Synthesis and thermal decomposition kinetics of the complexes [Sm(o‐NBA)3bipy]2·2H2O and [Sm(o‐BrBA)3bipy]2· 2H2O

Two new complexes [Sm(o‐NBA)₃bipy]₂·2H₂O ( 1 ) and [Sm(o‐BrBA)₃bipy]₂·2H₂O ( 2 ) (where o‐NBA is o‐nitrobenzoic acid, o‐BrBA is o‐bromobenzoic acid, and bipy is 2,2′‐bipyridine) were prepared and characterized by elemental analysis, IR, UV, and molar conductance, respectively. The thermal decomposition behaviors of the two complexes were investigated by means of TG–DTG and IR techniques. The thermal decomposition kinetics was studied by using advanced double equal‐double steps method, nonlinear integral isoconversional method, and nonlinear differential isoconversional method. The kinetic parameters of the second‐step process for the two complexes were obtained, respectively. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 607–616, 2008     

Two Heteroleptic Zinc(II) Complexes: [Zn(phen)(C9H15O6)2] and [Zn2(phen)2(H2O)2(C10H16O4)2] · 3H2O

Reactions of a freshly prepared Zn(OH)_2‐2x(CO₃)x · yH₂O precipitate, phenanthroline with azelaic and sebacic acid in CH₃OH/H₂O afforded [Zn(phen)(C₉H₁₅O₄)₂] ( 1 ) and [Zn₂(phen)₂(H₂O)₂(C₁₀H₁₆O₄)₂] · 3H₂O ( 2 ), respectively. They were structurally characterized by X‐ray diffraction methods. Compound 1 consists of complex molecules [Zn(phen)(C₉H₁₅O₄)₂] in which the Zn atoms are tetrahedrally coordinated by two N atoms of one phen ligand and two O atoms of different monodentate hydrogen azelaato groups. Intermolecular C(alkyl)‐H···π interactions and the intermolecular C(aryl)‐H···O and O‐H···O hydrogen bonds are responsible for the supramolecular assembly of the [Zn(phen)(C₉H₁₅O₄)₂] complexes. Compound 2 is built up from crystal H₂O molecules and the centrosymmetric binuclear [Zn₂(phen)₂(H₂O)₂(C₁₀H₁₆O₄)₂] complex, in which two [Zn(phen)(H₂O)]²⁺ moieties are bridged by two sebacato ligands. Through the intermolecular C(alkyl)‐H···O hydrogen bonds and π‐π stacking interactions, the binuclear complex molecules are assembled into layers, between which the lattice H₂O molecules are sandwiched. Crystal data: ( 1 ) C2/c (no. 15), a = 13.887(2), b = 9.790(2), c = 22.887(3)Å, β = 107.05(1)°, U = 2974.8(8)ų, Z = 4; ( 2 ) P1¯ (no. 2), a = 8.414(1), b = 10.679(1), c = 14.076(2)Å, α = 106.52(1)°, β = 91.56(1)°, γ = 99.09(1)°, U = 1193.9(2)ų, Z = 1.     

Synthesis,Crystal Structure and Thermal Decomposition Process of Complex [Sm(BA)3phen]2

A binuclear samarium(III) complex with benzoic acid and 1,10‐phenanthroline, [Sm(BA)₃phen]₂ was synthesized and characterized by elemental analysis, UV, IR and TG‐DTG techniques. The structure of the title complex was established by single crystal X‐ray diffraction. The crystal is triclinic, space group P1 with a = 10.8216(11) Å, b = 11.9129(13) Å, c = 12.425(2) Å, α = 105.007(2)°, β = 93.652(2)°, γ = 113.2630(10)°, Z = 1, D_c = 1.650 mg·m^?3, F(000) = 690. The carboxylate groups are bonded to the samarium ion in three modes: bidentate chelating, bidentate bridging, and tridentate chelating‐bridging. Each Sm³⁺ ion is coordinated to one bidentate chelating carboxylate group, two bidentate bridging and two tridentate chelating‐bridging carboxylate groups, as well as one 1,10‐phenanthroline molecule, forming a nine‐coordinate metal ion. Based on thermal analysis, the thermal decomposition process of [Sm(BA)₃phen]₂ has been derived.     

