Synthesis,crystal and molecular structure of [Na(B15C5)+]2[Hg3Cl8]2-·H2O

A crystal complex with the formula [Na(B15C5)⁺]₂ [Hg₃Cl₈]^2-·H₂O was synthesized by the reaction of benzo-15-crown-5 with sodium chloride and mercuric chloride. Its crystal and molecular structures were determined by X-ray diffraction. Crystal data: monoclinic, space group P2/n with cell dimensions of a= 17.809(4) Å, b= 13.938(4) Å, c= 17.984(4) Å, β=107.14°, Z=4, V= 4266.2 Ų. R and R_w are 0.043 and 0.053, respectively. The results obtained by spectral analysis are consistent with those of the structural analysis.     

f-ELEMENT/CROWN ETHER COMPLEXES 15. SYNTHESIS AND CRYSTAL STRUCTURE OF ([Lu(OH2)8]Cl3·1.5(12[sbnd]CROWN[sbnd]4)·2H2O

Abstract

The title complex was crystallized at 5°C from a reaction mixture of hydrated LuCl₃ and 12-crown-4 in a solution of CH₃OH:CH₃CN (1:3) after layering in pentane. The crystal and molecular structure of [Lu(OH₂)₈]Cl₃·1.5(12-crown-4)·2H₂O has been determined by single crystal X-ray diffraction. It crystallizes in the monoclinic space group P2₁/c with a=8.816(3), b=23.387(4), c=13.544(2)Å, β=95.14(2)°, and D_calc =1.73 g cm^?3 for Z=4. Least-squares refinement using 3819 independent observed [F₀  5σ(F₀ )] reflections led to the final conventional R value of 0.041. The Lu(III) cation is coordinated to eight water molecules (Lu[sbnd]O average 2.33(3)Å) in an approximate bicapped trigonal prismatic geometry. The crown ether molecules, chloride ions, and uncoordinated water molecules participate in hydrogen bonds to the cation. The hydrogen bonding of the [Lu(OH₂)₈]³⁺ cations to the crown ether molecules results in zigzag chains along c. The chains are further connected by hydrogen bonding to the chloride ions and uncoordinated water molecules. One crown ether resides around a crystallographic centre of inversion and has a C_i , conformation. The second crown has the C₄ conformation normally observed in metal complexes with this ligand.     

Nitro derivatives of <Emphasis Type="Italic">N</Emphasis>-alkylbenzoaza-15-crown-5: synthesis,structures, and complexation with metal and ammonium cations

A number of N-alkylnitrobenzoaza-15-crown-5 with the macrocycle N atom conjugated with the benzene ring were obtained. The structural and complexing properties of these compounds were compared with those of model nitrobenzo- and N-(4-nitrophenyl)aza-15-crown-5 using X-ray diffraction, ¹H NMR spectroscopy, and DFT calculations. The macrocyclic N atom of benzoazacrown ethers are characterized by a considerable contribution of the sp3-hybridized state and a pronounced pyramidal geometry; the crownlike conformation of the macrocycle is preorganized for cation binding, which facilitates complexation. The stability constants of the complexes of crown ethers with the NH₄ ⁺, EtNH₃ ⁺, Na⁺, K⁺, Ca²⁺, and Ba²⁺ ions were determined by 1H NMR titration in MeCN-d₃. The most stable complexes were obtained with alkaline-earth metal cations, which is due to the higher charge density at these cations. The characteristics of the complexing ability of N-alkylnitrobenzoaza-15-crown-5 toward alkaline earth metal cations are comparable with analogous characteristics of nitrobenzo-15-crown-5 and are much better than those of N-(4-nitrophenyl)aza-15-crown-5.     

