Self-Assembly of Two Isomorphous Thiocyanate Complexes of Co(II) and Ni(II) with 3-Hydroxypicolinamide

Abstract  

The synthesis, thermal and spectral characterization, and crystal structure of isomorphous thiocyanate cobalt(II) and nickel(II) complexes with 3-hydroxypicolinamide (3-OHpia), [M(C₆H₆N₂O₂)₂(NCS)₂]·2H₂O, are reported. The metal(II) ions are chelated by two cis-oriented 3-OHpia and two thiocyanate ligands in distorted octahedral geometry. The distortion within the coordination sphere is mainly imposed by formation of the chelate rings. The compounds crystallize in monoclinic space group P2/c with two symmetrically independent molecules and a = 14.4945(2) ?, b = 8.5906(1) ?, c = 16.3865(3) ?, β = 105.987(2)°, Z = 4 (1) and a = 14.4927(5) ?, b = 8.5912(3) ?, c = 16.2712(6) ?, β = 105.740(4)°, Z = 4 (2). Commonly observed supramolecular amide synthons are not robust enough to accommodate thiocyanate ions and H₂O molecules. But instead, neutral complexes are linked through hydrogen bonds leading to two different hydrogen bonding ribbon motifs involving amide moieties and H₂O molecules [C(8)R ₂²(12) along c axis] and amide moieties and thiocyanate ions [C(8)R ₂²(16) along b axis] for symmetrically related molecules labelled as 1 [Co1 (1) and Ni1 (2)] and 2 [Co2 (1) and Ni2 (2)], respectively.     

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.      

Synthesis and Crystal Structure of a Novel Five-Coordinate Complex from Zinc(II) and 1,3-Bis[2-(2-Hydroxybenzylideneamino)phenoxy]propan-2-ol Ligand

Abstract  

A novel five-coordinate Zn(II) complex of 1,3-bis[2-(2-hydroxybenzylideneamino)phenoxy]propan-2-ol (BHBAPP), namely [Zn₂(BHBAPP)₂](Pic)₂ · C₂H₅OH (Pic = picrate) has been synthesized and characterized by elemental analyses, IR spectra and X-ray single-crystal diffraction. The complex crystallizes in the triclinic space group P−1 with cell constants a = 9.8145(9), b = 13.2398(12), c = 14.5058(13) ?; α = 86.4560(10), β = 82.7260(10), γ = 73.0570(10)°, Mr = 1596.08, V = 1,788.0(3) ?³, Z = 1, Dc = 1.482 g/cm³, F(000) = 822, μ = 0.760 mm⁻¹. The structure was solved by direct methods and refined to R = 0.0390 (wR ₂ = 0.0996). Examination of the structure shows the Zn atoms are coordinated to four oxygen atoms and one nitrogen atom from BHBAPP ligand to form a distorted trigonal bipyramidal geometry. Further, in the crystal structure [Zn(BHBAPP)]⁺¹ cations and picrate anions are linked together via hydrogen bonding interactions tightly forming a three-dimensional supramolecular. It must be pointed out that the picrate anions play a special role in increasing the dimensionality of the supramolecular architecture.     

Two-Dimensional Hydrogen-Bonded Polymer from Nickel(II) Tetraaza Macrocyclic Complex and Succinate Ligand

Abstract  

The reaction of [Ni(L)]Cl₂·2H₂O (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0^1.18,0^7.12] docosane) with succinic acid (C₄H₆O₄) yields a 2D hydrogen-bonded polymer with formula [Ni(L)(C₄H₅O₄)₂] (1). This polymer complex has been characterized by X-ray crystallography, spectroscopy and cyclic voltammetry. The complex has a center of symmetry. The crystal structure of 1 exhibits a distorted octahedral geometry about Ni atom with four nitrogen atoms of the macrocycle and two oxygen atoms of the succinate ligand at the trans position. Compound 1 crystallizes in the monoclinic system C2/c with a = 14.8203(11), b = 12.3070(8), c = 17.4164(12) ?, β = 107.356(6)°, V = 3032.1(4) ?³, Z = 4. Electronic spectrum of 1 reveals a high-spin octahedral environment. Cyclic voltammetry of 1 undergoes two waves of a one-electron transfer corresponding to Ni^II/Ni^III and Ni^II/Ni^I processes.     