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.     

Preparation,Characterization and Non‐isothermal Kinetics of the Dehydration Process of [Sm(p‐MOBA)3bath]2·4H2O

The new complex of [Sm(p‐MOBA)₃bath]₂·4H₂O (p‐MOBA, p‐methoxybenzoate; bath, 4,7‐diphenyl‐1,10‐phenanthroline) was synthesized and characterized by elemental analysis, molar conductance, IR, UV and XRD patterns. The thermal decomposition of the complex was studied under the non‐isothermal condition by TG‐DTG and IR techniques. The most probable mechanism function of the dehydration process was obtained from the analysis of DSC curves of the complex employing the double extrapolated method on the basis of integral isoconversional non‐linear (NL‐INT) and Tang‐Wanjun integral equations. The integral function of the mechanism was [1? (1?α)^1/2]^1/2 and the corresponding kinetic parameters (activation energy E and the pre‐exponential factor A) were obtained.     

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.     

Crystal Structures of [Mn2(H2O)4(phen)2(C4H4O4)2] · 2 H2O and [Mn(phen)2(H2O)2][Mn(phen)2(C4H4O4)](C4H4O4) · 7 H2O

Reactions of 1,10‐phenanthroline monohydrate, Na₂C₄H₄O₄ · 6 H₂O and MnSO₄ · H₂O in CH₃OH/H₂O yielded a mixture of [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] · 2 H₂O ( 1 ) and [Mn(phen)₂(H₂O)₂][Mn(phen)₂(C₄H₄O₄)](C₄H₄O₄) · 7 H₂O ( 2 ). The crystal structure of 1 (P1 (no. 2), a = 8.257(1) Å, b = 8.395(1) Å, c = 12.879(2) Å, α = 95.33(1)°, β = 104.56(1)°, γ = 106.76(1)°, V = 814.1(2) ų, Z = 1) consists of the dinuclear [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] molecules and hydrogen bonded H₂O molecules. The centrosymmetric dinuclear molecules, in which the Mn atoms are octahedrally coordinated by two N atoms of one phen ligand and four O atoms from two H₂O molecules and two bis‐monodentate succinato ligands, are assembled via π‐π stacking interactions into 2 D supramolecular layers parallel to (101) (d(Mn–O) = 2.123–2.265 Å, d(Mn–N) = 2.307 Å). The crystal structure of 2 (P1 (no. 2), a = 14.289(2) Å, b = 15.182(2) Å, c = 15.913(2) Å, α = 67.108(7)°, β = 87.27(1)°, γ = 68.216(8)°, V = 2934.2(7) ų, Z = 2) is composed of the [Mn(phen)₂(H₂O)₂]²⁺ cations, [Mn(phen)₂(C₄H₄O₄)] complex molecules, (C₄H₄O₄)^2– anions, and H₂O molecules. The (C₄H₄O₄)^2– anions and H₂O molecules form 3 D hydrogen bonded network and the cations and complex molecules in the tunnels along [001] and [011], respectively, are assembled via the π‐π stacking interactions into 1 D supramolecular chains. The Mn atoms are octahedrally coordinated by four N atoms of two bidentate chelating phen ligands and two water O atoms or two carboxyl O atoms (d(Mn–O) = 2.088–2.129 Å, d(Mn–N) = 2.277–2.355 Å). Interestingly, the succinato ligands in the complex molecules assume gauche conformation bidentately to chelate the Mn atoms into seven‐membered rings.     

