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RESEARCH PRODUCT
Non-Isomorphic Chlorine—Bromine Substitution in the Copper(I) Halideπ-Complexes with 1-Allyl-4-aminopyridinium
Evgeny GoreshnikM. G. Mys'kivDieter Schollmeyersubject
chemistry.chemical_classificationHydrogen bondLigandchemistry.chemical_elementOnium010402 general chemistry010403 inorganic & nuclear chemistry01 natural sciencesCopper0104 chemical sciencesCoordination complexInorganic ChemistryCrystallographychemistryPolymer chemistryHalogenMoietyIsostructuraldescription
By alternating-current electrochemical synthesis crystals of {Cu[H2NC5H4N(C3H5)]Br2}˙H2O (I), {Cu[H2NC5H4N(C3H5)]Br0.65Cl1.35}˙H2O (II) and {Cu[H2NC5H4N(C3H5)]Cl2} (III) π-complexes have been obtained and structurally investigated. The I and II compounds are isostructural and crystallize in a monoclinic sp. gr. P21/c, I: a = 7.359(2)A, b = 12.3880(6)A, c = 13.637(3)A, β = 107.03(1)°, V = 1188.7(4)A3, Z = 4 for C8H13N2OBr2Cu composition, R = 0.0293 for 2140 reflections. II: a = 7.2771(6)A, b = 12.3338(3)A, c = 13.4366(7)A, β = 107.632(2)°, V = 1149.3(1)A3, Z = 4 for C8H13N2Br0.65Cl1.35Cu composition, R = 0.0463 for 2185 reflections. Metal and halogen atoms form centrosymmetric Cu2X4 dimers. Each copper atom is surrounded by three halogen atoms and by a weakly bonded C=C-group of the onium moiety. Isolated {Cu[H2NC5H4N(C3H5)]}2X4 dimers are combined into a three-dimensional network due to a bridging function of water molecules via a system of rather strong hydrogen bonds. Chlorine derivative III crystallizes in another structure type: sp. gr. C2/c, a = 21.568(7)A, b = 7.260(2)A, c = 13.331(3)A, β = 95.65(2)°, V = 2077(2)A3, Z = 8 for C8H11N2Cl2Cu composition. Copper atom, included in CuCl2— isolated fragment, is coordinated to a C=C-bond of ligand moiety. N-H…Cl hydrogen bonds unite Cu[H2NC5H4N(C3H5)]Cl2 subunits into infinite ribbons. π-Interaction in III appears to be more effective than in I and II. Nichtisomorphe Chlor—Brom-Substitution in Kupfer(I)-Halogenid-π-Komplexen mit 1-Allyl-4-aminopyridinium Durch elektrochemische Synthese mit Wechselstrom wurden Kristalle von {Cu[H2NC5H4N(C3H5)]Br2}·H2O (I), {Cu[H2NC5H4N(C3H5)]Br0.65Cl1.35}·H2O (II) und {Cu[H2NC5H4N(C3H5)]Cl2} (III) als π-Komplexe erhalten und strukturell untersucht. Die Verbindungen I und II sind isostrukturell und kristallisieren in der monoklinen Raumgruppe P21/c, I: a = 7.359(2)A, b = 12.3880(6)A, c = 13.637(3)A, β = 107.03(1)°, V = 1188.7(4)A3, Z = 4 fur C8H13N2OBr2Cu, R = 0.0293 fur 2140 Reflexe. II: a = 7.2771(6)A, b = 12.3338(3)A, c = 13.4366(7)A, b = 107.632(2)°, V = 1149.3(1)A3, Z = 4 fur C8H13N2Br0.65Cl1.35Cu, R = 0.0463 fur 2185 Reflexe. Metall- und Halogen-Atome bilden zentrosymmetrische Cu2X4-Dimere. Jedes Kupfer-Atom wird durch drei Halogen-Atome und durch eine schwach gebundene C=C-Gruppe der onium-Einheit umgeben. Isolierte {Cu[H2NC5H4N(C3H5)]}2X4-Dimere werden durch Wassermolekule in einem dreidimensionalen Netzwerk von Wasserstoffbruckenbindungen verbunden. Die Chlor-Verbindung III kristallisiert in anderem Struktur-Typ: Raumgruppe C2/c, a = 21.568(7)A, b = 7.260(2)A, c = 13.331(3)A, β = 95.65(2)°, V = 2077(2)A3, Z = 8 fur C8H11N2Cl2Cu. Das Cu-Atom der isolierten CuCl2-Einheit wird durch die C=C-Bindung eines Liganden koordiniert. Wasserstoffbindungen des N-H…Cl verbinden Cu[H2NC5H4N(C3H5)]Cl2-Subeinheiten zu endlosen Bandern.
year | journal | country | edition | language |
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2003-10-01 | Zeitschrift für anorganische und allgemeine Chemie |