Synthesis and crystal structure of bis(benzimidazolium) tetrahalocobaltate(II)

The crystal structures of benzimidazolium tetrahalocobaltates (HBz)₂[CoX₄] (X = Cl and Br) have been determined. The chloride salt is triclinic, P-1, with a = 7.670(3) Å, b = 8.307(3) Å, c = 15.730(2) Å, and = 87.37(3)°, = 84.99(3)°, = 67.72(2)°. The bromide salt is monoclinic, C2/c, with a = 15.568(2) Å, b = 8.063(3) Å, c = 5.762(2) Å and = 91.36(3)°. The structures of the two salts are closely related. Both the compounds contain isolated tetrahedral CoX₄ ^2– anions and benzimidazolium cations. In the chloride salt, three chloride ions are involved in strong hydrogen bonding while only two bromide ions participate in the bromide salt. The greater deviation from the ideal tetrahedral geometry in CoBr₄ ^2– can be related to the less extensive hydrogen-bonding network compared to the chloro complex.     

Crystal structure of bis(4-dimethylaminopyridinium) tribromocuprate(I) and bis(4-dimethylaminopyridinium) tetrabromocuprate(II)

The synthesis and crystal structures of two copper bromide salts of the 4-dimethylaminopyridinium (4DMAP⁺) cation are reported. The Cu(I) salt, (4DMAP)₂CuBr₃, crystallizes in the monoclinic space group C2/c, with a = 11.724(2), b = 11.055(3), c = 15.763(3) Å, = 107.64(3)°, and Z = 4. It contains isolated planar 4DMAP⁺ cations and trigonal planar CuBr₃ ^2– anions. Small distortions from idealized D _3h symmetry are observed for the anion. For the Cu(II) salt, (4DMAP)₂CuBr₄, a triclinic cell is observed with a = 8.2373(2), b = 9.2428(2), c = 14.4391(1) Å, = 93.760(1), = 94.576(1), = 105.249(1)°, and Z = 2. This compound contains discrete planar 4DMAP⁺ cations and flattened tetrahedral CuBr₄ ^2– anions. Small distortions are observed for ideal D _2d symmetry.     

Preparation and characterization of 1-butyl-3-methylimidazolium tetrakis(3,5-bis(trifluoromethyl) phenyl)borate, [bmim]BARF

Attempts to prepare novel air and moisture stable room-temperature ionic liquids have afforded a new 1,3-dialkylimidazolium tetraarylborate salt: 1-butyl-3-methylimidazolium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, [bmim]BARF, 1. Crystal data: C₈₀ H ₅₄ b ₂F₄₈N₄, monoclinic space group P2(1)/n, a = 21.2622(17) Å, b = 15.8037(13) Å, c = 26.227(2) Å, = 101.841(2) , V = 8625.3(12) ų, Z = 1.544.     

The preparation and crystal structures of some tricarbonylmanganese(I) octahedral complexes containing the 1,1-dimethylamino-2,2-diphenylphosphinoethane ligand

Four new complexes of (pn) the titled ligand have been prepared and characterized: (CO)₃Mn(pn)Br, 1; (CO)₃Mn(pn)N₃, 2; the triazalato (tz) complex, (CO)₃Mn(pn)(tz), 3 and [(CO)₄Mn(pn)]BF₄, 4. Crystal structures for the first three of these were determined. Crystal data for 1, monoclinic crystal system, space group = C2, a = 17.8587(6) Å, b = 7.9611(3) Å, c = 14.2349(4) Å, = 90.281(1)°, V = 2023.82(12) ų, Z = 4; for 2, monoclinic crystal system, space group = P2₁/c, a = 8.8933(14) Å, b = 13.844(2) Å, c = 16.361(3) Å, = 95.712(3)°, V = 2004.4(6) ų, Z = 4; for 3, orthorhombic crystal system, space group = Pbca, a = 17.9097(4) Å, b = 13.1308(4) Å, c = 21.2838(6) Å, V = 5005.3(2) ų, Z = 8.     

Crystal structures of [WI2(CO)3{Ph2P(CH2) n PPh2}] (n = 2 or 3)

[WI₂(CO)₃{Ph₂P(CH₂)₂PPh₂}] (1) crystallizes out in the monoclinic space group P2₁/n, with a = 13.852(7) Å, b = 14.789(19) Å, c = 14.915(19) Å, = 102.86(1)°, Z = 4. [WI₂(CO)₃{Ph₂P(CH₂)₃PPh₂}] (2) crystallizes out in the monoclinic space group P2₁/n, with a = 10.499(15) Å, b = 14.58(2) Å, c = 20.75(3) Å, = 103.59(1)°, Z = 4. Both structures show the metal in a seven-coordinate environment with a carbonyl in the unique capping position, two further carbonyls and a phosphorus in the capped face, and two iodides and the second phosphorus in the uncapped face.     