Coordination of 4-Aminoantipyrine to Rhenium(V)

Abstract  

The reactions of trans-[ReOX₃(PPh₃)₂] (X = Cl, Br) with 4-aminoantipyrine (H₂pap) were studied, and the complexes cis-[ReX₂(pap)(H₂pap)(PPh₃)](ReO₄) (X = Cl (1), Br (2)) were isolated. The crystal structure of 2 was determined by single-crystal X-ray diffraction. It crystallizes in the monoclinic space group P2₁ with a = 11.5145(6) ?, b = 11.5330(5) ?, c = 17.5492(9) ?, β = 105.322(2)°, V = 2247.6(2) ?³, Z = 2, C₄₀H₃₉N₆O₆PBr₂Re₂, M _r = 1262.97, D _c = 1.866 g cm⁻³, F(000) = 1208 and μ(Mo K _α) = 7.244 mm⁻¹, the final R = 0.0545 and wR = 0.1314. The ligand pap is coordinated through the doubly deprotonated amino nitrogen as an imide, and H₂pap acts as a neutral bidentate chelate, with coordination through the neutral amino nitrogen and the ketonic oxygen.     

Metal-betaine interactions. IV. Crystal structures of trans-tetraaquabis(betaine)nickel(II) nitrate and trans-diaquatetrakis(pyridine betaine)cobalt(II) bis[trichloro(pyridine betaine)cobaltate(II)]

Two transition metal(II) complexes of betaine (Me₃N⁺CH₂COO^–, designated as BET) and pyridine betaine (C₅H₅N⁺CH₂COO^–, pyBET) have been prepared and investigated by X-ray crystallography and infrared spectroscopy. [Ni(BET)₂(H₂O)₄] (NO₃)₂ (1), (R _F=0.054 for 2518 observed MoK data) comprises slightly distorted octahedral [Ni(BET)₂(H₂O)₄]²⁺ cations in which the Ni(II) atom is centrosymmetrically coordinated by four aqua ligands and twotrans-related unidentate BET ligands, and the uncoordinated carboxy oxygens form intramolecular hydrogen bonds with the aqua ligands. [Co(pyBET)₄(H₂O)₂]·2[Co(pyBET)Cl₃] (2) (R _F=0.029 for 4696 observed data) consists of discrete octahedral [Co(pyBET)₄(H₂O)₂]²⁺ cations and tetrahedral [Co(pyBET)Cl₃]^– anions. In the centrosymmetric cation each of the twotrans-related aqua ligands form a pair of intramolecular hydrogen bonds with the uncoordinated oxygen atoms of two unidentate pyBET ligands. In the anion the cobalt atom is coordinated by one unidentate pyBET ligand and three chloro ligands.     

Synthesis and Crystal Structure of a Polymeric Cobalt(II) Complex with 1,2-bis(1,2,4-triazol-1-yl)ethane

Abstract The title complex [Co₂(bte)₃(NCS)₄(H₂O)₂] _n (bte = 1,2-bis(triazol-1-yl)ethane) has been prepared. Single-crystal X-ray analysis reveals that the complex crystallizes in space group P ī with a = 7.7962(2), b = 8.3407(4), c = 14.7735(5) ?, α = 86.835(2), β = 76.2031(9), γ = 80.583(3)°. The crystal consists of two discrete complexes, [Co(bte)(NCS)₂(H₂O)₂] and [Co(bte)₂(NCS)₂]. The structure of [Co(bte)(NCS)₂(H₂O)₂] consists of neutral chain containing Co(II) bridged by bte molecules. The six-co-ordination of Co²⁺ is achieved by means of two trans NCS⁻ ions and water molecules. The structure of [Co(bte)₂(NCS)₂] demonstrates a one-dimensional neutral chain through bte-bridge, in which the Co(II) atom is in a distorted octahedral environment formed by four nitrogen atoms of the triazoles and two nitrogen atoms from two trans thiocyanato liagnds. Index abstract Synthesis and Crystal Structure of a Polymeric Cobalt(II) Complex with 1,2-bis(1,2,4-triazol-1-yl)ethane This paper reports the synthesis and crystal structure of complex [Co₂(bte)₃(NCS)₄(H₂O)₂]_n (bte = 1,2-bis(triazol-1-yl)ethane), which consists two different neutral chains containing Co(II) bridged by bte molecules.      

