Subsolidus Binary Phase Diagrams of C10ZnCl‐C16ZnCl and C12ZnCl‐C16ZnCl

Decylammonium tetrachlorozincate (n‐C₁₀H₂₁NH₃)₂ZnCl₄(C₁₀ZnCl), dodecylammonium tetrachlorozincate (n‐C₁₂H₂₅NH₃)₂ZnCl₄(C₁₂ZnCl) and hexadecylammonium tetrachlorozincate (n‐C₁₆H₃₃NH₃)₂ZnCl₄‐(C₁₆ZnCl) were synthesized and a series of their mixtures C₁₀ZnCl‐C₁₆ZnCl and C₁₂ZnCl‐C₁₆ZnCl were prepared. The experimental binary phase diagrams of C₁₀ZnCl‐C₁₆ZnCl and C₁₂ZnCl‐C₁₆ZnCl were established by means of differential scanning calorimetry (DSC), IR and X‐ray diffraction. In the phase diagram a stable solid compound and two eutectoid invariants were observed. It is noticeable that the phase diagram contains solid solution ranges.     

Phase diagrams of binary systems of alkylammonium tetrachlorometallates(II)

The phase diagrams of four binary systems (C₁₀H₂₁NH₃)₂CoCl₄?(C₁₆H₃₃NH₃)₂CoCl₄, (C₁₂H₂₅NH₃)₂CoCl₄?(C₁₆H₃₃NH₃)₂CoCl₄, (C₁₀H₂₁NH₃)₂ZnCl₄?(C₁₆H₃₃NH₃)₂ZnCl₄ and (C₁₂H₂₅NH₃)₂ZnCl₄?(C₁₆H₃₃NH₃)₂ZnCl₄ were investigated by means of DSC. These six compounds and their binary mixtures can retain energies between 74 and 115 J/g during solid-state transformations at temperatures between 70 and 105°C, and they are therefore being considered for potential use in solar energy systems.     

Subsolidus binary phase diagram of (n-CnH2n+1NH3)2ZnCl4 (n?=?14, 16, 18)

The thermotropic phase solid–solid transitions compound (n-C _n H_2n+1NH₃)₂ZnCl₄ (n = 14, 16, 18) were studied, and a series of their mixtures were prepared. These laminar materials contain bilayers sandwiched between metal halide layers. The low temperature crystal structures of the pure salts are characteristic of the piling of sandwiches in which a two-dimensional macro-anion ZnCl₄ ²⁻ is sandwiched between two alkylammonium layers. These layers become conformationally disordered in the high temperature phases. The subsolidus binary phase diagrams of (n-C₁₄H₂₉NH₃)₂ZnCl₄-(n-C₁₈H₃₇NH₃)₂ZnCl₄ and (n-C₁₆H₃₃NH₃)₂ZnCl₄-(n-C₁₈H₃₇NH₃)₂ZnCl₄ were established by differential thermal analysis and X-ray diffraction. In each phase diagram, an intermediate compound and two eutectoid invariants were observed. There are three noticeable solid solution ranges (α, β, γ) at the left boundary, right boundary, and middle of the phase diagram.     

Experimental Investigation on Binary Phase Diagram of the Thermotropic Phase Transitions Compounds (n‐CnH2n+1R3)2ZnCl4

The thermotropic phase transitions compounds (n‐C_nH_2n+1R₃)₂ZnCl₄ as well as a series of their binary mixtures were prepared by a solution reflux method from their ethanol solutions. The experimental subsolidus binary phase diagram of [n‐C₁₈H₃₇N(CH₃)₃]₂ZnCl₄‐[n‐(C₁₈H₃₇)₂N(CH₃)₂]₂ZnCl₄ is constructed over the entire composition range by differential scanning calorimetry(DSC) and X‐ray. Experi‐ mental results indicate one stable intermediate phase [n‐C₁₈H₃₇N(CH₃)₃] [n‐(C₁₈H₃₇)₂N(CH₃)₂]ZnCl₄ at W_C18C3Zn %=59.75 %, and two invariant three phase equilibria, which shows two eutectoid temperatures: Te₁ at 310±1 K for eutectoid point W_C18C3Zn %=36.24 %, Te₂ at 313±1 K for eutectoid point W_C18C3Zn %=80.17 %. These three noticeable solid‐solution ranges are α‐phase at the left, ?‐phase at the right, and ψ‐phase in the middle of the phase diagram. It is (n‐C_nH_2n+1R₃)₂ZnCl₄ systems as phase change materials that are characterized the phase transition temperatures T in the range of 310 to 340 K, the transition enthalpies ΔH in the range of 38.40 and 168.72 J/g between two polymorphic forms.     

