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 .     

Diaquabromo(18-crown-6)rubidium and triaqua(18-crown-6)barium dibromide monohydrate: Synthesis and crystal structures

Two complexes are synthesized: diaquabromo(18-crown-6)rubidium [RbBr(18-crown-6)(H₂O)₂] (I) and triaqua(18-crown-6)barium dibromide monohydrate [Ba(18-crown-6)(H₂O)₃]²⁺ 2Br^? · H₂O (II). The orthorhombic structure of compound I (space group Pnma, a = 10.124 Å, b = 15.205 Å, c = 12.544 Å, Z = 4) and the monoclinic structure of compound II (space group C 2/c, a = 17.910 Å, b = 10.315 Å, c = 14.879 Å, β = 123.23°, Z = 4) are determined by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.063 (I) and 0.042 (II) for all 2293 (I) and 3363 (II) independent measured reflections (CAD-4 automated diffractometer, λMoK _α). The complex molecule [RbBr(18-crown-6)(H₂O)₂] in compound I and the randomly disordered cation [Ba(18-crown-6)(H₂O)₃]²⁺ in compound II are of the host-guest type: their Rb⁺ or Ba²⁺ cation (its coordination number is nine) is located in the cavity of the 18-crown-6 ligand and coordinated by all six O atoms. In structure I, the coordination polyhedron of Rb⁺ is a distorted hexagonal pyramid with a triple apex at the Br^? ligand and two O atoms of the water molecules. In structure II, the Ba²⁺ polyhedron is a distorted hexagonal bipyramid with one apex at the O atom of the water molecule and the other split apex at two O atoms of water molecules.     

Synthesis and crystal structure of dibenzo-18-crown-6 oxonium perchlorate trihydrate

A hydrated crystalline ionized adduct of dibenzo-18-crown-6 and perchloric acid DB18C6 · H₃O⁺ · CiO ₄ ^? · 3H₂O (I) is synthesized and characterized by X-ray diffraction. The crystals of I are monoclinic: a = 17.760 Å, b = 12.922 Å, β = 124.27°, Z = 4, space group Cc. The structure of I is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.079 for 3294 independent reflections (CAD4 automated diffractometer, λMoK _α radiation). A DB18C6 molecule has a butterfly conformation with the rough symmetry C _2v . An H₃O⁺ · H₂O dimer is situated on one side of the DB18C6 macrocycle, and the ClO ₄ ^? anion and two other water molecules are on the other side. In the crystal of I, the DB18C6 molecules, H₃O⁺ and ClO ₄ ^? ions, and water molecules are linked through intermolecular (interionic) hydrogen bonds to form broad infinite chains running along the z axis.     

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.     

(18-crown-6)potassium tris(thiocyanato)nickelate(II): Synthesis and crystal structure

A new crystalline complex, (18-crown-6)potassium tris(thiocyanato)nickelate(II), [Ni(SCN)₃K(18-crown-6)] _n (I) was synthesized and studied by X-ray diffraction: space group Cmc2₁, a = 14.749, b = 15.045, c = 10.216 Å, Z = 4, direct method, least-squares full-matrix refinement in anisotropic approximation to R = 0.022 on 2214 independent reflection, CAD-4 automated diffractometer, λMoK _α. In crystal structure I, the [Ni(SCN)₃] _n ^? chains are directed along the axis z with the host-guest [K(18-crown-6)]⁺ fragments attached through the weak K-S bonds to the chains at the side. The complex cations and anions lie in crystallographic plane m. The Ni²⁺ cation has a distorted octahedral coordination. The coordination polyhedron of the K⁺ cation is a distorted hexagonal pyramid with six O atoms of the 18-crown-6 ligand in the base and bifurcate axial vertex at the S and S′ atoms of two SCN^? ligands.     

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.     

(Dibenzo-18-crown-6)potassium tetrachloroferrate(III): Synthesis and crystal structure

A new complex [K(Db18C6)]⁺[FeCl₄]^? (I) is synthesized and its structure is studied by X-ray diffraction analysis. The crystals are triclinic: space group P \(\bar 1\), a = 17.998, b = 18.670, c = 19.590 Å, α = 106.61°, β = 104.55°, γ = 113.87°, 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 = 0.057 by 13 670 independent reflections (CAD-4 automated diffractometer, λMoK _α). All the four independent complex cations [K(Db18C6)]⁺ are host-guest, and in each complex cation the K⁺ cation is localized in the cavity of the Db18C6 crown ligand. The coordination polyhedron of K⁺ (coordination number nine) is a distorted hexagonal bipyramid with the base of all six O atoms of the Db18C6 ligand, the axial vertex at the Cl atom of the [FeCl₄]^? anion, and another bifurcated axial vertex at two Cl atoms of another [FeCL₄]^? anion. All the four independent [FeCL₄]^? anions are orientationally disordered and have somewhat distorted tetrahedral structure. In crystal I, the alternating complex cations [K(Db18C6)]⁺ and [FeCL₄]^? anions form infinite polymer chains by the K-Cl bonds.     