Investigations on Preparation,Crystal Structure and Thermal Stability of Bis(O-ethylcarbonodithiolato-S,S′)(1,10-phenanthroline-N~1,N~(10))cobalt(II) Complex:[Co(Et-XA)_2·phen]·H_2O (XA=xanthate)

IntroductionTheincreasingcommercialvalueoftransitionmetalcomplexesofxanthateshasarousedconsiderableinterestintheirchemistry .Whiletheiranalyticalapplicationsarewellknown ,1theyarenowfindingextensiveuseinvulcan izationofrubber ,frothfloatationprocessforconcentrationofsulphideores ,asantioxidants ,lubricants ,2 ,3andhavebeenfoundtopossessfungicidalandinsecticidalactivi ties .4 Recently ,molecularrecognitionbetweenhostandguestmolecules ,inclusionphenomenaandnoncovalentmolecularinteractionarefunda…     

New Suberato‐bridged Supramolecular Layers: Crystal Structure of [Cu2(phen)2(C8H12O4)2] · 3 H2O with phen = 1,10‐phenanthroline

The reaction of CuCl₂ · 2 H₂O, 1,10‐phenanthroline (phen), suberic acid and Na₂CO₃ in a CH₃CN–H₂O solution yielded blue needle‐like crystals of [Cu₂(phen)₂(C₈H₁₂O₄)₂] · 3 H₂O. The crystal structure (monoclinic, P2₁/n, a = 10.756(2) Å, b = 9.790(2) Å, c = 18.593(4) Å, β = 91.15(3)°, Z = 2, R = 0.043, wR² = 0.1238) consists of suberato‐bridged [Cu₂(phen)₂(C₈H₁₂O₄)_4/2] layers and hydrogen bonded H₂O molecules. The Cu atoms are coordinated by two N atoms from one bidentate chelating phen ligand and three carboxyl O atoms from different suberato ligands to form distorted [CuN₂O₃] square‐pyramids with one carboxyl O atom at the apical position (d(Cu–N) = 2.017(2), 2.043(3) Å, basal d(Cu–O) = 1.936(2), 1.951(2) Å and axial d(Cu–O) = 2.389(2) Å). Two [CuN₂O₃] square‐pyramids are condensed via a common O–O edge to a centrosymmetric [Cu₂N₄O₄] dimer with the Cu…Cu distance of 3.406(1) Å indicating no interaction between Cu atoms. The resultant [Cu₂N₄O₄] dimers are interlinked by the tridentate suberato ligands to form [Cu₂(phen)₂(C₈H₁₂O₄)_4/2] layers parallel to (101). These are assembled via π‐π stacking interactions into 3D network with H₂O molecules in the tunnels extending in the [010] direction.     

Synthesis,Crystal Structures and Properties of Tetrametallic Complexes: [M2(phen)4(FCA)2](ClO4)2·(H2O)2 (M=Zn or Co,phen=1,10‐phenanthroline,FCA=anion of 3‐ferrocenyl‐2‐crotonic acid)

Two new complexes [Zn₂(phen)₄(FCA)₂](ClO₄)₂·(H₂O)₂ ( 1 ) and [Co₂(phen)₄ (FCA)₂](ClO₄)₂·(H₂O)₂ (2) (FCA=anion of 3‐ferrocenyl‐2‐crotonic acid, phen=1,10‐phenanthroline) have been synthesized, and characterized by elemental analysis, IR, UV‐Vis spectra, thermal analyses, and single‐crystal X‐ray diffraction. Two M(II) (M=Zn or Co) ions are bridged by two FCA anions with syn‐anti bridging ligands, leading to dimeric cores, [M₂(phen)₄(FCA)₂]²⁺, and each M(II) ion is six‐coordinated in a distorted octahedral geometry by two chelate phen ligands and two μ₂‐carboxylate oxygen atoms from two FCA groups. The M(II)…M(II) intradimer distances are 0.4391 and 0.4462 nm in 1 and 2 , respectively. Electrochemical properties of the complexes have been discussed.     

