The Preparation,Characterization and X-ray Structural Analysis of Tetrakis[1,3-dimethyl-2(3H)-imidazoleselone]cadmium(II) Hexafluorophosphate

Abstract A new compound, [Cd(dmise)₄][PF₆]₂, has been synthesized and characterized via standard solid and solution state methods including single crystal X-ray crystallography (dmise = 1,3-dimethyl-2(3H)-imidazoleselone). The title compounds crystallizes in orthorhombic space group P bcn with a = 12.783(3), b = 22.206(4), c = 13.153(3) ?, V = 3733.8(13) ?³, Z = 4. The complex is a high melting, yellow water soluble 2:1 electrolyte solid that state has a flattened tetrahedral CdSe₄ coordination geometry. To date this is the only structural study reported for a homoleptic selenourea complex of cadmium. Graphical abstract The Preparation, characterization and X-ray structural analysis of Tetrakis[1,3-dimethyl-2(3H)-imidazoleselone]cadmium(II) hexafluorophosphate Daniel J. Williams, Bradley J. McKinney, Ben Baker, Kevin P. Gwaltney and Donald VanDerveer Tetrakis[1,3-dimethyl-2(3H)-imidazoleselone][PF₆]₂ is prepared in 82% yield by direct combination of cadmium acetate dihydrate, ammonium hexafluorophosphate, and the ligand in boiling acetonitrile. X-ray crystallography shows a structure with a distorted tetrahedral coordination sphere around the cadmium. This is the first report of a structural characterization of a homoleptic cadmium selenourea complex. Electronic supplementary material The online version of this article (doi: ) contains supplementary material, which is available to authorized users.     

The preparation, characterization and X-ray structural analysis of tetrakis[1-methyl-3-(2-propyl)-2(3H)-imidazolethione]zinc(II) tetrafluoroborate and tetrakis[1-methyl-3-(1-butyl)-2(3H)- imidazolethione]zinc(II) tetrafluoroborate

Two compounds, [Zn(mipit)₄][BF₄]₂ (1) and [Zn(mnbit)₄][BF₄]₂ (2) have been synthesized and characterized via standard solid and solution state methods including single crystal X-ray crystallography (mipit: 1-methyl-3-(2-propyl)-2(3H)-imidazolethione and mnbit: 1-methyl-3-(1-butyl)-2(3H)-imidazolethione). Compound 1 crystallizes in monoclinic space group P2₁/n with a = 11.804(2) ?, b = 16.710(3) ?, c = 25.763(5) ?, γ = 90.14(3)° and Z = 4, whereas compound 2 crystallizes in tetragonal space group $${\rm I}\bar{4}$$ with a = b = 11.6517(16) ?, c= 16.820(3) ?, and Z = 2. Both complexes are high melting, colorless water soluble 2:1 electrolyte solids that state have flattened tetrahedral ZnS₄ coordination geometry. The isopropyl analog is slightly more distorted than the n-butyl analog, and the degree of distortion is not directly related to the steric bulk of the ligand.     

4-(E)-2-[3-(3-[(E)-2-(4-cyanophenyl)-1-diazenyl]perhydrobenzo[d]imidazol-1-ylmethyl)perhydrobenzo[d]imidazol-1-yl]-1-diazenylbenzonitrile: X-ray crystal structure

4-(E)-2-[3-(3-[(E)-2-(4-Cyanophenyl)-1-diazenyl]perhydrobenzo[d]imidazol-1-ylmethyl) perhydrobenzo[d]imidazol-1-yl]-1-diazenylbenzonitrile (1) has been synthesized by reac- tion of p-cyanobenzene diazonium chloride with a mixture of formaldehyde and trans-1,2-cyclohexanediamine. The crystal structure has been determined by single crystal X-ray diffraction analysis. The bis-triazene (1) does not adopt a folded conformation, unlike previously studied ethylenediamine analogues, and there is no indication of -stacking in the crystal packing. The dominant interaction between molecules is the van der Waal's attraction between cyclohexane rings. This result establishes the structure of the product of this diazonium coupling reaction as the 1-(1-imidazolidinylmethyl)imidazolidine derivative and not the alternate tetraazabicyclo[4.4.1]undecane derivative. Crystal data: 1 C₂₉H₃₄N₁₀, orthorhombic, space group Pbca, a = 17.946(1), b = 13.106(1), c = 24.108(1) Å, V = 5670.6(3) ų, for Z = 8.     

