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1.
[PhTe]2 and [(β‐naphthyl)Te]2 react with iodine and tetraethylammonium iodide in toluene/methanol to give (Et4N)[PhTeI4] and (Et4N)[(β‐Naphthyl)TeI4]. The complexes were analysed by single crystal X‐ray diffraction affording the centrosymmetric monoclinic space group P21/c. In the novel compounds only anionic interactions of the types Te···I and I···I take place, cation‐anion effective contacts do not occur. Both anions [PhTeI4] and [(β‐naphthyl)TeI4] exhibit square pyramidal coordination at tellurium, with the iodine atoms in the basal positions and the organic groups apical. The tellurium centers achieve an octahedral coordination in the whole lattices through Te···I secondary bonds with the adjacent ionic species. Only the Te–I‐ and I–I‐secondary bonds behave as structure‐forming interactions in the self‐organization of the supramolecular anionic gatherings. New evidences show that for organyltellurates (Q)[PhTeX4] (Q = protonated amines, amides or amino acids; X = Cl, Br, I), NH···X hydrogen bondings are able to hinder the anionic halogen‐halogen secondary interactions. In case of the more frequent I···I interactions, they have been observed only in the absence of NH···I hydrogen bonds.  相似文献   

2.
The syntheses and the structural characterization of the compounds [(mes)2Te–Te(I)mes], (PyH)[mesTeI3(I3)] (mes = mesityl = 2,4,6-trimethylphenyl; Py = pyridine), (PyH)3[dmephTeI2(I2)]2(I3) (dmeph = 2,6-dimethylphenyl), (PyH)2[RTeI4]2·(CH3)CO(CH3)·C6H5CH3 (R = p-tert-butylphenyl) and (PyH)2[PhTeI4]2 (Ph = phenyl) are presented. Some earlier analog preparations are compared and the influence of ortho substituents in the aryl group on the oxidation state of tellurium is discussed, as well as the observed conditions for the formation of poly-iodides chains.  相似文献   

3.
Potassium diphthalocyaninato(2–)metallate(III), K[M(pc2–)2] (M = Bi, La, Ce, Pr, Sm, Sb, In) has been prepared by melting the metal chloride, iodide or acetate with 1,2‐dicyanobenzene in the presence of potassium methylate. Crystallisation with tetra(n‐butyl)ammonium bromide or hydroxide ((nBu4N)Br/OH), tetra(n‐pentyl)ammonium chloride ((nPe4N)Cl) or bis(triphenylphosphine)iminium halide ((PNP)X; X = Br, I) yields the corresponding red‐purple complex salt (nBu4N)[M(pc2–)2] (M = Bi ( 1 ), La ( 3 ), Ce ( 2 )), (nBu4N)[M(pc2–)2] · x CH3OH (M = Bi ( 5 ), Pr ( 6 ), Sm ( 7 ); 0 9 x 9 1), (nPe4N)[La(pc2–)2] ( 4 ), (nBu4N)[Pr(pc2–)2] · 2 py ( 10 ), (nBu4N)[Sb(pc2–)2] · 2 thf ( 11 ), (PNP)2[M(pc2–)2]Br · 2 Et2O (M = Sb ( 12 ), Bi ( 13 )), and (PNP)2[In(pc2–)2]I · 2 Et2O ( 14 ). Bronze coloured diphthalocyaninato(1–)metal(III) polyiodide, [M(pc)2]I2 (M = Sc, Y) has been prepared similarly in the presence of ammonium iodide. Reduction with (nBu4N)OH provides (nBu4N)[M(pc2–)2] · x CH3OH (M = Y ( 8 ), Sc ( 9 ); 0 9 x 9 1). Spectral properties (UV/VIS/NIR; IR; resonance Raman) of diphthalocyaninates in their different ring oxidation states (2–/2–; 2–/1–; 1–/1–) are discussed. 1 – 3 crystallise in the tetragonal (P4/ncc), 5 – 9 in the orthorhombic (Pna21), 10 , 11 in the triclinic (P‐1), and 4 , 12 – 14 in the monoclinic crystal system ( 4 : P21/m; 12 : C2/c; 13 , 14 : P2/c). Ecliptic rotamers with skew angles ranging from 4.1° to 6.0° are found in 1 – 3 , and staggered rotamers with skew angles ranging from 35.8° to 45.0° are found in 4 – 14 . The mean M–Ni bond lengths and interplanar distances increase monotonically with the ionic radius of the metal ion. Both distances deviate notably from this linear correlation in the SbIII and BiIII derivatives. The discrepancy is presumably due to the sterical dominance of the ns2 lone‐pair character. The actual size of eight co‐ordinated SbIII and BiIII is estimated to be R8 ≈ 1.02(Sb)/1.11(Bi) Å. In every complex salt, the pc ligand is severely distorted from planarity and can adopt domed, saddled, waved and mixed non‐planar conformations; the crystal symmetry is the most important factor for the conformational heterogeneity.  相似文献   

