Crystal Structure of 4,7,13,16,21,24-Hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane Diiodide

The disordered crystal structure of 4'7'13'16'21'24-hexaoxa-1'10-diazoniabicyclo[8.8.8]hexa-cosane diiodide, [H₂(2.2.2-Crypt)]^{2 +}·2I^-, was studied by single crystal X-ray diffraction. The 2.2.2-cryptanddication is disordered, exists in the form of two different conformers A, B randomly occupying thesame place in the unit cell with 71.5 and 28.5% probability, respectively. In both conformers A and B, thehydrogen atoms at the bridgehead nitrogen atoms are directed inside the cavity (crypta) of the conformer. The geometric parameters (bond lengths, bond angles, torsion angles) of these conformers were found, and the packing of these cations and iodide anions in the crystal were determined. The iodide anions have contacts only with the methylene hydrogen atoms of conformers A and B.     

4,7,13,16,21,24-Hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane Bis[dibromodichloroiron(III)]: Synthesis and Crystal Structure

A novel complex salt, namely, 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane bis[dibromodichloroiron(III)] [H₂(Crypt-222)]²⁺[FeBr₂Cl₂] ₂ ^? (I), was synthesized and structurally characterized by X-ray diffraction analysis (monoclinic crystal system, a = 13.550 Å, b = 11.018 Å, c = 12.813 Å, β = 117.52°, space group C2, Z = 2). The structure was solved by the direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.089 from 2593 independent reflections (CAD4 automated diffractometer, λMoKα radiation). In the crystal structure I, four bifurcate positions of Br and Cl in the tetrahedral anion [FeBr₂Cl₂]^? are a randomly disordered mixture of these atoms. The dication of 2.2.2-cryptand (with two protonated N atoms) in the crystallographic axis 2 contains trifurcate N⁺-H (?O)₃ hydrogen bonds.     

Crystal Structure of 4,7,13,16,21,24-Hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane Triaquachlorolithium Dichloride

The crystal adduct (1 :1) 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane triaquachlorolithium dichloride, [H₂(Crypt-222)]²⁺ · 2Cl^– · [LiCl(H₂O)₃] (I), was synthesized and studied using X-ray diffraction analysis. Structure I (space group R3, a = 7.922 Å, c = 37.207 Å, Z = 3) was solved by direct methods and anisotropically refined by the full-matrix least-squares method to R = 0.034 for 1363 independent reflections (CAD4 autodiffractometer, MoK ). Crystal I consists of disordered 2.2.2-cryptand dications, chloride anions, and tetrahedral [LiCl(H₂O)₃] complexes. All of them lie on threefold axes. There are tridentate ⁺N–H (···O)₃ hydrogen bonds in the [H₂(Crypt-222)]²⁺ dication. The crystal structure of adduct I contains a complex interionic hydrogen bonding system.     

Crystal Structure of 4,7,13,16,21,24-Hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane Semihydrate Oxonium Tribromide

The crystal structure of 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo-[8.8.8]hexacosane semihydrate oxonium tribromide, [H₂(2.2.2-Crypt)·0.55H₂O]²⁺·H₃O⁺·3Br⁻ (I) was determined by XRD analysis. The triclinic structure of I (space group P , a = 10.026 Å, b = 11.292 Å, c = 13.115 Å, α = 78.37°, β = 72.11°, γ = 77.50°, Z = 2) was solved by direct methods; full-matrix least-squares refinement in an anisotropic approximation converged to R = 0.055 for all 4057 independent reflections collected (CAD-4 automatic diffractometer, λCuK _α).Original Russian Text Copyright © 2004 by A. N. Chekhlov__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 1136–1141, November–December, 2004.     

Tetrakis(Isothiocyanato)zinc(II) 4,7,13,16,21,24-Hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane: Synthesis and Crystal Structure

The salt tetrakis(isothiocyanato)zinc(II) 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane, [H₂(Crypt-222)]²⁺ · [Zn(NCS)₄]^2– (I), was synthesized and its structure was determined using X-ray diffraction analysis: space group P2₁/n, a = 13.734 Å, b = 11.627 Å, c = 20.816 Å, = 91.51°, Z = 4. The structure was solved by direct methods and anisotropically refined by the full-matrix least-squares method to R =0.093 for 4920 independent reflections (CAD4 autodiffractometer, CuK radiation). The structural units of crystal I are 2.2.2-cryptand dications (with two protonated nitrogen atoms) and complex anions [Zn(NCS)₄]^2–. The coordination polyhedron of the Zn²⁺ cation is a distorted tetrahedron. The 2.2.2-cryptand dication contains trifurcate N–H(...O)₃ hydrogen bonds.     

