Coordination molecular compounds of cadmium(II) iodide with dimethylpyridines

The reactions of CdI₂ with dimethylpyridines (Me₂Py is C₇H₉N) afford complexes CdI₂(2,3-Me₂Py)₂] (I), [CdI₂(2,6-Me₂Py) (II), and CdI₂(3,5-Me₂Py)₂ (III). The structures of compounds I and II are determined. The crystals of complex I are orthorhombic, space group Pbca, a = 7.930(1) Å, b = 15.537(1) Å, c = 29.943(1) Å, V = 3689.1(5) ų, ρ_calcd = 2.090 g/cm³, Z = 8. The crystals of complex II are monoclinic, space group C2/c, a = 14.784(1), b = 11.991(1), c = 17.711(1) Å, β = 90.39(1)°, V = 1081.1(2) ų, ρ_calcd = 2.908 g/cm³, Z = 4. The structure of compound I is built of discrete neutral complexes [CdI₂(2,3-Me₂Py)₂]. The Cd polyhedron is a distorted tetrahedron (Cd-I 2.289–2.295, Cd-N 2.708–2.734 Å, angles N(I)CdN(I) 103.1°-114.8°). Polymer chains [CdI₂(2,6-Me₂Py)]_∞ extended along the direction [100] are observed due to the bridging iodine atoms in structure II. The Cd polyhedron is a trigonal bipyramid containing iodine atoms at the axial vertices (Cd-I_aks 3.040 Å) and two iodine atoms and the nitrogen atom of the Me₂Py ligand in the equatorial plane Me₂Py (Cd-I_eq 2.840 Å, Cd-N 2.309 Å). The compounds in the solid state are photoluminescent.     

Cadmium(II) iodide molecular coordination compounds with 4-methylpyridine and 4-methylquinoline

The coordination compounds [CdI₂(4-MePy)₂] (I) and [CdI₂(4-MeQuin)₂] (II) where Quin is quinoline have been synthesized, and their structure has been solved. Crystals of complex I are monoclinic, space group C2/c, a = 13.353(1) Å, b = 16.653(1) Å, c = 14.380 (1) Å, β = 103.17(1)°, V = 3113.5(4) ų, ρ_calcd = 2.425 g/cm³, Z = 8. Crystals of complex II are monoclinic, space group P2₁/c, a = 10.647(1) Å, b = 25.264(1) Å, c = 8.610(1) Å, β = 113.73(1)°, V = 2120.1(3) ų, ρ_calcd = 2.044 g/cm³, Z = 4. Polymer [CdI₂(4-MePy)₂]_∞ chains running in the direction [001] are formed in the structure of complex I. Each of the two crystallographically nonequivalent Cd(1) and Cd(2) atoms are octahedrally surrounded by the four iodine and two nitrogen atoms of the 4-MePy ligand. The Cd(1)?Cd(2) distance in a chain is 4.33 Å. The structure of complex II is built of [CdI₂(4-MeQuin)₂] discrete neutral clusters. The two iodine and two nitrogen atoms of the 4-MeQuin ligand participate in the coordination of the Cd²⁺ ion. The cadmium coordination polyhedron is a distorted tetrahedron (Cd-I_avg, 2.72 Å; Cd-N_avg, 2.30 Å; angles N(I)CdN(I), 98.3–121.8°). The minimum and maximum values correspond to the ICdI angle and NCdN angle, respectively. Complex I is photoluminescent in the solid state at room temperature.     

Heteroligand zinc(II) and copper(II) complexes with naphthylacetic acid and monoethanolamine: Syntheses and crystal structures