4.
The reaction of tellurium(IV) tetrahalides with hydrochloric and hydrobromic acid leads to the formation of (H3O)2[TeX6], which reacts subsequently with (2‐Br‐C5NH5)+X to afford (2‐Br‐C5NH5)2[TeCl6] ( 1 ) and (2‐Br‐C5NH5)2[TeBr6] ( 2 ). The structure of the complex salts were analysed by X‐ray diffractometry affording the centrosymmetric space groups P21/n (monoclinic, 1 ) and P1¯ (triclinic, 2 ). Interionic hydrogen bondings hold their lattices in bidimensional supramolecular arrays not yet described in the literature. The lone electron pair of the AX6E‐system of the hexahalotellurates [TeX6]2‐ (X = Cl, Br) seems to be fully delocalized since only small octahedral deviations were observed for the anionic species. The structures of the title compounds were refined with the Te atoms occupying sites with full point symmetry, approximately m3¯m. In both cases the Te atoms enclose centers of inversion and the octahedrally dynamic structures are enforced and stabilized along the supramolecular lattices by the crystal field of the 2‐Br‐pyridinium cations.  相似文献   

5.
SnCl2 as a Bridging Ligand in [{(CO)5M}2Sn(Cl)2]2? (M = Cr, Mo, W) — Synthesis, Structure, and Reactivity [{(CO)5Cr}2Sn(Cl)2]2?, 1 , may be obtained from [(CO)5Cr]2? or [(CO)5CrSnCl2 · THF] in fair yields. Alternatively, 1 is accessible by the reaction of [Cr2(CO)10]2? with SnCl2. This procedure may be extended to the synthesis of [{(CO)5M}2Sn(Cl)2]2? (M = Mo, 2 ; M = W, 3 ). The compounds 1–3 are crystallized as their alkalimetal (12-crown-4)2 or [2,2,2]cryptand salts. X-ray analyses demonstrate bridging SnCl2-moieties with M? Sn? M-angles close to 130° in each case. The relation of the bonding situation in 1–3 to the ones observed for stannylene or ?inidene”? complexes, respectively, is discussed. The transformation of 1 into the rhombododecahedral (X-ray analysis) Sn? O-cage compound [{(CO)5CrSn}63-O)43-OH)4], 4 , demonstrates the reactivity of the dianions 1–3 .  相似文献   

6.
Synthesis and Spectroscopical Characterization of Di(halo)phthalocyaninato(1–)rhodium(III), [RhX2Pc1?] (X = Cl, Br, I) Bronze-coloured di(halo)phthalocyaninato(1–)-rhodium(III), [RhX2Pc1?] (X = Cl, Br) and [RhI2Pc1?] · I2 is prepared by oxidation of (nBu4N)[RhX2Pc2?] with the corresponding halogene. Irrespective of the halo ligands, two irreversible electrode reactions due to the first ringreduction (ER = ?0,90 V) and ringoxidation (EO = 0,82 V) are present in the cyclovoltammogram of (nBu4N)[RhX2Pc2?]. The optical spectra show typical absorptions of the Pc1?-ligand at 14.0 kK and 19.1 kK. Characteristic vibrational bands are at 1 366/1 449 cm?1 (i. r.) and 569/1 132/1 180/1 600 cm?1 (resonance Raman (r. r.)). The antisym. (Rh? X)-stretching vibration is observed at 294 cm?1 (X = Cl), 240 cm?4 (Br) and 200 cm?1 (I). Only the sym. (Rh? I)-stretching vibration at 133 cm?1 is r. r. enhanced together with a strong line at 170 cm?1, which is assigned to the (I? I)-stretching vibration of the incorporated iodine molecule. Both modes show overtones and combinationbands.  相似文献   

