Synthesis and Structure of the Molecular Rectangle [{MoO2(C17H14N2O6)}2]4–

Reaction of the dinucleating ligand N,N'-bis(2,3-dihydroxybenzoyl)-α, α-diaminopropane H₄-1 with molybdate results in the formation of the meso-helicate type molecular rectangle Δ, Λ-[{MoO₂( 1 )}₂]^4– as confirmed by NMR-spectroscopy and X-ray crystallography. Thereby the cis-dioxo Mo(VI) moieties act as shape defining corner units. The potassium salt of the complex crystallised in the centrosymmetric space group P1¯ with unit cell parameters a = 12.370(2), b = 13.900(3), c = 14.340(3) Å; α = 116.34(3), β = 99.12(3), γ = 96.68(3)°; V = 2132.6(7) ų; Z = 2.     

Crystal and Molecular Structure of 1-Methyl-6-O-p-toluenesulfonyl-alpha-D-glucopyranoside Dihydrate

Grown from aqueous solution, 1-methyl-6-O-p-toluenesulfonyl-alpha-D-glucopyranoside dihydrate is monoclinic, space group P2₁, a = 6.6236(4), b = 6.4708(4), c = 20.1758(11) Å; β = 92.836(2)°; Z = 2; V = 863.68(9) ų. The molecules are interconnected in the solid state by O─H … O hydrogen bonds involving bridging water molecules.     

A new type of liquid crystal involving hydrogen bonding: single crystal X-ray structure characterization and properties of the liquid crystal

A new liquid crystal involving hydrogen bonding between 4-hexyloxybenzoic acid and 4-octyloxylphenylethynylpyridine has been investigated by DSC, polarizing optical microscopy and X-ray diffraction. The mesogen shows a nematic phase and an unknown liquid crystalline phase. The liquid crystal crystallizes with a triclinic space group P-1 with the parameters: a = 8.879(2)Å, b = 10.137(2)Å, c = 17.629(4)Å; α = 104.16(3)°, β = 95.47(3)°, γ = 101.48(3)°; V = 1490.3(6)ų; Z = 2; F(000) = 572; μ = 0.076 mm^?1; λ(MoK_α) = 0.71073 Å; final R ₁ = 0.0435. The complex is formed by strong intermolecular hydrogen bonding.     

CRYSTAL STRUCTURES AND TRIBOLUMINESCENT ACTIVITIES OF SAMARIUM(III) COMPLEXES

Abstract

The triboluminescence spectra and crystal structures of 1,2-dimethylpyridinium tetrakis(2-thenoyltrifluoroacetonato)samarium(III) (1) and 1,2,6-trimethylpyridinium tetrakis(2-thenoyltrifluoroacetonato)samarium(III) (2) were determined. The triboluminescent maximums are similar to those of the photoluminescence. Complex 1 is centrosymmetric and the triboluminescent emission may correlate with the disorder of all S atoms, all CF₃ groups and the cation. The triboluminescent activity of complex 2 may correlate with its noncentrosymmetric space group. Complex 1 crystallizes in the monoclinic space group P2₁/a with cell parameters a = 19.874(2) Å, b = 22.922(2)Å, c = 21.188(1)Å, β = 108.126(6)°, V = 9173(1)ų; Z = 8; R = 0.0758 and R_w = 0.1315. Complex 2 crystallizes in the monoclinic space group Pn with cell parameters a = 11.2808(6)Å, b = 11.0199(5)Å c c = 18.4336(9)Å, β = 108.126(6)° V = 2285.28(19)ų; Z = 4; R = 0.0347 and R_w = 0.0900. All the structures were refined by full-matrix least squares methods.     

