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A 3: 1: 1 crystalline adduct of orthophosphoric acid, crown ether dibenzo-18-crown-6, and water, 3H3PO4 · Db18C6 · H2O (I), is synthesized and studied by X-ray diffraction analysis. The orthorhombic structure of compound I (space group Pmn21, a = 23.123 A, b = 12.595 A, c = 4.922 A, Z = 2) is solved by a direct method and refined by full-matrix least squares in the anisotropic approximation to R = 0.061 by all 1894 independent reflections. One H3PO4 molecule and Db18C6 and H2O molecules lie on the crystallographic plane m. The H3PO4 molecules are randomly disordered. The H atoms of the H3PO4 and H2O molecules are not objectively revealed because of high disordering. The Db18C6 and H2O molecules form the host-gust molecular complex [Db18C6 · H2O] through hydrogen bonds. All H3PO4 molecules are hydrogenbonded to form infinite layers lying parallel to the xz plane. The [Db18C6 · H2O] molecular complexes are arranged between the layers.

A new compound, (dibenzo-18-crown-6)ammonium bromide tetrahydrofuran solvate [NH4(Db18C6)]+ · Br− · THF (I), is synthesized and studied by X-ray diffraction analysis. The crystals of compound I are triclinic: a = 8.848 A, b = 9.696 A, c = 16.023 A, α = 73.75°, β = 86.93°, γ = 78.06°, Z = 2, space group P\( \bar 1 \). The structure of compound I is solved by a direct method and refined by full-matrix least squares in the anisotropic approximation to R = 0.095 by 5624 independent reflections (CAD-4 automated diffractometer, γMoKα). The Db18C6 molecule in structure I has a butterfly conformation with approximate symmetry C2v. The NH4+ cation where three disordered H atoms form hydrogen bonds with all six O atoms of the Db18C6 molecule is situated in the center of the cavity of the eighteen-membered macrocycle of the Db18C6 molecule. One ordered H atom of the NH4+ cation forms a strong hydrogen bond with the Br− anion.

We again synthesized host-guest complex, (2.2.2-cryptand)potassium iodide [K(Crypt-222)+ · I− and restudied it by single-crystal X-ray diffraction. The trigonal rhombohedral crystal structure (space group R\( \bar 3 \)c, a = 8.340 A, c = 60.164 A, Z = 6) is solved by a direct method and refined by full-matrix least squares in the anisotropic approximation to R = 0.049 by 1415 independent reflections (CAD-4 automated diffractometer, λMoKα). We found that Moras et al. [1] heavily lowered the real symmetry of the crystals and failed to notice their disorder.

The disordered crystal structure of tetraphenylphosphonium isocyanurate pentahydrate (Ph4P)+(C3H2N3O3)− · 5H2O was studied by X-ray diffraction. The monoclinic structure (space group C2/c, a = 16.236 A, b = 7.444 A, c = 22.712 A, β = 92.22°, Z = 4) was solved by direct methods and refined by full-matrix least-squares calculation in the anisotropic approximation to R = 0.084 for all 2670 measured independent reflections (CAD4 automated diffractometer, λMoK α). The Ph4P+ crystal is located on a twofold crystallographic axis and the P atom has a distorted tetrahedral coordination. The planar isocyanurate anion is positioned around a crystallographic inversion center and is statistically disordered with respect to the center. The structure of the crystals of anhydrous tetraphenylphosphonium isocyanurate differs from the pentahydrate structure.

A new complex [Pb(Crypt-222)(H2O)2]+ · 2(iso-PrO)2P(S)N−C(S)Ph (I) was prepared and studied by X-ray diffraction: space group C2/c, a = 16.170 A, b = 10.405 A, c = 34.116 A, β = 103.32°, Z = 4. The monoclinic structure of I was solved by direct methods and refined by full-matrix least-squares calculation in the anisotropic approximation to R = 0.098 for 6414 independent reflections (CAD4 automated diffractometer, λMoKα). In structure I, the host-guest [Pb(Crypt-222)(H2O)2]+ cation is located on a twofold crystallographic axis. The Pb2+ cation is coordinated by all eight heteroatoms (6O + 2N) of the cryptand ligand and by two O atoms of water molecules. The Pb2+ coordination polyhedron (CN = 10) is a highly distorted two-base-centered dicapped trigonal prism. The crystal structure of I contains one independent thiophosphoramidate anion with deprotonated nitrogen. In crystal I, the complex cation is connected to two thiophosphoramidate anions by ion-ion hydrogen bonds, O(w)-H...S.