Syntheses of diaza-18-crown-6 ligands containing two units each of 4-hydroxyazobenzene,benzimidazole, uracil,anthraquinone, or ferrocene groups

Six new diaza-18-crown-6 ligands each containing two aromatic side arms with responsive functions were prepared. Diaza-18-crown-6 containing two 4-hydroxyazobenzene ( 3 ) or two 4 -hydroxy- 4′ -(dimethyl-amino)azobenzene ( 4 ) substituents were prepared via a one-pot Mannich reaction. Diaza-18-crown-6 containing two benzimidazole ( 5 ), two uracil ( 6 ) or two 9,10-anthraquinone ( 7 ) substituents were prepared by treating the diazacrown with the appropriate chloromethyl-containing compound. Reductive amination using sodium triacetoxyborohydride, diaza-18-crown-6 and ferrocenecarboxaldehyde was used to prepare bisferrocene-substituted diaza-18-crown-6 ( 8 ). Interactions of compounds 3 , 5 , and 6 with Na⁺, K⁺, Ba²⁺, Ag⁺, and Cu²⁺ were evaluated by a calorimetric titration technique at 25° in methanol. All three ligands form more stable complexes with Ag⁺ and Cu²⁺ ( 5 forms a precipitate with Ag⁺) than with Na⁺ and K⁺. Ligand 5 also forms a highly stable complex with Ba²⁺.     

Diaquabromo(18-crown-6)rubidium and triaqua(18-crown-6)barium dibromide monohydrate: Synthesis and crystal structures

Two complexes are synthesized: diaquabromo(18-crown-6)rubidium [RbBr(18-crown-6)(H₂O)₂] (I) and triaqua(18-crown-6)barium dibromide monohydrate [Ba(18-crown-6)(H₂O)₃]²⁺ 2Br^? · H₂O (II). The orthorhombic structure of compound I (space group Pnma, a = 10.124 Å, b = 15.205 Å, c = 12.544 Å, Z = 4) and the monoclinic structure of compound II (space group C 2/c, a = 17.910 Å, b = 10.315 Å, c = 14.879 Å, β = 123.23°, Z = 4) are determined by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.063 (I) and 0.042 (II) for all 2293 (I) and 3363 (II) independent measured reflections (CAD-4 automated diffractometer, λMoK _α). The complex molecule [RbBr(18-crown-6)(H₂O)₂] in compound I and the randomly disordered cation [Ba(18-crown-6)(H₂O)₃]²⁺ in compound II are of the host-guest type: their Rb⁺ or Ba²⁺ cation (its coordination number is nine) is located in the cavity of the 18-crown-6 ligand and coordinated by all six O atoms. In structure I, the coordination polyhedron of Rb⁺ is a distorted hexagonal pyramid with a triple apex at the Br^? ligand and two O atoms of the water molecules. In structure II, the Ba²⁺ polyhedron is a distorted hexagonal bipyramid with one apex at the O atom of the water molecule and the other split apex at two O atoms of water molecules.     

Weak Interactions in Silver Complexes of 15-Crown-5

Abstract

The X-ray crystal structures of two closely related Ag(I) complexes of 15-crown-5 and benzo-15-crown-5 are reported. In the case of [Ag(15-crown-5)₂][SbF₆] 1, pointing one of its oxygen atoms away from the Ag⁺ cation enables one of the crown ligands to take part in an intermolecular C?H…O hydrogen bond. The analogous benzo-15-crown-5 species, [Ag(benzo-15-crown-5)₂][SbF₆] 2, is too rigid to attain the necessary conformation. Crystal data for 1: P2_1/c, a = 8.4481(3), b = 25.5813(9), c = 13.2773(4) Å, β = 101.354(2)°. Z = 4, unique data: 5187 R ₁ [F ² > 2σ(F ²)] 0.0259. Compound 2: P1, a = 8.6511 (15) Å, b =10.2322(18) Å, c = 19.291(3) Å, α = 103.704 (2)°, β = 101.274(2)°, γ = 95.952(2)°, Z = 2, unique data: 5803 R ₁ [F ²>2σ(F ²)] 0.0931.     

Crystal and molecular structure of 2,3-benzo-1,4,7,13-tetraoxa-10-selenacyclopentadeca-2-ene

The crystal structure of 2,3-benzo-1,4,7,13-tetraoxa-10-selenacyclopentadeca-2-ene was de-termined,C_(14)H_(20)O_4Se,M_r:331.27,orthorhombic,Pbca,a=18.445(3),b=16.334(4),c9.232(2),V=2781.3 ~3,Z=8,Dx=1.582 Mg m~(-3),λ(Mo K_α)=0.71073 ,μ=26.77 cm~(-1),F(000)=1360,T=297 K,R=0.0329,R_w=0.0438 for 2192 reflections with I>3 σ(I).The crystal structure is closelyrelated to that of benzo-15-crown-5(at 123 K),whereas the molecular geometry of the two coronandsis different according to their torsion angles calculated and the shapes exhibited.     