Chiral bisphosphanes XII: Synthesis and molecular structure of cis-{rac,trans-1,2-bis[bis(morpholin-4-yl)-phosphino]cyclopentane}dimethylplatinum(II), cis-[C5H8{P[N(C2H4)2O-cyclo]2}2Pt(CH3)2]

Crystals of the title compound are monoclinic, space group P2₁/c, with a = 10.2621(8), b = 15.372(5), c = 17.612(2) Å, = 95.928(9)°, and Z = 4. Coordination about the central metal deviates slightly from ideal square-planar geometry. The five-membered chelate ring adopts an envelope conformation with one of the two P atoms (P1) deviating from the least-squares plane spanned by the central metal, the bridging CH carbons, and donor atom P2. While the morpholino substituents at the latter show little axial-equatorial discrimination for their orientation with respect to the coordination plane, the spatial alignments of the N(C₂H₄)₂O rings attached to P1 differ significantly between a more equatorial and a more axial disposition. The conformationally dissimilar arrangement of the two P donor groups within the envelope-like chelate ring manifests itself in unequal Pt–P bond lengths: d(Pt–P1) = 2.2677(16), d(Pt–P2) = 2.2825(16) Å. The Pt–CH₃ distances amount to 2.114(6) (trans to P2) and 2.141(6) Å (trans to P1), respectively.     

The preparation, characterization, and X-ray structural analysis of dichlorobis[1-methyl-3-(2-propyl) -2(3H)-imidazolethione]mercury(II)

A new compound of mercury(II) chloride complexed to 1-methyl-3-(2-propyl) -2(3H)-imidazolethione (mipit) has been prepared and characterized via standard methods and X-ray crystallography. The structural significance of this study is that it shows one of the few monomeric examples of a mercury(II) chloride thione complex reported to date. The compound crystallizes in space group P2₁/c with a = 17.143(6) Å, b = 17.047(6) Å, c = 14.759(5) Å, = 105.899(5)°, V = 4148(2) ų, Z = 8. The coordination sphere is distorted tetrahedral with Hg–S bonds and Hg–Cl bond distances falling within the normally expected ranges. Bond angles ranged from 108.11(4)° to 115.51(4)° with the widest angle being observed for the S–Hg–S linkage. Ligand bond distances and angles including the C=S distance are within the normally expected values observed for this compound.     

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.      

Crystal structure of potassium tris[3-(2-pyridyl)pyrazolyl]hydroborate

The crystal structure of the potassium tris[3-(2-pyridyl)pyrazolyl]hydroborate has been determined. Potassium tris[3-(2-pyridyl)pyrazolyl]hydroborate crystallizes in the orthorhombic space group Pca2₁ with the parameters a=30.7323(5) ?, b=8.3083(1) ? and c=9.2173(2) ?, V=2353.48(7) ?³ with Z=4. The crystal structure reveals the formation of continuous chains where two bidentate arms of the hydroborate ligand are coordinated to one potassium and the third to another cation. The structures of numerous transition metal and actinide salts have been reported during the last decades but no alkali metal complexes were available.     

Crystal structure oftrans-tetrachlorobis[2-(2-1H-imidazolyl)-1H-imidazolium]cadmium(II), [Cd(H3biim)2Cl4]

The reaction between cadmium(II) chloride and 2,2'-bi-1H-imidazole (H₂biim) in an acidic solution affords [Cd(H₃biim)₂Cl₄] (H₃biim=2-(2-1H-imidazolyl)-1H-imidazolium) in 63% yield. The compound crystallizes in the triclinic space groupP1, wherea=8.072(2),b=8.100(2),c=8.593(2) Å, =75.89(2), =62.94(2), =63.29(1)°,V=446.4(2) ų, andZ=1. The central Cd atom exhibits an octahedral geometry composed of a Cl₄N₂ core. The Cd-N bond distance is 2.392(2) Å. Cd–Cl distances are 2.5919(9) and 2.671(1) Å.     

