Synthesis and Characterization of Nickel(II) Complex of 3,14-Dimethyl-2,6,13,17-Tetraazatricyclo[14,4,01.18,07.12]Docosane Containing Pyrazine-2-Carboxylate 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 pyrazine-2-carboxylic acid (H-pyc) yields mononuclear nickel(II) complex, [Ni(L)(pyc)₂]·2H₂O (1). This complex has been characterized by X-ray crystallography, electronic absorption and cyclic voltammetry. The crystal structure of 1 exhibits a distorted octahedral geometry with four nitrogen atoms of the macrocycle and two pyrazine-2-carboxylate ligands. It crystallizes in the triclinic system P-1 with a = 9.6643(17), b = 10.116(3), c = 16.99(4) ?, V = 1633(3) ?³, Z = 2. Electronic spectrum of 1 also 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.     

Self-Assembly of One-Dimensional Coordination Polymer from Nickel(II) Macrocyclic Complex and Malonate 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 malonic (H₂mal) acid yields a one-dimensional coordination polymer [Ni(L)(mal)₂]_n (1). The structure was characterized by X-ray crystallography, spectroscopic and magnetic susceptibility. Each nickel(II) ion has a distorted octahedral coordination environment with the four secondary amines of the macrocycle in which two carboxylate anions of the malonate ligand have assembled around each nickel center. The compound crystallizes in the monoclinic system C2/c with a = 19.487(4), b = 8.4143(12), c = 14.6036(18) ?, β = 102.232(11)°, V = 2340.2(6) ?³, Z = 4. Electronic spectrum of 1 exhibits a high-spin octahedral environment. The magnetic behavior of 1 reveals a weak intramolecular antiferromagnetic interaction with J values of −1.91(1) cm⁻¹.     

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 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.      

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.     

Syntheses and Crystal Structures of Two CuII Coordination Isomers [Cu(pmt)2] · 4H2O (1) and {[Cu(pmt)2] · 2H2O} n (2)

Abstract  A pair of Cu^II coordination isomers [Cu(pmt)₂] · 4H₂O (1) and {[Cu(pmt)₂] · 2H₂O} _n (2) [Hpmt = 2-(2-pyridylmethylamino) ethanesulfonic acid] have been prepared by reaction of the same proportion CuCl₂ · 2H₂O and Hpmt but with different experimental methods in water–methanol mixed solution, and were characterized by X-ray diffraction, elemental analysis, IR spectrum. X-ray analysis indicates that complex (1) is a mononuclear complex in which two deprotonated pmt ligands coordinate in a facial tridentate arrangement about the Cu^II atom. While complex (2) is a coordination polymer, in which four N atoms of pmt ligands coordinate to one Cu^II atom but its sulfonate O atoms bond to adjacent Cu^II atom. Thus 12-membered rings (–Cu–N–C–C–S–O–)₂ are obtained between two neighbouring Cu^II atoms and they connect one another to form this new polymer. Crystal data: [Cu(pmt)₂] · 4H₂O (1), Mr = 566.10, monoclinic, P2 ₁/c, a = 9.1950(8) ?, b = 11.5093(10) ?, c = 11.2304(10) ?, β  = 105.5550(10)°, Z = 2, V = 1144.96(17) ?³, R ₁  = 0.0407, wR ₂  = 0.1242 [I > 2σ (I)]; {[Cu(pmt)₂] · 2H₂O} _n (2), Mr = 530.07, triclinic, P-1, a = 7.6165(19) ?, b = 8.806(2) ?, c = 9.592(4) ?, α = 104.933(4)°, β = 106.732(4)°, γ = 109.503(3)°, Z = 1, V = 534.2(3) ?³, R ₁ = 0.0470, wR ₂ = 0.1082 [I > 2σ(I)]. Index Abstract  A pair of Cu^II coordination isomers [Cu(pmt)₂] · 4H₂O (1) and {[Cu(pmt)₂] · 2H₂O} _n (2) [Hpmt = 2-(2-pyridylmethylamino) ethanesulfonic acid] have been prepared by reaction of the same proportion CuCl₂ · 2H₂O and Hpmt but with different experimental methods in water–methanol mixed solution.      

