Crystal structure of an uncomplexed 25-crown-7 comprising one 2,6-pyridino and two 1,4-benzo condensations

Single crystal X-ray analysis of the uncomplexed crown macroring 1 is reported. Crystals are triclinic, , witha=10.809(1),b=10.945(1),c=10.256(1) Å, =107.85(1), =104.15(1), =87.27(1)°,D _c=1.318 g cm^–3,Z=2. Three torsion angles in the macrocycle take upgauche conformations in contrast to the usualanti conformation. The crystal structure is stabilized by intramolecular van der Waals forces and weak C–H...O and C–H...N hydrogen bond attractions. Stacking of pyridine rings is a noticeable packing feature in the crystal lattice. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82168 (6 pages).Macroring Uncharged Molecule Complexation. Part 20. For Part 19 of this series see Ref. [1].     

Thiazane-2, 4-dithione and its 3-aryl derivatives

Reaction of 2-thiothiazane-4-one and its 3-aryl derivatives with phosphorus pentasulfide in toluene or dichloroethane gives thiazane-2, 4-dithione, or the corresponding 3-aryl derivatives. The compounds are characterized by absorption maxima (or bends) at three bands, 244–262, 315–321, and 339–350 m. The IR spectra exhibit bands at 14.93 (C-S-C), 6.64, and 6.84 (N-C-S), and 7.34, 8.43, 7.14 (CH₂).     

Neutral molecule/crown ether interactions 5. Comparison of the C−H acidic interactions of nitromethane and acetonitrile with 18-crown-6 and dibenzo-18-crown-6. Crystal structures of dibenzo-18-crown-6·2 CH3NO2 and dibenzo-18-crown-6·2 CH3CN

Complete structural characterization of dibenzo-18-crown-6·2 CH₃NO₂ and dibenzo-18-crown-6·2 CH₃CN have been carried out, including location and refinement of the methyl hydrogen atoms. Dibenzo-18-crown-6·2 CH₃NO₂ is monoclinic,P2₁/c, with (at –150°C)a=9.573(2),b=14.636(2),c=33.471(7) Å, =93.77(2)°, andD _calc=1.37 g cm^–3 forZ=8. Interactions between the solvent methyl groups and the crown ethers and other solvent nitro groups associate the 1 : 2 complexes into polymeric chains alongb. The acetonitrile adduct exists as discreet 1 : 2 complexes in the solid state with C–H...O interactions exlusively to the ether. This complex is triclinic,P 1, with (at –150°C)a=9.458(6),b=9.570(5),c=14.404(5) Å, =73.18(4), =79.85(5), =66.82(6)°, andD _calc=1.28 g cm^–3 forZ=2. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82070 (22 pages).For part 4, see reference [1].     

Synthesis,spectroscopic and structural studies of tris(3-methyl-pyridinium)(3-ethylpyridinium)β-octamolybdate monohydrate

Summary Three isostructural compounds of general formula (3-MepyH) _x (3-EtpyH)_4–x [Mo₈O₂₆] (x=0, 2, 4) crystallize in the monoclinic system, space group P2₁/n, Z=2. Previously determined parameters for the compoundx=4 area=13.652(2),b=10.887(1),c=13.759(1) Å, =90.87(1)°,V=2044.8(4) ų,Dx=2.53,Do=2.54(1) mg m^–3,F(000)=1496. Slight differences in cell dimensions have been observed whenx=0 or 2. A nonisomorphous compound of formula (3-MepyH)₃(3-EtpyH)[Mo₈O₂₆]·H₂O crystallizes in the triclinic system, space group P2₁/n,Z=2,a=10.918(1),b=10.985(3),c=18.991(2) Å, =97.19(2), =91.45(2), =107.30(2)⁰,V=2152.8(7) ų,Dx=2.456,Do=2.456(5) mg m^–3,F(000)=1532. The distinguishing features of tris(3-methylpyridinium)(3-ethylpyridinium) -octamolybdate monohydrate are its non-centrosymmetric polyanion and its extensive hydrogen bonding. The asymmetric unit contains three independent 3-methylpyridinium and one 3-ethylpyridinium cations, one water molecule and the -octamolybdate anion. The planar cations are oriented to permit hydrogen bonds with either molybdate oxygen atoms or water oxygen atoms. Four different types of hydrogen bonds have been found: N–H...O (mono- and bifurcated); N–H...Ow (monofurcated); Ow–Hw...O (monofurcated); and C–H...O (monofurcated). The proposed hydrogen bonding interactions appear to stabilize the structure.     

