Synthesis,Characterization and Crystal Structure Determination of a Hepta-coordinated Cadmium(II) Complex with Thiocyanato-bridges

Abstract  A new cadmium(II) complex [(C₂₈H₂₄N₆)Cd(SCN)₂]₂(CH₃OH)₂ (1) has been synthesized and characterized by IR, UV spectra, TG-DTA technique and single crystal X-ray diffraction analysis. The crystallographic data for compound 1: triclinic P1ˉ, a = 9.630(2) Å, b = 11.123(3) Å, c = 15.396(4) Å, α = 106.93(1)°, β = 91.60(1)°, γ = 99.99(1)°, V = 1,548.5(6) Å³, Z = 1, Dc = 1.512 mg/m³, F(000) = 716, R ₁ = 0.0332, wR ₂ = 0.0907. The molecule contains a symmetrical dinuclear unit in which two Cd(II) ions are double bridged by two di-μ-1,3-SCN⁻ anoins with a cadmium–cadmium separation of 6.48 Å. Each Cd(II) ion is seven-coordinated with six nitrogen atoms and a sulfur atom to form a monocapped trigonal prism coordination geometry. In addition, the molecule is further connected by multiform intermolecular C–H···π, π···π interactions and hydrogen bonds to form a three-dimensional supramolecular structure. Graphical Abstract  A hepta-coordinated Cd(II) complex which exhibits a distorted a monocapped trigonal prism coordination geometry has been achieved by using bisbidentate Schiff-base ligand and thiocyanate anion.      

Synthesis,Structure and Luminescent Property of a Novel Lanthanide Metal-Organic Coordination Polymer Yb<Subscript>3</Subscript>(BDC)<Subscript>4.5</Subscript>(DMF)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>3</Subscript> · (DMF)<Subscript>2</Subscript>

Abstract  A three-dimensional lanthanide metal-organic coordination polymer Yb₃(BDC)_4.5(DMF)₂(H₂O)₃ · (DMF)₂ has been synthesized by the reaction of the lanthanide metal ion (Yb³⁺) with 1,4-benzenedicarboxylic acid (H₂BDC) under mild condition. The compound crystallizes in the triclinic system, space group PI with unit cell parameters a = 10.7428(9) Å, b = 11.2786(9) Å, c = 26.172(2) Å, α = 85.060(2)°, β = 88.1060(10)°, γ = 62.3670(10)°, V = 2798.9 (4) ų, Z = 2. The crystal structure exhibits one-dimensional channels along the [011] direction. The fluorescent results showed that there were two emission peaks at 375 and 420 nm when the compound was excited by a 235 nm excitation. Graphical Abstract  The preparation, X-ray structure and luminescent property are presented for a new lanthanide metal-organic coordination polymer Yb₃(BDC)_4.5(DMF)₂(H₂O)₃ · (DMF)₂.      

[KCl<Subscript>3</Subscript>{H<Subscript>2</Subscript>dabco}]: A Unique 3-D Charge-Assisted Hydrogen-Bonded Hybrid Network of Anionic KCl<Subscript>3</Subscript> Chains and Organic Cations

Abstract  The 3-D hybrid network [KCl₃{H₂dabco}] resulted from the assemblage of KCl and [{H₂dabco}Cl₂] (1,4-diazabicyclo[2.2.2]octane) in H₂O. The compound crystallizes in the trigonal space group R-3c with a = b = 16.0437(2) Å, and c = 22.3094(2) Å. The structure consists in polymeric chains of anionic {KCl₃}²⁻ linked to {H₂dabco}²⁺ units by hydrogen bonds. Each organic cation establishes such charge-assisted H···Cl interactions with two inorganic arrays leading to a 3-D network. Index Abstract  Assemblage of KCl and [{H₂dabco}Cl₂] (1,4-diazabicyclo[2.2.2]octane) in H₂O resulted in a 3-D hybrid network of inorganic {KCl₃}²⁻ chains H-bonded to bridging organic cations.      

