Syntheses and characterization of three mercury(II) complexes, [Hg(phen)2(SCN)2], [Hg(2,2′-bipy)2(SCN)2] and [Hg(phen)2(NO3)2], thermal and fluorescence studies

Mercury(II) complexes of 1,10-phenanthroline (phen) and 2,2′-bipyridine (bipy), [Hg(phen)₂(SCN)₂] (1), [Hg(2,2′-bipy)₂(SCN)₂] (2) and [Hg(phen)₂(NO₃)₂] (3) have been synthesized and characterized by elemental analysis, IR, ¹H NMR and ¹³C NMR spectroscopy. The thermal stability of 1–3 were studied by thermal gravimetric (TG) and differential thermal analyses (DTA). The structure of 1 has been confirmed by X-ray crystallography. The complex is a monomer and the Hg atom has an unsymmetrical six-coordinate geometry, formed by four nitrogen atoms of the two phen ligands and two sulfur atoms of the two thiocyanate anions. Solid-state luminescent spectra of phen, 2,2′-bipy and 1–3 indicate emission with the maximum intensity at ca 467 nm upon excitation at 295 nm.     

Synthesis and characterisation of [tris(1,3-dithiole-2-thione-4,5-dithiolato)-stannate]2−, [Q]2[Sn(dmit)3], [tris(1,3-dithiole-2-one-4,5-dithiolato)stannate]2−, [Q]2[Sn(dmio)3] and [tris(1,3-dithiole-2-thione-4,5-selenolato)stannate]2−, [Q]2[Sn(dsit)3], complexes: Analysis of the structural variations of the [Sn(dmit)3]2− and [Sn(dmio)3]2− dianions

[Tris(1,3-dithiole-2-thione-4,5-dithiolato)stannate]²⁻, [Q]₂[Sn(C₃S₅)₃], [tris(1,3-dithiole-2-one-4,5-dithiolato)stannate]²⁻, [Q]₂[Sn(C₃S₄O)₃], and [tris(1,3-dithiole-2-thione-4,5-diselenolato)stannate]²⁻ [Q]₂[Sn(C₃S₃Se₂)₃], complexes, have been synthesised and characterised. Crystal structure determinations of [Q]₂[Sn(C₃S₅)₃] (Q=1,4-dimethylpyridinium, monoclinic and orthorhombic forms; NMe₄, NEt₄, and PPh₄) and [NEt₄]₂[Sn(C₃S₄O)₃] revealed variations in the overall dianion structures. The geometry about tin in each case is essentially octahedral with the chelate bite angles in the range 80.7(5)–87.45(4)°: the range of Sn–S distances is 2.5207(18)–2.571(17) Å. A statistical analysis, carried out on the crystal structure data for the six complexes, indicated that the most critical factors in controlling the overall shape of the dianion were the distances of the Sn atom from the dithiolate ligand planes [Sn–OOP]. Interanionic S⋯S interactions, within the sum of the van der Waals’ radii for two S atoms, are affected by the size of the cation, Q; the secondary connectivity is 3-dimensional for the smallest cations, Q=1,4-dimethylpyridinium and NMe₄, in chains for the somewhat larger cation, NEt₄ and is absent for the still larger, PPh₄ cation.     

Reactions of [WI2(CO)(NCMe)(η2-RC2R)2] (R = Me or Ph) with carbon monoxide to give either [WI2(CO)2(η2-MeC2Me)2] or [W(-I) I(CO) (η2-PhC2Ph)2]2. Crystal structure of [WI2(CO) 2( η2-MeC2Me)2]

The complexes [WI₂(CO)(NCMe)(η2)-RC₂R)₂] (R = Me and Ph) react in CH₂Cl₂ with an excess of carbon monoxide to give initially the acetonitrile substituted products [WI₂(CO)₂(η²-RC₂R) ₂]. For R= Me, the complex [WI₂(CO)₂(η²- MeC₂Me)₂] (1) was isolated and its structure determined by X-ray crystallography. However, for R = Ph, dimerisation occurs to give the iodide-bridged compound [W(μ-I)I(CO)(η²-PhC₂Ph)₂]₂ (2) with loss of carbon monoxide. These reactions are reversible as 1 and 2 react with acetonitrile to give [WI₂(CO)(NCMe)(η²-RC₂R)₂]. The ¹³C NMR spectra of I and 2 indicate that the two alkyne ligands donate a total of six electrons to the tungsten in these complexes.     