7.
Hydrocarbon‐bridged Metal Complexes. XLIX. Coordination Chemistry of Bis(ferrocenyl) substituted 1,3 Diketonates with Ruthenium, Rhodium, Iridium, and Palladium The reactions of the enolates of diferrocenoylmethane and of spacer bridged bis‐, tris‐ and tetrakis(ferrocenoyl)‐1,3‐diketones with chlorobridged compounds [(R3P)PdCl2]2, [(η3‐C3H5)PdCl]2, [(p‐cymene)RuCl2]2, [Cp*MCl2]2 (M = Rh, Ir) give a series of mono‐, bis‐, tris‐ and tetrakis(chelate) complexes 2 – 18 . The structures of (Ph3P)(Cl)Pd[OC(Fe)CHC(Fc)O] ( 3 ) and (Tol3P)(Cl) · Pd[OC(Fc)CHC(O)–C(O)CHC(Fc)O]Pd(Cl)(PTol3) ( 11 ) were determined by X‐ray diffraction. The methine H atom of diferrocenoylmethane and of 3 was substituted by bromine using N‐bromosuccinimide. The electrophilic glycine equivalent α‐bromo‐N‐boc‐glycine ester was added to the methine C‐atom (C3) of diferrocenoylmethane and the product was used as O,O′ chelate ligand.  相似文献   

8.
Magnesium Phthalocyanines: Synthesis and Properties of Halophthalocyaninatomagnesate, [Mg(X)Pc2?]? (X = F, Cl, Br); Crystal Structure of Bis(triphenylphosphine)iminiumchloro-(phthalocyaninato)magnesate Acetone Solvate Magnesium phthalocyanine reacts with excess tetra(n-butyl)ammonium- or bis(triphenylphosphine)iminiumhalide ((nBu4N)X or (PNP)X; X = F, Cl, Br) yielding halophthalocyaninatomagnesate ([Mg(X)Pc2?]?; X = F, Cl, Br), which crystallizes in part as a scarcely soluble (nBu4N) or (PNP) complex-salt. Single-crystal X-ray diffraction analysis of b(PNP)[Mg(Cl)Pc2?] · CH3COCH3 reveals that the Mg atom has a tetragonal pyramidal coordination geometry with the Mg atom displaced out of the center (Ct) of the inner nitrogen atoms (Niso) of the nonplanar Pc ligand toward the Cl atom (d(Mg? Ct) = 0.572(3) Å; d(Mg? Cl) = 2.367(2) Å). The average Mg? Niso distance is 2.058 Å. Pairs of partially overlapping anions are present. The cation adopts a bent conformation (b(PNP)+: d(P1? N(K)) = 1.568(3) Å; d(P2? N(K)) = 1.587(3) Å; ?(P1? N(K)? P2) = 141.3(2)°). Electrochemical and spectroscopic properties are discussed.  相似文献   

9.
Reactions of copper(I) halides (Cl, Br, I) with 1‐methyl‐1, 3‐imidazoline‐2‐thione (mimzSH) in 1 : 2 molar ratio yielded sulfur‐bridged dinuclear [Cu2X2(μ‐S‐mimzSH)21‐S‐mimzSH)2] (X = I, 1 , Br, 2 ; Cl, 3 ) complexes. Copper(I) iodide with 1,3‐imidazoline‐2‐thione (imzSH2) and Ph3P in 1 : 1 : 1 molar ratio has also formed a sulfur‐bridged dinuclear [Cu2I2(μ‐S‐imzSH2)2(PPh3)2] ( 4 ) complex. The central Cu(μ‐S)2Cu cores form parallelograms with unequal Cu–S bond distances {2.324(2), 2.454(3) Å} ( 1 ); {2.3118(6), 2.5098(6) Å} ( 2 ); {2.3075(4), 2.5218(4) Å} ( 3 ); {2.3711(8), 2.4473(8) Å} ( 4 ). The Cu···Cu separations, 2.759–2.877Å in complexes 1 – 3 are much shorter than 3.3446Å in complex 4 . The weak intermolecular interactions {H2CH···S# ( 2 ); CH···Cl# ( 3 ); NH···I# ( 4 )} between dimeric units in complexes 2 – 4 lead to the formation of linear 1D polymers.  相似文献   

