Jian-Li Lin

A Zipper‐like Supramolecular Double‐Chain based on 1 D π‐π Stacking Interactions: Synthesis and Crystal Structure of [Cu(phen)(C4H4O4)(H2O)]2 · C4H6O4 (phen = 1,10‐phenanthroline)

[Cu(C12H8N2)(C4H4O4)(H2O)]2 · C4H6O4 was prepared by the reaction of succinic acid, CuCl2 · 2 H2O, 1,10-phenanthroline (phen = C12H8N2), and Na2CO3 in a CH3OH–H2O solution. The crystal structure (triclinic, P 1 (no. 2), a = 7.493(1), b = 9.758(1), c = 13.517(1) A; α = 68.89(1)°, β = 88.89(1)°, γ = 73.32(1)°, Z = 1, R = 0.0308, wR2 = 0.0799 for 3530 observed reflections (F  ≥ 2σ(F ) out of 3946 unique reflections) consists of hydrogen bonded succinic acid molecules and succinato bridged 1 D zipperlike supramolecular [Cu(phen)(C4H4O4)2/2(H2O)]2 double chains based on 1 D π-π stacking interactions between the chelating phen systems at distances of 3.71 A and 3.79 A. The Cu atoms are fivefold trigonal bipyramidally coordinated by two N atoms of the bidentate chelating phen ligand and three O atoms of one water molecule and two bidentate bridging succinate ligands. The water O atom and one phen N atom are at the apical positions (equatorial: d(Cu–O) = 1.945, 2.254(2) A, d(Cu–N) = 2.034(2) A; axial: d(Cu–O) = 1.971(2) A, d(Cu–N) = 1.995 A).

Two Succinato-bridged Zinc(II) Phenanthroline Complexes: [Zn(phen)L2/2](H2L) and [(phen)2Zn(μ-L)Zn(phen)2]L 11H2O with H2L = Succinic Acid

Two mixed ligand ZnII complexes [Zn(phen)L2/2](H2L) (1) and [(phen)2Zn(μ-L)Zn(phen)2]L � 11H2O (2) with H2L = suc-cinic acid were prepared and crystallographically characterized. Complex 1 crystallizes in the monoclinic space group C2/c (no. 15) with a = 13.618(1) A, b = 9.585(1) A, c = 15.165(1) A, β = 96.780(6)°, V = 1965.6(3)A3, Z = 4 and complex 2 in the triclinic space group P 1¯ (no. 2) with a = 12.989(2)A, b = 14.464(2)A, c = 18.025(3)A, α = 90.01(1)°, β = 109.69(1)°, γ = 112.32(1)°, V = 2917.4(8) A3, Z = 2. 1 consists of succinic acid molecules and 1D zigzag [Zn(phen)(C4H4O4)2/2] polymeric chains, in which the tetrahedrally coordinated Zn atoms are bridged by bis - monodentate succinato ligands. Succinic acid molecules play an important role in supramolecular assemblies of the polymeric chains into 2D layers as well as in the stacking of 2D layers. 2 is composed of [(phen)2Zn(μ-L)Zn(phen)2]2+ complex cations, succinate anions and hydrogen bonded water molecules. Within the divalent cations, Zn atoms are octahedrally coordinated by four N atoms of two phen ligands and two O atoms of one bis-chelating succinato ligand. Through the intermolecular π—π stacking interactions, the complex cations form positively charged 2D layers, between which the noncoordinating succinate anions and water molecules are sandwiched. Succinatverbruckte Zink-Phenanthrolin-Komplexe: [Zn(phen)L2/2](H2L) und [(phen)2Zn(μ-L)Zn(phen)2]L � 11H2O mit H2L = Bernsteinsaure Die ZnII—Komplexe [Zn(phen)L2/2](H2L) (1) und [(phen)2Zn(μ—L)Zn(phen)2]L�11H2O (2) mit H2L = Bernsteinsaure wurden dargestellt und rontgenographisch charakterisiert. 1 kristallisiert in der monoklinen Raumgruppe C2/c (Nr. 15) mit a = 13, 618(1) A, b = 9, 585(1) A, c = 15, 165(1) A, β = 96, 780(6)°, V = 1965, 6(3) A3 , Z = 4 und 2 in der triklinen Raumgruppe P 1¯ (Nr. 2) mit a = 12, 989(2) A, b = 14, 464(2) A, c = 18, 025(3) A , α = 90, 01(1)°, β = 109, 69(1)°, γ = 112, 32(1)°, V = 2917, 4(8) AA3, Z = 2. 1 setzt sich aus Bernsteinsaure-Molekulen und zickzackfomigen [Zn(phen)(C4H4O4)2/2]]—Ketten, in denen tetraederisch koordinierte Zn-Atome uber bis-einzahnige Succinato-Liganden verbruckt sind, zusammen. Die Bernsteinsaure-Molekule spielen eine wichtige Rolle beim supramolekularen Aufbau der polymeren Ketten zu 2D-Schichten. 2 wird von den [(phen)2Zn(μ-L)Zn(phen)2]2+-Kationen, den Succinat-Anionen und den uber H-Brucken gebundenen H2O—Molekulen gebildet. Innerhalb der zweiwertigen Kationen sind Zn-Atome oktaedrisch von vier N-Atomen zweier Phen-Liganden und zwei O-Atomen eines bis-chelatisierenden Succinato-Liganden koordiniert. Durch intermolekulare π—π—Wechselwirkungen bilden die komplexen Kationen positiv geladene 2D-Schichten, zwischen denen die nicht-koordinierenden Succinat-Anionen und H2O-Molekule eingelagert sind.