Influence of the spectator cation on the structure of anionic pyridine-2,6-dicarboxylato complexes of cobalt(II), nickel(II), and copper(II)

The structures of anionic pyridine-2,6-dicarboxylato (pdc^2–) complexes of cobalt, nickel, and copper have been studied. The stoichiometries and structures are very much dependent on whether KOH, Et₄NOH, or NaOH is used in the synthesis to deprotonate the H₂pdc ligand. Crystallographic results are: (1) K₂[Co(pdc)₂] · 7H₂O, orthorhombic, Pnna, Z = 4, a = 20.637(2)Å, b = 13.480(1)Å, c = 8.200(1)Å (2) K₂[Ni(pdc)₂] · 7H₂O, orthorhombic, Pnna, Z = 4, a = 20.648(1)Å, b = 13.375(1)Å, c = 8.2393(8)Å (3) [Co₂(H₂O)₅(pdc)₂] · 2H₂O, monoclinic, P2₁/c, Z = 4, a = 8.3880(6)Å, b = 27.384(2)Å, c = 9.6110(8)Å, = 98.271(6)° (4) [Ni(Hpdc)₂] · 3H₂O, monoclinic, P2₁/c, Z = 4, a = 13.679(1)Å, b = 10.0450(9)Å, c = 13.767(2)Å, = 115.184(7)° (5) Na₆[Co(H₂O)₆][Co(pdc)₂]₄ · 28H₂O, monoclinic, P2₁/n, Z = 2, a = 13.363(1)Å, b = 8.437(1)Å, c = 40.689(3)Å, = 91.288(5)° (6) Na[Ni(Hpdc)(pdc)] · 11.5H₂O, monoclinic, C2/m, Z = 4, a = 15.200(2)Å, b = 22.299(2)Å, c = 8.3596(7)Å, = 118.894(7)° (7) Na[Cu(Hpdc)(pdc)] · 3H₂O, monoclinic, P2₁/n, Z = 4, a = 9.516(4)Å, b = 14.917(6)Å, c = 12.247(5)Å, = 92.00(5)°. The potassium and sodium complexes have extensive K⁺—H₂O and Na⁺—H₂O networks. The fact the Et₄N⁺ ion does not appear in any of the complexes is likely due to the fact that it is incapable of forming the intricate cation—water and hydrogen-bonding networks observed in all of the other structures.     

Copper(II) complexes 1-phenylpropane-1,2-dione- and benzil bis(3-piperidylthiosemicarbazone): A structural study

The crystal and molecular structure of copper(II) complexes of benzil bis(3-piperidylthiosemicarbazone), [Cu(Bnzpip)] and 1-phenylpropane-1,2-dione bis(3-piperidylthiosemicarbazone), [Cu(Pmpip)] have been determined. [Cu(Bnzpip)] is monoclinic, space group P2₁/n with a = 13.9375(10) Å, b = 11.6621(4) Å, c = 16.4710(10) Å, = 100.667(2)°, and V = 2630.9(3) ų with Z = 4, for d _calc = 1.399 g/cm³. [Cu(Pmpip)] is also monoclinic, space group P2₁/n with a = 11.292(6) Å, b = 10.219(5) Å, c = 20.292(6) Å, = 101.50(3)°, and V = 2295(2) ų with Z = 4, for d _calc = 1.525 g/cm³. Both complexes involve N₂S₂ coordination, are relatively planar except for the phenyl rings and have similar bond distances and angles to copper(II) complexes of other 3-piperidylthiosemicarbazones.     

Synthesis, spectroscopy, and X-ray structures of fac-(CO)3(dppe)MnSC(S)H, fac-(CO)3(dppe)ReSC(S)H, fac-(CO)3(dppp)ReSC(S)H, and fac-(CO)3(dppb)ReSC(S)H

