Synthesis and structure of novel chiral amido-imine complexes of aluminum,gallium, and indium

The reactions of 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-BIAN, 1) with tri-iso-butylaluminum, triethylgallium or trimethylindium give the novel amido-imine complexes (Buⁱ—dpp-BIAN)AlBuⁱ ₂ (4), (Et—dpp-BIAN)GaEt₂ (5), and (Me—dpp-BIAN)InMe₂ (6), respectively. The reaction of (dpp-BIAN)AlI(Et₂O) (7) with allyl bromide affords analogous chiral amido-imine derivative (All—dpp-BIAN)AlBrI (8). Hydrolysis of 8 affords the amino-imino compound (All—dpp-BIAN)H (9). The new compounds 4–6, 8, and 9 have been characterized by ¹H NMR and IR spectroscopy. The molecular structures of 5, 6, and 9 were determined by single crystal X-ray analysis.     

Reduction of aromatic ketones with the (dpp-BIAN)AlI(Et2O) complex

Reduction of benzophenone and 4,4′-bis(methoxy)benzophenone with the aluminum complex (dpp-BIAN)AlI(Et₂O) (1) containing the dianionic dpp-BIAN ligand (dpp-BIAN is 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) affords the pinacolate complexes [(dpp-BIAN)AlI]₂[μ-O₂C₂Ph₄] (2) and [(dpp-BIAN)AlI]₂[μ-O₂C₂(C₆H₄OMe)₄] (3), respectively, which undergo the pinacolone rearrangement upon prolonged storage in diethyl ether to form [(dpp-BIAN)AlI]₂O (4). The reaction of 1 with fluoren-9-one produces stable pinacolate (dpp-BIAN)Al[μ-O₂(C₁₃H₈)₂] (7) and the (dpp-BIAN)AlI₂ complex (8). Compounds 2—4, 7, and 8 were characterized by ESR spectroscopy. Hydrolysis products of compounds 2 and 3 were characterized by ¹H NMR spectroscopy. The structures of complexes 4 and 7 were established by X-ray diffraction. dpp-BIAN is 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1134–1140, July, 2006.     

Aluminum complexes with mono-and dianionic diimine ligands

The metathesis reaction of the magnesium complex [(dpp-BIAN)²⁻Mg²⁺(THF)₃] (dpp-BIAN is 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) with one equivalent of AlCl₃ in toluene gave the [(dpp-BIAN)²⁻AlCl₂]⁻[Mg₂Cl₃(THF)₆]⁺ complex (1). Reduction of dpp-BIAN with aluminum metal in the presence of AlCl₃ and AlI₃ in toluene and diethyl ether afforded the radical-anionic complex [(dpp-BIAN)⁻AlCl²] (2) and the dianionic complexes [(dpp-BIAN)²⁻AlI(Et₂O)] (3) and [(dpp-BIAN)²⁻AlCl(Et₂O)] (4), respectively. Compounds 1–4 were isolated in the crystalline state and characterized by IR spectroscopy and elemental analysis. The structures of compounds 1–3 were established by X-ray diffraction. Compound 2 was characterized by ESR spectroscopy. Compounds 3 and 4 were studied by 1H and 13C NMR spectroscopy. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 409–415, March, 2006.     

Protonation of magnesium and sodium complexes containing dianionic diimine ligands. Molecular structures of 1,2-bis{(2,6-diisopropylphenyl)imino}acenaphthene (dpp-BIAN), [(dph-BIAN)H<Subscript>2</Subscript>(Et<Subscript>2</Subscript>O)], and [(dpp-BIAN)HNa(Et<Subscript>2</Subscript>O)]