Crystal Structures of [Mn2(H2O)4(phen)2(C4H4O4)2] · 2 H2O and [Mn(phen)2(H2O)2][Mn(phen)2(C4H4O4)](C4H4O4) · 7 H2O

Reactions of 1,10-phenanthroline monohydrate, Na2C4H4O4 · 6 H2O and MnSO4 · H2O in CH3OH/H2O yielded a mixture of [Mn2(H2O)4(phen)2(C4H4O4)2] · 2 H2O (1) and [Mn(phen)2(H2O)2][Mn(phen)2(C4H4O4)](C4H4O4) · 7 H2O (2). The crystal structure of 1 (P1 (no. 2), a = 8.257(1) A, b = 8.395(1) A, c = 12.879(2) A, α = 95.33(1)°, β = 104.56(1)°, γ = 106.76(1)°, V = 814.1(2) A3, Z = 1) consists of the dinuclear [Mn2(H2O)4(phen)2(C4H4O4)2] molecules and hydrogen bonded H2O molecules. The centrosymmetric dinuclear molecules, in which the Mn atoms are octahedrally coordinated by two N atoms of one phen ligand and four O atoms from two H2O molecules and two bis-monodentate succinato ligands, are assembled via π-π stacking interactions into 2 D supramolecular layers parallel to (101) (d(Mn–O) = 2.123–2.265 A, d(Mn–N) = 2.307 A). The crystal structure of 2 (P1 (no. 2), a = 14.289(2) A, b = 15.182(2) A, c = 15.913(2) A, α = 67.108(7)°, β = 87.27(1)°, γ = 68.216(8)°, V = 2934.2(7) A3, Z = 2) is composed of the [Mn(phen)2(H2O)2]2+ cations, [Mn(phen)2(C4H4O4)] complex molecules, (C4H4O4)2– anions, and H2O molecules. The (C4H4O4)2– anions and H2O molecules form 3 D hydrogen bonded network and the cations and complex molecules in the tunnels along [001] and [011], respectively, are assembled via the π-π stacking interactions into 1 D supramolecular chains. The Mn atoms are octahedrally coordinated by four N atoms of two bidentate chelating phen ligands and two water O atoms or two carboxyl O atoms (d(Mn–O) = 2.088–2.129 A, d(Mn–N) = 2.277–2.355 A). Interestingly, the succinato ligands in the complex molecules assume gauche conformation bidentately to chelate the Mn atoms into seven-membered rings. Kristallstrukturen von [Mn2(H2O)4(phen)2(C4H4O4)2] · 2 H2O und [Mn(phen)2(H2O)2][Mn(phen)2(C4H4O4)](C4H4O4) · 7 H2O Die Reaktion von 1,10-Phenanthrolinmonohydrat, Na2C4H4O4 · 6 H2O und MnSO4 · H2O in CH3OH/ H2O ergab ein Gemisch von [Mn2(H2O)4(phen)2(C4H4O4)2] · 2 H2O (1) und [Mn(phen)2(H2O)2][Mn(phen)2(C4H4O4)](C4H4O4) · 7 H2O (2). Die Kristallstruktur von 1 (P1 (Nr. 2), a = 8,257(1) A, b = 8,395(1) A, c = 12,879(2) A, α = 95,33(1)°, β = 104,56(1)°, γ = 106,76(1)°, V = 814,1(2) A3, Z = 1) besteht aus den dinuklearen [Mn2(H2O)4(phen)2(C4H4O4)2]Molekulen und den uber H-Brucken gebundenen H2O-Molekulen. Die zentrosymmetrischen dinuklearen Molekulen, in denen die Mn-Atome jeweils oktaedrisch von zwei N-Atomen eines Phen-Liganden und vier O-Atomen zweier H2O-Molekulen und zweier zweifach einzahniger Succinato-Liganden koordiniert sind, werden durch die π-π-Wechselwirkungen unter Bildung von 2 D-Schichten parallel zur (101)-Ebene zusammengehalten (d(Mn–O) = 2,123–2,265 A, d(Mn–N) = 2,307 A). Die Kristallstruktur von 2 (P1 (Nr. 2), a = 14,289(2) A, b = 15,182(2) A, c = 15,913(2) A, α = 67,108(7)°, β = 87,27(1)°, γ = 68,216(8)°, V = 2934,2(7) A3, Z = 2) setzt sich aus den [Mn(phen)2(H2O)2]2+-Kationen, [Mn(phen)2(C4H4O4)]-Molekulen, (C4H4O4)2–-Anionen und H2O-Molekulen zusammen. Die (C4H4O4)2–-Anionen und H2O-Molekulen bilden ein 3 D-Netzwerk uber Wasserstoffbruckenbindungen. Die Kationen und Komplexmolekule befinden sich in den Kanalen entlang [001] bzw. [011] und sind mit Hilfe der π-π-Wechselwirkungen unter Bildung von 1 D-Ketten verbunden. Die Mn-Atome sind oktaedrisch von vier N-Atomen beider Phen-Liganden und zwei O-Atomen zweier H2O-Molekulen oder zweier Carboxyl-O-Atomen koordiniert (d(Mn–O) = 2,088–2,129 A, d(Mn–N) = 2,277–2,355 A). Die Succinato-Gruppe in den Komplex-Molekulen fungiert als zweizahniger Chelatligand.

