X-ray crystal structure of the 1∶2∶2 pentaethyleneglycol dimethyl ether(pentaglyme)∶dichloropicric acid∶water complex. Infrared studies of the 1∶2∶2 complexes with tri-, tetra-, and pentaglyme

The 122 pentaglymedichloropicric acidwater adduct crystallizes in two polymorphic forms. Polymorph I is triclinic, space groupP¯1; at –96°Ca=11.629(6),b=12.566(8),c=12.877(16)Å,=89.19(8),=83.76(8), =85.95(5)°,D _x =1.599 g cm^–3,V=1866(5)ų,Z=2. Refinement on 7729 observed reflections yielded a finalR value of 0.045. Polymorph II is orthorhombic, space groupP2₁2₁2₁; at –87°Ca=13.631(7),b=26.441(8),c=5.182(6)Å,D _x =1.597(3) g cm^–3,V=1868(3)ų,Z=2. Refinement of 1610 observed reflections yielded a finalR of 0.071 for a disordered structure. The hydrogen bonding pattern in I is similar to that found in the analogous 18-crown-6 complex. Two pairs of alternate O atoms in the polyether are hydrogen bonded to two water molecules, each of which is hydrogen bonded to the phenol O atom of a neutral dichloropicric acid molecule. The bond distances and torsion angles in the S shaped polyether are similar to those in the cyclic polyether with C-C-O-C angles near 180° and O-C-C-O near±60°. The complex in II resembles that in I in overall shape and dimensions, also having normal bond distances and angles. The nonhydrogen atoms in water and the dichloropicric acid can be located unambiguously. However, the polyether molecule is disordered, and a satisfactory model for the disorder could not be found. Comparison of the IR spectra of the 122 tri-, tetra-, and pentaglymedichloropicric acidwater complexes suggests that the hydrogen-bonding in the tetraglyme complex is weaker than in the pentaglyme complex, but that in the triglyme complex is as strong or stronger.Deceased, March, 1993.     

Crystal and molecular structure of the H-bonded complex between 1-chloro-2-hydroxynaphthalene-3-carboxylic acid and dimethylformamide (1∶1)

Crystal structure determination of the title complex reveals that the dimethylformamide solvent is bound to the carboxylic function of the hydroxy acid, in the form of a 7-membered hydrogen-bonded loop involving both the expected O-HO and an apparently weak C-HO interaction between host and guest. There is a strong intramolecular hydrogen bond between the phenolic OH and the carbonyl oxygen. Close packing of the complex units is afforded by a herringbone type alignment of host molecules.     

Synthesis and structure of [Ca(triethyleneglycol)2](NO3)2·H2O

Crystallization of calcium nitrate from a toluene solution of triethyleneglycol (= 2,2-[1,2-ethanediylbis(oxy)]-bisethanol) resulted in the formation of the 1:2 solvate [Ca(triethyleneglycol)₂](NO₃)₂·H₂O. [Ca(C₆H₁₄O₄)₂](NO₃)₂·H₂O is monoclinic, P2₁/c, a = 15.775(1), b = 8.660(2), c = 16.342(1) Å, = 91.239(7)°, V = 2232.1(6) ų, Z = 4, and D _c = 1.429 g cm^–3. The eight-coordinate calcium has square antiprismatic geometry with two triethyleneglycol molecules straddling the metal center. The nitrate anions and water of crystallization are involved in hydrogen bonding with the alcoholic hydrogen atoms.     

Reaction of 1,2-bis(diphenylphosphino)cyclobutenedione (bpcbd) with fac-BrRe(CO)3(THF)2: X-ray diffraction structure of the dimeric complex [BrRe(CO)3]2(bpcbd) ⋅ CH2Cl2

Treatment of the diphosphine ligand 1,2-bis(diphenylphosphino)cyclobutenedione (bpcbd) with the THF adduct fac-BrRe(CO)₃(THF)₂ at room temperature furnishes the new dirhenium compound [BrRe(CO)₃]₂(bpcbd) instead of the expected mononuclear compound fac-BrRe(CO)₃(bpcbd). [BrRe(CO)₃]₂(bpcbd) was characterized in solution by IR spectroscopy, and the solid-state structure was solved by X-ray crystallography. [BrRe(CO)₃]₂(bpcbd), as the CH₂Cl₂ solvate, crystallizes in the space group P , a = 11.173(1), b = 13.362(1), c = 15.250(1) Å, = 108.973(7)°, = 99.477(8)°, = 110.466(7)°, V = 1915.0(3) ų, Z = 2, and d _calc = 2.143 g-cm^–3. The structure of [BrRe(CO)₃]₂(bpcbd) consists of two rhenium centers that are six-coordinate and possess nearly ideal octahedral geometry. The two Re(CO)₃ units are linked together by the bridging diphosphine ligand and two bridging bromide groups.     

