Complexation with diol host compounds. 13. Crystal structures and thermal analyses of inclusion compounds of 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol with cyclohexane,O-xylene,m-xylene and p-xylene

Abstract

It has been shown that host compound 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol is able to include polar guests and now we report on its ability to form clathrate compounds with apolar guests. The structures of this host with cyclohexane (1) and the ortho (2), meta (3) and para (4) xylenes have been determined and are discussed. Crystal data: (1) 2C₃₀H₂₂O₂C₆H₁₂, M _r = 913.20 g mol^?1, mono-clinic, C2/c, a = 22.851(6), b = 14.010(2), c = 17.076(6) Å, β = 108.71(3)°, V = 5178(2) ų, Z = 4, D _c = 1.17g cm^?3, N = 3326, R = 0.092. (2) 2C₃₀H₂₂O₂1 ½C₈H₁₀, M _r = 1976.5 g mol^?1, triclinic, P 1, a = 13.185(3), b = 15.466(3), c = 16.573(2) Å, α = 96.39(13)°, β = 106.96(15)°, γ = 114.94(18)°, V = 2822(2) ų, Z = 2, D _c = 1.16 g cm^?3, N = 6152, R = 0.075. (3) 2C₃₀H₂₂O₂1 ½C₈H₁₀, M _r = 1976.5 g mol^?1, triclinic, P 1, a = 13.267(5), b = 15.453(3), c = 16.654(5) Å, α = 97.12(2)°, β = 107.09(3)°, γ = 114.68(3)°, V = 2843(2) ų, Z = 2, D _c = 1.15 g cm^?3, N = 6505, R = 0.083. (4) 2C₃₀H₂₂O₂1 ½C₈H₁₀, M _r = 1976.5 g mol^?1, triclinic, P 1, α = 13.070(2), b = 15.348(3), c = 16.776(3) Å, α = 67.88<2)°, β = 74.27(1)°, γ = 65.29(1)°, V = 2817(1) ų, Z = 2, D _c = 1.15 g cm^?3, N = 6711, R = 0.050. Thermal analysis studies were also performed in order to examine their stability and the strength with which the guest species are held in the crystal lattice.     

Crystal structure of olanzapinium benzoate (1:1)

Olanzapinium benzoate, 1-methyl-4-(2-methyl-10H-thieno[2,3-b][1,5]benzodiazepin-4-yl)-piperazin-1-ium benzoate, (C₁₇H₂₁N₄S)⁺(C₇H₅O₂)^? (I), crystallizes in triclinic space group P-1 with unit cell dimensions a = 9.2957(6) Å, b = 11.2416(7) Å, c = 12.0003(8) Å; α = 64.585(1)°, β = 87.568(1)°, γ = 83.248(1)°; V = 1124.8(1) ų. The asymmetric part of the structure comprises a singly charged olanzapinium cation and a singly charged benzoate anion. The central 1,5-diazepine ring adopts the expected boat conformation, while the piperazine ring favors the chair conformation. The olanzapinium and benzoate ions are linked by intermolecular N-H...O hydrogen bonds forming infinite chains running along the c-axis of the crystal.     

A Thermodynamic Study of Chromotropico-Titanium(III) Complex from Spectrophotometric Measurements

The formation of 1 : 2 titanium(III) complex with chromotropic acid (4, 5-dihydroxy-2, 7-naphthalene-disulfonic acid) was observed by spectrophotometric measurements at various ionic strengths. An expression, [Ti(III)]/D=1/Δ? + α_H²+/KΔ?[H₂R^2?]², was derived for the determination of the formation constant, K=7.2×10² liter² mol^?2 for the Ti(III).(HR)₂ ion in the pH range of 1.3–1.8 at constant ionic strength, I=0.2 M, at 25°C. The thermodynamic data for the reaction, Ti(III)+2H₃R^2?=Ti(III) (HR)₂+2H⁺, were calculated to be ΔG° = ?16 kJ mol^?1 ΔH° = 18 kJ mol^?1, ΔS° = 110 JK^?1 mol^?1, at 25°C.     