Synthesis,Crystal Structure and IR Spectra of Complexes of Mn(II) by Indole-2-Carboxylic or Isoquinoline-1-Carboxylic Acids and 1,10-Phenanthroline

Abstract  

Two ternary complexes of manganese(II) indole-2-carboxylate (2-IC⁻) or isoquinolinecarboxylate (IQC⁻) with 1,10-phenanthroline (phen) in methanol or in dimethylacetamide (DMA) were synthesized and studied by X-ray diffraction and IR spectra. [Mn(C₉H₆NO₂)₂(C₁₂H₈N₂)₂]·CH₄O (1) crystallizes in the triclinic space group P-1 with cell parameters of a = 10.548(2) ?, b = 14.168(3) ?, c = 14.580(3) ?, α = 62.35(2)°, β = 69.16(2)°, γ = 78.61(2)°, V = 1802.4(6) ?³ and Z = 2; [Mn(C₁₀H₆NO₂)₂(C₁₂H₈N₂)].C₄H₉NO (2) crystallizes in the monoclinic space group P2₁/a with cell parameters of a = 15.304(5) ?, b = 12.871(5) ?, c = 17.421(5) ?, β = 114.39(1), V = 3125(2) ?³ and Z = 4. In 1, Mn is six-coordinate by two bidentate phen ligands and two 2-IC⁻ ligands and exhibits a very distorted octahedral geometry. This complex is solvated by methanol involved in hydrogen bonding. In 2, Mn atom is surrounded by one bidentate phen ligand and two bidentate IQC⁻ ligands. The complex exhibits a distorted octahedral geometry around the Mn^II atom. The crystal structure is completed by a disordered DMA solvate molecule. The IR spectra of both compounds are slightly different in the range 4000–2400 cm⁻¹ which may be attributed to hydrogen bond lack in 2.     

Synthesis,Crystal Structure and DNA Binding Property of Diaquadi(4-methylbenzoyloxy)bis[2-(4-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl 3-oxide]cobalt(II)

Abstract  

A novel cobalt(II) complex of [Co(4-MePhCOO)₂(NITpPy)₂(H₂O)₂] (1), where NITpPy is short for 2-(4-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxy 3-oxide(C₁₂H₁₆N₃O₂), was synthesized and structurally characterized by X-ray diffraction analysis. The X-ray diffraction analysis reveals that 1 crystallizes in the triclinic space group P-1 with a = 6.7910(10) ?, b = 12.4421(15) ?, c = 12.9169(16) ?, α = 89.8470(10)°, β = 89.8480(10)°, γ = 76.991(2)°, and Z = 1. The Co atom in the complex is located on the center of inversion and lies in a distorted octahedral geometry defined by an N₂O₄ donor set. The interaction of 1 with calf thymus DNA (CT-DNA) was investigated by UV–vis absorption and emission spectroscopy, which indicating that 1 could bind to DNA through electrostatic interaction.     

Synthesis and Characterization of Bis(methyl-2-pyridylmethylidenedrazinecarbodithioate)manganese(II)

Abstract  Brown crystals of title compound, bis(methyl-2-pyridylmethylidene-drazinecarbodithioate)manganese(II), was formed by reaction of methyl-2-pyridylmethylidenehydrazinecarbodithioate(HNNS) with manganese perchlorate at 323 K temperature and recrystallized from ethanol at room temperature, crystallizing in the monoclinic system, space group P2(1)/n, with a = 11.631(2), b = 14.010(3), c = 13.128(3) ?, β = 105.791(11)°; V = 2058.6(7)  ?³, D _c  = 1.533 g/cm³, Z = 4, C₁₆H₁₆N₆MnS₄, M _r  = 475.53, μ(M₀ K _α ) = 1.060 mm⁻¹, F (000) = 972. The structure was refined to R = 0.0441, wR = 0.1196 for 3,682 (I > 2σ(I)) reflections and S = 1.110. In title complex the coordination geometry about manganese is distorted octahedral and the two ligands in the mer configuration (S and tertiary N atom cis to each other and the iminic N atoms trans). Furthermore, the neutral molecule units Mn^II(NNS)₂ are connected by hydrogen bonds C–H···N and C–H···S and form a three dimensional ordered network structure. Graphical Abstract  The title compound, Mn(NNS)₂, exists as discrete molecules in which the central MnII atom is coordinated by two S atoms and four N atoms from two ligands NNS- molecules in a mer-octahedral configuration. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Crystal Structure and Photoluminescent Properties of Two Cadmium(II) Complexes with Orotic Acid