Aquabis(dibenzo-18-crown-6)(tetrabromocuprato(II))dipotassium: Synthesis and crystal structure

The novel complex [K(Db18C6)(H₂O)]⁺[K(Db1)] ⁺(CuBr₄)^2? (I) was obtained. Its crystal structure (space group P2₁/c, a = 17.970 Å, b = 29.838 Å, c = 9.074 Å, β = 103.11°, Z = 4) was studied by X-ray diffraction analysis, solved by the direct method, and refined by the least-squares method in the anisotropic approximation to R = 0.098 from 6220 independent reflections (CAD-4 automated diffractometer, λMo Kα). In both “guest-host” complex ions, the K⁺ cation is in the cavity of the crown ligand Db18C6 and is coordinated by all its O atoms, as well as by a Br atom of the complex anion [CuBr₄]^2? or the water O atom. The coordination of either K⁺ cation is extended to a hexagonal bipyramid by a weak K⁺ → π\((C\dddot ---C)\) bond to two C atoms of the benzene ring of the adjacent ligand Db18C6. In the crystal, the complex anions and cations are united into infinite double chains through the above contacts and the interion hydrogen bonds O-H…Br.     

Synthesis and crystal structure of dibenzo-18-crown-6 oxonium perchlorate

An ionized crystalline adduct of dibenzo-18-crown-6, perchloric acid, and water (H₃O)[DB 18K6](ClO₄) is synthesized and structurally studied by X-ray diffraction. The crystals are triclinic: a = 8.582 Å, b = 10.486 Å, c = 26.293 Å, α = 79.45°, β = 82.00°, γ = 79.36°, Z = 4, 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 = 0.098 for 5936 independent reflections (CAD4 automated diffractometer, λMoK _α radiation). The structure contains two independent DB18C6 molecules, two independent H₃O⁺ ions, and two independent ClO ₄ ^? ions. The H₃O⁺ ions each lie in the cavity of each of the two DB18C6 molecules and are retained there by three strong hydrogen bonds. Two DB18C6 molecules have close geometric parameters and a butterfly conformation with approximate symmetry C _2v . One of the two independent ClO ₄ ^? anions is disordered over two orientations.     

Synthesis and crystal structure of diaqua(trinitrato)iron(III) 18-crown-6

A novel complex adduct, diaqua(trinitrato)iron(III) 18-crown-6, [Fe(NO₃)₃(H₂O)₂] · 18-crown-6, was synthesized and its crystal structure was studied by X-ray diffraction: space group C2/c, a = 10.073, b = 18.069, c = 25.326 Å, β = 91.51°, Z = 8. The structure was solved by the direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.076 for 4090 independent reflections (CAD-4 automated diffractometer, λMoK_α). The structure contains isolated complex molecule [Fe(NO₃)₃(H₂O)₂] and two halves of independent molecules 18-crown-6, one of which is statistically disordered about axis 2, while another one is located around the inversion center and is somewhat disordered with respect to the latter. In the complex molecule, the coordination polyhedron of the Fe³⁺ cation is a distorted pentagonal bipyramid with five O atoms of three NO ₃ ^? ligands in a base and two O atoms of two water molecules in the axial vertices. The alternating complex molecules and the disordered 18-crown-6 molecules are joined by hydrogen bonds into “thick” infinite chains along the z axis.     

(18-Crown-6)sodium tribromide and (18-crown-6)potassium triiodide (with an admixture of bromodiiodide): Synthesis and crystal structure