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 A, 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.

A new complex compound bis[(dibenzo-18-crown-6)potassium]bis(μ2-chloro)-tetrachlorodicuprate( II), {[K(Db18c6)]2Cu2Cl6} (I) was prepared and its crystal structure was investigated by XRD analysis. Complex molecule I consist of anion [Cu2Cl6]2− located in a crystallographic center of inversion, and two centrosymmetrical to each other complex cations [K(Db18c6)]+ of “guest-host” type: the cation K+ is located in the cavity of the crown-ligand Db18c6 and is coordinated by all its six O atoms, and also by one Cl atom of anion [Cu2Cl6]2−. The coordination of this cation K+ is enlarged up to hexagonal-bipyramidal due to the formation of unusual coordination bond K+ → π( Open image in new window ) with two C atoms of a benzene ring of the adjacent complex molecule. In the crystal of this compound complex molecules I are connected into endless chains by these unusual coordination bonds.

A new mixed complex compound, aquabis(isothiocyanato)(18-crown-6)lead(II)(isothiocyanato)-(18-crown-6)(nitrato-O,O′)lead(II) [Pb(NCS)2(18-crown-6)(H2O)][Pb(NCS)(NO3)(18-crown-6)] is prepared, and its crystal structure is studied by XRD analysis. The structure was solved by the direct method and was refined by full-matrix least-squares method in anisotropic approximation to R = 0.044 for all 3648 measured independent reflexes (automatic diffractometr CAD-4, λMoKα). This crystal structure contains two symmetrically independent halves of the two individual and differing in type complex “guest-host” molecules. One of them (with the H2O ligand molecule) is located on the crystallographic axis 2, and the other is located around the crystallographic inversion center and is statistically disordered relative to this center (except for its crown-ligand).

New host-guest compounds are synthesized and studied by X-ray diffraction analysis: (18-crown-6) potassium 0.84(diiodobromide) 0.16(dibromoiodide), [K(18-crown-6)]+ · (Br1.16I1.84)−, (I) and diaqua (18-crown-6)chlororubidium, [RbCl(18-crown-6)(H2O)2], (II). The crystals of compound I are monoclinic (space group P21/n, a = 9.157 A, b = 8.589 A, c = 14.072 A, β = 102.27°, Z = 2). The structure of compound II is orthorhombic (space group Pnma, a = 9.813 A, b = 15.231 A, c = 12.629 A, Z = 4). The structures are solved by a direct method and refined by the full-matrix anisotropic least squares to R = 0.062 (I) and 0.079 (II) for 3149 (I) and 2840 (II) independent reflections (CAD-4 automated diffractometer, λMoKα radiation). The crystal structures of compounds I and II are different: compound I is built of infinite chains of the alternating cations [K(18-crown-6)]+ and mixed halide anions linked by weak coordination bonds K-Br or K-I, whereas individual molecules [RbCl(18-crown-6)(H2O)2] form structure II.

A new complex K(18-crown-6)][Dy(NO3)4(H2O)2] · CH3CN (I) is synthesized, and its structure is studied by X-ray diffraction analysis (space group P 21/c, a = 17.200 A, b = 13.377 A, c = 13.087 A, β = 94.21°, Z = 4, full-matrix anisotropic least squares to R = 0.033 for 5283 independent reflections, CAD-4 automated diffractometer, λMoKα radiation). The crystal structure of the compound exists as infinite polymer chains formed by coordination bonds and composed of alternating complex anions [Dy(NO3)4(H2O)2]− and cations [K(18-crown-6)]+.

