Crystal structure analysis of the carbon tetrabromide clathrate of hexakis(phenylseleno)benzene

The 12 inclusion compound of hexakis(phenylseleno)benzene (1) with CBr₄ is trigonal, space groupR , witha=14.474(3),c=21.487(4) Å, and three host and six guest molecules in a unit cell referred to hexagonal axes. A true clathrate structure is found and in each closed cage there are two carbon tetrabromide guest molecules, orientated such that a C–Br bond of each is colinear with thec-axis of the crystal. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82002. To obtain copies, see page ii of this issue.     

Inclusion compounds formed between α,ω-(long-carbon-chain)-diaminecademium(II) tetracyanonickelate(II) host and aromatic guest molecules

Inclusion compounds with the general formula Cd(NH₂(CH₂) _n NH₂)Ni(CN)₄·xG were prepared forn=4 to 8, and for G of such an aromatic guest molecule as pyrrole, benzene, aniline, toluene, toluidine, xylene, xylidine, dichlorobenzene, trimethylbenzene, tetramethylbenzene, ethylbenzene, styrene, or isopropylbenzene, with varyingx. Generally, longer chain lengths of ,-diamine in the host permit the inclusion of bulkier guest molecules. However, the presence of an amino group on the phenyl ring of the guest appears to impart a special affinity with the hosts.     

Inclusion Compounds of Cyclotriveratrylene (2,3,7,8,12,13-hexamethoxy-5,10-dihydro-15H-tribenzo[a,d,g]cyclononene) with Chlorinated Guests

Inclusion compounds were formed between the host cyclotriveratrylene, H, (2,3,7,8,12,13-hexamethoxy-5,10-dihydro-15H-tribenzo[a,d,g]cyclononene) and the guests carbon tetrachloride, 1,1,1-trichloroethane, 1,1,1-trichloropropane and 1,1,2-trichloroethane. 1 (H·CCl₄) has guest molecules in channels alternating with channels of host molecules. 2 (H·C₂H₃Cl₃·C₃H₅Cl₃) and 3 (H·2C₂H₃Cl₃) exhibit a slightly different packing arrangement with one guest molecule in the host cavity and the rest of the guest molecules in channels. The stability and reactivity of these inclusion compounds were investigated.     

Two clathrates of bis(isothiocyanato)tetrakis(4-methylpyridine)magnesium(II) as a host with 4-methylpyridine as a guest

Two clathrate modifications of the title host with 4-methylpyridine (4-CH₃C₅H₄N) as a guest have been determined at –50°C. [Mg(4-CH₃C₅H₄N)₄(NCS)₂] · 2/3(4-CH₃C₅H₄N) · 1/3H₂O is trigonal, space group , witha=27.630(7),c=11.219(3) ÅV=7417(4) ų,Z=9,D _calc=1.171 g cm^–3,(CuK )=18.506 cm^–1, finalR=0.064. [Mg(4-CH₃C₅H₄N)₄(NCS)₂] · (4-CH₃C₅H₄N) is tetragonal, space group I4_l/a, witha=16.944(7),c=23.552(9)Å,V=6762(5) Å,Z=8,D _calc=1.191 g cm^–3, (CuK )=18.200 cm^–1, finalR=0.071.The structures consist of molecular packings of the same host complex units and the guest species. The Mg(II) cation is octahedrally coordinated to theN-atoms of four 4-methylpyridine and twotrans-coordinated isothiocyanato ligands in the host molecule. The conformations of the molecule are considerably different both in symmetry and in geometry in these two structures. The guest 4-methylpyridine molecules are disordered into channels which have different topology in these two clathrates resulting in different thermal stability.     