Two crystalline host-guest complexes are synthesized and studied using X-ray diffraction analysis: (18-crown-6)sodium tribromide [Na(18-crown-6)]⁺ · Br ₃ ^? (I) and (18-crown-6)potassium tribromide (with an admixture of bromodiiodide) [K(18-crown-6)]⁺ · (Br_0.25I_2.75)^? (II). The structures of compound I (space group P2₁/_{n, a} = 8.957 Å, b = 8.288 Å, c = 14.054 Å, β = 104.80°, Z = 2) and compound II (space group Cc, a = 8.417 Å, b = 15.147 Å, c = 17.445 Å, β = 99.01°, Z = 4) are solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.098 (I) and 0.036 (II) for all 2311 (I) and 2678 (II) independent measured reflections on a CAD-4 automated diffractometer (λMoK _α). Similar crystalline complexes I and II exist as infinite chains of alternating complex cations and trihalide anions linked to each other through weak Na-Br or K-I coordination bonds. In [Na(18-crown-6)]⁺ and [K(18-crown-6)]⁺ complex cations, the Na⁺ or K⁺ cation (coordination number is eight) is located in the center of the cavity of the 18-crown-6 ligand and coordinated by the six O atoms and two terminal Br or I atoms of two trihalide anions lying on opposite sides of the rms plane of the crown ligand.     

Synthesis and crystal structure of (dibenzo-18-crown-6)bis(thiocyanato-S)mercury(II)

A new host-guest complex (dibenzo-18-crown-6)bis(thiocyanato-S)mercury(II), [Hg(SCN)₂(DB18C6], was synthesized and studied by X-ray diffraction method. The crystal structure (space group P2₁/n, a = 19.372, b = 8.199, c = 31.799 Å, β = 103.58°, Z = 8) was solved by the direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.092 for 6392 independent reflections; CAD-4 autodiffractometer, λMoK _α. In two independent similar complex molecules, the Hg²⁺ cation lies in the cavity of the DB18C6 crown ligand and is coordinated by all the six O atoms and is covalently bonded to two S atoms of the SCN^? ligands lying on the opposite sides of the mean plane of the six O atoms of the DB18C6 ligand. The coordination polyhedron of two independent Hg atoms is a distorted hexagonal bipyramid. Both independent DB18C6 ligands have the “butterfly” conformation with the approximate C _2v symmetry.     

Synthesis, crystal structure, and luminescent properties of a silver(I) perrhenate complex with phenazine

The silver complex with phenazine [Ag(Phz)₂(H₂O)]ReO₄ (Phz is C₁₂H₈N₂) has been synthesized, and its crystal structure has been determined. The crystals are triclinic: space group $P\bar 1$ , a = 9.587(1) Å, b = 10.875(1) Å, c = 11.668(1) Å, α = 104.98(1)°, β = 103.87(1)°, γ = 92.94(1)°, V = 1132.6(2) ų, Z = 2, ρ_calc = 2.160 g/cm³. The structure is composed of the [Ag(Phz)₂(H₂O)]⁺ silver cationic complexes and ReO ₄ ^? anions. The Ag⁺ ion is coordinated by two nitrogen atoms of independent phenazine molecules and the water oxygen atoms and has a T-shaped coordination (Ag-N_av 2.223 Å, Ag-O_w 2.498(8) Å). Phenazine, being an electron-donor ligand, forms columns due to π-π stacking interaction between the aromatic groups. The water molecules form hydrogen bonds with the oxygen atoms of water molecules of neighboring complexes and with oxygen atoms of the ReO ₄ ^? anions.     

Synthesis and crystal structure of bis(dibenzo-18-crown-6)cesium tetrachloroferrate(III)

A new complex [Cs(Db18C6)₂]⁺[FeCl₄]^? was prepared and studied by X-ray diffraction (orthorhombic, space groupP2₁2₁2,a = 22.934 Å,b= 24.024 Å,c= 16.665 Å,Z= 8; direct method, anisotropic full-matrix least-squares refinement,R= 0.087 for all 8800 independent reflections; CAD4 automated diffractometer, λMoK _α. Two independent [FeCl₄]^? anions have a slightly distorted tetrahedral structure. Two independent host-guest type complex cations [Cs(Db18C6)₂]⁺ have a sandwich structure. The Cs⁺ cation is located between two Db18C6 crown ligands below and above the centers of their 18-membered macrocycles and is coordinated by all 12 O atoms. The coordination polyhedron of Cs⁺ (C.N. 12) is a distorted hexagonal antiprism rotated toward a hexagonal prism.     

Triaqua(18-crown-6)strontium tetrachlorocuprate(II) hemihydrate: Synthesis and crystal structure

The new complex [Sr(18-crown-6)(H₂O)₃]²⁺[CuCl₄]^2? · 0.42H₂O was obtained; its crystal structure was determined by X-ray diffraction analysis: space group P2₁, a = 10.305 Å, b = 13.570 Å, c = 17.566 Å, β = 98.23 °, Z = 4 (direct method, anisotropic full-matrix least-squares method, R = 0.053 from independent reflections; CAD-4 automated diffractometer, λMoK _α). The asymmetric part of the unit cell comprises two independent “guest-host” complex cations [Sr(18-crown-6)(H₂O)₃]²⁺, two independent complex anions [CuCl₄]^2?, and a hydrate water molecule with a position population of 0.84(1).     