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 A, b = 13.570 A, c = 17.566 A, β = 98.23 °, Z = 4 (direct method, anisotropic full-matrix least-squares method, R = 0.053 from independent reflections; CAD-4 automated diffractometer, λMoKα). 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).

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 A, 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.

A new crystalline complex, bis[(2.2.2-cryptand)potassium] tetrakis(isothiocyanato)cobalt(II) ethanol solvate of the composition 2[K0.89Rb0.11(Crypt-222)]+ [Co(NCS)3.78Br0.22]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 A, b = 12.156 A, c = 12.264 A, 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, λMoKα radiation). The [Co(NCS)3.78Br0.22]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′ = (K1 − δ Rbδ)+) are almost identical inverted reflection of each other and have approximate D3 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.

New mixed complex compound bis(dibenzo-18-crown-6)(tetrachlorocuprato(II)-Cl, Cl′, Cl″, Cl‴) dipotassium diaqua(dibenzo-18-crown-6)potassium dichlorocuprate(I)dibenzo-18-crown-6 [(CuCl4)[K(Db18C6)]2]·[K(Db18C6)(H2O)2]+·[CuCl2]−·Db18C6 was prepared and its structure was studied by the X-ray structural analysis. The structure was found to be disordered. The asymmetric part of its unit cell contains 1/4 of each of its four components. For a given [CuCl4]2− anion its Cu2+ cation is disordered over two equally probable positions and its independent Cl atom is disordered over three positions differing by occupancy. In this structure two [K(Db18C6)]+ fragment of the complex molecule and the complex cation [K(Db18C6)(H2O)2]+ are of guest-host type with K+ cation as the guest. In this structure the statistically disordered alternating cations and Db18C6 molecules form infinite chains. The statistically disordered [CuCl2]− anions also form infinite chains.

A new complex compound (dibenzo-18-crown-6)(iodo)(trichlorometane)potassium was obtained. Its crystal structure was studied by X-ray structural analysis. The complex molecule is built by the “guest-host” type: its K+ cation is in the crown ligand hollow and is coordinated via its all six O atoms, and also via the iodine ligand I and one Cl atom of the ligand CHCl3 molecule. The coordination polyhedron of this K+ cation is a slightly distorted hexagonal bipyramid. In the crystal structure the complex molecules are connected in infinite chains by intercomplex hydrogen bonds Cl3C-H⋯I i between the ligand molecule CHCl3 and the iodine ligand of a neighboring complex molecule.

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 D2, while the approximate point symmetry of the complex cation is D3. 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.

A new complex [Cs(Db18C6)2]+[FeCl4]− was prepared and studied by X-ray diffraction (orthorhombic, space groupP21212,a = 22.934 A,b= 24.024 A,c= 16.665 A,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.

The first polymorph, κ″-(ET)2Cu[N(CN)2]Cl, of the well known Mott insulator κ-(ET)2Cu[N(CN)2]Cl has been prepared and its crystal and electronic structures have been examined. The polymorph has monoclinic symmetry in contrast with the orthorhombic one of the isostructural κ-salts of the family (ET)2Cu[N(CN)2]X (X=Cl, Br, I). The monoclinic phase exhibits a layered structure in which the conducting layers are packed in a κ-type arrangement and the anion sheets consist of polymeric zigzag chains formed by Cu[N(CN)2]Cl units. The main structural differences with the orthorhombic κ-salts are that the anion sheets are disordered and the ET molecules are less planar. The new polymorph shows metallic type resistivity down to 4.2 K.

New complex compound, diaqua(18-crown-6)sodium E-2-phenylethenylphosphonate 18-crown-6 E-2-phenylethenylphosphonic acid, [Na(18-crown-6)(H2O)2]+·HO3−PCH=CHPh·18-crown-6·H2O3PCH=CHPh, was obtained and its crystal and molecular structures were studied by the X-ray structural analysis. In this structure the complex cation [Na(18-crown-6)(H2O)2]+ is of guest-host type. The coordination polyhedron of its Na+ cation is a slightly screwed hexagonal bipyramid with the base consisting of all 6 O atoms of 18-crown-6 ligand and with two opposite apexes at two O atoms of two ligand water molecules. In the studied crystal structure the alternating complex cations and 18-crown-6 molecules as well as the molecules of acid and its anion HO3−PCH=CHPh form by means of hydrogen bonds the infinite chains of two different types.

