Bidentate Phen Research Articles

Crystal Structures and Magnetic Behaviors of Cyanido‐Bridged Dinuclear Dimetallic Systems Involving 3d–3d or 3d–5d Metal Centers

AbstractThree cyanido‐bridged FeIII–MnII dimers, [Fe(pzcq)(CN)3][Mn(phen)2(X)]·MeOH [X = Cl (1), Br (2); pzcq = 8‐(pyrazine‐2‐carboxamido)quinoline anion, phen = 1,10‐phenanthroline], [Fe(mpzcq)(CN)3][Mn(phen)2(Cl)]·MeOH [3; mpzcq = 8‐(5‐methylpyrazine‐2‐carboxamido)quinoline anion], and one WV–MnII dinuclear system, [W(bpy)(CN)6][Mn(phen)2(Cl)]·MeOH (4; bpy = 2,2′‐bipyridine), were prepared by assembling molecular precursors, [Fe(pzcq)(CN)3]–, [Fe(mpzcq)(CN)3]–, and [W(bpy)(CN)6]–, with Mn(phen)2X2. The absolute configurations of the Mn polyhedra surrounded by two bidentate phen ligands are packed in a –Δ–Λ–Δ–Λ– sequence in the crystal lattice. The aromatic rings of the coordinated phen ligands are sources of considerable interdimer π–π contacts, which eventually lead to the formation of two‐dimensional frameworks (1–3) and a one‐dimensional chain structure (4). Magnetic analyses of the FeIII–MnII dinuclear systems (1–3) reveal that a shorter Mn–N(cyanide) bond and a more linear Mn–N–C(cyanide) angle allow for stronger magnetic exchange coupling. Moreover, it is manifested that the 3d–5d magnetic coupling in 4 is stronger than the 3d–3d coupling in 1–3 under the given structural environments, which is due to the fact that the 5d orbital is more diffuse than the 3d orbital. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

Solid State Structure of [{[Ti](.MU.-.SIGMA.,.PI.-C.IDN.CSiMe3)2}Cu(1,10-phenanthroline)]-(BF4) ([Ti] = (.ETA.5-C5H4SiMe3)2Ti)

The title compound crystallizes in the monoclinic space group P21/n with a = 12.3727(4), b = 20.0249(5), c = 17.9607(6)A, β = 97.002(1)°, V = 4416.8(2)A3, and Z = 4. The crystal structure consists of a discrete [{[Ti](μ-σ,π-C≡CSiMe3)2}Cu(phen)]+ cation (phen=1,10-phenanthroline) and a non-coordinated BF4- counter-ion, whereby the copper(I) ion is four-coordinated by the two alkynyl ligands of the Ti(C≡CSiMe3)2 unit and the bidentate phen building block, and hence a 18-valence electron count is fullfilled. The Ti(C≡CSi)2 plane is oriented perpendicular to the planar [Cu(phen)]+ arrangement.

Synthesis and crystal and molecular structure of the mixed-ligand coordination compound ZnPhen(n-C4H9OCS2)2

A mixed-ligand complex ZnPhen(n-BuOCS2)2 has been synthesized. The structure of the compound was solved by X-ray diffractometry (X8 APEX diffractometer, MoK α radiation, 4254 F hkl , R = 0.0448). Triclinic crystals with the parameters a = 9.4464(3) A, b = 11.0279(4) A, c = 13.6528(6) A;α = 106.940(1)°, β = 98.382(1)°, γ = 106.347(1)°; V = 1264.72(8) A3; Z = 2, space group 1. P1¯. The structure consists of discrete mononuclear molecules. The polyhedron of the Zn atom is a trigonal bipyramid N2S3 formed by coordination of the N atoms of the bidentate Phen molecules and the sulfur atoms of the monodentate and cyclic bidentate xanthate ligands. Dimer assemblies are formed in the structure due to π-π interactions of Phen molecules.

