The Simultaneous Presence of Different Varieties of Intermolecular Hydrogen Bonds in a New Layer-Type Anionic Host Lattice Built of Thiourea,Fumaric Acid and Fumarate Anion

A new inclusion complex (n-C₄H₉)₄N⁺C₄H₃O ₄ ^?  · C₄H₄O₄ · (NH₂)₂CS has been prepared and characterized by X-ray crystallography. Crystal data: space group P \( \overline 1 \), a = 8.799(2) Å, b = 9.590(1) Å, c = 18.684(4) Å, α = 89.63(1)°, β = 79.56(1)°, γ = 79.74(1)°, V = 1525.2(5) ų, Z = 2, R ₁ = 0.0562 and wR = 0.1033. In the title compound, thiourea molecules, fumaric acid and fumarate anions are joined together by typical O–H···O, N–H···O and N–H···S, plus weak C–H···O and C–H···S, hydrogen bonds to generate a hydrogen-bonded layer corresponding to the (100) family of planes. The tetra-n-butylammonium cations are orderly arranged in a sandwich-like packing mode between the stacked layers. The simultaneous presence of different varieties of intermolecular hydrogen bonds is an interesting feature of the title compound.     

Crystal structure of 2-(thiophen-2-yl)-1-(5-thioxo-4,5-dihydro-1,3,4-oxadiazol-2-yl)ethenyl]benzamide : <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dimethylformamide (1 : 1)

The title compound, 2-(thiophen-2-yl)-1-(5-thioxo-4,5-dihydro-1,3,4-oxadiazol-2-yl)ethenyl] benzamide:N,N-dimethylformamide (1: 1), (C₁₅H₁₁N₃O₂S₂ · C₃H₇NO), was synthesized, and its structure was established by spectral analysis and X-ray diffraction studies. The compound crystallizes in the monoclinic space group P2₁/n with a = 10.8714(7), b = 9.0497(5), c = 19.8347(13) Å, β = 91.093(5)°, Z = 4. The crystal structure is stabilized by N–H···S, C–H···O and N–H···O hydrogen bonds. The π···π interactions are also observed between the rings.     

Synthesis and crystal structure of <Emphasis Type="Italic">catena</Emphasis>-bis(nicotinamide)aqua(μ-phthalato)copper(II) hemihydrate

The copper(II) phthalate complex with nicotinamide [CuL ₂(μ-Pht)(H₂O)] · 0.5H₂O(I) (where L is nicotinamide and Pht ^2? is an anion of phthalic acid) is synthesized and investigated using IR spectroscopy and X-ray diffraction. The crystals of compound I are monoclinic, a = 13.368(2) Å, b = 7.891(3) Å, c = 20.480(2) Å, β = 108.69(2)°, Z = 4, and space group P2₁/c. The structural units of crystal I are linear chains formed by bridging phthalate anions and crystallization water molecules. The copper atom is coordinated by two pyridine nitrogen atoms of two nicotinamide ligands (Cu-N, 2.001 and 2.045 Å), two oxygen atoms of different phthalate anions (Cu-O, 1.964 and 2.235 Å), and the oxygen atom of the H₂ O molecule (Cu-O, 2.014 Å). The coordination polyhedron of the copper atom is completed to an elongated (4 + 1 + 1) tetragonal bipyramid by the second (chelating) oxygen atom of the carboxyl group (Cu-O, 2.587 Å), which is one of the anions of phthalic acid. The linear polymer molecules are joined into complex macromolecular dimers with the closest internal contacts of the specific type. The macromolecular dimers are the main supramolecular ensembles of the crystal structure.     