微量热法研究 [Cu(phen)2]~(2 )、[Cu(bpy)_2]~(2 )与DNA的作用

用微量热法对菲咯啉合铜（ [Cu(phen)2]2＋）和联吡啶合铜（ [Cu(bpy)2]2＋）与小牛胸腺 DNA的相互作用进行了研究,依据 McGhee-Von Hippel邻近排斥方程确定了结合反应的平衡常数 K、结合位点距离 n及热力学参数Δ rHm、Δ rGm和Δ rSm。结果表明这两种铜的配合物与 DNA之间均可形成稳定的三元配合物,且反应为熵驱动过程, DNA与这些配合物的键合过程中同时存在插入和静电作用两种模式,插入作用的强弱与金属配合物中配体的平面性质有关。     

Ring and Cluster Structures of {Li[C(NtBu)2(HNtBu)]}2·(THF) and {Li2[C(NtBu)3]}2, Containing the Novel Anions [C(NtBu)2(HNtBu)]−- and [C(NtBu)3]2−

The reaction of tert.-butyl carbodiimide with one equivalent of LiNH^tBu in tetrahydrofuran at-78 °C produces {Li[C(N^tBu)₂(HN^tBu)]}₂-(THF) (1), which is an eight-membered Li₂C₂N₄ ring; the deprotonation of (1) with two equivalents of n-BuLi in tetrahydrofuran at -78 °C and recrystallisation of the product from n-pentane yielded the unsolvated dimer {Li₂[C(N^tBu)₃]}₂ (2), which adopts the structure of a distorted hexagonal prism.     

The coordination chemistry of mono and bis(di-2-pyridylamine)copper(II) complexes: preparation,characterization and crystal structures of [Cu(L)(NO2)2], [Cu(L)(H2O)2(SO4)], [Cu(L)2(NCS)](SCN)·0.5DMSO and [Cu(L)2(SCN)2]

The crystal structures of two mono(dpyam)copper(II) complexes, [Cu(dpyam)(NO₂)₂] (1) and [Cu(dpyam)(H₂O)₂(SO₄)] (2) and two dithiocyanate compounds containing bis(dpyam)copper(II) units, [Cu(dpyam)₂(NCS)](SCN)·0.5DMSO (3) and [Cu(dpyam)₂(SCN)₂] (4) have been determined by X-ray crystallography. The second orthorhombic form of the monomeric Cu(II) complex 1 was obtained by the reaction of di-2-pyridylamine (dpyam) with CuCl and NaNO₂ in water–methanol solution. Each copper(II) ion in 1 exhibits a tetrahedrally-distorted square base of the CuN₂O₂ chromophore, with off-the-z-axis coordinated nitrito groups weakly bound in approximately axial positions. Complex 2 is an example of a polymeric copper(II) derivative containing the bidentate bridging sulfate ligand in the long-bonded axial positions. Each copper(II) ion in 2 shows an elongated tetragonal octahedral stereochemistry. The CuN₄N′ chromophore of 3 involves a square-based pyramidal structure, slightly distorted towards a trigonal bipyramidal stereochemistry, τ=0.13. One of the SCN⁻ anions is bonded to the copper(II) ion via the N atom in the axial position of the square pyramid. Complex 4 is centrosymmetric and octahedrally elongated, with the SCN⁻ anions coordinating in axial positions via the S atom. The structures of complexes 1–4 and their ESR and electronic reflectance spectra are compared with those of related complexes.     

