SYNTHESIS AND STRUCTURE OF A POLYMERIC 1,3-BENZENEDICARBOXYLATO COMPLEX OF Mn(II) WITH PHENANTHROLINE

Abstract

A novel Mn(II) complex bridged by 1,3-benzenedicarboxylate (BDC) has been synthesized by the diffusion method. The complex crystallizes in space group P2₁/c with a = 8.345(2), b = 10.427(1), c = 18.756(2) Å, β = 100.19(1)°. Each BDC bridges three Mn(II) atoms through two carboxyl groups with different coordination modes to form a complex polymeric chain. The coordination geometry around the Mn(II) atom is seriously distorted from the normal octahedron. Large deviations of the donor atoms out of the coordination planes and unexpected bond angles around Mn(II) and donor O atoms suggest the existence of an electrostatic interaction between Mn(II) and donor atoms in the complex. Close stacking of aromatic rings is observed in the complex, the distance between the neighboring phen planes being 3.2085 Å.     

SYNTHESIS,CHARACTERIZATION AND CRYSTAL STRUCTURE OF A COMPLEX OF EUROPIUM PERCHLORATE WITH METHYLENE BIS(DIPHENYLPHOSPHINE OXIDE)

Abstract

A complex of europium perchlorate with methylene bis(diphenylphosphine oxide) (HMPPO), [Eu(HMPPO)₄](ClO₄)₃·2H₂O has been synthesized and characterized by X-ray crystallography, infrared spectroscopy and thermal analysis. The X-ray structure of the complex shows Eu(III) is coordinated by eight oxygen atoms from four HMPPO ligands, forming a distorted square antiprism coordination geometry. The complex crystallizes in space group P-1 with cell parameters a = 15.807(3), b = 17.868(4), c = 20.656(4) Å, α = 86.85(3)°, β = 82.33(3)°, γ = 66.75(3)°. The final R_l and R_w are 0.0803 and 0.1994, respectively, for 9540 observed reflections [I > 2[sgrave](I)]. Its luminescent properties have also been studied.     

The Structure of cis‐[Chloro(dimethylsulfoxide)bis(1, 10‐phenanthroline)ruthenium(II)]‐tetraphenylborate, [RuCl(DMSO)(1, 10‐phen)2][BPh4]

The complex cis‐[RuCl(DMSO)(phen)₂]BPh₄, where DMSO is dimethylsulfoxide and phen is 1, 10‐phenanthroline, crystallizes in the monoclinic space group P2₁/c with a = 19.505(4), b = 10.045(2), c = 21.199(4) Å, β = 90.137(4)°, V = 4153(2) ų, Z = 4, D_calc = 1.430 g cm^—3. The ruthenium coordination geometry is that of a slightly distorted octahedron with a cis‐RuN₄ClS arrangement of the ligand donor atoms. The Ru—Cl distance is 2.421(1) Å and the Ru—S distance 2.250(2) Å. The four Ru—N distances are 2.057(6), 2.066(4), 2.073(4), and 2.086(4) Å with the Ru—N bond trans to Cl the second shortest and the Ru—N bond trans to S the longest one.     

Bridging chlorides and hydroxides: syntheses and crystal structures of binuclear and tetranuclear NiII complexes derived from a reduced Schiff-base ligand 2-(2-pyridylmethylamino)ethanesulfonic acid

Two complexes, [Ni(pmt)(Cl)] (1) and [Ni₄(pmt)₄(OH)₄]·8H₂O (2) [Hpmt = 2-(2-pyridylmethylamino)ethanesulfonic acid], were synthesized by different experimental methods in methanol-water mixed solution. Compound 1 crystallizes in triclinic, space group P?1 with unit cell parameters: a = 8.315(2) Å, b = 8.383(2) Å, c = 9.128(2) Å, α = 103.654(2)°, β = 98.125(2)°, γ = 113.154(2)°, V = 548.6(2) ų, Z = 2. A pair of chlorides is μ ₂-bridges linking two Ni^II atoms in forming binuclear complex 1. The coordination environment at Ni^II is distorted square-pyramidal geometry. Compound (2) belongs to monoclinic, space group C2/c, with a = 16.5168(15) Å, b = 18.3718(17) Å, c = 17.5473(16) Å, α = γ = 90°, β = 93.3820(10)°, V = 5315.3(8) ų, Z = 4. Four hydroxides are μ ₃-bridges joining four Ni^II atoms to generate a cubic framework as a tetranuclear complex. The configuration at each Ni^II is distorted octahedral. Both π–π stacking of pyridine rings and intermolecular hydrogen bonds stabilize the solid state structures for 1 and 2.     