Self—assembly of Zinc Ions with Suberic Acid and Phenanthroline — Crystal Structures of five New Zinc Phenanthroline Suberato Complexes

Self—assembly of Zinc(II) ions with suberic acid and 1, 10-phenanthroline in CH3OH/H2O resulted in five new complexes [Zn(phen)3]L · 14H2O (1), [Zn2(phen)2(H2O)2L2] · 5H2O (2), Zn(phen)(HL)2 (3), [Zn(phen)2(HL)]NO3 · H2O (4) and [Zn(phen)3]2(L)(NO3)2(H2O)20 (5), which are characterized by X—ray diffraction (H2L = HOOC—(CH2)6—COOH). The suberate salts 1 and 5 are featured by hydrogen bonded 3D networks. Such 3D networks are built up by crystal water molecules and suberate anions in 1 or by crystal water molecules, suberate anions and nitrate anions in 5, and the tris—chelated [Zn(phen)3]2+ complex cations in the tunnels are assembled via π—π stacking interactions into 1D chains. The suberato compound 2 consists of the crystal water molecules and the centrosymmetric dinuclear [Zn2(phen)2— (H2O)2L2] complex molecules, which are assembled, via hydrogen bonding and π—π stacking interactions, to form a 3D open framework, and the crystal water molecules are located in the tunnels. The hydrogensuberato compound 3 crystallizes in the acentric monoclinic space group C2 and is made of [Zn(phen)(HL)2] complex molecules, which are interlinked by hydrogen bonds, but not by π—π stacking interactions, to a polar 3D network. In the hydrogensuberato compound 4, assembly of the [Zn(phen)2(HL)]+ complex cations via π—π stacking interactions forms 1D chains, which are further connected by nitrate anions and crystal water molecules to 2D layers. Selbstorganisation von Zink(II)-Ionen mit Korksaure und Phenanthrolin — Kristallstrukturen von funf neuen Zink-Phenanthrolin-Suberato-Komplexen Selbstorganisation von Zink(II)—Ionen mit Korksaure und Phenanthrolin in CH3OH/H2O ergab funf neue Komplexe: [Zn(phen)3]L · 14H2O (1), [Zn2(phen)2(H2O)2L2] · 5H2O (2), Zn(phen)(HL)2 (3), [Zn(phen)2(HL)]NO3 · H2O (4) und [Zn(phen)3]2(L)(NO3)2(H2O)20 (5), die durch Rontgenstrukturanalyse charakterisiert wurden (H2L = HOOC—(CH2)6—COOH). Die Suberate 1 und 5 sind durch ein uber H-Brucken verbundenes 3D-Netzwerk gekennzeichnet. Solche 3D-Netzwerke sind aus Kristallwasser-Molekulen und Suberat-Anionen in 1 bzw. aus Kristallwasser-Molekule, Suberat-Anionen und Nitrat-Anionen in 5 aufgebaut. Die dreifach-chelatisierenden [Zn(phen)3]2+-Komplex-Kationen in den Kanalen bilden durch π—π-Wechselwirkungen 1D-Ketten. Die Suberato-Verbindung 2 setzt sich aus Kristallwasser-Molekulen und zentrosymmetrischen dinuklearen [Zn2(phen)2— (H2O)2L2]-Molekulen zusammen, die uber H-Brucken und durch π—π-Wechselwirkungen zu einem offenen Gerust verbunden sind; die Kristallwasser-Molekule sind in den Kanalen lokalisiert. Die Hydrogensuberato-Verbindung 3 kristallisiert in der azentrischen, monoklinen Raumgruppe C2 und ist aus [Zn(phen)(HL)2]-Molekulen aufgebaut, die uber H-Brucken, aber nicht durch π—π-Wechselwirkungen, zu einem polaren 3D-Netzwerk verknupft sind. In der Hydrogensuberato-Verbindung 4 fuhrt die Bildung der [Zn(phen)2(HL)]+-Komplex-Kationen mit Hilfe der π—π-Wechselwirkungen zu Ketten, die weiterhin durch Nitrat-Anionen und Kristallwasser-Molekule zu Schichten verbunden sind.

Crystal Structures of ∞1{[Cd(phen)](C6H8O4)3/3} and ∞1{[Cd(phen)](C7H10O4)3/3} · 2H2O with C6H10O4 = Adipic Acid and C7H12O4 = Pimelic Acid

