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1.  Synthesis, Characterization, and Reactivity of Cobalt(III)–Oxygen Complexes Bearing a Macrocyclic N-Tetramethylated Cyclam Ligand 
Mononuclear metal–dioxygen species are key intermediates that are frequently observed in the catalytic cycles of dioxygen activation by metal-loenzymes and their biomimetic compounds. In this work, a side-on cobalt-(III)–peroxo complex bearing a macro-cyclic N-tetramethylated cyclam (TMC) ligand, [CoIII(15-TMC)(O2)]+, was synthesized and characterized with various spectroscopic methods. Upon protonation, this cobalt(III)–peroxo complex was cleanly converted into an end-on cobalt(III)–hydroperoxo complex, [CoIII(15-TMC)(OOH)]2+. The cobalt(III)–hydroperoxo complex was further converted to [CoIII(15-TMC-CH2-O)]2+ by hydroxylation of a methyl group of the 15-TMC ligand. Kinetic studies and 18O-labeling experiments proposed that the aliphatic hydroxylation occurred via a CoIV–oxo (or CoIII–oxyl) species, which was formed by O–O bond homolysis of the cobalt(III)–hydroperoxo complex. In conclusion, we have shown the synthesis, structural and spectroscopic characterization, and reactivities of mono-nuclear cobalt complexes with peroxo, hydroperoxo, and oxo ligands.
doi:10.1002/chem.201300107
PMCID: PMC3928501  PMID: 24038300
aliphatic hydroxylation; bioinorganic chemistry; cobalt; macrocyclic ligands; oxygen
2.  Bis(acetato-κO)bis­(pyridine-2-aldoxime-κ2 N,N′)nickel(II) 
In the mononuclear title compound, [Ni(CH3COO)2(C6H6N2O)2], the NiII atom is coordinated by two pyridine-2-aldoxime (PaoH) ligands and two acetate groups, with cis coordination for the pairs of identical ligands. While each acetate group binds to the NiII atom by one O atom, each PaoH chelates the NiII atom through two N atoms. The O atom on PaoH is not deprotonated and does not participate in bonding to the NiII atom. Thus, the NiII atom exhibits an octa­hedral environment. Intra­molecular O—H⋯O hydrogen-bonding inter­actions and inter­molecular C—H⋯O hydrogen-bonding inter­actions are present in the structure. Adjacent mol­ecules pack along [100] through van der Waals forces.
doi:10.1107/S1600536812014377
PMCID: PMC3344309  PMID: 22590075
3.  Tetra­ethyl­ammonium (2,2′-bipyridine)tetra­cyanidocobaltate(III) sesquihydrate acetonitrile solvate 
The title complex, (C8H20N)[Co(CN)4(C10H8N2)]·CH3CN·1.5H2O, consists of tetra­ethyl ammonium cations, mononuclear [CoIIIbpy(CN)4]− anions and uncoordinated water and acetonitrile mol­ecules. The CoIII atom is six-coordinated by two 2,2′-bipyridine (bpy) N atoms and four cyanide C atoms in a distorted octa­hedral geometry. The acute bite angle of the chelating bpy [82.28 (8)°] is the main factor accounting for this distortion. In addition, the tetra­ethyl­ammonium cation is significantly disordered [occupancy ratio 0.611 (3):0.389 (3)]. The presence of water mol­ecules, one of which is disordered over two positions about an inversion center, results in the formation of a network of O—H⋯N hydrogen bonds involving the cyanide N atoms.
doi:10.1107/S1600536810011311
PMCID: PMC2983854  PMID: 21580557
4.  Chloridobis(ethyl­enediamine-κ2 N,N′)(n-pentyl­amine-κN)cobalt(III) dichloride monhydrate 
The title complex, [CoCl(C5H13N)(C2H8N2)2]Cl2·H2O, comprises one chloridobis(ethyl­enediamine)(n-pentyl­amine)cobalt(III) cation, two chloride counter-anions and a water mol­ecule. The CoIII atom of the complex is hexa­coordinated by five N and one Cl atoms. The five N atoms are from two chelating ethyl­enediamine and one n-pentyl­amine ligands. Neighbouring cations and anions are connected by N—H⋯Cl and N—H⋯O hydrogen bonds to each other and also to the water mol­ecule.
