space group C2/c (no. 15) with a = 13.618(1) Å, b = 9.585(1) Å, c = 15.165(1) Å, β = 96.780(6)°, V = 1965.6(3)ų, Z = 4 and complex 2 in the triclinic space group P 1¯ (no. 2) with a = 12.989(2)Å, b = 14.464(2)Å, c = 18.025(3)Å, α = 90.01(1)°, β = 109.69(1)°, γ = 112.32(1)°, V = 2917.4(8) ų, Z = 2. 1 consists of succinic acid molecules and 1D zigzag [Zn(phen)(C₄H₄O₄)_2/2] polymeric chains, in which the tetrahedrally coordinated Zn atoms are bridged by bis ‐ monodentate succinato ligands. Succinic acid molecules play an important role in supramolecular assemblies of the polymeric chains into 2D layers as well as in the stacking of 2D layers. 2 is composed of [(phen)₂Zn(μ‐L)Zn(phen)₂]²⁺ complex cations, succinate anions and hydrogen bonded water molecules. Within the divalent cations, Zn atoms are octahedrally coordinated by four N atoms of two phen ligands and two O atoms of one bis‐chelating succinato ligand. Through the intermolecular π—π stacking interactions, the complex cations form positively charged 2D layers, between which the noncoordinating succinate anions and water molecules are sandwiched.     

Preparation,Crystal Structure and Spectroscopic Studies of Mixed valence Compound [(Cp4i Rh)2 (μ‐Cl)3] [Rh(CO)2Cl2]

[(Cp⁴ⁱ Rh)₂(μ‐Cl)₃] [Rh(CO)₂Cl₂] (Cp⁴ⁱ = tetraisopropyl‐cyclopenta‐dienyl) has been prepared and its crystal is in the space group of Pbar with a= 0.9417 (8), b = 1.4806 (3), c = 1.5062 (2) nm, a = 92.980(10), β = 97.42(3), γ = 93.98 (3)°, V = 2.0735(18) nm³ and Z = 2. The crystal structure consists of a cation of [(η⁵‐Cp⁴ⁱ) Rh (III)(μ‐Cl)₃ Rh (III) (η⁵‐Cp⁴ⁱ)]⁺ and an anion of [Rh (I) (CO)₂ Cl₂]. The two bulky tetraisopropylcyclopentadienyl ligands are in the ecliptic conformation with angle of 10.19° between two cyclopentadienyl ring planes.     

Two Novel CuII Phenanthroline Adipato Complexes with π‐π Stacking Interactions: [Cu(phen)2(C6H8O4)] · 4.5 H2O and [(Cu2(phen)2Cl2)(C6H8O4)] · 4 H2O

The blue copper complex compounds [Cu(phen)₂(C₆H₈O₄)] · 4.5 H₂O ( 1 ) and [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)] · 4 H₂O ( 2 ) were synthesized from CuCl₂, 1,10‐phenanthroline (phen) and adipic acid in CH₃OH/H₂O solutions. [Cu(phen)₂‐ (C₆H₈O₄)] complexes and hydrogen bonded H₂O molecules form the crystal structure of ( 1 ) (P1 (no. 2), a = 10.086(2) Å, b = 11.470(2) Å, c = 16.523(3) Å, α = 99.80(1)°, β = 115.13(1)°, γ = 115.13(1)°, V = 1617.5(5) ų, Z = 2). The Cu atoms are square‐pyramidally coordinated by four N atoms of the phen ligands and one O atom of the adipate anion (d(Cu–O) = 1.989 Å, d(Cu–N) = 2.032–2.040 Å, axial d(Cu–N) = 2.235 Å). π‐π stacking interactions between phen ligands are responsible for the formation of supramolecular assemblies of [Cu(phen)₂(C₆H₈O₄)] complex molecules into 1 D chains along [111]. The crystal structure of ( 2 ) shows polymeric [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)_2/2] chains (P1 (no. 2), a = 7.013(1) Å, b = 10.376(1) Å, c = 11.372(3) Å, α = 73.64(1)°, β = 78.15(2)°, γ = 81.44(1)°, V = 773.5(2) ų, Z = 1). The Cu atoms are fivefold coordinated by two Cl atoms, two N atoms of phen ligands and one O atom of the adipate anion, forming [CuCl₂N₂O] square pyramids with an axial Cl atom (d(Cu–O) = 1.958 Å, d(Cu–N) = 2.017–2.033 Å, d(Cu–Cl) = 2.281 Å; axial d(Cu–Cl) = 2.724 Å). Two square pyramids are condensed via the common Cl–Cl edge to centrosymmetric [Cu₂Cl₂N₄O₂] dimers, which are connected via the adipate anions to form the [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)_2/2] chains. The supramolecular 3 D network results from π‐π stacking interactions between the chains. H₂O molecules are located in tunnels.     