Hydrogen-bonded Three-dimensional Supramolecular Network Constructed by Dinuclear Ni(II) Macrocyclic Complex and 1,2,4,5-Benzenetetracarboxylate

Abstract  

A new coordination polymer [Ni₂(L)(H₂btec)]_n, (1) was obtained from the reaction of NiSO₄·6H₂O, macrocyclic ligand 3,6,9,17,20,23-hexaaza-29,30-dihydroxy-13,27-di-tert-butyl-tricyclo[23,3,1,1^11,15]triaconta-1(28),11,13,15(30),25,26-hexaene (H₂L), and 1,2,4,5-benzenetetracarboxylic acid (H₄btec) in methanol. Its structure was determined by X-ray diffraction analysis. The crystal is monoclinic C2/c space group with cell parameters a = 20.4923(3) ?, b = 14.2389(3) ?, c = 14.5130(2) ?, β = 97.441(2)°, V = 4199.05(12) ?³, and Z = 8. The X-ray analysis shows that each Ni (II) cation is six-coordinated by an O₃N₃ donor set. The macrocyclic complex [Ni₂L] ²⁺ are bridged by H₂btec²⁻ anions to form 1D chains, which are further joined via N–H···O hydrogen bonds to yield a 3D supramolecular structure. Thermogravimetric analysis (TGA) for the complex is discussed.     

Novel Assembly of a Cyanide-Bridged Copper(II)–Nickel(II) Binuclear Complex with a Copper(II) Macrocyclic Ligand

Abstract  

A mononuclear fragment [Cu(L)Cl]ClO₄ (1) and a cyano-bridged Cu^II–Ni^II binuclear complex [CuL][Ni(CN)₄]·0.25H₂O (2) (L = 1,3,6,8,11,14-hexaazatricyclo[12.2.1.18,11]-octadecane), have been prepared and characterized. X-ray single crystal analyses indicate that the both complexes crystallize in the monoclinic crystalline system. The complex of 1 in P1n1 space group with unit cell constants a = 6.1176(6) ?, b = 11.9147(10) ?, c = 12.2041(12) ?, β = 98.816(5)° and 2 in the P2₁/n space group with unit cell constants a = 8.1419(13) ?, b = 14.695(2) ?, c = 16.863(3) ?, β = 98.375(2)° have been revealed. The complex 2 assumes a binuclear structure in which the nickel(II) ion is in a square planar environment and the copper(II) is in a square-prism geometry environment.     

Molecular Association of Almotriptan with Oxalate and Terephthalate Anions

Abstract  

Crystal structures of anti-migraine drug almotriptan were crystallized with oxalic acid (I) and with terephthalic acid (II) and their crystal structures and molecular associations were determined using X-ray diffraction methods. Crystals of both (I) and (II) are monoclinic, space group P2₁/c, with a = 5.6270(4) ?, b = 27.6419(19) ?, c = 13.6228(9) ?, β = 93.057(1)°, V = 2115.9(3) ?³, Z = 4 (I) and a = 13.3756(15) ?, b = 15.6065(17) ?, c = 10.7238(12) ?, β = 98.017(2)°, V = 2216.7(4) ?³, Z = 4 (II). In almotriptan oxalate {systematic name: N,N-dimethyl-2-[5-(pyrrolidin-1-ylsulfonyl-methyl)-1H-indol-3-yl]-ethanaminium semioxalate}, C₁₇H₂₆N₃O₂S⁺, C₂HO₄ ⁻, (I) and in almotriptan hemi terephthalate hydrate {systematic name: N,N-dimethyl-2-[5-(pyrrolidin-1-ylsulfonyl-methyl)-1H-indol-3-yl]-ethanaminium hemi terephthalate monohydrate}, C₁₇H₂₆N₃O₂S⁺, 0.5(C₈H₄O₄ ²⁻), H₂O, (II), both the almotriptan cations form a trimer with the corresponding anions via N–H···O hydrogen bonds. In (I), the oxalate salt is monoprotonated and in (II), the terephthalic acid is located across the inversion centre and exists as doubly protonated anion. In (I), the cation and anion are interlinked by the N–H···O and O–H···O hydrogen bonds into continuous two-dimensional layers generate an R₆⁶(34) hydrogen-bonded motif tetramers running parallel to the (0 0 1) plane. In (II), the cation and water form a centrosymmetric tetramer of R₄⁴(22) hydrogen-bonded motif via N–H···O and O–H···O hydrogen bonds and further cross-linked by centrosymmetric anions to form an infinite three-dimensional supramolecular hydrogen-bonded networks.     