A new compound, dibenzo-18-crown-6 diaqua(dibenzo-18-crown-6)potassium triiodide [K(Db18C6)(H2O)2)+ · I3− · Db18C6 (I), is synthesized and studied by X-ray crystallography. The crystals of compound I are orthorhombic: a = 22.065 A, b = 22.140 A, c = 9.433 A, Z = 4, space group Pccn. Structure I is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.098 for all 5974 unique reflections. Structure I contains the following asymmetric units: a half of the I3− centrosymmetric anion and two halves of the mixed equally average [K(Db18C6)(H2O)2]+ host—guest complex cation (a) and a free Db18C6 molecule, each stacked on the axes 2 of the perpendicularly averaged plane of the eighteen-membered macroheterocycle. In complex I, both Db18C6 molecules (a and b) have a “butterfly” conformation with approximate symmetry C2v.

New mixed complex compound aqua(dibenzo-18-crown-6)potassium (dibenzo-18-crown-6)(tetrachlorocuprato(II)-Cl)potassium, [K(CuCl4)(Db18C6)]− · [K(Db18C6)(H2O)]+, is synthesized and its crystal structure is studied by the method of x-ray structural analysis. The structure includes two independent complex ions, both of guest-host type: two cations K+ are located in the respective cavities of the Db18C6 crown-ligand (one in each) and each is coordinated by all its six O atoms and one Cl atom of the anion-ligand [CuCl4]2− or O atom of the ligand water molecule. Coordination of these two K+ cations is completed to hexagonal pyramidal one by formation by each of unusually weak coordination bond K+ → π(\( C\dddot - C \)) with two C atoms of respective benzene ring in the neighboring Db18C6 ligand. In this crystal structure the complex anions and cations form dual infinite chains via these coordination bonds and interionic O-H⋯Cl hydrogen bonds.

A new complex, (2.2.2-cryptand)potassium N-benzoyldiisopropylphosphoramidate monohydrate [K(Crypt-222)]+ · (iso-PrO)2P(O)N−C(O)Ph · H2O (I), was synthesized. Its crystal structure was studied by X-ray diffraction analysis: space group P\( \bar 1 \), a = 11.804 A, b = 12.043 A, c = 15.607 A, α = 87.29°, β = 84.59°, γ = 61.32°, Z = 2. The triclinic structure of I was solved by direct methods and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.052 for all 5410 independent reflections (CAD-4 automated diffractometer, λMoKα). In structure I, the host-guest [K(Crypt-222)]+ complex cation has approximate D3 symmetry. Its K+ cation is coordinated by all the eight (6O + 6N) heteroatoms of the cryptand ligand. The coordination polyhedron of K+ (CN = 8) is a dicapped trigonal prism slightly distorted toward an antiprism. In the phosphoramidate anion (with the deprotonated nitrogen atom), eight non-hydrogen atoms of two terminal iso-PrO substituents are disordered each over two positions: main and low-occupancy positions. The water molecule in complex I is disordered, and its H atoms form hydrogen bonds.

A new complex [K(Db18C6)(THF)]3+[Fe(NCS)6]3− · 0.31 H2O (I) was prepared and studied by X-ray diffraction (space group C2/c, a = 21.954, b = 26.496, c = 15.902 A, β = 102.24°, Z = 4; direct method, leastsquares refinement in the anisotropic approximation to R = 0.098 for 5944 independent reflections; CAD4 automated diffractometer, λMoKα). The [Fe(NCS)6]3− anion (on twofold axis) having a slightly distorted octahedral structure is connected by two K-S bonds with two complex cations connected by a twofold axis. Two independent complex cations [K(Db18C6)(THF)]+ are of the host-guest type, one being statistically disordered with respect to the twofold axis with site populations of 0.5. The coordination polyhedra of K+ are a distorted hexagonal bipyramid and pyramid.

