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.     

Disordered crystal structure of 4,7,13,16,21,24-hexaoxa-1-aza-10-azoniabicyclo[8.8.8]hexacosane isocyanurate

X-ray spectral analysis has been applied to study the crystal structure of 4,7,13,16,21,24-hexaoxa-1-aza-10-azoniabicyclo[8.8.8]hexacosane isocyanurate of an unusual composition: [H_1.2(Crypt-222)]^1,2+ · [H_0.8(Crypt-222)]^0.8+·2(C₃H₂N₃O₃)^? (I). The structure of I (space group C2/c, a = 37.840 Å, b = 13.760 Å, c = 19.456 Å, β = 91.21°, Z = 8) was solved by a direct method and refined by the full-matrix least-squares technique in the anysotropic approximation up to R = 0.119 over 6500 independent reflections measured (autodiffractometer CAD-4, λ-MoK _α). The structure of I has two independent cations of 2.2.2-cryptand linked by the proximate pseudo-center of inversion and they have a rare conformation of exo-exo type, in which H atom or lone pair at both their node atoms N are directed outward their cavity. In the structure of I, all H atoms at N atoms of cations and half of H atoms of isocyanurate anions are disordered and have the populations of positions 0.7, 0.5, and 0.3. There is a developed system of interionic hydrogen bonds in the crystal structure of I.     

Disordered crystal structure of 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane <Emphasis Type="Italic">bis</Emphasis>(picrate) hydrate

For 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane bis(picrate) hydrate [H₂(Crypt-222)]²⁺·2Pic^?·1.19 H₂O (I), its disordered crystal structure has been determined by X-ray diffraction (XRD) analysis. The structure of I (space group \(P\bar 1\), a = 10.662 Å, b = 12.586 Å, c = 15.342 Å, α = 107.73°, β = 102.33°, γ = 90.49°, Z = 2) was solved by direct methods and refined by full-matrix least-squares in an anisotropic approximation to R = 0.111 for all 5000 independent reflections collected (CAD-4 automatic diffractometer, CAD-4, λMoK_α). The 2.2.2-cryptand dication is disordered and has two different conformations with probabilities of 66.7% and 33.7%. In addition to one independent water molecule, the cavity of the dication has a low-probability site of another water molecule, whose occupancy is 0.19. In the two independent picrate anions, some of their NO₂ groups are disordered over two orientations. The crystal structure of I has various interionic (intermolecular) and intracation hydrogen bonds.     

Novel copper(II) complex with unusual π-stacking structure, [Cu(SSC)Cl]<Subscript>2</Subscript>·CH<Subscript>3</Subscript>OH·2H<Subscript>2</Subscript>O (SSC = salicylaldehyde semicarbazone anion)

The crystal structure of [Cu^II(SSC)Cl]₂·CH₃OH·2H₂O (SSC = salicylaldehyde semicarbazone anion) was determined by the single crystal X-ray diffraction method at 293 K. Crystal data for Cu₂C₁₇H₂₄Cl₂N₆O₇: a = 10.272(2) Å, b = 10.297(2) Å, c = 11.462(2) Å, α = 82.860(3)°, β = 78.384(3)°, γ = 81.330(2)°, triclinic, space group P1¯, Z = 2, d _calc = 1.769 g/cm³, R ₁ = 0.038. One N and two O atoms of SSC^? occupy three coordination sites around Cu(II). The fourth site is occupied by Cl^? to yield distorted square-planar environment. Two molecules of the complex form a planar dimer through intermolecular N-H?O hydrogen bonds. The most striking feature of the crystal structure is the packing of the planar dimers within the crystal. The interplanar distances between adjacent two layers are 3.280 Å, indicative of strong π-π noncovalent interactions. The methanol solvent and water molecules are included as additional components in the crystal.     

Crystal structure and triboluminescence of the [Eu(TTA)2(NO3)(TPPO)2] complex

The crystal structure of [Eu(TTA)₂(NO₃)(TPPO)₂] (I) (TTA = thenoyltrifluoroacetone, TPPO = triphenylphosphine oxide) possessing intense triboluminescence was established by X-ray crystallography. The crystals are triclinic, noncentrocymmetrical: a = 11.047(3) Å, b = 11.794(3) Å, c = 12.537(3) Å; α = 102.635 (4)°, β = 102.088(4)°,γ = 117.765(3)°; space group P1, Z = 1. The central Eu(III) atom coordinates two oxygen atoms of two TPPO molecules at distances of 2.271 Å and 2.282 Å, two oxygen atoms of the nitrate group at distances of 2.478 Å and 2.481 Å, four oxygen atoms of two TTA ions at distances of 2.365 Å, 2.381 Å, and 2.363 Å, 2.371 Å (coordination number is 8). The coordination polyhedron of the Eu(III) atom is a distorted dodecahedron. Possible reasons for spectral differences in the Stark structure of photo-and triboluminescence of I are discussed.     

