Phenanthroline Molecules Research Articles

Trans-Bis(1,10-phenanthroline)-trans-bis(2,4,6-trinitrophenolato-O,O')calcium(II)

In the title compound, [Ca(C 6 H 2 N 3 O 7 ) 2 (C 12 H 8 N 2 ) 2 ], the Ca 2+ ion exhibits eightfold coordination with four O atoms, two from each 2,4,6-trinitrophenolate (picrate) molecule, and four N atoms from two phenanthroline molecules, forming a twisted square antiprism. The N atoms of the phenanthroline molecule are polarized by the cation so that the Ca-N distances are comparable to the Ca-O(NO) distances.

Aqua(1,10-phenanthroline)(L-serinato)copper(II) Nitrate

The unit cell of the title complex, [Cu(C 3 H 6 NO 3 )(C 12 H 8 N 2 )(H 2 O)]NO 3 , contains two nitrate anions and two complex cations, each with two chiral centers, one in the serine molecule and the other at the Cu ion. Each Cu ion displays slightly distorted square-pyramidal coordination, with the water molecule in the apical position and the base defined by the aliphatic N atom and one of the O atoms from the aminocarboxylate ligand and the two N atoms from the phenanthroline molecule. The relative position of the apical water molecule generates the chiral center at the Cu ion. In both molecules, the five-membered chelate ring defined by atoms N1, C12, C11, N2 and Cu is roughly planar, while the ring defined by atoms N3, C13, C14, O1 and Cu has a distorted half-chair conformation.

Endoreceptors with Convergent Phenanthroline Units: A Molecular Cavity for Six Guest Molecules

Three docking sites ensure that six guests jostle in the cavity of a new endo receptor. Three phenanthroline molecules are brought into close proximity by coordination of each with a CuI ion. In the FAB mass spectrometer the host complete with all six guests exists as the molecular supercomplex 1. Three bulky guest molecules are not„ invited”︁ simultaneously (R = CH3, p-C6H4CH3; R′ = H) because of the limited space in the cavity.

Synthesis, electron paramagnetic resonance and X-ray structure characterization of copper(II) ternary complexes of p-aminobenzoic and 3,4-dimethoxyhydrocinnamic acid with phenanthrolines

Dimers of the type [Cu(pAb)(phen)(H2O)]2(NO3)2· 2pAbH · 2H2O (1) and [Cu(DPP)(4,7-phen)(H2O)]2(NO3)2· 2H2O (2)(pAbH =p-aminobenzoic acid, DPPH = 3,4-dimethoxhydrocinnamic acid, phen = 1,10-phenanthroline and 4,7-phen = 4,7-dimethyl-1,10-phenanthroline) have been synthesized and characterized by means of EPR spectra in the solid and liquid states at room and low temperature, by magnetic measurements and by X-ray structure (1). Antiferromagnetic coupling of the unpaired electrons on each copper atom is evidenced by EPR spectra for both the compounds. They are, in fact, characteristic of dimers in which bridging nitrogen ligands are present. The Cu–Cu distance is 3.060 (1)A and the dimer results through the bridging of two symmetry-related pAb molecules by bidentate carboxylic groups. The two phenanthroline molecules in the dimer are stacked with a minimum distance of 3.39 (1)A.

Structural and bonding investigation of the donor?acceptor complex 1-Sn(phenanthroline)-2, 3-[Si(CH3)]3]2-2,3-C2B4H4: A comparative study of the group 14 metallacarborane-Lewis base complexes