10.
Supermesityl selenium diimide [Se{N(C6H2tBu3‐2, 4, 6)}2; Se{N(mes*)}2] can be prepared in a good yield from the reaction of SeCl4 and (mes*)NHLi. The molecule adopts an unprecedented anti, anti‐conformation, as deduced by DFT calculations at PBE0/TZVP level of theory and supported by 77Se NMR spectroscopy and a crystal structure determination. An analogous reaction involving (C6H2Me3‐2, 4, 6)NHLi [(mes)NHLi] unexpectedly lead to the reduction of selenium and afforded the selenium diamide Se{NH(mes)}2 that was characterized by X‐ray crystallography and 77Se NMR spectroscopy. The Se‐N bonds of 1.847(3) and 1.852(3) Å show normal single bond lengths. The <NSeN bond angle of 109.9(1)° also indicates a tetrahedral AX2E2 bonding arrangement around selenium. Two N‐H···N hydrogen bonds link the Se{NH(mes)}2 molecule with two discrete (mes)NH2 molecules. In the solid state selenium diamide adopts the anti‐conformation, whereas in solution the presence of both syn‐ and anti‐isomers could be observed. PBE0/TZVP calculations of the shielding tensors of 28 different types of selenium‐containing molecules, for which the 77Se chemical shifts are unambiguously known, were carried out to assist the spectral assignment of Se{N(mes*)}2 and Se{NH(mes)}2.  相似文献   

11.
tBu2P–PLi–PtBu2·2THF reacts with [cis‐(Et3P)2MCl2] (M = Ni, Pd) yielding [(1,2‐η‐tBu2P=P–PtBu2)Ni(PEt3)Cl] and [(1,2‐η‐tBu2P=P–PtBu2)Pd(PEt3)Cl], respectively. tBu2P– PLi–PtBu2 undergoes an oxidation process and the tBu2P–P–PtBu2 ligand adopts in the products the structure of a side‐on bonded 1,1‐di‐tert‐butyl‐2‐(di‐tert‐butylphosphino)diphosphenium cation with a short P–P bond. Surprisingly, the reaction of tBu2P–PLi–PtBu2·2THF with [cis‐(Et3P)2PtCl2] does not yield [(1,2‐η‐tBu2P=P–PtBu2)Pt(PEt3)Cl].  相似文献   

12.
The self‐assembly of NiCl2·6H2O with a diaminodiamide ligand 4,8‐diazaundecanediamide (L‐2,3,2) gave a [Ni(C9H20N4O2)(Cl)(H2O)] Cl·2H2O ( 1 ). The structure of 1 was characterized by single‐crystal X‐ray diffraction analysis. Structural data for 1 indicate that the Ni(II) is coordinated to two tertiary N atoms, two O atoms, one water and one chloride in a distorted octahedral geometry. Crystal data for 1: orthorhombic, space group P 21nb, a = 9.5796(3) Å, b = 12.3463(4) Å, c = 14.6305(5) Å, Z = 4. Through NH···Cl–Ni (H···Cl 2.42 Å, N···Cl 3.24 Å, NH···Cl 158°) and OH···Cl–Ni contacts (H···Cl 2.36 Å, O···Cl 3.08 Å, OH···Cl 143°), each cationic moiety [Ni(C9H20N4O2) (Cl)(H2O)]+ in 1 is linked to neighboring ones, producing a charged hydrogen‐bonded 1D chainlike structure. Thermogrametric analysis of compound 1 is consistent with the crystallographic observations. The electronic absorption spectrum of Ni(L‐2,3,2)2+ in aqueous solution shows four absorption bands, which are assigned to the 3A2g3T2g, 3T2g1Eg, 3T2g3T1g, and 3A2g3T1g transitions of triplet‐ground state, distorted octahedral nickel(II) complex. The cyclic volammetric measurement shows that Ni2+ is more easily reduced than Ni(L‐2,3,2)2+ in aqueous solution.  相似文献   