Structural Correlations in High-Spin Complexes of [Fe{HC(3,5-Me2pz)3}2]2+: Solid State Structure of [Fe{HC(3,5-Me2pz)3}2][Fe2OCl6]

Abstract  The cation in the solid state structure of [Fe{HC(3,5-Me₂pz)₃}₂][Fe₂OCl₆] (pz = pyrazolyl ring) contains an octahedral iron(II) center with an average Fe–N bond distance of 2.17 Å, indicating that the iron(II) is in the high-spin form. While M–N bond distances of this length with κ³-[HC(3,5-Me₂pz)₃] ligands generally cause tilting of pz to open up the “bite” angle, in this structure the average tilting angle is only 3.1°, a much lower value than observed in earlier structures of this same cation paired with different anions. The crystals are monoclinic, space group P2₁/n, with a = 11.1671(12) Å, b = 10.8091(11) Å, c = 17.4385(17) Å, α = γ = 90°, β = 95.685(2)°, and Z = 2. Graphical Abstract  The cation in the solid state structure of [Fe{HC(3,5-Me₂pz)₃}₂][Fe₂OCl₆] (pz = pyrazolyl ring) contains an octahedral iron(II) center in the high-spin form with unusual orientations of the pyrazolyl rings.      

A Sodium Supported Borate Ester: Synthesis,Spectral Characterization and Crystal Structure of dimeric Sodium Organoborate Complex [Na(py)][B(hyncaH<Subscript>−2</Subscript>)<Subscript>2</Subscript>]<Subscript>2</Subscript>

Abstract  A dimeric sodium supported borate complex, [Na(py)][B(hyncaH₋₂)₂]₂ (1) (py = pyridine, hynca = 1-hydroxynaphthalene-2-carboxylic acid), has been synthesised by the reaction of NaBH₄ with two equivalents of hynca in anhydrous THF and following crystallization from py/H₂O solution afforded borate ester derivative. The complex has been fully characterized by FT-IR in the solid state and by NMR (¹H and ¹³C) spectroscopy and electrospray ionization mass spectrometry in solution. The molecular structure of the title compound was determined by single crystal X-ray diffraction. Structure analysis of complex 1 confirmed the presence of an anionic complex [B(hyncaH₋₂)₂]⁻ in which boron atom is coordinated simultaneously by two hynca ligands utilising both alkoxide and carboxylate groups for bonding. The Na atom is six- coordinate to five O atoms of hydroxy carboxylic acid and one pyridine N atom. Crystal data: crystal system, monoclinic, a = 10.971(3) Å, b = 6.839(3) Å, c = 30.545(5) Å, β = 92.20(2)°, space group P2₁/c (#14), V = 2,290(1) Å³, Z = 4. Index Abstract  There are limited examples of alkali metal supported borate ester complexes.      

Crystal Structure of Hydrated Potassium Pentafluorophenolate: Interactions Between Fluorine Atoms and Metal Ions

Abstract  Crystals of potassium pentafluorophenolate dihydrate (PfpOK · 2H₂O) have been obtained. The title compound formulated as [K(C₆F₅O)(H₂O)₂] crystallizes in monoclinic system, space group C2/c with a = 9.353(2), b = 18.329(6), c = 6.8679(17) Å, β = 132.272(3)°, V = 871.2(4) Å³, Z = 4. The main features of the structure are the aromatic stacking of PfpO⁻ with opposite dipole orientation and, more astonishing, coordination of the metal to fluorine atoms instead of the expected bonding to the phenolate oxygen atom (shortest PfpO–K distance = 4.357(1) Å). The coordination sphere of the K cation contains four water molecules and four F atoms. The phenolate oxygen binds to four water molecules through hydrogen-bonding. B3LYP/6-31+G(d) calculation suggest a charge of −0.69 for O1 versus −0.39, −0.38 and −0.40 for the fluorines atoms respectively, providing insight into the unusual bonding modes. Graphical Abstract  Crystals of potassium pentafluorophenolate dihydrate (PfpOK·2H₂O) show unusual anti-parallel aromatic stacking of PfpO⁻ and, even more astonishing location of the octa-coordinated K⁺ remote from the oxygen anion.      

Synthesis and crystal structure of 5,7-diallyloxy-4-methylcoumarin

The title compound, 5,7-diallyloxy-4-methyl-2H-[1]-benzopyran-2-one, (C₁₆H₁₆O₄), was prepared by condensation of ethyl acetoacetate with phloroglucinol followed by allylation of the 5,7-dihydroxy-4-methylcoumarin thus obtained. The compound crystallizes into monoclinic space group P2₁/c with unit cell parameters a = 7.531(1) Å, b = 22.596(4) Å, c = 8.090(1) Å, β = 92.74(2)°, Z = 4. The crystal structure was solved by direct methods using single crystal X-ray diffraction data and refined to R = 0.0596 for 2166 observed reflections. The coumarin moiety is perfectly planar, with dihedral angle between the two fused rings of 0.46(5)°. The two allyloxy groups have different behaviour, one of them being disordered. Molecules form chains of weak C–HO and C–Hπ hydrogen bonds.     

