Synthesis and crystal structure of (2.2.2-cryptand)potassium nitrate hydrate

(2.2.2-Cryptand)potassium nitrate hydrate, [K(Crypt-222)](NO₃) · 1.5H₂O (I) was synthesized and studied by X-ray diffraction method. Crystals I are triclinic (space group P ī, a = 11.262 Å, b = 12.033 Å, c = 12.181 Å, α = 60.48°, β = 86.17°, γ = 66.20°, Z = 2). The structure was solved by the direct method and refined by the full-matrix least-squares method in anisotropic approximation to R = 0.065 from 3377 independent reflections (CAD-4 automated diffractometer, λMoK _α). In complex I, the host-guest complex cation [K(Crypt-222)]⁺ has approximate D ₃ symmetry. The coordination polyhedron of the K⁺ cation is a two-base-centered trigonal prism, which is slightly distorted toward antiprism. The disordered NO ₃ ^? anions and water molecules are united by hydrogen bonds into infinite chains along the x-axis.     

Synthesis and crystal structure of (2.2.2-cryptand)(nitrato-O,O’)lead(II) nitrate monohydrate

A new complex, (2.2.2-cryptand)(nitrato-O,O’)lead(II) nitrate monohydrate [Pb(NO₃)(Crypt-222)]⁺ · NO ₃ ^? · H₂O, is synthesized and characterized by X-ray crystallography. The structure of the complex (space group Pbca, a = 14.196 Å, b = 14.001 Å, c = 26.745 Å, Z = 8) is solved by direct methods and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.073 for 3474 unique reflections (CAD4 automated diffractometer, λMOK _α). The structure contains the host-guest complex cation [Pb(NO₃)(Crypt-222)]⁺. The Pb²⁺ cation is located in the cavity of the 2.2.2-cryptand ligand and is coordinated by all eight heteroatoms (6O + 2N) of the cryptand ligand and two O atoms of the NO ₃ ^? ligand. The coordination polyhedron of the Pb²⁺ cation (ten-coordinate) is a strongly distorted hexagonal bipyramid with a base of four O atoms and two N atoms of the cryptand ligand and with two bifurcated axial vertices at two O atoms of the nitrate ligand and two O atoms of the cryptand ligand. The disordered NO ₃ ^? anion and the water molecule are linked by hydrogen bonds.     

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.     

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

A new crystalline complex salt, 4,7,13,16,21,24-hexaoxa-1,10-diazaniabicyclo[8.8.8]hexacosane tetra(nitrato-O)copper(II) [H₂(Crypt-222)]²⁺ · [Cu(NO₃)₄]^2?(I), is synthesized and studied using X-ray diffraction analysis (space group P2₁/c, a = 10.264 Å, b = 14.798 Å, c = 19.516 Å, β = 100.20°, 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 = 0.032 for 4050 independent reflections (CAD-4 automated diffractometer, λMoK _α radiation). Salt I exist in crystals as individual ions: the [Cu(NO₃)₄]^2? complex anion and the slightly disordered dication of 2.2.2-cryptand with two protonated nitrogen atoms. The Cu²⁺ cation has a square coordination somewhat distorted toward a flattened tetrahedron with four coordination bonds with the O atoms of the four NO ₃ ^? ligands. Trifurcate hydrogen bonds of the [H₂(Crypt-222)]²⁺ type are observed in the N-H(? O)₃ dication.     

Synthesis and crystal structure of bis(2,2,2-cryptand potassium) tetrakis(isocyanato)cuprate(II)

A new complex compound, bis(2,2,2-cryptand potassium) tetrakis(isocyanato)cuprate(II), 2[K(Crypt-222)]⁺ [Cu(NCS)4]^2? was prepared and its crystal structure was studied by X-ray structural analysis. The structure includes one symmetrically independent complex cation [K(Crypt-222)]⁺ of a guest-host type and independent one half of [Cu(NCS)₄]^2? anion. Through the center of the anion passes crystallographic symmetry axis 2, the approximate point symmetry of the anion is D ₂, while the approximate point symmetry of the complex cation is D ₃. The coordination polyhedron of the [Cu(NCS)₄]^2? anion (four N atoms) conjugated with Cu²⁺ cation is a nonplanar square considerably screwed into a flattened tetrahedron. The K⁺ cation (coordination number 8) of the complex cation [K(Crypt-222)]⁺ is coordinated by all eight heteroatoms (6O + 2N) of the 2,2,2-cryptand ligand, and its coordination polyhedron can be described as bis-basecentered trigonal prism slightly screwed into an anti-prism.     