Crystalline inclusion compounds of tetrabenzo-18-crown-6 with uncharged organic molecules. Solid-state structure of the nitroethane complex

Tetrabenzo-18-crown-6 (1) shows distinct solid-state inclusion properties towards a number of OH-acidic, CH-acidic and low-polar uncharged organic molecules. The single crystal X-ray analysis of the inclusion complex between1 and EtNO₂ (11) is reported. Crystals are monoclinic,P2₁/c, witha=12.887(1),b=19.365(2),c=10.776(1) Å, =96.33(2)^o,D _c=1.321g cm^–1,Z=4. The host macroring has a conformation similar to a dentist's-chair. The complex is stabilized mainly by C–H...O type interactions involving the methyl group of the EtNO₂ guest molecule which is highly disordered. The nitroethane guests are trapped in channels formed by the host macrocycles. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82150 (11 pages)     

Diaqua[N,N-di(2-carboxyethyl)-o-anisidinato]copper(II) Dihydrate [Cu(o-Andp)(H2O)2] · 2H2O: Synthesis and Crystal Structure

Crystals of [Cu(o-Andp)(H₂O)₂] · 2H₂O (where o-Andp^2–is -anisidine-N,N-di-3-propionate) were synthesized and studied using X-ray diffraction analysis. The crystals are triclinic: a= 12.063(1) Å, b= 12.483(3) Å, c= 13.586(2) Å, = 91.29(1)°, = 111.67(1)°, = 104.00(1)°, V= 1830.5(5) ų, space group P , Z= 2, and R= 0.0528 for 5965 reflections with I2(I). The two crystallographically independent complexes are isostructural. The tetragonal–bipyramidal coordination of copper(III) involves three O atoms, the N atom of the tetradentate ligand o-Andp^2–, and two O atoms from water. The aminodipropionate group of the ligand (average Cu–O 1.939 Å and Cu–N 2.051 Å) and one of the coordinated water molecules (Cu–O(w) 1.991 Å) lie in the equatorial plane. The second water molecule (Cu–O(w) 2.32 Å) and the methoxy O atom of o-Andp^2–(Cu–O 2.37 Å) are in the apical positions of the bipyramid.     

Crystal Structure of Curcumenol: Evidence of Asymmetric O–H...O (bridged) Hydrogen-Bonded Closed Dimer

Curcumenol, C₁₅H₂₂O₂, was isolated from Globba malaccensis Ridl. The compound was crystallized from ethylacetate/hexane solution in the monoclinic system, space group C2, with cell dimensions a = 16.8467(4) , b = 7.6799(2) , c = 11.8613(10) , = 115.9970(10)°. The molecules form a distorted centrosymmetric dimer linked by hydrogen bonds between the hydroxyl O2 atom and the bridged O1 ether atom (O2...O1(–x+2, y, –z+1), 2.8297(15) ; (O2–H2O–O1), 169(2)°). This is an interesting example of an O–H...O (bridged ether) asymmetric hydrogen-bonded dimer.     

Coordination chemistry of alkali and alkaline earth cations. Barium-crown encapsulation studies: The synthesis and crystal structure of barium(picrate)2(benzo-15-crown-5) monohydrate