doi:10.1107/S1600536809022764
PMCID: PMC2969482  PMID: 21582753
5.  Synthesis and Biological Activity of Manganese (II) Complexes of Phthalic and Isophthalic Acid: X-Ray Crystal Structures of [Mn(ph)(Phen)2(H2O)]· 4H2O, [Mn(Phen)2(H2O)2]2(Isoph)2(Phen)· 12H2O and {[Mn(Isoph)(bipy)]4· 2.75biby}n(phH2 = Phthalic Acid; isoph = Isophthalic Acid; phen = 1,10-Phenanthroline; bipy = 2,2-Bipyridine) 
Metal-Based Drugs  2000;7(5):275-288.
Manganese(II) acetate reacts with phthalic acid (phH2) to give [Mn(ph)]·0.5H2O (1). Reaction of 1 with 1,10-phenanthroline produces [Mn(ph)(phen)]·2H2O (2) and [Mn(ph)(phen)2(H2O)]·4H2O (3). Reaction of isophthalic acid (isophH2) with manganese(II) acetate results in the formation of [Mn(isoph)]·2H2O (4). The addition of the N,N-donor ligands 1,10-phenanthroline or 2,2'-bipyridine to 4 leads to the formation of [Mn2 (isoph)2(phen)3)]·4H2O (5), [(Mn(phen)2(H2O)2]2(isoph)2(phen)·12H2O (6) and {[Mn(isoph)(bipy)]4·2.75 biby}n (7), respectively. Molecular structures of 3, 6 and 7 were determined crystallographically. In 3 the phthalate ligand is bound to the manganese via just one of its carboxylate groups in a monodentate mode with the remaining coordination sites filled by four phenanthroline nitrogen and one water oxygen atoms. In 6 the isophthalates are uncoordinated with the octahedral manganese center ligated by two phenanthrolines and two waters. In 7 the Isophthalate ligands act as bridges resulting in a polymeric structure. One of the carboxylate groups is chelating a single manganese with the other binding two metal centres in a bridging bidentate mode. The phthalate and isophthalate complexes, the metal free ligands and a number of simple manganes salts were each tested for their ability, to inhibit the growth of Candida albicans. Only the “metal free” 1,10-phenanthroline and its manganese complexes were found to be active.
doi:10.1155/MBD.2000.275
PMCID: PMC2365232  PMID: 18475957
6.  Di-μ2-acetato-diacetato-bis­{μ2-3,3′,5,5′-tetra­meth­oxy-2,2-[ethane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato}tricobalt(II,III) dichloro­methane disolvate 
The trinuclear title compound, [Co3(CH3COO)4(C20H22N2O6)2]·2CH2Cl2, contains mixed-valence cobalt ions in the following order CoIII–CoII–CoIII where all the three cobalt ions are hexa­coordinated. The central cobalt ion is situated on an inversion centre and is in an all-oxygen environment, coordinated by four phenolate O atoms and two O atoms from bridging acetate groups, while the terminal cobalt ion is hexa­coordinated by two phenolate O atoms, two acetate O atoms and two imine N atoms. This complex contains a high-spin central CoII and two terminal low-spin CoIII i.e. CoIII(S = 0)–CoII(S = 3/2)-CoIII(S = 0). There are weak inter­molecular C—H⋯O inter­actions involving the meth­oxy groups, as well as inter­molecular C—H⋯O inter­actions involving the acetate anions. In addition, the dichoromethane solvate mol­ecules are held in place by weak C—H⋯Cl inter­actions.
doi:10.1107/S1600536811003783
PMCID: PMC3052101  PMID: 21522241
7.  (2-Acetyl­phenolato)(2-{1-[2-(morpholin-4-yl)ethyl­imino]­eth­yl}phenolato)(thio­cyanato-κN)­cobalt(III) 
The title mononuclear cobalt(III) complex, [Co(C14H19N2O2)(C8H7O2)(NCS)], was obtained by the reaction of 2-acetyl­phenol, 2-(morpholin-4-yl)ethyl­amine, ammonium thio­cyan­ate and cobalt nitrate in methanol. The CoIII atom is coordinated by one phenolate O, one imine N, and one amine N atom of the tridentate Schiff base ligand, two O atoms of the 2-acetyl­phenolate anion and one thio­cyanate N atom. This results in a fairly regular fac-CoN3O3 octa­hedral coordination geometry for the metal ion. The dihedral angle between the two benzene rings is 88.3 (3)°.
doi:10.1107/S1600536811025116
PMCID: PMC3151850  PMID: 21836833
8.  Oxidative Stress and Antimicrobial Activity of Chromium(III) and Ruthenium(II) Complexes on Staphylococcus aureus and Escherichia coli 
BioMed Research International  2013;2013:906912.