Investigation of 2-(3,4-dimethoxyphenyl)-5,6-dimethoxy-1H-indene by X-ray crystallography and NMR spectroscopy

2-(3,4-Dimethoxyphenyl)-5,6-dimethoxy-1H-indene (obtained by acid treatment of 1,2-bis(3,4-dimethoxyphenyl)-1,3-propanediol) crystallizes in space groupP2₁/c witha=6.836(6),b=28.631(9),c=16.344(6) Å, =95.73(5)°, andZ=8. There are two molecules in the asymmetric unit; the conformations of these molecules exhibit minor differences. In the crystals the double bond in the five-membered ring of the compound is disordered over two positions. The nature of the bonds in the five-membered ring could be ensured by¹H-NMR and¹³C-NMR spectral examinations.     

1-[2-(p-Tolyl)-1-diazenyl]-3-({3-[2-(p-tolyl)-1-diazenyl] perhydrobenzo[d]imidazol-1-yl}methyl)perhydrobenzo[d]imidazole: synthesis,characterization and X-ray crystal structure

1-[2-(p-Tolyl)-1-diazenyl]-3-({3-[2-(p-tolyl)-1-diazenyl]perhydrobenzo[d]imidazol-1-yl}methyl)perhydrobenzo[d]imidazole(1) has been synthesized by reactionof a mixture of 1,2-diaminocyclohexane and formaldehyde withp-toluene diazonium chloride inaqueous solution. The product has been characterized by IR and NMRspectroscopy and elemental analysis. A crystal grown from solution ina mixed solvent system of ethyl acetate and hexanes was analyzed byX-ray crystallography. The solution of the crystal structure of(1) is important in establishing theconnectivity of this molecule and other compounds of similarstructure. The crystal structure of (1) is compared with the previously reportedstructure of the p-cyano analogue(2). Compounds (1) and (2)differ principally in the relative orientation of the heterocyclicrings; in (1), the molecule has adistinct V-shape, whereas compound (2) adopts a more extended conformation.Significant conjugation within the triazene moieties is evident inboth (1) and (2), as manifested in the N465=N andN–N bond lengths. The conjugation is greater in (2) due to the extended conjugation through tothe nitrile group. The title compound (1){C₂₉H₄₀N₈}crystallizes in the monoclinic, space group C2/c, with lattice constants: a = 30.532(6) ?,b =5.9050(12) ?, c= 15.463(3) ?, α = 90°,β = 99.94(3)°, γ = 90°,V =2746.0(10) ?³, Z = 4, D _c =1.209 mg m⁻³,F(000) = 1076, R ₁ = 0.0785,wR ₂= 0.1877.     

X-ray crystal and molecular structure of dichlorobis [2(1H)-pyridinethione-S]iron(II)

Attempts to prepare the mixed ligand complex, FeCl₂(pyS)(Ph₃P)₂ from the reaction of iron(III) chloride with 2(1H)-pyridinethione-S(HpyS) and triphenylphosphine(Ph₃P) in ethanol instead formed FeCl₂(HPyS)₂ characterized by X-ray crystallography. The structure was determined by the heavy atom method, using MoK diffractometer data, and refined by full-matrix least squares toR=0.049 for 1123 observed reflections. The molecule possesses twofold symmetry with a distorted tetrahedral geometry about the iron(II) center with S-Fe-S and Cl-Fe-Cl bond angles of 98.76(5)° and 115.79(5)° and Fe-S and Fe-Cl bond distances 2.345(1) Å and 2.288(1) Å, respectively. Hydrogen bonding between NH and chlorine atoms leads to a polymeric type structure of linked molecules running approximately parallel to thea axis.     

