научный журнал по химии Координационная химия ISSN: 0132-344X

DU J.L., LI L.W., LI S.H., LIU S.Y., WANG L.W., WANG S.X., ZHANG F.F., ZHANG J.C., ZHOU G.Q. — 2014 г.

Three novel palladium(II) complexes [Pd(Phen)(Bzile)] (I), [Pd(Phen)(p-mBzile)] (II), and [Pd(Phen)(p-NBzile)] · H2O (III), where Bzile = N-benzoyl-L-isolecine), p-MBzile = N-(p-methylbenzoyl)-L-isolecine), p-NBzile = N-(p-nitrobenzoyl)-L-isolecine), have been synthesized and characterized by elemental analysis, ES-MS, and IR. The crystal and molecular structure of the complex II has been determined by single crystal X-ray diffraction. The cytotoxicity was tested against carcinoma cell lines: KB, BGC-823, Bel-7402 and HL-60 by MTT assay. The results indicated that these complexes exerted cytotoxicity, but none of them showed higher cytotoxicity than cisplatin. The cytotoxicity against HL-60, BGC-823, Bel-7402 and KB cell lines decreases in the sequence: p-MBzile > Bzile > p-NBzile. It suggests that the acylated groups have important impact on the cytotoxicity of complexes.

CHANG H.S., LIU W., XU W., ZHENG Y.Q. — 2014 г.

A new coordination polymer of terbium tartrate [Tb(H2O)3(C4H5O6)(C4H4O6)] has been synthesized and crystallizes in the polar space group P41 with cell constants a = 6.0415(9), b = 6.0415(9), c = 36.516(7) A, V = 1332.8(4) A3, Z = 4. The terbium(III) ion of title complex is nine-coordinate through oxygen donors. Four different coordination modes of tartrate occur. This Tb(III) complex exhibits a characteristic luminescence in the visible region upon excitation at 353 nm. The temperature-dependent magnetic properties of the Tb(III) complex were investigated in the temperature range of 2–300 K. Title compound exhibits significant ferroelectric properties at room temperature (remnant polarization 2Pr = 0.160 C cm-2, coercive field 2Ec = 44.5 kV cm-1, saturation of the spontaneous polarization Ps = 0.176 C cm-2).

XU X.J. — 2014 г.

From hydrothermal treatment of benzene-1,2-diamine, pyrocatechol, and MoO3 in acetic acid solution, a new compound, [ ] · (C8H9N2)2 · 2H2O (I), constructed from pyrocatechol chelated dinuclear molybdenum units and 2-methylbenzimidazole has been synthesized. Single-crystal structure analysis reveals that the compound crystallizes in the monoclinic space group P21/c with a = 23.365(2), b = 7.2214(5), c = 19.3021(16) A, = 97.929(4), V = 3225.6(5) A3, Z = 4, M = 808.46, = 1.665 g/cm3, = 0.84 mm-1, F(000) = 1608, the final R = 0.0622 and wR = 0.1484 for 7385 independent reflections with Rint = 0.0393. Interestingly, an in situ condensation between acetic acid and benzene-1,2-diamine has occurred, and the unexpected 2-methyl-1-H-benzo[d] imidazoles serve as counterions and N–H donors to form stable hydrogen-bond network in the crystal. Furthermore, intermolecular hydrogen bonds are found among the cations, anions and crystalline water molecules. The double nuclear molybdenum units are connected by O–H···O hydrogen bonds with the crystalline water molecules to form one-dimensional chains, and the chains are further joined together by N–H···O to form a quasi-two dimensional structure.

ATAKOL A., ATAKOL O., ERGUN U., KUBRA INAL E., OZ S., SVOBODA I., YAKUT M., YLMAZ N. — 2014 г.

1,3-Propanediamine was put to react with 2-hydroxybenzaldehyde and 2-hydroxyacetophenone sequentially in aprotic medium. The crystalline product was examined by high performance liquid chromatography. The composition was 66% asymmetric Schiff base N(2-hydroxybenzylidene)-N(2-hydroxyacetophenone)-1,3-propanediamine (SALLACH2) and 33% bis-N,N(2-hydroxyacetophenylidene)-1,3-propanediamine (LACH2). As the crystals were uniform and of appropriate size, the molecular model of the material was revealed by X-ray diffraction. It was seen that two molecules of SALLACH2 and one molecule of LACH2 formed the mixed crystals. The substance was separated to its components and the asymmetric Schiff base was purified with a silica column. The substance was characterized with elemental analysis, FT-IR, MS, 1HNMR, and 13CNMR. In addition, six tri-nuclear complex with the nuclear structure of NiII NiII NiII, NiII CuII NiII, NiII MnII NiII were prepared from this Schiff base and stoichiometry was determined by elemental analysis, FT-IR and thermogravimetry. Finally, the molecular structures of two complexes were brought to light by XRD which highlights the asymmetry of the ligand more clearly.