New heteroligand Cu(II) and Zn(II) complexes with the α-naphthylacetic acid anion (NAA) and monoethanolamine (MEA), [M(NAA)₂(MEA)₂] (M = Cu²⁺, (I), Zn²⁺ (II)), are synthesized. The crystal structures of the obtained complexes are determined by X-ray diffraction analysis (CIF files CCDC 984097 (I) and 930946 (II)). The crystals are monoclinic, for I: a = 18.8140(9) Å, b = 4.82500(14) Å, c = 16.0360(7) Å, β = 115.135(6)°, V = 1317.87(11) ų, space group P2₁/c, Z = 2; for II: a = 32.9760(14) Å, b = 5.0911(3) Å, c = 15.7994(10) Å, β = 94.418(5)°, V = 2644.6(3) ų, space group C2/c, Z = 4. In the structure of complex I, the Cu²⁺ ion arranged in the symmetry center is coordinated at the vertices of the distorted octahedron by the oxygen atoms of two NAA molecules (Cu-O(2) 2.019(4) Å) and two MEA molecules. The latter is the bidentate-chelating ligand and coordinates the metal through the O and N atoms to form the five-membered metallocycle (Cu-O(3) 2.457(5), Cu-N(1) 1.986(5) Å). In complex II, the Zn atom (on axis 2) is coordinated at the vertices of the distorted tetrahedron by the oxygen atoms of two NAA molecules (Zn-O(2) 1.976(4) Å) and the nitrogen atoms of two MEA molecules (Zn-N 2.034(6) Å). The character of the interaction of coordinated NAA and MEA ligands and methods for packing complexes I and II are considered on the basis of the structural data.     

Stability and structure in solution of potassium and barium complexes with N,N’-diaryldiaza-18-crown-6: Crystal structure of N,N’-Bis(4-dimethylaminophenyl)diaza-18-crown-6 and its complex with barium perchlorate

It has been shown that N,N’-diaryldiaza-18-crown-6 ethers with p-dimethylamino-and p-methoxy groups in the benzene ring (aryl is 4-Mc₂NC₆H₄) (I) and 4-MeOC₆H₄ (II) form complexes with potassium and barium salts. The influence of these salts on the UV and ¹H NMR spectra of crown ethers I and II has been studied. The stability constants (logβ) of the complexes increase in the series II · Ba(ClO₄)₂ (2.0), I · Ba(ClO₄)₂ (2.3), II · KBr (2.8), I · KBr (3.0). N,N’-bis(4-dimethylphenylamine)diaza-18-crown-6 (L, I) and its complex with barium perchlorate Ba(ClO₄)₂ · L (III) are characterized by X-ray crystallography. The crystals of I are monoclinic: a = 13.778(2) Å, b = 5.9731(9) Å, c = 17.542(3) Å, β = 106.65(1)°, V = 1383.1(4) ų, Z = 2, space group P2₁/n, R = 0.0374 for 990 reflections with I > 2σ(I). The crystals of III are monoclinic: a = 17.275(4) Å, b = 8.017(2) Å, c = 26.935(4) Å, β = 100.47(2)°, V = 3669(1) ų, Z = 4, space group C2/c, R = 0.0320 for 1897 reflections with I > 2σ(I). The molecules of I and III are centrosymmetric. In III, the Ba atom is in the center of substituted diaza-18-crown-6 (DA18C6). The Ba atom is coordinated by all six donor atoms of diaza-18-crown-6 (av. Ba-O, 2.779(3) Å; Ba-N, 3.004(4) Å) and four oxygen atoms of two asymmetrically bound perchlorate groups (Ba-O, 2.832(4) and 3.031(4) Å) arranged below and above the plane of substituted diaza-18-crown-6. The conformations of the macrocycle in free and coordinated L are different.     

Syntheses and crystal structures of (18-crown-6)bis(perchlorato-O,O′)strontium and (18-crown-6)bis(perchlorato-O,O′)barium

Two complexes, namely, (18-crown-6)bis(perchlorato-O,O′)strontium (I) and (18-crown-6)bis(perchlorato-O,O′)barium (II), are synthesized. Their crystal structures are determined by X-ray diffraction analysis. The structures of I (space group P2₁/c, a = 15.266 Å, b = 11.080 Å, c = 13.235 Å, β = 109.20°, Z = 4) and II (space group P2₁/n, a = 8.330 Å, b = 11.202 Å, c = 11.752 Å, β = 98.38°, Z = 2) are solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.077 (I) and 0.041 (II) against 3714 (I) and 2478 (II) independent reflections (CAD-4 diffractometer, λMoK _α radiation). Complex molecules [Sr(18C6)(ClO₄)₂] in the structure of I and [Ba(18C6)(ClO₄)₂] in II (in the inversion center)—are of the host-guest type. The Sr²⁺ or Ba²⁺ cation is localized in the center of a cavity of the 18-crown-6 ligand and coordinated by its all six O atoms. In compounds I and II, the coordination polyhedron of the Sr²⁺ and Ba²⁺ cations (coordination number 10) can be described as a distorted hexagonal bipyramid with two bifurcated vertices at two O atoms of two ClO ₄ ^? ligands, which are disordered in I and II and each of them has two orientations.     