The interaction of barium with benzo-15-crown-5 (B15C5) has been followed under the competitive effect of various chelating organic anions (L), nitrophenolates and nitrobenzoates, in ethanol and ethanol-water (9:1). The rather heavily hydrated BaL₂ salts yield novel 1:1 stoichiometric products in monohydrated or anhydrous states. Use of excess crown does not under any condition lead to the formation of 1:2 charge separated complexes, expected in view of the cavity and the cation sizes. The 1:1 Ba–B15C5 interaction is counteracted by L in accordance with its nucleophilicity, i.e., the pK _a value of its parent acid, HL. The complex Ba(picrate)₂(B15C5)·H₂O (BaC₂₆H₂₆N₆O₂₀, FW=879.0), is monoclinic,P2₁/c,a=11.43(1),b=16.31(3),c=17.38(2) Å, =92.265(3)°,Z=4,D _c=1.77 g/cm³,D ₀=1.73 g/cm³, MoK, =0.71069 Å, 2 (4.0–50°), =13.5 cm^–1,F(000)=1752,T=–32°C. FinalR for the 5926 reflections was 0.049. The structure reveals barium to be 10-coordinated through all the five crown oxygens (Ba–O, 2.800 to 3.002 Å), the two bidentate picrates (Ba–O, 2.642 and 2.666 Å; Ba–ONO, 2.825 and 2.994 Å), and the water molecule (2.711 Å) so that the cation constitutes a pseudo-sandwich of the crown on one side and the anionic species on the other. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82007 (50 pages). To obtain copies, see page ii of this issue.     

Two-Dimensional Supramolecular from the Self-Assembly of Dissymmetrical Oxamidato-Bridged Heterometallic Trinuclear Building Blocks: Synthesis, Crystal Structure, and Magnetic Properties

Two heterometallic trinuclear complexes {[Cu(oxbp)]₂Co(H₂O)₂}1.5DMF0.5H₂O (complex 1) and {[Cu(oxbm)]₂Co(H₂O)₂}2DMF (complex 2) were obtained from the self-organization of two new dissymmetrical oxamidato-bridged copper(II) building blocks [Cu(oxbp)]^– and [Cu(oxbm)]^–[H₃oxbp=N-benzoato-N'-(3-aminopropyl)oxamido, H₃oxbm=N-benzoato-N'-(2-amino-2-methylethyl)oxamido, DMF=dimethylformamide]. The crystal structure of complex 1 has been determined. Complex 1 crystallize in triclinic system, space group P-1, a=8.0609(16) Å, b=10.661(2) Å, c=22.279(5) Å, =85.32(3), =86.64(3), =70.90(3), and Z=1. The crystal structure of complex 1 consists of neutral trinuclear complex units, and hydrogen bond involved DMF and water molecules. Through the hydrogen bonds, weak coordination and CuCu weak interactions, complex 1 features a 2-D supramolecular structure. Magnetic susceptibility measurements (5–100 K) indicate that the central Co(II) and terminal copper metal ions are antiferromagnetically coupled with J=–28.09 and J=–29.70 cm^–1 for complex 1 and 2, respectively.     

A new route to the asymmetric Schiff base ligands. The ligand exchange in [Mo(CN)<Subscript>3</Subscript>O(salhy)]<Superscript>2−</Superscript> ion. Kinetics and mechanism

The kinetics of the ligand exchange in (PPh₄)₂[Mo(CN)₃O(salhy)]. 6H₂O (Hsalhy = salicylaldehyde hydrazone) by a solvent molecule and by 2,2-bipyridine (bpy) have been studied in EtOH. For the ligand exchange by a solvent molecule the pseudo-first order rate constant equals k _obs = 3.2 (±0.2) × 10^–3 s^–1 (t=25 °C), H =67 (± 7) kJ mol^–1, S =–75 (±23) J mol^–1 K^–1, while for the exchange by a bpy molecule k _obs=3.5 (±0.2) × 10^–3 s^–1 (t=25 °C), H =56 (±7) KJ mol^–1, S = –104 (±8) J mol^–1 K^–1. It was found, that all reactions proceed via the same mechanism which involves the chelate ring opening cis to the Mo=O bond. The mechanism of the reaction was proposed and was proved by the synthesis of (PPh₄)₂[Mo(CN)₃O(N-pic)]. 2.5H₂O (N-pic denotes that the nitrogen of picolinic acid is trans to Mo=O) by ligand exchange in EtOH, while in aqueous solution the O-pic analogue is formed exclusively.     