CHEN J., HUANG Q., WANG J.J., ZHANG Y.J. — 2014 г.

Two new chelating radical ligands, NITphtrz (4,4,5,5-tetramethyl-2-(2-phenyl-1,2,3-triazole-4-yl)imidazoline-1-oxyl-3-oxide) and IMphtrz (4,4,5,5-tetramethyl-2-(2-phenyl-1,2,3-triazole-4-yl)imidazoline-1-oxyl), and their cobalt(II) complexes [Co(Hfac)2(NITphtrz)] (I) and [Co(Hfac)2(IMphtrz)] (II) (Hfac = hexafluoroacetylacetonate) have been prepared and characterized by IR, magnetic, and single-crystal X-ray analysis. The magnetic behaviors of the lignad NITphtrz and complex I have been discussed.

AHMAD S., AHMAD T., LEE S.C., MAHMOOD R. — 2014 г.

Two copper(I) iodide complexes, [Cu4(Metu)6I4] (I) and [Cu8(Diaz)12I8] (II) (Metu = N-methylthiourea; Diaz = 1,3-diazinane-2-thione), have been prepared and their structures been determined by X-ray crystallography. The crystal structures show that complex I is a tetranuclear, while II is an octanuclear cluster, both having a Cu : S ratio of 2 : 3, characteristic of metallothioneins. In I, each of the four copper atoms is coordinated to three thiourea ligands and one iodide ion in a distorted tetrahedral mode adopting admantane-like structure. In II, four types of core arrangements are observed around copper(I), which include, , , , and each having copper(I) tetrahedrally coordinated. The complexes were also characterized by IR and 1H and 13C NMR spectroscopy.

WANG F.M. — 2014 г.

Reaction of molybdenyl(IV) oxide bis(2,4-pentanedionate) with N-(3-ethoxy-2-hydroxybenzylidene)-2-methoxybenzohydrazide in methanol affords a mononuclear dioxomolybdenum(VI) complex containing MoO5N basic core. The complex has been characterized by various physicochemical techniques (IR and elemental analysis), and single crystal X-ray diffraction. X-ray crystal structure determination reveals that the complex crystallizes as monoclinic space group P21/c, with unit cell dimensions a = 9.251(1), b = 11.910(2), c = 17.636(3) A, = 103.220(2)°, V = 1891.7(5) A3, Z = 4, R1 = 0.0693, wR2 = 0.1691. The Mo atom in the complex is octahedrally coordinated, with the tridentate ONO ligand occupying the meridional sites. Thermal stability analysis was performed. The complex shows high catalytic property for the oxidation of various olefins.

GAO L. — 2014 г.

Reaction of Hg(NO3)2 with 4 equivalent KI in water afford K2[HgI4]. By using K2[HgI4] as the precursor, three new heterobimetallic compounds [Ni(N-MeIm)6][HgI4] (I), [Co(N-MeIm)6][HgI4] (II), and [Cu(N-MeIm)6][HgI4] (III) have been characterized by elemental analysis, IR spectra, and the single-crystal X-ray crystallorgraphy analysis. Three complexes are isomorphous and crystallized in monoclinic symmetry space group P21/c. The coordination around each center metal(II) atom is octahedral with six nitrogen atoms of N-MeIm ligand. Each structure contains one tetrahedral [HgI4]2 as an anion to balance the charge of the molecular. Thermogravimetry analysis indicates these complexes have the similar departure process and cyclic voltammogram exhibits a significant pair of redox peaks.

WEI F.Y., WEN P.H. — 2014 г.