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.     

Subsolidus phase diagram of binary system in the perovskite type layer compounds (<Emphasis Type="Italic">n</Emphasis>-C<Subscript>n</Subscript>H<Subscript>2n+1</Subscript>NH<Subscript>3</Subscript>)<Subscript>2</Subscript>MnCl<Subscript>4</Subscript>

The thermotropic phase transitions in the perovskite type layer compound (n-C₁₀H₂₁NH₃)₂MnCl₄ and (n-C₁₄H₂₉NH₃)₂MnCl₄ were synthesized and, at the same time, a series of their mixtures C₁₀Mn-C₁₄Mn were prepared. The experimental binary phase diagram of C₁₀Mn-C₁₄Mn was established by differential thermal analysis (DTA), IR and X-ray diffraction. In the phase diagram new material (n-C₁₀H₂₁NH₃)(n-C₁₄H₂₉NH₃)MnCl₄ and two eutectoid invariants were observed, two eutectic points temperatures are about 29.8 and 27.9°C. Contrasting other similar system, there are three noticeable solid solution ranges (α, β, γ) at the left and right boundary and middle of the phase diagram.     

Reaction of (η5‐C5H5)Fe(CO)2I with Anionic Bidentate Phosphine Ligands PPh2(o‐C6H4NHLi) or PPh2(o‐C6H4OLi)

The o‐substituted hybrid phenylphosphines, PPh₂(o‐C₆H₄NH₂) and PPh₂(o‐C₆H₄OH), could be deprotonated with LDA or n‐BuLi to yield PPh₂(o‐C₆H₄NHLi) and PPh₂(o‐C₆H₄OLi), respectively. When added to a solution of (η⁵‐C₅H₅)Fe(CO)₂I at room temperature, these two lithiated reagents produce a chelated neutral complex 1 (η⁵‐C₅H₅)Fe(CO)[C(O)NH(o‐C₆H₄)PPh₂‐C,P‐η²] for the former and mainly a zwitterionic complex 2 , (η⁵‐C₅H₅)Fe⁺(CO)₂[PPh₂(o‐C₆H₄O^?)] for the latter. Complex 1 could easily be protonated and then decarbonylated to give 4 [(η⁵‐C₅H₅)Fe(CO){NH₂(o‐C₆H₄)PPh₂‐N,P‐η²}⁺]. Complexes 1 and 4‐I have been crystallographically characterized with X‐ray diffraction.     

Decanedioic Acid (C10H18O4)/Dodecanedioic Acid (C12H22O4) System: Polymorphism of the Components and Experimental Phase Diagram

The experimental temperature/composition phase diagram of the binary system decanedioic acid (C₁₀H₁₈O₄)/dodecanedioic acid (C₁₂H₂₂O₄) was established by combining X‐ray powder diffraction (XRD), differential‐scanning calorimetry (DSC), infrared spectroscopy (IR), scanning electron microscopy (SEM), and thermo‐optical microscopy (TOM). Both compounds crystallize in the same ordered form, C (P2₁/c), which is the phase that melts in both cases. The C form melts in C₁₂H₂₂O₄ earlier than in C₁₀H₁₈O₄, in contrast to other unbranched‐chain compounds (alkanes, alkanols, and alkanoic acids) in which the melting temperatures increase as the C‐atom number rises. Contrary to what might be expected, total solid‐state miscibility is not observed. The C₁₀H₁₈O₄/C₁₂H₂₂O₄ binary system shows a complex phase diagram. At low temperatures, a new monoclinic form, C_i (P2₁/c), stabilizes as a result of the disorder of composition in the mixed samples; two [C+C_i] domains appear. Upon heating, four solid–solid and seven solid–liquid domains appear related by eutectic and peritectic invariants. All the crystallographic forms observed are isostructural.     

