Synthese,EPR und Röntgenkristallstrukturanalyse von mer-Trichloro(2,2′-bipyridin)nitridotechnetium(VI), einem neuen Nitridokomplex des Technetium(VI)

Synthesis, EPR and X-Ray Structure of mer-Trichloro(2,2′-bipyridine)nitridotechnetium(VI) — a new Technetium(VI) Nitrido Complex mer-Trichloro(2,2′-bipyridine)nitridotechnetium(VI) has been prepared by the reaction of (NBu₄)[TcNCl₄] with 2,2′-bipyridine in acetonitrile, whereas the same procedure gives in methanol the technetium(V) cation [TcNCl(bipy)₂]⁺. The EPR spectrum of [TcNCl₃(bipy)] suggests a meridional coordination of the three chloro ligands. [TcNCl₃(bipy)] crystallizes monoclinic in the space group P2₁/n; a = 8.572(1), b = 15.462(1), c = 10.110(1) Å, β = 104.21(1)°, Z = 4. The R value converged at 0.034 on the basis of 3 040 reflections. The technetium atom is distorted octahedrally coordinated with the chloro ligands meridionally cis with respect to the nitrido nitrogen. The Tc? N(1) bond length is 1.669(4) Å, and the Tc? N(3) bond (2.371(4) Å) is significantly lengthened due to the structural trans labilizing influence of the “N^3?” ligand.     

The phenomenon of conglomerate crystallization of organic compounds. Part 4. The structures of 2,2′-biphenyldisulfide (I) and 2,2′-biphenyldisulfide monoxide (II)

A racemic solution of 2,2′-biphenyldisulfide ( I ), C₁₂H₈S₂, produces conglomerate crystals of ( I ) belonging in space group P3₂21 (no. 154) with lattice constants: a = 7.38 (3) Å, b = 7.38 (3), c = 16.20 (2) Å; V = 766.6 ų and d(calc; M.W. = 216.32, z = 3) = 1.406 g-cm⁻³, d(meas) = 1.47 g-cm⁻³. A total of 1150 data were collected over the range of 4° ≤ 2θ ≤ 60° using film data (Weissenberg); of these, 448 [independent and with I ≥ 3σ(I)] were used in the structural analysis. Refinement converged to final residuals of 0.080 and 0.082 for R(F) and R_W(F), respectively. The molecule is located at the twofold axis of the space group. A solution of 2,2′-biphenyldisulfide mono-oxide ( II ), C₁₂H₈S₂O, produces centrosymmetric crystals of II belonging in space group P2₁/c with lattice constants: a = 9.947 (1) Å, b = 7.162 (2), c = 15.420 (3) Å, and β = 107.56 (1)°; V = 107.56 (1) ų and d(calc; M.W. = 232.31, Z = 4) = 1.473 g-cm⁻³. A total of 2114 data were collected over the range of 4° ≤ 2θ ≤ 50°; of these, 1089 [independent and with I ≥ 2.5σ(I)] were used in the structural analysis. Data were corrected for absorption (μ = 4.539 cm⁻¹), and the relative transmission coefficients ranged from 0.9198 to 0.9998. Refinement converged to final residuals of 0.0313 and 0.0300 for R(F) and R_w(F), respectively. For I , the central six-membered ring C₄S₂ contains a helical C₂S₂ fragment whose conformational chirality is defined by a torsional angle of 59.98°. The benzene rings are the expected, planar hexagons characteristic of aryl rings. By comparison with I , the torsional angle of the C₂S₂ fragment of the mono-oxide is diminished (52.9°) by the introduction of the S=O fragment. We believe alteration of molecules (such as functionalization) causing large changes in torsional angles of helical fragments of molecules may play a role in the selection of their crystallization mode; however, it is not the only factor dictating that choice, which is also affected by steric hindrance to the formation of short intermolecular contacts leading, in the solid state, to the formation of homochiral, infinite helical strings, as we shall demonstrate in the text. This study clearly shows the influence of those contacts on the formation of the strings. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:65–74, 1998     

Electrocrystallization of Tetra‐ and Hexa‐coordinated Silver(II) Compounds Based on 4,4′‐Dimethyl‐2,2′‐Bipyridine Ligand – Single Crystal Structures and Magnetic Studies

