Symmetry-related Anions Research Articles

Crystal structure of the salt bis-(tri-ethano-lamine-κ(4) N,O,O',O'')cadmium bis[2-(2-oxo-2,3-di-hydro-1,3-benzo-thia-zol-3-yl)acetate

The reaction of 2-(2-oxo-2,3-di-hydro-1,3-benzo-thia-zol-3-yl)acetic acid (NBTA) and tri-ethano-lamine (TEA) with Cd(CH3OO)2 resulted in the formation of the title salt, [Cd(C6H15NO3)2](C9H6NO3S)2. In its crystal structure, the complex cation [Cd(TEA)2](2+) and two independent NBTA(-) units with essentially similar geometries and conformations are present. In the complex cation, each TEA mol-ecule behaves as an N,O,O',O''-tetra-dentate ligand, giving rise to an eight-coordinate Cd(II) ion with a bicapped trigonal-prismatic configuration. All ethanol groups of each TEA mol-ecule form three five-membered chelate rings around the Cd(II) ion. The Cd-O and Cd-N distances are in the ranges 2.392 (2)-2.478 (2) and 2.465 (2)-2.475 (3) Å, respectively. O-H⋯O hydrogen bonds between the TEA hy-droxy groups and carboxyl-ate O atoms connect cationic and anionic moieties into chains parallel to [110]. Each NBTA(-) anion is additionally linked to a symmetry-related anion through π-π stacking inter-actions between the benzene and thia-zoline rings [minimum centroid-to-centroid separation = 3.604 (2) Å]. Together with additional C-H⋯O inter-actions, these establish a double-layer polymeric network parallel to (001).

I5–polymers with a layered arrangement: synthesis, spectroscopy, and structure of a new polyiodide salt in the nicotine/HI/I2system

AbstractThe reaction ofS-nicotine with hydroiodic acid in the presence of iodine gave the new polyiodide-containing salt nicotine-1,1′-diium bis(triiodide)-diiodine (1/1) (C10H16N2) [I3]2·I2(1). The title compound has been characterised by spectroscopic methods (Raman and IR) and single-crystal X-ray diffraction. The asymmetric unit of the title structure consists of one dication, two triiodide anions, and one iodine molecule, all located in general positions in the non-centrosymmetric space groupP1. One of the two crystallographically independent triiodide anions and the doubly protonated nicotinium dication form hydrogen-bonded chains alongb, which are arranged parallel to each other in the ½bcplane. The second crystallographically independent triiodide anion and the iodine molecule form an I5–moiety, which is end-on connected to two symmetry-related anions resulting in polyiode zig–zag chains along the [0 1 1̅] direction. These polyiodide chains are stacked parallel to each other in the 0bcplane. The Raman spectrum of the title compound shows characteristic lines in the 50–200 cm–1range, which are in excellent agreement with the findings derived from the crystal structure.

Catena-Poly[[diaquacobalt(II)]-μ2-7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylato-κ4O2,O3,O7:O2′

The polymeric title complex, [Co(C8H8O5)(H2O)2]n was synthesized by reaction of cobalt acetate with 7-oxabicyclo­[2,2,1]heptane-2,3-dicarb­oxy­lic anhydride. The CoII ion is six-coordinated in a distorted octa­hedral environment, binding to two water O atoms, to the ether O atom of the bicyclo­heptane unit, to two carboxyl­ate O atoms from two different carboxyl­ate groups of the same anion and to one carboxyl­ate O atom from a symmetry-related anion. The bridging character of the dianion leads to the formation of ribbons along [001]. The ribbons are linked into a layered network parallel to (010) by several O—H⋯O hydrogen-bonding inter­actions involving the coordinating water mol­ecules as donors and the carboxyl­ate O atoms of neighbouring ribbons as acceptors. The crystal under investigation was an inversion twin.

N,N'-Bis(2-amino-benz-yl)ethane-1,2-diaminium bis-(4-methyl-benzene-sulfonate).

The title salt, C16H24N4 2+·2C7H7O3S−, crystallizes with the dication situated on an inversion center and the anion in a general position. The cation contains two ammonium and two free amine groups, and the observed conformation for the chain linking the benzene rings is different from that found in the free tetra­amine and in the fully protonated tetra­amine. All amine and ammonium H atoms of the cation form hydrogen bonds with eight symmetry-related anions, using the sulfonate O atoms as acceptors. This arrangement for the ions precludes any π–π contacts between benzene rings in the crystal.

