Hexane‐1,6‐diaminium chloride [hydrogen bis(chloroacetate)]

In the structure of the title compound, C₆H₁₈N₂²⁺·H(C₂H₂ClO₂)₂⁻·Cl⁻, the hexane‐1,6‐diaminium dication is disordered over two sets of positions, with almost equal occupancies. Both alternative positions of the dication are in the fully extended conformation, situated on an inversion centre at (, , ). Two chloroacetic acid moieties, related by another centre of symmetry at (, , ), are connected by a very short symmetrical O...H...O hydrogen bond [O...O = 2.452 (2) Å], with the H atom at the centre of inversion. These two fragments thus effectively form the hydrogen bis(chloroacetate) monoanion, and the overall charge is balanced by an additional chloride anion which resides on a twofold axis. The ions form a layer structure, with alternating layers of dications and anions running along the [101] direction, linked via hydrogen bonds. There are two N—H...O interactions and two N—H...Cl⁻ interactions.     

The supramolecular architecture in 4,4′‐bipyridinium bis(hydrogen oxalate)

The asymmetric unit of the title compound, C₁₀H₁₀N₂²⁺·2C₂HO₄⁻, consists of one half of a 4,4′‐bipyridinium cation, which has inversion symmetry, and a hydrogen oxalate anion, in which an intramolecular hydrogen bond exists. The cations and anions are connected by O—H...O, N—H...O and C—H...O hydrogen bonds, forming a two‐dimensional network, whereas π–π stacking interactions involving the 4,4′‐bipyridinium cations lead to the formation of a three‐dimensional supramolecular structure. An unusual deca‐atomic ring is formed between two hydrogen oxalate anions, which are linked side‐to‐side via O—H...O hydrogen‐bonding interactions.     

Ethyl[tris(3‐tert‐butyl‐5‐methylpyrazol‐1‐yl)hydridoborato]zinc(II)

The X‐ray crystal structure of the title compound, [Zn(C₂H₅)(C₂₄H₄₀BN₆)], or Tp^tBu,MeZnEt [Tp^tBu,Me is tris(3‐tert‐butyl‐5‐methylpyrazolyl)hydridoborate], reveals a distorted tetrahedral geometry around the Zn atom. The Zn center is coordinated by three N atoms of the borate ligand and by one C atom of the ethyl group. The present structure and other tetrahedral Tp zinc alkyl complexes are compared with similar Ttz ligands (Ttz is 1,2,4‐triazolylborate), but no major differences in the structures are noted, and it can be assumed that variation of the substitution pattern of Tp or Ttz ligands has little or no influence on the geometry of alkylzinc complexes. Refinement of the structure is complicated by a combination of metric pseudosymmetry and twinning. The metrics of the structure could also be represented in a double‐volume C‐centered orthorhombic unit cell, and the structure is twinned by one of the orthorhombic symmetry operators not present in the actual structure. The twinning lies on the borderline between pseudomerohedral and nonmerohedral. The data were refined as being nonmerohedrally twinned, pseudomerohedrally twinned and untwinned. None of the approaches yielded results that were unambiguously better than any of the others: the best fit between structural model and data was observed using the nonmerohedral approach which also yielded the best structure quality indicators, but the data set is less than 80% complete due to rejected data. The pseudomerohedral and the untwinned structures are complete, but relatively large residual electron densities that are not close to the metal center are found with values up to three times higher than in the nonmerohedral approach.     