Crystal and molecular structures of the potassium salt of 2-methoxy-4-dimethylamino-6-dinitromethyl-1,3,5-triazine

The X-ray diffraction study of the potassium salt of 2-methoxy-4-dimethylamino-6-dinitromethyl-1,3,5-triazine is carried out. The crystals are triclinic; C₇H₉N₆O ₅ ^? ·2K⁺·2H₂O; a = 7.645(7) Å, b = 8.230(7) Å, c = 12.435(9) Å; α = 99.99(8)°, β = 91.52(7)°, γ = 113.86(8)°; V = 701(1) ų, ρ_calc = 1.58 g/cm³, Z = 2, space group P-1. The compound crystallizes as a crystalline hydrate with two water molecules. Two planar fragments of dinitromethyl and 2-methoxy-4-dimethylamino-1,3,5-triazine construct the anion. Their geometrical parameters are explored. The coordination of potassium cations and numerous hydrogen bonds are found which result in the development of a complex 3-D framework.     

Molecular structure and conformation of 2,3-dichloro-1-propene as determined by gas-phase electron diffraction

The molecular structure and conformation of 2,3-dichloro-1-propene have been determined by gas-phase electron diffraction at nozzle temperatures of 24, 90 and 273°C. The molecules exist as a mixture of two conformers with the chlorine atoms anti (torsion angle ∠φ = 0°) or gauche (∠φ = 109°) to each other and with the anti form the more stable. The composition (mole fraction) of the vapor with uncertainties estimated at 2σ was found to be 0.55 (0.08), 0.49 (0.08) and 0.41 (0.10) at 24, 90 and 273°, respectively. These values correspond to an energy difference with estimated standard deviation ΔE° = E°_g-E°_a = 0.7 ± 0.3 kcal mol^?1 and an entropy difference ΔS° = S°_g-S°_a = 0.6 ± 0.9 cal mol^?1 K^?1. Some of the diffraction results, together with spectroscopic observations, permit the evaluation of an approximate torsional potential function of the form 2V = V₁ (1 - cos φ) + V₂ (1 - cos 2φ) + V₃ (1 - cos 3φ); the results are V₁ = 4.4 ± 0.5, V₂ = ?2.9 ± 0.5 and V₃ = 4.8 ± 0.2, all in kcal mol^?1. The results at 24°C for the distance (r_a) and angle (∠_α) parameters, with estimated uncertainties of 2σ, are: r(C_sp²-H) = 1.098(0.020)Å, r(C_sp³-H) = 1.103(0.020)Å, r(CC) = 1.334(0.009)Å, r(C-C) = 1.504(0.013)Å, r(C_sp²-Cl) = 1.752(0.021)Å, r(C_sp³-Cl) = 1.776(0.020)Å, ∠C-CC = 127.6(1.1)°, ∠C_sp³-C_sp²-Cl = 110.2(1.0), ∠C_sp²-C_sp³-Cl = 113.1(1.2)°, ∠H-C_sp³-H = 109.5° (assumed), ∠CC-H = 120.0° (assumed) and ∠φ = 108.9(3.4)°.     

Thermodynamics of the second-stage dissociation of n-(2-acetamido)iminodiacetic acid in water from 5 to 55°c

The thermodynamic second dissociation constants of the protonated form of N-(2-acetamido)iminodiacetic acid were determined at 12 temperatures from 5–55°C by measurement of the electromotive force using a cell without liquid junction, with hydrogen and silver—silver bromide electrodes. At 25°C, pK₂is 6.844. The standard changes in Gibbs energy, enthalpy, entropy and heat capacity were derived from the change of the pK₂ values with temperature. At 25°C, ΔG° = 9335 cal mol^-1, ΔH° = 2928 cal mol^-1, ΔS^o = -21.5 cal K^-1 mol^-1, and ΔC°_p = -34 cal K^-1 mol^-1. The results are interpreted and compared with those of structurally related compounds.     