2-Aminopyrimidinium dihydrogen phosphate monohydrate

In the title compound, C4H6N3 +·H2O4P−·H2O, the pyrimidin­ium ring is essentially planar, with an r.m.s. deviation of 0.0016 Å. In the structure, pairs of symmetry-related anions are connected into centrosymmetric clusters via strong O—H⋯O hydrogen bonds forming six-membered rings with an R 2 2(6) motif. These clusters are inter­connected via water mol­ecules through OW—H⋯O hydrogen bonds, building an infinite layer parallel to the ab plane. Moreover, infinite chains of 2-amino­pyrimidinium cations spread along the a-axis direction. These chains are connected to the inorganic layer through N—H⋯O, C—H⋯O and C—H⋯N hydrogen bonds, which, together with electrostatic and van der Waals inter­actions, contribute to the cohesion and stability of the network in the crystal structure.

(5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene)nickel(II) bis[O,O′-bis(4-tert-butylphenyl) dithiophosphate

The title salt, [Ni(C16H32N4)](C20H26O2PS2)2, comprises a centrosymmetric [Ni(Me6[14]dieneN4)]2+ dication (Me6[14]dieneN4 is 5,7,7,12,14,14-hexa­methyl-1,4,8,11-tetra­aza­cyclo­tetra­deca-4,11-diene) and two O,O′-bis­(4-tert-butyl­phen­yl) dithio­phosphate anions. The NiII ion lies on an inversion centre and displays a slightly distorted NiN4 square-planar chelation arrangement with four N atoms from the Me6[14]dieneN4 macrocycle. Two S atoms from symmetry-related anions are located in pseudo-axial positions with respect to the NiII ion, with Ni⋯S distances of 3.2991 (7) Å. Inter­molecular N—H⋯S and C—H⋯S hydrogen bonds link the complex cation and pair of anions into a 1:2 type salt.

(C-meso-N-meso-5,12-Dimethyl-7,14-diphenyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene)nickel(II) bis[O,O′-bis(4-methylphenyl) dithiophosphate

The title complex, [Ni(C24H32N4)](C14H14O2PS2)2, comprises a centrosymmetric [Ni(meso-diphen­yl[14]dien)]2+ dication (meso-diphen­yl[14]dien is C-meso-N-meso-5,12-dimethyl-7,14-diphenyl-1,4,8,11-tetra­aza­cyclo­tetra­deca-4,11-diene) and two O,O′-bis­(4-methyl­phen­yl) dithio­phosphate anions. The NiII ion lies on an inversion center and is chelated by a tetra­amine macrocycle ligand in a slightly distorted NiN4 square-planar geometry. Two S atoms from symmetry-related anions are located in pseudo-axial positions with respect to the NiII ion, with Ni⋯S distances of 3.1869 (8) Å. In the crystal, bifurcated inter­molecular N—H⋯S(S) hydrogen bonds connect cations and pairs of anions into three-component clusters. Weak inter­molecular C—H⋯S hydrogen bonds link these clusters into chains along [100].

Poly[[aquacalcium(II)]-μ4-1H-imidazole-4,5-dicarboxylato

In the title compound, [Ca(C5H2N2O4)(H2O)]n, the Ca2+ cations are eigthtfold coordinated by six O atoms and one N atom of four symmetry-related anions and one water mol­ecule within an irregular polyhedron. These CaO7N polyhedra are connected via the anions into a three-dimensional network. The anions are additionally linked by N—H⋯O and O—H⋯O hydrogen bonding.

Di-n-butylammonium 2-[(3,5-di-tert-butyl-4-hydroxybenzyl)sulfanyl]benzoate

The title salt, C8H20N+·C22H27O3S−, is a proton-transfer compound derived from the recently reported parent carb­oxy­lic acid [Alhadi et al. (2010). Acta Cryst. E66, o1787] by the addition of a second equivalent of di-n-butyl­amine, yielding the di-n-butyl­ammonium carboxyl­ate salt. The structure of the carboxyl­ate anion resembles that of the parent carb­oxy­lic acid. The main difference lies in the position of the H atom in the 4-hy­droxy group. In the anion the O—H bond is perpendicular, rather than parallel, to the benzyl ring. This position appears to facilitate hydrogen bonding to an O atom of the carboxyl­ate group of a symmetry-related anion. In addition, there are three N—H⋯O hydrogen bonds. In contrast, the neutral species hydrogen bonds via a carboxylic acid dimer. The dihedral angle between the benzene rings in the anion is 79.19 (7)°.