X-ray diffraction study of Rb<Subscript>2</Subscript>[(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>(CrO<Subscript>4</Subscript>)<Subscript>3</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>] · 4H<Subscript>2</Subscript>O

The compound Rb₂[(UO₂)₂(CrO₄)₃(H₂O)₂] · 4H₂O was studied by X-ray diffraction. The crystals are monoclinic, a = 10.695(2) Å, b = 14.684(3) Å, c = 14.125(3) Å, β = 108.396(4)°, sp. gr. P2₁/c, Z = 4, V = 2104.9(7) ų, and R = 0.0491. The main structural units are layers consisting of [(UO₂)₂(CrO₄)₃(H₂O)₂]^2? anions belonging to the crystal-chemical group A ₂ T ₂ ³ B ²M ₂ ¹ (A = UL ₂ ²⁺ , T ³ and B ² are CrO ₄ ^2? , and M ¹ is H₂O) of uranyl complexes. The uranium-containing layered groups are held together by electrostatic interactions with rubidium cations, as well as by hydrogen bonds with the participation of inner- and outer-sphere water molecules.     

Crystal and molecular structure of phenanthrolinium peroxodisulfate dihydrate (C<Subscript>12</Subscript>H<Subscript>9</Subscript>N<Subscript>2</Subscript>)<Subscript>2</Subscript>S<Subscript>2</Subscript>O<Subscript>8</Subscript> · 2H<Subscript>2</Subscript>O

The crystal structure of (HPhen)₂S₂O₈ · 2H₂O is studied using X-ray diffraction. The crystals are monoclinic, a = 23.716(5) Å, b = 10.220(2) Å, c = 13.103(3) Å, β = 128.03(2)°, V = 2501.6(9) ų, Z = 4, space group C2/c, and R = 0.0745 for 1579 reflections with I > 2σ(I). The crystal is built of S₂O ₈ ^2? centrosymmetric anions, HPhen ⁺ cations, and molecules of crystallization water. Hydrogen bonds link the structural units into chains. Within a chain, stacking interactions are observed between the phenanthroline rings (the interplanar spacing between the rings is 3.8 Å, and the dihedral angle between their planes is 8°). The data of IR spectroscopy confirm the formation of the N(Phen)-H bond.     

Synthesis and Crystal Structure of a Four-coordinated Cobalt Complex with 1-Methylbenzimidazole

A four-coordinated complex, L₂Co(NCO)₂, (L = 1-methylbenzimidazole) has been synthesized and characterized by IR spectroscopy, elemental analyses, and single crystal X-ray diffraction. The crystal is monoclinic, a = 14.522(2) Å, b = 14.610(2) Å, c = 8.6850(13) Å, β = 92.037(3)°, Z = 4, sp. gr. P2₁/c. Bond lengths Co–N(L) are equal to 2.0165(16) and 2.0174(15) Å, Co–O(NCO) are 1.944(2) and 1.945(2) Å. Intermolecular C–H···O, C–H···N, and C–H···π interactions link the molecules into three-dimensional networks in the crystal.     

Synthesis and structure of the [Os<Emphasis Type="Italic">Thio</Emphasis><Subscript>6</Subscript>]Br<Subscript>3</Subscript> · H<Subscript>2</Subscript>O complex

A complex of the composition [OsThio ₆]Br₃ · H₂O is synthesized by the reaction of H₂OsBr₆ with thiourea in a 0.5 M HBr solution. The [OsThio ₆]Br₃ · H₂O complex is characterized using electronic absorption and infrared spectroscopy. The structure of the complex is determined by X-ray diffraction analysis. The crystals are orthorhombic with the unit cell parameters a = 20.510(4) Å, b = 11.186(2) Å, c = 11.892(2) Å, space group Pccn, and Z = 4. The thiourea molecules are coordinated to the osmium atom through the sulfur atom. The osmium atom has an octahedral coordination. The Os-S distances fall in the range 2.39–2.40 Å. The outersphere H₂O molecules and Br^? anions are involved in hydrogen bonds with the NH₂ groups of the thiourea molecules.     