Study of new molecular and crystal structures of 4,4,10,10-tetramethyl-1,3,7,9-tetraazospiro[5.5]undecane-2,8-dione and its salts: Monochloride,mononitrate, and tetraiodotellurate

This is the first work to synthesize 4,4,10,10-tetramethyl-1,3,7,9-tetraazospiro[5.5]undecane-2,8-dione monohydrate, monochloride, mononitrate, and teteraiodotellurate: C₁₁H₂₀N₄O₂·H₂O (I), C₁₁H₂₁N₄O ₂ ⁺ ·Cl^? (II), C₁₁H₂₁N₄O ₂ ⁺ ·NO ₃ ^? (III), and 2(C₁₁H₂₁N₄O ₂ ⁺ )·TeI ₄ ^2? ·C₃H₆O (IV) and determine their structures. Crystals of I are monoclinic: space group P2₁/c, at 298 K a = 5.7118(7) Å, b = 17.842(2) Å, and c = 13.5905(16) Å; β = 91.621(11)°; V = 1384.5(3) ų; d _x = 1.239 g/cm³, Z = 4. Crystals of II are tetragonal: space group P4₃, at 298 K a = 6.4134(3) Å and c = 34.292(2) Å; V = 1410.47(14) ų; d _x = 1.303 g/cm³; Z = 4. Crystals of III are triclinic: space group \(P\bar 1\) , at 298 K a = 8.7614(14) Å, b = 9.3904(18) Å, and c = 10.028(2) Å; α = 63.27(2)°, β = 78.591(16)°, and γ = 84.308(15)°; V = 722.3(2) ų; d _x = 1.40 g/cm³; Z = 2. Crystals of IV are triclinic: space group \(P\bar 1\) , at 100 K a = 10.4630(4) Å, b = 11.9372(6) Å, and c = 16.4118(5) Å; α = 72.058(3)°, β = 76.406(3)°, and γ = 87.029(3)°; V = 1895.04(12) ų; d _x = 2.06 g/cm³; Z = 2. The synthesis of s and p metals with spirocarbone in acetone medium is found to be impossible due to the protonation by the oxygen atom of the carbonyl group. The main crystalline product of the complexation reaction is a monosalt. Evidence is provided that the recrystallization and drying of the synthesized spirocarbone preparation yields monohydrate (I); its purity and monophasity is confirmed by a Rietveld refinement of the powder X-ray pattern. The lattice parameters at room temperature are: a = 5.6885(12) Å, b = 17.8496(12) Å, and c = 13.518(3) Å; β = 91.449(15)°; V = 1372.1(4) ų. The sample is monophasic.     

Crystal Structure and Ionic Conductivity of Cesium Trifluoromethyl Sulfonate,CsSO3CF3

The crystal structures of the room and the high temperature modifications of cesium trifluoromethyl sulfonate were solved from high resolution X‐ray powder diffraction data. At room temperature, α‐CsSO₃CF₃ crystallizes in the monoclinic space group P2₁ with lattice parameters a = 9.7406(2) Å, b = 6.1640(1) Å, c = 5.4798(1) Å, and β = 104.998(1)°; Z = 2. At temperatures above T = 380 K, a second order phase transformation towards a disordered C‐centered orthorhombic phase in space group Cmcm occurs with lattice parameters at T = 492 K of a = 5.5074(3) Å, b = 19.4346(14) Å, and c = 6.2978(4) Å; Z = 4. Within the crystal structures, the triflate anions are arranged in double layers with the apolar CF₃‐groups pointing towards each other. The cesium ions are located between the SO₃‐groups. CsSO₃CF₃ shows a specific ion conductivity ranging from σ = 1.06·10^?8 Scm^?1 at T = 393 K to σ = 5.18·10^?4 Scm^?1 at T = 519 K.     

Complex Interrupted Tetrahedral Frameworks in the Nitridosilicates M7Si6N15 (M=La,Ce, Pr)