Two coordination polymers {[Cd(phen)](C6H8O4)3/3} (1) and {[Cd(phen)](C7H10O4)3/3} · 2H2O (2) were structurally characterized by single crystal X-ray diffraction methods. In 1 (C2/c (no. 15), a = 16.169(2)A, b = 15.485(2)A, c = 14.044(2)A, β = 112.701(8)°, U = 3243.9(7)A3, Z = 8), the Cd atoms are coordinated by two N atoms of one phen ligand and five O atoms of three adipato ligands to form mono-capped trigonal prisms with d(Cd-O) = 2.271-2.583A and d(Cd-N) = 2.309, 2.390A. The [Cd(phen)] moieties are bridged by adipato ligands to generate {[Cd(phen)](C6H8O4)3/3} chains, which, via interchain π—π stacking interactions, are assembled into layers. Complex 2 (P1¯(no. 2), a = 9.986(1)A, b = 10.230(3)A, c = 11.243(1)A, α = 66.06(1)°, β = 87.20(1)°, γ = 66.71(1)°, U = 955.7(2)A3, Z = 2) consists of {[Cd(phen)](C7H10O4)3/3} chains and hydrogen bonded H2O molecules. The Cd atoms are pentagonal bipyramidally coordinated by two N atoms of one phen ligand and five O atoms of three pimelato ligands with d(Cd-O) = 2.213—2.721A and d(Cd-N) = 2.329, 2.372A. Through interchain π—π stacking interactions, the {[Cd(phen)](C7H10O4)3/3} chains resulting from [Cd(phen)] moieties bridged by pimelato ligands are assembled in to layers, between which the hydrogen bonded H2O molecules are sandwiched. Kristallstrukturen von {[Cd(phen)](C6H8O4)3/3} und {[Cd(phen)](C7H10O4)3/3} · 2H2O mit C6H10O4 = Adipinsaure und C7H12O4 = Pimelinsaure Zwei Koordinationspolymere {[Cd(phen)](C6H8O4)3/3} (1) und {[Cd(phen)](C7H10O4)3/3} · 2H2O (2) wurden mit rontgnographischen Methoden charakterisiert. Im Komplex 1 (C2/c (Nr. 15), a = 16, 169(2)A, b = 15, 485(2)A, c = 14, 044(2)A, β = 112, 701(8)°, U = 3243, 9(7)A3, Z = 8) sind die Cd-Atome jeweils von zwei N-Atomen eines Phen-Liganden und funf O-Atomen dreier Adipato-Liganden koordiniert unter Bildung einer einfach bekappten trigonalen Bipyramide mit d(Cd-O) = 2, 271—2, 583A und d(Cd-N) = 2, 309, 2, 390A. Die [Cd(phen)]-Bausteine sind uber die Adipato-Liganden zu den {[Cd(phen)](C6H8O4)3/3}-Ketten miteinander verbunden; sie werden durch die π—π-Wechselwirkungen zu Schichten zusammengehalten. Die Kristallstruktur von Komplex 2 (P1¯ (Nr. 2), a = 9, 986(1)A, b = 10, 230(3)A, c = 11, 243(1)A, α = 66, 06(1)°, β = 87, 20(1)°, γ = 66, 71(1)°, U = 955, 7(2)A3, Z = 2) setzt sich aus {[Cd(phen)](C7H10O4)3/3}-Ketten und den uber H-Brucken gebundenen H2O-Molekulen zusammen. Die Cd-Atome sind jeweils von zwei N-Atomen eines