13.
The analogy of chloride–chloride contacts in compounds containing Fe–Cl1···Cl2–Fe synthons with well-studied organic C–Cl1···Cl2–C interactions has been investigated. The crystal structures of the two tetrahaloferrate(III) salts, [(2-iodopyridinium)2FeX4]X (X = Cl, Br) have been determined. Analysis of these two isomorphous structures and related published structures shows that the arrangement of Fe–Cl1···Cl2–Fe synthons is similar to that of C–Cl1···Cl2–C with the Fe–Cl1···Cl2 and Cl1···Cl2–Fe angles being ~150°. While inter-chlorine distances are less than the sum of van der Waals radii in C–Cl1···Cl2–C units, they are equal to, or longer, than the sum of van der Waals radii in the corresponding Fe–Cl1···Cl2–Fe contacts. This might indicate that the arrangement of Fe–Cl1···Cl2–Fe synthons occurs predominately to reduce repulsive forces rather than as a result of attractive forces. However, it is observed that the halide–halide distance in [(2-iodopyridinium)2FeBr4]Br is shorter than in the isostructural chloride species, which can be explained by the fact that bromine is softer than chlorine. Several intermolecular forces unite the cations and anions within the crystalline lattice of [(2-iodopyridinium)2FeX4]X including N–H···X?, C–I···X–Fe, N(π)···X–Fe, N(π)···I–C, and Fe–X1···X2–Fe contacts. The calculated electron density and electrostatic potential of the [FeX4]? anions and the organic iodopyridinium cations was used to describe the arrangement of these synthons and the hierarchy of the strengths of the respective contacts.  相似文献   

14.
Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of (Ph4P)2[OsN(N3)5] and 15N NMR Chemical Shifts of Nitridoosmates(VI, VIII) The treatment of (Ph4P)[OsNCl4] with NaN3 yields (Ph4P)2[OsN(N3)5], which crystal structure has been determined by single crystal X‐ray diffraction analysis (monoclinic, space group P 21/a, a = 20.484(6), b = 11.168(1), c = 20.666(4) Å, β = 97.35(3)°, Z = 4). The IR and Raman vibrations were assigned by a normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constants are fd(Os≡N) = 8.52, fd(Os–Nα) = 1.99, fd(Nα–Nβ) = 12.42, fd(Nβ–Nγ) = 12.73 and for the azido ligand in trans‐position to the nitrido group fd(Os–Nα · ) = 1.84, fd(Nα · –Nβ · ) = 11.91, fd(Nβ · –Nγ · ) = 12.18 mdyn/Å. The 15N NMR spectra of various nitridoosmates reveal the chemical shifts δ(15N) for K[OsO315N] = 387.6, K2[Os15NCl5] = 446.7, (Ph4P)[Os15NCl4] = 352.9, [(n‐C6H13)4N]2[Os15N(N3)5] = 307.3 and for [(n‐Pr)4N]2[Os15N(15NCO)5] = 483,7 (Os≡N), –417,7 (OsNCOeq) und –392,8 ppm (OsNCOax).  相似文献   