Synthesis and crystal structure of [Co(phen)(H2O)4](SO4)⋅2(H2O)

The title complex, [Co(phen)(H₂O)₄](SO₄)2(H₂O) (phen = 1,10-phenanthroline) was prepared in aqua tert-butylperoxohydrogen solution. X-ray single crystal structure determination reveals that the complex consists of a phenanthrolinatocobalt(II)tetrahydrate dication, two uncoordinated water molecules and a sulfate anion. It crystallizes in the orthorhombic space group Pbca with a = 8.856(1), b = 18.318(3), c =21.918(5) Å, V = 3555.6(11) ų. The coordination geometry at each cobalt(II) atom is a slightly distorted octahedron.     

Model of the crystal structure of Np(VI) sulfate with dimethyl sulfoxide, NpO2SO4 ⋅ 2SO(CH3)2 ⋅ H2O

A new complex compound, neptunium(VI) sulfate, was grown from aqueous solutions and studied by the methods of X-ray structure analysis. The model of the crystal structure was determined by direct methods within the sp. gr. P2₁ and was refined in the anisotropic approximation (R = 6.2%, 1044 independent reflections). The structure is built by tetragonal and hexagonal Np bipyramids. A hexagonal bipyramid can be considered as a polyhedron derived from a pentagonal bipyramid, in which one equatorial O atom is replaced by two atoms located above and below the equatorial plane. The polyhedra are linked in chains through S-tetrahedra. The chains are linked into a three-dimensional framework by hydrogen bonds with the participation of DMSO groups.     

Molecular complexes of sulfonamides. 3. Structure of 5-methoxysulfadiazine (form II) and its 1∶1 complex with acetylsalicylic acid

The X-ray structure of the biologically most active polymorph (Form II) of 5-methoxysulfadiazine (1) and that of the 11 complex between this sulfonamide and acetylsalicylic acid (2) are reported. The polymorph1 is monoclinic, space groupP2₁/c witha=13.086(2) Å,b=5.583(1) Å,c=17.222(3) Å, =99.98(1)°,Z=4 and occurs as centrosymmetric hydrogen bonded (N–H...N) dimers in the crystal. This arrangement differs from that observed in other polymorphs of the drug. Complex2 is triclinic, ,a=8.102(1)Å,b=12.033(1) Å,c=12.170(2) Å, =111.67(1)°, =93.77(1)°, =103.82(1)°,Z=2. Complexation involves linear intermolecular hydrogen bonds, N–H...O=C and N...O–H, between the amide group and pyrimidinyl N atom of the sulfonamide and the carboxylic group of the acetylsalicylic acid. On complexation to form2, neither molecular component undergoes any major structural change.     

The structure of solvate [Cu2(DfH)4(4,4′-Bipy)] · 2DMF

The crystal structure of [Cu₂(DfH)₄(4,4′-Bipy)] · 2DMF prepared by the reaction of copper(II) acetate with diphenylglyoxime (DfH₂) and 4,4′-bipyridine (4,4′-Bipy) was established by X-ray diffraction. The crystals are monoclinic; a = 15.5192(9) Å, b = 16.2427(11) Å, c = 14.0753(7) Å, β = 101.36(3)°, V = 3478.5(5) ų, Z = 2, and sp. gr. P2₁/c. The crystal structure is composed of discrete dinuclear molecules [Cu₂(DfH)₄(4,4′-Bipy)] and dimethylformamide (DMF) molecules. The coordination polyhedron of the Cu atom (the coordination number is 5) is a tetragonal bipyramid formed by the nitrogen atoms of two monodeprotonated bidentate oxime groups and the bidentate bridging 4,4′-Bipy ligand. The DMF molecules occupy the cavities formed by the dinuclear molecules [Cu₂(DfH)₄(4,4′-Bipy)]. The compound was characterized by IR and NMR spectroscopy.     

Synthesis and crystal structure of cyanocadmate clathrate with 2-methylimidazole (2-Meim): [Cd3(CN)6(2-Meim)2] ⋅ 2Me2SO

The cyanocadmate clathrate with 2-methylimidazole, [Cd₃(CN)₆(2-Meim)₂] 2Me₂SO, has been prepared and its crystal structure analyzed by X-ray diffraction method. This clathrate crystallizes in the orthorhombic system, space group Pbcn, with a = 13.237(3), b = 14.870(3), c = 14.698(3) Å, V = 2893.1(10) ų, Z = 4. The three-dimensional (3D) host framework is built of the cyanide bridges among two kinds of Cd ions, octahedral and tetrahedral in a ratio of 1:2. The octahedral Cd(1) center is linked to six tetrahedral Cd atoms; the tetrahedral Cd(2) center is linked to three octahedral Cd atoms and ligated by one 2-methylimidazole ligand. The novel host structure provides two types of channel, vacant distorted-diamond channel and rectangular channel which is occupied by dimethylsulfoxide guest molecule and 2-methylimidazole ligand coordinated to the tetrahedral Cd site.     