Disordered Crystal Structure of Bis[(2.2.2-Cryptand)Sodium] Bis[Aqua(Isothiocyanato)(μ-Isothiocyanato)Sodium] 2[Na(2.2.2-Crypt)]+ · [Na2(NCS)2(μ-NCS)2(H2O)2]2–

Crystals of bis[(2.2.2-cryptand)sodium] bis[aqua(isothiocyanato)(-isothiocyanato)sodium]: 2[Na(C₁₈H₃₆N₂O₆)]⁺ · [Na₂(NCS)₂(-NCS)₂(H₂O)₂]^2– (I) were synthesized and studied by X-ray diffraction analysis. The disordered structure of I (a = 12.715 Å, b = 10.458 Å, c = 21.767 Å, = 102.56°, space group P2₁/n) was solved by the direct method and refined by the full-matrix least-squares method in anisotropic approximation to R = 0.058 from 3896 independent reflections (CAD4 automated diffractometer, MoK ). The crystal consists of two complex ions [I¹]⁺ and [I²]^2– (molar ratio 2 : 1). The Na⁺ cation of the host–guest cation I¹ is coordinated by all eight heteroatoms (6O + 2N) of the cryptand ligand. The coordination polyhedron of this Na⁺ cation is a distorted cube. The atoms of two groups (CH₂–CH₂ and CH₂–O–CH₂–CH₂) in the cryptand ligand are disordered over two positions. The independent cation Na⁺ of the centrosymmetric binuclear complex anion I² is coordinated by one bifurcated O atom of the disordered water molecule and by three N atoms of the SCN^– ligands (including two bridging ligands). The coordination polyhedron of this Na⁺ caiotn is a distorted tetrahedron. The complex ions in the crystal structure of I are united by hydrogen bonds.     

[Ni(cien)2]2[Mn(NCS)6]·H2O的合成、晶体结构

硫氰酸根的结构为N三C-S-,其两端的N原子和S原子分别有一对和三对孤对电子,因此,硫氰酸根可采用多种不同的配位模式与金属离子发生配位.硫氰酸根可作为单齿配体与一个金属离子配位,形成M-SCN或M-NCS的单核配合物,也可以作为桥联配体同时与两个、三个甚至四个金属离子配位形成多核配合物[1-3];另一方面,硫氰酸根是一个具有一定共轭性的偶极子,可传递磁相作用.因此,选择硫氰酸根作为桥联配体,将多个顺磁金属离子桥联形成一维、二维或三维结构的多核金属配合物分子,并研究它们的磁性已成为分子磁学的一个研究领域[4-6].本文仅报道标题配合物的合成与晶体结构.     

Palladium(II) saccharinate complexes trans-[Pd(sac)2(LH)2] with amino- and acetylamino-pyridine co-ligands: molecular structures of trans-[PdCl2(2-ampyH)2].2dmf (2-ampyH = 2-amino-3-methylpyridine) and trans-[Pd(κ2-2-acmpy)2] (2-acmpyH = 2-acetylamino-3-methylpyridine)

Reaction of Na₂[PdCl₄] with two equivalents of amino- or acetylamino-pyridines (LH) affords trans-[PdCl₂-(LH)₂] {LH = 2-amino-3-methylpyridine (2-ampyH), 3-aminopyridine (3-apyH), 2-acetylamino-3-methylpyridine (2-acmpyH), 3-acetylamino-pyridine (3-acpyH)}. An X-ray crystal structure of trans-[PdCl₂(2-ampyH)₂] shows that the 2-ampy-H ligands are coordinated in a monodentate fashion via the nitrogen atoms of the pyridine rings. Treatment of trans-[PdCl₂(2-acmpyH)₂] with NEt₃ affords the cyclometalated complex, trans-[Pd(κ²-2-acmpy)₂], the X-ray structure of which shows that the 2-acmpy ligand is coordinated to palladium in a bidentate fashion via the nitrogen atom of the pyridine ring and oxygen. Reaction of trans-[PdCl₂(LH)₂] with two equivalents of sodium saccharinate affords the bis(saccharinate) complexes, trans-[Pd(sac)₂(LH)₂], in which the saccharinate anions are coordinated via the amide nitrogen atom.     

The reaction of Sn[CH(SiMe3)2]2 with ethyne: formation of (HCC)Sn[CH(SiMe3)2]2(μ-trans-CHCH)Sn[CH-(SiMe3)2]2(CHCH2)

The reaction of Sn[CH(SiMe₃)₂]₂ and ethyne at ambient temperature affords a mixture of products, from which the title compound has been separated and identified by IR, ¹H, and ¹³C NMR spectroscopy.     

