Solvothermal synthesis and crystal structure of an inorganic–organic hybrid compound [DAMS]2[CdI4] (DAMS = 4-dimethylaminostyryl-1-methyl-pyridinium)

An inorganic–organic hybrid compound [DAMS]₂[CdI₄] (DAMS = 4-dimethyl-amino- styryl-1-methylpyridinium cation) was synthesized via the solvothermal reaction of equimolar CdI₂ and DAMSI^– in a mixture of acetonitrile and H₂O (2:1 in volume ratio) at 130°C. The product was characterized by X-ray single crystal structure analysis. The crystals of the title compound are triclinic, , with a = 12.9849(19) Å, b = 13.1935(13) Å, c = 13.8792(10) Å, = 106.798(6)°, = 109.827(6)°, = 108.206(9)°, V = 1906.0(4) ų, Z = 2. The cadmium atom was bonded to 4 iodine atoms to form a distorted tetrahedron, which was surrounded by DAMS cations. There exist – stacking interaction between the 2 adjacent antiparallelly arrayed DAMS cations.     

Synthesis and crystal structure of [CuL0.5(Ac)2] n ⋅0.5nCHCl3 (L = 2,5-bis(4-pyridyl)-1,3,4-oxadiazole)

A one-dimensional complex [CuL _0.5(Ac)₂] _n 0.5nCHCl₃ (L being 2,5-bis(4-pyridyl)- 1,3,4-oxadiazole) has been synthesized and structurally characterized by X-ray diffraction: Monoclinic, space group C2/c with a = 27.217(3) Å, b = 13.0383(11) Å, c = 8.5671(9) Å, = 103.215(3)°, V = 2959.6(5) ų, Z = 8. The crystal structure of the complex reveals that the familiar lantern-type structure that is characteristic of dimetal tetracarboxylates of Cu^II ions, and the binuclear units were bridged by the angular ligands to form a one-dimensional zigzag chain coordination polymer. Every metal center is present in a distorted square-pyramidal coordination environment, consisting of coordination with one N atom of the ligand in the axial position and four O atoms of CH₃COO^– anions in equatorial positions. The Cu^IICu^II distance is 2.6060(9) Å. The title complex resides in the formation of a 3D network through – stacking interactions.     

Synthesis and crystal structure of trans-[PdCl2(EtMeIm)2] (EtMeIm = N-ethyl-N′-methylimidazol-2-ylidene)

The palladium–carbene complex, trans-[Pd(EtMeIm)₂Cl₂] was prepared by carbene transfer via the Ag carbene species. The structure was determined by X-ray crystallography. It crystallizes in the monoclinic unit cell of dimensions of a = 8.0243(9), b = 8.5320(9), c = 11.7473(13) Å, = 100.151(2)° with space group of P2₁/n and Z = 2. The palladium atom is tetracoordinated by two chloride ions and two carbon atoms in a square planar geometry.     

Molecular and crystal structure of [NO2Py]2[Ni(mnt)2](NO2Py=1-(4-nitrobenzyl)pyridinium, mnt2−=maleonitriledithiolate)

The structure of [NO₂Py]₂[Ni(mnt)₂], as determined by x-ray single crystal analysis, consists of two 1-(4-nitrobenzyl)pyridinium cations and one [Ni(mnt)₂]^2– anion. The crystallographic data for the complex:monoclinic P2₁/n, a = 9.913(2) Å, b = 11.968(2) Å, c = 14.566(3) Å, = 100.36(3)°, V = 1699.9(6) ų, Z = 2. The [Ni(mnt)₂]^2– anion has a crystallographically imposed center of symmetry and exhibits a relatively planar structure. The cation, [NO₂Py]⁺, adopts a conformation where both the aromatic rings are twisted to the C11-C10-N3 reference plane. The anions (A) and the cations (C) consist of alternating layers (i.e., of type ···C₁A₁C₂A₂C₁A₁C₂···) along the c axis of the crystallographic unit cell.     