Synthesis of New Phenanthroline‐Based Heteroditopic Ligands – Highly Efficient and Selective Fluorescence Sensors for Copper(II) Ions

AbstractThe heteroditopic phenanthroline derivatives 5,6‐bis(2‐pyridylcarboxamido)‐1,10‐phenanthroline (H2L1) and 5,6‐bis[(4‐methoxy‐2‐pyridyl)carboxamido]‐1,10‐phenanthroline (H2L2) have been prepared and characterized, together with their luminescent ruthenium(II) complexes [Ru(bpy)2(H2L1,2)](PF6)2 and [Ru(H2L1)3](PF6)2 and the corresponding iron(II) complex [Fe(H2L1)3](PF6)2. In these complexes, the metal ion is coordinated by the bidentate phen site of H2L. The luminescence of the ruthenium complexes (λex = 450 nm, λem ca. 620 nm) is completely quenched by Cu2+ ions in the micromolar concentration range and, to a lesser extent, by other metal ions. At pH 5, the response of the luminescent sensors is highly Cu2+‐selective. Heterodinuclear complexes [Ru(bpy)2(LM)](PF6)2, [Ru(LM)3](PF6)2, and [Fe(LM)3](PF6)2 have been isolated for M = Cu2+, Ni2+, Co2+, and Pd2+. It is suggested that M is coordinated to the tetradentate N4 site of L by two deprotonated amide N atoms and two pyridyl groups. This coordination type is confirmed by the EPR spectrum of the compound [RuII(bpy)2(L1CuII)](PF6)2.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Crystal structures of mixed-ligand complexes [CoPhen{(i-C4H9)2PS2}2], [Co(2,2′-Bipy){(i-C4H9)2PS2}2] and the development of dimer assemblies in them

X-ray diffraction data have been used to determine crystal structures of coordination compounds [CoPhen{ (i-C4H9)2PS2}2] (I) and [Co(2,2′-Bipy){ (i-C4H9)2PS2}2] (II) (X8-APEX diffractometer, MoK α∔ -radiation, 3083 F hkl , R = 0.0647 for I and 5381 F hkl , R = 0.0597 for II). I is triclinic, a = 11.244(1) A, b = 14.892(2) A, c = 21.419(4) A, α = 71.867(4)°, β = 81.553(4)°, γ = 76.777(4)°, V = 3306,9(8) A3; Z = 4, ρcalc = 1.321 g/cm3, space group \(P\bar 1\); II is monoclinic, a = 14.693(2) A; b = 20.868(3) A, c = 11.417(1) A; β = 106.46(5)°; V = 3357.1(7) A3, Z = 4, ρcalc = 1.254 g/cm3, space group P21/c. The structures are built from discrete mononuclear molecules. Coordination polyhedra of Co atoms are distorted octahedra formed by four S atoms of two bi-dentate chelating ligands (i-C4H9)2PS 2 − and two N atoms of two bi-dentate chelating Phen or 2,2′-Bipy molecules. The interaction of the molecules in the structures of I and II has been analyzed. It has been found that the molecules of I and II form dimer ensembles owing to π-π-interactions of Phen or 2,2′-Bipy.

Crystal structure of [MnII (1,10-C12H8N2)3]2+[(B9C2H11)CoIII(B8C2H10)CoIII(B9C2H11)]2−·CH3CN

A novel compound, [MnPhen3][(B9C2H11)Co(B8C2H10)Co(B9C2H11)]· CH3CN (Phen = 1,10-phenantroline), comprising a Co(III) dicobaltacarborane cluster anion has been prepared and characterized by single crystal X-ray diffraction. Crystal data are the following: C44H59B26N7Co2Mn, M = 1139.84, triclinic, space group $$P\bar 1$$ , unit cell parameters: a = 13.2465(11) A, b = 14.521(2) A, c = 15.2536(15) A; α = 77.027(9)°, β = 88.500(8)°, γ = 77.274(9)°; V = 2788.5(5) A3, Z = 2, d calc = 1.358 g/cm3, T = 295 K, F(000) = 1162, μ = 0.853 mm−1. The structure was solved by the direct and Fourier methods and refined anisotropically (isotropically for hydrogen atoms) using the full-matrix technique to final factors R 1 = 0.0374, wR 2 = 0.0915 for 7397 I hkl ≥2σI of 9779 I hkl measured (diffractometer Enraf-Nonius CAD-4, λMoK α , graphite monochromator, θ/2θ-scanning). The structure is formed from [MnPhen3]2+ cations, [(B9C2H11)×Co(B8C2H10)Co(B9C2H11)]2− anions, and acetonitrile molecules CH3CN. Central Mn atom in the cation has a distorted octahedral coordination environment formed by six nitrogen atoms of three bi-dentate Phen ligands, average Mn-N bond length being 2.263(2) A. The anion has a chain-like structure built from three icosahedra sharing common vertices occupied by the cobalt atoms. The central icosahedron including ten light atoms (8B, 2C) provides two vertices for the cobalt atoms shared with the other icosahedra having 11 light atoms (9B, 2C). The arrangement of-C2-groups in the anion corresponds to a quasi-gauche-configuration of asymmetric sandwich complexes of both cobalt atoms.