Synthesis and Crystal Structure of [La(phen)2(H2O)2(NO3)2]NO3 · 2(phen)(H2O) with phen = 1,10‐phenanthroline

The title compound [La(phen)₂(H₂O)₂(NO₃)₂](NO₃) · 2(phen)(H₂O) with phen = 1,10‐phenanthroline was prepared by the stoichiometric reaction of La(NO₃)₃ · 6 H₂O and 1,10‐phenanthroline monohydrate in a CH₃OH–H₂O solution. The crystal structure (triclinic, P 1 (no. 2), a = 11.052(2), b = 13.420(2), c = 16.300(2) Å, α = 78.12(1)°, β = 88.77(1)°, γ = 83.03(1)°, Z = 2, R = 0.0488, wR² = 0.1028) consists of [La(phen)₂(H₂O)₂(NO₃)₂]²⁺ complex cations, NO₃^– anions, phen and H₂O molecules. The La atom is 10‐fold coordinated by four N atoms of two bidentate chelating phen ligands and six O atoms of two H₂O molecules and two bidentate chelating NO₃^2– ligands with d(La–O) = 2.522–2.640 Å and d(La–N) = 2.689–2.738 Å. The intermolecular π‐π stacking interactions play an essential role in the formation of two different 2 D layers parallel to (001), which are formed by complex cations and uncoordinating phen molecules, respectively. The uncoordinated NO₃^– anions and H₂O molecules are sandwiched between the cationic and phen layers.     

Direct Synthesis, Crystal Structure and Thermal Kinetics of Supramolecular Complex [Co（H2O）6]·（Hnip）2·（H2nip）2·（DMA）2·（H2O）8 （nip=5-nitroisophthalate, DMA=CH3NHCH3）

The crystal of [Co（H2O）6]·（Hnip）2·（H2nip）2·（OMA）2·（H2O）8 has been cultured using direct method and characterized by X-ray single crystal diffractometry, elemental analysis and FTIR spectroscopy. It crystallizes in triclinic system, P-1 space group with the cell parameters of a=0.7012（1） nm, b=1.1378（2） nm, c=1.6612（3） nm, α= 84.92（3）°, β=85.19（3）°, γ=85.91（3）°, V= 1.3128（5） nm^3, Z=1, Dc= 1.573 g·cm^-3. Final R indices [1〉2σ（I）] are： R1 =0.0279, wR2=0.0765 while R indices for all data are： R1 =0.0327, wR2=0.0806. The Co coordination octahadra are each surrounded by two Hnip, two H2nip, two DMA and eight water molecules that are linked by hydrogen bonds and π-π stacking interactions. Thermal analyses of DSC and TG-DTG have been performed on the complex to predict its thermal decomposition mechanism and determine the most probable kinetic model function using Kissinger, Ozawa, integral and differential methods.     

Synthesis,Crystal Structure and Properties of [Cu(phen)3][Cu(pheida)2]·10H2O and [(phen)2Cu(μ‐BAAP)Cu(μ‐BAAP)Cu(phen)2][Cu(BAAP)2]·8.5H2O (H2pheida = N‐phenetyl‐iminodiacetic acid,H2BAAP = N‐benzylaminoacetic‐2‐propionic acid)

The salts [Cu(phen)₃][Cu(pheida)₂]·10H₂O ( 1 ) and [(phen)₂Cu(μ‐BAAP)Cu(μ‐BAAP)Cu(phen)₂][Cu(BAAP)₂]·8.5H₂O ( 2 ) (H₂pheida = N‐phenetyl‐iminodiacetic acid, H₂BAAP = N‐benzylaminoacetic‐2‐propionic acid, phen = 1, 10‐phenanthroline) have been prepared and studied by thermal, spectroscopic and X‐ray diffraction methods. 1 has the rather unusual [Cu(phen)₃]²⁺ cation and two non‐equivalent [Cu(pheida)₂]^2— anions with a coordination type 4+2 but quite different tetragonality (T = 0.848 and 0.703 for anions 1 and 2, respectively). The crystal consists of multi‐π, π‐stacked chains (…anion 2 — cation — cation — anion 2…) connected by hydrophobic interactions; these chains build channels which are partially filled by anions 1 and water molecules. In contrast, compound 2 has a mixed‐ligand trinuclear cation with a bridging central moiety close similar to the counter anion. The formation of such a trinuclear cation is discussed as a consequence of the most advantageous molecular recognition process between [Cu(phen)₂(H₂O)_{1 or 2}]²⁺ and [Cu(BAAP)₂]^2— in solution. In the crystal of 2, multi‐π, π‐stacked arrays of C₆‐rings from phen and (BAAP)^2— ligands of trinuclear cations generate channels where counter anions and water molecules are located.     