Closo-1-Sn-2,3-[Si(CH3)3]2-2,3-C2B4H4 (1) reacts with 1,10-phenanthroline to form the complex 1-(C12H8N2)Sn-2, 3-[Si(CH3)3]2-2,3-C2B4H4. When crystals of this complex were grown slowly from benzene, a crystalline modification (2) was obtained in which the unit cell consisted of four identical molecules of the base-stannacarborane and six benzene molecules of solvation. When the complex was sublimed, a second crystalline modification (3) was obtained whose unit cell consisted of two crystaliographically different molecules (3-1 and3-2). In all three forms the tin was not symmetrically bonded to the carborane but was slipped toward the boron side of the C2B3 face, and the phenanthroline molecules were oriented opposite to the cage carbons so that the plane of the base and the carborane faces gave acute dihedral angles. However, the three forms showed a great deal of variation in the extent of slippage and the magnitudes of the base-carborane dihedral angles. Since these distortions are common structural features of base-group 14-carborane and cyclopentadienyl systems, MNDO-SCF molecular orbital calculations were carried out on the model compounds 1-(C12H8N2)Sn-2,3-C2B4H6, 1-[C10H8N2)Sn-2, 3-C2B9H11, and [(C10H8N2)-SnC5(CH3)5]+ to determine what factors dictate the structures of these complexes. The results showed that competing bonding interactions give rise to a very broad minimum in energy as a function of slippage and base orientation. Small energy variations, such as those produced by crystal packing forces, could produce large structural changes. Complex2 crystallizes in the monoclinic space group P21/n witha=11.096 (9) A,b=26.51(2) A,c=11.729 (7) A,β=107.43 (6) ∘,U=3291 (4) A3, andZ=4. Full-matrix least-squares analysis converged atR=0.044 andRw=0.055. Complex3 crystallizes in the triclinic space group P¯1 witha=10.251 (3) A,b= 13.845(9) A;c=19.168 (9) A,α=71.12 (5) ∘,β=89.29 (3) ∘,γ=84.62 (4) ∘,U=2562 (2) A3, andZ=4. The structure refined atR=0.079 andRw=0.125.

X-ray photoelectron spectroscopic evidence of interlayer complex formation between Co(II) and N-heterocycles in α-Zr(hpo 4) 2 · H 2O

Evidence from XPS Spectroscopy for coordination of the Co(II) in zirconium phosphate-phen composite is described. Analysis of the shape of the Co2 p photoelectron peak indicates that high-spin N-coordinated Co(II) is present mixed with O-coordinated Co(II). Comparison of the N1 s peak with those in parent α-Zr(HPO 4) 2(phen) 0.5 · 2H 2O confirms that Co(II) is indeed N-coordinated, but that some phenanthroline molecules anchored to the host are also present.

Palladium carbonyl hydride complexes

1. The action of carbon monoxide or the consecutive action of hydrogen and carbon monoxide on solutions of palladium acetate containing 1,10-phenanthroline gives polynuclear palladium carbonyl hydride complexes containing phenanthroline. 2. The hydrogen atoms in the a position of the coordinated phenanthroline molecules may serve as a source of the hydride atoms bound to palladium.

Solvation and Protonation of 1,10-Phenanthroline in Aqueous Dioxane Solutions

Abstract Solvation and protonation of 1,10-phenanthroline (phen) have been studied by potentiometry and calorimetry in various aqueous dioxane solutions. Protonation reactions were studied in the mixtures (the dioxane content x=0–0.4 mole fraction) containing 0.3 mol dm−3 NaCl as a constant ionic medium at 25 °C. Potentiometric and calorimetric titration curves obtained in the range of −log[H+]=2–7 were well explained in terms of the formation of Hphen+ and H(phen)2+, and the formation constants, enthalpies and entropies of formation of the species were determined. The formation constants of the both species gradually decreased with increasing x, and then the formation of H(phen)2+ became negligibly small at x>0.1, while the enthalpy and entropy of formation of Hphen+ first decreased and then increased with increasing x and thus minima were found at x=0.05. Enthalpies of solution of anhydrous 1,10-phenanthroline were also determined in both neutral (x=0–1) and acidic (0.1 mol dm−3 HCl, x=0–0.4) aqueous dioxane solutions. By knowing enthalpies of solution of 1,10-phenanthroline in acidic solutions and of formation of Hphen+ in the mixed solvents, enthalpies of solution of 1,10-phenanthroline in neutral solutions (ΔH°s(phen)) were evaluated and compared with those directly obtained in the neutral solutions (ΔH°s,neutral). A significant difference was found between ΔH°s(phen) and ΔH°s,neutral in the range x<0.3, which could be ascribed to the formation of stacked species of 1,10-phenanthroline molecules, (phen)n. The variation of ΔH°s(phen) with x was explained in terms of the enhanced solvation of dioxane to phenanthroline molecules owing to breaking of the hydrophobic water structure around them. Solvent effects on the formation of Hphen+ and H(phen)2+ were discussed in terms of different solvation behavior of 1,10-phenanthroline and proton with x.