Monosodium [1‐hydroxy‐2‐(1H‐imidazol‐3‐ium‐4‐yl)ethane‐1,1‐diyl]bis(phosphonate) tetrahydrate (monosodium isozoledronate)

The title compound, Na⁺·C₅H₉N₂O₇P₂^?·4H₂O, is an isomer of zoledronate, a potent bone antiresorptive bis­phospho­nate drug having significant activity against several parasitic protozoa. The crystal structure of isozoledronate consists of bisphosphonate dimers coordinated by two Na⁺ ions. The dimers are held together through an extensive hydrogen‐bonding network. The crystals exhibit non‐merohedral twinning that roughly superimposes the a and b axes, and inverts the c axis.     

catena‐Poly[[silver(I)‐μ‐1,3‐bis(4‐pyridyl)propane] hemi(naphthalene‐1,5‐disulfonate) dihydrate]: a three‐dimensional metallo‐supramolecular sandwich lamellar network

The title compound, {[Ag(C₁₃H₁₄N₂)](C₁₀H₆O₆S₂)_0.5·2H₂O}_n, (I), features a three‐dimensional supramolecular sandwich architecture that consists of two‐dimensional cationic layers composed of polymeric chains of silver(I) ions and 1,3‐bis(4‐pyridyl)propane (bpp) ligands, linked by Ag...Ag and π–π interactions, alternating with anionic layers in which uncoordinated naphthalene‐1,5‐disulfonate (nds²⁻) anions and solvent water molecules form a hydrogen‐bonded network. The asymmetric unit consists of one Ag^I cation linearly coordinated by N atoms from two bpp ligands, one bpp ligand, one half of an nds²⁻ anion lying on a centre of inversion and two solvent water molecules. The two‐dimensional {[Ag(bpp)]⁺}_n cationic and {[(nds)·2H₂O]²⁻}_n anionic layers are assembled into a three‐dimensional supramolecular framework through long secondary coordination Ag...O interactions between the sulfonate O atoms and Ag^I centres and through nonclassical C—H...O hydrogen bonds.     

Bis(dihydronium) naphthalene‐1,5‐disulfonate

The title compound is a salt, 2H₅O₂⁺·C₁₀H₆O₆S₂²⁻, in which the anion lies across an inversion centre in the space group C2/c, while the cation contains a short but noncentred O—H...O hydrogen bond. The ionic components are linked by charge‐assisted O—H...O hydrogen bonds into a three‐dimensional framework structure.     

Phosphino[tris(trimethylsilyl)methyl]Boranes and 2,4‐Bis[tris(trimethylsilyl)methyl]‐1,3,2,4‐diphosphadiboretanes [1]

The reaction of tris(trimethylsilyl)methylboron dihalides (Me₃Si)₃CBX₂ (X = Cl, F) with the lithium phosphides LiPHtBu and LiPHmes leads to the phosphinoboranes (Me₃Si)₃CBX‐(PHR), (Me₃Si)₃CB(PHR)₂ or the 1,3,2,4‐diphosphadiboretanes [(Me₃Si)₃CB(PR)]₂, depending on the ratio of the reagents, the reaction temperature and concentration. High dilution and low temperatures are required for the synthesis of (Me₃Si)₃CB(Hal)PHR ( 1–3 ) in order to prevent the formation of (Me₃Si)₃CB(PHR)₂ ( 4 and 5 ). The latter compounds are best prepared in a two step phosphination from (Me₃Si)₃CBHal₂ and LiPHR. At higher temperatures the four‐membered 1,3,2,4‐diphosphadiboretanes [(Me₃Si)₃CB(PR)]₂ 6 and 7 are the most stable compounds. On the other hand, compounds of type (Me₃Si)₃CB(Hal)PR₂, 8 and 9 , are thermally more stable than the monophosphinoboranes 1 – 3 . Phosphinoboranes of type (Me₃Si)₃CB(PR₂)₂ (R = tBu, mes) could not be prepared. NMR and mass spectral data are in accord with the monomeric nature of compounds 1 to 9 .     