Molecular and crystal structures of Ph2P(O)(CH2)2OH and Ph2P(O)CH2(C6H6)OH

The molecular and crystal structures of Ph₂P(O)(CH₂)₂OH and Ph₂P(O)CH₂(C₆H₆)OH have been determined. For the first compound the space group is with unit cell dimensions a=10.505(2), b=13.720(2), c=14.782(3) Å; =72.58(6), =76.95(6), =72.49(6)° for Z=6 (Syntex diffractometer,MoK radiation, 2996 reflections, R=3.2%). The second compound crystallizes in the space group P2₁2₁2₁ with unit cell dimensions a=9.371(3), b=9.014(3), c=18.461(5) Å for Z=4 (DAR-UM diffractometer,CuK radiation, 909 reflections, R=4.9%). In Ph₂P(O)(CH₂)₂OH, three independent molecules differing in structural details are linked by the P=O...O hydrogen bonds (O...H is 1.84, 1.80, and 1.86 Å), to form a chain. In Ph₂P(O)CH₂(C₆H₆)OH, the molecules are joined by pairs of the P=O...H–O bonds (O...H is 1.81 Å) to form 16-membered dimeric associates.Institute of Chemical Physics, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 3, pp. 109–118, May–June 1993.Translated by T. Yudanova     

Endo and Exo Coordination to Cofacial Binuclear Copper(II) Complexes

A structural study of internal (endo) and external (exo) coordination to cofacial binuclear complexes is reported.Cu₂(NBA)₂(NBAH₂=3,3'-[2,7-naphthalenediylbis(methylene)]-bis(2,4-pentanedione)) is large enough to accommodate 2-methylpyrazine as an intramolecularly coordinated guest molecule Cu₂(NBA)₂((2Mepyz))4CH₂Cl₂Cu₂C₅₃H₅₈N₂O₈Cl₈, orthorhombic, space group Pnma (No. 62); a = 22.4674(11); b = 22.230(2); c = 11.4520(6) Å V = 5719.6(6) ų (at 100 K); Z = 4; R = 0.058; R _w = 0.167 for 344 parameters and 5339 reflections with I > 2(I). The Cu₂(NBA)₂(-(2-Mepyz)) molecules possess crystallographic m symmetry, with the CuCu vector (CuCu' 7.4801(8) Å) perpendicular to the mirror plane; this requires disorder in the 2-Mepyz guests. The two ``Cu(acac)₂' moieties (acacH = 2,4-pentanedione) are not quite parallel (dihedral angle between (acac)₂ planes = 3.93(7)^circ), forming a slightly wider opening on the side of the methyl group in the 2-Mepyz guest. On the other hand, the cavity in Cu₂(XBA)₂ (XBAH₂ = 3,3'-[1,3-phenylenebis(methylene)]-bis(2,4-pentanedione)) is smaller, so that CH₃CN must bind externally.Cu₂(XBA)₂(CH₃CN)₂1.5CH₃CNH₂O,Cu₂C₄₃H_52.5N_3.5O₉, monoclinic, space group P2₁/c (No. 14); a = 11.7361(16); b = 14.197(3); c = 13.299(3) Å; = 92.22(2)^{^}; V = 2214.3(7) ų (at 100 K); Z = 2; R = 0.044; R _w = 0.124 for 275 parameters and 4983 reflections with I > 2 (I). This structure contains centrosymmetric Cu₂(XBA)₂ units (CuCu' 4.8302(12) Å) with externally coordinated CH₃CN ligands. The crystal packing in Cu₂(NBA)₂((2Mepyz))4CH₂Cl₂,which contains close contacts between layers of Cu₂(NBA)₂(-(2-Mepyz)) moieties, is also similar to that in three other crystalline host–guest adducts M₂(NBA)₂(-G). Cu₂(XBA)₂(CH₃CN)₂1.5CH₃-CNH₂O does not contain similar layers of molecules, presumably because the adduct molecules do not have the same type of exposed flat surfaces.     

Tin(IV) complexes ofSchiff bases derived from salicylaldehyde and aminoalcohols

11 and 12 molar reactions of tin(IV) chloride with theSchiff bases, HO–C₆H₄CHNROH [where R=–(CH₂)₂–, –CH₂–, –CH(CH₃)–, –(CH₂)₃–, and –CH(C₂H₅)CH₂–] have been studied in different stoichiometric ratios and derivatives of the type SnCl₄(SBH₂) and SnCl₄(SBH₂)₂ (whereSBH₂ represents theSchiff base molecule) have been isolated. These have been characterised by elemental analysis, conductivity measurements and I.R. spectral studies.     