Synthesis, crystal structures, and luminescence spectra of the coordination compounds of cadmium(II) iodide with hexamethylenetetramine

Coordination compounds [Cd_1.5I₃(HMTA) · H₂O] (I) and [CdI₂(HMTA) · H₂O] (II) are synthesized by the reaction of CdI₂ with hexamethylenetetramine (HMTA, C₆H₁₂N₄) with the 1: 1 ratio in ethanol, and their structures are determined. The crystals of compound I are triclinic, space group P $ \bar 1 $ , a = 8.027(1), b = 9.391(1), c = 10.382(1)?, ?? = 66.64(1)°, ?? = 86.18(1)°, ?? = 73.63(1)°, V = 749.2(1) ?³, ??_calcd = 3.136 g/cm³, Z = 2. The crystals of compound II are triclinic, space group P $ \bar 1 $ , a =7.713(1), b = 8.192(1), c = 12.101(1)?, ?? = 80.32(1)°, ?? = 89.57(1)°, ?? = 7.30(1)°, V = 725.0(1) ?³, ??_calcd = 2.402 g/cm³, Z = 2. Structure I includes two types of cadmium complexes. The Cd(1) atom is coordinated through the octahedral mode by three pairs of the I, N(HMTA), and O(H₂O) atoms. The coordination polyhedron of the Cd(2) atom is a distorted tetrahedron (three I atoms and one N atom). The structure contains infinite strips consisting of tetranuclear cyclic fragments joined by the Cd(1) atoms due to the bridging iodine and nitrogen atoms. In structure II, the Cd atom is coordinated through the tetrahedral mode by two iodide ions and the N(HMTA) and O(H₂O) atoms. The interaction between the complexes occurs due to hydrogen bonds O-H??N to form supramolecular chains along the direction [010]. In each HMTA molecule, one of four nitrogen atoms is a proton acceptor in the hydrogen bonds, one nitrogen atom is coordinated, and two N atoms are terminal. Compound II in the solid state has photoluminescence with maxima at 443, 470, and 518 nm.     

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 structures of π complexes of copper(I) halides with diallyl disulfide 2CuX · DADS (X = Cl, Br; DADS = CH2=CH-CH2-S-S-CH2-CH=CH2)

Compounds 2CuCl · DADS (I) and 2CuBr · DADS (II) (DADS is diallyl disulfide) are prepared by the ac electrochemical synthesis, and their crystal structures are determined. The complexes are isostructural, space group P2₁/n, Z = 4; I: a = 8.995(2) Å, b = 12.541(2) Å, c = 9.644(2) Å, β = 98.74(2)°, V = 1075.3(4) ų, II: a = 9.064(2), b = 12.878(3), c = 9.832(2) Å, β = 98.61(3)°, V = 1134.7(4) ų. In complexes I and II, the tetradentate DADS ligand is chelate-bridging and is coordinated by two crystallographically independent copper atoms of two inorganic Cu₄X₄ fragments. An insignificantly distorted tetrahedral environment of each of the two copper atoms consists of the olefin group, sulfur atom, and two halogen atoms. The complexes are stabilized additionally by the formation of C-H?S hydrogen bonds involved in characteristic seven-membered rings in the structures.     

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,crystal structures,and biological property of dinuclear oxovanadium(V) complexes derived from tridentate Schiff bases

A pair of structurally similar dinuclear oxovanadium(V) complexes, [VO₂L¹]₂ (I) and [VO₂L²]₂ (II), where L¹ and L² are the mono-anionic form of 2-[(2-isopropylaminoethylimino)methyl]-4-methylphenol (HL¹) and 4-fluoro-2-[(2-isopropylaminoethylimino)methyl]phenol (HL²), respectively, have been synthesized and characterized by elemental analysis, FT-IR spectra, and single crystal X-ray determination. The crystal of I is monoclinic: space group P2₁/c, a = 12.528(1), b = 12.266(1), c = 9.432(1) Å, β = 104.814(3)°, V = 1401.2(3) ų, Z = 2. The crystal of I is monoclinic: space group P2₁/n, a = 12.3128(5), b = 6.5124(3), c = 17.1272(7) Å, β = 105.863(1)°, V = 1321.1(1) ų, Z = 2. The V…V distances are 3.210(1) Å in I and 3.219(1) Å in II. The V atoms in the complexes are in octahedral coordination. Biological assay indicates that complex II, bearing fluoro-substitute groups, has stronger antimicrobial activity against most bacteria than complex I which bearing methyl-substitute groups.     