A new diaza‐18‐crown‐6 ligand containing two quinolin‐8‐ylmethyl side arms: Crystal structures and characterization of the ligand,the protonated ligand and its mononuclear barium(II) and dinuclear copper(II) complexes

A new 7,16‐bis(quinolin‐8‐ylmethyl)‐1,4,10,13‐tetraoxa‐7,16‐diazacyclooctadecane ligand, L, has been prepared and its crystal structure reported. In addition, the structure of the protonated ligand H₂L has been determined. H₂L is of interest because of interatomic interactions between the ligand and perchlorate ions. The mononuclear Ba(II) (Ba L ), and dinuclear Cu(II) (Cu₂L) complexes of L have been prepared and their crystal structures determined. Stability constants and other thermodynamic data valid in methanol at 23 or 25° for these and several other complexes of L have been obtained. Among the metal ions studied, L forms the most stable complex with Ba²⁺. In addition, L selectively binds Cu²⁺ over Ni²⁺ by about 3 orders of magnitude. Some of the complexes have been studied using nmr and uv‐vis spectroscopic techniques. Crystal data are given for L, space group, P2₁c, a = 8.8325(14) Å, b = 13.808(3) Å, c = 13.310(3) Å; β = 94.72(2)° Z=2, R = 0.0727; for H₂ L , space group, P2₁/c, a = 14.685(3) Å, b = 15.035(6) Å, c = 17.369(4) Å, β = 90.366(12)°, Z = 4, R = 0.0781; for Ba L , space group, Pbcn, a = 17.314(3) Å, b = 9.539(2) Å, c = 22.081(3) Å, Z = 4, R = 0.0354; and for Cu₂ L , space group, Cc, a = 19.762(2) Å, b = 14.413(2) Å, c = 14.935(2) Å, β = 98.753(12)°, Z = 4, R = 0.0564. Cu²⁺ forms a hydroxo‐bridged dinuclear complex with L while Ba²⁺ forms a mononuclear complex with L in which its two side arms are not involved in complexation.     

The Syntheses and crystal structures of trans-dichlorobis (10-thiabenzo-15-crown-5)-palladium(Ⅱ)and trans-dichlorobis-(10-selenabenzo-15-crown-5)palladium(Ⅱ)

The preparation and X-ray crystal structures of the adducts of 10-thiabenzo-15-crown-5 and 10-selenabenzo-15-crown-5 with PdCl2 are reported. [PdCl2(C14H20O4S)2] (1): or-thorhombic, space group Pbca with cell dimensions of a=17.285(5), 6=8.354(3), c=21.689(4) A, K=3131.9 A3, Z=4;R=0.0330 for 2301 reflections with I > 3o(I), [PdCl2(C14H2oO4Se)2] (2): monoclinic, space group P21/n with cell dimensions of a=18.928(4), b=8.912(3), c=9.813(2) A, β=96.90(2)0, V=1643.4 A3, Z=2; R=0.0289 for 2617 reflections with I> 3σ(I), Both complexes are monomeric, square-planar palladiurn(Ⅱ) compounds with the Pd(Ⅱ) ion situating on a crystal-lographic inversion centre, and the crown ligands all adopt the axial coordination with the Pd-S bond of 2.3233(7) A and the Pd-Se bond of 2.4357(3) A. Their complexing characteristics are discussed in brief.     

catena‐Poly­[[bis­(nitrato)(pyrimidine)­copper(II)]‐μ‐pyrimidine‐N:N′]

The title compound, [Cu(NO₃)₂(C₄H₄N₂)₂]_n, crystallizes as a linear polymeric compound with one pyrimidine ligand bridging between two Cu^II atoms and a second pyrimidine ligand coordinated in a monodentate manner. The distorted octahedral geometry around the Cu^II atom consists of two pyrimidine N atoms at distances of 2.033 (4) and 2.025 (4) Å, and two nitrate O atoms at distances at 1.987 (3) and 1.973 (3) Å. The apical positions are occupied by an N atom of a bridging pyrimidine ligand [2.291 (4) Å] and a nitrate O atom at a long distance of 2.781 (3) Å. The basal plane is almost planar, with trans angles of 176.23 (14) and 165.34 (15)°.     