Abstract  

Assembly of orotic acid (2,6-dioxo-1,2,3,6-tetrahydropyrimidine-4-carboxylic acid, H₃dtpc) and Cd(OAc)₂·2H₂O gave rise to two complexes [Cd₂(H₂dtpc)₂(H₂O)₆] (I) and [Cd(H₂dtpc)(bpy)(H₂O)]_n (II) (bpy = 2,2′-bipyridine). Complex (I) and (II) have been characterized by X-ray single crystal diffraction, IR, PXRD, TGA and fluorescence spectra. Structural analyses reveal that (I) is a binuclear structure, and complex (II) possesses a one-dimensional infinite zig-zag chain architecture and the chains are further assembled into 2D supramolecular network by strong hydrogen bonding interactions. Crystal data for (I): Monoclinic, space group P2(1)/n, a = 9.3221(19) ?, b = 6.6315(13) ?, c = 15.322(3) ?, β = 102.31(3)°, V = 925.4(3) ?³, Z = 4, R1 = 0.0269, and wR2 = 0.0604; for (II): Monoclinic, space group P2(1)/c, a = 9.9880(2) ?, b = 14.5085(2) ?, c = 11.6957(2) ?, β = 107.976(2)°, V = 1612.10(5) ?³, Z = 4, R1 = 0.0234 and wR2 = 0.0554.     

Synthesis and Crystal Structure of a Mixed-Ligand Cobalt(II) Complex with 2-Aminobenzimidazole

Abstract  The cobalt(II) complex, [Co(abz)₂(SCN)₂] 1, has been synthesized by the reaction of cobalt(II) nitrate with ammonium thiocyanate and abz ligands (abz = 2-aminobenzimidazole), and was fully structurally characterized by elemental analysis, IR spectra, X-ray diffraction and thermogravimetric experiments. It crystallizes in the triclinic P-1 space group with a = 8.6316(10), b = 9.3426(10), c = 13.254(2) ?, α = 95.793(2), β = 95.870(2), γ = 115.7380(10), V = 945.1(2) ?³, and Z = 2. The central cobalt(II) atom is four-coordinated to nitrogen donors from two neutral abz ligands and two isothiocyanate anions respectively, adopting a slightly distorted tetrahedral geometry. In addition, the intermolecular N–H···N and N–H···S hydrogen bonds interactions link the discrete mononuclear units into infinite three-dimensional networks. Index Abstract  The essence sentence of the paper: In the mixed-ligand mononuclear complex, [Co(abz)₂(SCN)₂], the four coordinated cobalt(II) atom exhibits a slightly distort tetrahedron, which is further assembled into 3D infinite network by intermolecular hydrogen interactions.      

Synthesis and Crystal Structure of a Novel Mixed Ligand Cadmium(II) Complex of Benz-1,3-Thiazoline-2-Thione and 1,10-Phenanthroline