Synthesis and characterization of cobalt(II) and manganese(II) xylaratogermanates: The molecular and crystal structures of the [M(H2O)6][Ge(μ3-L)2{M(H2O)2}2] · 4H2O · nCH3CN Complexes (M = Co, n = 0; M = Mn, n = 1)

A synthetic procedure was developed, and heteropolynuclear coordination compounds—the products of the interaction of germanium tetrachloride with xylaric (trihydroxyglutaric) acid HOOC-CH(OH)-CH(OH)-CH(OH)-COOH (H₅L) and the acetates of the 3d metals Mn(II) and Co(II)—were prepared. The compounds were characterized by elemental analysis, thermogravimetry, and IR spectroscopy. The X-ray diffraction analysis of the [M(H₂O)₆][Ge(μ₃-L)₂{M(H₂O)₂}₂] · 4H₂O · nCH₃CN complexes, where M = Co, n = 0 (I) and M = Mn, n = 1 (II), was performed. The crystals of I are monoclinic, a = 10.752(2) Å, b = 11.830(2) Å, and c = 10.772(2) Å, β = 94.741(3)°, V = 1365.4(5) ų, Z = 2, space group P2₁/n, R1 = 0.0309 for 3200 reflections with I > 2σ(I). The crystals of II are triclinic, a = 9.5330(17) Å, b = 9.7415(17) Å, and c = 10.3935(18) Å, α = 115.024(2)°, β = 97.580(3)°, γ = 111.535(3)°, V = 764.9(2)ų, Z = 1, space group $P\bar 1$ , R1 = 0.0621 for 3028 reflections with I > 2σ(I). The bimetallic anions [Ge(μ₃-L)₂{M(H₂O)₂}₂]^2?, the cations [M(H₂O)₆]²⁺, and crystal water molecules form the basis of compounds I and II (the acetonitrile molecule is also a constituent of compound II). In the centrally symmetrical trinuclear complex anion, the Ge(1) atom is bound to two M(1) atoms through two completely deprotonated bridging ligands. The Ge(1) atom is coordinated to the six alcohol oxygen atoms of two ligands L^5? at the apexes of a distorted octahedron (the average Ge(1)-O distances in I and II are 1.8858(14) and 1.892(3)Å, respectively). The coordination polyhedron of the M(1) atom in the complex anion is a strongly distorted octahedron. The base of the coordination polyhedron is formed by the two bridging alcohol oxygen atoms (the average M(1)-O distances in I and II are 2.1756(14) and 2.255(3) Å, respectively) of two L^5? ligands and by the oxygen atoms of two water molecules (the average M(1)-O distances in I and II are 2.0693(17) and 2.175(4) Å, respectively). In the centrally symmetrical complex cation, the coordination polyhedron of the M(2) atom is a somewhat distorted octahedron. The M(2)-O(H₂O) bond lengths in I and II vary in the ranges of 2.0137(17)-2.1555(17) and 2.140(5)-2.172(4) Å, respectively (the average lengths are 2.0375(17) and 2.166(4) Å, respectively). The cations and anions are joined by a branched system of hydrogen bonds.     

Crystal structures of cesium and rubidium 2-thiobarbiturates

The crystal structures of cesium 2-thiobarbiturate C₄H₃CsN₂O₂S (I) and rubidium 2-thiobarbiturate C₄H₃N₂O₂RbS (II) (C₄H₄N₂O₂S is 2-thiobarbituric acid, H₂TBA) have been determined. Isostructural crystals are monoclinic; a = 7.9609(3) Å,b = 11.8474(3) Å, c = 7.7317(2) Å, β = 101.285(3)°, V = 715.13(4) ų, space group C2/m, Z = 4 for I and a = 7.6369(2) Å, b = 11.7690(3) Å, c = 7.5568(2) Å, β = 100.212(1)°, V = 668.44(3) ų, space group C2/m, Z = 4 for II. Each metal ion in complexes I and II is bonded to four oxygen atoms and two sulfur atoms at the vertices of a six-vertex polyhedron. N-H…O hydrogen bonds link HTBA-ions into chains. The structure is also stabilized by the “head-to-tail” π-π interaction of HTBA-ions.     