Crystal structures of complexes of the <Emphasis Type="Italic">cys-syn-cys</Emphasis> isomer of dicyclohexano-18-crown-6 with oxonium hexafluorotantalate and oxonium hexafluoroniobate

The crystal structures of [(cys-syn-cys-dicyclohexano-18-crown-6 · H₃O)][TaF₆] and [(cys-syn-cys-dicyclohexano-18-crown-6 · H₃O)][NbF₆] complex compounds are determined using X-ray diffraction analysis. The tantalum complex has two polymorphic modifications, namely, the monoclinic (I) and triclinic (II) modifications. The unit cell parameters of these compounds are as follows: a = 8.507(4) Å, b = 11.947(5) Å, c = 27.392(12) Å, β = 93.11(1)°, Z = 4, and space group P2₁/n for modification I; and a = 10.828(1) Å, b = 11.204(1) Å, c = 12.378(1) Å, α = 72.12(1)°, β = 79.40(1)°, γ = 73.70(1)°, Z = 2, and space group P-1 for modification II. The triclinic niobium complex [(cys-syn-cys-dicyclohexano-18-crown-6 · H₃O)][NbF₆] (III) with the unit cell parameters a = 10.796(3) Å, b = 11.183(3) Å, c = 12.352(3) Å, α = 72.364(5)°, β = 79.577(5)°, γ = 73.773(4)°, Z = 2, and space group P-1 is isostructural with tantalum complex II. The structures of all three complexes are ionic in character. The oxonium cation in complexes I–III is encapsulated by the crown ether and thus forms one ordinary and two bifurcated hydrogen bonds with the oxygen atoms of the crown ether. This macrocyclic cation is bound to the anions through the C-H...F contacts (H...F, 2.48–2.58 Å). The conformation of the macrocycle in complex I differs substantially from that in complex II (III).     

Synthesis and crystal structure of the [Co<Subscript>2</Subscript>(Nicotinamide)<Subscript>4</Subscript>(C<Subscript>4</Subscript>H<Subscript>9</Subscript>COO)<Subscript>4</Subscript>(H<Subscript>2</Subscript>O)] complex

The [Co₂ L ₄(C₄H₉COO)₄(H₂O)] coordination compound of cobalt(II) valerate with nicotinamide (L) is synthesized and studied by IR spectroscopy. The crystal structure of the synthesized compound is determined. The crystals are triclinic, and the unit cell parameters are as follows: a = 10.2759(10) Å, b = 16.3858(10) Å, c = 16.4262(10) Å, α = 100.538(10)°, β = 101.199(10)°, γ = 90.813 (10)°, Z = 2, and space group P \(\bar 1\). The structural units of the crystal are dimeric molecular complexes in which pairs of cobalt atoms are linked by triple bridges formed by oxygen atoms of two bidentately coordinated valerate anions and a water molecule. The octahedral coordination of each cobalt atom is complemented by the pyridine nitrogen atoms of two nicotinamide ligands and the oxygen atom of the monodentate valerate group. The hydrocarbon chains of the valerate anions are disordered over two or three positions each.     

Crystallization,crystal-structure refinement,and IR spectroscopy of a synthetic hexahydroborite analog

The crystal structure of the hexahydroborite analog Ca[B(OH)₄]₂ · 2H₂O (a = 7.9941(3) Å, b = 6.6321(2) Å, c = 7.9871(3) Å, β = 104.166(4)°, V = 410.58(3) ų, sp. gr. P2/c, Z = 2, ρ_calc = 1.891 g/cm³; Xcalibur S CCD automated diffractometer, 1196 reflections with I > 2σ(I), λMoK _α), which was synthesized by the hydrothermal method via the recrystallization of calciborite CaB₂O₄ (M) in the M ? B₂O₃ ? H₂O system (t = 250°C and P = 70–80 atm), was refined by the least-squares method with anisotropic displacement parameters (H atoms were located; R ₁ = 0.0260). The structure of synthetic hexahydroborite consists of infinite columns running along the c axis. The columns are formed by Ca polyhedra linked together and to [B(OH)₄] orthotetrahedra by sharing edges. Along the two other axes, the translationally equivalent columns are linked only by hydrogen bonds. The presence of a stronger bond between the discrete (Ca-B-O) columns along the shortest (b = 6.6 Å) axis accounts for the possibility of the shift of the columns by 1/2T _b and the formation of the second modification of Ca[B(OH)₄]₂ · 2H₂O. The crystals of synthetic hexahydroborite were studied by IR spectroscopy. A crystal-chemical analysis was performed for a series of natural metaborates with the general formula CaB₂O₄ · nH₂O (CaO: B₂O₃ = 1: 1, n = 0–6), including calciborite CaB₂O₄ and hexahydroborite CaB₂O₄ · 6H₂O as the end members.     