Crystal structures and luminescence properties of [Eu(ODA)·(phen)·4H 2O] +, [Tb(ODA)·(phen)·4H 2O] + and [Tb(ODA) 3] 3− (ODA: oxydiacetate, phen: 1,10-phenanthroline)

Two novel complexes of Eu(III) and Tb(III) with mixed oxydiacetate (ODA) and 1,10-phenanthroline (phen) ligands and a Tb(III) complex with homoleptic ODA were prepared and their crystal structures were determined: [Eu(ODA)·(phen)·4H 2O]Cl·5H 2O, monoclinic, P2 1/n, a = 12.3197(12) Å, b = 16.7992(17) Å, c = 12.6754(10) Å, β = 107.981(8)°, V = 2495.2(4) Å 3, Z = 4, R(| F|) = 0.0324 for 5728 data; [Tb(ODA)·(phen)·4H 2O]Cl·5H 2O monoclinic, P2 1/n, a = 12.2846(13) Å, b = 16.7560(14) Å, c = 12.6681(11) Å, β = 108.144(8)°, V = 2478.0(4) Å 3, Z = 4, R(| F|) = 0.0279 for 4364 data; Na 3[Tb(ODA) 3]·8H 2O monoclinic, Cc, a = 15.751(3) Å, b = 9.8030(14) Å, c = 18.189(4) Å, β = 105.513(15)°, V = 2706.2(9) Å 3, Z = 4, R(| F|) = 0.0406 for 3435 data. In these structures, the rare earth ions satisfy nine-coordination via binding to tridentate ODA, bidentate phen or water molecules. The geometry of the nine-coordinate polyhedron is discussed in terms of the dihedral angle and the mean plane. Photoluminescence (PL) and excitation spectra of Eu(III) and Tb(III) complexes with mixed ODA and phen ligands and with homoleptic ODA are reported. The complexes of [Eu(ODA)·(phen)·4H 2O] + and [Tb(ODA)·(phen)·4H 2O] + excited by UV light produce very bright red and green emissions, respectively, via the nonradiative energy-transfer from phen to the metals. For [Eu(ODA)·(phen)·4H 2O] + and [Tb(ODA)·(phen)·4H 2O] +, the quantum yields of the sensitized luminescence ( Q = 6.6 and Q = 75.7%, respectively) are much greater than those of the nonsensitized luminescence ( Q = 2.0 and Q = 21.0%, respectively).

Rhenium(IV)−Copper(II) Heterobimetallic Complexes with a Bridge Malonato Ligand. Synthesis, Crystal Structure, and Magnetic Properties

The Re(IV) complex [ReCl4(mal)]2-, in the form of two slightly different salts, (AsPh4)1.5(HNEt3)0.5[ReCl4(mal)] (1a) and (AsPh4)(HNEt3)[ReCl4(mal)] (1b), and the Re(IV)-Cu(II) bimetallic complexes [ReCl4(mu-mal)Cu(phen)2].CH3CN (2), [ReCl4(mu-mal)Cu(bpy)2] (3), and [ReCl4(mu-mal)Cu(terpy)] (4) (mal=malonate dianion, AsPh4=tetraphenylarsonium cation, HNEt3=triethylammonium cation, phen=1,10-phenanthroline, bpy=2,2'-bipyridine and terpy=2,2':6',2' '-terpyridine) have been synthesized and the structures of 1a, 1b, 2, and 3 determined by single-crystal X-ray diffraction. The structures of 1a and 1b are made up of discrete [ReCl4(mal)]2- anions and AsPh4+ and HNEt3+ cations, held together by electrostatic forces and hydrogen bonds. The Re(IV) atom is surrounded by four chloride anions and a bidentate malonate group, in a distorted octahedral environment. The structure of 2 consist of neutral dinuclear units [ReCl4(mu-mal)Cu(phen)2], with the metal ions united through a bridge carboxilato. The environment of Re(IV) is nearly identical to that in the mononuclear complex, and Cu(II) is five coordinate, being surrounded by four nitrogen atoms of two bidentate phen ligands and one oxygen atom of the malonato ligand. In 3, there are also dinuclear units, [ReCl4(mu-mal)Cu(bpy)2], but the Cu(II) ions complete a distorted octahedral coordination by binding with the free malonato oxygen atom of a neighbor unit, resulting in an infinite chain. The magnetic properties of 1-4 were also investigated in the temperature range 2.0-300 K. The magnetic behavior of 1a and 1b is as expected for a Re(IV) complex with a large value of the zero-field splitting (2D ca. 110 cm(-1)). For the bimetallic complexes, the magnetic coupling between Re(IV) and Cu(II) is antiferromagnetic in 2 (J=-0.39 cm(-1)), ferromagnetic in 4 (J=+1.51 cm(-1)), and nearly negligible in 3 (J=-0.09 cm(-1)).