Crystal and molecular structures of ZnPhen(C2H5OCS2)2 and Zn(2,2′-Bipy)(n-C4H9OCS2)2 mixed-ligand coordination compounds

ZnPhen(EtOCS₂)₂ (I) and Zn(2,2′-Bipy)(n-BuOCS₂)₂ (II) mixed-ligand complexes have been synthesized. The structures were solved from X-ray diffraction data (CAD-4 and X8-APEX diffractometers, MoK _α radiation, 1879 and 3637 F _hkl , R = 0.0374 and 0.0315). Crystals I are monoclinic with parameters a = 11.678(3) Å, b = 19.215(3) Å, c = 9.655(1) Å; β = 101.23(1)°; V = 2125.0(7) ų; Z = 4, space group P2₁/c; crystals II are triclinic with parameters a = 8.7875(3) Å, b = 11.833(1) Å, c = 13.3454(6) Å; α = 112.154(2)°, β = 108.503(1)°, γ = 92.787(2)°; V = 1196.2(1) ų; Z = 2, space group 1 $P\bar 1$ . The structures are composed of discrete mononuclear molecules. The polyhedra of the Zn atoms are distorted trigonal bipyramids N₂S₃ formed by coordination of the N atoms of Phen or 2,2′-Bipy molecules and sulfur atoms of the monodentate and cyclic bidentate xanthogenate ligand. In structures I and II, dimer assemblies are formed by π-π interactions of Phen or 2,2′-Bipy molecules.     

Coordination behavior of 1,4-diallylpiperazinium and 1-allyloxybenzotriazole toward silver(I) in the crystalline π-complexes [Ag2(C4H8N2(C3H5)2(H+)2)(H2O)2(NO3)2](NO3)2 and [Ag(C6H4N3(OC3H5)(NO3))]

Reactions of a solution of AgNO₃ in aqueous methanol with solutions of 1,4-diallylpiperazine (acidified with HNO₃ to pH = 4) and 1-allyloxybenzotriazole in ethanol gave the crystalline silver(I) π-complexes [Ag₂(C₄H₈N₂(C₃H₅)₂(H⁺)₂)(H₂O)₂(NO₃)₂](NO₃)₂ (I) and [Ag(C₆H₄N₃(OC₃H₅)(NO₃))] (II). Their crystal structures were determined by X-ray diffraction. Crystals of complexes I and II are monoclinic, space group P2₁/c; for I: a = 7.053(3)Å, b = 9.389(3)Å, c = 15.488(4)Å, β = 91.60°, V = 1025.3(6)ų, Z = 4; for II: a = 10.650(4)Å, b = 15.062(5)Å, c = 7.412(4)Å, β = 104.20(3)°, V = 1152.6(8)ų, Z = 4. In both structures, the organic components act as bidentate ligands forming with AgNO₃ 34- and 14-membered topological rings, respectively. In complex I, the nearly tetrahedral environment of the Ag(I) atom is made up of the olefinic C=C bond, the O atoms of the nitrate anions, and the water molecule. 1-Allyloxybenzotriazole in structure II causes the deformation of the coordination polyhedron of Ag into a trigonal pyramid via inclusion of the ligand N atom in its coordination sphere. The topological units of the complexes form infinite polymer layers linked by anionic NO ₃ ^? bridges. In structure I, these layers are united through a system of hydrogen bonds into a three-dimensional framework.     