TRANSITION METAL COMPLEXES WITH THIOSEMICARBAZIDE-BASED LIGANDS. PART 25. SYNTHESIS AND X-RAY CRYSTAL STRUCTURE OF CIS-DIOXO [(SALICYLALDEHYDE THIOSEMICARBAZONATO(1-))] AQUOMOLYBDENUM (VI)CHLORIDE MONOHYDRATE, [MoO2(HL)H2O]Cl·H2O

Abstract

The synthesis and crystal structure analysis of the diamagnetic complex [MoO₂(HL)H₂O]Cl·H₂O(HL = monoanion of salicylaldehyde thiosemicarbazone) are reported. The complex crystallizes in the space group P2₁/a (No. 14) with a = 11.003(1), b = 8.444(1), c = 15.364(1) Å, β = 104.96(1)°, V = 1379.1(2) ų. X-ray structure determination revealed that the complex possesses the usual cis-MoO₂ ²⁺ core and that the thiosemicarbazide ligand is present as a monoanionic tridentate donor coordinating through ONS. According to a search in the Cambridge Structural Database (state April 1994) this complex is the first in which the sixth coordination site at Mo(VI) is occupied by a water molecule forming a distorted octahedral coordination geometry together with the tridentate ligand.     

THE CRYSTAL AND MOLECULAR STRUCTURE OF BIS(p-NITROPHENACETURO)DIAQUOCOPPER(II)

Abstract

The crystal and molecular structure of [Cu(p-NO₂C₆ H₅CH₂CONHCH₂CO₂)₂ (H₂O)₂] has been determined by single-crystal, x-ray diffraction techniques. The compound is centrosymmetric crystallizing in a monoclinic unit cell (P2₁/c) with two molecules per unit cell. The cell dimensions are: a = 11.588(1)A, b = 11.405(1)A, c = 8.041(1)Å and β = 93.47 · (1). The structure was solved by Patterson methods and refined to a value of R = 0.063. The coordination about the copper assumes an unexpected square planar geometry in which two phenaceturic moieties are each coordinated through the carboxylic oxygen (Cu—O = 1.933A) and the two waters complete the coordination (Cu—O_w = 1.959Å). The overall conformation of the phenaceturic acid is retained although there is a rotation of 180° about the peptide C—N bond.     

SYNTHESIS,CHARACTERIZATION AND STRUCTURAL ANALYSES OF THREE LANTHANIDE CYANIDE-BRIDGED COMPLEXES

Abstract

Three lanthanide (Ln) complexes (DMF)₄(H₂O)₃LnFe(CN)₆ · H₂O, where Ln = Er, Yb, and Lu, were structurally determined by means of three-dimensional single-crystal X-ray diffraction analysis. These systems crystallize in the centrosymmetric monoclinic space group P2₁/c (No. 14) with Z = 4 and respective lattice constants of a = 13.956(2), 13.952(1), 13.937(3); b = 8.867(4), 8.864(1), 8.862(2); c = 24.857(3), 24.812(2), 24.770(5) Å; and β = 96.30(1)°, 96.33(1)°, 96.30(3)°. Final least-squares full-matrix refinements based on 3499, 3367, and 2555 unique reflections yielded reliability (R) index factors of 0.071, 0.051, and 0.032, respectively. In each complex, the coordination about the central Ln ion is eight in a square-antiprism arrangement and the coordination about the Fe ions is six, oriented octahedrally. Cyanide bridging links the Ln ions to the FeC₆ groups. Molecules in the crystal lattice of each complex are held together by van der Waals forces and a network of hydrogen bonding. Characterization includes physical property determinations, conoscopical studies, thermal gravimetric analyses, and IR spectrometric identifications. Selected bond lengths and angles are tabularized and a synthesis of these compounds is presented.     