Thermochemistry on dodecylamine hydrochloride and <Emphasis Type="Italic">bis</Emphasis>-dodecylammonium tetrachlorozincate

Dodecylamine hydrochloride C₁₂H₂₅NH₃·Cl(s) and bis-dodecylammonium tetrachlorozincate (C₁₂H₂₅NH₃)₂ZnCl₄(s) were synthesized by the method of liquid phase reaction. The constant-volume energy of combustion of dodecylamine hydrochloride was measured by means of a RBC-II precision rotating-bomb combustion calorimeter at T = (298.15 ± 0.001) K. The standard molar enthalpy of formation of C₁₂H₂₅NH₃·Cl(s) was calculated to be \Updelta_f H_m^o \Updelta_{\rm{f}} H_{\rm{m}}^{\rm{o}} (C₁₂H₂₅NH₃·Cl, s) = −(706.79 ± 3.97) kJ mol⁻¹ from the constant-volume energy of combustion. In accordance with Hess’ law, a reasonable thermochemical cycle was designed and the enthalpy change of the synthesis reaction of the complex (C₁₂H₂₅NH₃)₂ZnCl₄(s) was determined by use of an isoperibol solution-reaction calorimeter. The standard molar enthalpy of formation of (C₁₂H₂₅NH₃)₂ZnCl₄(s) was calculated as \Updelta_f H_m^o \Updelta_{\rm{f}} H_{\rm{m}}^{\rm{o}} [(C₁₂H₂₅NH₃)₂ZnCl₄, s] = −(1862.14 ± 7.95) kJ mol⁻¹ from the standard molar enthalpy of formation of C₁₂H₂₅NH₃·Cl(s) and other auxiliary thermodynamic data.     

Assembled synthesis of luminescent mono/double‐layered 2D and 3D Zn (II)‐based coordination polymers tuned by flexible bis (pyridyl)propane‐1,2‐diamines and diverse organic dicarboxylates

Six mono/double‐layered 2D and three 3D coordination polymers were synthesized by a self‐assembly reaction of Zn (II) salts, organic dicarboxylic acids and L1/L2 ligands. These polymeric formulas are named as [Zn(L1)(C₄H₂O₄)_0.5 (H₂O)]_n·0.5n(C₄H₂O₄)·2nH₂O ( 1 ), [Zn₂(L2)(C₄H₂O₄)₂]_n·2nH₂O ( 2 ), [Zn(L1)(m‐BDC)]_n ( 3 ), [Zn₂(L2)(m‐BDC)₂]_n·2nH₂O ( 4 ), [Zn₃(L1)₂(p‐BDC)₃(H₂O)₄]_n·2nH₂O ( 5 ), [Zn₂(OH)(L2) (p‐BDC)_1.5]_n ( 6 ), [Zn₂(L1)(p‐BDC)₂]_n·5nH₂O ( 7 ), [Zn₂(L2)(p‐BDC)₂]_n·3nH₂O ( 8 ) and [Zn₂(L1)(C₄H₄O₄)_1.5(H₂O)]_n·n(ClO₄)·nH₂O ( 9 ) [L1 = N,N′‐bis (pyridin‐4‐ylmethyl)propane‐1,2‐diamine, L2 = N,N′‐bis (pyridin‐3‐ylmethyl)propane‐1,2‐ diamine, m‐BDC^2? = m‐benzene dicarboxylate, p‐BDC^2? = p‐benzene dicarboxylate]. Meanwhile, these polymers have been characterized by elemental analysis, infrared, thermogravimetry (TG), photoluminescence, powder and single‐crystal X‐ray diffraction. Polymers 1–6 present mono‐ and double (4,4)‐layer motifs accomplished by L1/L2 ligands with diverse conformations and organic dicarboxylates, and the layer thickness locates in the range of 5.8–15.0 Å. In three 3D polymers, the L1 and L2 molecules adopt the same cis‐conformations and join adjacent Zn (II) cations together with p‐BDC^2? or succinate, giving rise to different binodal (4,4)‐c nets with (4.5².8³)(4.5³.7²) ( 7 ), pts ( 8 ) topology and twofold interpenetrated binodal (5,5)‐c nets with (3².4⁴.5².6²)(3.4³.5².6⁴) ( 9 ). Therefore, the diverse conformations of the two bis (pyridyl)‐propane‐1,2‐diamines and the feature of different organic dicarboxylate can effectively influence the architectures of these polymers. Powder X‐ray diffraction patterns demonstrate that these bulk solid polymers are pure phase. TG analyses indicate that these polymers have certain thermal stability. Luminescent investigation reveals that the emission maximum of these polymers varies from 402 to 449 nm in the solid state at room temperature. Moreover, 1 , 3 and 5–8 show average luminescence lifetimes from 8.81 to 16.30 ns.     