Abstract  A novel cadmium complex [Cd(C₇H₄NS₂)₂(phen)] was synthesized by the reaction of a polymeric complex, [Cd(C₇H₄NS₂)₂] _n , with 1,10-phenanthroline (phen) as a ligand. The crystal structure was determined by single-crystal X-ray diffraction. The crystallographic data are: triclinic , a = 8.3670(6) ?, b = 10.9898(8) ?, c = 17.1404(13) ?, α = 95.567(2)o, β = 95.881(2)o, γ = 109.034(1)o, V = 1471.26(19) ?³ and Z = 2. The final R value is 0.0375 for 7154 reflections. The compound [Cd(C₇H₄NS₂)₂(phen)] is monomeric revealing a coordination sphere of N₄S₂ type. The Cd atom is surrounded by two thiazole N atoms, two exocyclic S atoms from two bidentate 1,3-benzothiazole-2-thiolate anions and two 1,10-phenanthroline N atoms. The Cd cation is six-coordinate with a distorted octahedral geometry. Graphical Abstract  The synthesis and crystal structure of a novel monomeric complex ‘[Cd(C₇H₄NS₂)₂(phen)]’ obtained by the reaction of polymeric complex, [Cd(C₇H₄NS₂)₂] _n , with 1,10-phenanthroline is reported.      

Synthesis and Crystal Structure Determination of Dimeric Co(II) and Ni(II) with Pyridine 2,6-Dicarboxylic Acid

Abstract  

Two new dimeric complexes of Ni and Co with pyridine 2,6-dicarboxylic acid were synthesized, the structure of both these complexes were determined by single crystal X-ray crystallography and was characterized spectrally with the help of IR and UV spectrometers and the magnetic moments of both the reported complexes were recorded. Both of these complexes crystallize in the monoclinic space group P 2₁/c1. For the dimeric cobalt complex, formula C₁₄ H₂₁ Co₂ N₂ O₁₅; a = 8.3950(3) ?; α = 90°, b = 27.3702(8) ?; β = 98.211(2)°, c = 9.6235(3) ?; γ = 90° and Z = 3. For the dimeric Nickel complex, formula C₁₄ H₂₁ Ni₂ N₂ O₁₅, a = 8.330(10) A; α = 90°, b = 27.266(5) A; β = 98.61(10)^o, c = 9.653(10) A; γ = 90° and Z = 4. Both the dimeric complexes were observed to be hexa-coordinated with two different types of donor atoms (nitrogen and oxygen). Details of the synthesis, structures and spectroscopic properties have been discussed.     

Synthesis and Crystal Structure of the Hydrated Nickel(II) Complex of Tartrate

Abstract  A new dinuclear hydrated nickel(II) tartrate has been isolated and structurally characterized by single-crystal X-ray diffraction. The title compound formulated as [Ni₄(C₄H₄O₆)₄(H₂O)₈](EtOH)_0.5(H₂O)_10.25 (C₁₇H_55.5Ni₄O_42.75) crystallizes in monoclinic system, space group P2(1)/c with a = 13.684(5), b = 17.143(6), c = 18.586(6) ?, β = 96.638(6)°, V = 4331(3) ?³, Z = 4. The unit cell contains two crystallographic independent dimeric units of [Ni₂(C₄H₄O₆)₂(H₂O)₄] without significant structural difference, half of menthol molecule and ten and a quarter packing water molecules. In each dimeric unit, one (R,R)-tartrato dianion chelates two Ni(II) ions by the use of two hydroxy oxygen and two carboxyl oxygen atoms as donor atoms, and another tartrato dianion chelates the same pair of Ni(II) cations in the same way. Each Ni(II) atom is six-coordinated by six O atoms from two tartrate units and two water molecules. Index Abstract  The crystal structure of complex [Ni₄(C₄H₄O₆)₄(H₂O)₈](EtOH)_0.5(H₂O)_10.25 contains two crystallographic independent dimeric units of [Ni₂(C₄H₄O₆)₂(H₂O)₄] without significant structural difference. In each dimeric unit, one (R,R)-tartrato dianion chelates two Ni(II) ions by the use of two hydroxy oxygen and two carboxyl oxygen atoms as donor atoms, and another tartrato dianion chelates the same pair of Ni(II) cations in the same way.      