In this paper we report on the potential dependent electrocrystallization of [Ag(4,4′‐dimethyl‐2,2′‐bipyridine)₂(NO₃)₂] ( 1 ) and Ag(4,4′‐dimethyl‐2,2′‐bipyridine)(NO₃)₂ ( 2 ) from the same electrolytic bath. Thus it has been shown for the first time that the coordination number of silver ion to ligands can be tuned by the electrocrystallization potential. The single crystal structure analysis [ 1 : C2/c, a = 18.6308(15), b = 14.5708(12), c = 11.5867(10) Å, β = 126.5910(10)°, Z = 4, R = 3.9 %] [ 2 : P2₁/c, a = 8.5865(11) b = 11.0157(14) c = 16.4554(10) Å, β = 111.102(10), Z = 4 , R = 3.5 %] show divalent silver to be in an approximately square planar surrounding. Both complexes are paramagnetic following Curie's law with magnetic moments of 1.86 μ_B and 1.72 μ_B respectively.     

Polymorphism of [Zn(2,2′‐bipy)(H2PO4)2]2

Two polymorphs of a zero‐dimensional (molecular) zinc phosphate with the formula [Zn(2,2′‐bipy)(H₂PO₄)₂]₂ have been synthesized by a mild hydrothermal route and their crystal structures were determined by single crystal X‐ray diffraction (triclinic, space group (No. 2), Z = 2, α‐form: a = 8.664(1), b = 8.849(2), c = 10.113(2) Å, α = 97.37(2)°, β = 100.54(2)°, γ = 100.98(2)°, V = 737.5(3) ų; β‐form: a = 7.5446(15), b = 10.450(2), c = 10.750(2) Å, α = 67.32(3)°, β = 81.67(3)°, γ = 69.29(3)°, V = 731.4(3) ų). Both structures consist of distorted trigonal‐bipyramidal ZnO₃N₂ units condensed with PO₂(OH)₂ tetrahedra through common vertices giving rise to dimers [Zn(2,2′‐bipy)(H₂PO₄)₂]₂. The structures are stabilized by extensive inter‐ and intramolecular hydrogen bond interactions. Both modifications display subtle differences in their packing originating from the hydrogen bond interactions as well as π…π interactions between the organic ligands.     

Einfluss von H‐Brückenbindungen auf die Jahn–Teller‐Verzerrung in den Kettenstrukturen von 2,2′‐bipyMn(H2PO4)F2·H2O und 2,2′‐bipyMn(H2PO4)2F

In the system 2,2′‐bipyridine/Mn^III/HF/H₃PO₄/H₂O two compounds with chain structures could be prepared and characterised by X‐ray structure analyses. 2,2′‐bipyMn(H₂PO₄)F₂·H₂O ( 1 ): monoclinic, twinned, space group P2₁/c, Z = 4, a = 6.7883(4), b = 10.9147(5), c = 17.8102(8) Å, β = 100.142(4)°, R = 0.0328. 2,2′‐bipyMn(H₂PO₄)₂F ( 2 ): triclinic, space group P , Z = 2, a = 6.675(1), b = 10.715(1), c = 11.013(1) Å, α = 107.595(9)°, β = 90.994(9)°, γ = 95.784(8)°, R = 0.0252. Both compounds show chain structures with trans‐bridging dihydrogenphosphate ligands and bipy and two fluorine ligands for ( 1 ), or bipy, fluorine and an additional dihydrogenphosphate, respectively, for ( 2 ) in equatorial positions. Due to the pseudo‐Jahn–Teller effect, Mn^III shows elongated octahedral coordination with ferrodistortive ordering along the chain direction. The distortion is remarkably higher in ( 1 ) than in ( 2 ). This is discussed in context with additional hydrogen bonds along the chain in ( 2 ).     

2,2′‐Bipyridinium bis(perchlorate)

The title compound, [H₂bipy](ClO₄)₂ or C₁₀H₁₀N₂²⁺·2ClO₄^?, was obtained at the interface between an organic (2,2′‐bi­pyridine in methanol) and an aqueous phase (perchloric acid in water). The compound crystallizes in space group P and comprises discrete diprotonated trans‐bipyridinium cations, [H₂bipy]²⁺, and ClO₄^? anions. The cations and anions are connected through N—H?O and C—H?O hydrogen bonds [distances N?O 2.817 (4) and 2.852 (4) Å, and C?O 3.225 (6)–3.412 (5)Å]. The C—C bond distance between the two rings is 1.452 (5) Å. The bipyridinium cation has a trans conformation and the N—C—C—N torsion angle is 152.0 (3)°.     