Phen-Liganden und funf O-Atomen dreier Pimelato-Liganden pentagonal-bipyramidal koordiniert mit d(Cd-O) = 2, 213—2, 721A and d(Cd-N) = 2, 329, 2, 372A. Ebenso durch die π—π-Wechselwirkungen sind die {[Cd(phen)](C7H10O4)3/3}- Ketten, die aus den [Cd(phen)]-Bausteine uber die Pimelato-Liganden resultieren, zu Schichten zusammengehalten, zwischen denen die uber H-Brucken gebundenen H2O-Molekule eingebaut sind.

Adipato‐Bridged Mixed Ligand catena Complexes:

Three adipato bridged mixed ligand catena complexes {[M(phen)(H2O)]-(C6H8O4)2/2} with M = NiII (1), CuII (2), ZnII (3) were synthesized. Structure determination based on X-ray diffraction shows that they crystallize isostructurally in the monoclinic space group C2/c (no. 15) with cell dimensions of: 1a = 22.451(4)A, b = 9.041(1)A, c = 17.440(2)A, β = 103.41(1)°, U = 3443.4(9)A3, Z = 8; 2a = 22.479(2)A, b = 9.067(1)A, c = 17.494(3)A, β = 103.67(1)°, U = 3464.6(8)A3, Z = 8; 3a = 22.635(3)A, b = 9.052(1)A, c = 17.571(3)A, β = 103.24(1)°, U = 3504.5(9)A3, Z = 8. The crystal structure consists of 1D{[M(phen)(H2O)]-(C6H8O4)2/2} zigzag chains, in which the metal atoms are all octahedrally coordinated by two N atoms of one phen ligands and four O atoms of one H2O molecule and two adipato ligands. The zigzag chains are held together by interchain π-π stacking interactions and interchain hydrogen bonds. Adipato-verbruckte, kettenformige Gemischt-Liganden-Komplexe:{[M(phen)(H2O)]L2/2} mit M = NiII, CuII, ZnII; H2L = Adipinsaure Drei Adipato-verbruckte, kettenformige Gemischt-Liganden-Komplexe {[M(phen)(H2O)](C6H8O4)2/2} mit M = NiII (1), CuII (2), ZnII (3) wurden synthetisiert. Die rontgnographischen Kristallstrukturbestimmungen zeigen an, das sie isotyp in der monoklinen Raumgruppe C2/c (Nr. 15) kristallisieren mit den Gitterkonstanten: 1: a = 22, 451(4)A, b = 9, 041(1)A, c = 17, 440(2)A, β = 103, 41(1)°, U = 3443, 4(9)A3, Z = 8; 2: a = 22, 479(2)A, b = 9, 067(1)A, c = 17, 494(3)A, β = 103, 67(1)°, U = 3464, 6(8)A3, Z = 8; 3: a = 22, 635(3)A, b = 9, 052(1)A, c = 17, 571(3)A, β = 103, 24(1)°, U = 3504, 5(9)A3, Z = 8. Die Kristallstrukturen setzen sich aus 1D-{[M(phen)(H2O)](C6H8O4)2/2}-Zickzack-Ketten zusammen, in denen die Metall-Atome jeweils von zwei N-Atomen eines Phen-Liganden und vier O-Atomen aus H2O-Molekulen und zwei Adipat-Liganden oktaederisch koordiniert sind. Die Zickzack-Ketten werden durch π-π-Wechselwirkungen und Wasserstoffbruckenbindungen zusammengehalten.