Crystalline and molecular structures of two halogenated propionamides CF2XCF2CONH2 (X = H, Cl)

Using the XRD method, the crystalline and molecular structures of two halogenated propionamides, CF₂XCF₂CONH₂, X = H (I) and Cl (II), have been studied. Crystals I and II are monoclinic: space group P2₁/c, Z = 4; (I) a = 10.967 Å, b = 5.406 Å, c = 10.063 Å, β = 107.86°; (II) a = 11.979 Å, b = 5.608 Å, c = 10.042 Å, β = 99.31°. Structures I and II were solved by the direct method and refined by the full-matrix least-square method to R = 0.112 (I) and 0.139 (II) over all 1299 (I) and 1175 (II) independent measured reflections (a CAD-4 autodiffractometer, λMoK _α).     

Crystal and molecular structure of 2-(<Emphasis Type="Italic">o</Emphasis>-hydroxyphenyl)-4,6-diphenylpyridine

Crystal and molecular structure of 2-(o-hydroxyphenyl)-4,6-diphenylpyridine C₂₃H₁₇NO (I) has been studied by single crystal XRD. The structure (monoclinic, space group P2₁/c, a = 8.757(2) Å, b = 20.682(4) Å, c = 9.743(2) Å, β = 108.14(2)°, Z = 4) was solved by the direct method and refined anisotropically in the full-matrix approximation to R = 0.076 using all 2660 measured independent reflections (automated diffractometer CAD-4, CuK_α). OH group of the molecule of I is disordered in the crystal over three positions with occupation factors 70%, 15% and 15%. The structure contains a very strong intramolecular hydrogen bond O-H?N disordered over three directions.     

Crystal and molecular structure of the [Zn(HL)Cl]·EtOH compound, (H2L = chiral bis(menthane)propylenediaminodioxime)

The crystal structure of a solvate [Zn(HL)Cl]·EtOH is determined by single crystal X-ray crystallography (150 K, Bruker X8 Apex CCD autodiffractometer, MoK _α radiation). The crystals are triclinic, unit cell parameters are: a = 7.4755(4) Å, b = 13.9701(11) Å, c = 14.4593(19) Å, α = 82.277(2)°, β = 75.410(2)°, γ = 75.356(1)°, space group P1. The structure of the solvate contains two crystallographically independent complex [Zn(HL)Cl] molecules and two non-coordinated ethanol molecules. In each of the molecules, Zn²⁺ ions coordinate N atoms of tetradentate chelating ligands HL^? and a Cl atom. ClN₄ polyhedra have a distorted tetragonal pyramidal geometry. EtOH molecules make H-bonds with the complex molecules, thus facilitating the formation of chains along the x axis.     

New crystal modification of the di(nitrato)di(aqua)palladium(II) complex β-trans-[Pd(NO3)2(H2O)2]

Single crystals of a new modification of the di(nitrato)di(aqua)palladium(II) complex β-trans-[Pd(NO₃)₂(H₂O)₂] were obtained. Their crystal structure was determined: monoclinic crystal system, a = 5.7469(4) Å, b = 5.3942(6) Å, c = 10.0956(10) Å, β = 97.401(3)°, P2₁/c, Z = 2, d _calc = 2.851 g/cm³, Bruker X8 APEX CCD, MoK _α , 836 independent reflections, room temperature. The square-plane coordination of the Pd atom is formed by four oxygen atoms (Pd-O(NO₃) 2.003(3) Å and Pd-O(H₂O) 2.021(4) Å) and completed to a distorted bipyramid by two intramolecular contacts (Pd…O(NO₃) 2.893 Å). A comparative crystal-chemical analysis with α-trans-[Pd(NO₃)₂(H₂O)₂] was carried out.     