The monodentate dithioformato complexes, fac-(CO)₃(dppe)MnSC(S)H (1), fac- (CO)₃(dppe)ReSC(S)H (2), fac-(CO)₃(dppp)ReSC(S)H (3), and fac-(CO)₃ (dppb)ReSC(S)H (4), where dppe is 1,2-bis(diphenylphosphino)ethane, dppp is 1,3-bis(diphenylphosphino)propane, and dppb is 1,4-bis(diphenylphosphino)butane, were synthesized from the treatment of the corresponding hydrides, fac-(CO)₃ (P-P)MSC(S)H with CS₂. Compounds 1–4 crystallize in the monoclinic crystal system: for 1, space group = P2₁/c, a = 15.3139(3) Å, b = 9.7297(4) Å, c = 19.0991(6) Å, = 105.928(1), V = 2736.5 ų, Z = 4; for 2, space group = P2₁/c, a = 15.6395(8) Å, b = 9.8182(5) Å, c = 19.4153(11) Å, = 106.741(1), V = 2854.9(3) ų, Z = 4; for 3, space group = P2₁/n, a = 11.3570(10) Å, b = 19.465(2) Å, c = 15.5702(14) Å, = 104.776(2), V = 3328.3(5) ų, Z = 4; and for 4, space group = C2/c, a = 32.078(2) Å, b = 10.4741(6) Å, c = 19.0608(9) Å, = 94.315(2), V = 6386.1(6) ų, Z = 8.     

Crystal structure of bis(2,3,5-trimethylpyridine N-oxide) 2,4,6-trinitrophenolate: Cation complex tied by the extremely strong OHO hydrogen bonding

The salt of bis(2,3,5-trimethylpyridine N-oxide) 2,4,6-trinitrophenolate, C₂₂H₂₅N₅O₉, crystallizes in monoclinic space group C2/c with a=12.411(2)Å, b=15.326(3)Å, c=13.559(3)Å, =113.13(1)°, V=2371.8(8)ų, Z=4, D _c=1.410 mg/m³, F(000)=1056. The molecule of 2,3,5-trimethylpyridine N-oxide is protonated. Two pyridine N-oxide molecules are linked by extremely strong OHO hydrogen bonding (2.378(4)Å) to form a cation complex. CHO hydrogen bonding and – interactions also play important role in stablizing the structure of the salt.     

Racemic and (+)-ethyl 2-acetamido-2-carboxy-5-oxohexanoate

Racemic ethyl 2-acetamido-2-carboxy-5-oxohexanoate has been isolated by single hydrolysis of the corresponding diethyl ester and resolved essentially quantitatively by diastereomeric salt formation with (–)-quinine. The (+)-isomer was retrieved from the less-soluble quininium salt. Racemate crystals, (plusmn;)-1, are monoclinic, space group P2₁/c, a = 7.609(4)Å, b = 16.731(7)Å, c = 10.746(5) Å, = 99.83(4)° enantiomeric crystals, (+)-1, are monoclinic, space group P2₁, a = 5.857(2)Å, b = 15.282(4)Å, c = 7.618(2)Å, = 95.62(2)°. Molecular packing is similar in the two structures; the enantiomer has a 0.7% higher volume per molecule and the lower fusion temperatures by 3°C. In both structures, carboxylic acids donate hydrogen bonds to the amide carbonyls of adjacent molecules without reciprocation. Amides form three-centered hydrogen bonds to carboxy oxygen of an intramolecular carboxylic acid group and to oxygen of a ketone carbonyl in an adjacent molecule.     

The structures of three trimethylarsine-boron trihalide adducts: (CH3)3AsBCl3, (CH3)3AsBBr3, and (CH3)3AsBI3

An X-ray structure analysis of three trimethylarsine-boron trihalide adducts has been undertaken. Crystals of (CH₃)₃AsBCl₃ and (CH₃)₃AsBBr₃ are monoclinic with space groupP2₁/m (No. 11) withZ=2 while those of (CH₃)₃AsBI₃ are orthorhombic with space groupPnma (No. 62) withZ=4. For (CH₃)₃AsBCl₃,a=6.497(3) Å,b=10.735(3) Å,c=7.070(2) Å,=111.8(3)°,V=458.4(3) ų,R=0.0343. For (CH₃)₃AsBBr₃,a=6.672(4) Å,b=11.135(7) Å,c=7.199(4) Å,=111.5(1)°,V=497.7(5) ų,R=0.0434. For (CH₃)₃ÅsBI₃,a=13.113(7) Å,b=11.733(5) Å,c=7.387(3) Å,V=1136.5(5) ų,R=0.0329. The As-B bond lengths are 2.065(6), 2.04(1), and 2.03(1) Å, respectively, for the chloride, bromide, and iodide. These and other structural parameters are discussed with reference to previous predictions based on vibrational spectra and previous structural studies on the trimethyl-phosphine and trimethylamine adducts.     