Thulium(III) trifluoroacetates Tm(CF3COO)3 · 3H2O and Tm2(CF3COO)6 · 2CF3COOH · 3H2O: Synthesis and crystal structure

Thulium trifluoroacetate compounds have been synthesized, Tm(CF₃COO)₃ · 3H₂O (I) and Tm₂(CF₃COO)₆ · 2CF₃COOH · 3H₂O (II). The structure of I has been refined by the Rietveld method on the basis of the structural data for Cd(CF₃COO)₃ · 3H₂O. The structure of II has been solved in a single-crystal X-ray diffraction study. Compound I has been studied by thermal analysis. Crystals of I and II are monoclinic: for I a = 9.062(2) Å, b = 18.678(3) Å, c = 9.687(2) Å, β = 113.93(1)°, Z = 2, space group P2₁/c, R ₁ = 0.062; for II a = 8.560(4) Å, b = 19.866(5) Å, c = 20.813(7) Å, β = 101.69(4)°, Z = 8, space group C2/c, R ₁ = 0.0392. In the molecular structure of I, thulium atoms are bonded in pairs through four bridging trifluoroacetate anions to form dimers. The coordination polyhedron of the thulium atom also includes the three O atoms of the water molecules and the O atom of the monodentate trifluoroacetate group; the coordination number of the thulium atom is eight. In the chain structure of II, there are two crystallographically independent thulium atoms with coordination numbers 8 and 9. The coordination polyhedra of the Tm(1) and Tm(2) atoms are a distorted monocapped tetragonal antiprism and a distorted tetragonal antiprism, respectively. The Tm-O bond lengths are in the range 2.28(1)–2.85(2) Å. The thulium atoms are bound into chains through carboxylate groups. These chains are linked into layers through hydrogen bonds.     

Hydrothermal synthesis, crystal structure, and photoluminescence of Pb(II) and Mn(II) coordination polymers based on imidazo[4,5-f][1,10]phenanthroline

Two new coordination polymers, [Pb(IDPT)₂(NO₃)₂] (I) and [Mn(IDPT)(SO₄)(H₂O)₂] (II) (IDPT = imidazo[4,5-f][1,10]phenanthroline), were synthesized by hydrothermal method and characterized by elemental analysis and single-crystal X-ray diffraction technique. The results reveal that the complex I belongs to monoclinic crystal system, space group C2/c and complex II belongs to monoclinic crystal system, P2₁/c space group. The cell parameters are: a = 19.1970(13), b = 7.3875(5), c = 17.3825(12) Å, β = 100.47(10)°, V = 2424.0(3) ų, Z = 4, F(000) = 1488 for I; a = 10.9135(6), b = 7.0230(4), c = 19.7034(10) Å, β = 99.32(10)°, V = 1490.25(14) ų, Z = 4, F(000) = 828 for II. In the structure of complex I, the metal center Pb(II) is six-coordinated, displays an octahedral geometry. Each molecule is further connected with neighboring one via π-π interactions into 1D chain. In complex II, Mn(II) is six-coordinated to form a distorted octahedral geometry. Compound II displays 1D supramolecular chain formed through hydrogen bonds. Additionally, the fluorescent properties for the complexes were investigated. Complexes I and II exhibit strong photoluminescence with emission maximum at 583 and 529 nm at room temperature.     

Synthesis and crystal structure of lanthanum(III) Iodomercurate(II) complexes with ɛ-Caprolactam

The X-ray diffraction study of the crystalline products of the reaction between potassium tetraiodomercurate(II), ?-caprolactam, and lanthanum(III) nitrate at a ratio of 3: 16: 2 in an aqueous solution has shown the presence of the following three new crystalline compounds: [LaCpl₈]₂[HgI₄]₃ (I), [LaCpl₈][HgI₄]I₃ (II), and [LaCpl₇(H₂O)]₂[HgI₄]₂[Hg₂I₆] (III), where Cpl is ?-caprolactam ?-C₆H₁₁NO. Compounds I and II crystallize in tetragonal crystal system, space groups P4₂/n and $I\bar 4$ , respectively. For compound I, a = 18.59320(10) Å, c = 19.5782(3) Å, V = 6738.32(12) ų, Z = 2, and ρ_calc = 2.067 g/cm³. For compound II, a = 13.2245(10) Å, c = 20.0310(3) Å, V = 3503.17(6) ų, Z = 2, ρ_calc = 2.022 g/cm³. The crystals of compound III are monoclinic (space group P _{2 1}/n, a = 20.1202(6) Å, b = 14.0569(4) Å, c = 46.3228(12) Å, β = 93.4770(10)°, V = 13077.3(6) ų, Z = 4, ρ_calc = 2.274 g/cm³). [La(Cpl)₈]₂[Hg₂I₆]₃ (IV), a new double ionic complex salt, has also been synthesized and studied by X-ray diffraction. The crystals of compound IV are triclinic (space group $P\bar 1$ , a = 12.5021(3) Å, b = 14.6436(3) Å, c = 21.4695(4) Å, α = 84.2300(10)°, β = 87.2230(10)°, γ = 74.9970(10)°, V = 3776.30(14) ų, Z = 1, ρ_calc = 2.452 g/cm³). All complexes have a dicrete ionic structure, and the nearest surrounding of a La atom is distorted square-prismatic or trigonal-dodecahedral. The crystal packing of cations is distorted face-centered cubic (I and II) or body-centered cubic (III and IV) with anions located in its cavities.     