Hydrolysis of magnesium complexes containing the dianionic acenaphthenediimine ligands, (dpp-BIAN)Mg(thf)₃ (1), (dph-BIAN)Mg(thf)₃ (2), and (dtb-BIAN)Mg(thf)₂ (3) (dpp-BIAN is 1,2-bis{ (2,6-diisopropylphenyl)imino}acenaphthene; dph-BIAN is 1,2-bis{(2-diphenyl)imino}acenaphthene; dtb-BIAN is 1,2-bis{(2,5-di-tert-butylphenyl)imino}acenaphthene), affords the corresponding diamines (dpp-BIAN)H₂ (4), (dph-BIAN)H₂(Et₂O) (5), and (dtb-BIAN)H₂ (6). Compounds 4 and 5 were isolated in the crystalline state and characterized by UV-Vis, IR, and ¹H NMR spectroscopy. Partial hydrolysis of (dpp-BIAN)Na₂(Et₂O)₃ gave the crystalline (dpp-BIAN)HNa(Et₂O)₂ complex (7), which was also characterized by spectroscopic methods. The structures of compounds 5 and 7 and free diimine dpp-BIAN were established by X-ray diffraction analysis.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2634–2640, December, 2004.     

Reactions of germanium(II), tin(II), and antimony(III) chlorides with acenaphthene-1,2-diimines

Reactions of diimines dtb-BIAN and dph-BIAN with GeCl₂ afford germanium(II) complexes with radical-anionic ligands, (dtb-BIAN)GeCl (5) and (dph-BIAN)GeCl (6a), respectively, where dtb-BIAN is 1,2-bis[(2,5-di-tert-butylphenyl)imino]acenaphthene and dph-BIAN is 1,2-bis[(2-biphenyl)imino]acenaphthene. The latter reaction gives 6a along with [(dph-BIAN)GeCl]⁺[GeCl₃]⁻ (6b). The reactions of tin(II) and antimony(III) chlorides with dtb-BIAN and dpp-BIAN produce complexes of these halides with neutral coordinated diimines, viz., (dtb-BIAN)SnCl₂ (7) and (dpp-BIAN)SbCl₃ (8) (dpp-BIAN is 1,2-bis[(2,6-di-isopropylphenyl)imino]acenaphthene). Paramagnetic complexes 5 and 6a were studied by ESR spectroscopy. Diamagnetic compounds 7 and 8 were characterized by ¹H NMR spectroscopy. The structures of complexes 5, 6a,b, 7, 8, and (dpp-BIAN)Ge (9) were established by X-ray diffraction analysis. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 71–80, January, 2006.     

Sodium cation migration above the diimine pi-system of solvent coordinated dpp-BIAN sodium aluminum complexes (dpp-BIAN=1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene)

The reactions of the disodium salt of the 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-BIAN) ligand with one equivalent of Me2AlCl in diethyl ether, toluene, and benzene produced the complexes [Na(Et2O)2(dpp-BIAN)AlMe2] (1), [Na(eta6-C7H8)(dpp-BIAN)AlMe2] (2) and [Na(eta6-C6H6)(dpp-BIAN)AlMe2] (3), respectively. Recrystallization of 1 from hexane afforded solvent-free [{Na(dpp-BIAN)AlMe2}n] (4) or [Na(Et2O)(dpp-BIAN)AlMe2] (5) depending on the temperature of the solvent. The molecular structures of 1-5 have been determined by single-crystal X-ray diffraction. The sodium cation coordinates either one of the naphthalene rings (1) or the diimine part of the dpp-BIAN ligand (2-5). In the complexes 2 and 3, the sodium cation additionally coordinates the toluene (2) or benzene molecule (3) in an eta6-fashion.     

Anionic and neutral bis(diimine)lanthanide complexes

Oxidation of ytterbium(II) complex (dpp-BIAN)Yb(DME)₂ (1) with dpp-BIAN affords an ionic compound [(dpp-BIAN)₂Yb]^?[(dpp-BIAN)Yb(DME)₂]⁺ (2) (dpp-BIAN = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene), in which the oxidation states of the metals in anionic and cationic counterparts are different. Structurally related lanthanum(III) complex [(dpp-BIAN)₂La]^?[(dpp-BIAN)La(DME)₂]⁺ (3) has been prepared reacting excess of metallic lanthanum with dpp-BIAN. Compound [(dpp-BIAN)₂La]^?[K(Et₂O)₄]⁺ (4) has been isolated from the reaction of LaI₃ with three molar equivalents of potassium and one molar equivalent of dpp-BIAN in diethyl ether. The reaction of SmI₂ with dpp-BIAN and potassium affords complex [(dpp-BIAN)₂Sm]^?[K(C₆H₆)]⁺ (5). Treatment of compound 5 with 0.5 molar equivalent of iodine produces neutral complex (dpp-BIAN)₂Sm (6). Molecular structures of complexes 2–6 have been determined by X-ray crystallography.     