Synthesis and crystal structure of KBi(C6H4O7) · 3.5H2O

A novel compound, KBi(C₆H₄O₇) · 3.5H₂O (I), has been synthesized in the Bi(NO₃)₂-K₃(HCit) system (HCit^3? is an anion of citric acid C₆H₈O₇) at a component ratio (n) of 8 in a water-glycerol mixture, and its crystal structure has been determined. The crystals are unstable in air. The crystals are triclinic: a = 7.462 Å, b = 10.064 Å, c = 17.582 Å, α = 100.27°, β = 99.31°, γ = 105.48°, V = 1221.2 ų, Z = 2, space group $P\bar 1$ . In the structure of I, asymmetric binuclear fragments [Bi₂(Cit^4?)₂(H₂O)₂]^2? are linked through inversion centers into polymeric chain anions. Ions K⁺ and crystal water molecules are arranged in channels between the chains. The Bi(1)...Bi(2) distances in the binuclear fragment are 4.62 Å, and the Bi(1)...Bi(1) and Bi(2)...Bi(2) distances between bismuth atoms in the chain are 5.83 and 5.95 Å, respectively. The chains are linked through bridging oxygen atoms of the ligands Cit to form layers. In the centrosymmetric four-membered chelate ring Bi₂O₂ formed through Bi-O(Cit) bonds, the distances Bi(1)-Bi(1) are equal to 4.55 Å, and Bi(1)-O are 2.66 and 2.84 Å. The Bi-O bond lengths in I are in the range 2.12–3.16 Å. The Cit ligands act as hexadentate chelating/bridging ligands.     

Synthese,Struktur und Reaktionen von Vanadiumsäureestern VO(OR)3: Umesterung und Reaktion mit Oxalsäure

Synthesis, Structure, and Reactions of Vanadium Acid Esters VO(OR)₃: Transesterification and Reaction with Oxalic Acid The reaction of tert.‐Butyl Vanadate VO(O‐tert.Bu)₃ ( 1 ) with H₂C₂O₄ in the primary alcohols ethanol and propanol results in the formation of (ROH)(RO)₂OV^V(C₂O₄)V^VO(OR)₂(HOR) (with R = C₂H₅ 2 and R = C₃H₇ 3 ). Compounds 2 and 3 are the first structurally characterized neutral, binuclear oxo‐oxalato‐complexes with pentavalent vanadium. The two vanadium atoms are connected by a bisbidentate oxalate group. The {VO₆} coordination at each vanadium site is completed by a terminal oxo group, an alcohol ligand and two alcoxide groups. The binuclear molecules are connected to chains by hydrogen bonding. In the case of 2 a reversible isomorphic phase transition in the temperature range of –90 °C to –130 °C is observed. From methanolic solution the polymeric Methyl Vanadate [VO(OMe)₃] ( 4 ) was obtained by transesterification. A report on the crystal structures of 1 , 2 and 3 as well as a redetermination of the structure of 4 is given. Crystal data: 1, orthorhombic, Cmc2₁, a = 16.61(2) Å, b = 9.274(6) Å, c = 10.784(7) Å, V = 1662(2) ų, Z = 4, d_c = 1.144 gcm^–1; 2 (–90 ° C) , monoclinic, I2/a, a = 33.502(4) Å, b = 7.193(1) Å, c = 15.903(2) Å und β = 143.060(3)°, V = 2303(1) ų, Z = 4, d_c = 1.425 gcm^–1; 2 (–130 ° C) , monoclinic, I2/a, a = 33.274(4) Å, b = 7.161(1) Å, c = 47.554(5) Å, β = 142.798(2)°, V = 6851(1) ų, Z = 12, d_c = 1.438 gcm^–1; 3 , triklinic, P1, a = 9.017(5) Å, b = 9.754(5) Å, c = 16.359(9) Å, α = 94.87(2)°, β = 93.34(2)°, γ = 90.42(2)°, V = 1431(1) ų, Z = 2, d_c = 1.340 gcm^–1; 4 , triklinic, P1, a = 8.443(2) Å, b = 8.545(2) Å, c = 9.665(2) Å, α = 103.202(5)°, β = 96.476(5)°, γ = 112.730(4)°, V = 610.2(2)ų, Z = 4, d_c = 1.742 gcm^–1.     