Synthesis,and Structural Characterization of [{CH3(C5H4N)}Ga(SCH2(CO)O)2] −[(4-MepyH)]+, A Novel Ga(III) Five-Coordinate Complex

The synthesis and structural characterization of a novel ionic Ga(III) five-coordinate complex [{CH₃(C₅H₄N)}Ga(SCH₂(CO)O)₂]^?[(4-MepyH)]⁺, (4-Mepy=CH₃(C₅H₅N)) from the reaction between Ga₂Cl₄ with sodium mercapto-acetic acid in 4-methylpyridine is described. Under basic reaction conditions the mercapto ligand is found to behave as a 2e^? bidentate ligand. Single crystal X-ray diffraction studies show the complex to have a distorted square-pyramidal geometry with the [(^?SCH₂(CO)CO^?)] ligands trans. The compound crystallizes in the P2₁/c (No. 14) space group with a=7.7413(6)Å, b=16.744(2)Å, c=14.459(2)Å, V,=1987.1(6)&Aringsup3;, R(F, _o)=0.032 and R_W =0.038.     

Theoretical and Experimental Study of Complex Ions from Reactions of Al+ (Cu+) with Amine Molecules

The gas phase reactions of metal ions (Al⁺, Cu⁺) with amine molecules [CH₃NH₂=MA, (CH₃)₂NH=DMA] were investigated using a laser ablation‐molecular beam method. The directly associated product complex ions,Al⁺‐MA and Al⁺‐DMA, and the dehydrogenation product ions, Cu⁺(CH₂NH) and Cu⁺(C₂H₅N), as well as hydrated ion Cu⁺(NC₂H₅·H₂O), have been obtained and recorded from the reactions of the metal ions and organic amine molecules, and density functional theory (B3LYP) calculations have been performed to reveal the optimized geometry, energetics, and reaction mechanism of the title reactions with basis set 6‐311+G(d,p) adopted.     

Hydrothermal Synthesis,Structure, and Optical Properties of Two Nanosized Ln26@CO3 (Ln=Dy and Tb) Cluster‐Based Lanthanide–Transition‐Metal–Organic Frameworks (Ln MOFs)

Two Ln₂₆@CO₃ (Ln=Dy and Tb) cluster‐based lanthanide–transition‐metal–organic frameworks (Ln MOFs) formulated as [Dy₂₆Cu₃(Nic)₂₄(CH₃COO)₈(CO₃)₁₁(OH)₂₆(H₂O)₁₄]Cl ? 3 H₂O ( 1 ; HNic=nicotinic acid) and [Tb₂₆NaAg₃(Nic)₂₇(CH₃COO)₆(CO₃)₁₁(OH)₂₆Cl(H₂O)₁₅] ? 7.5 H₂O ( 2 ) have been successfully synthesized by hydrothermal methods and characterized by IR, thermogravimetric analysis (TGA), elemental analysis, and single X‐ray diffraction. Compound 1 crystallizes in the monoclinic space group Cc with a=35.775(12) Å, b=33.346(11) Å, c=24.424(8) Å, β=93.993(5)°, V=29065(16) ų, whereas 2 crystallizes in the triclinic space group P with a=20.4929(19) Å, b=24.671(2) Å, c=29.727(3) Å, α=81.9990(10)°, β=88.0830(10)°, γ=89.9940(10)°, V=14875(2) ų. Structural analysis indicates the framework of 1 is a 3D perovskite‐like structure constructed out of CO₃@Dy₂₆ building units and Cu⁺ centers by means of nicotinic acid ligand bridging. In 2 , however, nanosized CO₃@Tb₂₆ units and [Ag₃Cl]²⁺ centers are connected by Nic^? bridges to give rise to a 2D structure. It is worth mentioning that this kind of 4d–4f cluster‐based MOF is quite rare as most of the reported analogous compounds are 3d–4f ones. Additionally, the solid‐state emission spectra of pure compound 2 at room temperature suggest an efficient energy transfer from the ligand Nic^? to Tb³⁺ ions, which we called the “antenna effect”. Compound 2 shows a good two‐photon absorption (TPA) with a TPA coefficient of 0.06947 cm GM^?1 (1 GM=10^?50 cm⁴ s photon^?1), which indicates that compound 2 might be a good choice for third‐order nonlinear optical materials.     