Reactions of (dpp-BIAN)Mg(thf)<Subscript>3</Subscript> complex (dpp-BIAN is 1,2-bis{(2,6-diisopropylphenyl)imino}acenaphthene) with halogen-containing reagents

The reactions of the acenaphthenediimine complex (dpp-BIAN)Mg(thf)₃ (1) (dpp-BIAN is 1,2-bis{ (2,6-diisopropylphenyl)imino}acenaphthene) with various chlorine-, bromine-, and iodine-containing reagents afforded the unsymmetrical compounds [(dpp-BIAN)MgCl(thf)]₂ (6), [(dpp-BIAN)MgBr(thf)]₂ (7), and (dpp-BIAN)MgI(DME) (8). The reaction of complex 1 with Me₃SiCl in THF is accompanied by the cleavage of the THF molecule to form [{dpp-BIAN(CH₂)₄OSiMe₃}MgCl]₂ (9), in which the trimethylsilanyloxybutyl group is bound to one of the carbon atoms of the diimine fragment. The reaction of complex 1 with Me₂NCH₂CH₂Cl in THF produces the [dpp-BIAN(H)(CH₂)₂NMe₂] compound (10) containing no magnesium. Paramagnetic complexes 6–8 were characterized by ESR spectroscopy. Diamagnetic compounds 9 and 10 were studied by ¹H and ¹³C NMR spectroscopy. The molecular structures of complexes 6–10 were established by X-ray diffraction analysis. In the crystalline state, compounds 6, 7, and 9 exist as halogen-bridged dimers. In all magnesium derivatives, BIAN serves as a chelate ligand.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2641–2651, December, 2004.     

一系列由柔性N,N'-双(3-吡啶甲基)胺构筑的螺旋配合物的合成、结构和性质

合成和表征了5个螺旋配位聚合物{[Cu(Hbpma)(H₂O)₄]₂(SO₄)₃·3.5H₂O}_n (1)、{[Ni(Hbpma)(H₂O)₄]₄(SO₄)₆·10.75H₂O}_n (2)、{[Mn(Hbpma)(H₂O)₄](SO₄)_1.5·3H₂O}_n (3)、{[Zn(Hbpma)(H₂O)₄]₄(SO₄)₆·4H₂O·4CH₃OH}n (4)和{[Cu(Hbpma)2(H₂O)₂](SO₄)₂·9H₂O}_n (5), 其中bpma代表N,N'-双(3-吡啶甲基)胺。晶体结构分析表明配合物1~4为一维链状结构, 配合物5为二维层状结构, 其中金属离子由质子化的bpma配体桥连。值得注意的是, 采取反-反式构象的柔性bpma配体使得配合物1和2为假螺旋链结构, 配合物3和4为螺旋链结构, 配合物5为螺旋层结构。同时研究了配合物的磁性和热稳定性。     

Copper complexes of 1-[(2-carboxyethyl)benzene]-3-[2-pyridine]triazene

The triazenide, 1-[(2-carboxyethyl)benzene]-3-[2-pyridine]triazene (HL), has been synthesized. In the presence of Et₃N, the reaction of HL with Cu(OAc)₂·H₂O or CuCl₂·2H₂O gives the tetranuclear copper(II) complexes {Cu₄(L)₂(μ₂-OH)₂(OAc)₄} 1 and {Cu₄L₄(μ₄-O)Cl₂} 2, respectively. The X-ray crystal structures of both complexes have been obtained. Magnetic studies indicate significant antiferromagnetic coupling between the copper(II) centers for both complexes, with coupling constants (J) of −493.4 cm⁻¹ for 1 and −165 cm⁻¹ for 2.     