Bis[(2.2.2-cryptand)potassium] tetrakis(isothiocyanato)cobalt(II) ethanol solvate with the 22% RbBr molar admixture: Synthesis and crystal structure

A new crystalline complex, bis[(2.2.2-cryptand)potassium] tetrakis(isothiocyanato)cobalt(II) ethanol solvate of the composition 2[K_0.89Rb_0.11(Crypt-222)]⁺ [Co(NCS)_3.78Br_0.22]^2? EtOH (I), was synthesized with 22 mol % RbBr and studied by X-ray diffraction. Complex I contains two mixed host-guest complex cations and the mixed complex anion. The triclinic structure of complex I (space group P1, a = 12.060 Å, b = 12.156 Å, c = 12.264 Å, α = 80.45°, β = 61.28°, γ = 71.98°, Z = 1) was solved by a direct method and refined by the full-matrix least squares in the anisotropic approximation to R = 0.066 for all 4400 independent reflections (CAD-4 automated diffractometer, λMoK _α radiation). The [Co(NCS)_3.78Br_0.22]^2? anion is tetrahedral, and its two SCN^? ligands are partially replaced by two Br^? ligands. In structure I, two independent host-guest complex cations [K′(Crypt-222)]⁺ (K′ = (K_{1 ? δ} Rb_δ)⁺) are almost identical inverted reflection of each other and have approximate D ₃ symmetry. Their mixed cation K′ is coordinated by all eight heteroatoms (6O + 2N) of the 2.2.2-cryptand ligand, and the coordination polyhedron K′ is a dibase-centered trigonal prism (coordination number eight) slightly distorted toward an antiprism.     

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.     

Isomorphous crystal structures of 4,7,13,16,21,24-hexaoxo-1,10-diaziniabicyclo[8.8.8]·hexacosane bis(tribromide) and bis(bromoiodide)

Two compounds, 7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane bis(tribromide) and bis(bromodiiodide) — [H₂(Crypt-222)]²⁺·2Br ₃ ^? (I) and [H₂(Crypt-222)]²⁺·1.45(BrI₂)^?·0.4(Br₂I)^?·0.15 I ₃ ^? (II) — are prepared and characterized by single crystal XRD; the refinement of the second compound was more accurate. Isomorphous monoclinic structures (I, space group C2/c, Z = 4, a = 12.090, b = 15.833 Å, c = 15.732 Å, β = 95.83°; II, a = 12.548 Å, b = 16.417 Å, c = 15.748 Å, β = 94.53°) are solved by a direct method and refined in the anisotropic full-matrix approximation to R = 0.057 (I) and 0.044 (II) using all 2635 (I) and 2852 (II) measured independent reflections (automated CAD-4 diffractometer, λMoK _α). In the structures of I and II one of the trihalide anions sits at the inversion center i(000), and the second trihalide anion and the dication [H₂(Crypt-222)]²⁺ are situated at crystallographic axis 2. In the structure of II iodine is located in the center of trihalide anions, while the terminal atoms are disordered and are represented by a statistical combination of iodine and bromine atoms.     

Synthesis and crystal structure of aqua(2.2.2-cryptand)(perchlorato-O)lead(II) diaqua(2.2.2-cryptand)lead(II) tris(perchlorate)

A mixed complex aqua(2.2.2-cryptand)(perchlorato-O)lead(II) diaqua(2.2.2-cryptand)lead(II) tris(perchlorate), [Pb(2.2.2-Crypt)(CIO₄)(H₂O)]⁺ [Pb(2.2.2-Crypt)(H₂O)₂]²⁺ (ClO ₄ ^? )₃, is synthesized and studied by X-ray diffraction analysis. The crystals are orthorhombic: space group Pbca, a = 19.118 Å, b = 15.360 Å, c = 39.020 Å, Z = 8. The structure is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.089 for 7712 reflections (CAD-4 automated diffractometer, λMoK _α radiation). In each of the two complex cations of the host-guest type in the structure, the Pb²⁺ cation is coordinated by all the eight heteroatoms (6O + 2N) of the cryptand ligand and by two O atoms of the water molecule and ClO ₄ ^? anion or by two O atoms of two water molecules. In the crystal, alternating complex cations and ClO ₄ ^? anions are linked into infinite chains (along the z axis) through interionic hydrogen bonds O-H···O-Cl.     