Non‐Isomorphic Chlorine—Bromine Substitution in the Copper(I) Halide π‐Complexes with 1‐Allyl‐4‐aminopyridinium

By alternating‐current electrochemical synthesis crystals of {Cu[H₂NC₅H₄N(C₃H₅)]Br₂} ˙ H₂O ( I ), {Cu[H₂NC₅H₄N(C₃H₅)]Br_0.65Cl_1.35} ˙ 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)Å, b = 12.3880(6)Å, c = 13.637(3)Å, β = 107.03(1)°, V = 1188.7(4)ų, Z = 4 for C₈H₁₃N₂OBr₂Cu composition, R = 0.0293 for 2140 reflections. II : a = 7.2771(6)Å, b = 12.3338(3)Å, c = 13.4366(7)Å, β = 107.632(2)°, V = 1149.3(1)ų, Z = 4 for C₈H₁₃N₂Br_0.65Cl_1.35Cu 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)Å, b = 7.260(2)Å, c = 13.331(3)Å, β = 95.65(2)°, V = 2077(2)ų, 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 .     

Crystal structure of 1-cyclohexylpiperazine-1,4-diium dichromate(VI)

Single crystals of 1-cyclohexylpiperazine-1,4-diium dichromate(VI), (C₁₀H₂₂N₂)[Cr₂O₇], were obtained by slow evaporation at room temperature from an aqueous solution of potassium dichromate, hydrochloric acid and 1-cyclohexylpiperazine. (C₁₀H₂₂N₂)[Cr₂O₇] is triclinic (P\(\bar 1\)) with a = 10.351(2) Å, b = 12.766(3) Å, c = 6.111(1) Å, α = 91.50(2)°, β = 104.26(3)°, γ = 94.91(2)°, V = 778.8(3) ų, and Z = 2. The structure determination performed from single crystal X-ray diffraction data leads to R₁/wR₂ reliability factors of 0.032/0.078. The asymmetric unit of the title salt C₁₀H₂₂N₂²⁺·Cr₂O₇^2?, consists of one 1-cyclohexylpiperazine-1,4-diium dication and one dichromate dianion. These entities are linked together by N–H···O hydrogen bonds to form {(C₁₀H₂₂N₂)[Cr₂O₇]}_n infinite chains lying parallel to the (100) plane and running along the c axis. The intermolecular N–H···O hydrogen bonds link these chains into a two-dimensional network structure consolidated through C–H···O weak interactions.     

Second crystal modification of 1,10-diazonia-18-crown-6 dichloride

The second crystal modification (II) of 1,10-diazonia-18-crown-6 dichloride [H₂DA18C6]²⁺·2Cl^?, where [H₂DA18C6]²⁺ is the 1,10-diaza-18-crown-6 dication (DA18C6) with two protonated nitrogen atoms, was investigated by XRD. The monoclinic modification (II) (space group P2₁/n, a = 9.600 Å, b = 5.689 Å, c = 15.749 Å, β = 91.03°, Z = 2) was solved by direct methods and refined by full-matrix least squares analysis in an anisotropic approximation to R = 0.032 for all 2494 independent reflections collected (CAD-4 automatic diffractometer, λMoK _α). In modification II, the conformation of the DA18C6 dication and the ion packing differ from those in triclinic modification I investigated previously.     