Preparation and thermal decomposition reaction kinetics of a dysprosium(III) p‐chlorobenzoate 1,10‐phenanthroline complex

The title complex [Dy(p‐ClBA)₃Phen]₂·2H₂O was synthesized, where p‐ClBA is p‐chlorobenzoate and Phen is 1,10‐phenanthroline. The complex was characterized by various techniques including elemental analysis, IR, XRD, and molar conductance. The thermal decomposition of the complex was studied under the nonisothermal condition by TG‐DTG and IR techniques. The kinetic parameters of dehydration process were obtained from the analysis of DSC curves of the complex by the NL‐DIF and Popescu methods, respectively. © 2007 Wiley Periodicals, Inc. 40: 66–72, 2008     

Hexachloroplatinates of the Lanthanides: Syntheses and Thermal Decomposition of [M(NO3)2(H2O)6]2[PtCl6]·2H2O (M = La,Pr) and [M(NO3)(H2O)7][PtCl6]·4H2O (M = Gd,Dy)

The reaction of the nitrates M(NO₃)₃·6H₂O (M = La, Pr) and (H₃O)₂PtCl₆ led to yellow single crystals of [M(NO₃)₂(H₂O)₆]₂[PtCl₆]·2H₂O (M = La, Pr) (monoclinic, P2₁/c, Z = 2, La/Pr: a = 697.4(3)/695.5(1), b = 1654.5(1)/1652.5(2), c = 1317.7(6)/1318.5(3) pm, β = 93.97°(7)/93.93°(2), R_all = 0.0169/0.0659) while the reaction of M(NO₃)₃·5H₂O (M = Gd, Dy) and (H₃O)₂PtCl₆ yielded yellow single crystals of [M(NO₃)(H₂O)₇][PtCl₆]·4H₂O (monoclinic, P2₁/n, Z = 4, Gd/Dy: a = 838.72(3)/838.40(2), b = 2131.98(6)/2139.50(7), c = 1142.63(3)/1143.10(3) pm, β = 95.670(4)/95.698(3), R_all = 0.0475/0.0337). The crystal structures consist of octahedral [PtCl₆]^2? anions and complex [M(NO₃)₂(H₂O)₆]₂⁺ and [M(NO₃)(H₂O)₇]²⁺ cations, respectively. The thermal decomposition of both types of compounds leads via various steps to elemental platinum and the oxide chlorides MOCl (M = La, Pr, Gd, Dy).     

Syntheses,Crystal Structures,and Properties of the Isotypic Pair [Cr(H2O)6]2[B12H12]3·15H2O and [In(H2O)6]2[B12H12]3·15H2O

Single crystals of [Cr(H₂O)₆]₂[B₁₂H₁₂]₃ · 15H₂O and [In(H₂O)₆]₂[B₁₂H₁₂]₃ · 15H₂O were obtained by reactions of aqueous solutions of the acid (H₃O)₂[B₁₂H₁₂] with chromium(III) hydroxide and indium metal shot, respectively. The title compounds crystallize isotypically in the trigonal system with space group R$\bar{3}$ c (a = 1157.62(3), c = 6730.48(9) pm for the chromium, a = 1171.71(3), c = 6740.04(9) pm for the indium compound, Z = 6). The arrangement of the quasi‐icosahedral [B₁₂H₁₂]^2– dianions can be considered as stacking of two times nine layers with the sequence …ABCCABBCA… and the metal trications arrange in a cubic closest packed …abc… stacking sequence. The metal trications are octahedrally coordinated by six water molecules of hydration, while another fifteen H₂O molecules fill up the structures as zeolitic crystal water or second‐sphere hydrating species. Between these free and the metal‐bonded water molecules, bridging hydrogen bonds are found. Furthermore, there is also evidence of hydrogen bonding between the anionic [B₁₂H₁₂]^2– clusters and the free zeolitic water molecules according to B–H^δ– ··· ^δ+H–O interactions. Vibrational spectroscopy studies prove the presence of these hydrogen bonds and also show slight distortions of the dodecahydro‐closo‐dodecaborate anions from their ideal icosahedral symmetry (I_h). Thermal decomposition studies for the example of [Cr(H₂O)₆]₂[B₁₂H₁₂]₃ · 15H₂O gave no hints for just a simple multi‐stepwise dehydration process.     