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 = Br0.75Cl0.25 (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 A, c = 11.262 A) and II (a = 11.945 A, c = 11.337 A) 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, λMoKα). In structures I and II, the host-guest [M(Crypt-222)]+ complex cation lies on the threefold crystallographic axis and has the approximate D3 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.

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 A, b = 15.205 A, c = 12.544 A, Z = 4) and the monoclinic structure of compound II (space group C 2/c, a = 17.910 A, b = 10.315 A, c = 14.879 A, 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, λMoKα). 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.

A new complex compound, [K2(18-crown-6)2[K(18-crown-6)(EtOH)]2[Er(NCS)6](SCN) (I), was synthesized and its crystal structure was studied by X-ray diffraction. In this work, the synthes and X-ray difraction stady of the crystals of a new complex, hexakis (isothiocyanato) erbiu(III) thiocyanate bis(18-crown-6) dipotassium bis(18-crown-6) ethanolpotassium], [K2(18-crown-6)2][K(18-crown-6)(ETON)]2[Er(NCS)6(SCN)(I)] are described. In crystal I, the alternating [Er(NCS)6]3− anions and binuclear complex cation [K(18-crown-6)2]2+ from infinite chains via the F-S bonds, while two complex cations [K(18-crown-6)(ETON)]+ and the statistically disordered SCN− anion between them are linked by the hydragen bonds O-H…S and O-H…N. Complex I contains the host-guest complex cations [K2(18-crown-6)2)]2+ and [K(18-crown-6)(ETON)]+ [1]. The alternating octabedral [Er(NCS)6]3− anions and binuclear complex cations [K2(18-crown-6)2]2+of crystal I form infinite chains via the K-S bonds, while two complex cations [K(18-crown-6)(EtOH)]+ and the statistically disordered SCN− anion lying between them are linked by interionic hydrogen bonds O-H…S and O-H…N. Complex I contains the host-guest complex cations [K2(18-crown-6)2]2+ and [K(18-crown-6)(EtOH)]+ [1].

A new complex compound, bis[(18-crown-6)oxonium]tetrabromomanganese(II), 2[(H3O)+(18-crown-6)]·[MnBr4]2–, was prepared and studied by X-ray diffraction to reveal its unusual cubic crystal structure, space group Fd\( \bar 3 \), a 20.424 A, and Z 8. In this crystal structure, the complex cation [(H3O)+(18-crown-6)] the point symmetry \( \bar 3 \) position and the anion [MnBr4]2− with the point symmetry 23. The complex cation [(H3O)+(18-crown-6)] has a guest-host structure, and, unlike metal complexes by hydrogen bonds between H3O+ hydrogens and 18-crown-6 oxygens, rather than by coordination bonds. The pyramidal cation H3O+ in this crystal structure is statistically disordered, and the tetrahedral anion [MnBr4]2− is reorientationally disordered.

Two crystal modifications of a novel complex bis(μ2-chloro)tetrachlorodicuprate(II) bis[(18-crown-6)potassium, [K{(18-crown-6)}2Cu2Cl6] were synthesized and studied by X-ray diffraction. The structures of two monoclinic modifications—Iα (space group P21/n, a = 9.053, b = 33.815, c = 13.469 A, β = 101.29°, Z = 4) and Iβ (space group P21/c, a = 10.991, b = 8.187, c = 22.542 A, β = 98.15°, Z = 2) were solved by the direct method and refined by the full-matrix least-squares method in anisotropic approximation to R = 0.073 (Iα) and 0.068 (Iβ) for 4883 (Iα) and 3525 (Iβ) independent reflections (CAD-4 automated diffractometer, λMoK α). The molecules of Iα and Iβ consist of the central binuclear complex anion [Cu2Cl6]2− and two peripheral host-guest cationic fragments [K(18-crown-6)]+, each linked with the [Cu2Cl6]2− anions through the K-Cl bonds. The molecule of Iα and centrosymmetric Iβ molecule have different structures, since they have different orientation of the [K(18-crown-6)]+ fragments relative to the central [Cu2Cl6]2− anion. The coordination polyhedron of the Cu2+ cation in the latter anion in Iα and Iβ is intermediate between flattened tetrahedron and square. In the [K(18-crown-6)]+ ions of Iα and Iβ, the K+ cation has the distorted hexagonal pyramidal coordination polyhedron with six O atoms of the 18-crown-6 ligand in a base and bifurcate vertex at two Cl atoms of the [Cu2Cl6]2− anion. The 18-crown-6 ligands of Iα and Iβ have standard crown conformation.