Solvent and Temperature Dependence of 59Co NMR Chemical Shifts of Tris(acetylacetonato)cobaIt(III) and Tris(dipivaloylmethanato)cobalt(III)

Cobalt-59 NMR chemical shifts of Co(acac)₃, and Co(dpm)₃ (acac^– = acetylacetonate ion and dpm^– = dipivaloylmethanate ion) in 14 organic solvents, C₆H₁₄, C₆H₆, CH₂Cl₂, CHCl₃, CCl₄, CH₃CN, CH₃OH, C₂H₅OH, CH₃CH(OH)CH₃, (C₂H₅)₂O, (CH₃)₂CO, (CH₃)₂SO, (CH₃)₂NCHO and C₆H₅NO₂, were measured at five temperatures ranging from 289 to 329 K. The observed chemical shift (_obs) was linearly correlated to the maximum absorption wavelength in the visible spectra (_max) corresponding to the d-d electronic transition energy between the ground ¹A_1g and excited ¹T_1g states. The _obs-_max relation was explained by the ligand field theory. The temperature coefficients of _obs, of each complex showed a negative correlation with _obs. The _obs, of Co(acac)₃ decreased with the increasing electrophilic ability of the solvent (Mayer's acceptor number), whereas no tendency was observed in the case of Co(dpm)₃.     

Synthesis and Crystal Structure of Diaqua(2.2.2-Cryptand)strontium Dichloride Trihydrate

Absract—Diaqua(2.2.2-Cryptand)strontium dichloride trihydrate [Sr(2.2.2-Crypt)(H₂O)₂]²⁺ · 2Cl^– · 3H₂O (I) was prepared and studied by X-ray diffraction. The triclinic structure of I (space group P , a = 9.152 Å, b = 10.140 Å, c = 15.219 Å, = 88.84°, = 88.19°, = 87.62°, Z = 2) was solved by the direct method and refined by full-matrix least-squares calculations in the anisotropic approximation to R = 0.050 for 4188 independent reflections (CAD4 automated diffractometer, CuK radiation). The structure contains the [Sr(2.2.2-Crypt)(H₂O)₂]²⁺ host–guest cation. The Sr²⁺ cation resides in the 2.2.2-cryptand cavity and is coordinated by all eight heteroatoms (6O + 2N) of the cryptand ligand and by two O atoms of water molecules. The Sr²⁺ coordination polyhedron (C.N. 10) is a highly distorted dibase-centered two-cap trigonal prism. The crystal structure of I contains a branched system of ion–ion (intermolecular) hydrogen bonds O(w)–H···Cl^–, which connect the complex cations, the Cl^– anions, and the crystal water molecules to form infinite thick layers parallel to the yz plane.     

Supramolecular inclusion of a pillared double-layered host by an anion-directed second-sphere coordination

In this paper, we have illustrated the utilisation of a second-sphere coordination approach to construct supramolecular inclusion solids with varieties of guest molecules. A flexible molecule N,N,N′,N′-tetra-p-methylbenzyl-ethylenediamine (L1) bearing doubly protonated H-bond donors was designed, capable of forming N–H…Cl hydrogen bonds with a crystallographically unique chloride anion, to construct an anion-directed ligand. The pillared double-layered host framework was constructed by an anion-directed ligand and primary coordination sphere [CoCl₄]^2 ?  through weak C–H…Cl hydrogen-bonding interactions. A variety of guest molecules, such as p-anisaldehyde, 1,4-dimethoxy-2,5-bis(methoxymethyl)benzene, can be included, leading to the formation of novel supramolecular inclusion solids: [L1]·4[H]⁺·[CoCl₄]^2 ? ·2Cl^? ·1.5[C₈H₈O₂]·0.25[CH₃OH] (1) and [L1]·4[H]⁺·[CoCl₄]^2 ? ·2Cl^? ·1.5[C₁₂H₂₀O₄]·0.5[CH₃OH] (2).