Crystal Structure, Phase Transition, and Thermodynamic Properties of Bis-dodecylammonium Tetrachlorozincate (C12H25NH3)2ZnCl4(s)

The crystal structure and composition of (C₁₂H₂₅NH₃)₂ZnCl₄(s) were characterized by chemical and elemental analysis, X‐ray powder diffraction technique and X‐ray crystallography. The lattice energy of the title compound was calculated to be U_POT=888.82 kJ·mol^?1. Low temperature heat capacities of the title compound have been measured by a precision automated adiabatic calorimeter over the temperature range from 80 to 403 K. An obvious solid to solid phase transition occurred in the heat capacity curve, and the peak temperature, molar enthalpy and molar entropy of the phase transition of the compound were determined to be T_trs= (364.02±0.03) K, (_trsH_m= (77.567±0.341) kJ·mol^?1, and (_trsS_m= (213.77±1.17) J·K^?1·mol^?1, respectively. Experimental molar heat capacities before and after the phase transition were respectively fitted to two polynomial equations. The smoothed molar heat capacities and fundamental thermodynamic functions of the sample relative to the standard reference temperature 298.15 K were calculated and tabulated at an interval of 5 K.     

Combining valproate and bipyridyl ligands to construct a 0D core‐shell Zn5(μ3‐OH)2 cluster and a 2D layered coordination network with a [Zn3(μ3‐OH)]2 SBU

Starting from the proposed zinc carboxylate cluster tetrakis(μ‐2‐propylpentanoato)dizinc(II), Zn₂(μ₂‐valp)₄ ( I ), of valproic acid, a branched short‐chain fatty acid, and bipyridine ligands, two new mixed‐ligand coordination compounds, namely, bis(2,2′‐bipyridine)di‐μ₃‐hydroxido‐hexakis(μ‐2‐propylpentanoato)bis(2‐propylpentanoato)pentazinc(II), [Zn₅(C₈H₁₅O₂)₈(OH)₂(C₁₀H₈N₂)₂] ( II ), and poly[[bis(μ‐4,4′‐bipyridine)di‐μ₃‐hydroxido‐octakis(μ‐2‐propylpentanoato)bis(2‐propylpentanoato)hexazinc(II)] dimethylformamide disolvate], {[Zn₆(C₈H₁₅O₂)₁₀(OH)₂(C₁₀H₈N₂)₂]·2C₃H₇NO}_n ( III ), were synthesized. Compound II is a core‐shell‐type zero‐dimensional discrete Zn₅(μ₃‐OH)₂ metal–organic cluster with Zn ions in double‐triangle arrangements that share one Zn ion coincident with an inversion centre. The cluster contains three crystallographically non‐equivalent Zn ions exhibiting three different coordination geometries (tetrahedral, square pyramidal and octahedral). The cluster cores are well separated and embedded in a protective shell of the aliphatic branched short chains of valproate. As a result, there is no specific interaction between the discrete clusters. Conversely, compound III , a 2D layered coordination network with a secondary building unit (SBU), is formed by Zn₆(μ₃‐OH)₂ clusters exhibiting a chair‐like hexagonal arrangement. This SBU is formed from two Zn₃(μ₃‐OH) trimers related by inversion symmetry and connected by two syn–anti bridging carboxylate groups. Each SBU is connected by four 4,4′‐bipyridine ligands producing a 6³‐hcb net topology. 2D coordination layers are sandwiched within layers of dimethylformamide molecules that do not interact strongly with the network due to the hydrophobic protection provided by the valproate ligands.     