Structures and Characterization of [Zn(n-chlorosalicylato)2(N-methylnicotinamide)2(H2O)2] (n?=?4 or 5) Ligand Isomers

Abstract  

Two ligand isomers [Zn{4-ClC₆H₃-2-(OH)COO}₂(Menia)₂(H₂O)₂] (I) and [Zn{5-ClC₆H₃-2-(OH)COO}₂(Menia)₂(H₂O)₂] (II) (Menia = N-methylnicotinamide) were prepared and characterized by elemental analysis, IR spectroscopy and thermal analysis. The X-ray crystal structures of complexes (I) and (II) were determined. Compound (I) crystallizes in the triclinic space group P[`1] P\bar{1} with a = 8.105(1) ?, b = 10.036(2) ?, c = 10.545(2) ?, α = 109.088(9)°, β = 91.416(8)°, γ = 102.757(9)°, V = 786.2(2) ?<sup>3</sup>, Z = 1. Compound (II) crystallizes in the triclinic space group P[`1] P\bar{1} . Its cell parameters are: a = 8.133(1) ?, b = 10.119(2) ?, c = 10.428(1) ?, α = 66.44(1)°, β = 74.32(1)°, γ = 80.16(1)°, V = 755.5(2) ?³, Z = 1. The molecular structure of both isomers is monomeric. Each Zn(II) atom is hexacoordinated by three pairs of unidentate ligands in trans-positions (ZnO₄N₂). The 5-Clsal complex is somewhat less distorted than 4-Clsal complex (Cl-sal = chlorosalicylate). The structural data are compared with those found in similar [Zn(RCOO)₂(NL)₂(H₂O)₂].     

Crystal Structure and Characterization of [Ni(RPOEt)<Subscript>2</Subscript>(C<Subscript>2</Subscript>H<Subscript>5</Subscript>OH)<Subscript>2</Subscript>](ClO<Subscript>4</Subscript>)<Subscript>2</Subscript> [RPOEt = bis{(diphenylphosphinyl)methyl}ethyl phosphinate]

Abstract  

The compound [Ni(RPOEt)₂(C₂H₅OH)₂](ClO₄)₂ (1) [RPOEt = bis{(diphenylphosphinyl)methyl}ethyl phosphinate] has been prepared in the form of single crystals and characterized by elemental and thermal analyses, IR spectroscopy and by a single crystal X-ray diffraction study. The complex crystallizes in the triclinic P[`1] P\bar{1} space group with a = 9.8773(5), b = 13.741(1), c = 14.287(1) ?, α = 64.313(9), β = 70.280(5), γ = 89.973(7)o, V = 1620.5(2) ?³, and Z = 1. The nickel(II) atom in 1, situated at the centre of symmetry, is coordinated by four oxygen atoms from two RPOEt ligands and two oxygen atoms from two ethanol molecules in a slightly distorted octahedral environment. The third phosphoryl-oxygen atom from the phosphinate ligand is hydrogen bonded to the oxygen atom of the ethanol molecule coordinated to nickel(II). The complex [Ni(RPOEt)₂(C₂H₅OH)₂]²⁺ cations are linked by the C–H···O hydrogen bonds into one-dimensional chains and by the composite π···π and C–H···π phenyl interactions into a final three-dimensional structure.     