Synthesis and Crystal Structures of Group 10 Metal Bis(dithiolate) Complexes Constructed by 2,3-Naphtho-15-Crown-5 or 2,3-Naphtho-18-Crown-6

Five novel 2,3-naphtho crown ether group 10 metal bis(dithiolate) complexes, [Na(N15C5)₂]₂[Pd(mnt)₂] (1), [Na(N15C5)]₂[Pd(i-mnt)₂] (2) and [K(N18C6)]₂[M(i-mnt)₂] (3 5) (where mnt = 1,2-dicyanoethylene-1,2-dithiolate, i-mnt = 1,1-dicyanoethylene-2,2-dithiolate and M = Ni, Pd, Pt for complexes 3–5, respectively), have been synthesized and characterized by elemental analysis, FT-IR, UV–Visible spectra and single crystal X-ray diffraction. X-ray diffraction analyses reveal that complexes 1 and 2 have different structural features while complexes 3–5 are structurally isomorphous. Complex 1 consists of two [Na(N15C5)₂]⁺ sandwich complex cations and one [Pd(mnt)₂]²⁻ anion, affording a zero-dimensional structure. For 2, the [Na(N15C5)]⁺ mono-capped complex cations act as the bridges linking the [Pd(i-mnt)₂]²⁻ anions into a 1D infinite chain through Na–N interactions and SȮFC and SȮFπ interactions are observed in the resulting chain. Complexes 3–5 all consist of two [K(N18C6)]⁺ complex cations and one [M(i-mnt)₂]²⁻ (M = Ni, Pd or Pt) anion and the complex molecules are linked into␣1D␣chains by the bridging K–O(ether) interactions between the adjacent [K(N18C6)]⁺ units. What’s novel is that the resulting chains are assembled into novel 2D networks through interchain π–π stacking interactions between the neighboring naphthylene moieties of N18C6. The stack model of naphthylene group in complexes 3–5 is discussed.     

Kinetics of Anodic Dissolution of Some Metals in Electrolytes Based on Complexes of Triethylaluminum with Alkali Metal Fluorides and Tetraethylammonium Chloride

The dissolution kinetics of M* anodes (M* = Al, Cd, Sn, Sb, Bi) during electrolysis of molten complexes M[Al₂Et₆] (M = Na, K, Rb, Et₄N; = F, Cl) is studied. Parallel dissolution paths are discovered: through a limiting discharge of electrolyte components and through a limiting electrooxidation of adatoms and clusters of M* present at the electrode surface. Substantiated is a mechanism of electrosynthesis of ethyl derivatives M*Et _n involving the formation of adsorbed complexes (M*Et_{1 k n – 1})_ads via the scheme AlEt₄ ^– + M* – e M*(Et)_ads + (AlEt₃); M*(Et)_ads + (AlEt₄ ^–) – e = M*(Et₂)_ads + (AlEt₃); ...; M*(Et _{n – 1})_ads + (AlEt₄ ^–) – e AlEt₃ + M*Et _n .     

Syntheses, crystal structures and spectral properties of three chiral complexes [M((R, R)-et-pybox)Cl2] (M=Zn and Mn) and [Ni((R, R)-et-pybox)(H2O)2Cl]Cl

Three chiral complexes: [M((R, R)-et-pybox)Cl₂] (M=Zn, 1, and Mn, 2) and [Ni((R, R)-et-pybox)(H₂O)₂Cl]Cl (3) ((R, R)-et-pybox is C₂-symmetric 2,6-bis[4′-(R)-ethoxyoxazolin-2′-yl]pyridine) have been synthesized and characterized by elemental analysis, IR, UV, TG and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analyses show that 1 is isostructural to 2, the obtained complexes are of isolated mononuclear and the metal atoms of 1 and 2 have distorted trigonal bipyramidal coordination environment. A feature of interest is noted in the unit cell of 3, there exist two types of molecules, which similarly have a distorted octahedral geometry but only slightly differ in the orientation of the coordinated atoms to the central Ni atom. These two types of molecules interact with each other by O–H···Cl hydrogen bonds, giving rise to one-dimensional ribbon structure.     