Synthesis, crystal structures, and anti-convulsant activities of ternary [Zn II(3,5-diisopropylsalicylate) 2], [Zn II(salicylate) 2] and [Zn II(aspirinate) 2] complexes

Following observations that bis(3,5-diisopropylsalicylato)diaquazinc II, [Zn II(3,5-DIPS) 2(H 2O) 2], had anti-convulsant activity, bis(acetylsalicylate)diaquazinc II, [Zn II(aspirinate) 2(H 2O) 2], and the Zn II ternary 1,10-phenanthroline (phen), 2,9-dimethyl-1,10-phenanthroline (neocuproine, NC) or dimethyl sulfoxide (DMSO) complexes of Zn II3,5-diisopropylsalicylate, salicylate, and acetylsalicylate were synthesized and spectroscopically characterized. Anti-convulsant and Rotorod toxicity activities of these complexes were determined to examine their anti-convulsant and undesirable central nervous stimulant or depressant activities of these Zn II non-steroidal anti-inflammatory agent complexes. Bis(3,5-diisopropylsalicylato)-1,10-phenanthorlinezinc II, [Zn II(3,5-DIPS) 2(phen)], ( 1) has one bidentate phen ligand and two mono-deprotonated 3,5-DIPS ligands. One of the carboxylates bonds in an asymmetric chelating mode. The Zn II atom exhibits a distorted bicapped rectangular pyramidal environment N 2O 2OO (4 + 1 + 1∗). In the neocuproine complex, bis(3,5-diisopropylsalicylato)-2,9-dimethyl-1,10-phenanthorlinezinc II, [Zn II(3,5-DIPS) 2(NC)] ( 2), the Zn II atom has a much more distorted bicapped rectangular pyramidal environment, N 2O 2O 2 (4 + 2∗), compared to 1. The two carboxylate ligands exhibit the same asymmetric coordinating mode with longer metalloelement–oxygen bond distances compared to 1. The space group of [Zn II(aspirinate) 2(H 2O) 2] ( 3), which has been reported as Cc is corrected to C2/c. The zinc atom exhibits a (4 + 2∗) bicapped square pyramidal environment. While the two ternary phenanthroline-containing complexes, 1 and 2, evidenced weak protection against maximal electroshock (MES)- and subcutaneous Metrazol (scMET) induced seizures, [Zn II(3,5-DIPS) 2(DMSO) 2], [Zn II(aspirinate) 2(H 2O) 2], and bis(salicylato)-1,10-phenanthorlinezinc II, [Zn II(salicylate) 2(phen)], were found to be particularly useful in protecting against MES and scMET seizures and [Zn II(aspirinate) 2(H 2O) 2] and [Zn II(salicylate) 2(phen)] were found to have activity in protecting against Psychomotor seizures, without causing Rotorod toxicity. Activities of these and other Zn II complexes of non-steroidal anti-inflammatory agents are consistent with the well-known anti-inflammatory responses of Zn II-dependent enzymes. There was also some evidence of Rotorod toxicity consistent with a mechanism of action involving sedative-hypnotic activity of recognized anti-epileptic drugs.

A novel heterometallic FeII–Na+phase: 1,10-phenanthrolinium aquabis(1,10-phenanthroline)sodium(I) pentacyanonitrosoiron(II) monohydrate

The structure of the title compound, (C12H9N2)[Na(C12H8N2)2(H2O)][Fe(CN)5(NO)]·H2O, is built up from FeII-containing anions, Na+-containing cations, non-coord­inated 1,10-phenanthrolinium (Hphen) cations and water mol­ecules. The sodium cation is coordinated to two N,N′-bidentate phen ligands and one water mol­ecule in approximate square-based pyramidal geometry, with the O atom occupying the axial site. The non-coordinated Hphen and water mol­ecules link the metal complexes through O—H⋯N and N—H⋯O hydrogen bonds, forming a three-dimensional network.