1,10-Phenanthroline substitution in trans-dioxotetracyanomolybdate(IV)ions. The crystal structure of Na[MoO(CN) 3(Phen)]·2Phen·CH 3OH·H 2O

The crystal structure of Na[MoO(CN) 3(phen)]·2phen·CH 3OH·H 2O was determined from three-dimensional X-ray data. The brown-black crystals are monoclinic, space group P2 1/c, with cell dimensions a = 15.090, b = 14.584, c = 18.126 Å, β = 111.55° and containing four molecules per unit cell. The structure was solved from 3655 observed reflections. The anisotropic refinement converged to R = 0.075 The [MoO(CN) 3(phen)] − ion is a distorted octahedron with the oxygen and a cyanide ligand trans-orientated to the bidentate ligand atoms. The two MoN bonds (2.173(8) and 2.363(7) Å) differ significantly with the longer one trans to the strong MoO = 1.669(8) Å bond. The cyanide ligands have two normal MoC av = 2.15(1) Å bond distances and a significantly shorter MoC = 2.09(1) Å bond trans to the shorter MoN bond. The distorted six-atom environment of each sodium ion originates from one methanol, one water and two phenanthroline molecules

Highly resolved electronic absorption and luminescence spectra of some phenanthrolines in Shpolskii matrices: Part II. Fluorescence and S1←S0 absorption spectra

Highly resolved fluorescence and S 1←S 0 absorption spectra of some phenanthrolines in n-alkane matrices were obtained at 77 K. The vibrational analysis of the spectra was carried out. Mirror symmetry distortions of the fluorescence and absorption spectra were attributed to vibronic coupling between 1(π, π ∗) states. It was shown that vibronic mixing of S 1(π, π ∗) and S 2(π, π ∗) states occurs in phenanthroline molecules with S 1-S 2 energy gap not exceeding 3000 cm -1 (i.e., 4,7-, 1,7- and 1,10-Phen), whereas in other phenanthrolines the coupling of S 1 and S 3(π, π ∗) plays a dominant role. Fluorescence quantum yields of phenanthroline liquid solutions were measured. Changes of luminescence efficiencies due to the change of the polarity of the media point to a weak coupling of the lowest 1(π, π ∗) and 1(n, π ∗) states.