Hexa­aqua­bis­(di­methyl sulfoxide)­yttrium(III) trichloride

The title compound, [Y(C₂H₆OS)₂(H₂O)₆]Cl₃, contains the cation [Y(H₂O)₆{(CH₃)₂SO}₂]³⁺ with a distorted square antiprismatic geometry of the eight coordinated O atoms. The six water mol­ecules are coordinated with an average Y—O distance of 2.38 (2) Å, ranging from 2.360 (3) to 2.404 (3) Å. Each water mol­ecule forms two hydrogen bonds to the chloride anions with O—Cl distances ranging from 3.068 (4) to 3.422 (4) Å. The two di­methyl­ sulfoxide ligands, situated in the cis position with the O—Y—O angle equal to 83.22 (11)°, have Y—O distances of 2.269 (3) and 2.278 (3) Å.     

[1‐Allylpyridinium][Cu2Cl3]: Synthesis,X‐ray Structure and the Regularity of Crystal Architecture of 1‐Allyl/(amino)‐pyridinium Copper(I) Chloride π‐Complexes

By alternating‐current electrochemical technique crystals of copper(I) π‐complex with 1‐allylpyridinium chloride of [C₅H₅N(C₃H₅)][Cu₂Cl₃] ( 1 ) composition have been obtained and structurally investigated. Compound 1 crystallizes in monoclinic system, space group C2/c a = 24.035(1) Å, b = 11.4870(9) Å, c = 7.8170(5) Å, β = 95.010(5)°, V = 2150.0(2) ų (at 100 K), Z = 8, R = 0.028, for 4836 independent reflections. In the structure 1 trigonal‐pyramidal environment of π‐coordinated copper(I) atom is formed by a lengthened to 1.376(2) Å C=C bond of allyl group and by three chlorine atoms. Other two copper atoms are tetrahedrally surrounded by chlorine atoms only. The coordination polyhedra are combined into an original infinite (Cu₄Cl₆^2—)_n fragment. Structural comparison of 1 and the recently studied copper(I) chloride π‐complexes with 3‐amino‐, 2‐amino‐, 4‐amino‐1‐allylpyridinium chlorides of respective [LCu₂Cl₃] ( 2 ), [L₂Cu₂Cl₄] ( 3 ), and [LCuCl₂] ( 4 ) compositions allowed us to reveal the trend of the inorganic fragment complication which depends on pKa (base) value of the corresponding initial heterocycle.     

Ionothermal Synthesis and Structural Characterization of a Novel Open Framework Zinc Diphosphonate with Carboxylate‐like Linker

A novel crystalline zinc diphosphonate, (CH₃NH₃ )₄Zn₂ (xbp)₂•H₂O , denoted as compound 1 , was ionothermally synthesized from tetraethyl‐p ‐xylylenebisphosphonate (Texbp) and Zn(OAc )₂ in a protic eutectic mixture with urea/methylamine hydrochloride. Its structure was determined by single‐crystal X‐ray diffraction data and had a special three‐dimensional open framework with rhombic channels. Compound 1 belongs to the monoclinic system (space group C2 /c ), with lattice parameters a =22.6876(19) Å, b =8.73 76(7) Å, c =8.1673(9) Å, β =108.146(2)°, V =1538.5(2) ų, Z =2. Its structure is totally different from the typical organic pillared structure, only two oxygens of the phosphonate group are coordinated with zinc atoms, and the third oxygen exists in the terminal form, which is similar to the popular dicarboxylate linkers in MOFs . The organic cations [CH₃NH₃ ]⁺ of the eutectic mixture played a structure‐directing role for constructing this framework and were confined in the pore channels to balance the negative charges resulting from the zinc phosphonate inorganic chains.     