Synthesis,Structure and Magnetism of Bis[1,2,4‐tris(trimethylsilyl)cyclopentadienyl]europium

Bis[tris(trimethylsilyl)cyclopentadienyl]europium, Eu{C₅H₂[Si(CH₃)₃]₃}₂ (1) , has been synthesized by a modified transmetallation route between Tl{C₅H₂[Si(CH₃)₃]₃} and europium powder in toluene. 1 crystallizes in the monoclinic space group C2/c (No. 15) with a = 20.293(5) Å, b = 20.221(5) Å, c = 9.654(2) Å, β = 106.412(5)°, V = 3800.1(15) ų, Z = 4. The unit cell contains monomeric molecules that adopt a bent metallocene conformation with two partially staggered Cp? ligands. Magnetic susceptibility measurements in the temperature range 2–300 K display ideal Curie paramagnetic behaviour of the 4f⁷ system with Curie constant C = 9.6 × 10^?5 m³ K mol^?1 corresponding to temperature independent μ_eff = 7.8.     

Unique Bridging Function of the Triazole Core in Copper(II) Chloride Complexes with 1‐Allylbenzotriazole

During alternating‐current electrochemical synthesis of copper(I) π‐complex of [CuCl{C₆H₄N₃(C₃H₅)}] composition, starting from ethanol solution, containing CuCl₂·2H₂O and 1‐allylbenzotriazole, green crystals of intermediate [Cu^II₃Cl₆{C₆H₄N₃(C₃H₅)}₄] ( I ) compound has been obtained upon 24 h. After some days these crystals transform into red ones of [Cu^II₂Cl₄{C₆H₄N₃(C₃H₅)}₃] ( II ). Both compounds were X‐Ray structurally investigated. Crystals of I are triclinic, sp.gr. a = 9.1329(9), b = 10.0352(4), c = 12.239(3) Å, α = 76.443(13), β = 84.470(14), γ = 76.808(7)°, V = 1060.5(3) ų, R = 0.0414 for 3311 reflections. II : monoclinic, C2/c, a = 13.828(1), b = 15.044(2), c = 10.702(1) Å, β = 91.36(1)°, V = 2225.7(4) ų, R = 0.050 for 1495 reflections. In both compounds each benzotriazole core coordinates two copper atoms using two nitrogen atoms in 2 and 3 positions. Isolated Cu₃Cl₆ fragments in I are condensed along [001] direction into infinite chains [CuCl₂]_n in II. Finally, red crystals of II transform into colorless ones of the earlier studied copper(I) π‐complex of CuCl·C₆H₄N₃(C₃H₅) composition.     

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) Å, b = 8.395(1) Å, c = 12.879(2) Å, α = 95.33(1)°, β = 104.56(1)°, γ = 106.76(1)°, V = 814.1(2) ų, 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 Å, d(Mn–N) = 2.307 Å). The crystal structure of 2 (P1 (no. 2), a = 14.289(2) Å, b = 15.182(2) Å, c = 15.913(2) Å, α = 67.108(7)°, β = 87.27(1)°, γ = 68.216(8)°, V = 2934.2(7) ų, 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 Å, d(Mn–N) = 2.277–2.355 Å). Interestingly, the succinato ligands in the complex molecules assume gauche conformation bidentately to chelate the Mn atoms into seven‐membered rings.     

Triethylaluminum-Based Ferrocenylalanes. Synthesis and Crystal Structure of (η5−C5H5)Fe[η5−C5H4Al2(C2H5)4Cl]

Abstract

The trietheylaluminum based ferrocenylalane (η⁵?C₅H₅)Fe[η⁵?C₅H₄Al₂(C₂H₅)₄Cl] was prepared from the reaction of triethylaluminum with chloromercuriferrocene in toluene and characterized by single crystal X-ray diffraction. The compound crystallizes in the triclinic space group P 1 with unit cell dimensions a = 9.353(3) Å, b = 10.281(7) Å, c = 11.599(9) Å, α = 79.64(7)°, β = 69.41(6)°, γ = 84.33(4)°, and Z = 2 for D_c = 1.27 g cm^?3. Full-matrix least-squares refinement has led to a final R factor of 0.068 based on 1866 independent observed reflections. The two diethylaluminum units are bridged by a chlorine atom and one carbon atom of a cyclopentadienyl group, thus forming an Al-Cl-Al-C ring. The four-membered ring is planar to within 0.02 Å. The Al-Cl distances are 2.404(4) Å and 2.266(5) Å. The Al-Cl-Al angle is 78.9(1)° while the Al-C-Al angle is 91.3(4)°. No significant aluminum-iron interaction is observed (Al… Fe = 3.137(4) Å).     