Crystal structure of acrylamide

The crystal structure of acrylamide is re-determined by single crystal X-ray diffraction (133(1) K, BRUKER SMART 1000 CCD, a = 8.228(1) Å, b = 5.759(1) Å, c = 9.760(1) Å, β = 120.04(1)°, V = 400.3(1) Å,³, space group P2₁/c, Z = 4, R = 0.0543 for 867 reflections). In the structure strong hydrogen bonds N-H...O join the molecules of C₃H₅NO into bi-molecular layers that make C...C molecular contacts. It is demonstrated that the process of solid phase polymerization of acrylamide should proceed through the cleavage of double bonds C(1)=C(2) in the monomers and formation of bonds C(1)-C(1) and C(2)-C(2) between the closest carbon atoms of different layers.     

Crystal structures of 6-[(2-hydroxy-1,1-bis-hydroxymethyl-ethylamino)-methylene]-4-nitro-cyclohexa-2,4-dienone hydrate and 6-[(2-hydroxy-1,1-bis-hydroxymethyl-ethylamino)-methylene]-4-bromo-cyclohexa-2,4-dienone

Crystal structures of 6-[(2-hydroxy-1,1-bis-hydroxymethyl-ethylamino)-methylene]-4-nitro-cyclohexa-2,4-dienone hydrate (I) and 6-[(2-hydroxy-1,1-bis-hydroxymethyl-ethylamino)-methylene]-4-bromo-cyclohexa-2,4-dienone (II) have been determined. The crystals of I are monoclinic, a = 16.957(1) Å, b = 10.729(2) Å, c = 7.240(3) Å; β = 99.56(3)°, space group P2₁/c, Z = 4, R = 0.0492. The crystals of II are triclinic, a = 10.282(2) Å, b = 7.189(3) Å, c = 16.831(3) Å; α = 90.67(3)°, β = 100.10(3)°, γ = 95.87(3)°; space group P-1, Z = 4, R = 0.0591. The independent part of the unit cell of I contains one unique molecule and water of crystallization, while in II — two unique molecules A and B. C(CH₂OH)₃ fragment of the molecule B manifests the disordering of alcohol oxygen atoms. Both in I and II, the salicylidene fragment of the molecules exists in the quinoid tautomeric form.     

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).     

The absence of nitrone form in re-determined crystal structure of 2-hydroxyimino-3-methyl-4-nitro-2,5-dihydrothiophene 1,1-dioxide

Crystal and molecular structures of 2-hydroxyimino-3-methyl-4-nitro-2,5-dihydrothiophene-1,1-dioxide C₅H₆N₂O₅S (I) have been re-determined by single crystal X-ray diffraction analysis. The structure of I (space group P2₁2₁2₁, a = 6.124(1) Å, b = 9.205(2) Å, c = 14.884(3) Å, Z = 4) was solved by the direct method and refined anisotropically in the full-matrix approximation to R = 0.064 using all 1756 measured independent reflections (automated diffractometer CAD-4, λCuK_α, anomalous scattering taken into account). This study proves that the compound I contains a disordered group H-O-N=C, but not the isomeric nitrone group O←N(H)=C, as it has been concluded by the workers who pioneered single crystal X-ray diffraction study of I and erroneously took the second low-occupied oxygen position of the disordered hydroxyimine group for H at N atom.     

Synthesis and crystal structure of octaaqua(di-μ-bromo)dimanganese(II) dibromide 18-crown-6

A new crystalline complex octaaqua(di-μ-bromo)dimanganese(II) dibromide 18-crown-6, [Mn₂Br₂(H₂O)₈]Br₂ · 18C6, is synthesized and studied by X-ray diffraction analysis. The crystals of compound I are triclinic, space group $P\bar 1$ , a = 9.093 Å, b = 9.683, Å, c = 10.032 Å, α = 111.35°, β = 116.23°, γ = 92.64°, Z = 1. The structure is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.028 for 3276 independent reflections (CAD4 automated diffractometer, λMoK _α radiation). The [Mn₂Br₂(H₂O)₈]²⁺ complex cation lying at the inversion center is binuclear with two bridging Br atoms and eight water molecules. The coordination polyhedron of one Mn²⁺ cation is a distorted cis-octahedron with two Br atoms and four O atoms of the water molecules at its corners. The centrosymmetric 18C6 molecule has an usual conformation. A crystal of compound I contains a developed three-dimensional network of intermolecular (interionic) hydrogen bonds.     

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.     