3,3′‐Dinitro‐2,2′‐dithiodipyridine

In the title compound, C₁₀H₆N₄O₄S₂, (I), the molecule has a centre of inversion. The structure is a positional isomer of 5,5′‐dinitro‐2,2′‐dithiodipyridine [Brito, Mundaca, Cárdenas, López‐Rodríguez & Vargas (2007). Acta Cryst. E 63 , o3351–o3352], (II). The 3‐nitropyridine fragment of (I) shows excellent agreement with the bonding geometries of (II). The most obvious differences between them are in the S—S bond length [2.1167 (12) Å in (I) and 2.0719 (11) Å in (II)], and in the C—C_ipso—N_ring [119.8 (2)° in (I) and 123.9 (3)° in (II)] and S—C—C [122.62 (18)° in (I) and 116.0 (2)° in (II)] angles. The crystal structure of (I) has an intramolecular C—H...O interaction, with an H...O distance of 2.40 (3) Å, whereas this kind of interaction is not evident in (II). The molecules of (I) are linked into centrosymmetric R⁴₄(30) motifs by a C—H...O interaction. There are no aromatic π–π stacking and no C—H...π(arene) interactions. Compound (I) can be used as a nucleophilic tecton in self‐assembly reactions with metal centres of varying lability.     

一个新颖的由Zn配合物修饰的Keggin型钴钨酸盐：[Zn(2,2’-bipy)3]3{[Zn(2,2’-bipy)2(H2O)]2 [HCoW12O40] 2 }.H2O

通过水热合成技术,一个新颖的基于Zn配合物修饰的Keggin型钴钨酸的有机-无机杂化化合物：[Zn(2,2’-bipy)3]3{[Zn(2,2’-bipy)2(H2O)]2 [HCoW12O40] 2 }.H2O已经被合成,化合物通过红外光谱、热重分析和单晶X-射线衍射进行了表征。单晶X-射线衍射的结果显示标题化合物是由一个单支撑的{[Zn(2,2’-bipy)2(H2O)]2 [HCoW12O40] 2}6-多阴离子,三个[Zn(2,2’-bipy)3]2+阳离子和一个水分子构成。有趣的是[Zn(1)(2,2’-bipy)3]2+阳离子通过氢键连接在一起形成螺旋链。另外标题化合物在空气中是稳定的,并且在室温下显示了强的荧光。     

Structural and Photophysical Properties of Lanthanide Nitrate 1:1 Complexes with planar tridentate nitrogen ligands analogous to 2,2′:6′,2′-terpyridine

The ligand 2,6-bis(1-methylbenzimidazol-2-yl)pyridine (mbzimpy, 1 ) reacts with Eu^III to give [Eu(mbzimpy)(NO₃)₃(CH₃OH)] [ 4 ] whose crystal structure (EuC₂₂H₂₁N₈O₁₀, a = 7.658(3) Å, b = 19.136(2) Å, c = 8.882 Å, β = 104.07(1)°, monoclinic, P2₁, Z = 2) shows a mononuclear structure where Eu^III is ten-coordinate by a meridional tridentate mbzimpy ligand, three bidentate nitrates, and one CH₃OH molecule, leading to a low-symmetry coordination sphere around the metalion. Essentially the same coordination is found in the crystal structure of [Eu(obzimpy)(NO₃)₃] ( 8 ) (EuC₃₅H₄₅N₈O₉, a = 9.095(2) Å, b = 16.624(2) Å, c = 26.198(6) Å, β = 95.85(1)°, monoclinic, P2₁/c, Z = 4) obtained by reaction of 2,6-bis(1-octylbenzimidazol-2-yl)pyridine (obzimpy, 2 ) with Eu^III. Detailed photophysical studies of crystalline [Ln(mbzimpy)(NO₃)₃(CH₃OH)] and [Ln(obzimpy)(NO₃)₃] complexes (Ln = Eu, Gd, Tb, Lu) show that 1 and 2 display ¹ππ* and ³ππ* excited states very similar to those observed in 2,2′:6′,2″-terpyridine, leading to efficient ligand to Ln^III intramolecular energy transfer. Spectroscopic results show that an extremely efficient mbzimpy-to-Eu^III transfer occurs in [Ln(mbzimpy)(NO₃)₃(CH₃OH)] and in the case of Tb^III, a Tb^III-to-mbzimpy back transfer is also implied in the deactivation process. The origin of these peculiar effects and the influence of ligand design by going from mbzimpy to obzimpy are discussed. ¹H-NMR and luminescence data indicate that the structure found in the crystal is essentially maintained in solution.     