A 3-D cobalt(II)-coordination polymer with mixed-connected network topology constructed from 4-pyridin-3-yl-benzoic acid

A new coordination polymer, [Co₂(μ-H₂O)(4,3-pybz)₄] _n (1), has been hydrothermally synthesized from Co(NO₃)₂ · 6H₂O and an unsymmetrical 4-pyridin-3-yl-benzoic acid (4,3-Hpybz), which is characterized by IR, elemental analysis, thermogravimetric analysis, and single crystal X-ray diffraction. This compound crystallizes in monoclinic, space group C2/c with a = 11.876(3) Å, b = 15.462(3) Å, c = 21.545(4) Å, β = 94.873(5)°, V = 3942.0(15) ų, Z = 4, Dc = 1.565 g cm^?3, F(000) = 1904, GOF = 1.025, μ = 0.910 mm^?1, R ₁ = 0.0456, wR ₂ = 0.0983. Compound 1 shows a 3-D (3,6)-connected coordination framework with (3.4.5)(3².4⁴.5⁵.6².7²) topology, in which cobalt is a six-connected node, and the 4,3-Hpybz ligands serve as two-connected spacers and three-connected nodes. In addition, the magnetic and thermal properties of 1 have also been investigated.     

Syntheses and crystal structures of Zn(II) and Co(II) complexes with ofloxacin and enoxacin

[Zn(Ofl) · (H₂O)] · 2H₂O (1) and [Co(Enox)₂] · 4H₂O (2) were obtained by hydrothermal reactions. The solid-state structures have been characterized by IR spectroscopy and single crystal X-ray diffraction analyses. Complex 1 crystallizes in the triclinic system, space group P 1, with lattice parameters a = 9.2923(5), b = 11.3432(6), c = 17.7722(10) Å, α = 92.839(3), β = 94.826(3), γ = 91.909(3)°, V = 1863.01(18) ų, Z = 2, D _Calcd = 1.494 mg m^?3. The coordination environment around Zn²⁺ is a slightly distorted square pyramid. Complex 2 crystallizes in the triclinic system, space group P2(1)/c, with lattice parameters a = 5.97980(10), b = 21.4183(3), c = 13.1539(2) Å, V = 100.2810(10), Z = 2, D _Calcd = 1.526 mg m^?3, Co(II) ion is a distorted octahedral geometry.     

Dinuclear copper(II) complex and 1-D copper(II) complex with taurine Schiff base: synthesis,crystal structure,and properties

A dinuclear copper(II) compound, [Cu(btssb)(H₂O)]₂ · 4(H₂O) (1), and a 1-D chain copper(II) compound, [Cu(ctssb)(H₂O)] _n (2) [where H₂btssb is 2-[(5-bromo-2-hydroxy-benzylidene)-amino]-ethanesulfonic acid and H₂ctssb is 2-[(3,5-dichloro-2-hydroxy-benzylidene)-amino]-ethanesulfonic acid], were prepared and characterized. Compound 1 crystallizes in the monoclinic space group P2₁/c, with a = 10.109(2) Å, b = 20.473(4) Å, c = 6.803(1) Å, β = 100.32(3)°, V = 1385.1(5) ų, and Z = 2; R ₁ for 1796 observed reflections [I > 2σ(I)] was 0.0357. The geometry around each copper(II) can be described as slightly distorted square pyramidal. The Cu^II ··· Cu^II distance is 5.471(1) Å. Compound 1 formed a 1-D network through O–H ··· O hydrogen bonds and 1-D water chains exist. The 1-D chain complex 2 crystallizes in the triclinic space group P 1, with a = 5.030(2) Å, b = 7.725(2) Å, c = 17.011(5) Å, α = 92.706(4)°, β = 97.131(4)°, γ = 102.452(3)°, V = 638.6(3) ų, and Z = 2; R ₁ for 1897 observed reflections [I > 2σ(I)] was 0.0171. In 2, Cu(II) was also a slightly distorted square pyramid formed by two oxygens and one nitrogen from ctssb, one oxygen from another ctssb, and one water molecule. The complex formed a 1-D chain through O–S–O bridge of ctssb ligand. The 1-D chain further constructed a double chain through O?H ··· O hydrogen bonds.     