Synthesis and structures of two uranyl β-diketonate complexes [UO2(DBM)2(DEDPU)] and [UO2(PMBP)2(DEDPU)]

Two new uranyl β-diketonate complexes [UO₂(DBM)₂(DEDPU)] (1) and [UO₂(PMBP)₂(DEDPU)](CH₃C₆H₅)_0.5 (2), (HDBM?=?dibenzoylmethane, HPMBP?=?1-phenyl-3-methyl-4-benzoyl-5-pyrazolone, DEDPU?=?N,N′-diethyl-N,N′-diphenylurea) were synthesized and characterized. The coordination geometries of the uranyl atoms in 1 and 2 are distorted pentagonal bipyramidal, coordinated by one oxygen atom of DBDPU molecule and four oxygen atoms of two chelating DBM molecules in 1 and PMBP molecules in 2.     

[Phthalocyaninato(2–)]­antimony(III) chloride

The title antimony(III) complex, [Sb(C₃₂H₁₆N₈)]Cl or [SbPc]Cl (where Pc = C₃₂H₁₆N₈²⁻), has been obtained from the reaction of pure powdered antimony with 1,2-di­cyano­benzene under a stream of ICl vapour. The asymmetric unit of this complex consists of an [SbPc]⁺ cation and a Cl⁻ anion. The phthalocyaninate residue [SbPc]⁺ is not planar. The Sb atom lies 1.057 (3) Å from the plane defined by the four iso­indole N atoms. A combination of ionic and donor–acceptor interactions links the [SbPc]Cl mol­ecules to form centrosymmetric [(SbPc)Cl]₂ pseudo-dimers in the crystal. The Sb—Cl distances in the pseudo-dimer are not equivalent [3.043 (2) and 3.201 (2) Å]. The pseudo-dimers are weakly linked through Cl⃛H—C_benzo interactions to form a three-dimensional network. As a result of these interactions, the four Sn—N_isoindole bond lengths in the [SbPc]⁺ residue are not equivalent and the symmetry of the Sb—N core is only close to C_s.     

CRYSTAL STRUCTURE OF [Et_4N]_2[Mo_2O_2(μ-S)_2(S_2)_2]

<正> [(C2H5)4N]2[Mo2o2S2(S2)2], Mr = 676. 74, monoclinic, P21/c, a = 13.510(2), b = 14.373(2), c=14. 777(3)(?), β = 97.53(2)°, V = 2844.7(9) (?)3, Z = 4, Dc= 1. 58g/cm3, μ(MoKα) = 13.0cm-1, F(000) = 1384, R =0. 033 for 1803 observed reflections. The structure contains discrete [Mo2O2S2(S2)2]2- anions and Et4N+ cations. The two oxygen atoms bonded to the Mo atoms are in cis-form with respect to the Mo2S2 bridging unit, with an average Mo- O distance of 1. 678 (?), The Mo…Mo distance is 2. 832(1)(?).     

THE PHENOMENON OF CONGLOMERATE CRYSTALLIZATION. PART 50. THE CRYSTALLIZATION BEHAVIOR OF [trans-Co(en)2(NO2)2]ClO4 (I), MESO-[Co-trans-Me-(N-Me-ETHYLENEDIAMINE)2-trans-(NO2)2]ClO4 (II), K[trans-Co(β-ALANINATO)2(NO2)2] (III) AND THE ISOLATION AND PARTIAL STRUCTURAL DESCRIPTION OF (H5O2)[trans-Co(β-ALANINATO)2(NO2)2] (IV)

Abstract

[trans-Co(en)₂(NO₂)₂]ClO₄ (I) crystallizes, at 22°C, from a deionized water solution, as a racemate, in space group P$1 (No. 2), with lattice constants: a = 6.581(2)Å, b = 8.274(1) Å, c = 12.660(3)Å, α = 77.28(2)Å, β = 76.58(2)°, γ = 75.20(2)° V = 638.71;ų and d(calc; MW = 370.59,z = 2) = 1.927gcm^?3. A total of 2233 data were collected over the range of 4° ≤ 2θ ≤ 50° of these, 1961 (independent and with I ≤ 3σ(I)) were used in the structural analysis. Data were corrected for absorption (μ = 15.989 cm^?1) and the relative transmission coefficients ranged from 0.6792 to 0.9874. The final R(F) and R≤(F) residuals were, respectively, 0.0738 and 0.0763. Two half cations are located at inversion centers; the anions are in general positions.