Crystal and molecular structure of the spin-crossover complex bis(pyridine) [N,N′-ethylenebis (3-carboxysalicylaldimine)] cobalt (II)

The average structure of the title compound, Co(H₂fsa₂en)(py)₂, which has been shown previously to exhibit a thermally induced high-spin low-spin crossover, has been investigated by single-crystal X-ray diffraction. This structure has been solved in the monoclinic space groupC2/c (No. 15), with cell dimensionsa=16.641(5),b=9.496(4),c=16.329(6) Å, and=95.47(3)°;V=2569(3) ų,M _r =571.46,Z=4,D _x =1.478 mg m^–3; MoK radiation (graphite crystal monochromator),=0.71073 Å,(MoK)=7.138 cm^–1;T=295 K andR=0.081 for 681 observed [I>3(I)] independent reflections. The cobalt(II) ion resides on a twofold axis in an elongated octahedral environment, the length of the apical bond (formed with pyridine) being 2.262(12) Å and the mean length of the equatorial bonds (formed with the Schiff base) 2.079(12) Å. These values are consistent with the magnetic behavior, which suggested a distorted surrounding for the metal atom. The packing is essentially governed by the parallelism of the salicylaldimine ligands. The two pyridine rings of the molecule are twisted by ~98° on each side of the basal plane; they are probably affected by orientational disorder or, if ordered, they might be described in a superstructure not yet established.     

Influence of CH ⋅ ⋅ ⋅ O interactions on the structure of a pseudorotaxane based on an Hg(II) complex of 18-crown-6

The X-ray crystal structure of [Hg(NO₃)₂(18-crown-6)] (1) prepared from mercury(II) acetate and 18-crown-6 in nitric acid is reported. Crystals are monoclinic, space group P2₁/c with a = 8.3063(17) Å, b = 14.331(3) Å, c = 8.0030(16) Å, and = 99.528(3)°. In contrast to the usual perpendicular arrangement of the crown ether macrocycle mean plane and X–Hg–X in other Hg(II) crown ether complexes and related species, compound 1 shows a marked inclination as a result of a CH    O interactions.     

Crystal and molecular structure of [Pd(η5-C5H5) (bis-1,2-diphenylphosphinoethane)] [CF3SO3]

The crystal structure of the complex [Pd( ⁵-C₅ H₅) (PPh₂) CH₂CH₂PPh₂]⁺ [CF₃SO₃]^– has been determined from single crystal X-ray data and refined by least-squares methods toR=0.046. The monoclinic crystals have unit cell dimensionsa=9.832(3),b=12.104(4),c=13.765(4)Å,=111.22(3)°, space group P2₁, andz=2. In the cationic complex the palladium atom is coordinated to the ⁵-cyclopentadienyl moiety and to the phoshorus atoms of the chelating diphosphine. The arrangement of the two phosphorus atoms and the centroid of the cyclopentadienyl ring is approximately trigonal.     

Crystal and molecular structure of five coordinate copper(II) complex with 2,6-bis[1-(methoxycarbonylmethyl–hydrazono)ethyl] pyridine

The title compound was obtained by a template synthesis from 2,6-diacetylpyridine, ethylhydrazinoacetate and CuCl₂·2H₂O (molar ratio 1:2:1, in methanol), and its structure has been determined by single-crystal X-ray diffraction: monoclinic space group P2₁/c, a = 13.906(5), b = 18.199(6), c = 16.641(6) Å, = 107.18(3)°, and z = 4. The ligand was found to be tridentate in a trigonal-bipyramidal coordination geometry with two chloride ligands. There are two independent complex molecules, one of which is hydrogen bonded to the water of crystallization.     

X-ray crystal structure of the 1∶2 triethyleneglycol dimethyl ether (triglyme): Dichloropicric acid adduct

The anhydrous 12 triglyme:Dichloropicric acid adduct is triclinic, space group ; at 24°Ca=8.703(5),b=10.381(4), c=10.404(3) Å, =114.42(3), =99.69(5), =106.40(6)°,D _x=1.656 g cm^–3, V = 776(2)ų,Z=1. Bond lengths and angles are normal except that one C–C–O–C torsion angle in the triglyme is approximately 90° rather than the expected 60 or 180°. Each phenolic OH group hydrogen bonds with a terminal OCH₃ of the polyether. The O...O distance, 2.557(3) Å, is in fair agreement with the 2.52 Å estimated from the single observed IRv (OH) stretch at 1714 cm^–1.     