Synthesis and Crystal Structure of a New Ion-Pair Complex Based on [Ni(tdas)<Subscript>2</Subscript>]<Superscript>2−</Superscript> Anion and Triphenylphosphinium Cation

Abstract  A new ion-pair complex, bis(1-benzyltriphenylphosphinium) bis(1,2,5-thiadiazole-3,4-dithiolato)nickelate(II), [BzTPP]₂[Ni(tdas)₂](1), has been prepared and characterized by elemental analyses, UV, IR, MS spectrum, molar conductivity and single crystal X-ray diffraction. The title complex crystallizes in the triclinic space group P-1, a = 9.098(1) Å, b = 9.666(1) Å, c = 29.573(3) Å, α = 83.81(1)°, β = 81.97(1)°, γ = 78.83(1)°, V = 2,517.5(4) ų, Z = 2. The unit cell contains two [BzTPP]⁺ and two halves of [Ni(tdas)₂]²⁻ anions in which the anion exhibits a quasi-planar structure. The [BzTPP]⁺ cation adopts a conformation where four phenyl rings are twisted to the C–C–P reference plane. The weak cation–cation C–H···π, π···π interactions and anion–cation C–H···N hydrogen bonds between the anion and cation play an important role in the stacking and stabilizing of the title complex. Graphical Abstract  The title new ion-pair complex, bis(1-benzyltriphenylphosphinium) bis(1,2,5-thiadiazole-3,4-dithiolato)nickelate(II), [BzTPP]₂[Ni(tdas)₂](1), contains two [BzTPP]⁺ and two halves of [Ni(tdas)₂]²⁻ anions in which the weak cation–cation C–H···π, π···π interactions and anion−cation C–H···N hydrogen bonds between the anion and cation play an important role in the stacking and stabilizing of the title complex.      

Synthesis and Structural Characterization of Bis[(cyclohexylamino)pent-2-en-4-onato]-Chromium(II)

Abstract  Addition of one equivalent of CrI₂ to two equivalents of lithium cyclohexylamino-pent-2-en-4-onate results in bis[(cyclohexylamino)pent-2-en-4-onato]-chromium(II). Crystallization in diethylether reaction solvent forms the hemi-etherate A with the asymmetric unit showing two target compounds and one molecule of cocrystallized diethylether in the P-1 space group with crystal cell parameters a = 12.931(4) Å, b = 13.207(4) Å, c = 16.104(5) Å, α = 66.559(5)°, β = 77.670(5)°, γ = 81.562(5)°, V = 2,459.1(14) Å³ and Z = 4. Drying A in vacuo and recrystallization in pentane yields a nonsolvated crystalline phase B with an asymmetric unit displaying only one molecule of the target compound in the P2₁/c space group with crystal cell parameters a = 14.290(7) Å, b = 14.082(7) Å, c = 11.246(6) Å, β = 94.807(8)°, V = 2,255.1(19) Å³ and Z = 4. Graphical Abstract  A Cr(II) complex supported by two β-enaminoketiminato ligands, bis[(cyclohexylamino)pent-2-en-4-onato]-chromium(II), has been synthesized and has been structurally characterized in two different crystal phases.      

Synthesis,Crystal Structure,Ab Initio Studies and Fingerprint Plots of 2-Chloro-1,3-dioxo-2,3-dihydro-1H-inden-2-yl acetate

Abstract  

2-Chloro-1,3-dioxo-2,3-dihydro-1H-inden-2-yl acetate, C₁₁H₇ClO₄ (Fig. 1), has been synthesized and the structure has been solved by IR and X-ray diffraction studies. The crystals are triclinic, space group P [`1] \bar{1} , with a = 7.62060(10) ?, b = 11.5944(2) ?, c = 13.0753(3) ?, α = 97.2820(10)°, β = 101.5740(10)°, γ = 101.7930(10)°, Mr = 238.62, V = 1090.82(3) ?³, Z = 4 and R = 0.0557. In the title compound there are two molecules in the asymmetric unit. The molecules are linked via weak C–H···O hydrogen bonds forming R₄⁴(28) rings. The intermolecular interactions were analysed by means of the fingerprint plots derived from the Hirshfeld surfaces. The fingerprint plots evidenced subtle differences in the intermolecular contacts for the two independent molecules.      