Preparation and Structure of Melemium Melem Perchlorate HC6N7(NH2)3ClO4·C6N7(NH2)3

A new perchlorate salt of melem (2,6,10‐triamino‐s‐heptazine, C₆N₇(NH₂)₃) was obtained from an aqueous solution of HClO₄ at lower concentration than the ones reported for the synthesis of melemium perchlorate monohydrate (HC₆N₇(NH₂)₃)ClO₄·H₂O. The new salt was identified as melemium melem perchlorate (HC₆N₇(NH₂)₃)ClO₄·C₆N₇(NH₂)₃ representing a melem adduct of water free melemium perchlorate. The crystal structure was solved by single‐crystal X‐ray methods ( , no. 2, Z = 2, a = 892.1(2), b = 992.7(2), c = 1201.5(2) pm, α = 112.30(3), β = 96.96(3), γ = 95.38(3)°, V = 965.8(4)·10⁶ pm³, 4340 data, 387 parameters, R1 = 0.039). Melemium melem perchlorate crystallizes in a layer‐like structure containing both protonated HC₆N₇(NH₂)₃ and non protonated C₆N₇(NH₂)₃ moieties in the coplanar layers as well as perchlorate ions between them, all of which being interconnected by hydrogen bonds. Vibrational spectroscopic investigations (FTIR and Raman) of the salt were conducted.     

Homo‐ and Heteropentanuclear Coordination Compounds with Td Symmetry – the Solid State Structures of [MZn4(L)4(L′)6] (M = CoII or Zn; L = chloride or acac; L′ = 1,2,3‐benzotriazolate)

The syntheses of homo‐ and heteropentanuclear coordination compounds with the molecular formulae [MZn₄(L)₄(L′)₆] (M = Co^II or Zn; L = chloride or acac; L′ = 1,2,3‐benzotriazolate) are reported. These compounds display a highly symmetric coordination unit consisting of a central metal ion (M = Co^II or Zn) which is octahedrally coordinated by 6 tridentate benzotriazolate‐type ligands via their N(2) donor atom. The benzotriazolate ligands span the edges of an imaginary tetrahedron thus providing four coordination sites at the corners of the tetrahedron, which are then filled by four zinc ions. The coordination shell of the latter are completed by bidentate acetylacetonate (acac) ligands or by chloride anions, respectively. The solid state structures of two homopentanuclear metal complexes, namely [Zn₅(acac)₄(bta)₆]·4C₆H₁₂ ( 1 ) (acacH = acetylacetone; btaH = 1,2,3‐benzotriazole), and [Zn₅Cl₄(Me₂bta)₆]·2DMF ( 2 ) (Me₂btaH = 5,6‐dimethyl‐1,2,3‐benzotriazole) were determined by single crystal X‐ray structure analysis. The heteropentanuclear metal complex [Co^IIZn₄Cl₄(Me₂bta)₆]·2DMF ( 3 ) is isostructural with compound 2 . Compound 1 was synthesized from stoichiometric amounts of Zn(acac)₂ and btaH employing dichloromethane as solvent. The synthesis of compound 2 requires addition of an auxiliary base to the DMF solution of anhydrous ZnCl₂ and Me₂btaH. For compound 3 a stoichiometric ratio of Co(NO₃)₂·6H₂O, anhydrous ZnCl₂ and Me₂btaH was employed during synthesis. Phase purity of all compounds was proved by X‐ray powder diffraction (XRPD) analysis, IR spectroscopy, and elemental analysis. Crystal data: for 1 (C₈₀H₁₀₀N₁₈O₈Zn₅): monoclinic, space group P2₁/c with a = 23.781(5) Å, b = 16.000(3) Å, c = 25.170(5) Å, β = 115.29(3)°, V = 8659(3) ų, Z = 4, ρ = 1.357 g cm^?3. For 2 (C₅₄H₆₂Cl₄N₂₀O₂Zn₅): cubic, space group with a = 23.367(3) Å, V = 12759(3) ų, Z = 8, ρ = 1.553 g cm^?3. For 3 (C₅₄H₆₂Cl₄CoN₂₀O₂Zn₄): cubic, space group with a = 23.443(3) Å, V = 12884(3) ų, Z = 8, ρ = 1.532 g cm^?3.     