Two Schiff base iron(III) complexes, [FeL1(AHA)] · H2O (I) and [Fe(L2)2] · ClO4 (II), where AHA is the deprotonated form of acetohydroxamic acid, and L1 and L2 are the anionic form of N,N-bis(3-ethoxysalicylidene)propane-1,2-diamine and 2-[1-(2-aminopropylimino)ethyl]phenol, respectively, have been synthesized and characterized by physical chemical methods and single crystal X-ray diffraction. Crystallographic data for I: orthorhombic, space group Iba2, a = 20.781(3), b = 23.527(3), c = 10.071(2) A, V = 4923.7(12) A3, Z = 8, R1 = 0.0374, wR2 = 0.0900. Crystallographic data for II: triclinic, space group P , a = 12.748(1), b = 13.401(1), c = 19.007(1) A, = 106.623(2)°, = 97.462(2)°, = 112.543(2)°, V = 2784.9(4) A3, Z = 4, R1 = 0.0892, wR2 = 0.2434. X-ray crystal structural study indicated that the coordination environment around each Fe atom in the complexes is a six-coordinated distorted octahedron. The antibacterial activities of the complexes were assayed.

DAI C.H., MAO F.L. — 2014 г.

Two new Schiff-base cobalt(III) complexes, [CoL1(En)N3]Cl (I) and [CoL2N3(OH2)] (II), where L1, L2, and En are 2-[1-(2-aminoethylimino)ethyl]phenolate, bis(5-chlorosalicylidene)ethane-1,2-diamine, and 1,2-ethylenediamine, respectively, have been prepared and characterized by physicochemical methods and single crystal X-ray determination. Complex I crystallizes in monoclinic system space group P21/n with a = 7.113(1), b = 21.385(1), c = 10.599(1) A, = 106.067(2)°, V = 1549.2(3) A3, Z = 4, R1 = 0.0322, and wR2 = 0.0800. Complex II crystallizes in monoclinic system space group P21/c with a = 1.679(1), b = 11.145(1), c = 12.493(1) A, = 110.553(2)°, V = 1783.5(2) A3, Z = 4, R1 = 0.0360, and wR2 = 0.0838. Single crystal X-ray diffraction analysis reveals that the Co atoms in the complexes are six-coordinated in octahedral geometry. The complexes were screened in vitro for their antibacterial activity against Bacillus subtillis, Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruguinosa.

GAO R.M., GUO M.W., LI G., LI J. — 2014 г.

By employing a newly designed ligand, 2-(p-tert-butylphenyl)-1H-imidazole-4,5-dicarboxylic acid (H3BuPhIDC) to react with manganese(II) or nickel(II) ions, two coordiantion polymers [Mn2( 3-HBuPhIDC)2(CH3OH)2] (I) and [Ni( 2-HBuPhIDC)(H2O)2] (II) have been solvothermally synthesized and structurally characterized by elemental analyses, IR spectroscopy, and single crystal X-ray diffraction. Polymer I shows a 3D framework bearing 1D octagonal channels constructed from left- and right-handed helical chains. Polymer II exhibits an infinite chain structure, which are joined through the interactions and intramolecular hydrogen bonds to form a 3D architecture. The thermal properties of the polymers have been investigated as well. The coordination ability and modes of H3BuPhIDC have been investigated from both theoretical and experimental aspects.

HUANG D., LI Y.N., QIAN S.S., WANG Y.N., YOU Z.L., ZHEN M.M., ZHU H.L. — 2014 г.

Reaction of [MoO2(Acac)2] (Acac = acetylacetonate) with two similar hydrazone ligands in methanol yielded two mononuclear molybdenum(VI) oxocomplexes with general formula [MoO2(L)(CH3OH)], where L = L1 = (4-nitrophenoxy)acetic acid [1-(3-ethoxy-2-hydroxyphenyl)methylidene]hydrazide (H2L1) and L = L2 = (4-nitrophenoxy)acetic acid [1-(5-bromo-2-hydroxyphenyl)methylidene]hydrazide (H2L2). Crystal and molecular structures of the complexes were determined by single crystal X-ray diffraction method. All investigated compounds were further characterized by elemental analysis and FT-IR spectra. Single crystal X-ray structural studies indicate that the hydrazone ligands coordinate to the MoO2 cores through enolate oxygen, phenolate oxygen, and azomethine nitrogen. The Mo atoms in both complexes are in octahedral coordination.

JIANG C., JIANG X., LIAO G., XIA H. — 2014 г.