μ‐1,4‐Benzenedicarboxylato‐bis[trans‐aqua(1,4,8,11‐tetraazacyclotetradecane)nickel(II)] diperchlorate forms a three‐dimensional hydrogen‐bonded framework

The title compound, [Ni₂(C₈H₄O₄)(C₁₀H₂₄N₄)₂(H₂O)₂](ClO₄)₂, contains two independent octahedral Ni^II centres with trans‐NiN₄O₂ chromophores. The bridging benzene­dicarboxyl­ate ligand is bonded to the two Ni atoms, each via one O atom of each carboxyl­ate, while the other O atom participates in an intramolecular N—H?O hydrogen bond, forming an S(6) motif. The cations are linked to the perchlorate anions via O—H?O and N—H?O hydrogen bonds [O?O 2.904 (6) and 2.898 (6) Å; O—H?O 158 (6) and 165 (6)°; N?O 3.175 (7) and 3.116 (7) Å; N—H?O 168 and 166°] to form molecular ladders. These ladders are linked by further O—H?O and N—H?O hydrogen bonds [O?O 2.717 (6) and 2.730 (5) Å; O—H?O 170 (4) and 163 (6)°; N?O 3.373 (7) and 3.253 (7) Å; N—H?O 163 and 167°] to form a continuous three‐dimensional framework. The perchlorate anions both participate in three hydrogen bonds, and both are thus fully ordered.     

Influence of the Counterions on the Structures of Ternary Zn/Sn/Se Anions: Synthesis and Properties of [Rb10(H2O)14.5][Zn4(μ4‐Se)2(SnSe4)4] and [Ba5(H2O)32][Zn5Sn(μ3‐Se)4(SnSe4)4]

Reactions of rubidium or barium salts of the ortho‐selenostannate anion, [Rb₄(H₂O)₄][SnSe₄] ( 1 ) or [Ba₂(H₂O)₅][SnSe₄] ( 2 ) with Zn(OAc)₂ or ZnCl₂ in aqueous solution yielded two novel compounds with different ternary Zn/Sn/Se anions, [Rb₁₀(H₂O)_14.5][Zn₄(μ₄‐Se)₂(SnSe₄)₄] ( 3 ) and [Ba₅(H₂O)₃₂][Zn₅Sn(μ₃‐Se)₄(SnSe₄)₄] ( 4 ). 1 – 4 have been determined by means of single crystal X‐ray diffraction: 1 : triclinic space group lattice dimensions at 203 K: a = 8.2582(17) Å, b = 10.634(2) Å, c = 10.922(2) Å, α = 110.16(3)°, β = 91.74(3)°, γ = 97.86(3)°, V = 888.8(3) ų; R₁ [I > 2σ(I)] = 0.0669; wR₂ = 0.1619; 2 : orthorhombic space group Pnma; lattice dimensions at 203 K: a = 17.828(4) Å, b = 11.101(2) Å, c = 6.7784(14) Å, V = 1341.5(5) ų; R₁ [I > 2σ(I)] = 0.0561; wR₂ = 0.1523; 3 : triclinic space group ; lattice dimension at 203 K: a = 17.431(4) Å, b = 17.459(4) Å, c = 22.730(5) Å, α = 105.82(3)°, β = 99.17(3)°, γ = 90.06(3)°, V = 6563.1(2) ų; R₁ [I > 2σ(I)] = 0.0822; wR₂ = 0.1782; 4 : monoclinic space group P2₁/c; lattice dimensions at 203 K: a = 25.231(5) Å, b = 24.776(5) Å, c = 25.396(5) Å, β = 106.59(3)°, V = 15215.0(5) ų; R₁ [I > 2σ(I)] = 0.0767; wR₂ = 0.1734. The results serve to underline the crucial role of the counterion for the type of ternary anion to be observed in the crystal. Whereas Rb⁺(aq) stabilizes a P1‐type Zn/Sn/Se supertetrahedron in 3 like K⁺, the Ba²⁺(aq) ions better fit to an anionic T3‐type Zn/Sn/Se cluster arrangement as do Na⁺ ions. It is possible to estimate a radius:charge ratio for the stabilization of the two structural motifs.