A chloro(2‐pyridinecarboxaldehyde)(2,2′:6′,2′′‐ter­pyridine)­ruthenium(II) complex

The aldehyde moiety in the title complex, chloro(2‐pyridinecarboxaldehyde‐N,O)(2,2′:6′,2′′‐terpyridine‐κ³N)ruthenium(II)–chloro­(2‐pyridine­carboxyl­ic acid‐N,O)(2,2′:6′,2′′‐ter­pyridine‐κ³N)­ruthenium(II)–perchlorate–chloro­form–water (1.8/0.2/2/1/1), [RuCl­(C₆H₅NO)­(C₁₅H₁₁N₃)]_1.8[RuCl­(C₆H₅­NO₂)(C₁₅H₁₁N₃)]_0.2­(ClO₄)₂·­CHCl₃·­H₂O, is a structural model of substrate coordination to a transfer hydrogenation catalyst. The title complex features two independent Ru^II complex cations that display very similar distorted octahedral coordination provided by the three N atoms of the 2,2′:6′,2′′‐ter­pyridine ligand, the N and O atoms of the 2‐pyridine­carbox­aldehyde (pyCHO) ligand and a chloride ligand. One of the cation sites is disordered such that the aldehyde group is replaced by a 20 (1)% contribution from a carboxyl­ic acid group (aldehyde H replaced by carboxyl O—H). Notable dimensions in the non‐disordered complex cation are Ru—N 2.034 (2) Å and Ru—O 2.079 (2) Å to the pyCHO ligand and O—C 1.239 (4) Å for the pyCHO carbonyl group.     

New organic–inorganic frameworks incorporating iso‐ and heteropolymolybdate units and a 3,3′,5,5′‐tetramethyl‐4,4′‐bi‐1H‐pyrazole‐2,2′‐diium multiple hydrogen‐bond donor

Poly[bis(3,3′,5,5′‐tetramethyl‐4,4′‐bi‐1H‐pyrazole‐2,2′‐diium) γ‐octamolybdate(VI) dihydrate], {(C₁₀H₁₆N₄)₂[Mo₈O₂₆]·2H₂O}_n, (I), and bis(3,3′,5,5′‐tetramethyl‐4,4′‐bi‐1H‐pyrazole‐2,2′‐diium) α‐dodecamolybdo(VI)silicate tetrahydrate, (C₁₀H₁₆N₄)₂[SiMo₁₂O₄₀]·4H₂O, (II), display intense hydrogen bonding between the cationic pyrazolium species and the metal oxide anions. In (I), the asymmetric unit contains half a centrosymmetric γ‐type [Mo₈O₂₆]⁴⁻ anion, which produces a one‐dimensional polymeric chain by corner‐sharing, one cation and one water molecule. Three‐centre bonding with 3,3′,5,5′‐tetramethyl‐4,4′‐bi‐1H‐pyrazole‐2,2′‐diium, denoted [H₂Me₄bpz]²⁺ [N...O = 2.770 (4)–3.146 (4) Å], generates two‐dimensional layers that are further linked by hydrogen bonds involving water molecules [O...O = 2.902 (4) and 3.010 (4) Å]. In (II), each of the four independent [H₂Me₄bpz]²⁺ cations lies across a twofold axis. They link layers of [SiMo₁₂O₄₀]⁴⁻ anions into a three‐dimensional framework, and the preferred sites for pyrazolium/anion hydrogen bonding are the terminal oxide atoms [N...O = 2.866 (6)–2.999 (6) Å], while anion/aqua interactions occur preferentially viaμ₂‐O sites [O...O = 2.910 (6)–3.151 (6) Å].     