15.
A series of six new Zn (II) compounds, viz., [Zn(HLASA)2(Py)2] ( 1 ), [Zn(HLMASA)2(Py)2] ( 2 ), [Zn(HLMASA)2(4‐MePy)2] ( 3 ), [Zn(HLCASA)2(4‐MePy)2] ( 4 ), [Zn(HLBASA)2(Py)2] ( 5 ), [Zn(HLBASA)2(4‐MePy)2] ( 6 ) and representative Cu (II) and Cd (II) complexes, viz., [Cu(HLASA)2(Py)2(H2O)] ( 7 ) and [Cd(HLBASA)2(Py)3] ( 8 ) [(HLXASA)? = para‐substituted 5‐[(E)‐2‐(aryl)‐1‐diazenyl]‐2‐hydroxybenzoate with X = H (ASA), Me (MASA), Cl (CASA) or Br (BASA); Py = pyridine; 4‐MePy = 4‐methylpyridine] have been synthesized and characterized by spectroscopic techniques and single‐crystal X‐ray diffraction analysis. The structural characterization of the compounds revealed distorted tetrahedral ( 1 – 6 ), square‐pyramidal ( 7 ) and pentagonal‐bipyramidal ( 8 ) coordination geometries around the metal atom, in which the aryl‐substituted diazosalicylate ligands are coordinated only through the oxygen atoms of carboxylate groups, either in an anisobidentate or isobidentate mode; meanwhile, the 2‐hydroxy groups of the monoanionic ligand (HLXASA)? are involved only in intramolecular O‐H···O hydrogen bonds with the carboxylate function. In the crystal structures of 1 – 8 , the complex molecules are assembled by π‐stacking interactions giving mostly infinite 1D strands. The intermolecular binding in the solid state structures is accomplished by diverse additional non‐covalent contacts including C‐H···O, C‐H···N, C‐H···π, C‐H···Br, O···Br, Br···π and van der Waals contacts. Although the primary and secondary ligands in the Zn (II) complex series 1 – 6 carry different substituents at the periphery (X = H, Me, Cl, Br for (HLXASA)? and R = H, Me for 4‐Py‐R), five of the crystal structures were isostructural. Additionally, the antimicrobial activity of the pro‐ligands H2LXASA and their Zn (II), Cu (II) and Cd (II) compounds were studied in a comparative manner, showing high sensitivity (IZD ≥ 20) against Bacillus subtilis.  相似文献   

16.
Neutralization of 4‐[(2,2,3,3‐tetrafluoropropoxy)methyl]pyridine with hydrohalo acids HX (X = Cl and Br) yielded the pyridinium salts 4‐[(2,2,3,3‐tetrafluoropropoxy)methyl]pyridinium chloride, C9H10F4NO+·Cl, (1), and 4‐[(2,2,3,3‐tetrafluoropropoxy)methyl]pyridinium bromide, C9H10F4NO+·Br, (2), both carrying a fluorous side chain at the para position of the pyridinium ring. Single‐crystal X‐ray diffraction techniques revealed that (1) and (2) are isomorphous. The halide anions accept four hydrogen bonds from N—H, ortho‐C—H and CF2—H groups. Two cations and two anions form a centrosymmetric dimeric building block, utilizing complimentary N—H…X …H—Csp 3 connections. These dimers are further crosslinked, utilizing another complimentary Csp 2—H…X …H—Csp 2 connection. The pyridinium rings are π‐stacked, forming columns running parallel to the a axis that make angles of ca 44–45° with the normal to the pyridinium plane. There are also supramolecular C—H…F—C interactions, namely bifurcated C—H…F and bifurcated C—F…H interactions; additionally, one type II C—F…F—C halogen bond has been observed.  相似文献   

17.
利用水热法合成了两种过渡金属配合物为模板剂的含水硼酸盐晶体Co(en)3[B4O5(OH)4]Cl·3H2O(1) 和 [Ni(en)3][B5O6(OH)4]2·2H2O (2),并通过元素分析、X射线单晶衍射、红外光谱及热重分析对其进行了表征。化合物1晶体结构的主要特点是在所有组成Co(en)33+, [B4O5(OH)4]2–, Cl– 和 H2O之间通过O–H…O、O–H…Cl、N–H…Cl和N–H…O四种氢键连接形成网状超分子结构。化合物2晶体结构的特点是[B5O6(OH)4]–阴离子通过O–H…O氢键连接形成沿a方向有较大通道的三维超分子骨架,模板剂[Ni(en)3]2+阳离子和结晶水分子填充在通道中。  相似文献   