Crystal structure of <Emphasis Type="Italic">p</Emphasis>-carboxyphenylhydrazone benzoylacetone

The crystal structure of p-carboxyphenylhydrazone benzoylacetone is determined. The crystals are monoclinic, a = 13.614(4) Å, b = 11.388(2) Å, c = 20.029(6) Å, β = 104.82(2)°, V = 2339(9) ų, Z = 8, space group C2/c, and R = 0.038 for 1622 reflections with I > 2σ(I). The crystal is built of C₁₇H₁₄N₂O₄ neutral molecules that are linked by O-H?O hydrogen bonds between the carboxyl groups into centrosymmetric pseudodimers. The effect of carboxylation of the phenylhydrazone fragment and the position of the carboxyl group on the molecular packing in the crystal is determined. The N(1)-H(1N)?O(1) intramolecular hydrogen bond (N-H, 0.94 Å; H?O, 1.87 Å; N?O, 2.59 Å; and the N-H?O angle, 133°) is formed in the molecule.     

Synthesis,characterization, and crystal structure of 5,5″-Difluoro-1<Emphasis Type="Italic">H</Emphasis>,1″<Emphasis Type="Italic">H</Emphasis>-[3,3′:3′,3″-terindol]-2′(1′<Emphasis Type="Italic">H</Emphasis>)-one

The new indole derivative, 5,5′′-Difluoro-1H,1′′H-[3,3′:3′,3′′-terindol]-2′(1′H)-one C₂₄H₁₅F₂N₃O, is synthesized in 87% yield, and its crystal structure is determined by X-ray structure analysis. The crystals are monoclinic, sp. gr. P2₁/n, a = 15.4563(7), b = 10.8340(6), c = 16.4718(6) Å, β = 102.403(4)°, Z = 4. Bicyclic indole moieties form dihedral angle of 61.92(5)° with each other; the oxindole ring is twisted with respect to them at angles of 85.70(5)° and 75.62(5)°. The crystal structure is stabilized by N–H···O and C–H···O hydrogen bonds involving both the DMSO solvent molecules. In addition, one C–H···π interaction is observed.     

Crystal chemistry of elpidite from Khan Bogdo (Mongolia) and its K- and Rb-exchanged forms

Elpidite Na₂ZrSi₆O₁₅ · 3H₂O [space group Pbcm, a = 7.1312(12), b = 14.6853(12), and c = 14.6349(15) Å] from Khan Bogdo (Mongolia) and its K- and Rb-exchanged forms K_1.78Na_0.16H_0.06ZrSi₆O₁₅ · 0.85H₂O [Cmce, a = 14.054(3), b = 14.308(3), and c = 14.553(3) Å] and Na_1.58Rb_0.2H_0.22ZrSi₆O₁₅ · 2.69H₂O [Pbcm, a = 7.1280(10), b = 14.644(3), and c = 14.642(3) Å] that were obtained by cation exchange at 90°C, as well as K_1.84Na_0.11H_0.05ZrSi₆O₁₅ · 0.91H₂O [Cmce, a = 14.037(3), b = 14.226(3), and c = 14.552(3) Å] and Rb_1.78Na_0.06H_0.16ZrSi₆O₁₅ · 0.90H₂O [Cmce, a = 14.2999(12), b = 14.4408(15), and c = 14.7690(12) Å], obtained at 150°C are studied by single-crystal X-ray diffraction and IR spectroscopy. The base of the structures is a heteropolyhedral Zr-Si-O framework whose cavities accommodate Na (K, Rb) cations and H₂O molecules.     