Die Kristallstruktur von [MoO2F2(2,2′-Bipyridyl)]

The Crystal Structure of [MoO₂F₂(2,2′-bipyridyl)] The title compound crystallizes in the space group P2₁/n with a = 869.6(1), b = 1390.1(3), c = 959.0(1) pm, β = 110.967(5)°, Z = 4; structure determination with 1718 observed independent reflections, R = 0.031. The compound consists of molecules having two cis oxo ligands and a bipyridyl chelate in the MoO₂ plane.     

Dinuclear and Mononuclear Platinum(II) and Palladium(II) Complexes with Modified 2,2′‐Dipyridylamine Ligands Featuring a Cisplatin Analogous Structure Motif

In modern cancer therapy the clinical application of platinum‐based drugs is more and more limited by the occurrence of intrinsic or acquired resistances. In this context the potential use of dinuclear platinum complexes in chemotherapy is increasingly relevant. The novel complexes Pd(Bzdpa)Cl₂, Pd₂(C₄H₈(dpa)₂)Cl₄, and Pt₂(C₄H₈(dpa)₂)Cl₄ allow a direct comparison of mono‐ and dinuclear palladium and platinum complexes respectively deriving from a 2,2′‐dipyridylamine (Hdpa) ligand system. They were characterized by single crystal X‐ray analysis as well as infrared spectroscopy and elemental analysis. The cisplatin analogous mononuclear palladium complex Pd(Bzdpa)Cl₂ ( 1 ) (Bzdpa: (2,2′‐dipyridylbenzyl)amine) belongs to a range of 2,2′‐dipyridylamine‐based compounds which were extensively studied in our laboratories. 1 crystallizes in the orthorhombic space group Pna2₁ with a = 13.722(3), b = 13.457(3), c = 9.483(2), V = 1751.1(6) ų, and Z = 4. The metal binding motif of 1 was expanded by a flexible butyl‐linker to form the tetradentate C₄H₈(dpa)₂ ligand. The resulting isotypic dinuclear complexes Pd₂(C₄H₈(dpa)₂)Cl₄·2CH₃CN ( 2 ) and Pt₂(C₄H₈(dpa)₂)Cl₄·2CH₃CN ( 3 ) crystallize in the triclinic space group with a = 7.8427(2), b = 8.7940(2), c = 11.7645 (3), α = 79.219(2)°, β = 84.033(2)°, γ = 87.744(2)°, V = 792.58(3) ų ( 2 ) and a = 7.831(5), b = 8.814(5), c = 11.817(5), α = 79.271(5)°, β = 83.571(5)°, γ = 88.063(5)°, V = 796.3(8) ų ( 3 ), both with one centrosymmetrical molecule in the unit cell.     

Synthesis,Crystal Structure,and Magnetic Properties of (2,2′‐dipyridylamine)(X−) Copper(II) Complexes (X−: Cyanate,Dicyanamide, Acetate,Thiocyanato)

The synthesis, structure, and magnetic properties of four 2,2′‐dipyridylamine ligand (abbreviated as Hdpa) containing copper(II) complexes. There is one binuclear compound, which is [Cu₂(μ_1,1‐NCO)₂(NCO)₂(Hdpa)₂] ( 1 ), and three mononuclear compounds, which are [Cu{N(CN)₂}₂(Hdpa)₂] ( 2 ), [Cu(CH₃CO₂)(Hdpa)₂·N(CN)₂] ( 3 ), and [Cu(NCS)(Acac)] ( 4 ). Compounds 1 and 4 crystallize in the monoclinic system, space group P2(1)/c and Z = 4, with a = 8.2465(6) Å, b = 9.3059(7) Å, c = 16.0817(12) Å, β = 91.090(1)°, and V = 1233.90(16) ų for 1 and a = 7.6766(6) Å, b = 21.888(3) Å, c = 10.4678(12) Å, β = 90.301(2)°, and V= 1758.8(4) ų for 4 . Compounds 2 and 3 crystallize in the triclinic system, space group P‐1 and Z = 1, with a = 8.1140(3) Å, b = 8.2470(3) Å, c = 9.3120(4) Å, β = 102.2370(10)°, and V = 592.63(4) ų for 2 and a = 7.4780(2) Å, b = 12.5700(3) Å, c = 13.0450(3) Å, β = 96.351(2)°, and V = 1211.17(5) ų for 3 . Complex ( 1 ), the magnetic data was fitted by the Bleaney‐Bowers equation (1). A very good fit was derived with J = 23.96, Θ = ?1.5 (g = 1.97). Complex ( 1 ) shows the ferromagnetism. Complexes ( 2 ), ( 3 ) and ( 4 ) of have the it is the typical paramagnetic behavior of unpaired electrons. Under a low temperature around 25 K, complexes ( 2 ) and ( 3 ) show weak ferromagnetic behavior. They are the cause of hydrogen bonds.     