Three new crystalline complexes are synthesized: [K(18-crown-6)]+ · An, where An = [FeCl4]−(I), [FeBr2Cl2]− (II), and [FeBr4]− (III). The crystals of compounds I–III are cubic and isomorphic, space group Fd\( \bar 3 \) (Z = 16): a = 20.770(2) A for I, 20.844(3) A for II, and 20.878(4) A for III. Structures I–III are solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.047 (I), 0.059 (II), and 0.098 (III) for all 680 (I), 684 (II), and 686 (III) independent reflections. In two tetrahedral anions [Fe(1)X4]− and [Fe(2)X4]− in structures I–III, all halogen atoms (X = Cl and Br) are randomly disordered over three close positions relative to the crystallographic axes 3. Structures I–III contain the [K(18-crown-6)]+ host-quest complex cation. The K+ cation (CN = 8) resides in the cavity of the 18-crown-6 ligand and coordinated by its six O atoms and two disordered halogen X atoms. The coordination polyhedron of the K+ cation in complexes I–III is a distorted hexagonal bipyramid.

Two crystalline host-guest complexes are synthesized and studied using X-ray diffraction analysis: (18-crown-6)sodium tribromide [Na(18-crown-6)]+ · Br3− (I) and (18-crown-6)potassium tribromide (with an admixture of bromodiiodide) [K(18-crown-6)]+ · (Br0.25I2.75)− (II). The structures of compound I (space group P21/n, a = 8.957 A, b = 8.288 A, c = 14.054 A, β = 104.80°, Z = 2) and compound II (space group Cc, a = 8.417 A, b = 15.147 A, c = 17.445 A, 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 (λMoKα). 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.

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 A, 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, λMoKα. 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 ClO4− ligand in the axial vertices.

A new complex salt, 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane penta(nitrato)lanthanate(III) (H2(Crypt-222)]2+ · [La(NO3)5]2−), is synthesized. Its crystal structure is studied using X-ray diffraction analysis (space group Pbcm, a = 9.517 A, b = 13.358 A, c = 24.585 A, Z = 4; direct method, full-matrix least-squares in the anisotropic approximation, R = 0.039 for 4650 measured independent reflections). The [La(NO3)5]2− complex anion lies on the m plane, and the 2 axis passes through the 2.2.2-cryptand dication with two protonated nitrogen atoms. The coordination polyhedron of the La3+ cation (coordination number 11) is a distorted octahedron with five bifurcated vertices, each containing two O atoms from the same NO3−. ligand. The [La(NO3)5]2− anions are joined into infinite polymer chains along the y axis through the NO3− bridging ligand.

A new complex, [K(18-crown-6)(NO3)(HNO3)] (I), is synthesized, and its crystal structure is studied using X-ray diffraction analysis: space group P\( \bar 1 \) , a = 8.253 A, b = 9.277 A, c = 13.903 A, α = 95.89°, β = 104.30°, γ = 91.89°, Z = 2. The triclinic structure of compound I was solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.059 for all 3573 independent reflections (CAD4 automated diffractometer, γMoKα radiation). The structure of compound I contains two independent halves of two centrosymmetric complex molecules with different coordination modes of the K+ cations. Two NO3− and HNO3 ligands are randomly disordered relative to the symmetry center and are presented by two average independent H0.5N31/2−, ligands, which are also orientationally disordered.

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.