A new structure type of nitridosilicates with an interrupted framework has been identified for M₇Si₆N₁₅ with M=La, Ce, and Pr. The materials have been synthesized in a radio‐frequency furnace at temperatures between 1550–1625 °C, starting from the respective metals, metal nitrides, and silicon diimide. The crystal structure of Ce₇Si₆N₁₅ has been determined by using single‐crystal X‐ray diffraction. Besides ordered crystals 1 with a complicated triclinic superstructure and multiple twinning (P , no. 2; a=13.009(3), b=25.483(5), c=25.508(10) Å; α=117.35(3), β=99.59(3), γ=99.63(3)°; V=7114(2) ų; Z=18; R1=0.0411), disordered crystals 2 with identical composition exhibiting a trigonal average structure (R , no. 148) have also been observed (a=43.420(6), c=6.506(2) Å; V=10 623(3) ų; Z=27; R1=0.0309). Pr₇Si₆N₁₅ ( 3 ) and La₇Si₆N₁₅ ( 4 ) are isostructural with 1 as evidenced by twinned single‐crystal data for 3 (P , no. 2; a=12.966(3), b=25.449(10), c=25.459(10) Å; α=117.28(3), β=99.70(4), γ=99.60(4)°; V=7068(4) ų; Z=18; R1=0.0526) and powder diffraction data for 4 (P , no. 2; a=13.109(9), b=25.606(18), c=25.609(18) Å; V=7223(12) ų; Z=18; R_P=0.0194; R_F=0.0936). The crystal structure of M₇Si₆N₁₅ (M=La, Ce, Pr) is built up exclusively of corner‐sharing tetrahedrons that appear as Q²‐, Q³‐, and Q⁴‐type tetrahedrons forming different ring sizes within a less condensed three‐dimensional network. Among the characteristic structural motifs are saw‐blade‐shaped 12‐rings and finite chains consisting of four corner‐sharing SiN₄ tetrahedrons. High‐resolution transmission electron micrographs indicate both ordered and disordered crystallites. In the diffraction patterns of disordered rhombohedral crystals, diffuse maxima appear in reciprocal space at those positions in which sharp superstructure reflections are found in the case of the respective ordered crystallites. Magnetic susceptibility measurements of Ce₇Si₆N₁₅ show paramagnetic behavior with an experimental magnetic moment of 2.29 μ_B per Ce, thereby corroborating the existence of Ce³⁺.     

Crystal and Molecular Structure of the bis-Ethyl Urethane of 5,7-Dodecadiyn-1,12,diol (ETCD)

Grown from ethyl acetate solution, the bis-ethylurethane of 5,7-dodecadiyn-1,12-diol is a monoclinic crystal, a = 16.9740(16), b = 4.9770(5), c = 11.0874(11) Å; β = 101.869(6)°; Z = 2; V = 916.63(16) ų. The crystal structure contains two N─H…O hydrogen bonds per molecule and has nearly ideal parameters (d = 4.977 Å, ? = 45.8°, R = 3.477 Å) for solid-state polymerization.     

Structures cristallines et moléculaires des muscs macrocycliques. I. La cis-civettone et les variétés polymorphes α et β de sa 2,4-dinitrophénylhydrazone

Crystal and Molecular Structure of Macrocyclic Musks. I. cis-Civetone and polymorphous α- and β-forms of his 2,4-dinitrophenylhydrazone cis-Civetone (C₁₇H₃₀O) forms tetragonal plastic crystals, space groupe 14¹; a = 9.95(4), c = 32.79(1) Å; Z = 8. The plastic phase exists in a wide temperature range and 731 reflexions could be collected at 153 K. The highly disordered structure model was obtained by the use of direct methods. The molecules appear as ring-shaped diffuse electron-density distributions located in special position. Two polymorphous crystalline forms were isolated for the 2,4-dinitrophenyl-hydrazone of cis-civetone (DNPHCC). Both forms are triclinic, space group P1 . Z = 2 (α-Form: a = 6.279(5), b = 12.605(8), c = 15.253(10) Å, α = 105.49(7). β = 100.31 (6), γ = 91.23(7)°; β-Form: a = 7.950(2). b = 8.405 (2). c = 18.233(4) Å, α = 100.28(2), β = 92.29(3), γ = 94.18(2)°). The structures were solved by direct methods and refined to R = 0.11. Each polymorph is associated with a different quinquangular conformation of the macrocycle. In the crystals the intermolecular interactions between macrocycles and aromatic substituents are minimized, the DNPH group being oriented in a face-to-face arrangement across a centre of symmetry. Empirical force field calculations show that the overall intluence of the DNPH moiety on the attached cycle does not significantly modify its conformation with regard to that of the ketone itself.     