Synthesis and structural characterization of [VS4(CuPPh3)4Br]·CH2Cl2

Heating a solid mixture of (NH₄)₃VS₄, CuCl, PPh₃, and NEt₄Br at 100°C for 10 h and extraction with CH₂Cl₂ yielded [VS₄(CuPPh₃)₄Br]·CH₂Cl₂. Crystallographic data: Triclinic, P1¯, a = 15.189(3), b = 20.093(6), c = 12.031(3) Å, = 102.39(2), = 100.05(2), = 82.86(2)°, V = 3517(3) ų, and Z = 2. The configuration of the VS₄Cu₄Br core can be described as a distorted cubane with an additional face. The V atom has retained the tetrahedral geometry of the free [VS₄]^3– moiety. The four Cu atoms have three different coordination environments, strongly distorted tetrahedral, nearly trigonal planar, and strictly trigonal planar. The infrared, electronic, and ⁵¹V NMR spectra have also been reported.     

Synthesis and structural characterization of [Co(tren)(Tsal)]ClO4·H2O and [Ni(pn)(py)2(NCS)2]

Complexes [Co(tren)(Tsal)]ClO₄·H₂O 1 and [Ni(pn)(py)₂(NCS)₂] 2, (tren = tris(2-aminoethyl)amine, Tsal = thiosalicylate ion, pn = 1, 2-diamino propane and py = pyridine) have been synthesized and structurally characterized. Both complexes crystallize in the monoclinic space group C2/c with a = 21.3340(6), b = 11.7754(2), c = 14.8076(5) Å, = 100.3831(10)°, Z = 8 (1), and a = 7.2573(8), b = 17.8810(11), c = 15.2681(12) Å, = 101.170(2)°, Z = 4 (2). The metal atoms in both cases have distorted octahedral geometry. In 1, the tren ligand is quadridentate and Tsal is bidentate chelate. In 2, the pn ligand forms a bidentate chelate with the NCS ligands in trans positions. Complex 1 is diamagnetic whereas 2 shows paramagnetism with a magnetic moment of 3.10 B. M.     

Reactions of [Mn2(μ-pyS)2(CO)6] with bidentate phosphines: X-ray structure of [Mn(η2-pyS) (η2-dppp)(CO)2] [dppp = Ph2P(CH2)3PPh2, pySH = pyridine-2-thiol]

The dimeric complex [Mn₂(-pyS)₂(CO)₆] (1) reacted with 2 molar equivalents of Ph₂P(CH₂)₃PPh₂ (dppp) and Ph₂P(CH₂)₂PPh₂ (dppe) to give the respective monomeric chelate complexes [Mn(²-pyS)(²-dppp)(CO)₂] (2) and [Mn(²-pyS)(²-dppe)(CO)₂] (3). In contrast, with 2 molar equivalents of Ph₂P(CH₂)₅PPh₂ (dpppe), 1 gave the highly insoluble polymeric complex [Mn(²-pyS)(-dpppe)(CO)₂]n (4). An X-ray structure determination shows that 2 crystallizes in the monoclinic space group P2₁/n with a = 10.721(2) Å, b = 19.712(5) Å, c = 14.846(4) Å, = 109.06(2)°, V = 2965.5(14) ų, and Z = 4. The complex has a distorted octahedral geometry with the dppp ligand, one CO group and the N atom of the chelating pyS ligand occupying equatorial sites, and one CO group and the S atom of the pyS ligand lying in the axial positions.     

2-pyridylbis(diphenylphosphino)methane chemistry. Synthesis and structures of [Cu(μ−η2:η1(Ph2P)2−CHC5H4N)(THF)]2(BF4)2 and [Ni(Ph2PCH2C5H4N)2]-[NiCl4]·0.85CH2Cl2and [Ni(Ph2PCH2C5H4N)2]-[NiCl4]·0.85CH2Cl2