meso-[Co-trans-Me-(N-Me-ethylenediamine)₂-trans(NO₂)₂]ClO₄ (II) [(N-Meen) = N-methyl-ethylenediamine] crystallizes at 22°C, from a deionized water solution in space group Pbca (No. 61) with lattice constants: a = 16.882(5) Å, b = 11.990(3) Å, c = 15.017(5) Å; V = 3039.72 ų and d (calc;MW = 398.64, z = 8) = 1.742g cm^?3. A total of 5281 data were collected over the range of 4° ≤ 2θ ≤ 50° of these, 1779 (independent and with I ≤ 2.5σ(I) were used in the structural analysis. Data were corrected for absorption (μ = 13.501 cm^?1 and the transmission coefficients ranged from 0.7956 to 0.9947. The final refinement of the structure (anisotropic thermal parameters for the heavy atoms; idealized hydrogens for the cation) are R(F) = 0.045 and R_w (F) = 0.052). The -NO₂ ligands are trans to one another in the axial direction while the N-methyl groups are trans to one another across the basal plane. The cations are located in general positions and the torsional angles of the en rings are δ(N1-C1-C2-N2 = 52.0°) and δ(N3-C3-C4-C4 = 51.0°), in contrast with those of (I) which are of opposite helical chirality. This compound is one of two trans-Co(III)X₂ cations of which we are aware that, while sitting at a general position of the space group, has two ethytenediamine rings of the same helical chirality.

K[trans-Co(β-alaninato)₂(NO₂)₂] (III) obtained after several batches of crystals of (TV) had separated from the mother liquor (see Syntheses). (III) crystallizes at 22°C, in space group Cc (No. 9) with lattice constants: a = 12.385(6)Å, b=13.109(5)Å, c = 8.290(5)Å, β=115.19° V = 1217.97 ų and d(calc; MW = 366.22, z = 4) = 1.997 g cm^?3. A total of 1238 data were collected over the range of 4° ≤ 2θ 50° of these, 1016 (independent and with I ≤ 2.5σ(I) were used in the structural analysis. Data were corrected for absorption (μ 17.90cm^?1) and the transmission coefficients ranged from 0.5322 to 0.6627. The final R(F) and R_w (F) residuals were, respectively 0.020 and 0.022. Solution of the structure, using the first batch of crystals, proved that the compound isolated was the (H₅O₂)⁺ derivative (see below and Discussion). A later batch of crystals contained (III). We have previously observed the precipitation of hydronium salts, trapped by amine carboxylato salts of cobalt (see Discussion). The anions consist of two six-membered rings formed by the metal and two (O,N)-bound β-alaninato ligands; and, both have chair conformations.

(H₅O₂) [trans-Co(β-alaninato)₂(NO₂)₂] (IV) is the substance that first crystalized from an aqueous solution of (III) (see Experimental). It crystallizes, at 22°C, in space group Cc (No. 9) or C2/c (No. 15) with lattice constants: a=12.389(39)Å, b=13.120(11)Å, c=8.299(9) Å, β=115.09(19)° V=1221.72 ų and d(calc; MW=364.15, z=4) = 1.980 g cm^?3. An incomplete data set of 1592 reflections was collected over the range 4° ≤ 2θ ≤ 50° because the crystal decomposes in air due to rapid loss of water of crystallization, as shown by differential scanning calorimetry. 956 data were independent with I ≤ 2.5°(I) and were used in the structural analysis. Data were not corrected for absorption because of decomposition of the crystal. The final R(F) and R_w (F) residuals were, respectively, 0.14 and 0.16. To the precision of such a data set, the anions are identical with those found in (III); however the cation, which sits at an inversion center, consists of a proton sandwiched between the oxygens of two waters thus forming (H₅O₂)⁺ cations similar to those we have described in the past (see Refs. [15–18]).     