Two new one-dimensional coordination polymers: {[Cu(L1)(H4TTHA)] · H2O}n (I), {[Cu2(L2)2(H4TTHA)2] · 10H2O}n (II) (L1 = 1,3,10,12,15,18-hexaazatetracyclodocosane; L2 = 3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane), based on a flexible hexapodal ligand H6TTHA (1,3,5-triazine-2,4,6-triamine hexaacetic acid), have been synthesized and structure characterized. Single-crystal X-ray diffraction analyses indicated that the central metal atom displays distorted six-coordinate octahedral coordination geometry by coordination with four nitrogen atoms of L1 or L2, and two oxygen atoms of H6TTHA liagand. Both of the compounds show one-dimensional chain structures, which are constructed of [Cu(L)]2+ and [H4TTHA]2 anion with 1 : 1 ratio. Interestingly, the nature of the macrocycle influences the structure of the coordination polymer produced with H6TTHA for each of the two compounds. TG, IR, PXRD, and photoluminescent of the compounds are investigated.

LIANG P., PENG C.H., TIAN W.M., WEI C.Y., XIAO H., YIN X.H. — 2014 г.

The synthsis, crystal structure, thermal analysis and spectroscopic studies of two novel zinc(II) coordination polymers Zn4(NA)4Dpa)2 (I) and Zn(Inic)(Bpdc)0.5 (II) (NA = niacin, Inic = isonictinic acid, Dpa = 2,2-biphenyldicarboxylate, Bpdc = 4,4-biphenyldicarboxylate) are presented here. The crystal structure of I is a two-dimensional network whose tetranuclear unit is a slightly distorted square. Two kinds of ligand connect adjacent zinc(II) ions, respectively, in a coordinate direction. The structure of II is a three-dimensional and it consist of corrugated square layers of isonictinic acid–bridged zinc(II) ions which are pillared by 4,4-biphenyldicarboxylate. The rod-ligands in II appear as useful tools to control the interlayer metal–metal separation. Each zinc(II) ion in I and II is four-coordinated with three oxygen atoms and one nitrogen atom building distorted tetrahedron environments.

CHENG G.P., XUE L.W., ZHANG C.X. — 2014 г.

The Schiff base 2-bromo-6-[(2-isopropylaminoethylimino)methyl]phenol (HL), derived from 3-bromosa-licylaldehyde with N-isopropylethane-1,2-diamine, and its zinc(II) and nickel(II) complexes [Zn(HL)2(NCS)2] (I) and [Ni(HL)2(N3)2)] · 0.25H2O (II) have been prepared and characterized by elemental analyses, IR, and single crystal X-ray crystallographic determination. The crystal of I is orthorhombic: space group Pbca, a = 13.6928(9), b = 9.7203(6), c = 22.926(1) A, V = 3051.4(3) A3, Z = 4. The crystal of II is triclinic: space group P–1, a = 8.0212(7), b = 12.744(1), c = 15.590(2) A, = 104.802(3)°, = 90.561(3)°, = 103.130(3)°, V = 1496.6(2) A3, Z = 1. The zwitterionic Schiff base ligands coordinate to the metal atoms through phenolate O, imine N, and amine N atoms. Each metal atom in the complexes is in octahedral coordination. The effect of these complexes on the antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Candida albicans were studied.

ГЕРАСИМЕНКО А.В., ЗАЕВА А.С., ИВАНОВ А.В. — 2014 г.

При взаимодействии [Cd2{S2CN(CH2)6}4] (I) с морфолином выделен кристаллический аддукт N,N-цикло-гексаметилендитиокарбамата кадмия, [Cd{NH(CH2)4O}2{S2CN(CH2)6}2] (II), внутренняя сфера которого включает две молекулы донорного основания. Структурная организация и термическое поведение II изучено методами РСА и синхронного термического анализа в сравнении с исходным биядерным комплексом кадмия I. Комплексообразователь (КЧ 6) координирует две молекулы морфолина и два структурно-эквивалентных S,S-анизобидентатных лиганда HmDtc, образуя хромофор [CdN2S4] со строением искаженного октаэдра. Термическая деструкция II протекает в два этапа и включает последовательные стадии диссоциации связей Cd–N с последующей десорбцией морфолина и термолиза дитиокарбаматной части аддукта с образованием CdS в качестве конечного продукта. Для корректного сопоставления геометрических характеристик I и II уточнена структура биядерного [Cd2{S2CN(CH2)6}4].