Reaction of 2-pyridylbis(diphenylphosphino)methane (NPP) with [Cu(NCMe)₄]BF₄ and with [Ni(H₂O)₆]Cl₂ forms [Cu(NPP)(THF)]₂(BF₄)₂ (after recrystallization in the presence of THF) (1) and NiCl₂(NPP) (2) respectively Attempts to recrystallize2 led ultimately to the ligand cleavage product [Ni(Ph₂PCH₂C₅H₄N)₂][NiCl₄]·0.85CH₂Cl₂ (3). Complex1 crystallizes in the monoclinic space groupP2₁/n witha=13.148(2),b=19.221(2),c=13.458(2) ų, β=108.61(1)^o,V=3222.6(8) ÅZ=2. The structure was refined onF ² toR1=0.11,wR2=0.14 (R1=0.044 forI≥2σ(I)) for 5661 observed reflections. Complex3 crystallizes in the triclinic space groupP1 witha=12.795(2),b=17.535(1),c=10.203(1) Å, α=107.564(6), β=114.260(8), γ=78.435(8)^o,V=1982.1(8) ų;Z=2. The structure was refined onF toR1=0.044,R _w=0.059 for 3534 observed reflections. Dinuclear complex1 has crystallographically imposed centrosymmetry with the NPP ligands arranged in a head-to-tail fashion. The Cu...Cu separation of 3.372(1) Å is too long to support significant metal-metal interaction. Complex3 results from the cleavage of a {PPh₂} unit from the NPP ligand and contains an approximately square nickel atom surrounded by two Ph₂PCH₂C₅H₄N ligands coordinated in a head-to-head fashion.     

CF4气氛中生长Re: LiM(Re=Tm,Ce;M=Lu,Y)F4晶体

本文在CF4气氛中以提拉法成功地生长出高质量的掺入Tm3+、Ce3+的LiLuF4和LiYF4晶体,对比了Ar和CF4气氛中生长的LiYF4晶体的红外光谱特性,讨论了CF4气氛对LiM(M=Y,Lu)F4晶体生长的影响.同时测试了Tm3+、Ce3+在LiLuF4和LiYF4晶体中的有效分凝系数,从离子半径和晶胞畸变的角度,讨论了Tm3+、Ce3+在LiLuF4和LiYF4晶体中有效分凝系数差别的产生原因.     

Crystal and molecular structure of [Cu2(3,5-dihydroxybenzoate)4 (acetonitrile)2] ⋅ 8H2O

The crystal and molecular structure of the title compound, [Cu₂(3,5-dihydroxybenzoate)₄ (acetonitrile)₂] 8H₂O 1, is reported. Crystal data for 1: tetragonal, space group I 4/m, a = 11.720(2) Å, c = 15.304(3) Å, V = 2102.4(6), and D _c = 1.53 g/cm³, for Z = 2. The metal and organic components crystallize to form a Cu paddle-wheel complex, of idealized D_4h symmetry, that assembles in the solid-state, along with eight equivalents of water, to form a 3D hydrogen-bonded network held together by O–H O hydrogens bonds. The metal complexes pack to form a 2D layered structure.     

Molecular structures of [CpRu(PPh3)(dtoxa-H2O)]BF4 and {[CpRu(PPh3)2]2(μ-dtoxa)}(BF4)2, dtoxa=dithiooxamide

The reaction of [CpRu(PPh₃)₂(n-C₃H₇SH)]BF₄ with dithiooxamide (dtoxa) gave two products: {[CpRu(PPh₃)₂]₂(-dtoxa)} (BF₄)₂,1, and [CpRu(PPh₃)(dtoxa-H₂O)]BF₄,2. The structures of both complexes were determined by X-ray diffraction techniques. Compound1 crystallized in the triclinic space groupP _¯1,a=12.822(4),b=14.16(1),c=23.631(8) Å,=84.57(4),=83.64(3), =83.57(4)°,Z=2,R=0.069,R _w =0.084. The structure of1 shows two CpRu(PPh₃)₂ ⁺ units bridged through the S atoms of the dtoxa ligand. Ru-S distances are 2.377(6)Å for Ru1-S1 and 2.368(6) Å for Ru2-S2. Compound2 crystallized in the monoclinic space groupP2₁/c,a=13.446(3),b=13.461(7),c=31.214(7) Å,=100.78(3)°,Z=8,R=0.054,R _w =0.055. The structure of2 has two molecules in the asymmetric unit. The Ru is chelated to the dtoxa through the S atoms: Ru1-S1, 2.307(4); Ru1-S2, 2.300(4); Ru2-S3, 2.295(4); Ru2-S4, 2.287(4) Å. The coordination sphere of the Ru in2 is completed by a cyclopentadienyl ligand and a triphenylphosphine.     