Structures of Three New (Phenylsulfonyl)Indole Derivatives

Abstract  

Three new 1-(phenylsulfonyl)indole derivatives, 3-acetyl-2-ethyl-1-(phenylsulfonyl)indole, (I), 2-benzyl-1-(phenylsulfonyl)indole, (II), and 3-trimethylsilylethynyl-1-(phenylsulfonyl)indole, (III), have been synthesized and their crystal structures determined by single crystal X-ray crystallography. (I), C₁₈H₁₇NO₃S, is triclinic with space group P-1 and cell constants: a = 8.6129(2) Å, b = 8.8366(2) Å, c = 11.0108(2) Å, α = 72.7920(1)°, β = 75.0120(1)°, γ = 77.2550(1)°, V = 763.79(3) ų and Z = 2. (II), C₂₁H₁₇NO₂S, is monoclinic with space group P21/n and cell constants: a = 10.8355(18) Å, b = 10.6987(19) Å, c = 14.472(3) Å, β = 75.0120(1), V = 1675.2(5) ų and Z = 4. (III), C₁₉H₁₉NO₂SSi, is monoclinic with, space group P21/c and cell constants: a = 12.9596(1) Å, b = 10.543(3) Å, c = 13.543(2) Å, β = 93.58°, V = 1846.8(6)ų and Z = 4. All three have the same (phenylsulfonyl)indole skeleton with different ligands attached to the 2- and 3-sites of the indole ring. The angle between the mean planes of the indole and benzyl groups is 76.9(6)° (I), 82.9(3)° (II), 89.6(2)° (III) and between the sulfonyl group with the indole and benzyl rings is 61.2(9)° (I), 59.0((5)° (II), 51.5(6)°, 42.5(8)° (III) and 51.5(6)°(I), 44.3(8)° (II), 47.2(8)° (III), respectively. In addition to the ligand substitutions, weak intermolecular C–H···O hydrogen bond interactions and π stacking interactions between the π orbitals of nearby indole and phenyl rings influence these twist angles. Comparison to a MOPAC AM1 computational calculation supports these observations.     

Crystal Structure of [Zn(2-Bromobenzoato)<Subscript>2</Subscript>]<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> and [Zn(2-Bromobenzoato)<Subscript>2</Subscript>(<Emphasis Type="Italic">N</Emphasis>-Methylnicotinamide)]<Subscript>2</Subscript>

Abstract  

The syntheses and structural characterizations of two novel 2-bromobenzoatozinc(II) complexes—[Zn(2-BrC₆H₄COO)₂] _n (I) and [Zn(2-BrC₆H₄COO)₂(mnad)]₂ (II), where mnad is N-methylnicotinamide are reported. Compound (I) crystallized with a monoclinic lattice (space group P2₁/c) and is polymeric in solid state. Its cell parameters are: a = 7.37220(10) Å, b = 19.9639(3) Å, c = 30.2756(5) Å, β = 94.7510(7)°, V = 4440.59(12) ų, Z = 4. The coordination environments of all zinc atoms are distorted tetrahedra built from four carboxylate oxygen atoms coming from four 2-bromobenzoato ligands. Compound (II) crystallized with a monoclinic lattice (space group P2₁/c) with a = 11.7488(2) Å, b = 20.3683(3) Å, c = 9.30130(10) Å, β = 100.3941(11)°, V = 2189.30(5) ų, Z = 2. This dimeric molecule features a paddle-wheel [Zn₂O₈] cage in solid state; the coordination environment of the central atom is square pyramidal consisting of four carboxylate oxygen atoms and the pyridine N atom of the mnad ligand.     