Barium vanadium(III) hydrogen ­phosphate,Ba3V2(HPO4)6

Hydro­thermally prepared Ba₃V₂(HPO₄)₆ contains a three‐dimensional network of V^IIIO₆ octahedra [d_av(V—O) = 2.014 (2) Å] and HPO₄ [d_av(P—O) = 1.537 (3) Å] tetrahedra, sharing vertices. 12‐coordinate Ba²⁺ cations [d_av(Ba—O) = 2.944 (4) Å] complete the structure.     

Synthesis,crystal structure,and vibrational spectrum of lithium <Emphasis Type="Italic">N</Emphasis>-(4′-benzo-15-crown-5)-5-bromo-2-hydroxyphenylaldiminatozinc perchlorate dihydrate

The synthesis, the IR absorption spectrum, and X-ray diffraction analysis of the complex [ZnLi(L¹)₂(H₂O)](ClO₄) · H₂O (I) (HL¹ = N-(4′-benzo-15-crown-5)-5-bromo-2-hydroxyphenylaldimine) are described. The crystals of I are monoclinic, a = 19.840(4) Å, b = 13.947(3) Å, c = 19.956(4) Å, β = 117.06(3)°, V = 4917.4(17) ų, Z = 4, space group P2₁/n, R = 0.0609 for 1409 reflections with I > 2σ(I). In the complex cation [ZnLi(L¹)₂(H₂O)]⁺, the Zn atom is bound to a distorted tetrahedral array of two N atoms (av. Zn-N, 2.027(10) Å) and two O atoms (av. Zn-O, 1.8968(8) Å) of two deprotonated L¹ ligands. The Li atom linked to the five ether oxygen atoms (av. Li-O_ether, 2.254(3) Å) sits atop the benzo-15-crown-5 (B15C5) macrocyclic plane of one coordinated L¹ ligand. The Li coordination is completed by water oxygen (Li-O(w1), 1.83(5) Å). The B15C5 cavity of the second coordinated ligand L¹ is vacant.     

Low‐dimensional compounds containing cyano groups. XII.)copper(II) perchlorate

The title compound, [Cu(C₂N₃)(C₃H₁₀N₂)₂]ClO₄, is made up of [Cu(tn)₂{N(CN)₂}]⁺ complex cations (tn is 1,3‐diamino­propane) and ClO₄⁻ anions. The Cu^II atom is coordinated by four N atoms of two equatorial tn ligands, with an average distance of 2.041 (7) Å, and one nitrile N atom of the dicyanamide anion in an axial position, at a distance of 2.236 (3) Å, in a manner approaching square‐planar coordination geometry. The complex has C_s symmetry, with the mirror plane lying through the central C atoms of both tn ligands and the dca ligand. The ClO₄⁻ anion might be considered as very weakly coordinated in the opposite axial position [Cu—O = 2.705 (3) Å], thus completing the Cu^II coordination to asymmetric elongated octa­hedral (4+1+1*). The Cu atom and the perchlorate anion both lie on mirror planes.     

Synthesis,Crystal Structure,Bonding, and Properties of (Ba6O)(OsN3)2

The new barium nitridoosmate oxide (Ba₆O)(OsN₃)₂ was prepared by reacting elemental barium and osmium (3:1) in nitrogen at 815–830 °C. The crystal structure of (Ba₆O)(OsN₃)₂ as determined by laboratory powder X‐ray diffraction ( , No 148: a=b=8.112(1) Å, c=17.390(1) Å, V=991.0(1) ų, Z=3), consists of sheets of trigonal OsN₃ units and trigonal‐antiprismatic Ba₆O groups, and is structurally related to the “313 nitrides” AE₃MN₃ (AE=Ca, Sr, Ba, M=V–Co, Ga). Density functional calculations, using a hybrid functional, likewise indicate the existence of oxygen in the Ba₆ polyhedra. The oxidation state 4+ of osmium is confirmed, both by the calculations and by XPS measurements. The bonding properties of the OsN₃^5? units are analyzed and compared to the Raman spectrum. The compound is paramagnetic from room temperature down to T=10 K. Between room temperature and 100 K it obeys the Curie–Weiss law (μ=1.68 μ_B). (Ba₆O)(OsN₃)₂ is semiconducting with a good electronic conductivity at room temperature (8.74×10^?2 Ω^?1 cm^?1). Below 142 K the temperature dependence of the conductivity resembles that of a variable‐range hopping mechanism.