Structure of 4,6-dimethylisothiazolo[5,4-b]pyridin-3(2H)-one and its 2-[4-(2-methylphenyl) piperazin-1-ylmethyl] derivative

The crystal and molecular structures of 4,6-dimethylisothiazolo[5,4-b]pyridin-3(2H)-one, C₈H₈N₂OS, 1, and its 2-[4-(2-methylphenyl)piperazin-1-ylmethyl] derivative, C₂₀H₂₄N₄OS, 2c, are described. These compounds crystallize in the monoclinic system in the space group P2 ₁/c. The cell constants for compound 1 are a = 5.049(1), b = 14.897(1), c = 11.330(1) Å, = 98.07(1)°, Z = 4, T = 293 K, and D _cal = 1.419 g cm^–3, and for compound 2c are a = 15.525(1), b = 12.021(1), c = 10.911(1) Å, = 106.42(1)°, Z = 4, T = 293 K, and D _cal = 1.253 g cm^–3 The structures were solved by direct methods and refined to R values of 0.0411 and 0.0380 for 1640 and 3504 reflections for 1 and 2c, respectively. The analysis of the geometry and difference electron density map reveal that the dimethylisothiazolopyridine 1 exists in the amino tautomeric form in the crystalline state. The conformation of the o-methylphenylpiperazine part of the molecule 2c strongly depends on the substituents effect in the phenyl ring and is very similar to those observed in crystals for other investigated arylopiperazine derivatives of the isothiazolopyridine.     

4-(<Emphasis Type="Italic">E</Emphasis>)-2-[3-(3-[(<Emphasis Type="Italic">E</Emphasis>)-2-(4-cyanophenyl)-1-diazenyl]hexahydro-1-pyrimidinylmethyl)hexahydro-1-pyrimidinyl]-1diazenylbenzonitrile: X-ray crystal structure

4-(E)-2-[3-(3-[(E)-2-(4-cyanophenyl)-1-diazenyl]hexahydro-1-pyrimidinylmethyl)hexahydro-1-pyrimidinyl]-1-diazenylbenzonitrile (1) has been synthesized by reaction of p-cyanobenzene diazonium chloride with a mixture of formaldehyde and 1,3-propanediamine. The crystal structure has been determined by single crystal X-ray diffraction analysis. The bis-triazene (1) adopts a folded conformation, similar to previously studied ethylenediamine analogues, and there is evidence of -stacking in the crystal packing. The two planar phenyltriazenyl groups are almost parallel, forming an angle of 6.6(1), and display weak intermolecular s interactions between molecules. This result establishes the structure of the product of this diazonium coupling reaction as the 1-(1-hexahydropyimidinylmethyl)hexahydropyrimidine derivative and not the alternate tetraazabicyclo[5.5.1]tridecane derivative. Crystal data: 1C₂₃H₂₆N₁₀, monoclinic, space group P2₁/c, a = 10.717(1) Å, b = 7.749(1) Å, c = 28.252(2) Å, = 97.223(2), V = 2327.5(5) ų, for Z = 4.     

Synthesis and Crystal Structure of bis [2-(3-(2-((2-Hydroxybenzylidene) Amino)Ethyl)Oxazolidin-2-yl)Phenol]Cerium (IV) 1,4-Dioxane Monosolvate

The metal complex, bis [2-(3-(2-((2-hydroxybenzylidene)amino)ethyl) oxazolidin-2-yl)phenol]cerium(IV) 1,4-dioxane monosolvate was synthesized and characterized by infrared, ¹H NMR, elemental analysis, single-crystal, and powder X-ray diffraction. The coordination polyhedra of cerium shows a distorted square-antiprismatic geometry. No classical hydrogen bonds were observed. The crystal packing was influenced by weak C-H···O (intermolecular) and van der Waals interactions.     