The prevalence of antibiotic resistance has resulted in the need for new approaches to be developed to combat previously easily treatable infections. The main aim of this work was to establish the potential of the synthetic α-diimine chromium(III) and ruthenium(II) complexes (where the α-diimine ligands are bpy = 2,2-bipyridine, phen = 1,10-phenanthroline, and dppz = dipyrido[3,2-a:2′,3′-c]-phenazine) like [Cr(phen)3]3+, [Cr(phen)2(dppz)]3+, [Ru(phen)3]2+, and [Ru(bpy)3]2+ as antibacterial agents by generating oxidative stress. The [Cr(phen)3]3+ and [Cr(phen)2(dppz)]3+ complexes showed activity against Gram positive and Gram negative bacteria with minimum inhibitory concentrations (MICs) ranging from 0.125 μg/mL to 1 μg/mL, while [Ru(phen)3]2+ and [Ru(bpy)3]2+ do not exhibit antimicrobial activity against the two bacterial genera studied at the concentration range used. When ciprofloxacin was combined with [Cr(phen)3]3+ for the inhibition of Staphylococcus aureus and Escherichia coli, an important synergistic effect was observed, FIC 0.066 for S. aureus and FIC 0.064 for E. coli. The work described here shows that chromium(III) complexes are bactericidal for S. aureus and E. coli. Our results indicate that α-diimine chromium(III) complexes may be interesting to open new paths for metallodrug chemotherapy against different bacterial genera since some of these complexes have been found to exhibit remarkable antibacterial activities.
doi:10.1155/2013/906912
PMCID: PMC3777176  PMID: 24093107
9.  Tetra­kis[μ-2-(3,4-dimeth­oxy­phen­yl)acetato]-κ3 O 1,O 1′:O 1;κ3 O 1:O 1,O 1′;κ4 O 1:O 1′-bis­{[2-(3,4-dimeth­oxy­phen­yl)acetato-κ2 O 1,O 1′](1,10-phenanthroline-κ2 N,N′)erbium(III)} 
In the dimeric centrosymmetric title complex, [Er2(C10H11O4)6(C12H8N2)2], the ErIII ion is nine-coordinated by five 2-(3,4-dimeth­oxy­lphen­yl)acetic acid (DMPA) ligands via seven O atoms and two N atoms from a bis-chelating 1,10-phenanthroline (phen) ligand in a distorted tricapped trigonal-prismatic geometry. The DMPA ligands are coordinated to the ErIII ion in bis-chelate, bridging and bridging tridentate modes. Relatively weak intra­molecular C—H⋯O inter­actions reinforce the stability of the mol­ecular structure. Inter­molecular C—H⋯O inter­actions are also observed.
doi:10.1107/S1600536810040298
PMCID: PMC3009341  PMID: 21588841
10.  Bis(N,N-diethyl­dithio­carbamato)(1,10-phenanthroline)cobalt(III) tetra­fluorido­borate 
The cationic complex in the structure of the title compound, [Co(Et2NCS2)2(C12H8N2)]BF4, has a CoIII atom with a distorted octa­hedral coordination formed by four S atoms of two diethyl­dithio­carbamate and two N atoms of 1,10-phenanthroline ligands. The crystal structure features head-to-tail stacking of the phenanthroline ligands. The tetra­fluorido­borate anions are positioned in the channels between the cation stacks running along the a axis, and form weak C—H⋯F interactions.