Hydrogen Bonded 3D Supramolecular Architectures of Two Organic Salts Assembled from 2-Aminoheterocyclic Compounds and Phosphoric Acid

Abstract  

Two phosphate salts (2-aminopyrimidine): (phosphoric acid): H₂O [HL1⁺ (H₂PO₄) ⁻ ]·H₂O (1), and (4-phenylthiazol-2-amine): (phosphoric acid) [HL2⁺·(H₂PO₄)⁻] (2) based on 2-aminoheterocyclic compounds, 2-aminopyrimidine (L1), and 4-phenylthiazol-2-amine (L2) were prepared and structurally characterized by X-ray crystallography. Compound 1 crystallizes in the triclinic, space group P-1, with a = 6.2201(7) Å, b = 8.6139(9) Å, c = 9.4800(10) Å, α = 109.685(2)°, β = 106.3340(10)°, γ = 95.4450(10)°, V = 448.72(8) Å³, Z = 2. For 1, the cations were linked to each other via intermolecular C–H···N hydrogen bonds to form a 1-D chain structure running along the a-axis direction. The anions and the water molecules were connected alternatively along the a-axis direction through O–H···O hydrogen bonds to form a 1-D chain also. The cationic chains and the anionic chains were alternatively connected along the c-axis direction through N–H···O and C–H···O hydrogen bonds to form a 2D corrugated sheet. Adjacent sheets were combined together through π–π interaction to form double sheet. These double sheets were further joined together by O–H···O and N–H···O hydrogen bonds to produce a 3D network structure. Compound 2 crystallizes in the Orthorhombic, space group Pbca, with a = 10.1929(10) Å, b = 8.4406(9) Å, c = 27.589(2) Å, α = 90°, β = 90°, γ = 90°, V = 2373.6(4) Å³, Z = 8. In 2, the phosphates formed 1D chain along the b-axis through two P–O–H···O = P hydrogen bonds. The cations formed 1D zigzag chain along the b-axis direction under the CH–π interaction. The anionic chains were intercalated between two adjacent cationic chains through N–H···O, O–H···O, C–H···O, and O–S contacts. Such stacking repeated along the c-axis direction to form a 3D network structure.     

Conformational diversity: Six conformers side-by-side in the crystal cell of 2,2′,7,7′-tetramethoxy-9,9′-spiro-9-silabifluorene

X-ray crystal structure analysis of a sublimation-grown spiro silabifluorene, that is highly fluorescent in the violet-blue, established that there are six cocrystallized ordered conformers in the asymmetric unit. Crystals were grown by a vapor transport method under argon gas flow at temperatures between 255–280°C. As expected, there are no cocrystallized solvent molecules. There is no π-stacking of the aryl groups. There is no possibility for normal hydrogen bond formation; however, several CH⋯π bonds occur. The packing is efficient with a density of 1.24 g/cc. Each conformer deviates from tetrahedral geometry around the Si atom. Cell data are: C₂₈H₂₄O₄Si×12, sp. gr. P, a=16.2750(5) ?, b=20.6613(5) ?, c=23.8289(5) ?, α=102.025(2)°, β=94.252(2)°, and γ=109.916(2)°, V=7275(1) ?³.     

N,N′-Dihydrogenpiperazonium dichloridobis(dimethylglyoximato-k2N,N′)cobaltate(III) Dihydrate

Abstract  

The title complex: C₄H₁₂N₂[Co(C₄H₇N₂O₂)₂Cl₂]₂·2H₂O, viz., PpH₂[Co(dmgH)₂Cl₂]₂·2H₂O, where, dmgH⁻ = dimethylglyoximate and Pp = piperazine was synthesized and analyzed by single crystal XRD studies. The complex was grown as brown crystals by the slow evaporation method in ethanol. The complex crystallizes as triclinic with the space group p[`1] p\overline{1} and unit cell parameters a = 8.4521 (10) Å, b = 10.0999 (11) Å, c = 10.8952(13) Å; α = 94.066(6)°, β = 106.047(6)° and γ = 100.901(6)°. There are two complex molecules present in the unit cell. The short intra molecular O–H···O hydrogen bonds link the glyoximate moieties in the crystal.     