Crystal and Molecular Structure of (±)-8,8-Dimethyl-6,7-diazabicyclo[3.3.0]octa-1,6-diene 7-oxide

The exclusive product of thermal rearrangement of (±)-7-isopropylidene-2,3-diazabicyclo[2.2.1]hept-2-ene N-oxide (2) has been identified as the title compound (1). The compound crystallizes in the orthorhombic space group Pbca (No. 61), with a= 8.953 (2), b= 12.740 (2), c=14.446 (3) Å; Z= 8; p_x=1.227 g cm^?3. The details of the molecular structure are not unusual, except for a long C–N distance (C(8)–N(7), 1.560 (4) Å). No significant short intermolecular contacts are observed in the crystal.     

Synthesis,spectroscopic characterization,and X-ray crystal structure of tris(trimethylsilyl)cyanurate

Tris(trimethylsilyl)cyanurate, C₁₂H₂₇N₃O₃Si₃ (1), has been synthesized and characterized by elemental analysis, IR, Raman, ¹³C and ²⁹Si NMR, and thermogravimetric methods. The molecular and crystal structure has been determined by single crystal X-ray diffraction. This compound crystallized in space group P6₃/m (176), Z = 2 with a = 11.017(2), b = 11.017(2), c = 9.676(3) Å; α = 90°, β = 90°, γ = 120°. The geometry of the molecule is compared with tris(trimethylsilyl)cyamelurate.     

Melamine–Melem Adduct Phases: Investigating the Thermal Condensation of Melamine

By studying the thermal condensation of melamine, we have identified three solid molecular adducts consisting of melamine C₃N₃(NH₂)₃ and melem C₆N₇(NH₂)₃ in differing molar ratios. We solved the crystal structure of 2 C₃N₃(NH₂)₃?C₆N₇(NH₂)₃ ( 1 ; C2/c; a=21.526(4), b=12.595(3), c=6.8483(14) Å; β=94.80(3)°; Z=4; V=1850.2(7) ų), C₃N₃(NH₂)₃?C₆N₇(NH₂)₃ ( 2 ; Pcca; a=7.3280(2), b=7.4842(2), c=24.9167(8) Å; Z=4; V=1366.54(7) ų), and C₃N₃(NH₂)₃?3 C₆N₇(NH₂)₃ ( 3 ; C2/c; a=14.370(3), b=25.809(5), c=8.1560(16) Å; β=94.62(3)°; Z=4; V=3015.0(10) ų) by using single‐crystal XRD. All syntheses were carried out in sealed glass ampoules starting from melamine. By variation of the reaction conditions in terms of temperature, pressure, and the presence of ammonia‐binding metals (europium) we gained a detailed insight into the occurrence of the three adduct phases during the thermal condensation process of melamine leading to melem. A rational bulk synthesis allowed us to realize adduct phases as well as phase separation into melamine and melem under equilibrium conditions. A solid‐state NMR spectroscopic investigation of adduct 1 was conducted.     

SYNTHESIS OF ONE-AND TWO-DIMENSIONAL ZINC AND CADMIUM COMPLEXES WITH 4, 4′-BIPY

Abstract

The zinc(II) and cadmium(II) complexes [Zn(4, 4′-bipy)(SCN)₂]_∞ 1 and [Cd(4, 4′-bipy)-(SCN)₂]_n 2 have been synthesized and their crystal structures determined by X-ray crystallography. Complex 1 is monoclinic, space group C2/c, with a = 18.076(5), b = 5.190(1), c = 17.315(4)Å; β = 115.54(2), V = 1465.8(8)ų, calculated density 1.530gcm^?3, Z = 4. In this compound, the rod-like ligand 4, 4′-bipy bridges Zn(II) centres, and the NCS groups are terminally coordinated. (N-Zn-N) is 108.5°, resulting in the formation of a zigzag Zn-bipy-Zn chain. These chains are arranged in parallel fashion. The 4, 4′-bipy ligands of adjacent layers are separated by 3.95 (Å). Complex 2 is monoclinic, space group C2/c, a = 11.902(2), b = 11.745(2), c = 10.500(2)Å; β = 109.71(3), V = 1381.8(4)ų calculated density 1.849gcm^?3, Z = 4. In this structure, the cadmium(II) ion is slightly distorted octahedral and the SCN groups act as doubly bridging ligands connecting cadmium atoms to form zigzag chains, separated by 4, 4′-bipy to create two-dimensional planes.     