4,7,13,16,21,24-Hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane hydrogen phosphate octahydrate: Synthesis and crystal structure

A crystalline hydrated salt of the 2.2.2-cryptand and phosphoric acid, [H₂(Crypt-222)](HPO₄) · 8H₂O (I), is synthesized. Its crystal structure is studied using X-ray diffraction analysis (space group P2₁/n, a = 9.244 Å, b = 25.750 Å, c = 13.218 Å, β = 95.87°, Z = 4; direct method, full-matrix least-squares method in the anisotropic approximation to R = 0.055 for 4622 reflections, CAD4 automated diffractometer, λMoK _α radiation). The structure contains the 2.2.2-cryptand dication with the rare exo-exo, conformation with two H atoms at two N atoms directed outside from the cavity. A P atom of the HPO ₄ ^2? anion has a considerably distorted tetrahedral coordination. The crystal of compound I contains a branched infinite three-dimensional system of intermolecular (interionic) hydrogen bonds.     

Synthesis and crystal structure of octaaquaerbium(III) 4,7,13,16,21,24-Hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane pentabromide hydrate

A new complex salt [Er(H₂O)₈]³⁺·[H₂(Crypt-222)]²⁺·5Br^?·1.5H₂O(I) is synthesized, and its crystal structure is studied by single-crystal X-ray diffraction analysis (space group P2₁, a = 8.315 Å, b = 32.000 Å, c = 8.383 Å, β = 120.03°, Z = 2; direct method, anisotropic full-matrix least-squares approximation, R = 0.050 for 3755 independent reflections; CAD4 automated diffractometer, λMoK _α radiation). The structural units of crystal I are complex cations [Er(H₂O)₈]³⁺, disordered dications of the 2.2.2-cryptand (with two protonated nitrogen atoms), Br^? anions, and water molecules. The coordination polyhedron of the Er³⁺ cation is a tetragonal antiprism with the oxygen atoms of eight water molecules at its vertices. The disordered [H₂(Crypt-222)]²⁺ dication contains trifurcate hydrogen bonds N⁺-H(?O)₃.     

4,7,13,16,21,24-Hexaoxa-1,10-diazoniabicyclo[8.8.8]-hexacosane Bis[tetrabromoiron(III)]: Synthesis and Crystal Structure

A new complex salt, 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]-hexacosane bis[tetrabromoiron(III)], [H₂(Crypt-222)]²⁺ · 2[FeBr₄]^? (I), is synthesized, and its crystal structure is studied using X-ray diffraction analysis (space group C2, a = 13.605 Å, b = 11.144 Å, c = 12.977 Å, β = 117.27°, Z = 2, direct method, full-matrix least-squares method in the anisotropic approximation, R = 0.074 for 2673 reflections, CAD4 automated diffractometer, λMoK _αradiation). In the structure of salt I, the tetrahedral [FeBr₄]^? anion is somewhat distorted. The 2.2.2-cryptand dication (with two protonated nitrogen atoms) lies on the crystallo-graphic axis 2and contains N⁺-H(?O)₃ trifurcate hydrogen bonds.     

Synthesis of 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane Dinitrate Hydrate and Its Disordered Crystal Structure

4,7,13,16,21,24-Hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane dinitrate hydrate [H₂(Crypt-222)]²⁺?2NO ₃ ^? ?H₂O is prepared as a crystalline salt and studied by single crystal X-ray diffraction. In its crystal structure the 2,2,2-cryptand dication is disordered and has two different conformations with 55.3 and 44.7% probabilities. Hydrogen atoms of this dication at the two protonated bridgehead nitrogen atoms are directed inside the cavity. One of two NO ₃ ^? anions is also disordered and has two different orientations with 77 and 23% probabilities. Geometric parameters of the molecular ions and water molecule (bond lengths, bond angles, etc.) are determined with a reasonable accuracy, and their packing in the crystal structure is established.     