Dichloro-{bis(Pyrazol-1-yl)}Palladium(II) Complexes: Structures of a DMSO Solvated Dichloro-{bis(3,5-Dimethylpyrazol-1-yl)Acetic Acid}Palladium(II) and Dichloro-{bis(3,5-Ditertbutylpyrazol-1-yl)Methane}Palladium(II)

Abstract  Two new palladium(II) complexes, dichloro-{bis(3,5-dimethylpyrazol-1-yl)acetic acid}palladium(II)PdCl₂(3,5-Me₂bpza)], (1) (3,5-Me₂bpza = 3,5-dimethylpyrazol-1-yl)acetic acid) and dichloro-{bis(3,5-ditertbutylpyrazol-1-yl)acetic acid}palladium(II), [PdCl₂(3,5-^tBu₂bpza)], (2a) [3,5- ^t Bu₂bpza = 3,5-ditertiarybutylpyrazol-1-yl)acetic acid] complexes, were synthesized from the reactions of pyrazol-1-yl ligands with palladium salts. Attempts to crystallize 2a led to a hydrolyzed product, dichloro-{3,5-ditertbutylpyrazol-1-yl}palladium(II) (2b), in which the acetic acid moiety in the ligand backbone of 1 is lost. Both complexes 1 and 2b have been characterized by single-crystal X-ray crystallography. Both complexes crystallized in triclinic system (P − 1 space group). The cell parameters are: complex 1 (a = 8.7960(14) Å, b = 16.238(2) Å, c = 16.430(2) Å, α = 78.038(10)°, β = 77.817(11)°, γ = 89.970(10)°) and complex 2b (a = 10.1492(2) Å, b = 12.4001(2) Å, c = 13.108(3) Å, α = 103.0690(10)°, β = 97.4120(10)°, γ = 107.2450(10)°). The asymmetric unit of 1 contains two crystallographic independent monomeric units of 1 and three molecules of DMSO solvent, whilst that of 2b has got one monomeric unit with one molecule of chloroform solvent. Index Abstract  Two palladium complexes, dichloro-{bis(3,5-dimethylpyrazol-1-yl)acetic acid}palladium(II), PdCl₂(3,5-Me₂bpza)], (1) (3,5-Me₂bpza = 3,5-dimethylpyrazol-1-yl)acetic acid) and dichloro-{bis(3,5-ditertbutylpyrazol-1-yl)acetic acid}palladium(II), [PdCl₂(3,5- ^t Bu₂bpza)], (3,5- ^t Bu₂bpza = 3,5-ditertiarybutylpyrazol-1-yl)acetic acid) complexes, were synthesized from the reactions of pyrazol-1-yl ligands with palladium salts. Attempt to obtain crystals of tertiarybutylpyrazolyl analogue led to hydrolysis, the crystal structure of the hydrolysis product was established by single crystal X-ray crystallography.      

Ethynyl and Propynylpyrene Inhibitors of Cytochrome P450

Abstract  

The single-crystal X-ray structures and in vivo activities of three aryl acetylenic inhibitors of cytochromes P450 1A1, 1A2, 2A6, and 2B1 have been determined and are reported herein. These are 1-ethynylpyrene, 1-propynylpyrene, and 4-propynylpyrene. To investigate electronic influences on the mechanism of enzyme inhibition, the experimental electron density distribution of 1-ethynylpyrene has been determined using low-temperature X-ray diffraction measurements, and the resulting net atomic charges compared with various theoretical calculations. A total of 82,390 reflections were measured with Mo Kα radiation to a (sinθ/λ)_max = 0.985 Å⁻¹. Averaging symmetry equivalent reflections yielded 8,889 unique reflections. A least squares refinement procedure was used in which multipole parameters were added to describe the distortions of the atomic electron distributions from spherical symmetry. A map of the model electron density distribution of 1-ethynylpyrene was obtained. Net atomic charges calculated from refined monopole population parameters yielded charges that showed that the terminal acetylenic carbon atom (C18) is more negative than the internal carbon (C17). Net atomic charges calculated by ab initio, density functional theory, and semi-empirical methods are consistent with this trend suggesting that the terminal acetylenic carbon atom is more likely to be the site of oxidation. This is consistent with the inhibition mechanism pathway that results in the formation of a reactive ketene intermediate. This is also consistent with assay results that determined that 1-ethynylpyrene acts as a mechanism-based inhibitor of P450s 1A1 and 1A2 and as a reversible inhibitor of P450 2B1. Crystallographic data: 1-ethynylpyrene, C₁₈H₁₀, P2₁/c, a = 14.571(2) Å, b = 3.9094(5) Å, c = 20.242(3) Å, β = 105.042(2)°, V = 1,113.5(2) Å³; 1-propynylpyrene, C₁₉H₁₂, P2₁/n, a = 8.970(2) Å, b = 10.136(1) Å, c = 14.080(3) Å, β = 99.77(2)°, V = 1,261.5(4) Å³; 4-propynylpyrene, C₁₉H₁₂, Pbca, a = 9.904(1) Å, b = 13.174(2) Å, c = 19.401(1) Å, V = 2,531.4(5) Å³.     