The crystal and molecular structure of phenothiazine-10-propionitrile. The effect of crystal packing on the dihedral angle of phenothiazine heterocycles

Phenothiazine-10-propionitrile, C₁₂H₈SNC₂H₄CN, crystallizes in the centrosymmetric monoclinic space group P2₁/n, with a = 5.785(1)Å, b = 15.427(3)Å, c = 14.497(4)Å, β = 92.50(1)°, Z = 4, D_meas = 1.29(1) g cm³ and D_calc = 1.28 g cm³ at 23°. Three dimensional X-ray data were collected with a manual diffractometer using MoKα (λ 0.71069Å) radiation and by multiple film Weissenberg techniques using CuKα (λ 1.5418Å) radiation. The structure was determined by Patterson and Fourier methods and refined with 519 observed reflections by full matrix least-squares methods to an R of 0.077. The dihedral angle between the two planes of the o-phenylene rings is 135.4(3)°. In the folded heterocyclic ring the C-S-C angle is 97.8(7)° and the average C? S bond is 1.76(1)Å. A comparison of this structure to that of phenothiazine-10-propionic acid shows the two chemically similar molecules have the same dihedral angles in spite of completely different solid state packing patterns.     

Seltenerdhalogenide Ln4X5Z. Teil 1: C und/oder C2 in Ln4X5Z

Rare Earth Halides Ln₄X₅Z. Part 1: C and/or C₂ in Ln₄X₅Z The compounds Ln₄X₅C_n (Ln = La, Ce, Pr; X = Br, I and 1.0 < n < 2.0) are prepared by the reaction of LnX₃, Ln metal and graphite in sealed Ta‐ampoules at temperatures 850 °C < T < 1050 °C. They crystallize in the monoclinic space group C2/m. La₄I₅C_1.5: a = 19.849(4) Å, b = 4.1410(8) Å, c = 8.956(2) Å, β = 103.86(3)°, La₄I₅C_2.0: a = 19.907(4) Å, b = 4.1482(8) Å, c = 8.963(2) Å, β = 104.36(3)°, Ce₄Br₅C_1.0: a = 18.306(5) Å, b = 3.9735(6) Å, c = 8.378(2) Å, β=104.91(2)°, Ce₄Br₅C_1.5: a = 18.996(2) Å, b = 3.9310(3) Å, c = 8.282(7) Å, β = 106.74(1)°, Pr₄Br₅C_1.3: a = 18.467(2) Å, b = 3.911(1) Å, c = 8.258(7) Å, β = 105.25(1)° and Pr₄Br₅C_1.5: a = 19.044(2) Å, b = 3.9368(1) Å, c = 8.254(7) Å, β = 106.48(1)°. In the crystal structure the lanthanide metals are connected to Ln₆‐octahedra centered by carbon atoms or C₂‐groups. The Ln₆‐octahedra are condensed via opposite edges to chains and surrounded by X atoms which interconnect the chains. A part n of isolated C‐atoms is substituted by 1‐n C₂‐groups. The C‐C distances range between 1.26 and 1.40Å. In the ionic formulation (Ln³⁺)₄(X^?)₅(C^4?)_n(C₂^m?)_1?n·e^? with 0 < n < 1 and m = 2, 4, 6 (C₂^2?, C₂^4? C₂^6?), there are 1 < e^? < 5 electrons centered in metal‐metal bonds.     