Synthesis, Characterization, and Physical Properties of Two Trinuclear, Mixed-Valence Species of Type [μ3-OMnIIMnIII 2(O2CCF3)6(R)3] (R=H2O, CH3COOH)

The preparation and characterization of two new mixed-valence, trinuclear species, [Mn₃O(O₂CCF₃)₆(H₂O)₃]CF₃COOH4/3H₂O (1) and [Mn₃O(O₂CCF₃)₆(CH₃COOH)₃] (2), is reported. Compound 1 crystallizes in the triclinic space group, P¯1 (No. 2), with the parameters, a=12.3131(9) Å, b=12.4427(9) Å, c=12.965(1) Å, =72.593(4)°, =73.453(5)°, =68.345(4)°, V=1727.2(2) ų, and Z=2. A total of 14060 reflections were collected in the range 1.6827.52°. The final weighted and non-weighted agreement indices, R1=0.0589 and wR2=0.1445 were based on a total of 6953 unique reflections with an R _int value of 0.0542. Compound 2 crystallizes in the monoclinic space group, P2₁/n (No. 14), with the parameters, a=12.876(3) Å, b=12.212(4) Å, c=17.732(4) Å, =100.40(3)°, V=3640.4(1) ų, and Z=4. A total of 32197 reflections were collected in the range 1.7227.13°. The final weighted and non-weighted agreement factors, R1=0.0647 and wR2=0.1609 were based on a total of 8018 unique reflections with an R _int value of 0.0462. An investigation of the physical properties revealed that both compounds display an intermediate ground state of S=3/2 as a consequence of intramolecular antiferromagnetic coupling. The magnetic data for compound 1 was best fit to the parameters g=2.09, J=–5.5 cm^–1, J=–3.4 cm^–1, and D _Mn(III)=–4.5 cm^–1; the data for compound 2 was best fit to the parameters g=2.10, J=–2.9 cm^–1, J=–5.5 cm^–1, and D _Mn(III)=–4.5 cm^–1.     

Gas Electron Diffraction and Quantum-Mechanical Study of Dimethyloxalate

The geometrical structure and conformation of dimethyloxalate, CH₃OC(O)–C(O)OCH₃, have been studied by gas electron diffraction (GED) and quantum-chemical calculations (MP2 and B3LYP methods with 6-31G* and cc-pVTZ basis sets). The GED analysis with a dynamic model (T = 323 K) results in a mixture of two planar conformers, anti (C_2h symmetry) and syn (C_2v symmetry) orientation of the two C=O bonds. The energy difference between these conformers is 0.02(0.18) kcal/mol and barrier to internal rotation around the C–C bond is 0.44(0.41) kcal/mol. The CH₃ groups occupy synperiplanar positions with respect to the C=O bonds. The following main geometrical parameters for the anti conformer (Å and degrees) have been derived: r_g(C–C) = 1.532(3), r_g(C=O) = 1.203(2), r_g(C_sp3–O) = 1.436(3), r_g(C_sp2–O) = 1.333(3), (C_sp2–C_sp2–O) = 111.9(1.9), (C_sp2–O–C_sp3) = 116.3(1.6), (O–C= O) = 127.0(1.8).This paper is devoted to the 75th anniversary of gas electron diffraction method.     

Aminosulfuric acid: An excellent guest for crown ether complexation. Crystal structure of the 1∶1∶1 molecular complex between aminosulfuric acid,water and 18,19-benzo-1, 16-diaza-4,7,10,13-tetraoxacycloeicosa-17,20-dione

The twenty-membered macrocycle, 18,19-benzo-1, 16-diaza-4,7,10,13-tetraoxacycloeicosa-17,20-dione, C₁₈H₂₆N₂O₆ (1), aminosulfuric acid and water form a stoichiometric 111 inclusion compound. The crystal structure of [1·NH ₃ ⁺ SO ₃ ^– ]·H₂O has been determined by X-ray crystallography. The crystal is monoclinic, space groupP2₁/c, a=7.967(1),b=13.447(3),c=20.779(4) Å, =90.20(2) Å;Z=4. The finalR-value is 0.0434 for 4638 unique reflections withI>2(I). The structure consists of the 11 molecular complexes between the crown host and aminosulfuric acid revealing hydrogen bonding with the ligand ether and carbonyl oxygen atoms. The complexes are united in the layer-like structure by NH...O host-guest and NH...O=CF _obs,F _calc, tables of anisotropic displacement parameters, and fractional atomic coordinates of hydrogen atoms.     