We have presented herein the utilisation of a second-sphere coordination approach to construct supramolecular inclusion solids with a variety of guest molecules. A novel type of a pillared double-layered host framework was constructed by a second-sphere coordination between the anion-directed ligand (L1 = N,N,N′,N′-tetra-p-methylbenzyl-ethylenediamine) and [CoCl₄]^2 ?  through weak C–H…Cl hydrogen-bonding interaction, and a variety of guest molecules, such as p-anisaldehyde, 1,4-dimethoxy-2,5-bis(methoxymethyl)benzene, can be included, leading to the formation of supramolecular inclusion solids: [L1]·4[H]⁺·[CoCl₄]^2 ? ·2Cl^? ·1.5[C₈H₈O₂]·0.25[CH₃OH] (1) and [L1]·4[H]⁺·[CoCl₄]^2 ? ·2Cl^? ·1.5[C₁₂H₂₀O₄]·0.5[CH₃OH] (2)

     

A Dumbbell Shaped Fullerene Dimer with An Inorganic Linker. Addition of C60 and Tetracyanoethylene to Ir2(CO)2Cl2(Ph2P(CH2)nPPh2)2 (n=5 or 7)

The centrosymmetric dimers, ( ²-C₆₀)₂Ir₂(CO)₂Cl₂(-Ph₂P(CH₂)₇PPh₂)₂ and ( ²-TCNE)₂Ir₂(CO)₂Cl₂(-Ph₂P(CH₂)₅PPh₂)₂, have been prepared by the reactions of C₆₀ with Ir₂(CO)₂Cl₂(-Ph₂P(CH₂)₇PPh₂)₂ and of tetracyanoethylene (TCNE) with Ir₂(CO)₂Cl₂(-Ph₂P(CH₂)₅PPh₂)₂, respectively. The structures of both adducts have been elucidated by single crystal X-ray diffraction studies.     

The crystal structures of α,ω-diaminoalkanecadmium(II) tetracyanonickelate(II)-aromatic molecule inclusion compounds. I. 1,4-diaminobutanecadmium(II) tetracyanonickelate(II)-2,5-xylidine (1/1): Cd(NH2(CH2)4NH2)Ni(CN)4. (CH3)2C6H3NH2

The title compound crystallizes in monoclinic space group P2₁/m with a=9.795(2), b=15.010(2), c=7.125(1) Å, =105.56(1)^o, and Z=2. The structure has been refined to the weighted Rw=0.042 for 2742 reflections collected by counter method. Two-dimensionally extended but wavy cyanometal complex layers are bridged by 1,4-diaminobutane (dabn) to give a three-dimensional host structure which provides a channel-like cavity with the guest 2,5-xylidine molecule. The skeleton of the bridging dabn takes a trans-cis conformation to make the packing efficient between the cavity and the guest molecule. The series of Hofmann-dabn-type Cd(NH₂ (CH₂)₄NH₂) Ni (CN)₄. nG inclusion compounds are described for several aromatic guest molecules G with various stoichiometric coefficients n. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82020 (22 pages).     

Encapsulation of Halocarbons in a Tetrahedral Anion Cage

Caged supramolecular systems are promising hosts for guest inclusion, separation, and stabilization. Well‐studied examples are mainly metal‐coordination‐based or covalent architectures. An anion‐coordination‐based cage that is capable of encapsulating halocarbon guests is reported for the first time. This A₄L₄‐type (A=anion) tetrahedral cage, [(PO₄)₄ L ₄]^12?, assembled from a C₃‐symmetric tris(bisurea) ligand ( L ) and phosphate ion (PO₄^3?), readily accommodates a series of quasi‐tetrahedral halocarbons, such as the Freon components CFCl₃, CF₂Cl₂, CHFCl₂, and C(CH₃)F₃, and chlorocarbons CH₂Cl₂, CHCl₃, CCl₄, C(CH₃)Cl₃, C(CH₃)₂Cl₂, and C(CH₃)₃Cl. The guest encapsulation in the solid state is confirmed by crystal structures, while the host–guest interactions in solution were demonstrated by NMR techniques.     