Crystal structure of aquo (hydroxo) (ethylenediaminetetraacetato) sodium(I) tin(IV), NaSn(OH)(edta)(H2O)

NaSn(OH)(edta)(H₂O) is monoclinic, space groupP2₁/c, witha=9.747(3)Å,b=9.121(3)Å,c=16.430(6)Å, =98.69(4)°, ų, andZ=4. The coordination environment of Sn(IV) is a capped octahedron. Sn–O distances range from 1.990(6)Å to 2.351(7)Å. Na(I) is five coordinated to three different edta molecules. Na–O distances range from 2.283(9)Å to 2.414(7)Å. The edta ligand presents the E, G/R conformation. The crystal structure is composed of sheets parallel to (001): inside a sheet Sn(OH)(edta) molecules are connected to each other by the Na(I) interactions.     

Two-dimensional nickel(II) tetraaza macrocyclic complex linked by hydrogen bonds

The complex [Ni(L)](PDC) 2H₂O (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[16,4, 0^1.18,0^7.12]docosane; PDC = 3,5-pyrazoledicarboxylate) has been synthesized and characterized by X-ray crystallography. It crystallizes in the monoclinic system P2₁/c with a = 9.739(4) Å, b = 10.491(3) Å, c = 16.884(3) Å, = 97.17(2)°, V = 1711.5(8) ų, Z = 4. The coordination environment around the nickel(II) ion exhibits a slightly distorted square-plane with four secondary amines of the macrocycle. The title compound is interconnected to give a two-dimensional network through the hydrogen-bonding interactions.     

Crystal structures of (I) 2-(9,9-dipropylfluorene-2-yl)-9,9- dipropylfluorene and (II) 2-(1,1-dimethylpropyl)-7- {4-[(1,1-dimethylpropyl)-9,9-diethylfluoren-2-yl]phenyl}-9,9-diethylfluorene and (III) 2-(4-ethylphenyl) -7-[7-(ethylphenyl)-9,9-dipropylfluoren-2-yl]-9,9-dipropylfluorene

The crystal structures of the three fluorene related molecules, (I) 2-(9,9-dipropylfluorene-2-yl)-9,9-dipropylfluorene, [Exalite 384, C₃₈H₄₂], (II) 2-(1,1-dimethylpropyl)-7-{4-[(1,1-dimethylpropyl)-9,9-diethylfluoren-2-yl] phenyl}-9,9-diethylfluorene, [Exalite 404, C₅₀ H₅₈], and (III) 2-(4-ethylphenyl)-7-[7-(ethylphenyl)-9,9-dipropylfluoren-2-yl]-9,9-dipropylfluorene, [Exalite 416, C₅₄H₅₈], have been determined. Structural details reveal a novel new bonding arrangement at the C2 atoms of symmetry-related fluorene moieties in all three molecules producing a linear type array with an inversion center connecting adjacent asymmetric units within each molecule. Exalite 384 is monoclinic, space group P2₁/c with a = 9.002(2) Å, b = 16.275(4) Å, c = 10.525(1) Å, = 103.05(1), and V = 1502.1(5) ų with Z = 4, for d _calc = 1.103 g/cm³. Exalite 404 is triclinic, space group P1 with a = 10.383(1) Å, b = 13.404(2) Å, c = 7.7007(9) Å, = 105.296(9), = 104.23(1), = 73.707(9), and V = 974.9(2) ų with Z = 2, for d _calc = 1.141. Exalite 416 is monoclinic, space group P2₁/c with a = 15.99(10) Å, b = 11.178(8) Å, c = 23.766(4) Å, = 104.21(4), and V = 4117(4) ų with Z = 4, for d _calc = 1.141 g/cm³.     

Crystal structure of p-formylphenyl, di(p-methylphenyl)amine, and p-bromophenyl, di(o-bromo-p-methylphenyl)amine

p-Formylphenyl, di(p-methylphenyl)amine (1), and p-bromophenyl, di(o-bromo-p-methylphenyl)amine (2) were prepared and characterized by X-ray crystallography. Formyl-substituted triphenylamine(1) crystallizes in the monoclinic space group P2₁/c with a = 9.068(1), b = 17.115(2), c = 11.297(2) Å, = 106.73(1)°, V = 1679.0(5) ų and Z = 4. Bromo-substituted compound 2 crystallizes in the monoclinic space group P2₁/n with a = 16.170(4), b = 7.9477(8), c = 16.906(4) Å, = 117.67(2)°, V = 1924.1(7) ų and Z = 4. The N atoms deviate slightly from the plane of the bonded C atoms and the benzene ring planes are rotated by 25–67° to avoid overlap of the ortho-substituted atoms. The major force of crystal formation comes from the multiple phenyl embraces (MPE).     