Crystal and molecular structure of barium cyclohexane-1,2-diamine-<Emphasis Type="Italic">N,N,N′,N′</Emphasis>-tetraacetatonickeloate decahydrate Ba[Ni(<Emphasis Type="Italic">Cdta</Emphasis>)] · 10H<Subscript>2</Subscript>O

The X-ray diffraction study of Ba[Ni(Cdta)] · 10H₂O is performed (R1 = 0.0441 for 5136 observed reflections). The crystals are triclinic, a = 8.833(2) Å, b = 9.025(2) Å, c = 16.922(3) Å, α = 80.56(3)°, β = 82.77(3)°, γ = 76.98(3)°, Z = 2, and space group \(P\bar 1\). The crystal is built of the [Ni(Cdta)]^2? anionic complexes, the [Ba(H₂O)₆]²⁺ hydrated cations, and crystallization water molecules. The distorted octahedral coordination of the Ni atom includes two N and four O atoms of the Cdta^4? ligand (mean Ni-N, Ni-O_G, and Ni-O_R re 2.080, 2.082, and 2.036 Å, respectively). The irregular nine-fold coordination of the Ba atom consists of six O atoms of water molecules and three O(Cdta) atoms from three anionic complexes (Ba—O, 2.715–3.090 Å). With consideration for the bonds with three Ba atoms, the Cdta^4? ligand is octadentate (2N + 6O) and fulfills the pentadentate μ₄-bridging function. The structural units are linked through an extended network of hydrogen bonds.     

Synthesis,conductivity, and the crystal structure of a new stable metal, β″-(<Emphasis Type="Italic">DOEO</Emphasis>)<Subscript>2</Subscript>HSeO<Subscript>4</Subscript> · H<Subscript>2</Subscript>O

The stable metal β″-(DOEO)₂HSeO₄ · H₂O I) based on a new donor compound, 3,4-(1,4-dioxanediyl-2,3-dithio)-3′,4′-ethylenedioxo-2,5,2′,5′-tetrathiafulvalene] (DOEO), is synthesized and structurally characterized for the first time. The synthesis is performed by the electrocrystallization technique (direct current density j = 2 × 10^?6 A/cm²). The crystals are triclinic, and the unit cell parameters are as follows: a = 5.495(1) Å, b = 9.715(2) Å, c = 16.878(3) Å, α = 83.52(3)°, β = 82.54(3)°, γ = 73.51(3)°, Z = 1, and space group \(P\bar 1\). The salt has a layered structure. The DOEO^1/2+ radical cation layers are aligned parallel to the ab planes. The HS_eO ₄ ^? · H₂O solvated anions are located in channels along the a axis and are disordered over two positions near the center of symmetry (1/2 0 0) with a probability of 50%. The conductivity of the salt is equal to 300–400 Ω^?1 cm^?1 at room temperature and increases upon cooling to the boiling point of liquid helium (4.2 K) by a factor of 100–200 depending on the sample.     

Synthesis,thermal analysis,and crystal structure of manganese(II) 9-molybdocobaltate(III)

Manganese(II) 9-molybdocobaltate(III) of the composition [Mn(H₂O)₄] · [CoMo₉O₂₇(OH)₅] · 7H₂O (I) has been synthesized for the first time and investigated using X-ray diffraction and thermal gravimetric analyses. Compound I crystallizes in the trigonal system with the following unit cell parameters: a = 15.926(1) Å, c = 12.363(1) Å, V = 2715.6(4) ų, M = 1692.55, Z = 3, ρ_(calcd) = 3.105 g/cm³, space group R32.     

Crystal and molecular structures of [Co(<Emphasis Type="Italic">D</Emphasis>H)(<Emphasis Type="Italic">o-phen</Emphasis>)<Subscript>2</Subscript>][BF<Subscript>4</Subscript>]<Subscript>2</Subscript> · 2H<Subscript>2</Subscript>O

The crystal structure of a new mixed-ligand complex [Co(DH)(o-phen)₂][BF₄]₂ · 2H₂O is determined by X-ray diffraction. The crystal is monoclinic, a = 12.2081(11) Å, b = 14.3474(9) Å, c = 17.7393(16) Å, β = 104.95(1)°, and space group P2₁/c. The coordination octahedron of Co³⁺ is formed by two nitrogen atoms of the dimethylglyoxime molecule and four nitrogen atoms of o-phenanthroline molecules. The dimethylglyoxime molecule is singly deprotonated and acts as DH^?. The mean Co-N distances for dioxime and o-phenanthroline are 1.911 and 1.964 Å, respectively. The key role in the formation of the crystal structure is played by [BF₄]^? outer-sphere anions and crystallization water molecules, which form an extended hydrogen-bond system.     