Synthesis and crystal structure of diaquabis(nitrato-O,O′)ethanoliron(III) 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane trinitrate

A new complex salt diaquabis[nitrato-O,O′)ethanoliron(III)] 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane trinitrate, [Fe(NO₃)₂(EtOH)(H₂O)₂]⁺ · [H₂(Crypt-222)]²⁺ · (NO ₃ ^? )₃, is synthesized. Its crystal structure has been determined by X-ray diffraction analysis: space group P 2₁/c, a = 14.147 Å, b = 11.443 Å, c = 23.127 Å, β = 103.66°, 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 = 0.064 for 5050 independent measured reflections (CAD-4 automated diffractometer, λMoK _α radiation). In the [Fe(NO₃)₂(EtOH)(H₂O)₂]⁺ complex cation, the coordination polyhedron of the Fe³⁺ cation is a distorted pentagonal bipyramid with its base formed by four O atoms of two bidentate NO ₃ ^? ligands, one O atom of the water molecule, and its axial vertices occupied by the O atoms of the EtOH molecule and the second water molecule. The alternating complex cations and NO ₃ ^? anions multiplied by the 2₁ axis are hydrogen-bonded into infinite chains running along the y axis.     

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.     

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.     

Synthesis and crystal structure of triaqua(18-crown-6)calcium bis(perchlorate) 18-crown-6 monohydrate

A complex [Ca(18C6)(H₂O)₃]²⁺(ClO ₄ ^? · 18C6 · H₂O is synthesized and studied by X-ray diffraction analysis. The structure (space group P2₁/n, a = 11.570 Å, b = 16.024 Å, c = 22.225 Å, β = 98.89°, Z = 4) is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.075 for 5305 independent reflections (CAD4 automated diffractometer, λMoK _α radiation). In the complex cation of the host-guest type, the Ca²⁺ cation lies in the cavity of the 18-crown-6 ligand and is coordinated by all the six O atoms and three O atoms of three water molecules. In a crystal, the alternating complex anions, 18C6 molecules, and water molecules are joined by hydrogen bonds into broad infinite chains along the y axis. The disordered ClO ₄ ^? anions are bonded to these chains on the side through hydrogen bonds.     

Synthesis and crystal structure of aqua(dibenzo-18-crown-6)potassium (dibenzo-18-crown-6)(perchlorato-O)potassium perchlorate

A new compound, aqua(dibenzo-18-crown-6)potassium (dibenzo-18-crown-6)(perchlorato-O)potassium perchlorate ([K(DB18C6)(H₂O)]⁺ · [K(ClO₄)(DB18C6)] · ClO ₄ ^? ; compound I) is synthesized and studied by X-ray crystallography. The crystals are triclinic: a = 9.050 Å, b = 9.848 Å, c = 26.484 Å, α = 82.87°, β = 84.16°, γ = 77.93°, Z = 2, space group P $\bar 1$ . The structure is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.058 for 5960 independent reflections (CAD4 diffractometer, λMoK _α radiation). A complex cation [K(DB18C6)(H₂O)]⁺ and a complex molecule [K(ClO₄)(DB18C6)] are of the host-guest type; they are linked into a dimer through two K⁺ → π(C) bonds formed by one of the two K⁺ cations with two C atoms of the benzene ring of the DB18C6 ligand from the adjacent complex. Both DB18C6 ligands in I have a butterfly conformation with approximate symmetry C _2v .     

Crystal structure of 4,7,13,16,21,24-hexaoxa-1-aza-10-azoniabicyclo[8.8.8]hexacosane monohydrate picrate

The crystal structure of 4,7,13,16,21,24-hexaoxa-1-aza-10-azoniabicyclo[8.8.8]hexacosane monohydrate picrate, [H(Crypt-222) H₂O]⁺·Pic^? (I), has been studied by X-ray crystallography. The structure of I (space group P2₁/c, a = 9.336 Å, b = 19.497 Å, c = 16.420 Å; β = 94,84°, Z = 4) was solved by direct methods and refined by full-matrix least squares in an anisotropic approximation to R = 0.056 for all 3877 independent reflections collected (CAD-4 automatic diffractometer, λMoK _α). This compound is one of the few representatives of the class of crystal salts containing a 2.2.2-cryptand cation with a protonated nitrogen atom that have been synthesized and studied by X-ray crystallography. The void of the cation contains a water molecule held by three H bonds. Crystal I also has unusual H bonds of C-H…O type that link the neighboring 2.2.2-cryptand cation and the picrate anion.     