一系列由柔性N,N'-双(3-吡啶甲基)胺构筑的螺旋配合物的合成、结构和性质

合成和表征了5个螺旋配位聚合物{[Cu(Hbpma)(H₂O)₄]₂(SO₄)₃·3.5H₂O}_n (1)、{[Ni(Hbpma)(H₂O)₄]₄(SO₄)₆·10.75H₂O}_n (2)、{[Mn(Hbpma)(H₂O)4](SO₄)_1.5·3H₂O}_n (3)、{[Zn(Hbpma)(H₂O)₄]₄(SO₄)₆·4H₂O·4CH₃OH}_n (4)和{[Cu(Hbpma)2(H₂O)₂](SO₄)2·9H₂O}_n (5),其中bpma代表N,N'-双(3-吡啶甲基)胺。晶体结构分析表明配合物1~4为一维链状结构,配合物5为二维层状结构,其中金属离子由质子化的bpma配体桥连。值得注意的是,采取反-反式构象的柔性bpma配体使得配合物1和2为假螺旋链结构,配合物3和4为螺旋链结构,配合物5为螺旋层结构。同时研究了配合物的磁性和热稳定性。     

Magnesium and calcium complexes with two diimine radical-anion ligands. Molecular structure of the Ca complex with 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene

Four- and five-coordinate magnesium and calcium complexes containing two diimine radical-anion ligands with compositions (dpp-BIAN)₂Mg (1), (dpp-BIAN)₂Ca (2), (dtb-BIAN)₂Mg (3), and (dtb-BIAN)₂Ca(THF) (4) (dpp-BIAN is 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene and dtb-BIAN is 1,2-bis[(2,5-di-tert-butylphenyl)imino]acenaphthene) were synthesized. At 120 K, the ESR spectra of complexes 1–4 in a toluene matrix show signals characteristic of biradical derivatives. The molecular structure of compound 2 was established by X-ray diffraction analysis. At 293 K, the magnetic moments of compounds 1, 2, 3, and 4 are 2.55, 2.57, 2.76, and 2.79 μ_B, respectively, which are indicative of the presence of two unpaired electrons localized on the ligands.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2051–2055, October, 2004.     

Synthesis and Characterization of One-dimensional Dicyclohexyl-18-crown-6 Complexes with M2[Cd(mnt)2] (M = Na, K)

Two supramolecular crown ether complexes [Na(DC18C6-A)(H₂O)]{[Na(DC18C6-A)][Cd(mnt)₂]} (1) and [K(DC18C6-A)]₂[Cd(mnt)₂] (2) (DC18C6-A = cis-syn-cis-dicyclohexyl-18-crown-6, isomer A; mnt = maleonitriledithiolate) have been synthesized and characterized by elemental analysis, FT-IR spectroscopy and X-ray single crystal diffraction. Complex 1 is composed of one [Na(DC18C6-A)(H₂O)]⁺ complex cation and one {[Na(DC18C6-A)][Cd(mnt)₂]}⁻ complex anion and displays an infinite chain-like structure through N–Na–N interactions. In complex 2, [K(DC18C6-A)]⁺ complex cation and [Cd(mnt)₂]²⁻ complex anion afford a novel 1D ladder-like structure by N–K–N, N–K–S interactions.     

Synthesis and crystal structures of silver(I) and copper(II) complexes with <Emphasis Type="Italic">p</Emphasis>-xylylene-bridged bipyrazolyl ligands

Two semi-rigid bipyrazolyl ligands, namely 2,3,5,6-tetramethyl-1,4-bis[(3′,5′-dimethyl-1H -pyrazol-4′-yl)methylene]benzene (H₂L) and 2,3,5,6-tetramethyl-1,4-bis[(3′,5′-diphenyl-1H -pyrazol-4′-yl)methylene]benzene (H₂L′), and their Ag(I) and Cu(II) complexes have been prepared and structurally characterized by means of X-ray analysis. In the structures of the metal complexes, namely [Ag₂(H₂L)₂](BF₄)₂·2H₂O (1), [Ag(H₂L)(NO₃)]_n (2), [Cu₂(H₂L)₄(SO₄)₂]·11H₂O (3), and {[Ag(H₂L′)]BF₄}_n (4), the bipyrazoles act as bridging ligands to connect two metal atoms. Complexes 2 and 4 exhibit 1-D polymeric structures, while 1 and 3 are discrete molecules with a rectangular dimer or tetragonal prismatic shapes, respectively. Two different conformations, namely cis and trans, have been observed for these bipyrazolyl ligands.     