Osmium(IV) Binuclear Nonelectrolytic Oxo-Bridged Carboxylates. Molecular Structure of [Os2 IV(μ-O)(μ-O2CCCl3)2Cl4(PPh3)2] · CH2Cl2

The reactions between trans-[Os^VIO₂Cl₂L₂] (L = PPh₃, AsPh₃, SbPh₃) and carboxylic acids RCO₂H (R = CH₃, C(CH₃)₃, CH₂Cl, CCl₃, CF₃) are studied. The resulting binuclear compounds were found to have the general formula [Os₂ ^IV(-O)(-O₂CR)₂Cl₄(L)₂] (L = PPh₃; R = CH₃, C(CH₃)₃, CH₂Cl, CCl₃, CF₃, and L = AsPh₃; R = CH₃, CH₂Cl, CCl₃, CF₃). X-ray diffraction analysis revealed that the [Os₂ ^IV(-O)(-O₂CCCl₃)₂Cl₄(PPh₃)₂] · CH₂Cl₂ complex crystallizes in a triclinic system with space group P ; a = 10.747(2) Å, b = 19.291(4) Å, c = 24.614(5) Å, = 100.08(3)°, = 90.63(3)°, = 97.05(3)°, V = 4983.5(17) ų, Z = 4. The Os(-O)Os angle is 142.2(7)°. The interaction of trans-[Os^VIO₂Cl₂(SbPh₃)₂] with all the acids under study is attended by intramolecular redox reaction resulting in SbCl₂Ph₃.     

Zur Koordinationschemie des Rhenium(VII). V. Trioxo-trichlororhenate(VII) mit stickstoffhaltigen Kationen

Coordination Chemistry of Rhenium(VII). V. Trioxotrichlororhenates(VII) with Nitrogen-containing Cations Complex compounds of the composition A₂ReO₃C₃ were obtained by reaction of ReO₃Cl with the chlorides ACl (A = (CH₃)₄N⁺, (C₂H₅)₄N⁺, PyH⁺, ChinH⁺ (CH₃)₃NH⁺ and CH₃Py⁺) in inert solvents. It has been decuced from the Re? O stretching vibrations of the IR spectra, that the anion ReO₃Cl in connection with the cations (CH₃)₄N⁺ resp. (C₂H₅)₄N⁺ has the symmetry C_3v (cis-configuration). It is probable, that in cations including a NH-group a decrease of the symmetry towards C_s arises by means of the hydrogen bondings.     

Layer arrangement in the structure of octakis-(trimethylsiloxy)octasilsesquioxane and dodecakis-(trimethylsiloxy)cyclohexasiloxane

Layers of [(CH₃)₃SiO]₈(SiO_1.5)₈ and [(CH₃)₃SiO]₁₂(SiO)₆ organosilicon compounds obtained by chemical vapor deposition were investigated by X-ray diffraction (DRON-RM4, R = 192 mm, CuK radiation) and Raman spectroscopy (Triplemate, SPEX). The layers were found to be ideally oriented polycrystalline films. The octakis-(trimethylsiloxy)octasilsesquioxane polycrystals are oriented in one crystallographic direction — [001], while the dodecakis-(trimethylsiloxy)cyclohexa-siloxane polycrystals are oriented in the and directions. Crystal structure analysis in these directions yielded the type of the planar lattice followed by the molecules and their orientation relative to the support.Original Russian Text Copyright © 2004 by S. A. Gromilov, T. V. Basova, D. Yu. Emelyanov, A. V. Kuzmin, and S. A. ProkhorovaTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 497–501, May–June 2004.     

Synthesis and Characterization of the Isocyanide Ligated Centered Zirconium Halide Cluster [(Zr6Be)Cl12(CNXyl)6]

The first isocyanide ligated hexanuclear zirconium halide cluster is reported. The unoxidized [(Zr₆Be)Cl₁₂(CNXyl)₆] (CNXyl = 2,6-dimethylphenyl isocyanide) was obtained from the solid state precursor K₃Zr₆Cl₁₅Be by dissolution in CH₃CN in the presence of CNXyl. The CNXyl ligands occupy all the axial positions on the cluster. The compound was recrystallized from CH₂Cl₂ and Et₂O. [(Zr₆Be)Cl₁₂(CNXyl)₆].2CH₂Cl₂ crystallizes in the space group (#2) with a = 12.092(5) Å, b=12.728(5) Å, c = 14.102(8) Å, = 104.98(4)°, =107.11°, = 100.94°, V = 1919(2) ų, Z = l, R = 11.3% and R _W = 27.0%. For the bound isocyanide ligands, v _CN increases to 2140 cm^–1.     