The X-ray crystal structure of Hg(C6H4OMe-4) (C6F5): an unexpected twist

The X-ray crystal structure of Hg(C₆H₄OMe-4)(C₆F₅) reveals the first example of perpendicular rings in a diarylmercurial complex. Hg(C₆H₄OMe-4) (C₆F₅) crystallizes in monoclinic space group P2₁/c with a = 11.4004(14), b = 7.5683(9), c = 15.0247(18) Å, = 104.849 (2)° with calculated density 2.517 g cm^–3 for Z = 4.     

Synthesis, spectroscopy, magnetism, and X-ray structures of hexakis(1-(2-chloroethyl)-tetrazole-N4)copper(II) salts

The compounds hexakis(1-(2-chloroethyl)-tetrazole-N4)copper(II) tetrafluoroborate mono(1-(2-chloroethyl)-tetrazole) (1) and hexakis(1-(2-chloroethyl)-tetrazole-N4) copper(II) perchlorate mono(1-(2-chloroethyl)-tetrazole) (2) were obtained from the crystallization of 1-(2-chloroethyl)-tetrazole (teec) with the respective copper salt. The X-ray structures are reported. Both compounds crystallize in the monoclinic space group C2/c for 1: a = 25.754(3) Å, b = 18.162(3) Å, c = 10.298(2) Å = 104.294(7)° and Z = 4 and for 2: a = 25.745(3) Å, b = 18.197(3) Å, c = 10.29355(3) Å = 104.512(10)° and Z = 4. The Cu^II ions are octahedrally surrounded by six teec ligands. One free teec ligand is present in the structures. The Cu–N distances in the centrosymmetrical units are 2.01, 2.04, and 2.39 Å in both compounds, consistent with a Jahn–Teller elongated octahedron. The ligand field spectra of both compounds show a signal in the visible range at about 15.200 cm^–1 and by an EPR spectrum the following values are found: g _| = 2.29 and g = 2.03. The compounds are both paramagnetic and the T value of 0.37 cm^–1 K mol^–1, which is associated with S = 1/2, is what would be expected for a mononuclear Cu^II complex.     

Molecular structure of ThBr4(DME)2 (DME = 1,2-dimethoxyethane)

The molecular structure of ThBr₄(DME)₂ (DME = 1,2-dimethoxyethane), the first structurally characterized thorium complex containing a simple bidentate ether ligand, is described. The eight-coordinate complex presents a distorted dodecahedral geometry, with Th—Br and Th—O bond lengths in the ranges 2.8516(13)–2.8712(13) Å and 2.564(8)–2.620(8) Å, respectively. ThBr₄(DME)₂ is monoclinic, space group P2₁/n, a = 7.672(1), b = 14.581(1), c = 15.847(2) Å, = 102.24(1)°, V = 1732.4(3) ų, and Z = 4.     

Structure of bis(2-amino-5-methylpyridinium) tetrachlorozincate at 298 and 150 K

Reaction of 2-amino-5-methylpyridine with zinc chloride and HCl in aqueous solution yields bis(2-amino-5-methylpyridinium) tetrachlorozincate. The complex crystallizes in the monoclinic space group P2₁/c, with minimal tetrahedral distortion of the ZnCl₄ ^2– ion at both 298 and 150 K; at 298 K, a = 8.090(2) Å, b = 14.795(6) Å, c = 15.850(4) Å, = 101.93 (2); at 150 K, a = 8.0986(2) Å, b = 14.7190(5) Å, c = 15.7684(7) Å, = 102.862(2). The anisotropic cell contraction results in significant changes in nonbonding Cl Cl contacts.     

Synthesis and crystal structure of (Z)-1-(phenylsulphenyl)-2-phenylethenyl p-toluenesulfonate

The reaction between 1-phenylsulphenyl-2-phenylethyne and p-toluenesulfonic acid in methylene chloride gives (Z)-1-(phenylsulphenyl)-2-phenylethenyl p-toluenesulfonate (1) in good yields. This reaction is both a regio- and a stereospecific cis addition, confirmed by X-ray crystal structure analysis of the title compound. 1 crystallizes in the monoclinic space group P2₁/n with the lattice parameters a = 10.556(3), b = 9.730(3), c = 19.687(3) Å, = 105.05(2)°, V = 1952.7(8) ų, and Z = 4. The results of elemental analysis, IR and NMR spectroscopy are included.