Polymorphic inclusion structure types of solvated 2,4-dichloro-5-carboxy-benzsulfonimide. A study of solvation patterns and their influence on molecular conformation

The inclusion behavior of 2,4-dichloro-5-carboxy-benzsulfonimide in protic (water, acetic acid and methanol) and aprotic (N,N-dimethylacetamide) environments has been examined by crystal structure determinations of the solvated compound, providing an illustration of the relationship between solvation effects and structural polymorphism. Three different crystal structure types of the corresponding complexes in which the benzsulfonimide moiety, C₁₄H₇Cl₄NO₈S₂, exhibits different conformations have been observed [I (with 4 mol of water) – ,a=8.227,b=8.964,c=16.945 Å, =89.64, =97.51, =114.28°;II (with acetic acid + 2 H₂O) – ,a=7.857,b=11.379,c=13.831 Å, =92.50, =101.21, =101.12° andIII (with methanol + 2H₂O) – orP1,a=7.840,b=11.235,c=13.697 Å, =95.56, =102.05, =102.21°;IV (with 2N,N-dimethylacetamide + 2H₂O) –P2₁2₁2₁,a=14.838,b=14.818,c=14.500 Å]. Crystallization from water and from acetic acid leads to layered structures consisting of alternating zones of the host (with a folded conformation) and the solvent. Crystals obtained fromN,N-dimethylacetamide are composed of a three-dimensional lattice of loosely packed host species (with an extended conformation) which are interspaced by solvent molecules. This polymorphism can be correlated to hydrogen bonding in that the extended conformation of the title compound is favored in a solvent which is a poor hydrogen donor, while the folded conformation is induced in solvation environments that are good donors of hydrogen bonds. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82005 (8 pages). To obtain copies, see p. ii of this issue.     

Crystal and Molecular Structure of Cu(II) Bis-(2-methoxy-2,6-dimethyl-3-imino-5-heptanonate)

A new compound from the series of alkoxyketoiminates, Cu(II) bis-(2-methoxy-2,6-dimethyl-3-imino-5-heptanonate), has been synthesized and studied by X-ray crystallography. Crystal data for CuO₄N₂C₂₀H₃₆: a=10.154(1), b=9.921(1), c=11.684(2) , =96.17(1)°, space group P2₁/c, Z=2, dcalc =1.226 g/cm³, R=0.037. The structure is molecular and built from isolated trans-complexes. The copper atom has a plane square environment of two oxygen atoms (Cu–O 1.93 ) and two nitrogen atoms (Cu–N 1.90 ). The O–Cu–N chelate angle is 91.7°. The complex has an intramolecular hydrogen bond, N–H...O 2.16 , involving the alkoxy oxygen atom. The molecular packing in the crystal is close to that of copper(II) dipivaloylmethanate. The calculated van der Waals intermolecular interaction energies and thermogravimetric characteristics of the complexes are compared.     

The structure of a 1:4 adduct between 1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown-6) and thiourea

The structure of 18-crown-6·4 thiourea has been determined by single crystal X-ray methods. The unit cell is monoclinic and the space group isP2₁, witha=9.251(3),b=19.285(8),c=16.556(7) Å and =90.85(6)°. There are two formula units, C₁₂H₂₄O₆·4CH₄N₂S, in the asymmetric unit; finalR=0.086. One thiourea is attached at either side of the macrocycle (biangular conformation) via N–N...O bonds and the patterns in the two crystallographically-independent adductsA andB differ slightly, involving two bifurcated hydrogen bonds inA. Core adducts are linked by additional thiourea molecules via N–H...S bonds. As compared to the analogous 18-crown-6·5 urea, the present 1:4 stoichiometry might be attributed to the longer S...N hydrogen bonding distance, i.e., to the bigger van der Waals radius of sulphur. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82004 (31 pages). To obtain copies, see p. ii of this issue.     