Melamine–Melem Adduct Phases: Investigating the Thermal Condensation of Melamine

By studying the thermal condensation of melamine, we have identified three solid molecular adducts consisting of melamine C₃N₃(NH₂)₃ and melem C₆N₇(NH₂)₃ in differing molar ratios. We solved the crystal structure of 2 C₃N₃(NH₂)₃?C₆N₇(NH₂)₃ ( 1 ; C2/c; a=21.526(4), b=12.595(3), c=6.8483(14) Å; β=94.80(3)°; Z=4; V=1850.2(7) ų), C₃N₃(NH₂)₃?C₆N₇(NH₂)₃ ( 2 ; Pcca; a=7.3280(2), b=7.4842(2), c=24.9167(8) Å; Z=4; V=1366.54(7) ų), and C₃N₃(NH₂)₃?3 C₆N₇(NH₂)₃ ( 3 ; C2/c; a=14.370(3), b=25.809(5), c=8.1560(16) Å; β=94.62(3)°; Z=4; V=3015.0(10) ų) by using single‐crystal XRD. All syntheses were carried out in sealed glass ampoules starting from melamine. By variation of the reaction conditions in terms of temperature, pressure, and the presence of ammonia‐binding metals (europium) we gained a detailed insight into the occurrence of the three adduct phases during the thermal condensation process of melamine leading to melem. A rational bulk synthesis allowed us to realize adduct phases as well as phase separation into melamine and melem under equilibrium conditions. A solid‐state NMR spectroscopic investigation of adduct 1 was conducted.     

Reductive Hydrogenation of Cs‐C70(CF3)8 and C1‐C70(CF3)10

CF₃‐derivatized fullerenes prove once again to be promising scaffolds for regioselective fullerene functionalization: now with the smallest possible addends—hydrogen atoms. Hydrogenation of C_s‐C₇₀(CF₃)₈ and C₁‐C₇₀(CF₃)₁₀ by means of reduction with Zn/Cu couple in the presence of water proceeds regioselectively, yielding only one major isomer of C₇₀(CF₃)₈H₂ and only two for C₇₀(CF₃)₁₀H₂, whose addition patterns are combined in the only abundant isomer of C₇₀(CF₃)₁₀H₄. The observed selectivity is governed by the electronic structure of trifluoromethylated substrates. Interestingly, we discovered that Clar's theory can be utilized to predict the regiochemistry of functionalization, and we look forward to testing it on forthcoming cases of derivatization of pre‐functionalized fullerene building blocks.     

Synthesis and Characterization of Metal Complexes (M = Al,Ti, W,Zn) Containing Pyrrole‐imine Ligands

A series of metal compounds (M = Al, Ti, W, and Zn) containing pyrrole‐imine ligands have been prepared and structurally characterized. The reactions of AlMe₃ with one and three equivs of pyrrole‐imine ligand [C₄H₃NH‐(2‐CH=N? CH₂Ph)] ( 1 ) generated aluminum compounds Al[C₄H₃N‐(2‐CH=N? CH₂Ph)]Me₂ ( 2 ) and Al[C₄H₃N‐(2‐CH=NCH₂Ph)]₃ ( 3 ), respectively, in relatively high yield. Reacting two equivs of 1 with Ti(OⁱPr)₄, W(NH^tBu)₂(=N^tBu)₂, or ZnMe₂ afforded Ti[C₄H₃N‐(2‐CH=NCH₂Ph)]₂(OⁱPr)₂ ( 4 ), W[C₄H₃N‐(2‐CH=NCH₂Ph)]₂(=N^tBu)₂ ( 5 ), and Zn[C₄H₃N‐(2‐CH=NCH₂Ph)]₂ ( 6 ), respectively. All the compounds have been characterized by ¹H and ¹³C NMR spectroscopy. Compounds 3 – 6 have also been characterized by single‐crystal X‐ray structural analysis. The biting angles of pyrrole‐imine ligand with metals decrease and their related M? N_pyrrole and M? N_imine bond lengths increase in the order of 6 , 3 , 4 , and 5 .     