Hydrothermal syntheses and crystal structures of two 4,4′-biphenyldicarboxylate copper(II) complexes with 1,10-phenanthroline

Two structurally diverse compounds, [Cu(Hbpdc) 2(phen)] ( 1) and [Cu(bpdc)(phen)(H 2O)] n ( 2) (H 2bpdc=4,4′-biphenyldicarboxylic acid, phen=1,10-phenanthroline), were synthesized under hydrothermal conditions. Copper atom in 1 is four-coordinated to one bidentate phen ligand and two monodentate partly deprotonated 4,4′-biphenyldicarboxylates. As expected, the structure of 1 is a monomeric species and affords an extended two-dimensional hydrogen bonding architecture. Each copper atom in 2 is five-coordinated to one phen, one water molecule, and two bis-monodentate fully deprotonated 4,4′-biphenyldicarboxylates. Therefore, the structure of 2 is a one-dimensional chain.

Diaquabis(1,10-phenanthroline-kappa(2)N,N')manganese(II) thiodiglycolate bis(1,10-phenanthroline-kappa(2)N,N')(thiodiglycolato-kappa(2)O,O')manganese(II) tridecahydrate.

The title compound, [Mn(C(12)H(8)N(2))(2)(H(2)O)(2)](C(4)H(4)O(4)S).[Mn(C(4)H(4)O(4)S)(C(12)H(8)N(2))(2)].13H(2)O, contains one dianion of thiodiglycolic acid (tdga(2-)) and two independent manganese(II) moieties, viz. [Mn(phen)(2)(H(2)O)(2)](2+) and [Mn(tdga)(phen)(2)], where phen is 1,10-phenanthroline. The Mn(II) atoms are octahedrally coordinated by four N atoms of two bidentate phen ligands [Mn-N = 2.240 (2)-2.3222 (19) A] and either two water O atoms or two tdga carboxyl O atoms [Mn-O = 2.1214 (17)-2.1512 (17) A]. The tdga ligand chelates as an O,O'-bidentate ligand, forming an eight-membered ring with one Mn atom. The free tdga(2-) dianion is hydrogen bonded to an [Mn(phen)(2)(H(2)O)(2)](2+) ion, with O.O distances of 2.606 (2) and 2.649 (2) A. The crystal structure is further stabilized by an extensive network of hydrogen bonds involving 13 water molecules.

A nickel(II) fumarate complex witho-phenanthroline

In the dinuclear and centrosymmetric title complex, μ-fumarato-bis[aquabis(1,10-phenanthroline)nickel(II)] fumar­ate hexadecahydrate, [Ni2(C4H2O4)(C12H8N2)4(H2O)2](C4H2O4)·16H2O or [Ni2(phen)4L(H2O)2]L·16H2O, where phen = 1,10-phenanthroline and L2− = fumarate, the nickel(II) cation is six-coordinated by two O atoms, one from a water mol­ecule and the other from one end of a bridging L2− anion, and four N atoms from two bidentate phen ligands. Each of the two independent L2− anions is located about an inversion centre. Interestingly, one L2− anion is bridging and the other acts as a counter-ion. The [Ni2(phen)4L(H2O)2]2+ cations, water mol­ecules and L2− anions are connected through complex hydrogen-bonding interactions to form a three-dimensional structure.

Dithiosquarate (dtsq) complexes of nickel(II). Syntheses and crystal structures of [Ni(phen) 2(1,2-dtsq)]·3.5H 2O, [Ni(phen) 2(1,3-dtsq)] and [Ni(tren)(1,2-dtsq)] [phen=1,10-phenanthroline; tren=tris(2-aminoethyl)amine