Structure of bis(dipropyldithiocarbamate) cadmium(II), [Cd2(n-Pr2dtc)4] (dtc = dithiocarbamate)

The cadmium complex of bis(dipropyldithiocarbamate), [Cd₂(n-Pr₂dtc)₄] (dtc = dithiocarbamate) was crystallized from ethylether. It crystallizes in the monoclinic system, space group P _2I/c, with lattice parameters, a = 8.2532(1), b = 19.4519(1), c = 13.4163(2) Å, = 99.243(1)°, and Z = 4. The X-ray single-crystal structure of [Cd₂(n-Pr₂dtc)₄] reveals that the complex is binuclear in the solid state and the Cd atom has a distorted square-pyramidal coordination environment and four equatorial donors are the two bidentate chelate sulfur atoms from two dtc ligands, of which the sulfur atom from the bridging dtc ligand occupies the apical position of the symmetry-related Cd atom in the dimer structure.     

Methyl 4-((E)-2-{3-[(3-{ (E)-2-[4-(methoxycarbonyl)phenyl]- 1-diazenyl}-5,5-dimethylhexahydro-1-pyrimidinyl)methyl]-5,5-dimethylhexahydro-1-pyrimidinyl-1-diazenyl) benzoate. X-ray crystal structure

Methyl 4-((E)-2-{3-[(3-{(E)-2-[4-(methoxycarbonyl)phenyl]-1-diazenyl}-5, 5-dimethyl hexahydro-1-pyrimidinyl)methyl]-5, 5- dimethylhexahydro-1- pyrimidinyl}-1- diazenyl) benzoate (1) has been synthesized by reaction of a mixture of formaldehyde and 2,2-dimethyl-1,3-propanediamine with p-methoxycarbonylbenzenediazonium chloride. The crystal structure of 1 has been determined by single crystal X-ray diffraction analysis. The crystals of 1 displayed problems of disorder; the asymmetric unit is built up by two independent molecules, which display disorder within a methoxycarbonyl group. The two independent molecules in the asymmetric unit are very similar, differing only slightly about the mutual orientation of the aryltriazenyl groups. With respect to the N–C–N bridge between the hexahydropyrimidinyl rings, the two equivalent fragments containing the triazene moieties are in a cis orientation. The N–N single bonds, in the range 1.319(4)–1.348(4) Å, and the N=N double bonds, in the range 1.255(5)–1.275(4) Å, indicate significant conjugations within the triazene moieties. All the hexahydropyrimidine six-membered rings adopt a chair conformation as shown by their puckering parameters. The crystal packing is determined only by simple van der Waals interactions. The crystal structure of 1 is compared with the previously reported structure of the unbranched hexahydropyrimidine analogue 2. Crystal data: 1 C29H40N8O4, triclinic, space group P-1, a = 13.9652(2), b = 14.2908(3), c = 16.6129(4) Å, = 97.279(1), = 90.872(1), = 107.385(1), V = 3133.6(1) ų, for Z = 4.     

Synthesis and crystal structure of a terephthalato-bridged copper(II) complex [Cu2(tpt)(bpy)2(H2O)4] [Cu2(tpt)3 (bpy)2(H2O)2]

A terephthalato-bridged copper(II) complex [Cu₂(tpt)(bpy)₂(H₂O)₄][Cu₂(tpt)₃(bpy)₂ (H₂O)₂] (1) (tpt = terephthalate, bpy =; 2,2'-bipyridine) was synthesized by the reaction of Cu(ClO₄)₂ 6H₂O and terephthalic acid in the presence of 2,2'-bipyridine in H₂O solution. Crystal structure of 1 was determined by X-ray diffraction analysis in the triclinic space group P , with a = 10.7327(10) Å, b = 11.1658(11) Å, c = 17.3768(16) Å, = 108.063(2), = 91.064(2), = 116.721(2), V = 1737.5(3) ų, and Z = 2. Both the anion and the countercation in 1 are copper(II) complexes linked by terephthalate bridges in the bis(monodentate) (syn–anti) mode. The anion and the countercation are also linked by two hydrogen bonds between coordinating water molecules and terephthalate ligand.