Synthesis and crystal structure of bis(carbamide)chromatoneptunyl NpO2CrO4 · 2[OC(NH2)2]

The crystal structure of the hexavalent neptunium complex NpO₂CrO₄ · 2[OC(NH₂)₂] is determined. The crystal data are a = 7.192(2) Å, b = 12.902(4) Å, c = 11.226(3) Å, β = 92.19(2)°, V = 1040.9(4) ų, space group P2₁/n, Z = 4, d _calcd = 3.223 g/cm³, R = 0.045, and R _w = 0.130. The coordination polyhedron of the Np atom is the pentagonal bipyramid whose equatorial plane is formed by the oxygen atoms of the chromate ions and carbamide molecules.     

Primary to secondary sphere coordination of 15-crown-5 to lanthanide(III) chlorides: structural analysis of [MCl3(15-crown-5)] (M=La,Ce) and [Er(OH2)8]Cl3·15-crown-5

Complexes of LaCl₃·7H₂O and CeCl₃·7H₂O directly coordinated to 15-crown-5 were prepared by placing the reactants in 31 CH₃CNCH₃OH on opposite sides of a fine porosity glass frit in a U-shaped cell and passing a 10 A current through the cell. The crystal structures of the two anhydrous 8-coordinate complexes, [MCl₃(15-crown-5)] (M=La, Ce) have been determined. Each contains the lanthanide in a bicapped trigonal prismatic geometry. The two complexes are isostructural crystallizing in the monoclinic space groupP2₁/c with (at 20°C) for M=La:a=8.217(8),b=14.298(2),c=14.341(9) Å, =104.79(8)°, andD _calc=1.90 g cm^–3 forZ=4; for M=Ce:a=8.208(9),b=14.263(6),c=14.270(8) Å, =104.74(7)°, andD _calc=1.92 g cm^–3 forZ=4. Direct reaction of ErCl₃·6H₂O with 15-crown-5 in 31 CH₃CNCH₃OH resulted in the crystallization of the second sphere hydrogen bonded complex [Er(OH₂)₈]Cl₃·15-crown-5. This complex is monoclinic,P2₁/n with (at 18°C)a=9.193(3),b=17.235(9),c=15.216(5) Å, =92.48(3)°, andD _calc=1.76 g cm^–3 forZ=4. The Er³⁺ ion is dodecahedral.     

Hydrothermal crystallization and X-ray structure determination of a new decavanadate with mixed cations [Mn(H2O)6]2[N(CH3)4]2[V10O28]·2H2O

A new decavanadate with mixed cations, [Mn(H₂O)₆]₂[N(CH₃)₄]₂[V₁₀O₂₈]·2H₂O (1), was crystallized from a hydrothermal reaction between MnCO₃ and V₂O₅ in the presence of N(CH₃)₄Br at 100°C. The structure of 1, as determined by x-ray single crystal analysis, consists of cations and anions of hexa-aqua manganese [Mn(H₂O)₆]²⁺, tetramethyl ammonium [N(CH₃)₄]⁺ and decavanadate [V₁₀O₂₈]^6–. The extended H-bonding between the [Mn(H₂O)₆]²⁺ and [V₁₀O₂₈]^6– ions gives rise to a pseudo- two-dimensional network in the crystal lattice x-ray crystallographic data for 1: monoclinic P2₁/n, a = 9.1499(5), b = 12.8725(7), c = 18.625(1) Å, = 92.252(1)°, V = 2192.0(2) ų, MZ = 2, and D _calcd = 2.22 g cm^–3.     