The new nickel(II) complexes [Ni(phen) 2(1,2-dtsq)]·3.5H 2O ( 1), [Ni(phen) 2(1,3-dtsq)] ( 2) and [Ni(tren)(1,2-dtsq)] ( 3) [1,2-dtsq=dianion of 3,4-dimercapto-3-cyclobutene-1,2-dione, 1,3-dtsq=dianion of 3-hydroxy-4-mercapto-2-thioxo-3-cyclobuten-1-one, phen=1,10-phenanthroline and tren=tris(2-aminoethyl)amine] have been synthesized and characterized by single-crystal X-ray diffraction. Their structures are made up of neutral [Ni(phen) 2(1, n-dtsq)] [ 1 ( n=2) and 2 n=3)] and [Ni(tren)(1,2-dtsq)] ( 3) mononuclear units. The nickel atom is six-coordinated in all three cases: four nitrogen atoms from two bidentate phen ( 1 and 2) or a tetradentate tren ( 3) groups and either two sulfur ( 1 and 3) or a sulfur and an oxygen atoms ( 2) atoms from the dithiosquarate (dtsq) ligands form a distorted octahedron around the metal atom. The NiN(phen) bond lengths [2.082(5)–2.103(5) Å for 1 and 2.075(8)–2.124(9) Å for 2] are very close to that of NiN(tren) [2.088(2)–2.140(2) Å for 3]. The NiS bond distances are 2.4598(15) and 2.4817(15) Å for 1, 2.497(3) Å for 2 and 2.4362(6) and 2.6446(7) Å for 3. The values of the angle subtended at the metal atom by the 1,2-dtsq [91.06(4) ( 1) and 89.61(2)° ( 3)] and 1,3-dtsq [88.4(2)° ( 2)] ligands are very close to the ideal value of 90° in spite of their asymmetric bidentate coordination. The influence of the number and position of sulfur atoms of these ligands on their coordination modes is analyzed and discussed in the light of the available structural data.

Synthesis, crystal structure and IR spectroscopy of Mn II(2-IC) 2(NC)(DMSO) and [Mn II(2-IC) 2(phen)(H 2O)]·DMA; (2-HIC, indole-2-carboxylic acid; phen, 1,10-phenanthroline; NC, 2,9-dimethyl-1,10-phenanthroline; DMSO, dimethyl sulfoxide; DMA, dimethyl acetamide); catalysts for the disproportionation of hydrogen peroxide

Two ternary complexes of manganese(II) indole-2-carboxylate (2-IC) with 2,9-dimethyl-1,10-phenanthroline (NC) and 1,10-phenanthroline (phen) in dimethyl sulfoxide (DMSO) or dimethylacetamide (DMA) were synthesized, their X-ray crystal structure and IR spectroscopy characteristics were determined. In compound Mn II(2-IC) 2(NC)(DMSO) ( 1), Mn(II) is six-coordinate by one bidentate NC ligand and two bidentate 2-IC anionic ligands. The crystal structure has revealed a seven-coordinate Mn(II) when a moderately long contact distance MnO (DMSO 2.643(2) Å) is included in the coordination list: the Mn(II) configuration can be described as a distorted capped octahedron. Individual molecules are linked into chains running parallel to the a axis by intermolecular hydrogen bonding. In compound Mn II(2-IC) 2(phen)(H 2O)]·DMA ( 2), the manganese atom is six-coordinate by one bidentate phen ligand and two 2-IC anionic ligands one of which is monodentate, and the other is bidentate. The coordination sphere is completed by one water molecule, the Mn(II) environment can be described as a very distorted octahedron. The individual molecules are associated in dimmer structure by intermolecular hydrogen bonding. The crystal structure of 2 is completed by a disordered DMA solvate molecule. These two complexes are catalysts for the disproportionation of H 2O 2 in the presence of added imidazole.

Crystal Structure of the Mixed-Ligand Compound [HgPhen{(C2H5)2NCS2}2] and the Character of Intermolecular Interactions in [MPhen{(C2H5)2NCS2}2] (M = Zn, Cd, Hg)

Single crystals of the mixed-ligand complex compound [HgPhen(Et2NCS2)2] were obtained. The crystal structure of the compound was determined by X-ray diffraction analysis (CAD-4 diffractometer, Mo $$K_\alpha $$ radiation, 3640 F hkl , R = 0.0280). Triclinic crystals with cell parameters a = 10.308(2), b = 11.171(3), c = 11.552(2) A, α = 94.16(2), β = 96.66(1), γ = 105.17(2)°, V = 1267.8(5) A3, Z = 2, d calc = 1.774 g/cm3, space group $$P\bar 1$$ . The structure is composed of discrete monomer molecules. The coordination polyhedron of the Hg atom is a distorted octahedron formed by four S atoms of the two cyclic bidentate Et2 $$NCS_{2^ - } $$ ligands and two N atoms of the cyclic bidentate Phen ligand. The character of interactions between [MPhen(Et2NCS2)2] (M = Zn, Cd, Hg) molecules and their packing in the structure are considered.