doi:10.1107/S160053680801725X
PMCID: PMC2961857  PMID: 21202776
11.  [2-(2-Carboxy­phen­yl)benzoato]bis­(1,10-phenanthroline)zinc(II) 2-(2-carboxy­phen­yl)benzoate monohydrate 
In the title compound, [Zn(C14H9O4)(C12H8N2)2](C14H9O4)·H2O, the ZnII atom of the complex cation is six-coordinated in an octa­hedral geometry by four N atoms from two 1,10-phenanthroline ligands and two O atoms of a carboxyl­ate group from a singly deprotonated diphenic acid. The phenanthroline and carboxylate ligands act as chelating ligands. The dihedral angles between the two benzene rings in the deprotonated diphenic acid groups are 81.05 (2) (ligand) and 89.10 (2)° (anion). O—H⋯O and C—H⋯O hydrogen bonds link the components into a three-dimensional network.
doi:10.1107/S1600536808005862
PMCID: PMC2961034  PMID: 21201991
12.  Tetra­kis(μ2-2-phen­oxy­propionato)-κ3 O,O′:O′;κ3 O:O,O′;κ4 O:O′-bis­[(1,10-phenanthroline-κ2 N,N′)(2-phen­oxy­propionato-κ2 O,O′)cerium(III)] 
In the centrosymmetric binuclear title complex, [Ce2(C9H9O3)6(C12H8N2)2], the two CeIII ions are linked by four 2-phen­oxy­propionate groups in bi- and tridentate bridging modes. Each CeIII ion is nine-coordinated by one 1,10-phenanthroline mol­ecule, two O atoms from a chelating carboxyl­ate, two O atoms derived from a μ3-carboxylate and two O atoms derived from two μ2-carboxylate ligands in a distorted CeN2O7 monocapped square-anti­prismatic geometry.
doi:10.1107/S1600536811036129
PMCID: PMC3201429  PMID: 22064783
13.  Tris(2,2′-bipyridine-κ2 N,N′)cobalt(III) bis­[bis­(pyridine-2,6-dicarboxyl­ato-κ3 O 2,N,O 6)cobaltate(III)] perchlorate dimethyl­formamide hemisolvate 1.3-hydrate 
In the title compound, [Co(C10H8N2)3][Co(C7H3NO4)2]2(ClO4)·0.5C3H7NO·1.3H2O, the CoIII atom in the complex cation is pseudoocta­hedrally coordinated by six N atoms of three chelating bipyridine ligands. The CoIII atom in the complex anion is coordinated by two pyridine N atoms and four carboxyl­ate O atoms of two doubly deprotonated pyridine-2,6-dicarboxyl­ate ligands in a distorted octa­hedral geometry. One dimethyl­formamide solvent mol­ecule and two water mol­ecules are half-occupied and one water mol­ecule is 0.3-occupied. O—H⋯O hydrogen bonds link the water mol­ecules, the perchlorate anions and the complex anions. π–π inter­actions between the pyridine rings of the complex anions are also observed [centroid–centroid distance = 3.804 (3) Å].
doi:10.1107/S1600536812037208
PMCID: PMC3470129  PMID: 23125573
14.  Tetra­kis[μ-2-(3,4-dimeth­oxy­phen­yl)acetato]-κ4 O:O′;κ3 O,O′:O;κ3 O:O,O′-bis­{[2-(3,4-dimeth­oxy­phen­yl)acetato-κ2 O,O′](1,10-phenanthroline-κ2 N,N′)samarium(III)} 
In the centrosymmetric dinuclear title complex, [Sm2(C10H11O4)6(C12H8N2)2], the SmIII ion is nine-coordinated by seven O atoms of five 2-(3,4-dimeth­oxy­phen­yl)acetate (DMPA) ligands and two N atoms of one bis-chelating 1,10-phenanthroline (phen) ligand, forming a distorted tricapped trigonal-prismatic environment. The DMPA ligands coordinate in bis-chelate, bridging and bridging tridentate modes. An intra­molecular C—H⋯O hydrogen bond occurs. Inter­molecular C—H⋯O inter­actions are also present in the crystal.