Hydrogen bis[tris(4‐fluorophenyl)phosphane oxide] triiodide

In the title compound, C₃₆H₂₅F₆O₂P₂⁺·I₃⁻, hydrogen‐bonded [{(p‐FC₆H₄)₃PO}₂H]⁺ dimers assemble along the crystallographic c axis to form channels that house extended chains of triiodide anions. Although the I—I bond lengths of 2.9452 (14) and 2.9023 (15) Å are typical, the inter‐ion I...I distance of 3.5774 (10) Å is unusually short. A posteriori modelling of nonmerohedral twinning about (100) has been only partially successful, achieving a reduction in the maximum residual electron density from 5.28 to 3.24 e Å⁻³. The inclusion of two low‐occupancy I‐atom sites (total 1.7%), which can be interpreted as translational disorder of the triiodide anions along the channels, reduced the maximum residual electron density to 2.03 e Å⁻³. The minor fractional contribution volume of the nonmerohedral twin domains refined to 0.24 and simultaneous refinement of the inversion twin domains showed the crystal to be a 0.5:0.5 inversion twin.     

Synthesis and antiosteoclast activity of Di(1‐oxo/thioxoperhydro‐1λ5‐[1,3,2] diazaphospholo [1,5‐a]pyridine‐1‐yl) (4‐substituted phenyl) boronates

A new family of di(1‐oxo/thioxoper‐hydro‐1λ⁵‐[1,3,2]diazaphospholo[1,5‐a]pyridine‐1‐yl)(4‐substituted phenyl) boronates ( 4a – j ) has been synthesized in a two‐step process. A reaction of (±)‐piperidin‐2‐yl‐methanamine ( 1 ) phosphoryl/phosphorothioyl chloride in the presence of triethylamine in dry tetrahydrofuran formed the intermediate monochloride ( 2 ), which on condensation with p‐substituted phenylboronic acids ( 3a – j ) afforded the titled compounds ( 4a – j ). They were characterized by elemental, IR, ¹H, ¹³C, ³¹P NMR, and mass spectral analyses. All these compounds showed moderate to high antiosteoclast and osteoblast activity. © 2012 Wiley Periodicals, Inc. Heteroatom Chem 23:247–253, 2012; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21010     

Unusual Coordination Modes of Tris(pyrazol‐1‐yl)borates: Synthesis and Solid State Structures of Sodium[(dimethylamino)tris(pyrazol‐1‐yl)borate], Potassium[(dimethylamino)tris(pyrazol‐1‐yl)borate], and Potassium[phenyltris(pyrazol‐1‐yl)borate]

We report the optimized syntheses and the solid state structures of the alkali metal tris(pyrazol‐1‐yl)borates M[Me₂NBpz₃] (M = Na⁺ ( 1 ), K⁺ ( 2 ); pz = pyrazol‐1‐yl) and K[PhBpz₃] ( 3 ). Even though 1 and 2 consist of polymeric chains in the solid state, it is possible to identify subunits where the [Me₂NBpz₃]^? ion acts as tridentate ligand towards Na⁺ and K⁺ and binds via two of its pyrazolyl rings and its dimethylamino nitrogen atom (κ³N_pz,N_pz,N_NMe). In 3 , the ligand [PhBpz₃]^? employs two pyrazolyl donors and the π‐face of its phenyl substituent for potassium coordination (κ³N,N,C).     

Di‐μ‐chloro‐bis({2‐[N,N‐bis(2‐aminoethyl)amino‐κ3N]ethylaminium}copper(II)) bis(naphthalene‐1,5‐disulfonate) pentahydrate

The title compound, [Cu₂(C₆H₁₉N₄)₂Cl₂](C₁₀H₆O₆S₂)₂·5H₂O, is comprised of discrete [Cu₂(tren)₂Cl₂]²⁺ dimers {tren is 2‐[N,N‐bis(2‐amino­ethyl)­amino]­ethyl­aminium} and naphthalene‐1,5‐di­sulfonate anions. Two Cl^? anions bridge two Cu^II ions, each of which is also coordinated by two of the primary and the tertiary amino N atoms of the tren ligand, giving each metal atom a distorted square‐pyramidal coordination geometry. The cation lies about an inversion centre and the asymmetric unit also has two independent anions lying about inversion centres.     