Syntheses,Crystal Structures,and Thermal Behavior of Co(phen)(HL)2 and [Co2(phen)2(H2O)4L2]·H2O with H2L = Pimelic Acid

Two Co^II complexes, Co(phen)(HL)₂ ( 1 ) and [Co₂(phen)₂(H₂O)₄L₂]·H₂O ( 2 ) (H₂L = HOOC‐(CH₂)₅‐COOH), were synthesized and structurally characterized on the basis of single crystal X‐ray diffraction data. In complex 1 the Co atoms are tetrahedrally coordinated by two N atoms of one phen ligand and two O atoms of different hydrogenpimelato ligands. Through π—π stacking interactions between carboxyl group and phen ligand, the complex molecules are assembled into 1D columnar chains, which are connected by intermolecular hydrogen bonds. Complex 2 consists of the centrosymmetric dinuclear [Co₂(phen)₂(H₂O)₄L₂] molecules and hydrogen bonded H₂O molecules. The Co atoms are each octahedrally surrounded by two N atoms of one phen ligand and four O atoms from two bis‐monodentate pimelato ligands and two H₂O molecules at the trans positions. The results about thermal analyses, which were performed in flowing N₂ atmosphere, on both complexes were discussed. Crystal data: ( 1 ) C2/c (no. 15), a = 13.491(1)Å, b = 9.828(1)Å, c = 19.392(2)Å, β = 100.648(1)°, U = 2526.9(4)ų, Z = 4; ( 2 ) P1 (no. 2), a = 11.558(1)Å, b = 11.947(3)Å, c = 15.211(1)Å, α = 86.17(1)°, β = 75.55(1)°, γ = 69.95(1)°, U = 1910.3(3)ų, Z = 2.     

{[Eu(ox)(H2O)4]·[CuBr(2‐pzc)2]·4H2O}: Hydrogen Bonding Directed Assembly to Supramolecular Network

A new 3d–4f heterometallic coordination framework, {[Eu(ox)(H₂O)₄] · [CuBr(2‐pzc)₂] · 4H₂O} ( 1 ) [ox = oxalate; 2‐pzc = pyrazine‐2‐carboxylate] was synthesized and characterized by elemental analysis, IR spectroscopy and thermal analysis, as well as single‐crystal X‐ray diffraction. Complex 1 represents one 3D supramolecular heterometallic coordination framework that is assembled from rare lanthanide‐ox anionic chains and CuBr(2‐pzc)₂ cationic units through hydrogen bonds.     

Zu den Kristallstrukturen der Übergangsmetall(II)‐Dodekahydro‐closo‐Dodekaborat‐Hydrate Cu(H2O)5,5[B12H12]·2,5 H2O und Zn(H2O)6[B12H12]·6 H2O