Synthesis and crystal structure of a tetranuclear manganese(IV) cluster [L4Mn4O6](ClO4)4·2H2O (L = 1,4,7-triazacyclononane)

A tetranuclear manganese (IV) complex, [L₄Mn₄O₆](ClO₄)₄·2H₂O (1), with 1,4,7-triazacyclononane (L) as the capping ligands, has been synthesized and characterized by X-ray diffraction; monoclinic, space group P2₁/n with a = 21.335(6) Å, b = 11.387(3) Å, c = 21.788 (6) Å, = 111.410 (6)°, V = 4928 (2) Å, Z = 4. Each manganese atom has a distorted octahedral environment comprised of three facially coordinated amine nitrogen atoms and three oxygen atoms, and the cation is an idealized tetrahedron. The Mn₄O₆ ⁴⁺ cation corresponds to an adamantane skeleton.     

Crystal and molecular structure of complex compound [Fe3O(CH3COO)6(H2O)3]2[ZnCl4] ⋅ 2H2O

The X-ray crystal structure of trinuclear iron acetate [Fe₃O(CH₃COO)₆(H₂O)₃]₂ [ZnCl₄] ? 2H₂O was determined. The crystal has a ionic structure. It is monoclinic, a = 25.363(7), b = 14.533(4), c = 15.692(4) Å, β = 103.11(2)°, space group _C2/c, and R = 0.0685. The structure of the cationic complex [Fe₃O(CH₃COO)₆(H₂O)₃]⁺ is typical of trinuclear iron(III) compounds containing a μ₃-O bridge: the iron atoms are situated at the vertices of an almost equilateral triangle with the O atom at the center. Each Fe atom is coordinated by four O atoms of bridging carboxy groups, the μ₃-bridging O atom, and the water molecule in the trans position to the latter O atom. Mössbauer spectroscopy evidence indicates the high-spin state (_S = 5/2) of the iron(III) ions.     

Self-assemblies of Ni(II) with phenanthroline and maleate anions: [Ni(H2O)3(phen)L] ⋅ H2O (1) and [Ni(H2O)2(phen)L] ⋅ 2H2O (2) with H2L = maleic acid

The complex [Ni(H₂O)₃(phen)(C₄H₂O₄)] H₂O (1), which was obtained by reaction of phenanthroline, Ni(NO₃)₂ 6H₂O, and maleic acid in CH₃OH/H₂O at pH = 7.05, crystallized in the monoclinic space group P2₁ (no. 4) with cell dimensions: a = 9.350(1) Å, b = 7.631(1) Å, c = 12.821(1) Å, = 106.25(1), and D _calc = 1.607 g/cm³ for Z = 2. The Ni atoms are each octahe drally coordinated by one chelating phen ligand, three H₂O molecules and one monodentate maleato ligand to form [Ni(H₂O)₃(phen)(C₄H₂O₄)] complex molecules with d(Ni–O) = 2.038–2.090 Å, d(Ni–N) = 2.066, 2.089 Å. The formed complex molecules are, via the intermolecular hydrogen bonds, assembled into columnar 1D chains. Interdigitation of the chelating phen ligands of the neighboring chains leads to 2D layers and the crystal H₂O molecules are hydrogen bonded to the oxygen atoms of the maleate not coordinated to the Ni atom. However, reaction of NiCO₃, phen, and maleic acid in CH₃OH/H₂O at pH = 6.33 afforded [Ni(H₂O)₂(phen)(C₄H₂O₄)] 2H₂O (2), which crystallized in the triclinic space group (no. 2) with cell dimensions: a = 7.971(1) Å, b = 8.237(1) Å, c = 13.304(1) Å, = 81.005(6)°, = 87.877(8)°, = 78.322(8)°, and D _calc = 1.671 g/cm³ for Z = 2. The Ni atoms are each octahedrally coordinated by two N atoms of one phen ligand and four O atoms of two H₂O molecules and two bis–monodentate maleato ligands with d(Ni–O) = 2.041–2.120 Å and d(Ni–N) = 2.095 Å. The Ni atoms are bridged by the maleato ligands to generate 1D ¹ [Ni(H₂O)₂(phen)(C₄H₂O₄)_2/2] chains along [100]. The supramolecular assemblies of the 1D chains via – stacking inter- actions result in thick 2D layers parallel to (001), between which the noncoordinating H₂O molecules are sandwiched. The paramagnetic [Ni(H₂O)₂(phen)(C₄H₂O₄)_2/2] 2H₂O (2) obeys the Curie–Weiss law _m(T-) = 1.139cm³ mol^–1 K with the Weiss constant = –0.95 K.     