X-Ray crystal structure determination of a series of 1-aryl- 2-[3-(3-[2-aryl-1-diazenyl]-1,3-diazepan-1-ylmethyl)-1, 3-diazepan-1-yl]-1-diazenes obtained from the reaction of diazonium salts with mixtures of formaldehyde and 1,4-diaminobutane

A new series of bis-triazenes, the 1-aryl-2-[3-(3-[2-aryl-1-diazenyl]-1,3-diazepan-1-ylmethyl)-1,3-diazepan-1-yl]-1-diazenes has been synthesized from the reaction of diazonium salts with a mixture of 1,4-diaminobutane and formaldehyde. The structures of 1-(p-bromophenyl)-2-[3-{3-[2-(p-bromophenyl)-1-diazenyl]-1,3-diazepan-1-ylmethyl}-1,3-diazepan-1-yl]-1-diazene(1), 1-(p-cyanophenyl)-2-[3-{3-[2-(p-cyanophenyl)-1-diazenyl]-1,3-di azepan-1-ylmethyl}-1,3-diazepan-1-yl]-1-diazene(2), and 1-(p-methoxyphenyl)-2-[3-{3-[2-(p-methoxy-phenyl)-1-diazenyl]-1,3-diazepan-1-ylmethyl}-1,3-diazepan-1-yl]-1 diazene(3) have been unequivocally determined by X-ray crystallography. The new bis-triazenes are important since the structure contains the novel saturated heterocycle, 1,3-diazepane. The general conclusion of this study is that alkanediamines with 3 or 4 carbon atoms in the spacer link between the nitrogen atoms give rise to the linear bicyclic molecules of type 5, in contrast to the case of ethylenediamine (spacer link 2 carbon atoms), which affords molecules of type 6, which exemplify the general cage structure of type 4. The crystal structures of 1, 2 and 3 are compared with the previously reported structure of the hexahydropyrimidine analogue 8a(X=CN); compounds 2 and 8a(X=CN) are homologous with respect to the alkane spacer moiety. The structures of 2 and 8a(X=CN) are very different in one respect; in 2 the aryldiazenyl-1,3-diazepanyl groups are in the s-trans orientation around the central methylene group whereas in 8a(X=CN) the arrangement of the aryldiazenyl-hexahydropyrimidinyl groups is the s-cis orientation.Crystal data: 1 C₂₃H₃₀N₈Br₂, triclinic, space group P-1, a=8.3979(2), b=10.7828(3), c=14.4692(5) ?, α=83.670(1), β=78.662(1), γ=78.758(1)°, V=1256.48(6) ?³, for Z=2. 2 C₂₅H₃₀N₁₀, monoclinic, space group P2 ₁ /n, a=13.4046(6), b=9.4482(4), c=10.6913(4)?, β=103.239(2)°, V=2490.5(2) ?³, for Z=4. 3 C₂₅H₃₆N₈O₂, triclinic, space group P-1, a=8.5223(3), b=10.6913(4), c=14.4034(7)?, α=85.657(2), β=78.731(2), γ=80.153(1)°, V=1266.88(9) ?³, for Z=2.     

Synthesis and Crystal Structures of Anionic Gallium(II) and Gallium(III) Heterocyclic Compounds Derived from a Gallium(I) N-Heterocyclic Carbene Analogue

Abstract  

The addition of the N–H bond of the formamidine, ArN(H)C=NAr (Ar = C₆H₃Pr₂ⁱ-2,6), to the gallium(I) center of [K(tmeda)][:Ga(Ar-DAB)] (Ar-DAB={(Ar)NC(H)}₂) yields K[(Ar-DAB)Ga^III(H){N(Ar)C=NAr}] 1. The crystal structure of this and two other related anionic compounds, [K(18-crown-6)][(Ar-DAB)Ga^III{N(H)N=Fl}{(H)Fl}] (Fl = fluorendiyl) 2 and [K(OEt₂)₃][(Ar-DAB)Ga^II(CH₂Ph)Ga^II(Ar-DAB)] 3, have been determined. The cell parameters of the compounds are 1: P2₁/c, a = 20.2350(9), b = 14.1760(7), c = 19.6441(10), β = 111.307(1); 2: P2₁/c, a = 13.115(3), b = 21.799(4), c = 22.646(5), β = 90.20(3); 3: P2₁/n, a = 16.783(3), b = 21.635(4), c = 19.814(4), β = 92.34(3). The crystal structures of all complexes exhibit distorted tetrahedral gallium centers, and interactions between anion aryl substituents and the potassium cations.     