Poly[(μ-4,4′-bipyridine)(μ-naphthalene-1,4-dicarboxylato)iron(II)

The asymmetric unit of the title compound, [Fe(C12H6O4)(C10H8N2)], consists of two independent Fe(II) atoms, two naphthalene-1,4-dicarboxyl­ate anions and two 4,4′-bipyridine ligands. The Fe(II) atoms are each coordinated by four O atoms of the naphthalene-1,4-dicarboxyl­ate anions and two N atoms of the 4,4′-bipyridine ligands within a distorted octa­hedron. Two Fe(II) atoms are bridged via the carboxyl­ate groups of two symmetry-related anions into dimers, which are further connected into chains. These chains are linked by additional anions into layers that are finally connected by the 4,4′-bipyridine ligands into a three-dimensional coordination network.

Dicyclohexylammonium bis(chlorodifluoroacetato-κO)cyclopentyldiphenylstannate(IV)

The five-coordinate Sn atom in the title mixed organyl stannate compound, (C12H24N)[Sn(C5H9)(C6H5)2(C2ClF2O2)], is in a trans-C3SnO2 trigonal–bipyramidal coordination environment. The NH2 groups of the cations act as hydrogen-bond donors to two symmetry-related anions, resulting in the formation of linear chains. One of the phenyl rings is disordered over two sites with equal occupancies.

2-Aminopyridinium 2-hydroxy-2,2-diphenylacetate

In the title salt, C5H7N2 +·C14H11O3 −, the cation and anion interact through N—H...O hydrogen bonds involving the protonated NH group of the cation and the hydroxyl group of the anion. Both H atoms of the NH2 group in the cation are engaged in N—H...O hydrogen bonds with the carbonyl groups of two symmetry-related anions, forming an infinite one-dimensional chain in the [100] direction.

Bis(2-aminopyridinium) diaquabis(malonato-κ2O,O′)cuprate(II)

The CuII ion in the title compound, (C5H7N2)2[Cu(C3H2O4)2(H2O)2], is located on an inversion centre and coordinated by four O atoms from two bidentate malonate (mal) ligands in the equatorial plane and two O atoms from two coordinated water mol­ecules in the axial positions, forming an elongated octa­hedral geometry. Each [Cu(mal)2(H2O)2]2− anion bridges two 2-amino­pyridinium cations via N—H⋯O hydrogen bonds and symmetry-related anions via O—H⋯O hydrogen bonds, to form an infinite one-dimensional chain. Additional O—H⋯O and C—H⋯O hydrogen bonds generate two-dimensional sheets that are joined into a three-dimensional network via N—H⋯O, C—H⋯O and inter­layer π–π inter­actions between amino­pyridinium cations (symmetry code: 1-x,1-y,2-z).

Poly[hexaaquatris(μ3-3-carboxypyrazole-5-carboxylato)(3-carboxypyrazole-5-carboxylato-κO)(μ2-pyrazole-3,5-dicarboxylato)dicerium(III)

In the title compound, [Ce2(C5H2N2O4)(C5H3N2O4)4(H2O)6]n, each Ce atom is nine-coordinated by three water mol­ecules, four 3-carboxy­pyrazole-5-carboxyl­ate monoanions (two pairs of symmetry-related anions), and a pyrazole-3,5-dicarboxyl­ate dianion. Two symmetry-related Ce atoms are bridged by a pyrazole-3,5-dicarboxyl­ate dianion, which lies across a twofold rotation axis. There are two independent 3-carboxy­pyrazole-5-carboxyl­ate monoanions which differ in their coordination modes; one is monodentate and the other is tetra­dentate. The Ce atoms are bridged by both pyrazole-3,5-dicarboxyl­ate dianions and 3-carboxy­pyrazole-5-carboxyl­ate monoanions, generating a three-dimensional network structure.

Bis(μ-5-chloro-2-hydroxyacetophenone 4-nitrobenzoylhydrazonato)bis[dipyridinecadmium(II)

The title dinuclear complex, [Cd2(C15H10ClN3O4)2(C5H5N)4], lies on a centre of inversion. The deprotonated Schiff base spans the meridional sites of the octahedron surrounding the Cd atom through its O, N and O atoms; the hydroxy O atom of the symmetry-related anion forms a square plane with these atoms, and the other two sites of the octahedron are occupied by the N atoms of the pyridine ligands.