Electrochemical synthesis of Nickel(II) Complexes of schiff bases: The crystal structure of 2,2′-bipyridine bis{2-[(phenyl)iminomethyl]pyrrolato}nickel(II)

The electrochemical oxidation of anodic nickel in acetonitrile solution containing both (a) a Schiff base HL derived from H-pyrrole-2-carbaldehyde and a substituted aniline, and (b) a nitrogen ligand (1, 10-phenanthroline (phen), 2,2′-bipyridine (bipy) or pyridine (py)) yielded the mixed complexes NiL₂ · phen, NiL₂ · bipy and NiL₂ · (py)₂. The crystal structure of 2,2′-bipyridine bis{2-[(phenyl)iminomethyl]pyrrolato}nickel(II) was determined by X ray diffraction. Crystals are triclinic space group P1 , with four molecules in the unit cell of dimensions a = 12.316(1), b = 13.169(4), c = 17.251(3) Å, α = 82.67(3)°, β = 83.66(1)° and γ = 87.34(2)°, and consist of monomeric molecules in which the central NiN₆ unit has a distorted octahedral geometry.     

2,2′‐Anhydro‐1‐(3′,5′‐di‐O‐acetyl‐β‐D‐arabinofuranosyl)uracil,a cyclouridine nucleoside with a C4′‐endo furanosyl conformation

2,2′‐Anhydro‐1‐(3′,5′‐di‐O‐acetyl‐β‐D‐arabinofuranosyl)uracil, C₁₃H₁₄N₂O₇, was obtained by refluxing 2′,3′‐O‐(methoxymethylene)uridine in acetic anhydride. The structure exhibits a nearly perfect C4′‐endo (⁴E) conformation. The best four‐atom plane of the five‐membered furanose ring is O—C—C—C, involving the C atoms of the fused five‐membered oxazolidine ring, and the torsion angle is only −0.4 (2)°. The oxazolidine ring is essentially coplanar with the six‐membered uracil ring [r.m.s. deviation = 0.012 (5) Å and dihedral angle = −3.2 (3)°]. The conformation at the exocyclic C—C bond is gauche–trans which is stabilized by various C—H...π and C—O...π interactions.     

Über die Reaktion von 2,2-Dimethylpropylidinphosphan mit Molybdänpentachlorid; die Kristallstruktur von [Mo2Cl6(α,α′-Dipyridyl)3]

Reaction of 2,2-Dimethylpropylidynephosphine with Molybdenum Pentachloride; Crystal Structure of [Mo₂Cl₆(α,α′-dipyridyl)₃] 2,2-Dimethylpropylidynephosphine and molybdenum pentachloride dissolved in POCl₃ react with oxydation of the phosphorus and reduction of the molybdenum atom to give the alkyne complex [Mo₂Cl₄(μ-Cl)₂(μ-H₉C₄? C?C? C₄H₉)(OPCl₃)₂]. Addition of α,α′-dipyridyl or of methyltriphenylphosphonium chloride in dichloromethane results in a displacement of the ligands POCl₃ and H₉C₄? C?C? C₄H₉ from this complex and in the formation of [Mo₂Cl₆(dipy)₃] or [(H₅C₆? )₃P? CH₃]₃[Mo₂Cl₉]. Besides the latter compound small amounts of [(H₅C₆? )₃P? CH₃]₂[MoCl₆] can be isolated from the reaction mixture. [Mo₂Cl₆(dipy)₃] which has already been prepared by other methods crystallizes in the monoclinic space group P2₁/c with {a = 1612; b = 148; c = 1296 pm; γ 109.3°; Z = 4} at 20°C. As shown by a crystal structure determination the complex is built up from [MoCl₂(dipy)₂]⁺ cations and [MoCl₄(dipy)]^? anions. The molybdenum atoms are both octahedrally surrounded. With average values of 238 and 243 pm the Mo? Cl bond distances in the cation, where a cis-arrangement of the chlorine atoms is observed, and in the anion differ significantly from each other. [Mo₂Cl₆(dipy)₃] which has already been prepared by other methods crystallizes in the monoclinic space group P2₁/c with {a = 1612; b = 148; c = 1296 pm; γ = 109.3°; Z = 4} at 20°C. As shown by a crystal structure determination the complex is built up from [MoCl₂(dipy)₂]⁺ cations and [MoCl₄(dipy)]^? anions. The molybdenum atoms are both octahedrally surrounded. With average values of 238 and 243 pm the Mo? Cl bond distances in the cation, where a cis-arrangement of the chlorine atoms is observed, and in the anion differ significantly from each other.     