The adduct bis(phenylethynyl)mercury-1,10-phenanthroline

Hg(C6Hs-C-=C)2.C12HsN2, M r = 583.06, monoclinic, P2Jn , a = 22.564 (3), b = 9.577 (5), c = 10.339 (5) A, # = 96.20 (1) °, Z = 4, O c = 1.73 g cm -3, //(Mo Ktt) = 71.0 cm-L The structure was refined by least-squares procedures to R -5.9% for all measured reflexions. The Hg atom is fourcoordinated, with geometry far from tetrahedral. The two Hg--N distances and the C(11)--Hg--C(1) angle indicate a weak interaction between the phenanthroline molecule and the Hg-containing moiety. Introduction. An IR study of several bisalkynyl derivatives of Hg with 1,10-phenanthroline and 2,9-dimethyl1,10-phenanthroline has been reported by CanoEsquivel, Santos-Macias & BaUester-Reventos (1977). For Hg(C6Hs-C=C)2.CI2HsN2, the absence of some IR absorption bands prevented a clear understanding of the donor-acceptor interactions between the two moieties, so the crystal structure determination was undertaken. A crystal 0-17 x 0.07 x 0.37 mm was chosen for the data collection on an automatic four-circle PW l l00 diffractometer with Mo Ka radiation monochromated by graphite (2 = 0.7107 A). 4834 independent reflexions were measured in the 09/20 scan mode within 2 < 0 < 27 °. 1231 reflexions for which I < 2tr(I) were considered as unobserved. The systematic absences were hOt for h + I odd and 0k0 for k odd. The intensities were corrected for absorption by ORABS (Schwarzenbach, 1972)and Lorentz and polarization corrections were applied. Scattering factors for neutral atoms were taken from International Tables for X-ray Crystallography (1974). Anomalous dispersion factors for Hg were those of Cromer & Liberman (1970). The structure was solved by Patterson and Fourier syntheses allowing the location of all the non-hydrogen atoms. After anisotropic block full-matrix least-squares refinement, R was 5.9% for the measured reflexions. A difference synthesis with reflexions with sin 0/2 < 0.5 * Also at Departamento de Quimica Inorgfinica, Facultad de Quimicas, Universidad Complutense, Madrid, Spain. Table 1. Weighting scheme applied in the least-squares refinement w = K l a 2 K = 0.5263 a = a + blFol

Compounds with intermediate spin. II. The crystal structure of tris(1,10-phenanthroline)iron(II) iodine dihydrate

Abstract The crystal structure of tris(1,10-phenthroline)iron(II) iodide dihydrate, Fe(C12N2H8)3I2·2H2O, has been determined from X-ray intensity data collected on a four circle diffractometer. The space group is P21/a with four formula units in the cell. The cell dimensions are a = 10.623(2), b = 16.402(2), c = 20.375(4) A , and β = 104.48(1)°. The structure was refined by least-squares methods to a conventional R factor of 7.2%. Each Fe is pseudo-octahedrally coordinated by three phenanthroline molecules with FeN distances in the range 1.96–1.99 A. The coordination polyhedra are packed in layers parallel to the ab-plane with Fe close to z = 0.25 and 0.75. The water molecules and the iodide ions form hydrogen bond chains between the layers of the metal complexes. The FeO distances are in the range 4.90–5.54 A, and the FeI distances 6.06–6.43 A.

Adducts of bis(acetylacetonato)- and bis(trifluoroacetylacetonato) oxovanadium(IV) with 1,10-phenanthroline and related nitrogen bases

Bis(acetylacetonato)oxovanadium(IV), VO(acac) 2, reacts with 1,10-phenanthroline in methanol to afford an adduct VO(acac) 2(phen) · 2CH 3OH ( 1). The IR and electronic spectra of 1 show a close resemblance to those of the corresponding α- and β-naphthoquinoline adducts, and 1 is assumed to have a trans octahedral structure containing the phenanthroline molecule as a unidentate ligand. Although 1 attains a reversible dissociation equilibrium in dichloromethane, the trifluoroacetylacetonato complex VO(tfac) 2(phen) ( 2) is quite stable even in solution. The cis octahedral structure is assigned to 2 and also to the corresponding pyridine, α- and β-naphthoquinoline adducts VO(tfac) 2L on the basis of IR data.

ChemInform Abstract: CRYSTAL STRUCTURE OF O‐PHENANTHROLINEBIS(THIOUREA)COPPER(I) IODIDE O‐PHENANTHROLINE‐ STEREOCHEMISTRY OF (M(BIDENTATE)(UNIDENTATE)2) COORDINATION