Syntheses,Crystal Structures and Physical Properties of Cd(II) and Mn(II) Complexes with <Emphasis Type="Italic">Trans</Emphasis>-1,2-di(4-pyrindyl)ethylene and <Emphasis Type="Italic">P</Emphasis>-(carboxyl-methyloxy)-benzenecarboxylic Acid

Abstract  

Two complexes [Cd₂(dpe)₃(H₂O)₈]·(dpe)·(hssal)₂·(H₂O)₂ 1, [Mn(dpe)₂(Hpcmb)₂·(H₂O)₂] 2, (dpe = trans-1,2-di(4-pyrindyl)ethylene; H₂hssal = sulphosalicylic acid; H₂pcmb = p-(carboxyl-methyloxy)-benzenecarboxylic acid) has been prepared, and was characterized by elemental analysis, FT-IR and single-crystal X-ray diffraction. Structure indicates in complex 1 that Cd(II) is a distorted octahedral coordination geometry. The hssal²⁻ anions are localized between 2-D sheets {[Cd(dpe)₂(H₂O)₄]²⁺(dpe)}n and {{[Cd(dpe)₂(H₂O)₄]²⁺}n as count anions and bridge to further connect these 2-D sheets through hydrogen bond O–H···O to form 3-D structure. The complex 2 is a single molecule structure. In 2, Each Mn(II) atom is six-coordinated with a distorted octahedral coordination geometry. The single molecule units are extended into three-dimensional structure via π–π, hydrogen bonding interactions. The thermogravimetric behavior and luminescent property of complex 1 were investigated.     

Synthesis, Crystal Structure and Electrochemical Property of New Rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene)bis(azido)cobalt(III) Nitrate Methanol Solvate Complex

Abstract  

The new cobalt compound, [Co(C₁₆H₃₅N₁₀]⁺(NO₃)⁻·CH₃OH (1), have been synthesized and characterized. It’s structure and electrochemical property were investigated using single-crystal X-ray diffraction and cyclic voltammetry in solutions of dimethyl sulfoxide (DMSO) and methanol (CH₃OH). The X-ray diffraction analysis reveals that 1 crystallizes in the monoclinic space group P2₁/c with a = 9.8339 (10) ?, b = 16.4048 (17) ?, c = 15.3628 (16) ?, β = 104.96 (9)° and Z = 4. The complex 1 consists of one [Co(C₁₆H₃₅N₁₀)]⁺ cation, one NO₃ ⁻ anions and one solvent CH₃OH molecule. The metal center of complex 1 is six-coordinated, with the four nitrogens of the macrocycle defining an equatorial plane and two axially ligated [N₃]⁻ ions completing the cobalt coordination sphere. Moreover, hydrogen bonds of O–H⋯N, O–H⋯O and N–H⋯O and static force connect two components of the compound and maintain the crystal structure. Additionally, in situ spectro-electrochemical measurements support Co(III)/Co(II) reversible reduction processes with the observation of the corresponding spectral changes with the applied potentials E _app = −1.5 and 0.5 V. The results obtained by the method are in agreement with those by the CV methods.     

Crystal Structure of 2-(4,5-Bis(4-methoxyphenyl)-5<Emphasis Type="Italic">H</Emphasis>-chromeno[4,3-<Emphasis Type="Italic">b</Emphasis>]pyridin-2-yl)phenol

Abstract  

The title compound 2-(4,5-bis(4-methoxyphenyl)-5H-chromeno[4,3-b]pyridin-2-yl)- phenol (C₃₂H₂₅NO₄, Mr = 487.53) was synthesized and crystallized. The crystal belongs to monoclinic, space group P2(1)/c with a = 12.4170 (11), b = 18.313 (2), c = 11.7103 (10) ?, β = 111.569(2)°, V = 2476.4(4) ?³, Mr = 487.53, Z = 4, Dc = 1.308 g/cm³, μ(MoK _α ) = 0.086 mm⁻¹, F(000) = 1024, the final R ₁ = 0.0632 and wR ₂ = 0.1454. X-ray analysis reveals that the atoms of C(1), C(2), C(3), C(4), C(5) and N(1) form a planar six-membered ring, while the atoms of C(1), C(2), C(6), C(7), C(12) and O(1) form a six-membered ring of envelope conformation.