Crystal structure of (ethylenediammonium-N,N′-di-3-propanoic acid) tetrachloropalladate(II) complex

The title compound was obtained by a synthesis from ethylenediamine-N,N-di-3-propanoic acid dihydrochloride (H₂eddp2HCl) and potassium hexachloropalladate(IV) (molar ratio 1:1, in water). Its structure has been determined by single-crystal X-ray diffraction: monoclinic space group P2₁/n, a = 8.198(1), b = 10.282(1), c = 9.080(1) Å, = 103.62(1)°, V = 743.9(2) ų, and Z = 2. The dianionic complex has a square-planar coordination geometry with four chloro ligands, and ethylenediamine-N,N-di-3-propanoic acid as dication in the second coordination sphere. This is the first reported Pd(II) structure with uncoordinated H₂eddp.     

Synthesis and crystal structure of Nd(III)–Zn(II) complex

A novel heteronuclear complex, [NdZn₂L₆(NO ₃)(phen)₂] (HL = -methylacrylic acid, phen = 1,10-phenanthroline), was synthesized and characterized by elemental analysis, infrared absorption spectra (IR) and its molecular structure was also determined by X-ray structure analysis. The title complex contains a discrete trinuclear ZnNdZn molecule bridged by carboxylate groups between Zn and Nd ions and crystallizes in space group P¯1 with the cell dimensions: a = 13.601(3) Å, b = 16.859(2) Å, c = 12.575(2) Å, = 110.09(1), = 112.21(1), = 81.10(2).     

Crystal and molecular structure of the cycloaddition product between maleic anhydride,cyclopentadiene, and 1,2-bis(dibromomethyl)benzene as DMF solvate (1∶2)

Crystal structure determination reveals that the unknown cycloaddition product between maleic anhydride, cyclopentadiene, and 1,2-bis(dibromomethyl)benzene has a nona-cyclic centrosymmetric structure. The compound was studied as DMF solvate (12). There is no significant intermolecular interaction between the title molecule and the DMF. Packing is in layers for both molecular species. A possible mechanism of formation of the title compound is discussed.     

Preparation and crystal structure of the new ionic bis-[hydrazido]-molybdenum complex [Mo(NNPh2)2(acac)(PPh3)2]+OTf−

The title compound [Mo(NNPh₂)₂ (acac)(PPH₃)₂]⁺OTf^?, Mr=1233.1, crystallizes in the triclinic space group $P\bar 1$ , witha=12.881 (4),b=13.795(3),c=17.160(5)Å, α=90.95(1), β=91.31(1), ψ=103.53(1)°, andZ=2. The structure was solved by Patterson methods, and refined with some difficulties due to extensive disorder in the counterion. The Mo ion is hexacoordinated in an octahedral environment, with two O and two N defining the basal plane, and two P atoms in the apical sites.     

Crystal and molecular structure of β-resorcylidene aminoguanidine copper(II) complex

The tridentate Schiff base, -resorcylidene aminoguanidine (RAG)1 was synthesized from 2,4-dihydroxybenzaldehyde and aminoguanidine and complexed with copper(II) to form a copper(II)--resorcylidene aminoguanidine (Cu-RAG)2 complex. X-ray diffraction analysis of compound2 (orthorhombic, Pnma,a=11.674(1);b=6.7198(7);c=17.836(2) ) revealed a square-planar copper(II) cation with a tridentate·ligand bound through two nitrogen atoms (N1 and N3) of the aminoguanidine moiety and an oxygen (O1) of the monodeprotonated dihydroxybenzaldehyde function. The remaining coordination site was occupied by chloride and the structure was rigidly planar as demanded by the restrictions of the crystallographic space group. The unit cell contents exhibited an extended sheet-like structure constructed via hydrogen bonds both intermolecularly and involving two water molecules (O3 and O4) also restricted by the same mirror symmetry. The remaining water (O5) provided for interlayer hydrogen bonding.     

Investigation of the structure and properties of (K x (NH4)1 − x )3H(SO4)2 single crystals

The influence of isomorphous replacement in the cation sublattice on the kinetics of the phase transition in single crystals of the solid solutions (K _x (NH₄)_{1 ? x} ) _m H _n (SO₄)_{(m + n)/2} · yH₂O belonging to the K₃H(SO₄)₂-(NH₄)₃H(SO₄)₂-H₂O salt system was studied. Superproton phase transitions for the end compositions of this system have been found earlier. The optical and thermal properties of crystals with the composition (K,NH₄)₃H(SO₄)₂ in the temperature range from 295 to 500 K were investigated, and the crystal structure was determined at 295 K. The results of the study and the comparison with the literature data show that the replacement of potassium atoms with ammonia leads to a fundamental change in the kinetics of the phase transition, the phase-transition temperature remaining virtually unchanged.