{_{\infty}^1}

Syntheses of the sky blue complex compounds [Ni(H2O)3(phen)(C5H6O4)] · H2O (1) and [Ni(H2O)2(phen)(C5H6O4)] (2) were carried out by the reactions of 1,10-phenanthroline monohydrate, glutaric acid, NiSO4 · 6 H2O and Na2CO3 in CH3OH/H2O at pH = 6.9 and 7.5, respectively. The crystal structure of 1 (P 1 (no. 2), a = 14.289 A, b = 15.182 A, c = 15.913 A, α = 67.108°, β = 87.27°, γ = 68.216°, V = 2934.2 A3, Z = 2) consists of hydrogen bonded [Ni(H2O)3- (phen)(C5H6O4)]2 dimers and H2O molecules. The Ni atoms are octahedrally coordinated by two N atoms of one phen ligand, three water O atoms and one carboxyl O atom from one monodentate glutarato ligand (d(Ni–N) = 2.086, 2.090 A; d(Ni–O) = 2.064–2.079 A). Through the π-π stacking interactions and intermolecular hydrogen bonds, the dimers are assembled to form 2 D layers parallel to (0 1 1). The crystal structure of 2 (P21/n (no. 14), a = 7.574 A, b = 11.938 A, c = 18.817 A, β = 98.48°, V = 1682.8 A3, Z = 4) contains [Ni(H2O)2(phen)(C5H6O4)2/2] supramolecular chains extending along [010]. The Ni atoms are octahedrally coordinated by two N atoms of one phen ligand, two water O atoms and two carboxyl O atoms from different bis-monodentate glutarato ligands with d(Ni–N) = 2.082, 2.105 A and d(Ni–O) = 2.059–2.087 A. The supramolecular chains are assembled into a 3 D network by π-π stacking interactions and interchain hydrogen bonds. A TG/DTA of 2 shows two endothermic effects at 132 °C and 390 °C corresponding to the complete dehydration and the lost of phen. Supramolekulare Anordnung von mononuklearen und polymeren Nickelglutarato-Komplexen uber π-π-Wechselwirkungen und Wasserstoffbruckenbindungen: [Ni(H2O)3(phen)(C5H6O4)] · H2O und [Ni(H2O)2(phen)(C5H6O4)] Die Darstellung der himmelblauen Komplexverbindungen [Ni(H2O)3(phen)(C5H6O4)] · H2O (1) und [Ni(H2O)2(phen)(C5H6O4)] (2) erfolgte durch Reaktionen von 1,10-Phenanthrolinmonohydrat, Glutarsaure, NiSO4 · 6 H2O und Na2CO3 in CH3OH/H2O bei pH = 6.9 bzw. 7.5. Die Kristallstruktur von 1 (P 1 (Nr. 2), a = 14,289 A, b = 15,182 A, c = 15,913 A, α = 67,108°, β = 87,27°, γ = 68,216°, V = 2934,2 A3, Z = 2) enthalt durch Wasserstoffbruckenbindungen verknupfte Dimere [Ni(H2O)3(phen)(C5H6O4)]2 sowie H2O-Molekule. Die Ni-Atome sind oktaederisch koordiniert von zwei N-Atomen eines Phen-Liganden und vier O-Atomen von drei H2O-Molekulen und einem einzahnigen Glutarato-Liganden (d(Ni–N) = 2,086, 2,090 A; d(Ni–O) = 2,064–2,079 A). π-π-Wechselwirkungen und intermolekulare Wasserstoffbruckenbindungen verbinden die Dimeren zu 2 D-Schichten parallel (0 1 1). Die Kristallstruktur von 2 (P21/n (Nr. 14), a = 7,574 A, b = 11,938 A, c = 18,817 A, β = 98,48°, V = 1682,8 A3, Z = 4) enthalt 1 D-Ketten [Ni(H2O)2(phen)(C5H6O4)2/2] entlang [010]. Die Ni-Atome sind oktaederisch koordiniert von zwei N-Atomen eines Phen-Liganden und vier O-Atomen von zwei H2O-Molekulen und zwei zweifach einzahnigen Glutarato-Liganden mit d(Ni–N) = 2,082, 2,105 A und d(Ni–O) = 2,059–2,087 A. π-π-Wechselwirkungen und Wasserstoffbruckenbindungen sind fur die Ausbildung des supramolekularen Ensembles der Ketten verantwortlich. Die TG/DTA von 2 zeigt zwei endotherme Effekte bei 132 °C und 390 °C, welche mit der vollstandigen Abspaltung von H2O bzw. Phen zusammenhangen.