New Diphosphopentamolybdate K<Subscript>5</Subscript>[HP<Subscript>2</Subscript>Mo<Subscript>5</Subscript>O<Subscript>23</Subscript>] · 10H<Subscript>2</Subscript>O: Synthesis,Structure, and Characterization

A new diphosphopentamolybdate(VI) K₅[HP₂Mo₅O₂₃] · 10H₂O has been prepared employing solution method and characterized by single crystal X-ray diffraction, energy dispersive analysis, infrared spectroscopy, thermal stability analysis, cyclic voltammetry analysis, and ultraviolet visible spectroscopy. The compound crystallizes in the orthorhombic sp. gr. Pcab: a = 15.9661(10) Å, b = 19.0832(10) Å, c = 20.0970(9) Å, V = 6123.27(10) Å3, Z = 8. The crystal structure contains the polyanion units [HP₂Mo₅O₂₃]^5– around the potassium cations and lattice water. The [HP₂Mo₅O₂₃]^5– subunits are connected together through K?O?Mo bridges and hydrogen bonds. The crystal shape morphology was simulated using the Bravais–Friedel–Donnay–Harker model.     

Crystal Structure of 3′-(4-Methoxyphenyl)-2-Phenyl-4′-(4-Ethoxyphenyl)-1,2-Dihydro-4H,4′H-Spiro [Isoquinoline-3,5′-Isoxazol]-4-One

The title compound, 3′-(4-methoxyphenyl)-2-phenyl-4′-(4-ethoxyphenyl)-1,2-dihydro-4H,4′H-spiro[isoquinoline-3,5′-isoxazol]-4-one was synthesized from the reaction of dipolarophile with p-methoxybenzadoxime in the presence of sodium hypochlorite in chloroform solution. The structure of the synthesized compound was determined by IR, ¹H NMR, mass spectroscopic data, ¹³C NMR spectroscopy, elemental analysis and X-ray crystallography. The structure was solved in monoclinic, space group C2/c with a = 21.941 (4), b = 17.233 (3), c = 15.404 (3) Å, β = 122.193 (2), V = 4928.9 (16) Å³, Z = 8 and with R_int = 0.154. The geometry of the title compound showed that the piperidine ring adopts a half-chair conformation. In the crystal structure, molecules are linked by C–H···O and C–H···N contacts. Weak C–H···π interactions plays an important role in stabilizing the supramolecular structure.     

Crystal structure and properties of K<Subscript>2</Subscript>[OsO<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>] · 2H<Subscript>2</Subscript>O

The synthesis and X-ray diffraction study of the compound K₂[OsO₂(C₂O₄)₂] · 2H₂O are performed. The compound crystallizes in the triclinic crystal system, space group P \(\bar 1\), a = 6.545(1) Å, b = 6.835(2) Å, c = 7.595(2) Å, α = 85.76(2)°, β = 65.33(2)°, γ = 71.14(2)°, and Z = 1. The osmium atom is located at the center of symmetry and has a distorted octahedral coordination formed by oxygen atoms: two oxygen atoms of the osmyl group occupy the apical positions [Os-O, 1.730(2) Å], and four oxygen atoms of the oxalate ions lie in the equatorial plane. The K⁺ cation is surrounded by ten oxygen atoms located at different K-O distances in the range from 2.787(2) to 3.158(2) Å. The assignment of the absorption bands in the IR spectrum of K₂[OsO₂(C₂O₄)₂] · 2H₂O is performed. The electronic absorption spectra of the compound are recorded in different solvents, and the thermal behavior in air is studied.