四氯合锌酸正九烷铵的晶体结构及热化学性质

合成了四氯合锌酸正九烷铵复合物(C₉H₁₉NH₃)₂ZnCl₄(s) (C₉Zn(s)), 并使用X射线单晶衍射、化学分析以及元素分析确定了其晶体结构和化学组成. 利用其晶体学数据推导了C₉Zn(s)的晶格能U_POT=952.94 kJ·mol^-1. 在298.15 K下, 利用恒温环境溶解-反应热量计测定了C₉Zn(s)在不同质量摩尔浓度下的摩尔溶解焓. 在Pitzer电解质溶液理论基础上确定了C₉Zn(s)的无限稀释摩尔溶解焓Δ_sΗ_m^∞=20.09 kJ·mol^-1, 以及Pitzer焓参数组合(4β_C9H19NH3,Cl^(0)L+2β_Zn,Cl^(0)L+θ_C9H19NH3,Zn^L)和(2β_C9H19NH3,Cl^(1)L+β_Zn,Cl^(1)L)的值.     

First Characterization of an Extended Ammonium‐Ammonia Complex [{NH4(NH3)4}+(μ‐NH3)2] in the Crystal Structure of [NH4(NH3)4][Co(C2B9H11)2] · 2 NH3

The compound [NH₄(NH₃)₄][Co(C₂B₉H₁₁)₂] · 2 NH₃ ( 1 ) was prepared by the reaction of Na[Co(C₂B₉H₁₁)₂] with a proton‐charged ion‐exchange resin in liquid ammonia. The ammoniate 1 was characterized by low temperature single‐crystal X‐ray structure analysis. The anionic part of the structure consists of [Co(C₂B₉H₁₁)₂]^‐ complexes, which are connected via C‐H···H‐B dihydrogen bonds. Furthermore, 1 contains an infinite equation/tex2gif-stack-2.gif[{NH₄(NH₃)₄}⁺(μ‐NH₃)₂] cationic chain, which is formed by [NH₄(NH₃)₄]⁺ ions linked by two ammonia molecules. The N‐H···N hydrogen bonds range from 1.92 to 2.71Å (DHA = Donor···Acceptor angles: 136‐176°). Additional N‐H···H‐B dihydrogen bonds are observed (H···H: 2.3‐2.4Å).     

Coordination Chemistry of Acrylamide 4. Crystal Structures and IR Spectroscopic Properties of Acrylamide Complexes with CoII,NiII, and ZnII nitrates

Acrylamide complexes of metal nitrates: [M(O‐OC(NH₂)CHCH₂)_n(H₂O)_m][NO₃]₂ (M = Co( 1 ), Ni( 2 ) (n = 6 and m = 0) and Zn( 3 ) (n = 4 and m = 2)) have been determined by using single crystal X‐ray diffraction analysis. All complexes crystallize in the triclinic space group . The structures of 1 and 2 represent octahedral species [M(AAm)₆]²⁺ (AAm = O‐OC(NH₂)CHCH₂ and M = Co or Ni) and uncoordinated nitrate ions. The structure of 3 involves the octahedral cation [Zn(AAm)₄(H₂O)₂]²⁺ in which the Zn²⁺ environment includes oxygen atoms of four acrylamide and two water molecules that are stabilized using ionic nitrate ions. The observations of the solid‐state IR spectroscopic vibrational frequencies of these acrylamide complexes are in agreement with the crystal structures.