4,7,13,16,21,24-Hexaoxa-1,10-diazaniabicyclo[8.8.8]-hexacosane dichloride monohydrate: Synthesis and crystal structure

A new crystalline hydrated salt of 2.2.2-cryptand and hydrochloric acid [H₂(Crypt-222)]²⁺. 2CI^?, H₂O is synthesized and studied using single-crystal X-ray diffraction. The structure (space group C2/c, a = 13.203 Å, b = 23.807 Å, c = 8.728 Å, β = 117.16°, Z = 4) is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.055 for 2152 independent reflections (CAD4 automated diffractometer, λMoK _α radiation). The 2.2.2-cryptand dication lies on axis 2 and has a rare conformation of the exo-exo type, in which two H atoms at the two N atoms are directed outside of the cavity. The water molecule is half-occupied and randomly disordered relative to another similar axis, 2, and the chloride anion is disordered over two (the main and poorly occupied) positions. The alternating 2.2.2-dications, chloride anions, and water molecules are hydrogen-bonded to form infinite chains.     

Ammonium (18-Crown-6)(Triphenylphosphine Oxide) Perchlorate: Synthesis and Crystal Structure

A new compound, ammonium (18-crown-6)(triphenylphosphine oxide) perchlorate (I), is synthesized, and its crystal structure is studied using X-ray diffraction analysis (space group R3m, a = 14.432 Å, c = 14.034 Å, Z = 3, direct method, full-matrix least-squares method in the anisotropic approximation, R = 0.064 for 1945 independent reflections, CAD4 automated diffractometer, λMoKα radiation). In the structure, the NH ₄ ⁺ cation resides in the 18-crown-6 macrocycle cavity and is hydrogen-bonded with three symmetrically equivalent O atoms of the 18-crown-6 molecule and with the phosphoryl O atom of the Ph₃PO molecule. The P=O H-N and Cl atoms occupy the partial position 3m. The oxygen atoms of the ClO ₄ ^? anion are disordered over the 3m position.     

Syntheses and crystal structures of (2.2.2-cryptand)potassium chloride and (2.2.2-cryptand)ammonium bromide<Subscript>(0.75)</Subscript>chloride<Subscript>(0.25)</Subscript> hydrates

Two new complexes were synthesized, namely, 7: 2 (2.2.2-cryptand)potassium chloride and (2.2.2-cryptand)ammonium bromide_(0.75)chloride_(0.25) hydrates: [M(Crypt-222)]⁺ · Hal^? · 3.5H₂O, where M = K, Hal = Cl (I) and M = NH₄, Hal = Br_0.75Cl_0.25 (II). The structures of two isomorphous crystals were studied by X-ray diffraction analysis. Trigonal (space group P \(\bar 3\), Z = 2) structures I (a = 11.763 Å, c = 11.262 Å) and II (a = 11.945 Å, c = 11.337 Å) were solved by direct methods and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.057 (I) and 0.065 (II) for all 2626 (I) and 1654 (II) independent measured reflections (CAD-4 automated diffractometer, λMoK _α). In structures I and II, the host-guest [M(Crypt-222)]⁺ complex cation lies on the threefold crystallographic axis and has the approximate D ₃ symmetry. In complex I, the coordination polyhedron of the K⁺ cation (CN = 8) is a bicapped trigonal prism somewhat distorted toward an antiprism. Complexes I and II contain H-bonded disordered cubes of the water molecules and the Cl^? or Br^? anions.     

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.     

4,7,13,16,21,24-Hexaoxa-1,10-diazaniabicyclo[8.8.8]-hexacosane Bis(dihydrogenphosphate) dihydrate: Synthesis and crystal structure

A crystalline hydrated salt of 2.2.2-cryptand and orthophosphoric acid [H₂(Crypt-222)]²⁺ · 2H₂PO ₄ ^? · 2H₂O is synthesized and studied using single-crystal X-ray diffraction. The crystals are triclinic, space group $P\bar 1$ , a = 7.969 Å, b = 8.253 Å, c = 24.858 Å, α = 89.08°, β = 80.86°, γ = 62.35°, 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 = 0.068 for all 3718 independent reflections (CAD4 automated diffractometer, λMoK _α radiation). In the structure, the 2.2.2-cryptand dication has a rare exo-exo conformation, in which two H atoms at the two N atoms are directed outside of its cavity. The P atoms of two independent H₂PO ₄ ^? anions have considerably distorted tetrahedral coordination. The crystal structure contains a developed three-dimensional system of intermolecular (interionic) hydrogen bonds.