Crystal structures of allyltriphenyl-phosphonium halogenocuprates(I)

Alternating-current electrochemical synthesis is used to obtain for the first time halogenocuprates of an allyl derivative of phosphonium of the composition (CH₂=CHCH₂(C₆H₅)₃P)CuX₂ (X = Br (I), Cl (II)). Compound I crystallizes in the space group P2₁, a = 9.6341(3) Å, b = 12.4167(4) Å, c = 9.9618(4) Å, β = 117.484(5)°, Z = 2. Compound II crystallizes in the space group P2₁/n, a = 9.9725(5) Å, b = 15.4586(8) Å, c = 13.7557(5) Å, β = 90.429(4)°, Z = 4. In the structures of I and II quasilinear CuX ₂ ^? anions are held by C-H…X hydrogen bonds inside a framework formed by the stacking of phenyl groups from CH₂=CHCH₂(C₆P₅)₃P⁺ cations. Allyl groups are not involved in coordination with copper(I) atoms.     

Bis(citrato)germanate complexes with organic cations: Crystal structure of (HNic)2[Ge(HCit)2]·3H2O

Bis(citrato)germanate complexes with organic cations—protonated nicotinic acid ((HNic)₂[Ge(HCit)₂]·3H₂O (I)), protonated nicotinamide ((HNad)₂[Ge(HCit)₂]·3H₂O (II)), and protonated isonicotinic acid hydrazide ((HInd)₂[Ge(HCit)₂] (III)) (H₄Cit is citric acid)—have been synthesized for the first time. Complexes I–III were studied by chemical and X-ray powder diffraction methods, thermal analysis, and IR spectroscopy. The X-ray diffraction study of complex I was carried out. The crystals are monoclinic, a = 10.931(7) Å, b = 11.420(1) Å, c = 23.188(6) Å, β = 101.54(4)°, V = 2836(2) ų, z = 4, space group P2₁/n, R = 0.0334 for 1959 reflections with I > 2σ(I). In the complex anion [Ge(HCit)₂]^2? of the molecule of I, the coordination polyhedron of the Ge atom is a distorted octahedron formed by six O atoms of two tridentate chelating ligands HCit^3? (Ge-O, 1.806–1.957 Å). In the structure of I, anions, cations, and water molecules are linked together by an intricate system of hydrogen bonds.     

Synthesis and crystal structure of the Ag(I) complex with a cyclic β-diketone, 2-(diphenylacetyl)indan-1,3-dione (L), and the HL molecule

An Ag(I) complex with HL (I), AgL (AgC₂₃H₁₅O₃, II), has been synthesized. Compounds I and II have been studied by X-ray diffraction. The crystals are monoclinic, I: space group P2₁/n, a = 10.459(2) Å, b = 12.354(2) Å, c = 13.390(3) Å, β = 96.67(3)°, Z = 4; II: space group P2₁/c, a = 10.764(2) Å, b = 10.683(2) Å, c = 15.939(3) Å, β = 101.57(3)°, Z = 4. The structural units of the crystal of I are neutral molecules with intramolecular hydrogen bonds. In structure II, the Ag₂O₆ dimeric groups and the ligands form infinite openwork layers perpendicular to the x axis and containing cavities. The layers are penetrated by channels with an oblong cross section. In the crystal of II, all intermolecular distances exceed the sums of the van der Waals radii of the corresponding atoms.