ИЛЮХИН А.Б., ПЕТРОСЯНЦ С.П. — 2014 г.

Синтезированы и структурно охарактеризованы ассоциаты тиоцианата иттрия [Y(H2O)5(NCS)3] · H2O с 4,7-фенантролином (4,7-Phen). В присутствии 4,7-Phen происходит преимущественное образование мономерных комплексов иттрия: [Y(H2O)7(NCS)](NCS)2 · 5(4,7-Phen) · 5(H2O), [Y(H2O)5(NCS)3] · 2(4,7-Phen) · 2(H2O), {H(4,7-Phen)}2[Y(H2O)7(NCS)](NCS)4 · 2(4,7-Phen) · 5(H2O). В ассоциатах отсутствует контакт дитопных молекул с иттрием; стекинг-взаимодействие объединяет молекулы 4,7-Phen в стопки.

ВЛАСЕНКО В.Г., КОГАН В.А., ЛЕВЧЕНКОВ С.И., ЛУКОВ В.В., ПОПОВ Л.Д., СУПОНИЦКИЙ К.Ю., ЦАТУРЯН А.А., ЩЕРБАКОВ И.Н. — 2014 г.

Синтезирован биядерный комплекс меди(II) состава [Cu2L(CH3COO)] (I), где L3 – трианион азометина на основе 1-фенил-3-метил-4-формилпиразолона-5 и 1,3-диаминопропанола-2, а также его ДМСО-аддукт (II), в котором молекула ДМСО выполняет функцию дополнительного мостикового лиганда. Структура комплекса II установлена методом РСА, структурные параметры хелатных узлов комплекса I определены методом EXAFS спектроскопии. Показано, что 2-координация молекулы ДМСО в II приводит к смене знака параметра обменного взаимодействия. В комплексе I между ионами меди(II) реализуется обменное взаимодействие антиферромагнитного (2J = –169 см-1), в комплексе II – ферромагнитного типа (2J = 174 см-1). С помощью квантово-химических расчетов параметров магнитного обмена методом теории функционала плотности в рамках подхода “нарушенной симметрии” показано, что роль молекулы ДМСО как “переключателя” характера обменного взаимодействия состоит исключительно в стабилизации “искаженной” конформации металлоциклов.

ГОЛУБНИЧАЯ М.А., КАМАЛОВ Г.Л., КОЦЕРУБА В.А., ЛЕВЧЕНКО О.А., НЕФЕДОВ С.Е., НЕФЕДОВА И.В., УВАРОВА М.А., ЧИХИЧИН Д.Г. — 2014 г.

Основным продуктом окисления кислородом воздуха при комнатной температуре смеси комплекса состава (СоII)3( -OOCBut)6(NEt3)2 и дибензилового эфира (DBE) в растворе дихлорметан–бензол (4 : 1) является гексаядерный комплекс [(CoIII)6( 4-O)2( 3-O)2( -OOCBut)9(OH)2(HOOCBut)](HNEt3) · 0.5DBE · C6H6 (I). Mеталлоостов I, по данным РСА, содержит псевдокубановый фрагмент [Co4( 4-O)2( 3-O)2], связанный с двумя “периферийными” ионами кобальта(III). Обсуждаются возможность функционирования полученного комплекса в качестве интермедиата-катализатора жидкофазного окисления DBE и особенности конформационных изменений в молекуле DBE, обусловленные характером адаптации последней соответствующим металлокомплексом.

АБХАИРОВА С.В., КОННИК О.В., МЕШКОВА С.Б., МИНИН В.В., РУСАНОВ Э.Б., ШУЛЬГИН В.Ф. — 2014 г.

Синтезированы и исследованы методами ИК-спектроскопии и термогравиметрии координационные соединения состава LnL3 · Phen (Ln = Nd, Sm, Eu, Gd, Tb, Dy, Yb; HL = 3-метил-1-фенил-4-формилпиразол-5-он, Phen = 1,10-фенантролин). Структура комплекса состава TbL3 · Phen изучена методом РСА. Координационный полиэдр тербия – искаженная квадратная антипризма, построенная шестью атомами кислорода трех анионов 4-формил-5-пиразолона и двумя атомами азота молекулы 1,10-фенантролина. Поликристаллические образцы исследованных комплексов излучают в характерных для Ln(III) областях спектра.