On the Crystal Structures of the Transition‐Metal(II) Dodecahydro‐closo‐Dodecaborate Hydrates Cu(H₂O)_5.5[B₁₂H₁₂]·2.5 H₂O and Zn(H₂O)₆[B₁₂H₁₂]·6 H₂O By neutralization of an aqueous solution of the free acid (H₃O)₂[B₁₂H₁₂] with basic copper(II) carbonate or zinc carbonate, blue lath‐shaped single crystals of the octahydrate Cu[B₁₂H₁₂]·8 H₂O (≡ Cu(H₂O)_5.5[B₁₂H₁₂]·2.5 H₂O) and colourless face‐rich single crystals of the dodecahydrate Zn[B₁₂H₁₂]·12 H₂O (≡ Zn(H₂O)₆[B₁₂H₁₂]·6 H₂O) could be isolated after isothermic evaporation. Copper(II) dodecahydro‐closo‐dodecaborate octahydrate crystallizes at room temperature in the monoclinic system with the non‐centrosymmetric space group Pm (Cu(H₂O)_5.5[B₁₂H₁₂]·2.5 H₂O: a = 768.23(5), b = 1434.48(9), c = 777.31(5) pm, β = 90.894(6)°; Z = 2), whereas zinc dodecahydro‐closo‐dodecaborate dodecahydrate crystallizes cubic in the likewise non‐centrosymmetric space group F23 (Zn(H₂O)₆[B₁₂H₁₂]·6 H₂O: a = 1637.43(9) pm; Z = 8). The crystal structure of Cu(H₂O)_5.5[B₁₂H₁₂]·2.5 H₂O can be described as a monoclinic distortion variant of the CsCl‐type arrangement. As characteristic feature the formation of isolated [Cu₂(H₂O)₁₁]⁴⁺ units as a condensate of two corner‐linked Jahn‐Teller distorted [Cu(H₂O)₆]²⁺ octahedra via an oxygen atom of crystal water can be considered. Since “zeolitic” water of hydratation is also present, obviously both classical H–O^δ?···^+δH–O and non‐classical B–H^δ?···^+δH–O hydrogen bonds play a significant role for the stabilization of the structure. A direct coordinative influence of the quasi‐icosahedral [B₁₂H₁₂]^2? anions on the Cu²⁺ cations has not been determined. The zinc compound Zn(H₂O)₆[B₁₂H₁₂]·6 H₂O crystallizes in a NaTl‐type related structure. Two crystallographically different [Zn(H₂O)₆]²⁺ octahedra are present, which only differ in their relative orientation within the packing of the [B₁₂H₁₂]^2? anions. The stabilization of the crystal structure takes place mainly via H–O^δ?···^+δH–O hydrogen bonds, since again the hydrogen atoms of the [B₁₂H₁₂]^2? anions have no direct coordinative influence on the Zn²⁺ cations.     

Synthesis,Crystal Structure,and Thermal Properties of the Energetic Coordination Compound [Co(DAT)2(H2O)4](HTNR)2·2H2O (DAT = 1,5‐diaminotetrazole)

A new coordination complex, [Co(DAT)₂(H₂O)₄](HTNR)₂ · 2H₂O [DAT = 1,5‐diaminotetrazole, HTNR = 2,4,6‐trinitroresorcinol (styphnic acid)], was obtained in high yield and characterized by elemental analysis and Fourier‐transform infrared (FT‐IR) spectroscopy. The molecular structure of [Co(DAT)₂(H₂O)₄](HTNR)₂ · 2H₂O in the crystalline state is determined by X‐ray crystallography is as follows: monoclinic, C2/c, a = 19.216(3) Å, b = 5.4992(8) Å, c = 30.418(5) Å, β = 104.500(5), V = 3112.0(8) ų, Z = 4, ρ_calc. = 1.851 g · cm^–3, R₁ = 0.0271 and wR₂ = (all data) 0.0674. The central cobalt(II) cation is coordinated by two nitrogen atoms of two DAT and four oxygen atoms of four H₂O ligand molecules to form a six‐coordinate and slightly distorted octahedral structure. Extensive intermolecular hydrogen bonds link molecular units of [Co(DAT)₂(H₂O)₄(HTNR)₂ · 2H₂O together to form a 3D net structure with pore canals. The thermal decomposition mechanism for the title compound was predicted based on DSC, TG‐DTG, and FT‐IR analyses and non‐kinetic parameters of the first exothermic process were estimated by applying the Kissinger, Starink, and Ozawa–Doyle methods.