Aqua(nitrilotriacetato)(1,10-phenanthroline)iron(III) monohydrate: a seven-coordinate iron(III) complex.

Reaction of 1,10-phenanthroline (phen) with iron trichloride in the presence of sodium nitrilotriacetate (NTA) resulted in the formation of red crystals of the title complex, [Fe(C6H6NO6)(C12H8N2)(H2O)]*H2O. The Fe atom has a distorted capped trigonal prismatic coordination comprised of one tetradentate NTA, one bidentate phen molecule and a water molecule. Intermolecular O-H...O hydrogen bonds link the molecules into infinite chains. The chains are crosslinked by hydrogen bonds involving the solvent water molecule, leading to an infinite ladder packing mode.

Molecular Packing in the Crystal Structures of Mixed-Ligand Complexes [ZnPhen{(i-C 4 H 9 ) 2 PS 2 } 2 ] and [Zn(2,2′-Bipy){(i-C 4 H 9 ) 2 PS 2 } 2

Volatile mixed-ligand complexes of Zn(i-Bu2PS2)2 with Phen and 2,2′-Bipy have been synthesized. The crystal structures of the complexes ZnPhen{(i-C4H9)2PS2}2 and Zn(2,2′-Bipy){(i-C4H9)2PS2}2 were determined by single crystal X-ray diffractometry (CAD-4 diffractometer, MoKα radiation, 2100 Fhkl, R = 0.0423 for the first complex and 2003 Fhkl, R = 0.0486 for the second). The crystals are monoclinic with cell dimensions a = 17.580(4), b = 9.969(2), c = 19.175(4) A, β = 90.33(3)°, V = 3360(1) A3, Z = 4, d calc = 1.313 g/cm3, space group P2/n (for the Phen complex); a = 24.219(5), b = 11.386(2), c = 24.916(5) A, β = 97.70(3)°, V = 6809(2) A3, Z = 8, d calc = 1.249 g/cm3, space group C2/c (for the 2,2′-Bipy complex). The complexes are constructed from discrete monomer molecules. The coordination polyhedra of the Zn atoms are distorted tetrahedra formed by two S atoms of the two monodentate i-Bu2PS 2 - ligands and two N atoms of the cyclic bidentate Phen or 2,2′-Bipy molecules. Intermolecular interactions and packings in the structures are analyzed.

Bis

The crystal structure of the title compound, [NiCl(C12H8N2)2(CH4N2S)]2(NO3)­Cl·­2C2H6O, is formed by [Ni(phen)2(thio­urea)Cl]+ cations (phen = 1,10-phenanthroline), chloride and nitrate counter-ions, and ethanol solvate mol­ecules. The Ni atom is octahedrally coordinated to two bidentate phen ligands, a monodentate thio­urea and a chloride ion. Both the chloride and nitrate anions, which provide charge balance, are located at special positions on a twofold symmetry axis. Hydro­gen bonds play a key role in the packing and conformation of the cation and create a three-dimensional network.

Synthesis, crystal structure and thermal behaviour of Ba(hfa) 2(Phen) 2 and the crystal structure of Ba 2(hfa) 2(μ 2-CF 3COO) 2(Phen) 4 (hfa=hexafluoroacetylacetonate, Phen= o-Phenanthroline)

Ba(hfa) 2(Phen) 2 ( I) was obtained by the interaction of Ba(hfa) 2 and Phen and by the reaction of metallic barium with hexafluoroacetylacetone and Phen. Crystal structures of I and the by-product, Ba 2(hfa) 2(μ 2-CF 3COO) 2(Phen) 4 ( II), were determined by single crystal X-ray diffraction. Complex I has a mononuclear structure with four oxygen and four nitrogen atoms in the coordination sphere of the central Ba 2+ ion. The average distances are: Ba–O (2.71 Å) and Ba–N (2.89 Å). In centrosymmetric dimeric molecules of II, both barium ions are eight-coordinated as a result of the coordination of one bidentate hfa-ligand, two bidentate Phen ligands and two oxygen atoms of both bridge tfa-ligands. The average distances of Ba–O and Ba–N are 2.71 Å and 2.91 Å, respectively. The geometry of the Ba coordination sphere and the packing in I and II are discussed. Thermal gravimetric analyses showed that I sublimed with the evolution of Phen and the formation of volatile Ba(hfa) 2(Phen).