Antimony(III) fluoride: inclusion complexes with crown ethers

Four crystalline molecular complexes between antimony(III) fluoride and 18-membered crown ethers have been obtained and their structures investigated by single crystal X-ray diffraction techniques: [18-crown-6·SbF₃], C₁₂H₂₄F₃O₆Sb,P2₁2₁2₁,a=8.328(4),b=11.573(4),c=18.094(4),V=1744(1)³,Z=4; [benzo-18-crown-6·SbF₃], C₁₆H₂₄F₃O₆Sb,P2₁/n,a=10.490(2),b=13.714(1),c=13.442(2), =101.94(1)°,V=1892(1)³,Z=4; [cis-syn-cis-dicyclohexano-18-crown-6·SbF₃·CH₃OH], C₂₁H₄₀F₃O₇Sb,P2₁/n,a=8.270(4),b=23.386(3),c=12.772(1), =96.31(2)°,V=2455(1)³,Z=4; [cis-anti-cis-dicyclohexano-18-crown-6·SbF₃], C₂₀H₃₆F₃O₆Sb,Pna2₁,a=21.091(8),b=12.829(5),c=8.437(3),V=2283(2)³,Z=4. All species are the perching-type complexes with the antimony fluoride above the cavity and the metal lone pair pointed toward the center of the crown ring. The antimony atom interacts with all six crown oxygen atoms with Sb–O distances of 2.837(2)–3.344(2) . The antimony atom is displaced from the least square plane of the crown oxygen atoms at the distances of 1.288–1.383 .     

Two Mononuclear Compounds with bis(Pyrimidin-2-yl)amine as a Ligand and as a Hydrogen-bonded Lattice Molecule. Synthesis, Structure and Spectroscopy of {[M(dipm)(H2O)(A)](dipm)(A)(H2O)} (M?=?Cd with A?=?ClO4; and Zn with A?=?BF4)

Abstract  Two isostructural mononuclear compounds with formula {[Cd(dipm)(H₂O)(ClO₄)](dipm)(ClO₄)(H₂O)} (1) {[Zn(dipm)(H₂O)(BF₄)](dipm)(BF₄)(H₂O)} (2) and (in which dipm = bis(pyrimidin-2-yl)amine) have been synthesised and characterised by X-ray crystallography and infrared spectroscopy. The structure of compound 1 has been solved in the space group P2₁/n with a = 18.860(4), b = 8.579(2), c = 20.917(4) ?, β = 101.33(3)°, V = 3318.4(12) ?³, Z = 4 with final R = 0.0454. The structure of compound 2 has also been solved in the space group P2₁/n with a = 19.026(4), b = 8.389(1), c = 20.720(4) ?, β = 101.37(3)°, V = 3242.2(10) ?³, Z = 4 with final R = 0.0689. The geometry around the metal ions is octahedral, and is constituted by four nitrogen atoms from two dipm molecules, an oxygen atom from a water molecule and a semi-coordinating anion atom ( for compound 1 and for compound 2). In the lattice are also present: a non-coordinating water molecule, an anion molecule and a dipm molecule. For compound 1, the Cd–N distances are between 2.296 and 2.328 ?. The distance is 2.310 ? and the is 2.477 ?. The Zn–N distances in compound 2 are between 2.121 and 2.164 ?. The distance is 2.147 ? and the distance is 2.373 ?. A hydrogen bond interaction of the Watson–Crick type is observed between the amine N atom of a dipm ligand to a pyrimidyl N atom and a non-coordinating dipm ligand with N···N distances, which vary from 3.066(5) to 3.109(5) ?. Furthermore medium to strong hydrogen bond interactions are present between oxygen atoms of the water molecules and the anions of the compounds. Index Abstract  Two isostructural mononuclear compounds with formula {[Cd(dipm)(H₂O)(ClO₄)](dipm)(ClO₄)(H₂O)} (1) {[Zn(dipm)(H₂O)(BF₄)](dipm)(BF₄)(H₂O)} (2) and (in which dipm = bis(pyrimidin-2-yl)amine) have been synthesised and characterised by X-ray crystallography and infrared spectroscopy. . Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.