Synthesis,characterization and crystal structures of two alkaline-earth metal complexes of olsalazine

Two one-dimensional linear coordination polymers, [Mg(L)?·?4(H₂O)] (H₂L?=?olsalazine) and 2 [Ca(L)?·?4(H₂O)] were obtained from self-assembly of CaCl₂ or MgSO₄ with olsalazine and their structures determined by single crystal X-ray diffraction. Both complexes are one-dimensional polymers, for complex 1 with crystal data: P2(1)/c, a?=?9.5224(18), b?=?11.309(2), c?=?16.211(3)?Å, β?=?106.648(3)°, V?=?1672.6(6)?ų, Z?=?4, R ₁?=?0.0695, wR ₂?=?0.2183, for complex 2 with crystal data: P4(3)2(1)2, a?=?10.4006(2), b?=?10.4006(2), c?=?32.0746(10)?Å, V?=?3469.59(14)?ų, Z?=?8, R ₁?=?0.0332, wR ₂?=?0.1015. In the complexes, Mg and Ca adopt totally different coordination modes. Alkaline-earth Mg is six-coordinate octahedronal geometry, however, in 2, the local coordination geometry around calcium atom can be best described as a slightly distorted pentagonal bipyramid crystallizing in a homo-chiral space group. Olsalazine in both compounds also adopts dissimilar coordination modes.     

NEW THREE DIMENSIONAL [Cd(CN)2]n FRAMEWORK FORMED WITH CADMIUM CYANIDE AND Cd(CN)2·(18-CROWN-6): CRYSTAL STRUCTURE OF [Cd(CN)2]·1/2[Cd(CN)2 (18-CROWN-6)]·3/2EtOH+

Abstract

The cadmium complex Cd(CN)₂·(18-crown-6) (1) was synthesized and its structure was determined by X-ray crystallography. The cadmium ion in 1 has a hexagonal bipyramidal geometry containing six equatorial oxygen atoms from the crown ether and two axial CN ligands. The NC-Cd-CN ‘rod’ is perfectly linear with an end-to-end distance of 6.509 (12) Å. When 1 was allowed to diffuse into a cadmium cyanide solution, the infinite coordination complex [Cd(CN)₂]·1/2[(Cd(CN)₂·(18-crown-6)]·3/2EtOH (2) was obtained in which the cadmium macrocycle 1 was trapped in a 10-faced-cage formed by the [Cd(CN)₂]n framework. The terminal nitrogen atoms of 1 bind two Cd centers across the cage. The trapped Cd(CN)₂·(18-crown-6) has a significantly bent NC-Cd-CN unit and the crown ether ligand disordered over two orientations. The [Cd(CN)₂]_n framework viewed down the c axis shows two types of channels, one octagonal and one tetragonal, which are filled with Cd(CN)₂·(18-crown-6) and ethanol molecules, respectively. Crystallographic data of 1: trigonal, space group R·3 (hexagonal axis), a = 11.757 (1), c = 12.105 (1) Å, V = 1449.1 (2) ų, Z = 3, R = 0.0566, R_w = 0.0674 for 827 unique reflections (I>3σ(I)). Crystallographic data of 2: orthorhombic, Pbcn, a = 16.632 (1), b = 17.391 (3), c = 15.685 (2) Å, V = 4536.8 (9) ų, Z = 8. R = 0.0486, R_w = 0.0492 for 929 unique reflections (I>3σ(I)).     

Octa(ɛ-caprolactam)erbium(III) hex(isothiocyanato)chromate(III): Synthesis and crystal structure

The ionic mixed-ligand bimetallic complex [Er(?-C₆H₁₁NO)₈][Cr(NCS)₆] has been synthesized and studied by X-ray diffraction analysis. The crystals are monoclinic, space group C2/c, a = 39.627(2) Å, b = 22.3406(11) Å, c = 23.7155(10) Å, β = 107.687(2)°, V = 20 002.9(16) ų, Z = 12, ρ_calcd = 1.467 g/cm³. The coordination polyhedron of the erbium atom is a distorted square antiprism formed by the oxygen atoms of the organic ligands. The Er-O bond lengths vary within 2.29–2.44 Å. The coordination polyhedron of the chromium atom is a slightly distorted octahedron, and the Cr-N bond lengths range from 1.99 to 2.01 Å.     