Inclusion complexes of the natural product gossypol. Recognition by gossypol of halogeno methanes. Structure of the dichloromethane complex of gossypol and single crystal conservation after decomposition

The structures of gossypol complexes are extremely sensitive to the halogenomethane present as the guest; e.g. changing the number of Cl atoms in chloromethane derivatives changes the structure of the gossypol complex. The crystals of C₃₀H₃₀O₈·CH₂Cl₂ are monoclinic, space groupC2/c,a=21.320(4),b=19.199(6),c=15.765(2)Å, =113.05(2)^o,V=5916(2)ų,Z=8,D _x=1.35 g/cm³,T=295 K. The structure has been solved by direct methods and refined to the finalR value of 0.084 for 1828 reflections. In the structure H-bonded gossypol molecules form columns, generating channels in the structure which are filled by guest molecules. After decomposition (desolvation) monocrystals of the complexes are conserved without destruction, in which there are rather wide and empty channels though slightly smaller than in the complex. An attempt is made to explain some peculiarities of the behavior of the gossypol polymorph formed on the basis of its structure with empty channels. Supplementary data relevant to this article have been deposited with the British Library Publication No. SUP 82165 (17 pages).     

Crystal Structure of the Diaqua(1,10-Diaza-18-Crown-6) (Tetrafluorosuccinato-O)barium Complex

The diaqua(1,10-diaza-18-crown-6)(tetrafluorosuccinato-O)barium complex [Ba(DA18C6)(C₄F₄O₄)(H₂O)₂] (I) is synthesized and studied using X-ray diffraction analysis: space group P2₁/n, a = 16.342 Å, b = 8.989 Å, c = 17.087 Å, = 107.09°, Z = 4. The structure was solved by the direct method and refined by the full-matrix least squares method in anisotropic approximation to R = 0.075 for all 3515 unique reflections (CAD4 automated diffractometer, MoK ). Complex I exists in the crystal as individual host–guest molecules of the aforementioned composition. The Ba²⁺ cation (coordination number 9) is located in the void of the DA18C6 macrocycle and is coordinated by its six O and N heteroatoms. It is also coordinated by the O atom of the tetrafluorosuccinate ligand and the O atom of the water molecule on one side of the macrocycle and by the O atom of the second water molecule on the other macrocycle side. The DA18C6 ligand has a crown conformation with approximate D _3d symmetry. The complex molecules in the crystal are combined into infinite two-dimensional layers by intermolecular hydrogen bonds.     

Schiff base complexes of silicon(IV)

Reactions of silicon tetraacetate with different types ofSchiff bases have been investigated in anhydrous benzene. Monofunctional bidentate, C₆H₅CHNXOH and HORCHNC₆H₅ [whereX=CH₂CH₂, CH₂CH(CH₃) or o-C₆H₄ and R=o-C₆H₄ or 2,1-C₁₀H₆], bifunctional tridentate, o-HOC₆H₄CHNYOH [whereY=CH₂CH₂ or CH₂CH(CH₃)] and bifunctional tetradentateSchiff bases, o-HOC₆H₄C(CH₃)N(CH₂) _n NC(CH₃)C₆H₄OH-o (wheren=2 or 3) have been shown to yield derivatives of the type, Si(OAc)_4– m L _m, Si(OAc)_4–2 n L _n and Si(OAc)₂ L (wherem=1,2 or 3;n=1 or 2 and HL, H₂ L and H₂ L represent the molecules of monofunctional bidentate, bifunctional tridentate and bifunctional tetradentateSchiff bases resp.) and have been found to be monomeric in boiling benzene. Tentative structures based on IR and in a few cases PMR spectra have been indicated for the resulting derivatives.With 2 Figures