Magnetic investigations of a two‐dimensional coordination polymer with a three‐dimensional supramolecular framework: poly[[bis[μ2‐1,4‐bis(1,2,4‐triazol‐1‐yl)butane]bis(thiocyanato‐κN)cobalt(II)] dihydrate]

In the title mixed‐ligand metal–organic polymeric complex, {[Co(NCS)₂(C₈H₁₂N₆)₂]·2H₂O}_n, the asymmetric unit contains a divalent Co^II cation, which sits on an inversion centre, two halves of two crystallographically distinct and centrosymmetric 1,4‐bis(1,2,4‐triazol‐1‐yl)butane (BTB) ligands, one N‐bound thiocyanate ligand and one solvent water molecule. The Co^II atom possesses a distorted {CoN₆} octahedral geometry, with the equatorial positions taken up by triazole N atoms from four different BTB ligands. The axial positions are filled by thiocyanate N atoms. In the crystal, each Co^II atom is linked covalently to four others through the distal donors of the tethering BTB ligands, forming a neutral (4,4)‐topology two‐dimensional rhomboid grid layer motif, which is coincident with the (11) crystal planes. Magnetic investigations show that weak antiferromagnetic coupling exists between Co^II atoms in the complex.     

Solvent–metal interactions in bis[1,2‐dicarba‐closo‐dodecaboran(12)‐1‐yl]mercury(II) dichloromethane solvate and bis[1,12‐dicarba‐closo‐dodecaboran(12)‐1‐yl]mercury(II) tetrahydrofuran solvate

The title compounds, bis­[1,2‐dicarba‐closo‐dodecaboran(12)‐1‐yl]­mercury(II) di­chloro­methane solvate, [Hg(C₂B₁₀H₁₁)₂]·CH₂Cl₂, (I), and bis­[1,12‐dicarba‐closo‐dodecaboran(12)‐1‐yl]­mercury(II) tetra­hydro­furan solvate, [Hg(C₂B₁₀H₁₁)₂]·C₄H₈O, (II), were prepared in excellent yields using a robust synthetic procedure involving the reaction of HgCl₂ with the appropriate monoli­thiocarborane. X‐Ray analysis of the products revealed strong interactions between the Hg atoms in both complexes and the respective lattice solvent. The distances between the Hg^II centers and the Cl atoms of the dichloromethane solvent molecule in the ortho‐carborane derivative, (I), and the O atom of the tetra­hydro­furan molecule in the para‐carborane complex, (II), are shorter than the sums of the van der Waals radii for Hg and Cl (3.53 Å), and Hg and O (3.13 Å), respectively, indicating moderately strong interactions. There are two crystallographically independent mol­ecules in the asymmetric unit of both compounds, which, in each case, are related by differing relative positions of the cages.     

The coordination polymer poly[bis[μ2‐2‐(2,2′‐bi‐1H‐imidazol‐1‐yl)acetato]cadmium]

The title compound, [Cd(C₈H₇N₄O₂)₂]_n, crystallizes in the centrosymmetric triclinic space group P with an asymmetric unit consisting of a bivalent Cd^II atom and two 2‐(2,2′‐bi‐1H‐imidazol‐1‐yl)acetate (BDAC⁻) anions. Two inversion‐related BDAC⁻ ligands are oppositely arranged and bind two Cd^II ions to form a [Cd₂(BDAC)₂] rhomboid subunit which is bridged by another BDAC⁻ ligand to form an infinite ladder along the a direction containing parallelogram grids. The three‐dimensional supramolecular architecture is formed by hydrogen bonds and C—H...π and π–π interactions.     

The ansa‐zirconocene [bis(η5‐cyclopentadienyl)phenylphosphine]dichloridozirconium(IV)

In the title compound, [Zr(C₁₆H₁₃P)Cl₂], the geometry at the metal atom is distorted tetrahedral; the Cl—Zr—Cl angle is 101.490 (16)° and the cyclopentadienyl (Cp) centroids subtend an angle of 122.63 (3)° at the Zr atom. The P atom lies 0.474 (3) and 0.496 (3) Å out of the planes of the Cp rings. The C—P—C angle of 91.42 (7)° reflects the pincer effect of the two Cp rings. Three C—H...Cl, one C—H...P, one C—H...π and one Cl...P interaction link the molecules to form thick layers parallel to the bc plane.     