Crystal structure refinement for trans-[Pd(NO3)2(H2O)2]

Single crystals of trans-[Pd(NO₃)₂(H₂O)₂] were obtained, and the crystal structure of this complex, previously obtained for polycrystals, was refined. Crystal data (BRUKER X8APEX diffractometer): a = 4.9973(7) Å, b = 10.5982(14) Å, c = 11.7008(17) Å, V = 619.70(15) ų, space group Pbca, Z = 4, d _calc = 2.856 g/cm³. The structure is composed of neutral complexes with a trans configuration. The square plane environment of the Pd atom is formed by four oxygen atoms (Pd-O(NO₃) 1.999(5) Å, Pd-O(H₂O) 2.030(5) Å) and completed to a distorted bipyramid by two intramolecular contacts (Pd…O(NO₃) 2.926 Å). The shortest hydrogen bonds are O…H 2.72 Å.     

Crystal structure of tris[(2.2.2-cryptand)× (nitrato-O,O′)lead(II)] pentakis(nitrato-O,O′)lead(II)

A novel coordination compound tris[(2.2.2-cryptand)(nitrato-O,O′)lead(II)] pentakis(nitrato-O, O′)lead(II), 3[Pb(NO₃)(Crypt-222)]⁺·[Pb(NO₃)₅]^3? (I) has been prepared and studied by the single crystal X-ray diffraction technique. The crystals of I are monoclinic: space group Pc, a = 25.944 Å, b = 18.389 Å, c = 17.145 Å, β = 93.33°, Z = 4. The structure of I has been solved by the direct and heavy atom methods and refined in a full-matrix anisotropic-isotropic approximation to R = 0.122 for the total of 11145 measured reflections (automated diffractometer CAD-4, λMoK _α). The structure of I includes six independent host-guest complex cations [Pb(NO₃)(Crypt-222)]⁺ and two independent complex anions [Pb(NO₃)₅]^3?. Coordination number of the cation Pb²⁺ equals ten in all these complex ions, and its coordination polyhedron in the first of them is a strongly distorted “hexagonal bipyramid” with two forked vertices, while for the latter ones it is a strongly distorted “square pyramid” with all five vertices forked.     

Crystal and molecular structure of <Emphasis Type="Italic">E</Emphasis>-3-(1,3-dimethylindol-2-yl)methylene-4-isopropylidenetetrahydrofuran-2,5-dione

The crystal and molecular structure of E-3-(1,3-dimethylindol-2-yl)methylene-4-isopropylidenetetrahydrofuran-2,5-dione, C₁₈H₁₇NO₃ (I), was investigated by XRD. The monoclinic structure of I (space group P2₁/c, a = 12.411(2) Å, b = 7.586(1) Å, c = 16.107(3) Å, β = 96.90(2)°, Z = 4) was solved by direct methods and refined by the full-matrix least squares in an anisotropic approximation to R = 0.044 for all 2842 independent reflections collected (CAD-4 automatic diffractometer, λCuK _α). The geometric parameters of sterically strained molecule I were determined with a high accuracy.     

Crystal structure of <Emphasis Type="Italic">trans</Emphasis>-bis(trifluoro-acetylacetonato)copper(II)

Triclinic modification of trans-bis(trifluoroacetylacetonato)copper(II) is studied by single crystal X-ray diffraction (diffractometer X8 APEX BRUKER, MoK _α radiation, T = 173(2) K). The structure is molecular. Square environment of the Cu atom (Cu-O_av 1.916 Å, ∠O-Cu-O_av 93.4°) is completed to a bipyramid by two atoms of neighboring molecules, Cu...C_γ 3.18 Å and 3.23 Å.     

Synthesis and crystal structure of divaleratobis(nicotinamide)copper(II)

A copper(II) valerate complex with nicotinamide (L) [CuL₂(C₄H₉COO)₂] (I) has been synthesized and studied by IR spectroscopy and thermogravimetry. The crystal structure has been determined. The crystals of 1 are monoclinic, a = 11.297(1) Å, b = 6.666(1) Å, c = 16.873(2) Å, b = 108.50(1)°, V = 1204.9(3) ų, Z = 2, space group P2₁/c. The structural units of the crystal of I are centrosymmetric tetragonal bipyramidal (4+2) complex molecules. The equatorial positions of the bipyramid are occupied by trans-arranged pairs of O (Cu-O, 1.973 Å) and N (Cu-N, 2.006 Å) atoms, and the axial positions are occupied by the second O atoms of the valerate anions located at longer distances (Cu-O, 2.506 Å). The supramolecular associates formed in the crystal are layers of hydrogen-bonded complexes. The disordered hydrocarbon “tails” of the valerate groups point toward the interlayer space.