{[M(phen)(H2O)]L2/2} with M = NiII, CuII, ZnII; H2L = Adipic Acid

The title compound [La(phen)2(H2O)2(NO3)2](NO3) · 2(phen)(H2O) with phen = 1,10-phenanthroline was prepared by the stoichiometric reaction of La(NO3)3 · 6 H2O and 1,10-phenanthroline monohydrate in a CH3OH–H2O solution. The crystal structure (triclinic, P 1 (no. 2), a = 11.052(2), b = 13.420(2), c = 16.300(2) A, α = 78.12(1)°, β = 88.77(1)°, γ = 83.03(1)°, Z = 2, R = 0.0488, wR2 = 0.1028) consists of [La(phen)2(H2O)2(NO3)2]2+ complex cations, NO3– anions, phen and H2O molecules. The La atom is 10-fold coordinated by four N atoms of two bidentate chelating phen ligands and six O atoms of two H2O molecules and two bidentate chelating NO32– ligands with d(La–O) = 2.522–2.640 A and d(La–N) = 2.689–2.738 A. The intermolecular π-π stacking interactions play an essential role in the formation of two different 2 D layers parallel to (001), which are formed by complex cations and uncoordinating phen molecules, respectively. The uncoordinated NO3– anions and H2O molecules are sandwiched between the cationic and phen layers.

Supramolecular Assemblies of Mononuclear and Polymeric Nickel(II) Glutarato Complexesvia π-π Stacking Interactions and Hydrogen Bonds: [Ni(H2O)3(phen)(C5H6O4)] · H2O and [Ni(H2O)2(phen)(C5H6O4)]