[Co(NioxH)2(PPh3)2]SiF5and [Co(NioxH)2(Thio)2]2SiF6· 3H2O Complexes: Synthesis and Structure

Compounds that form in the CoSiF₆· 6H₂O–NioxH₂–A–water–alcohol system, where A is thiourea (Thio) or triphenylphosphine (PPh₃) and NioxH₂is 1,2-cyclohexanedione dioxime, were synthesized and characterized by X-ray diffraction analysis. Crystal structures of the [Co(NioxH)₂(PPh₃)₂]SiF₅and [Co(NioxH)₂(Thio)₂]₂SiF₆· 3H₂O complexes were established. In octahedral Co(III) complexes, two radicals of 1,2-cyclohexanedione dioxime are bound by a hydrogen bond and are located in the equatorial plane. The intramolecular (– and H bonds) and intermolecular (C–H···F and H bonds) interactions in the crystal are discussed.     

Complexes [Cu(H2L)](NO3)2 and [Cu(H2L)Cl]2[CuCl2]Cl · 0.5H2O (H2L is chiral bis(menthane) propylenediaminodioxime): Synthesis and structure

The synthesis of the [Cu(H₂L)](NO₃)₂ complex (I) and of a mixed-valent complex [Cu(H₂L)Cl]₂[CuCl₂]Cl·0.5H₂O (II), where L is chiral bis(menthane) propylenediaminodioxime. According to the data of single-crystal X-ray diffraction analysis, compounds I and II have ionic structures. In complex cations, the Cu²⁺ ion coordinates four N atoms of tetradentate chelate ligand, namely, the H₂L molecule. The coordination surrounding of the Cu atom in I is a distorted square CuN₄, while in II, it is a distorted square pyramid CuN₄Cl. The complex anion [CuCl₂]^? in II has linear structure. The mutual arrangement of oxime groups in H₂L corresponds to amphi-configuration of a ligand and therefore, intramolecular hydrogen bond O...H-O are formed in H₂L. The complex cations in compound II are joined in dimers through hydrogen bonds Cl...H-O. The values μ_eff for I and II are equal to 1.82 and 2.82 μ_B, respectively.     

Synthesis and X-ray diffraction study of cs3[UO2(CH3COO)3]2[UO2(CH3COO)(NCS)2(H2O)] and Cs5[UO2(CH3COO)3]3[UO2(NCS)4(H2O)] · 2H2O

Cs₃[UO₂(CH₃COO)₃]₂[UO₂(CH₃COO)(NCS)₂(H₂O)] (I) and Cs₅[UO₂(CH₃COO)₃]₃[UO₂ (NCS)₄(H₂O)] · 2H₂O (II) have been synthesized via the reaction between uranyl acetate and cesium thiocyanate in aqueous solution. According to single-crystal X-ray diffraction data, both compounds crystallize in monoclinic system with the unit cell parameters a = 18.7036(5) Å, b = 16.7787(3) Å, c = 12.9636(3) Å, β = 92.532(1)°, space group C2/c, Z = 4, R = 0.0434 (I); and a = 21.7843(3) Å, b = 24.6436(5) Å, c = 13.1942(2) Å, β = 126.482(1)°, space group Cc, Z = 4, R = 0.0273 (II). Uranium-containing structural units of compound (I) are mononuclear [UO₂(CH₃COO)₃]^? and [UO₂(CH₃COO)(NCS)₂(H₂O)]^? moieties, which correspond to the AB ₃ ⁰¹ and AB⁰¹M ₃ ¹ crystallochemical groups (A = UO ₂ ²⁺ , B⁰¹ = CH₃COO^?, M¹ = NCS^? and H₂O). The structure of compound II is built of [UO₂(CH₃COO)₃]^? and [UO₂(NCS)₄(H₂O)]^2? complexes, which belong to the AB ₃ ⁰¹ and AM ₅ ¹ crystallochemical groups, respectively. Uranium-containing complexes in both structures are linked into a framework by hydrogen bonds and electrostatic interactions with cesium cations. The IR spectra of compounds I and II agree well with X-ray diffraction data.