doi:10.1107/S1600536810037153
PMCID: PMC3009179  PMID: 21588817
15.  (Acetyl­acetonato-κ2 O,O′)(phthalo­cyaninato-κ4 N)(phen­an­throline-κ2 N,N′)erbium(III) 
The title complex, [Er(C32H16N8)(C5H7O2)(C12H8N2)], possesses a mirror plane and the asymmetric unit is half of the mol­ecule. The ErIII cation, lying on the mirror plane, is eight-coordinated by two O atoms from acetyl­acetone, two N (Nphen) atoms from 1,10-phenanthroline and four isoindole N (Niso) atoms from the phthalocyanine ligand in an anti­prismatic geometry. The Er—N distances are in the range 2.376 (5)–2.529 (4) Å and the Er—O distance is 2.272 (3) Å. Notably, the Er—Niso bonds are shorter than the Er—Nphen bonds, but longer than the Er—O bonds.
doi:10.1107/S1600536812003972
PMCID: PMC3297219  PMID: 22412409
16.  (Carbonato-κ2 O,O′)bis­(1,10-phenan­throline-κ2 N,N′)cobalt(III) nitrate monohydrate 
The crystal structure of the title compound, [Co(CO3)(C12H8N2)2]NO3·H2O, consists of CoIII complex cations, nitrate anions and uncoordinated water mol­ecules. The CoIII cation is chelated by a carbonate anion and two phenanthroline ligands in a distorted octa­hedral coordination geometry. A three-dimensional supra­molecular structure is formed by O—H⋯O and C—H⋯O hydrogen bonding, C—H⋯π and aromatic π–π stacking [centroid–centroid distance = 3.995 (1)Å] inter­actions.
doi:10.1107/S1600536809052763
PMCID: PMC2980272  PMID: 21579944
17.  Supramolecular architectures and structural diversity in a series of lead (II) Chelates involving 5-Chloro/Bromo thiophene-2-carboxylate and N,N’-donor ligands 
Background
Lead is a heavy toxic metal element in biological systems and is one of the major pollutants as a result of its widespread use in industries. In spite of its negative roles the coordination chemistry of Pb(II) complexes is a matter of interest. The N,N’-bidentate aromatic bases such as BPY,4-BPY and PHEN (BPY = 2,2′bipyridine, 4-BPY = 4,4′-dimethyl-2,2′-bipyridine, PHEN = 1,10-Phenanthroline) are widely used to build supramolecular architectures because of their excellent coordinating ability and large conjugated system that can easily form π-π interactions among their aromatic moieties. A series of novel Pb(II) complexes in concert with 5-CTPC, 5-BTPC (5-CTPC = 5-chlorothiophen-2-carboxylate, 5-BTPC = 5-bromothiophen-2-carboxylate) and corresponding bidentate chelating N.N′ ligands have been synthesized and characterized.
Results
Five new Pb (II) complexes [Pb(BPY)(5-CTPC)2] (1), [Pb(4-BPY)(5-CTPC)2] (2), [Pb2(PHEN)2(5-CTPC)4] (3), [Pb(4-BPY)(5-BTPC)2] (4) and [Pb2(PHEN)2(5-BTPC)2(ACE)2] (5) have been synthesized. Even though in all these complexes the molar ratio of Pb, carboxylate, N,N-chelating ligand are the same (1:2:1), there is a significant structural diversity. These complexes have been characterised and investigated by elemental analysis, IR, 1H-NMR,13C-NMR, TGA, and photoluminescence studies. Single crystal X-ray diffraction studies reveal that complexes (1, 2) and (4) are mononuclear while (3 and 5) are dinuclear in nature which may result from the chelating nature of the ligands, various coordination modes of the carboxylates, and the coordination geometry of the Pb(II) ions.
Conclusions
The observation of structures 2,4 and 3,5 show the structural changes made just chloro/bromo substituent of the thiophene ring. A detailed packing analysis has been undertaken to delineate the role of valuable non covalent interactions like X…π, H…X, (X = Cl/Br). A quadruple hydrogen bond linking the monomeric units and generating a supramolecular architecture is observed in (1). The metal bite unit comprised of PbN2C2 (i.e. Pb-N-C-C-N-Pb) is the repeating unit in all the five complexes and they have almost same geometrical parameters. This metal bite has been identified as the self assembly unit in complexes.