18.
The first products of reactions between (PyH)3MoX6 (PyH = pyridinium, C5H6N+; X = Cl, Br) and pyridine are trans-(PyH)MoCl4Py2 and trans-(Py)2HMoBr4Py2. Trans-(Py)2H MoCl4Py2 can be obtained from the cold solution of trans-(PyH)MoCl4Py2 in pyridine. NaBH4 suspended in the mixture of isopropanol and pyridine reduces WX4Py2 to trans-(Py)2HWX4Py2 (X = Cl, Br). Trans-(Py)2HMX4Py2 (M = Mo, W; X = Cl, Br) decompose at room temperature to trans-(PyH)MX4Py2. Four trans-(Py)2HMX4Py2 compounds are isostructural and three of them crystallize in the triclinic unit cell. Pairs of trans-(PyH)MCl4Py2 and (PyH)MBr4Py2 have nearly equal sequence of interplanar spacings. Crystal structure of trans-(Py)2HWCl4Py2 has been solved. The compound has a triclinic P1 space group with: a = 9.373(3), b = 9.563(3), c = 15.009(6) Å, α = 78.21(1), β = 77.94(2), γ = 78.63(2)° and Z = 2. Two independent WCl4Py2? groups are located on the symmetry center. Average W? Cl and W? N (pyridine) bond lengths are 2.435(5) and 2.18(2) Å. The cation (Py)2H+ contains a hydrogen bond between pyridinium ion and pyridine. The N? N distance is 2,76 Å. (PyH)MX4Py2 react with pyridine giving mer-MX3Py3 (M = Mo, W; X = Cl, Br).  相似文献   

19.
Synthesis, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analyses of the Tetrahalogeno‐bis‐Pyridine‐Osmium(III) Complexes cis ‐( n ‐Bu4N)[OsCl4Py2] and trans ‐( n ‐Bu4N)[OsX4Py2], X = Cl, Br By reaction of (n‐Bu4N)2[OsX6], X = Cl, Br, with pyridine and (n‐Bu4N)[BH4] tetrahalogeno‐bis‐pyridine‐osmium(III) complexes are formed and purified by chromatography. X‐ray structure determinations on single crystals have been performed of cis‐(n‐Bu4N)[OsCl4Py2] ( 1 ) (triclinic, space group P1, a = 9.4047(9), b = 10.8424(18), c = 17.007(2) Å, α = 71.833(2), β = 81.249(10), γ = 67.209(12)°, Z = 2), trans‐(n‐Bu4N)[OsCl4Py2] ( 2 ) (orthorhombic, space group P212121, a = 8.7709(12), b = 20.551(4), c = 17.174(4) Å, Z = 4) and trans‐(n‐Bu4N)[OsBr4Py2] ( 3 ) (triclinic, space group P1, a = 9.132(3), b = 12.053(3), c = 15.398(2) Å, α = 95.551(18), β = 94.12(2), γ = 106.529(19)°, Z = 2). Based on the molecular parameters of the X‐ray structure determinations and assuming C2 point symmetry for the anion of 1 and D2h point symmetry for the anions of 2 and 3 the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants of 1 are in the Cl–Os–Cl axis fd(OsCl) = 1.58, in the asymmetrically coordinated N′–Os–Cl · axes fd(OsCl · ) = 1.45, fd(OsN′) = 2.48, of 2 fd(OsCl) = 1.62, fd(OsN) = 2.42 and of 3 fd(OsBr) = 1.39 and fd(OsN) = 2.34 mdyn/Å.  相似文献   

20.
Two trinuclear CoII and ZnII complexes, [(CoL)2(OAc)2Co] and [(ZnL)2(OAc)2Zn], with an asymmetric Salen‐type bisoxime ligand [H2L = 4‐(N,N‐diethylamine)‐2,2′‐[ethylenediyldioxybis(nitrilomethylidyne)]diphenol] were synthesized and characterized by elemental analyses, IR, UV/Vis, and fluorescent spectroscopy. The crystal structures of the CoII and ZnII complexes were determined by single‐crystal X‐ray diffraction methods. The CoII atom is pentacoodinated by N2O2 donor atoms from the (L)2– unit and one oxygen atom from the coordinated acetate ion, resulting in a trigonal bipyramid arrangement. With the help of intermolecular hydrogen bonding C–H ··· O and C–H ··· π interactions, a self‐assembled continual zigzag chain‐like supramolecular structure is formed. The ZnII atom is pentacoodinated by N2O2 donor atoms from the (L)2– unit and one oxygen atom from the coordinated acetate ion, resulting in an almost regular trigonal bipyramid arrangement. A self‐assembled continual 1D supramolecular chain‐like structure is formed by intermolecular hydrogen bonding C–H ··· O and C–H ··· π interactions. Additionally, the photophysical properties of the CoII and ZnII complexes were discussed.  相似文献   

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