Synthesis and Structural Studies of Cationic Bis- and Tris(pyrazol-1-yl)methane Acyl and Methyl Complexes of Ruthenium(II): Localization of the Counterion in Solution by NOESY NMR Spectroscopy

Complex fac-Ru(PMe3)(CO)3(Me)I (1) reacts with tris- and bis(pyrazol-1-yl)methane, in the presence of NaBPh4, affording cis-[Ru(PMe3)(CO)2(COMe)(η2-pz3-CH)]BPh4 (2) and cis-[Ru(PMe3)(CO)2(COMe)(pz2-CH2)]BPh4 (4), respectively. Complexes 2 and 4 decarbonylate leading to [Ru(PMe3)(CO)(COMe)(η3-pz3-CH)]BPh4 (3) and a mixture of three methyl stereoisomers of cis-[Ru(PMe3)(CO)2(Me)(pz2-CH2)]BPh4 (5−7), respectively. The byproduct of the synthesis of 1, fac,cis-Ru(PMe3)(CO)3(I)2 (8), reacts with bis(pyrazol-1-yl)methane affording cis-[Ru(PMe3)(CO)2(I)(pz2-CH2)]BPh4 (9). The stereochemistry of the complexes, the dynamic processes existing between them, and the interionic structures of all of the cationic complexes were investigated by the phase-sensitive 1H NOESY NMR spectra in CD2Cl2. The solid-state crystal structure of 4, obtained by single-crystal X-ray studies, was compared from the intramolecular and interionic point of views with that in solution with the help of 3-21G* ab initio and AMI−SM2 semiempirical quantum mechanical and docking mechanic calculations. In particular, the differences of interaction energy of the six solid-state ion pairs determined by the cation and the six symmetry-related anions surrounding it were estimated. The main result is that the averaged preferred position of the counterion in solution corresponds to the ion-pair electrostatically (ΔEel > 2.5 kcal/mol) and “sterically” (ΔEst > 3.7 kcal/mol) favored in the solid state.

Bis(acetonitrile-N)(1,4,8,12-tetraazacyclopentadecane)nickel(II) Bis(triiodide) and (1,4,8,12-Tetraazacyclopentadecane)palladium(II) Bis(triiodide)

In the first title compound, [Ni(C 2 H 3 N) 2 (C 11 H 26 N 4 )](I 3 ) 2 , the Ni II centre is coordinated octahedrally: all four N-donor atoms of the macrocyclic ligand occupy an equatorial plane and the coordination is completed by two axial acetonitrile ligands. Each N-H group forms a contact of 2.97-3.11 A to one I atom of an I 3 - anion. One of these anions participates in long I. . .I contacts of 4.008(3)A to form infinite chains of symmetry-related anions. In the second title compound, [Pd(C 11 H 26 N 4 )](I 3 ) 2 , each Pd II centre is coordinated in an equatorial plane by four N-donor atoms from the macrocyclic ligand and axially by a terminal iodine from each of two I 3 - anions at 3.525 (4) A. The same I atom forms an I...I contact of 4.094(3) A such that cations and pairs of anions alternate within one-dimensional zigzag chains.

Tetranuclear Ag(I) complexes with an octagonal Ag 4S 4 core: building large structures from small macrocycles

Reaction of the thioether macrocycles TT[9]OC and Me 2TT[9]OC with Ag + salts in a 1:1 ratio produces unique tetrameric cations containing an octagonal [Ag 4S 4] 4+ cavity. The X-ray crystal structures of three of these aggregates {[AgL][X]}4 (X =BF 4 −, L = TT[9]OC; X = CF 3SO 3 −, L = TT[9]OC; X = BF 4 −, L = Me 2TT[9]OC) were determined. In each case, the thiacyclophane ligand bonds in a facial coordination mode to one Ag(I) ion with the central S-donor bridging to the next Ag(I) ion. This completes a pseudotetrahedral geometry and results in cyclic tetramers with a [AgS] 4 4+ octagonal core. Each structure has two symmetry related anions (BF 4 − or CF 3SO 3 − included over the opposing faces of the large tetracationic cavity. {[Ag(TT[9]OC)][BF 4]} 4·2(MeCN): C 52H 70B 4F 16N 2S 12, P2 1 c , a=14.525(7), b=16.703(11), c = 16.250(6) Å, β = 115.54(3)°, V = 3557(6)Å 3 and Z=2. {[Ag(TT[9]OC)][CF 3SO 3]} 4: C 52H 64Ag 4F 12O 12S 16, P2 1 c , a=12.308(2), b=23.381(4), c=14.018(2) A, β = 113.30(1)°, V = 3705(5)Å 3 and Z=2. {[Ag(Me 2[9]OC)][BF 4]} 4·2(MeCN): C 60H 86Ag 4B 4F 16N 2S 12, P2 1 c , a=14.878(8), b=17.356(7), c = ]6.804([1) Å, P = 114.95(4)°, V = 3934(4) A3 and Z = 2.