Dihydrogen Phosphate and Hydrogen Sulphate of 1,4-Dimethyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium: Crystal Structures, Hydrogen Bonding and Infrared Spectra

Abstract  

The crystal structures of the title compounds consist of 1,4-dimethyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium cation [C₈H₁₈N₂]²⁺ and [H₂PO₄]⁻ or [HSO₄]⁻ anions. Both crystal structures are monoclinic, the structure of the dihydrogen phosphate (I) is non-centrosymmetric (P2₁) with a = 6.4090(2) ?, b = 13.6920(5) ?, c = 7.6140(3) ?, β = 94.620(2)°, V = 665.97(4) ?³, Z = 2; whereas the unit cell of the hydrogen sulphate (II) is centrosymmetric (P2₁/c) with a = 13.8460(2) ?, b = 12.6610(2) ?, c = 8.0360(2) ?, β = 99.5800(12)°, V = 1389.10(5) ?³, Z = 4. Both the structures are formed by the different bonding patterns of the anions interlinked by strong and moderate O–H···O hydrogen bonds. While the structure of (I) consists of a two-dimensional network of the hydrogen bonded dihydrogen phosphates, the infinite chains of the hydrogen bonded hydrogen sulphates are the basic building unit of the structure (II). In addition to the dominant electrostatic interaction the divalent cations stabilize themselves in the structures by forming several C–H···O hydrogen bonds to the oxygen atoms of the anions. The IR spectra of both the compounds are strongly affected by the hydrogen bonds whose influence on OH stretching vibrations is analysed by means of the DFT calculations in the solid state.     

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.     

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.     

The Zolmitriptan-Pyridine (1:1) and Zolmitriptan-Propiophenone (3:2) Inclusion Complex

Abstract  

The crystal structures of zolmitriptan with pyridine (I) and propiophenone (II) solvates have been determined by single crystal X-ray diffraction studies. Compound (I) crystallizes in the orthorhombic space group P2₁2₁2₁ with a = 8.5610(5) ?, b = 12.2709(7) ?, c = 19.6201(12) ?, V = 2061.1(2) ?³, and Z = 4, while compound (II) crystallizes in the monoclinic space group P2₁ with a = 15.085(1) ?, b = 19.656(12) ?, c = 21.0860(13) ?, β = 92.068(1)°, V = 6248(4) ?³ and Z = 4. The asymmetric unit of (I), C₁₆H₂₁N₃O₂·C₅H₅N, contains one zolmitriptan molecule and one pyridine solvate, while the asymmetric unit of (II), 3(C₁₆H₂₁N₃O₂)·2(C₉H₁₀O) comprises six zolmitriptan molecules and four propiophenone solvates. In both structures, the N–H···N hydrogen bonds, form an infinite helical chain and generate a C(11)-type motif in (I) and a D₂²(13)-type motif in (II). Both the complexes have layer structures, the layers being constructed from rings (cavity) of four zolmitriptan molecules, hydrogen bonded through N–H···N and N–H···O bonds, where the pyridine (I) and propiophenone (II) solvates are included in an R₄⁴(33) ring.     

Synthesis, Structure and Characterization of Two 1D Chain-like Cadmium Terephthalate Complexes: [Cd(tp)(H2O)3]?·?4H2O and [Ph4P][Cd(tp)0.5Cl2]?·?H2O