Synthesis and characterization of some methyl complexes of palladium(II). Part 2(1)

Summary Dichloro complexes of Pd^II, [Pd(L–L)Cl₂], where L–L=1-(thiomethyl)-2-(diphenylarsino)ethane (S–As) or 1-(thiomethyl)-2-(diphenylphosphino)ethane (S–P) andtrans-[PdL₂Cl₂], where L=diphenyl(2-phenylethyl)-phosphine (PE), diphenyl(1-naphthyl)phosphine (PN) orN-methyl-2-thiophenealdimine (SN), have been prepared and characterized. The reactions of these complexes with MeLi were investigated. The dimethyl complexes [Pd(L–L)Me₂] (L–L=S–As, S–P) and [Pd(PE)Me₂] were isolated and characterized. Reaction of [Pd(L–L)Me₂] (L–L=S–As, S–P) with HCl affords the monomethyl derivatives [Pd(L–L)Me(Cl)]. In contrast to the Pt analogues, [Pd(L–L)Me₂] and [Pd(L–L)Me(Cl)] are relatively less stable than [Pt(L–L)Me₂] and [Pt(L–L)Me(Cl)].     

Electrostriction of polymethylmethacrylates

Electrostriction of tactic polymethylmethacrylates in response to step-on and step-offdc-fields was investigated in the field strength range from 1 to 5 MV m^–1 at room temperature; one example of electrostriction under sinusoidal field is given.Three principal retardation time regions were found: ₁=1.5 s, ₂=30 s, and ₃=140 s, each field strength independent. The retardation strengths belonging to these electrostrictive processes depend on tacticity.The low frequency limit of the electrostrictive volume compliance for the investigated PMMA is _a =–1.2×10^–15 m² V ^–2 for atactic, _S =–2.3×10^–14 m² V ^–2 for syndiotactic, and _i=–4.5 × 10^–14 m² V ^–2 for isotactic PMMA.Herrn Prof. Dr. F. H. Müller gewidmet.     

Über Ferrocen-Acetylene, 4. Mitt.: Darstellung und Lichtabsorption von Ferrocenyl-thiophenen und Derivaten des Ferrocenyl-acetylens

Zusammenfassung 2-Ferrocenyl-thiophene wurden aus Ferrocenyl-diacetylenen durch Cyclisierung mit H₂S dargestellt.Durch eine intramolekulareWittig-Reaktion war Ferrocenyl-propiolsäureester und daraus der entsprechende Acetylenalkohol (Fc–CC–CH₂OH) und-aldehyd (Fc–CC–CHO) zugänglich. Di-ferrocenyl-propinon (X) und-penteninon (XIV) wurden über das Li-Derivat von Ferrocenyl-acetylen erhalten.Die UV-Spektren der Ferrocenyl-thiophene und-acetylene werden diskutiert.

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2-Ferrocenyl-thiophenes have been prepared from ferrocenyl-diacetylenes by cyclization with H₂S.By means of an intramolecularWittig reaction ethyl ferrocenyl propiolate was obtained and subsequently converted into the corresponding alcohol (Fc–CC–CH₂OH) and aldehyde (Fc–CC–CHO).Diferrocenyl-propynone (X) and diferrocenyl-pentenynone (XIV) have been obtained via lithium ferrocenylacetylide.The ultraviolet spectra of the ferrocenyl-thiophenes and ferrocenyl-acetylenes are reported and briefly discussed.

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Herrn Prof. Dr.H. Bretschneider zum 60. Geburtstag gewidmet.

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3. Mitt.:K. Schlögl undH. Egger, Mh. Chem.94, 376 (1963).

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22. Mitt.:H. Egger undK. Schlögl, J. Organomet. Chem.2, 398 (1964).     

Crystal and molecular structure of a 1:1 complex of potassium perchlorotriphenylmethide and 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane)

(C₆Cl₅)₃ C^– K⁺, C₁₂H₂₄O₆ is monoclinic, space groupP2₁ withZ=2,a=10.491(2),b=18.016(7),c=11.670(6) , =103.11(3)°,V=2148(1) ³, finalR=0.039 for 2339 observed reflections at room temperature. The overall shape of the perchlorotriphenyl free radical is given by the angles between the mean planes of each ring (around 70°). The K⁺ ion lies at the centre of the 18-membered macrocyclic ring. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. 82012 (19 pages).