Structural Aspects of the Dephosphorylation of Adenosine Triphosphate Catalyzed by Polyammonium Macrocycles

Abstract

Four polyammonium macrocycles were synthesized and characterized: two with 21-membered rings and differing numbers of oxygen and nitrogen heteroatoms, [21]N₆O (1) and [21]N₅O₂ (2), and two with bipyridine incorporated into the ring, [24]N₄O₂bipy (3) and [27]N₃O₂bipy (4). Their ability to catalyze the dephosphorylation of adenosine triphosphate was examined. It was found that ring size plays a crucial role in the catalytic ability of the macrocycles, with the 21-membered rings being superior to larger macrocycles. Also, rates of dephosphorylation were found to increase with increasing number of nitrogen atoms in the ring. For two of the macrocycles, crystal structures were determined. Macrocycle 2 crystallizes in the tricliriic space group PI, a = 10.692(1), b = 17.037(2), c = 8.1952(8)Å, a = 92.550(9), β = 100.816(9), γ = 106.77(1)°, V = 1396.1(3) ų; the structure was solved to R = 0.089 and R _w = 0.098. Macrocycle 4 crystallizes in the monoclinic space group P2₁/n, a = 14.589(1), b = 15.427(1), c = 16.382(1) Å, b = 90.137(6)°, V = 3687.0(9) ų; the structure was solved to R = 0.056 and R _w = 0.085.     

Crystal Structures of Hydrazinium(II) Salts of [SbF6]– and [Sb2F11]–

N₂H₆(Sb₂F₁₁)₂ was synthesized by the reaction of N₂H₆F₂ with excess of SbF₅ in anhydrous hydrogen fluoride (aHF). It crystallizes in the triclinic space group P$\bar{1}$ (No. 2) with a = 6.6467(3) Å, b = 8.3039(4) Å, c = 8.3600(5) Å, α = 76.394(5) ^o, β = 70.161(5) ^o, γ = 70.797(5) ^o, V = 405.90(4) ų at 150 K, Z = 2. When it is redissolved in aHF, it solvolysis with the release of SbF₅ yielding N₂H₆(SbF₆)₂ which crystallizes in the monoclinic C2/c space group (No. 15) with a = 7.3805(3) Å, b = 12.3248(5) Å, c = 10.4992(4) Å, β = 92.218(4) ^o, V = 954.33(7) ų at 150 K, and Z = 8. No other phases were observed in crystallization products when different molar ratios of N₂H₆F₂/SbF₅ (1:1,2:3,1:3) in aHF were used as starting materials.     

Crystal Structures of Alkali Metal Peroxodiphosphates

Peroxodiphosphates of alkali metals can be prepared from K₄P₂O₈, which is synthesized by electrolysis, in metathesis reactions with the corresponding perchlorates. Single crystals have been obtained by diffusion of methanol into aqueous solutions of the peroxodiphosphates. The crystal structures of Li₄P₂O₈·4H₂O (P2₁/n; a = 8.057(2) Å, b = 5.074(1) Å, c = 12.288(3) Å, β = 100.53(2)°; V = 493.9(2) ų; Z = 2), Na₄P₂O₈·18H₂O (at 130 K: P6₁; a = 9.0984(14) Å, c = 49.926(13) Å; V = 3579.2(12) ų; Z = 6) and K₄P₂O₈ (P2₁/c; a = 5.9041(15) Å, b = 10.254(2) Å, c = 7.356(2) Å, β = 99.05(3)°; V = 439.79(18) ų; Z = 2) have been determined by X‐ray diffraction. In the Li salt the cations are tetrahedrally coordinated by one water molecule and three oxygen atoms of the anions, whereas the Na salt is characterized by binuclear [Na₂(H₂O)₉]²⁺ complexes. At low temperatures, the latter undergoes a phase transition from a structure with disordered anions to a completely ordered phase. K₄P₂O₈ is solvent‐free and exhibits irregular cation coordination. The structure of the peroxodiphosphate anion is very similar in all compounds; the mean O–O distance is 1.49(1) Å. In addition, the structure determination of K₄(HPO₄)₂·3H₂O₂ (P2₁/n; a = 6.076(1) Å, b = 6.579(1) Å, c = 17.215(2) Å, β = 99.73(1)°; V = 678.26(17) ų; Z = 2), which can be mistaken for K₄P₂O₈, is presented.     