Abstract  Two new compounds, [Cd(tp)(H₂O)₃] · 4H₂O (1) and [Ph₄P][Cd (tp)_0.5Cl₂] · H₂O (2) (tp = terephthalate, [Ph₄P] = tetraphenylphosphonium), are metal-polycarboxylate coordination polymers prepared by similar hydrothermal synthesis techniques. Both compounds crystallize in the 1D chain-like architectures. 1 (C₈H₁₈CdO₁₁) is orthorhombic Pcca, Z = 4 (a = 7.3018(1) ?, b = 9.9975(3) ?, c = 19.9695(5) ?, V = 1457.77(6) ?³). 2 (C₂₈H₂₄CdCl₂O₃P) is triclinic P−1, Z = 2 (a = 9.5028(4) ?, b = 12.3130(5) ?, c = 12.7343(6) ?, α = 68.380(1)°, β = 73.723(1)°, γ = 89.624(1)°, V = 1321.8(1) ?³). Transition metal cadmium centers bridged by rigid linear tp ligands give rise to a 1D infinite zigzag chain polymer for 1 and a simple 1D infinite stepped chain polymer for 2. 1 presents an interesting plywood-like packing network while 2 shows a simple parallel rod-like stacking network. An intense fluorescent emission at 412 nm (λ_exc = 338 nm) for 1 in the solid state at room temperature is observed. Index Abstract  Polymeric compounds [Cd(tp)(H₂O)₃] · 4H₂O (1) and [Ph₄P][Cd (tp)_0.5Cl₂] · H₂O (2) crystallize in two remarkable 1D chain-like architectures prepared by similar hydrothermal synthesis techniques, showing an interesting plywood-like packing network in 1 and a simple parallel rod-like stacking network in 2, respectively. An intense fluorescent emission at 412 nm (λ_exc = 338 nm) for 1 in the solid state at room temperature is observed.      

Structures of Three Chalcones Derived from 6-Methoxy-2-naphthaldehyde

Abstract  In the molecular structures of three new structurally related chalcone derivatives, namely (2E)-1-(2-hydroxyphenyl)-3-(6-methoxy-2-naphthyl)prop-2-en-1-one, C₂₀H₁₆O₃, I, (2E)-1-(2-chloropyridin-4-yl)-3-(6-methoxy-2-naphthyl)prop-2-en-1-one, C₁₉H₁₄ClNO₂, II, and (2E)-3-(6-methoxy-2-naphthyl)-1-pyridin-4-ylprop-2-en-1-one, III, C₁₉H₁₅NO₂, the configuration of the keto group is syn with respect to the olefinic double bond. In all three structures the molecules pack with weak intermolecular C–H···O interactions utilizing both the methoxy and keto oxygen’s in I, the methoxy oxygen in II and the keto oxygen in III. These interactions link the molecules into chains diagonally along the (011) plane of the unit cell in I and III and along the (010) plane in II. The dihedral angle between the phenyl and 2-napthyl rings in I is 31.7(3)°. In II and III the dihedral angle between the pyridyl and 2-naphthyl rings is 14.4(9)° and 1.8(9)°, respectively. C–H···O hydrogen bonding interactions influence these twist angles of these rings in I–III while weak π–π stacking interactions between naphthyl rings in I and III and also between pyridyl and naphthyl rings in II help stabilize crystal packing. [I: P2 ₁ /c, a = 7.6635(4) ?, b = 11.8047(6) ?, c = 16.7584(7) ?, β = 99.271(5)°, V = 1496.25(13) ?³; II: Pbca, a = 14.1424(4) ?, b = 6.0957(2) ?, c = 33.1458(11) ?, V = 2857.43(16) ?³; III: P2 ₁ /c, a = 11.5155(4) ?, b = 6.0020(2) ?, c = 22.4645(8) ?, β = 103.002(4)°, V = 1512.85(9) ?³]. Index Abstract  Crystal structures from three Chalcones derived from 6-methoxy-2-naphthaldehyde are reported and their geometric and packing parameters described.     

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.     