doi:10.1186/1752-153X-7-139
PMCID: PMC3766206  PMID: 23945397
Metal bite; Lone pair; Phenanthroline; 5-chlorothiophen-2-carboxylic acid; Pb(II); Halogen bonding
18.  Tetra­aqua­(1,10-phenanthroline-κ2 N,N′)magnesium(II) bis­[(2,4-dichloro­phen­yl)acetate] 
In the mononuclear title complex, [Mg(C12H8N2)(H2O)4](C8H5Cl2O2)2, each MgII ion is hexa­coordinated by two N atoms from a 1,10-phenanthroline ligand [Mg—N = 2.233 (2) Å] and four water mol­ecules [Mg—OW = 2.033 (2) and 2.043 (1) Å] in a distorted octa­hedral geometry. A twofold rotation axis passes through the Mg atom. In the crystal structure, the cations and anions are linked by inter­molecular O—H⋯O hydrogen bonds and π–π stacking inter­actions [centroid–centroid distance = 3.804 (2) Å] into layers parallel to the ac plane.
doi:10.1107/S1600536808022150
PMCID: PMC2961968  PMID: 21203038
19.  Bis[4-chloro-2-(quinolin-8-yl­imino­meth­yl)phenolato-κ3 N,N′,O]cobalt(III) trichlorido­methano­lcobaltate(II) 
The reaction of 4-chloro-2-(quinolin-8-yl­imino­meth­yl)phenol (HClQP) with cobalt(II) dichloride hexa­hydrate in methanol/chloro­form under solvothermal conditions yielded the title compound, [Co(C16H10ClN2O)2][CoCl3(CH3OH)]. The CoIII atom is six-coordinated in a slightly distorted octa­hedral geometry by four N atoms and two O atoms of two tridentate HClQP ligands, which are nearly perpendicular to each other, making a dihedral angle of 86.95°. The CoII atom is four-coordinated by three Cl atoms and one O atom from a methanol ligand in a distorted tetra­hedral geometry. The crystal packing is consolidated by inter­molecular O—H⋯Cl, C—H⋯Cl and C—H⋯O hydrogen bonds, forming a three-dimensional supra­molecular structure, in which [CoIICl3(CH3OH)] anions are connected via O—H⋯Cl and C—H⋯Cl hydrogen bonds into centrosymmetric dimers. Neighboring cobalt(III) complexes form dimers through C—H⋯O hydrogen bonds, as well as π–π stacking [centroid–centroid distances = 3.30 (2) Å] between the planar quinoline systems of one HClQP ligand and the phenolate ring of another.
doi:10.1107/S1600536813010118
PMCID: PMC3647815  PMID: 23723781
20.  catena-Poly[[di­aqua­[μ2-4-(4-carb­oxy­phen­oxy)benzoato](μ2-4,4′-oxydibenzo­ato)praseodymium(III)] monohydrate] 
In the title compound, {[Pr(C14H8O5)(C14H9O5)(H2O)2]·H2O}n, the PrIII cation is eight-coordinated by six carboxyl O atoms from both a monoanionic 4-(4-carb­oxy­phen­oxy)benzoate and a dianionic 4,4′-oxydibenzoate ligand (four bridging with two from a bidentate chelate inter­action), and two O-atom donors from water mol­ecules. A single water mol­ecule of solvation is also present. The complex units are linked through carboxyl O:O′ bridges giving a two-dimensional sheet polymer lying parallel to (001). An overall three-dimensional network structure is generated through inter­molecular carb­oxy­lic acid and water O—H⋯O hydrogen bonds and weak C—H⋯O inter­actions.
doi:10.1107/S1600536813026421
PMCID: PMC3884249  PMID: 24454025
21.  Bis[4′-(4-cyano­phen­yl)-2,2′:6′,2′′-terpyridine]cobalt(II) dichloride 
The title complex, [Co(C22H14N4)2]Cl2, has been synthesized by a solvothermal reaction of the 4′-(4-cyano­phen­yl)-2,2′:6′,2′′-terpyridine ligand with CoCl2·6H2O. The cobalt(II) ion is six-coordinated by two tridentate ligands in a distorted octa­hedral geometry. The benzene rings form dihedral angles of 30.02 (7) and 30.26 (7)° with the mean planes of the terpyridine ring systems. The chloride anions are statistically disordered over two positions with refined site occupancies of 0.601 (2) and 0.399 (2).