Hydrothermal Synthesis and X‐ray Crystal Structure of Four Inorganic‐Organic Hybrid Compounds in Vanadium /Copper Iodate Family

Four inorganic‐organic hybrid compounds with the formulae (1,10‐phen)(VO₂)(IO₃) ( 1 ), (2,2′‐bipy)(VO₂)(IO₃) ( 2 ), [Cu₃(2,2′‐bipy)₃Cl₃(IO₃)₂]·I_1.5 ( 3 ), and [Cu(2,2′‐bipy)(H₂O)(IO₃)₂]· (H₂O)₂ ( 4 ) are hydrothermally synthesized at 120 °C for 6 d and characterized by single‐crystal X‐ray diffraction. The use of two different bidentate organodiamine ligands 1,10‐phen and 2,2′‐bipy in the V/I/O system gives rise to compounds 1 and 2 , which crystallize in a monoclinic system with the space group C2/c, a = 17.8131(6) Å, b = 15.0470(7) Å, c = 12.9902(4) Å, β = 133.095(2)°, V = 2542.49(17) ų for 1 and space group P2₁/c, a = 13.3095(5) Å, b = 15.0993(8) Å, c = 13.0454(4) Å, β = 116.971(2)°, V = 2335.88(17) ų for 2 . The use of the bidentate organodiamine ligand 2,2′‐bipy in the Cu/I/O system gives rise to the variety in the structure of products 3 and 4 , which crystallize in a triclinic system with the same space group . a = 8.5143(2) Å, b = 10.4908(3) Å, c = 22.8420(6) Å, α = 93.769(10)°, β = 91.723(10)°, γ = 112.111(10)°, V = 1882.83(9) ų for 3 and a = 6.731(6) Å, b = 10.110(4) Å, c = 12.899(6) Å, α = 106.00(5)°, β = 95.45(4)°, γ = 107.69(6)°, V = 788.4(9) ų for 4 . The solid‐state structures of the compounds 1 and 2 have chains with repeat units of alternative corner sharing of [VO₄N₂] octahedra and [IO₃] pyramids. Compound 3 is a chain containing [IO₃] pyramids and [VO₄N] square pyramids and compound 4 consists of Cu(2,2′‐bipy)²⁺ linked by one water molecule and two [IO₃] pyramids. The thermal stabilities of the compounds are investigated.     

Darstellung und Strukturen von (η6‐Diaren)TiII‐bis(tetrachloroaluminat)Komplexen,Diaren = Biphenyl oder 3,5,3′,5′‐Tetramethyl‐biphenyl

Syntheses and Crystal Structures of (η⁶‐Diarene)Ti^II‐bis(tetrachloroaluminate) Complexes, Diarene = Biphenyl or 3,5,3′,5′‐Tetramethyl‐biphenyl Syntheses of (η⁶‐diarene)Ti^II(AlCl₄)₂ complexes were performed by the Fischer‐Hafner method. The diarenes employed were biphenyl and 3,5,3′,5′‐tetramethyl‐biphenyl. In each of the resulting complexes, (η⁶‐C₁₂H₁₀)Ti^II(AlCl₄)₂ ( 1 ) and (η⁶‐C₁₆H₁₈)Ti^II(AlCl₄)₂ ( 2 ), only one C₆‐ring of a diarene is coordinatively active. 1 : Space group Pbca, Z = 8, lattice constants at 20 °C: a = 16.864(3), b = 13.931(3), c = 18.807(3) Å; R₁ = 0.048. 2 : Space group P2₁/n, Z = 4, lattice constants at 20 °C: a = 9.775(1), b = 13.720(1), c = 20.214(1) Å; β = 95.50(1)°; R₁ = 0.050.