4,7,13,16,21,24-Hexaoxa-1,10-diazoniabicyclo[8.8.8]-hexacosane Bis(nitrate-hydrogennitrate): Synthesis and crystal structure

A crystalline adduct of 2.2.2-cryptand and nitric acid, [H₂(Crypt-222)]²⁺·2(NO ₃ ^? ·HNO₃) (I), is synthesized and studied using X-ray diffraction analysis. The monoclinic structure of compound I (space group C2/c, a = 13.326 Å, b = 15.262 Å, c = 15.020 Å, β = 98.96°, Z = 4) is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.067 for 2647 independent reflections (CAD4 automated diffractometer, λMoK _α radiation). In the structure of compound I, the 2.2.2-cryptand dication lies on an axis 2 and has an endo-endo conformation, for which two H atoms at two protonated N atoms are directed inside the cavity. One of the NO ₃ ^? ·HNO₃ dimers is situated in the inversion center, and the other dimer lies on another axis 2 and is disordered over three orientations. All H atoms in the NO ₃ ^? ·HNO₃ dimers are equiprobably disordered over two close sites. Each of the two NO ₃ ^? ·HNO₃ dimers is formed by the very strong disordered N-O-H···O=N hydrogen bond between the nitric acid molecule and nitrate anion.     

Crystal structure of 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo [8.8.8]hexacosane nitrate-hydrogen nitrate perchlorate semihydrate

An adduct of 2.2.2-cryptand with nitric and perchloric acids of the [H₂(Crypt-222)· 0.52H₂O]²⁺·ClO ₄ ^? ·NO ₃ ^? ·HNO₃ composition (I) is prepared and characterized by single crystal X-ray diffraction. The triclinic structure of I (space group \(P\overline 1 \), a = 10.176 Å, b = 11.272 Å, c = 12.870 Å, α = 78.61°, β = 76.62°, γ = 79.88°, Z = 2) is solved by a direct method and refined in the full-matrix anisotropic approximation to R = 0.062 for all 3642 measured independent reflections (CAD-4 automated diffractometer, λMoK _α). The structure of I contains a dication of 2.2.2-cryptand in the endo-endo conformation, two hydrogen atoms at the protonated N atoms are directed inside the cavity which also includes a water molecule with a site occupation factor of 0.52. Tetrahedral ClO ₄ ^? anion in I is disordered. In I, the H atom of the NO ₃ ^? ·HNO₃ dimer is split over two close positions with occupation factors of 0.33 and 0.67; this dimer is joined by a very strong single disordered hydrogen bond N-O-H?O = N between the molecule of nitric acid and its anion.     

Synthesis and crystal structure of 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane sulfate tetrahydrate

A hydrated salt of 2.2.2-cryptand and sulfuric acid [H₂(Crypt-222)]²⁺ · SO ₄ ^2? · 4H₂O(I) was prepared and studied by X-ray diffraction. The structure of I (space group C2/c, a = 22.823, b = 9.610, c = 26.150 Å, β = 107.71°, Z = 8) was solved by the direct method and refined by full-matrix least-squares in the anisotropic approximation to R = 0.056 for 4032 independent reflections (CAD4 automated diffractometer, λMoK _α radiation). In the structure of I, the 2.2.2-cryptand dication (with approximate C ₂ symmetry) has a rare exo-exo conformation where two H atoms at two N atoms are directed away from the cavity. The tetrahedral SO ₄ ^2? anion is disordered over two orientations. In two water molecules, the H atoms are disordered, while in the other two water molecules all atoms are disordered. The crystal structure of I has an extensive three-dimensional system of ion-ion (intermolecular) hydrogen bonds in which infinite chains of alternating SO ₄ ^2? anions and 2.2.2-dications can be distinguished.     

Synthesis and crystal structure of 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane Bis(citrate) hydrate

A crystalline salt of 2.2.2-cryptand and citric acid, 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane bis(citrate) hydrate [H₂(Crypt-222)]²⁺·2(C₆H₇O₇)^? · 1.65H₂O, was synthesized and studied by single crystal X-ray diffraction. In the crystal structure of this salt, the 2.2.2-cryptand dication is somewhat disordered, and its H atoms at two protonated N atoms are oriented inside the cryptand cavity. Two independent citrate anions are essentially different, as different COOH groups in them are deprotonated. The geometric parameters (bond lengths, bond angles, etc.) of the molecular ions and water molecules are determined with a relatively high accuracy. The structural units form a three-dimensional system of intermolecular (interionic) hydrogen bonds.     

Synthesis and crystal structure of 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane bis(hydrogen oxalate)

A crystalline salt of 2.2.2-cryptand and oxalic acid, 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane bis(hydrogen oxalate), [H₂(Crypt-222)]²⁺·2(C₂HO₄)^?, was synthesized and studied by single crystal X-ray diffraction. In the crystal structure of this salt, the 2.2.2-cryptand cation has a rare conformation of the exo-exo type in which the H atoms at the two protonated N atoms are oriented outside the cryptand cavity. The geometric parameters (bond lengths, bond angles, torsion angles) of the [H₂(Crypt-222)]²⁺ cation and two independent C₂HO ₄ ^? anions were found with a fairly high accuracy, and the crystal packing was determined. These ions are linked by interionic hydrogen bonds to form thick infinite layers parallel to the (xz) plane.     