Novel Motif of Hydrogen Bonds in the Water-assisted Supramolecular Self-assembly of 2-acetylamino-6-methylpyridine-N-oxide and Hetero-assembly of 1:1 Co-crystal of o-Phenylenediamine with Catechol

Abstract

Water assisted supramolecular structures of 2-acetylamino-6-methylpyridine-1-oxide (1) and 1:1 complex of o-phenylenediamine with catechol (2) were determined. The crystal structure of 2-acetylamino-6-methylpyridine-1-oxide. H₂O (1), triclinic, a = 7.1276 (6), b = 7.8860 (6), c = 8.9938 (7) Å, α = 100. 143 (2), β = 91.493 (2), γ = 110.972 (1)°, V =462.47 (6) ų, Z = 2, D _calc = 1.323 mg.m^?3(293°K) reveals a novel centrosymmetric supramolecular assembly that is sustained by water molecules linking the dimers of pyridine-1-oxide through C—H…O, N—H…O, N⁺—O^? … H hydrogen bonds. The pyridine rings of the dimers are stacked at 3.473 Å apart, involving π- stacking interactions. Complex (2), C₆H₈N₂.—C₆ H₆O₂. 1/2H₂O crystallises in the monoclinic space group P2/c: a = 9.0498(2), b = 5.2275(1), c = 25.0771(2) A, β = 97.71°, V= 1175.62(4) ų, Z = 4. Refinement led to a final conventional R value of 0.041 for 2016 reflections. In these crystals (2), the water molecules lie on the twofold axis and they are linked to the pyrocatechol molecules through an O—H…O hydrogen bond.     

Unique Isle Anion [Cu6Cl10]4- in π-Complex of Cu(I) Chloride with 1-(2-Pyridyl)-4-allyl-piperazinium. Synthesis and crystal structure of [(C5H4NH)NC4H8NH(C3H5]2+[Cu3Cl5]2-

Single crystals of [(C₅H₄NH)NC₄H₈NH(C₃H₅)]²⁺[Cu₃Cl₅]^2? are obtained by ac synthesis in ethanol from 1-(2-pyridyl)-4-allyl-piperazinium and Cu(II) dichlorides and their structure is studied by X-ray diffraction analysis (space group P-1, a = 7.246(7) Å, b = 8.54(1) Å, c = 16.41(1) Å, α = 70.76(8)°, β = 77.24(8)°, λ = 80.42(9)°, V = 30(4) ų, Z = 2, R(F) = 0.0686. In the structure of this π-complex, the Cu and Cl atoms form unusual centrosymmetrical Cu₆Cl₁₀ fragments, each fragment being bonded to two 1-(2-pyridyl)-4-allyl-piper-azinium cations via π-interaction Cu-(C=C). A three-dimensional structure is formed by means of N-H…Cl hydrogen bonds. The trigonal-pyramidal surrounding of the Cu(1) atom includes three Cl atoms and the C=C bond, while the tetrahedral surrounding of Cu(2) and the trigonal surrounding of Cu(3) involve the Cl atoms only.     

4‐Iodo­anilinium 3‐nitro­phthalate(1–): tripartite sheets built from O—H...O and N—H...O hydrogen bonds

In the title compound, 4‐iodoanilinium 2‐carboxy‐6‐nitrobenzoate, C₆H₇IN⁺·C₈H₄NO₆⁻, the anions are linked by an O—H...O hydrogen bond [H...O = 1.78 Å, O...O = 2.614 (3) Å and O—H...O = 171°] into C(7) chains, and these chains are linked by two two‐centre N—H...O hydrogen bonds [H...O = 1.86 and 1.92 Å, N...O = 2.700 (3) and 2.786 (3) Å, and N—H...O = 153 and 158°] and one three‐centre N—H...(O)₂ hydrogen bond [H...O = 2.02 and 2.41 Å, N...O = 2.896 (3) and 2.789 (3) Å, N—H...O = 162 and 105°, and O...H...O = 92°], thus forming sheets con­taining R(6), R(8), R(13) and R(18) rings.