Syntheses and Crystal Structures of Three Polymeric Silver(I) Terephthalate Complexes with Organic N‐Donor Ligands: [Ag(pren)]2(tp)·2H2O, [Ag(en)][Ag(μ2‐tp)]·H2O,and [Ag2(μ4‐tp)(apy)2]

Three polymeric silver(I) complexes with terephthalate anions as counterions or ligands, [Ag(pren)]₂(tp)·2H₂O ( 1 ), [Ag(en)][Ag(μ₂‐tp)]·H₂O ( 2 ), and [Ag₂(μ₄‐tp)(apy)₂] ( 3 ) (where pren = 1, 2‐propylenediamine, tp =terephthalate dianion, en = ethylenediamine, and apy = 2‐aminopyridine) were synthesized and characterized by X‐ray single crystal analysis and infrared spectroscopy. 1 crystallizes in the monoclinic space group P2₁1/c with a = 11.3221(5), b = 7.1522(3), c = 14.8128(5)Å, V = 1015.77(7)ų, β = 122.132(2), and Z = 2. 2 crystallizes in the orthorhombic space group Pnma with a = 9.6144(6), b = 11.3465(7), c = 11.4810(7)Å, V = 1252.5(1)ų, and Z = 4. 3 crystallizes in the monoclinic space group P2₁/n with a = 8.2003(5), b = 5.8869(4), c = 18.3769(11)Å, β = 92.593(1), V = 886.2(1)ų, and Z = 4. Terephthalate dianions are not coordinated to the metal atoms in 1 , but act as a μ₂‐bridging ligand in 2 and as a μ₄‐bridging ligand in 3 .     

Crystal Structures of (18-Crown-6)-(2-Hydroxyethylammonium) Tetracyanonickelate(Ii) and 10-Amino-Decylammonium Tetracyanonickeltate(II)

Abstract

The crystal structures of the two title tetracyanonickelate(II) salts of organic ammonium ions, (18-crown-6)-(2-hydroxyethylammonium) tetracyanonickelate(II), I, and 10-aminodecylammonium tetracyano nick-elate(II), II, have been analyzed. I crystallizes in the monoclinic space group P2₁/n with a = 10.458(2), b = 8.267(3), c = 24.045(2) Å, β = 94.09(1)°, V = 2074(1) ų, Z = 2, R = 0.061 for 2274 reflections; II is triclinic P ₁ with a = 9.437(3), b = 10.094(3), c = 9.205(3)Å,a = 110.16(2), β = 112.72(3), γ = 69.16(2)°, V = 733.7(5) ų 2=1, R = 0.040 including all the hydrogen atoms refined for 2724 reflections. The square planar tetracyanonickelate(II) anion is in a favourable position to form hydrogen bonds via N with the hydroxyl group in I and the ammonio group in II, respectively.     

A Gadolinium Complex of the 5‐(1H‐Tetrazol‐5‐yl)isophthalic Acid Ligand: [Gd(C9H3N4O4)(H2O)3·2H2O]n

The reaction of Gd(ClO₄)₃·6H₂O with 5‐(1H‐tetrazol‐5‐yl)isophthalic acid affords a 3D framework gadolinium coordination polymer, [Gd(C₉H₃N₄O₄)(H₂O)₃·2H₂O]_n ( 1 ). Its crystal structure belongs to a triclinic system, space group , with a = 7.909(2) Å; b = 8.448(2) Å; c = 10.994(2) Å; α = 102.65(3)°; β = 124.32(2)°; γ = 96.28(3)°; V = 704.5(2) ų; Z = 2; R₁ = 0.0245 for 3225 reflections with I >2σ(I), wR₂ = 0.0556. Fluorescent analyses show that compound 1 exhibits purple fluorescence in the solid state at room temperature.