The blue copper complex [Cu2(H2O)2(phen)2(OH)2][Cu2(phen)2(OH)2(CO3)2] · 10 H2O, which was prepared by reaction of 1,10-phenanthroline monohydrate, CuCl2 · 2 H2O and Na2CO3 in the presence of succinic acid in CH3OH/H2O at pH = 13.0, crystallized in the triclinic space group P1 (no. 2) with cell dimensions: a = 9.515(1) A, b = 12.039(1) A, c = 12.412(2) A, α = 70.16(1)°, β = 85.45(1)°, γ = 81.85(1)°, V = 1323.2(2) A3, Z = 1. The crystal structure consists of dinuclear [Cu2(H2O)2(phen)2(OH)2]2+ complex cations, dinuclear [Cu2(phen)2(OH)2(CO3)2]2– complex anions and hydrogen bonded H2O molecules. In both the centrosymmetric dinuclear cation and anion, the Cu atoms are coordinated by two N atoms of one phen ligand, three O atoms of two μ-OH groups and respectively one H2O molecule or one CO32– anion to complete distorted [CuN2O3] square-pyramids with the H2O molecule or the CO32– anion at the apical position (equatorial d(Cu–O) = 1.939–1.961 A, d(Cu–N) = 2.026–2.051 A and axial d(Cu–O) = 2.194, 2.252 A). Two adjacent [CuN2O3] square pyramids are condensed via two μ-OH groups. Through the interionic hydrogen bonds, the dinuclear cations and anions are linked into 1D chains with parallel phen ligands on both sides. Interdigitation of phen ligands of neighboring 1D chains generated 2D layers, between which the hydrogen bonded water molecules are sandwiched. Synthese und Kristallstruktur von [Cu2(H2O)2(phen)2(OH)2][Cu2(phen)2(OH)2(CO3)2] · 10 H2O mit phen = 1,10-Phenanthrolin Der blaue Kupferkomplex [Cu2(H2O)2(phen)2(OH)2][Cu2(phen)2(OH)2(CO3)2] · 10 H2O, der durch Reaktion von 1,10-Phenanthrolinmonohydrat, CuCl2 · 2 H2O und Na2CO3 in Anwesenheit von Bernsteinsaure in CH3OH/H2O-Losung bei pH = 13.0 dargestellt wurde, kristallisiert in die trikline Raumgruppe P1 (Nr. 2) mit den Gitterkonstanten: a = 9,515(1) A, b = 12,039(1) A, c = 12,412(2) A, α = 70,16(1)°, β = 85,45(1)°, γ = 81,85(1)°, V = 1323,2(2) A3, Z = 1. Die Kristallstruktur besteht aus komplexen dinuklearen [Cu2(H2O)2(phen)2(OH)2]2+-Kationen, komplexen [Cu2(phen)2(OH)2(CO3)2]2–-Anionen und den uber H-Brucken gebundenen H2O-Molekulen. In den zentrosymmetrischen dinuklearen Kationen bzw. Anionen sind die Cu-Atome jeweils von zwei N-Atomen eines Phen-Ligandens und den drei O-Atomen zweier μ-OH-Gruppen sowie einem H2O-Molekul bzw. einem CO32–-Anion unter Bildung einer verzerrt-quadratischen [CuN2O3]-Pyramide koordiniert mit dem H2O-Molekul bzw. dem CO32–-Anion an der Spitze (aquatoriale Abstande d(Cu–O) = 1,939–1,961 A, d(Cu–N) = 2,026–2,051 A und axiale Abstande d(Cu–O) = 2,194, 2,252 A). Benachbarte [CuN2O3]-Pyramiden sind uber zwei μ-OH-Gruppen verbunden. Uber interionische Wasserstoffbruckenbindungen sind die dinuklearen Kationen und Anionen zu 1D-Ketten verknupft mit parallelen Phen-Liganden auf beiden Seiten. Uber die Phen-Liganden ordnen sich die 1D-Ketten zu 2D-Schichten, zwischen denen die uber H-Brucken gebundenen H2O-Molekule lokalisiert sind.

Synthesis and Crystal Structure of [La(phen)2(H2O)2(NO3)2]NO3 · 2(phen)(H2O) with phen = 1,10-phenanthroline

Blue crystals of [Cu(phen)(C10H16O4)] · 3 H2O were grown by evaporation of a CH3OH/H2O solution containing CuCl2 · 2 H2O, 1,10-phenanthroline (phen), sebacic acid and Na2CO3 at 55 °C. In the crystal structure (triclinic, P 1 (no. 2), a = 10.988(1), b = 11.121(1), c = 11.200(2) A, α = 110.64(1)°, β = 110.51(1)°, γ = 95.42(1)°, Z = 2, R = 0.0793, wR2 = 0.1566 for 3848 observed reflections), the Cu atoms are square-planar coordinated by the two N atoms of the phen ligand and two cis-O atoms of two bidentate bridging sebacate ligands with d(Cu–N) = 2.004(4), 2.015(4) A and d(Cu–O) = 1.949(4), 1.953(3) A. The sebacate ligands connect the Cu atoms to 1 D [Cu(phen)(C10H16O4)2/2] zigzag chains with the phen planes roughly parallel to the chain. By π-π stacking interactions between quinoline fragments of the phen ligands (3.38 A spacing), two adjacent chains are combined to 1 D supramolecular [Cu(phen)(C10H16O4)2/2]2 double-chains along [111]. Uncoordinated H2O molecules are placed in voids.