三维孔道结构钒磷酸盐[H3N(CH2)3NH3]2[H3N(CH2)3NH2][H2N(CH2)3NH2]-[V(H2O)2(VO)8(OH)4(PO4)4(HPO4)4]·4H2O的水热合成和结构表征

以1,3-丙二胺为模板,水热合成了三维孔道结构钒磷酸盐[H3N(CH2)3NH3]2[H3N(CH2)3NH2][H2N(CH2)3NH2][V(H2O)2(VO)8(OH)4(PO4)4(HPO4)4]·4H2O(DAP-V9P8).用单晶X射线衍射、红外光谱和热重法对该化合物的晶体结构进行了表征.DAP-V9P8的无机骨架由[VO5]、[VO6]、[PO4]和[HPO4]通过共顶点连接而成.孔道中充填的丙二胺分子随所处结晶学位置不同,有三种完全不同的分子构象.其中,位于//b轴直径达1.82nm椭圆形孔道中心的丙二胺分子碳链呈独特的直线状分布.晶体学参数:a=1.4820(9)nm,b=1.0255(4)nm,c=1.8181(9)nm,β=90.391(8)°;P21/n(No.14);R1=0.0772,wR2=0.2004(I＞(2σI)).与等结构的其它化合物进行了系统的结构比较.     

Synthesis and crystal structure of trans-bis(O, O′-diisopropylthiophosphoryl-1H-imidazole-N3) bis(O,O′-diisopropyldithiophosphato) nickel(II) complex: Ni[N3-ImSP(OiPr)2]2[S2P(OiPr)2]2 (Im = imidazole; iPr = isopropyl)

The mononuclear complex, Ni[N³-ImSP(OiPr)₂]₂[S₂P(OiPr)₂]₂ (Im = imidazole; iPr = isopropyl), was unexpectedly obtained in a reaction of bis(O,O-diisopropyl-dithiophosphato) nickel(II) complex with imidazole ligand, and its structure was determined by X-ray crystallography. It crystallizes in the triclinic system, space group P , with lattice parameters a = 12.437(3) Å, b = 13.181(3) Å, c = 8.4580(17) Å, = 93.16(3)°, = 101.93(3)°, = 65.26(3)°, and Z = 1. The Ni atom has almost perfect octahedral coordination geometry and is coordinated by two N atoms of imidazole from two O,O-diisopropylthiophosphoryl-1H-imidazole ligands in axial positions and four S atoms from two (O,O-diisopropyldithiophosphato) anions which act as bidentate ligands forming a four-membered chelate ring in the equatorial plane. The Ni—S bond distances are 2.469(1) and 2.507(1) Å, and the Ni—N bond distances are 2.097(2) Å. The IR spectra data are in agreement with the structural data.     

Synthesis and crystallographic characterization of [Cd(OH2)2 (μ-Br)4 (Cd(2-hydroxyethyl sulfide) (μ-Br))2]n

The reaction of equal millimolar quantities of CdBr₂ and 2-hydroxyethyl sulfide in 31 CH₃CNCH₃OH produced [Cd(OH₂)₂(Br)₄ (Cd(2-hydroxy ethyl sulfide) (-Br))₂]_n. The compound crystallizes as a bromide-bridged polymer with hydrogen bonding interactions between the polymeric chains. Each of the two unique metal centers has a distorted octahedral geometry. The thioether ligand is bidentate to one cadmium position with one alcoholic terminus uncoordinated. The uncoordinated portion of the molecule is disordered with each conformation participating in slightly different hydrogen bonding environments. The other unique cadmium center is coordinated to four bridging bromides and twotrans water molecules.