doi:10.1107/S160053680904046X
PMCID: PMC2971102  PMID: 21578106
22.  Bis[μ-2-(4-hy­droxy­phen­yl)acetato]-κ3 O,O′:O;κ3 O:O,O′-bis­{aqua­(4,4′-bipyridine-κN)bis­[2-(4-hy­droxy­phen­yl)acetato-κ2 O,O′]ytterbium(III)} monohydrate 
In the title dinuclear complex, [Yb2(C8H7O3)6(C10H8N2)2(H2O)2]·H2O, the YbIII atoms are coordinated by eight O atoms from four 2-(4-hy­droxy­phen­yl)acetate (HPAA) ligands and a water mol­ecule, and one N atom from a 4,4′-bipyridine (bipy) ligand in a distorted tricapped trigonal–prismatic geometry. Whereas four HPAA ligands coordinate to just two YbIII atoms, the remaining two ligands bridge the two YbIII atoms. In the crystal structure, O—H⋯O and O—H⋯N hydrogen bonds link the mol­ecules into a three-dimensional network.
doi:10.1107/S1600536810043643
PMCID: PMC3009163  PMID: 21588903
23.  Bis[μ-2-(4-hy­droxy­phen­yl)acetato]-κ3 O,O′:O;κ3 O:O,O′-bis­{aqua­(4,4′-bipyridine-κN)bis­[2-(4-hy­droxy­phen­yl)acetato-κ2 O,O′]dysprosium(III)} monohydrate 
In the title dinuclear complex, [Dy2(C8H7O3)6(C10H8N2)2(H2O)2]·H2O, the DyIII atoms are coordinated by eight O atoms from four 2-(4-hy­droxy­phen­yl)acetate (HPAA) ligands and a water mol­ecule, and one N atom from a 4,4′-bipyridine (bipy) ligand in a distorted tricapped trigonal prismatic geometry. Whereas four HPAA ligands coordinate to just two DyIII atoms, the remaining two ligands bridge the two DyIII atoms. In the crystal, O—H⋯O and O—H⋯N hydrogen bonds link the mol­ecules into a three-dimensional network.
doi:10.1107/S1600536810044107
PMCID: PMC3011410  PMID: 21589212
24.  Chlorido(pyridine-κN)(5,10,15,20-tetra­phenyl­porphyrinato-κ4 N)cobalt(III) chloro­form hemisolvate 
In the title complex, [CoCl(C44H28N4)(C5H5N)]·0.5CHCl3 or [CoIII(TPP)Cl(py)]·0.5CHCl3 (where TPP is the dianion of tetra­phenyl­porphyrin and py is pyridine), the average equatorial cobalt–pyrrole N atom bond length (Co—Np) is 1.958 (7) Å and the axial Co—Cl and Co—Npy distances are 2.2339 (6) and 1.9898 (17) Å, respectively. The tetra­phenyl­porphyrinate dianion exhibits an important nonplanar conformation with major ruffling and saddling distortions. In the crystal, mol­ecules are linked via weak C—H⋯π inter­actions. In the difference Fourier map, a region of highly disordered electron density was estimated using the SQUEEZE routine [PLATON; Spek (2009 ▶), Acta Cryst. D65, 148–155] to be equivalent to one half-mol­ecule of CHCl3 per mol­ecule of the complex.
doi:10.1107/S1600536812032564
PMCID: PMC3414153  PMID: 22904760
25.  Dichlorido(2-chloro-9-mesityl-1,10-phenanthroline-κ2 N,N′)cobalt(II) dichloro­methane hemisolvate 
The title compound, [CoCl2(C21H17ClN2)]·0.5CH2Cl2, crystallizes from dichloro­methane as a 2:1 solvate [CoCl2L]2·CH2Cl2 (L is 2-chloro-9-mesityl-1,10-phenanthroline). There are two independent CoCl2 L mol­ecules in the asymmetric unit and both mol­ecules have similar conformations. They are connected by a weak C—H⋯π inter­action involving the mesityl ring. The cobalt center is four-coordinated by the two N-atom donors of the bidentate ligand and two chloride ions in a distorted tetra­hedral geometry. The packing of the mol­ecules is stabilized by weak slipped π–π stacking inter­actions between symmetry-related phenanthroline groups.
doi:10.1107/S1600536808007320
PMCID: PMC2961318  PMID: 21202178

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