The crystal structure of the title compound, [Cu{CS(NH2)2}2(phen)] I,phen, has been determined by X-ray diffraction with direct methods, and refined by least squares to a residual of 0.043 for 5383 ?observed? reflections. Crystals are triclinic, Pī, a 13.263(8), b 12.449(2), c 10.214(2) Ǻ, α 113.20(2), β 90.16(2), γ 112.72(2)°, Z 2. The coordination about the copper is pseudo-tetrahedral, distorted by the bite of the phenanthroline ligand [Cu-S, 2.295(2), 2.280(1) Ǻ; Cu-N, 2.072(4), 2.089(5) Ǻ, N-Cu-N, 81.0(2)°; S-Cu-S, 117.31(6)°; N-Cu-S, 107.7(11)-117.23(9)°]. In addition the structure provides the first example of the determination of the geometry of the uncoordinated o- phenanthro-line molecule. The stereochemistry of the [M(bidentate)(unidentate)2] coordination type is considered in terms of a repulsion model.

Crystal structure of o-Phenanthrolinebis(thiourea)copper(I) iodide o-phenanthroline: Stereochemistry of [M(bidentate)(unidentate)2] coordination

The crystal structure of the title compound, [Cu{CS(NH2)2}2(phen)] I,phen, has been determined by X-ray diffraction with direct methods, and refined by least squares to a residual of 0.043 for 5383 ?observed? reflections. Crystals are triclinic, Pī, a 13.263(8), b 12.449(2), c 10.214(2) Ǻ, α 113.20(2), β 90.16(2), γ 112.72(2)�, Z 2. The coordination about the copper is pseudo-tetrahedral, distorted by the bite of the phenanthroline ligand [Cu-S, 2.295(2), 2.280(1) Ǻ; Cu-N, 2.072(4), 2.089(5) Ǻ, N-Cu-N, 81.0(2)�; S-Cu-S, 117.31(6)�; N-Cu-S, 107.7(11)-117.23(9)�]. In addition the structure provides the first example of the determination of the geometry of the uncoordinated o- phenanthro-line molecule. The stereochemistry of the [M(bidentate)(unidentate)2] coordination type is considered in terms of a repulsion model.

Molecular association without co-ordination in an adduct of 1,10-phenanthroline with a manganese(II) macrocyclic complex; X-ray crystal and molecular structure

In the 1 : 1 adduct formed between 1,10-phenanthroline and the seven-co-ordinate complex Mn(232-N5)(ClO4)2·2H2O the phenanthroline molecules are not co-ordinated to the metal but are sandwiched between adjacent macrocycle planes in a lamellar structure held together mainly by hydrogen bonds and probably also by π-donor–π-acceptor and dispersion forces.

Structure cristalline et moléculaire du cis-dithiocyanatobis(phénanthroline-1,10)mercure(II), Hg(SCN)2(C12H8N2)2

The compound cis-Hg(SCN)2(Phen)2 belongs to the triclinic space group [Formula: see text] with a = 13.252(5), b = 11.077(4), c = 8.443(3) Å, α = 105.20(3), β = 83.25 (3), γ = 90.92(3)°, and Z = 2. The structure was solved by the heavy atom method and refined on 1718 independent reflections to an R factor of 0.069. The crystal contains discrete molecules, in which mercury is coordinated to four nitrogen atoms from two phenanthroline molecules and to two sulfur atoms from thiocyanate groups. These donor atoms define a distorted octahedral geometry around mercury. The Hg—N bond lengths are in the range 2.42(2)–2.52(2) Å, whereas the Hg—S bonds are equal to 2.622(8) and 2.582(8) Å. The molecules are packed in layers parallel to the (110) planes and the layers are held together by normal van der Waals interactions. Within the layers, the packing of the complex is characterized by parallel stacking of phenanthroline ligands at distances of ∼3.4 Å. The terminal nitrogen atoms of the thiocyanate groups are uncoordinated.

A Mössbauer study of iron(II)–1,10-phenanthroline complexes

Compounds of the type Fe phen2X2 and [Fe phen3]X2 have been made and studied by Mossbauer spectroscopy supplemented by infrared spectroscopy and reflectance spectra in the visible region. The results are in accordance with a cis structure for the bisphenanthroline compounds. The interactions between the phenanthroline molecules, the anionic ligands, and the iron atoms are discussed.