Crystal structure of 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo [8.8.8]hexacosane (2S,3S)-tartrate

Crystal structure of (2S,3S)-tartrate of 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo-[8.8.8]hexacosane, [H₂(Crypt-222)]²⁺·(C₄H₄O₆)^2? (I) has been studied by single crystal X-ray diffraction. Triclinic structure of I (space group P1, a = 8.424 Å, b = 13.011 Å, c = 13.806 Å; α = 116.37°, β = 106.45°, γ = 91.81°; Z = 2) was solved by the direct method and refined in the full-matrix anisotropic approximation to R = 0.140 for 5850 measured independent reflections (automated diffractometer CAD-4, λMoK _α). In the structure of I, two independent dications of 2.2.2-cryptand (nitrogen atoms are protonated) are linked to the approximate inversion symmetry and have a rare conformation of exo-exo type, when two atoms sitting on N atoms are protruded out of their cavity. The centroids of two crystallographically unique (2S,3S)-tartrate dianions are bound with the same approximate inversion center. An extended system of hydrogen bonds is developed in the crystal of I.     

4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]-hexacosane tetra(nitrato)zinc(II): Synthesis and crystal structure

A new complex salt 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]-hexacosane tetra(nitrato)zinc(II), [H₂(Crypt-222)][Zn(NO₃)₄]^2?, is synthesized and studied by X-ray diffraction analysis: space group $P\bar 1$ , a = 10.556 Å, b = 11.089 Å, c = 14.536 Å, α = 104.63°, β = 109.23°, γ = 99.22°, Z = 2. The structure is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.031 for 3897 independent reflections (CAD-4 automated diffractometer, λMoK _α radiation). The structural units of the crystal are the [Zn(NO₃)₄]^2? complex anion and somewhat disordered 2.2.2-cryptand dication (with two protonated nitrogen atoms). The Zn²⁺ cation forms four strong coordination bonds with the O atoms of four NO ₃ ^? ligands and four weak (secondary) bonds with the second O atoms of these ligands. While ignoring the latter, the Zn²⁺ cation has a strongly distorted tetrahedral configuration. The [H₂(Crypt-222)]²⁺ dication contains trifurcate hydrogen bonds N-H(…O)₃.     

Disordered crystal structure of 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane dibromide dihydrate

The disordered crystal structure of 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane dibromide dihydrate, [H₂(2.2.2-Crypt)]²⁺·2Br^?2H₂O (I) was studied by X-ray diffraction (XRD) analysis. The orthorhombic structure of I (space group Aba2, a = 21.036(3) Å, b = 14.453(2) Å, c = 8.525(1) Å, Z = 4) was solved by direct methods and refined by full-matrix least squares in anisotropic approximation to R = 0.045 over all 2695 independent (taking into account anomalous scattering) reflections collected (CAD-4 automatic diffractometer, λCuK_α).     

Synthesis and crystal structure of 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane bis[dichloro(thiocyanato)copper(II)]

A new complex salt [4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane bis[dichloro(thiocyanato)copper(II)], [H₂(Crypt-222)][CuCl₂(SCN)]₂, is synthesized and studied by X-ray diffraction analysis. The crystals are monoclinic (space group C2/c, a = 14.603 Å, b = 8.330 Å, c = 25.091 Å, β = 100.76°, Z = 4). The structure is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.047 for 2943 independent reflections (CAD-4 automated diffractometer, λMoK _α radiation). The Cu²⁺ cations and Cl^? and SCN^? anions form infinite polymeric chains of spiro-conjugated alternating centrosymmetric four-membered CuCl₂Cu cycles and eight-membered Cu(SCN)₂Cu cycles through coordination bonds. The coordination polyhedron of the Cu²⁺ cation is a distorted trigonal bipyramid. The [H₂(Crypt-222)]²⁺ dication contains trifurcate N⁺-(…O)₃ bonds on axis 2.     

Synthesis of 1,10-dimethylbicyclo[8.8.8]hexacosane and 1,10-dihydroxybicyclo[8.8.8]hexacosane

[structure: see text] 1,10-Dimethylbicyclo[8.8.8]hexacosane (1) and 1,10-dihydroxybicyclo[8.8.8]hexacosane (2) were prepared in 4% yield over seven steps and in 18% yield over three steps, respectively, starting from 1,10-cyclooctadecanedione. The identities and out,out conformations of these compounds were established by single-crystal X-ray analysis.