Crystal structure of hexakis(thiourea)-bis((μ-perchlorato-O,O’)-(perchlorato-O)-bismuth) diperchlorate

The complex[Bi₂(Tu)₆(ClO₄)₄](ClO₄)₂ (I) (Tu is thiourea) was synthesized and studied by X-ray diffraction. The crystallographic data of I are: a = 14.205(1) Å, b = 13.083(1) Å, c = 22.078(2) Å, β = 96.182(1)°, V = 4079.1(7) ų, space group C2/c, Z = 4. The molecule is located on a twofold axis and consists of the binuclear cation [Bi₂(Tu)₆(ClO₄)₄]²⁺ and two outer-sphere anions Cl ₄ ^? . The Bi-S bond lengths are 2.61–2.62 Å. For each terminal and bridging ClO ₄ ^? ion, one Bi-O distance varies from 2.744 to 3.048 3.269 structure contains a hydrogen bond network involving all hydrogen atoms. The IR and Raman spectroscopy data confirm the thiourea coordination by the sulfur atom.     

Synthesis and crystal structure of hexaaquamagnesium 18-crown-6 dibromide dihydrate

A new complex compound [Mg(H₂O)₆]Br₂ · 18-crown-6 · 2H₂O(I) is synthesized, and its structure is studied by X-ray diffraction analysis. The crystals are monoclinic: space group P2₁/c, a = 7.128 Å, b = 18.584 Å, c = 9.598 Å, Å = 103.01°, Z = 2; R = 0.039 for 2180 independent reflections (CAD-4 automated diffractometer, λMoK _α radiation). The coordination polyhedron of the Mg²⁺ cation is a slightly distorted octahedron. The 18-crown-6 molecule has the conformation of a distorted crown with the approximate D _3d symmetry. The crystal contains a branched three-dimensional network of intermolecular (interionic) 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.     

Synthesis and crystal structure (1,10-diaza-18-crown-6-N,N′,O,O′)dichloromanganese(II)

A new crystalline complex (1,10-diaza-18-crown-6-N,N′,O,O′)dichloromanganese(II) [MnCl₂(DA18C6)] (I) is synthesized and studied by single-crystal X-ray diffraction. The structure of compound I (space group P2₁/c, a = 11.827 Å, b = 7.580 Å, c = 19.715 Å, β = 98.76°, Z = 4) is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.026 for all 3055 independent measured reflections (CAD4 automated diffractometer, λMoK _α radiation). The [MnCl₂(DA18C6)] complex molecule in I is of the host-guest type: its Mn²⁺ cation is asymmetrically arranged in the cavity of the DA18C6 ligand and coordinated by its four heteroatoms, namely, the two N atoms and two O atoms, and by the two Cl^? anions. The coordination polyhedron of the Mn²⁺ cation (six-coordination) may be described as a distorted pentagonal bipyramid with one unfilled vertex or as a distorted square pyramid with one split vertex at the two O atoms of the DA18C6 ligand. The DA18C6 ligand in I has an unusual asymmetric conformation. The complex molecules in a crystal of I are linked by a pair of N-H···Cl intermolecular hydrogen bonds into centrosymmetric dimers.     

Synthesis and crystal structure of (18-crown-6)(perchlorato-O)(triphenylphosphine oxide)potassium

A new complex, (18-crown-6)(perchlorato-O)(triphenylphosphine oxide)potassium, was synthesized and its structure was studied by X-ray diffraction. The crystals are trigonal: a = 14.419,c = 13.895 Å, Z = 3, space group R3m; the structure was solved by the direct method and refined by the anisotropic full-matrix least-squares method, R = 0.079 on 1930 independent reflections, CAD-4 automated diffractometer, λMoK _α . The structure contains a highly symmetric host-guest complex molecule [K(ClO₄)(18-crown-6)(Ph₃PO)] in position 3m (with three Ph rings of the Ph₃PO ligand and all the O atoms of a crown ligand lying in three m planes). The coordination polyhedron of the K⁺ cation is a distorted hexagonal bipyramid with six O atom of the 18-crown-6 ligand in a base and the O atom of the Ph₃PO ligand and disordered O atom of the ClO ₄ ^? ligand in the axial vertices.