A new complex, bis(triethylene glycol-O,O′,O′’,O‴)manganese(II) dibromide [Mn(TEG)2]2+·2Br−, was prepared. Its structure was studied by single crystal X-ray diffraction. The complex cation [Mn(TEG)2]2+ is of the host-guest type with two TEG ligands (podands) as hosts. Both TEG ligands are disordered and tetradentate, with all the four oxygen atoms of each ligand participating in the coordination. The Mn2+ cation has coordination number 8, and its coordination polyhedron is a distorted bisdisphenoid (trigonal dodecahedron). The geometric parameters (bond lengths, bond and torsion angles) of the complex were determined relatively accurately. In the crystal structure, the ions form infinite thick layers by interionic hydrogen bonds O-H···Br−.

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 A, 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.

A new polymeric complex, catena-(μ3-bromo)di(μ2-bromo)bromo(18-crown-6)dilead(II), [Pb2Br(μ2-Br)2(μ3-Br)(18-crown-6)]n (I), is synthesized, and its crystal structure is studied using X-ray diffraction analysis (space group P\( \bar 1 \), a = 7.970, b = 16.048, c = 19.153 A, α = 72.75°, β = 88.57°, γ = 87.92°, Z = 4, direct method, full-matrix least-squares method in the anisotropic approximation, R = 0.076 for 6093 independent reflections, CAD4 automated diffractometer, λMoKα radiation). The crystal structure of complex I contains infinite chains of the PbBr6 octahedra along the x axis with the bridging Br− anions as common edges. The [PbBr(18-crown-6)]+ host-guest complex fragments are attached through weak Pb-Br bonds to these chains on the side. In two independent terminal fragments, the coordination polyhedra of the Pb2+ cations are distorted hexagonal bipyramids with bases of six O atoms of the crown ligand and two Br− anions in the axial vertices. Two Pb2+ cations from the [PbBr3]n− infinite polymer chain have a distorted octahedral coordination.

A new complex, bis[(18-crown-6)potassium] tetrakis(isothiocyanato)zinc(II) [[K(18-crown-6)2] [Zn(NCS)4]] (I), is synthesized. Its crystal structure is studied using X-ray diffraction analysis (space group Pna21, a = 17.604 A, b = 14.190 A, c = 17.625 A, Z = 4) by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.099 for all 3994 measured independent reflections (CAD4 automated diffractiometer, λMoKα radiation).

A new complex compound, i.e., tetrakis(isothiocyanato)manganese(II) bis[aqua(18-crown-6)potassium] (18-crown-6)(thiocyanato)potassium, was synthesized and its crystal structure was studied by X-ray diffraction (space group P21/m, a = 13.377, b = 14.690, c = 17.499 A, β = 108.96°, Z = 2) and refined by the least-squares method in anisotropic approximation to R = 0.060 for 4715 independent reflections (CAD-4 automated diffractometer, λMoK α). In the crystal, infinite chains are formed through the coordination bonds between its components. The monomer fragment of a chain [Mn(NCS)5K3(18-crown-6)3(H2O)2] lies in plane m; three of the five SCN− ligands and one of the two water molecules behave as bridges. The [Mn(NCS)4]2− anion has the tetrahedral structure. The coordination polyhedron of each of the three K+ cations is a distorted hexagonal bipyramid with six O atom of the corresponding crown ligand in a base. Three 18-crown-6 ligands have standard crown conformation.

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 A, b = 25.750 A, c = 13.218 A, 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, λMoKα 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 HPO42− anion has a considerably distorted tetrahedral coordination. The crystal of compound I contains a branched infinite three-dimensional system of intermolecular (interionic) hydrogen bonds.

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 A, 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, λMoKα). 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.

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 A, c = 14.034 A, 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 NH4+ 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 ClO4− anion are disordered over the 3m position.

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 A, b = 11.144 A, c = 12.977 A, 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.