X-RAY CRYSTAL STRUCTURE OF AN ORGANOINDIUM ALKOXIDE DIMER, (Ph2InOSiMe3)2

Abstract

The solid-state structure of (Ph₂InOSiMe₃)₂, 1, has been established by single-crystal X-ray analysis. Monoclinic crystals of 1 belong to space group P2₁/c, with a = 9.136(1), b = 15.503(2), c = 11.836(1) Å, β=102.46(1)°, Z = 2. Refinement of atomic parameters converged at R = 0.050 (R _w = 0.063) over 1718 observed reflections with I > 3.0σ(I). The dimeric molecule lies on a crystallographic centre of symmetry with In-O = 2.159(7) and 2.149(8) Å, O-In-O = 78.9(3)°, and In-O-In = 101.1(3)°. Compound 1 is only the second example of a simple dimeric organoindium alkoxide to be structurally characterized in this manner.     

Synthesis,crystal structures and toxicity of bicadmium(ii) complexes with macrocyclic,hexaaza-bearing,hydroxyethyl pendants

Three bicadmium(II) complexes with hydroxyethyl pendants were synthesized by [2?+?2] Schiff-base condensation of 2-[bis(2-aminoethyl)amino]ethanol with sodium 2,6-diformyl-4-R-phenolate (for Complex 1, R?=?F; Complex 2, R?=?Cl; Complex 3, R?=?CH₃) in the presence of Cd²⁺. Crystals of 1 were monoclinic, space group P2₁/c, with a?=?16.251(9), b?=?21.424(11), c?=?12.994(7)?Å and β?=?106.622(9)°. Both Cd(II) atoms were heptacoordinated with monocapped-octahedral geometry. Complex 3 crystals were isolated as triclinic, space group P?1 with α?=?15.502(4), b?=?16.060(4), c?=?16.642(5)?Å and α?=?68.813(4), β?=?80.836(4), γ?= 86.551(4)°. The coordination number and coordination geometry of the Cd ion in one cationic unit of 3 are similar to that of 1, while in the other cationic unit, one Cd atom is N₃O₄ heptacoordinated and the other Cd atom has an N₃O₃ coordination environment and possesses a distorted octahedral geometry. The toxicity of these complexes was evaluated by testing antimicrobial activity against bacterial strands.     

Lanthanoid Antimonides Ln2Sb5 (Ln = Sm,Gd, Tb,Dy) and Rationalization of Chemical Bonding within the Antimony Polyanion by Combining the Zintl‐Klemm Concept with Bond‐Length Bond‐Strength Relationships

The title compounds are formed by peritectic reactions. Single crystals could be isolated from samples with high antimony content. Their structure was determined for Dy₂Sb₅ from four‐circle X‐ray diffractometer data: P2₁/m, a = 1306.6(1) pm, b = 416.27(4) pm, c = 1458.4(1) pm, β = 102.213(8)°, Z = 4, R = 0.061 for 2980 structure factors and 86 variable parameters. All dysprosium atoms have nine antimony neighbors forming tricapped trigonal prisms with Dy–Sb distances varying between 308 and 338 pm. The antimony atoms occupy ten different sites with greatly varying coordination. One extreme case is an antimony atom surrounded only by dysprosium atoms in trigonal prismatic arrangement, the other one is an antimony atom in distorted octahedral antimony coordination. The various antimony‐antimony interactions (with Sb–Sb distances varying between 284 and 338 pm) are rationalized by combining the Zintl‐Klemm concept with bond‐length bond‐strength considerations.     

Synthesis,crystal structure,and properties of a new zinc coordination polymer [Zn(PMP)2Cl] n

A new coordination polymer [Zn(PMP)₂Cl] _n (PMP = 1-phenyl-3-methyl-5-pyrazolone) has been prepared by the reaction of zinc chloride and PMP, and characterized by elemental analysis, IR, UV, and fluorescence spectra, TG/DTA, and electrochemical analysis. Single crystal X-ray diffraction revealed that the complex is monoclinic, space group P 2(1)/n, with a = 10.850(17), b = 17.578(2), c = 10.997(18) Å, β = 104.999(3)°, V = 2025.8(5) ų, Z = 4, D_c = 1.470 mg m^?3, F(000) = 920, goodness-of-fit = 0.905, and R ₁ = 0.0441. The complex is a 1-D coordination polymer, and the coordination geometry of Zn(II) is a distorted tetrahedron.     