N‐[(R)‐1‐(2‐Hydr­oxy‐5‐methyl­phen­yl)­eth­yl]‐N‐[(R)‐1‐(2‐meth­oxy‐5‐methyl­phen­yl)‐2‐phenyl­eth­yl]aminium chloride

The title compound, C₂₅H₃₀NO₂⁺·Cl⁻, has been synthesized, and the crystal structure shows that it is mainly stabilized through inter­molecular N—H·Cl and O—H·Cl and intra­molecular N—H·O hydrogen bonds. The absolute configuration of the new stereogenic center (the C atom adjacent to the N atom on the phenol side) was determined to have an R configuration.     

Bis[μ‐1‐(1,10‐phenanthrolin‐2‐yl)‐2‐pyridone]bis{aqua[1‐(1,10‐phenanthrolin‐2‐yl)‐2‐pyridone]cadmium(II)} tetrakis(perchlorate)

In the title centrosymmetric binuclear complex, [Cd₂(C₁₇H₁₁N₃O)₄(H₂O)₂](ClO₄)₄, the Cd^II ion assumes a distorted octahedral geometry. There are π–π stacking interactions between the pyridine and 1,10‐phenanthroline ring systems of adjacent ligands at the same Cd^II centre. Intermolecular hydrogen bonds between the coordinated aqua ligand and the O atom of a keto group connect adjacent complex cations into extended chains. Hydrogen bonds also exist between the complex cations and the perchlorate anions. Compared with the fluorescence spectrum of the organic ligand, the complex displays strong fluorescent emission and an ipsochromic shift of the emission peaks, which may be attributed to the structural character.     

Two molybdenum pentacarbonyl complexes with electroneutral phosphane ligands: [bis(morpholin‐4‐yl)(pentafluoroethyl)phosphane‐κP]pentacarbonylmolybdenum(0) and pentacarbonyl[(pentafluoroethyl)bis(piperidin‐1‐yl)phosphane‐κP]molybdenum(0)

The crystal structures of the title compounds, [Mo{(C₄H₈NO)₂P(C₂F₅)}(CO)₅], (1a), and [Mo{(C₅H₁₀N)₂P(C₂F₅)}(CO)₅], (2a), were determined as part of a larger project that focuses on the synthesis and coordination chemistry of phosphane ligands possessing moderate (electroneutral, i.e. neither electron‐rich nor electron‐deficient) electronic characteristics. Both complexes feature a slightly distorted octahedral geometry at the metal center, due to the electronic and steric repulsions between two of the four equatorial CO groups and the pentafluoroethyl group attached to the phosphane ligand. Bond length and angle data for (1a) and (2a) support the conclusion that the free phosphane ligands are electroneutral. For complex (1a), the Mo—P, Mo—C_ax and Mo—C_eq(ave) bond lengths are 2.5063 (5), 2.018 (2) and 2.048 (2) Å, respectively, and for complex (2a) these values are 2.5274 (5), 2.009 (3) and 2.050 (3) Å, respectively. Geometric data for (1a) and (2a) are compared with similar data reported for analogous Mo(CO)₅ complexes.     

Synthesis of some symmetrically substituted compounds derived from 1,3‐bis(6‐azauracil‐1‐yl)benzene and 1,3,5‐tris(6‐azauracil‐1‐yl)benzene

The 3,5‐bis(5‐carboxy‐6‐azauracil‐1‐yl)aniline ( 7 ) and 1,3,5‐tris(5‐carboxy‐6‐azauracil‐1‐yl)benzene ( 10 ) were prepared from 3‐amino‐5‐nitroacetanilide ( 1 ) via intermediates 2–6 . A series of other substituted 6‐azauracil derivatives 9, 11‐14 were also prepared.