New multicomponent radical cation salts derived from bis(ethylenedithio)tetrathiafulvalene (ET) were prepared: bis(ethylenedithio)tetrathiafulvalene dicyanamide dihydrate α″-(ET)2N(CN)2·2H2O and bis-(ethylenedithio)tetrathiafulvalene nitrate α‴-(ET)6(NO3)3·2C2H5O2N3 containing two biuret molecules (C2H5O2N3). The crystal structures of the compounds were determined, and their conducting properties were examined. Both salts have layered structures in which radical cation layers alternate with nonconducting anionic layers. The radical cation layers in the salts α″-(ET)2N(CN)2·2H2O and α‴-(ET)6(NO3)3·2C2H5O2N3 are packed in the α″ and α‴ fashion, respectively. Anionic layers consist of polymeric chains formed by hydrogen bonding between [N(CN)2]− anions and water molecules in α″-(ET)2N(CN)2·2H2O or between NO−3 anions and biuret molecules in α‴-(ET)6(NO3)3·2C2H5O2N3. Both salts show semiconductor conductivity.

The new conducting radical cation salt, bis(ethylenedithio)tetrathiafulvalene cyanurate, was synthesized. This salt is an organic metal down to 4 K. The crystal structure, conductivity, and optical properties of the salt were studied.

Two complex salts, i.e., 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane tetrachloromanganese(II) and tetrachlorozinc(II) hydrates, [H2(Crypt-222)][MnCl4] · 1.5H2O (I) and [H2(Crypt-222)][ZnCl4] · 2H2O (II) were synthesized and their crystal structures were studied by X-ray diffraction. Crystals I and II are trigonal (space group R \(\bar 3\) c, Z = 12); I: a = 11.033, c = 77.775 A; II: a = 11.046, c = 77.555 A (the structures were solved by the direct method and refined by the full-matrix least-squares method in anisotropic approximation to R = 0.056 (I) and 0.065 (II) for all 2634 (I) and 2636 (II) independent reflections; CAD-4 automated diffractometer, λMoK α). The [MnCl4]2− or [ZnCl4]2− anion in structures I or II and the 2.2.2-cryptand dication (with two protonated N atoms) lie on crystal axis 3. The dication contains trifurcate hydrogen bonds N+-H(…O)3. The bond lengths and bond angles in tetrahedral anions [MnCl4]2− or [ZnCl4]2− are disproportional, probably, due to the Jahn-Teller effect. The molecules of water of crystallization in crystals I, II are disordered over two positions.

Two complexes, namely, triaqua(18-crown-6)strontium dibromide monohydrate (I) and diaquabromo(18-crown-6)barium bromide (II), are synthesized. Their crystal structures are determined by X-ray diffraction analyses. For complex I, space group C2/c, a = 17.547 A, b = 10.246 A, c = 14.786 A, β = 123.08°, Z = 4. For complex II, space group Pnma, a = 17.753 A, b = 17.465 A, c = 6.629 A, Z = 4. The structures are solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.056 (I) and 0.042 (II) for 2696 (I) and 2440 (II) independent reflections (CAD-4 automated diffractometer, λMoKα radiation). Both complex cations—randomly disordered [Sr(18C6)(H2O)3]2+ in complex I and [BaBr(18C6)(H2O)2]+ in complex II—are of the host-guest type. The Sr2+ (Ba2+) cation resides in the cavity of the 18-crown-6 ligand and coordinated by all six O atoms. In the structures complexes I and II, the coordination polyhedra of the Sr2+ and Ba2+ cations (coordination number 9) can be described as distorted hexagonal bipyramids with one apex at the O atom of the water molecule in complex I or at the Br− ligand in complex II and the other split apex at the O atoms of two water molecules.

A new complex salt 2[H2(Crypt-222)]2+ · [Dy(NO3)6]3− · NO 3 − · 2H2O is synthesized, and its crystal structure is studied by X-ray diffraction analysis (space group R \(\bar 3\), a = 11.445 A, c = 38.981 A, Z = 3; direct method, full-matrix least-squares method in the anisotropic approximation, R = 0.027 for 3555 independent reflections; CAD4 automated diffractometer, λMoK α radiation). The [Dy(NO3)6]3− anion and 2.2.2-cryptand dication lie on axis \(\bar 3\). The [Dy(NO3)6]3− ligand in the [Dy(NO3)6]3− anion is disordered. The Dy3+ cation has slightly distorted octahedral coordination with all six split vertices at the O atoms of the six symmetrically equivalent disordered NO 3 − ligands.