The Structure of the Copper(II) Complex with 4,5-Dichlorophthalic Acid: The 1:1 Complex ‘Adduct’ Salt <Emphasis Type="Italic">trans</Emphasis>-Tetraaqua(2-carboxy-4,5-dichlorobenzoato)(4,5-dichlorobenzene-1,2-dicarboxylic acid)copper(II) 2-Carboxy-4,5-dichlorobenzoate

Abstract  

The unusual (1:1) complex ‘adduct’ salt of copper(II) with 4,5-dichlorophthalic acid (H₂DCPA), having formula [Cu(H₂O)₄(C₈H₃Cl₂O₄) (C₈H₄Cl₂O₄)]·(C₈H₃Cl₂O₄) has been synthesized and characterized using single-crystal X-ray diffraction. Crystals are monoclinic, space group P2₁/c, with Z = 4 in a cell with dimensions a = 20.1376(7), b = 12.8408(4) c = 12.1910(4) Å, β = 105.509(4)°. The complex is based on discrete tetragonally distorted octahedral [CuO₆] coordination centres with the four water ligands occupying the square planar sites [Cu–O, 1.962(4)–1.987(4) Å] and the monodentate carboxyl-O donors of two DCPA ligand species in the axial sites. The first of these bonds [Cu–O, 2.341(4) Å] is with an oxygen of a HDCPA monoanion, the second with an oxygen of a H₂DCPA acid species [Cu–O, 2.418(4) Å]. The un-coordinated ‘adduct’ molecule is a HDCPA counter anion which is strongly hydrogen-bonded to the coordinated H₂DCPA ligand [O···O, 2.503(6) Å] while a number of peripheral intra- and intermolecular hydrogen-bonding interactions give a two-dimensional network structure.     

Investigations of 2-Thiazoline-2-thiol as a Ligand: Synthesis and X-ray Structures of [Mn2(CO)7(μ-NS2C3H4)2] and [Mn(CO)3(PPh3)(κ2-NS2C3H4)]

Abstract  Treatment of Mn₂(CO)₁₀ with 2-thiazoline-2-thiol in the presence of Me₃NO at room temperature afforded the dimanganese complexes [Mn₂(CO)₇(μ-NS₂C₃H₄)₂] (1) and [Mn₂(CO)₆(μ-NS₂C₃H₄)₂] (2) in 51 and 34% yields, respectively. Compound 1 was quantitatively converted into 2 when reacted with one equiv of Me₃NO. Reaction of 1 with triphenylphosphine at room temperature furnished the mononuclear complex [Mn(CO)₃(PPh₃)(κ ²-NS₂C₃H₄)] (3) in 66% yield. All three new complexes have been characterized by elemental analyzes and spectroscopic data together with single crystal X-ray diffraction studies for 1 and 3. Compound 1 crystallizes in the orthorhombic space group Pbca with a = 12.4147(2), b = 16.2416(3), c = 19.0841(4) ?, β = 90°, Z = 8 and V = 3848.01(12) ?³ and 3 crystallizes in the monoclinic space group P 2₁/n with a = 10.41730(10), b = 14.7710(2), c = 14.9209(2) ?, β = 91.1760(10)°, Z = 4 and V = 2295.45(5) ?³. Graphical Abstract  Two new dimanganese complexes [Mn₂(CO)₇(μ-NS₂C₃H₄)₂] (1) and [Mn₂(CO)₆(μ-NS₂C₃H₄)₂] (2) were formed when [Mn₂(CO)₁₀] was treated with 2-thiazoline-2-thiol in the presence of Me₃NO. Compound 2 reacts with PPh₃ to give the monomeric complex [Mn(CO)₃(PPh₃ )(κ ²-NS₂C₃H₄)]. The structures of 1 and 3 were established by crystallography. Shishir Ghosh, Faruque Ahmed, Rafique Al-Mamun, Daniel T. Haworth, Sergey V. Lindeman, Tasneem A. Siddiquee, Dennis W. Bennett, Shariff E. Kabir Investigations of 2-thiazoline-2-thiol as a ligand: Synthesis and X-ray structures of [Mn₂(CO)₇(μ-NS₂C₃H₄)₂] and [Mn(CO)₃ (PPh3)(κ ²-NS₂C₃H₄)].