Ethylaluminum oxide catalysts from Et2AlOLi–Et2AlCl binary system in relation to species of AlEt3–water catalyst

Equimolar reaction of Et₂AlOLi and Et₂AlCl gave Et₂AlOAlEt₂. The catalyst behavior for polymerization of acetaldehyde, propylene oxide, and epichlorohydrin was compared with that of the AlEt₃–H₂O (1:0.5) catalyst system. The thermal disproportionation product of Et₂AlOAlEt₂ derived from Et₂AlOLi–Et₂AlCl had the structure, ? (EtAlO)_n? , and it showed catalyst behavior quite similar to that of the product obtained by the same treatment of AlEt₃–H₂O (1:0.5). These ethylaluminum oxides can be regarded as species predominating in AlEt₃–H₂O (1:0.5) and AlEt₃–H₂O (1:1), respectively. Stereospecific or high molecular weight polymerizations of these species were investigated.     

Preparation and X-Ray Study of Inclusion Complexes of (4Z,5E)-Pyrimidine-2,4,5,6(1 H,3H)-Tetraone 4,5-Dioxime and the Product of Its Cyclization, (1,2,5)-Oxadiazolo(3,4-d)-Pyrimidine-5,7(4 H,6H)-Dione with Two 18-Membered Macrocycles

The novel dioxime, (4Z,5E)-pyrimidine-2,4,5,6(1H,3H)-tetraone 4,5-dioxime (H₂-PTD) was obtained by the interaction of 6-amino-5-nitrosopyrimidine-2,4(1H,3H)-dione with hydroxylamine hydrochloride. X-ray structural analysis determined the 4Z,5E-configuration of the corresponding monoanion, pyrimidine-2,6(1H,3H)-dione-4-iminole-5-iminolate in the inclusion complexes with diazonia-18-crown-6 (1,4,10,13-tetraoxa-7,16-diazoniacyclooctadecane) (H₂-DA18C6)²⁺ (complex (1), stoichiometry 2 : 1), and its ammonium salt in the complex with the cis-syn-cis isomer of dicyclohexano-18-crown-6(DCHA) (cis-syn-cis-2,5,8,15,18,21-hexaoxatricyclo (20.4.0.0^9,14)hexacosane) (complex (2), stoichiometry 1 : 1). X-ray data were also obtained for the complex of the product of (H₂-PTD) cyclization, (1,2,5)-oxadiazolo(3,4-d)pyrimidine-5,7(4H,6H)-dione (OPD) with diaqua diaza-18-crown-6 (complex (3), stoichiometry 2 : 2 : 1).In (1) the (H-PTD)^- anions are joined into dimers through the bifurcated OH...N and OH...O hydrogen bonds and alternate with diazonia-18-crown-6 cations in the chains sustained by the NH(crown) ... O and NH(crown) ...N interactions. The chains are further combined into the 3D network via NH...O(crown) hydrogen bonds. In (2) the self-complementarity of the (H-PTD)^- anions facilitates their assembly into the chain via OH...N, NH...O and OH...O interactions. The ammonium cations bridge each anion and the DCHA macrocycle with the formation of a ribbon developed along the [101] direction in the unit cell. Ternary complex (3) is built of the neutral species, diaza-18-crown-6, water molecules and dimers of OPD alternated in the chains and held together by OH...O and NH...O hydrogen bonds.     

苯并15冠5与钼多酸的组装

以苯并15冠5和钼多酸为原料, 用水热法合成了两个新颖的超分子配合物[Na(B30C10)][Mo₆O₁₉] (1)和[NaL(CH₃CN)][NaL][α-PMo₁₂O₄₀][NaL₂] (L＝B15C5) (2), 并用单晶X射线衍射测定了它们的晶体结构. 配合物1属单斜晶系, 空间群为C2/m, 它包含三个基本单元: Na^＋, B15C5和Mo₆O , 冠醚分子和Na^＋配位, 并通过静电作用力和多酸分子相连. 配合物2属三斜晶系, 空间群为P-1, 它包含一个[α-PMo₁₂O₄₀]^3－离子和三个钠离子配合物. [Na(B15C5)]^＋通过Mo-O-Na-O键和多酸阴离子相连.