DIRECT SYNTHESIS OF LEAD(II) COMPLEXES WITH TRIETHANOLAMINE USING LEAD(II) OXIDE AS STARTING MATERIAL

Abstract

A number of lead(II) complexes containing triethanolamine (L) is reported. The compounds were identified and characterized by chemical analyses and IR investigations. The crystal structure of bis(triethanolamine)lead(II) acetate was determined by X-ray crystallographic analysis. The compound crystallizes in space group C2/c with a = 10.373(2), b = 16.079(2), c = 13.707(3) Å, β = 99.36(2)°, V = 2255.7 ų, Z = 4, d(calculated) = 1.84 g cm^?3. The structure was refined by least-squares methods to a final value of the R of 0.025 for 3185 reflections with I > 3σ(I). The complex consists of eight coordinated [PbL₂]²⁺ cations and two CH₃COO^? anions joined together by hydrogen bonds between the oxygen atoms of the carboxyl groups and the hydroxyl hydrogens of ligands. The lead atom lies on a two-fold rotation axis and the structure of the coordination polyhedron is a distorted trigonododecahedron.     

Self-assembly of a Novel One-dimensional Zigzag Coordination Polymer

Abstract

Reaction of anhydrous NiBr₂ with pyrazine and disodium terephthalate in the presence of water results in the formation of a one-dimensional (1D) coordination polymer [Ni(pyrazine)₂(H₂O)₄] · (terephthalate) 1 which demonstrates a linear zigzag coordination pattern running along the crystallographic c-axis. The title compound crystallizes in the monoclinic space group C2/c with a = 16.833(2), b = 9.173(1), c = 11.107(1) Å, β = 119.373(2)°, and D_c = 1.667 for Z = 4. Final refinement based upon 4345 observed reflections led to a final R value of 0.052 for the polymeric product. The included terephthalate anion participates in eight O—H…O hydrogen bonds to coordinated water molecules.     

Synthesis and structural studies of early transition metalloporphyrin complexes. 1. X-ray structures of meso-5,10,15,20 tetratolyl hafnium(IV) μ-dioxo dimer complex and meso-5,10,15,20 tetratolyl porphyrin vanadium(IV) oxo complex

Abstract

(TTP) hafnium dichloride, 1, where TTP = meso-5,10,15,20 tetratolyl porphyrin dianion, has been synthesized and spectroscopically characterized as a precursor to 2. Hydrolysis of 1 gives (TTP) hafnium μ-dioxo dimer, 2. (TTP) vanadium oxo complex, 3, can be obtained by hydrolysis of the corresponding chloro complex. Compound 2 has been characterized by spectroscopic and single crystal X-ray diffraction analyses. [(TTP)HfO]₂-toluene crystalizes in the space group C2/c, a = 31.906(6) Å, b = 16.864(3) Å, c = 19.180(4) Å, β = 117.52(3)°, V = 9152(3) ų, d_calcd = 1.369 g/cm³, Z = 8, 6029 unique observed reflections, final R = 0.077. The Hf atom is 1.02 Å from the plane of the porphyrin ring; Hf-O bond lengths are 2.1 Å. The hafnium atoms are 3.06(1) Å from each other and the average Hf-O-Hf angle is 94°. The porphyrin rings are 5.4° from being parallel and the distance between the centers of the porphyrin rings is ～ 5.1 Å. TTPVO·mesitylene, 3, crystallizes from mesitylene in the space group P1, a = 8.365(2), b = 10.320(3), c = 14.380(5) Å, α = 91.91(3), β = 91.44(3), γ = 108.26(2)°, V = 1177.2(6) ų, d_calcd = 1.27 g/cm³, Z = 1, 1851 observed unique reflections, final R = 0.069. The average V - N distance = 2.016 Å. The coordination geometry around the vanadium is distorted C_4V. The V = O group is disordered about the center of inversion. The vanadium atom resides 0.57 Å above the plane of the nitrogens. The (ring center) -V = O angle is 165.9° while the V = O vector is essentially colinear with the vector normal to the plane of nitrogens.