Syntheses and X-ray structures of the bridging and chelating isomers of Os3(CO)10(dmpe)

The substitution chemistry of the activated clusters Os₃(CO)₁₀(MeCN)₂ (1) and Os₃(CO)₁₀(1,5-cod) (2) has been investigated with the bidentate ligand 1,2-bis(dimethylphosphino)ethane (dmpe). Both starting clusters react rapidly with dmpe at room temperature to give the corresponding substitution product Os₃(CO)₁₀(dmpe) (3), whose isomeric composition is shown to depend on the nature of the starting cluster. Whereas the bridged cluster 1,2-Os₃(CO)₁₀(dmpe) (3b) was formed almost exclusively upon reaction with Os₃(CO)₁₀(MeCN)₂, a near statistical mixture of bridging (3b) and chelating (3c) isomers of Os₃(CO)₁₀(dmpe) was found in the reaction employing Os₃(CO)₁₀(1,5-cod). Both dmpe isomers have been characterized in solution by 3iP NMR spectroscopy and their solid-state structures established by X-ray crystallography. The bridged cluster 1,2-Os₃(CO)₁₀(dmpe) crystallizes in the monoclinic space group P2₁/n, a = 9.867(2) Å, b = 17.081(3) Å, c = 14.198(2) Å, β = 95.902(3)°, V = 2380.4(6) ų, Z = 4, and d _calc = 2.793 Mg/m³; R = 0.0435, R _w = 0.0466 for 3519 reflections with I > 2σ(I). The chelated cluster 1,1-Os₃(CO)₁₀(dmpe) crystallizes in the orthorhombic space group C222(1), a = 8.329(3) Å, b = 19.028(6) Å, c = 15.008(5) Å, V = 2379(1) ų, Z = 4, and d _calc = 2.795 Mg/m³; R = 0.0390, R _w = 0.0718 for 2360 reflections with I > 2σ(I).     

Synthesis and crystal structure of the copper(I) complex with 2-[(o-pyridyl)-sulfanylmethyl]-pyrimidine ligand

The reaction of a flexible monothioether ligand, 2-[(o-pyridyl)-sulfanylmethyl]-pyrimidine (L), with CuI leads to the formation of a novel complex [Cu₄I₄(L)₂] (1), which has been characterized by elemental analyses, IR spectroscopy, and single-crystal X-ray diffraction analysis: monoclinic, space group P2₁/n, with a = 10.921(5), b = 10.824(5), c = 13.128(6) Å, β = 109.333(5)° and Z = 2. Single-crystal X-ray analyses show that complex 1 is tetranuclear structure with a distorted chair-like Cu₄I₄ skeleton. Cu···Cu interactions are found to exist in this tetranuclear molecule. In the packing mode of complex 1, there exist N⋯⋯⋯I weak interactions and intermolecular π–π contacts. These weak interactions not only stabilize the structure of complex, but also further link the tetranuclear molecules into a high-dimensional supramolecular architecture.     

Crystal structure analyses of bis(triphenyl- phosphoranyliden)ammonium bis(pentafluoroethyl) argentate, [Ph3P=N=PPh3][Ag(C2F5)2] and bis[bis(triphenylphosphoranyliden)ammonium] tetrachloro-diargentate, [Ph3P=N=PPh3]2[ClAg(μ-Cl)2AgCl]

Bis(triphenylphosphoranyliden)ammonium bis(pentafluoroethyl)argentate, [Ph₃P=N= PPh₃][Ag(C₂F₅)₂] (1) and bis[bis(triphenylphosphoranyliden)ammonium]tetrachloro-diargentate, [Ph₃P=N=PPh₃]₂[ClAg(μ-Cl)₂AgCl] (2) were crystallized from the reaction mixture of pentafluoroethylsilver(I) and bis(triphenylphosphoranyliden)ammonium chlo-ride. Crystallization of 1 occurs in the centrosymmetric monoclinic space group P2₁/c (No. 14) with a = 17.083(2) Å, b = 11.600(2) Å, c = 19.833(2) Å, β = 109.66(1)°, V = 3700.8(7) ų, Z = 4. 2 crystallizes in the centrosymmetric orthorhombic space group Pbca (No. 61) with a = 19.540(1) Å, b = 15.926(1) Å, c = 20.160(1) Å, V = 6273.6(3) ų, Z = 8.     

Synthesis and crystal structure of 5-amino-4-cyano-1-[(5-methyl-1-t-butyl-4-pyrazolyl)carbonyl]-3-methylthio-1H-pyrazole

The title compound, 5-amino-4-cyano-1-[(5-methyl-1-t-butyl-4-pyrazolyl)carbonyl]-3-methylthio-1H-pyrazole 5, was synthesized by the treatment of 4 (5-methyl-1-t-butylpyrazole-4-carbohydrazide) with 2-cyano-3, 3-dimethylthio-acrylonitrile, and its crystal structure was determined by X-ray diffraction method. The crystal belongs to monoclinic, space group P2₁/c with unit cell parameters a = 13.566(4) Å, b = 10.833(3) Å, c = 11.202(3) Å, α = 90°, β = 98.073(5)°, γ = 90°, V = 1629.9(8) ų, Z = 4, D _c = 1.298, M _r = 318.40, μ = 0.210 mm⁻¹, F(000) = 672, R ₁ = 0.0488 and wR ₂ = 0.1250.     

π–π Interactions in diimine Pt(II) complexes with thiacrown ligands: The crystal structure of (1,4,7-trithiacyclononane)(3,4,7,8-tetramethyl-1, 10-phenanthroline)platinum(II) hexafluorophosphate

We wish to report the crystal structure for the heteroleptic platinum(II) complex with the crown thioether 1,4,7-trithiacyclononane (9S3) and the diimine ligand 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen), [Pt(9S3)(tmphen)](PF₆)₂ (1). The Pt(II) center is surrounded by a cis-S₂N₂ ligand environment formed by the bidentate diimine and two of the three sulfur atoms from the 9S3 ligand. These two sulfurs are positioned 2.2665(10) and 2.2612(11) Å from the Pt(II), but the third sulfur shows a long distance interaction at 2.8849(13) Å to form an elongated square pyramidal structure. An examination of the structure reveals π–π-intermolecular stacking of the phen groups with alternating distances of 3.53 and 3.62 Å between the planes of the phen ligands. A detailed survey of 12 other divalent Pt(II) and Pd(II) diimine complexes of 9S3 reveals three different stacking motifs involving π–π interactions in the solid state. Crystal Data for (1): P-1, a = 10.868(2) Å, b = 11.292(2) Å, c = 11.513(2) Å, α = 93.76(3)°, β = 90.82(3)°, γ = 92.28(3)°, V = 1408.5(5) Å³, Z = 2.

Chlorine-atom abstraction and cluster fragmentation in the reaction of H3Re3(CO)10(MeCN)2 with the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd): X-ray diffraction structure of fac-ClRe(CO)3(bpcd)

Treatment of the activated trirhenium cluster H₃Re₃(CO)₁₀(MeCN)₂ with the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) in CH₂Cl₂ does not afford the expected cluster product H₃Re₃(CO)₁₀(bpcd) but rather the mononuclear complex fac-ClRe(CO)₃(bpcd). The identity of fac-ClRe(CO)₃(bpcd) was determined in solution by IR and NMR (¹H and ³¹P) spectroscopies and the solid-state structure was established by X-ray diffraction analysis. fac-ClRe(CO)₃(bpcd) crystallizes in the triclinic space P-1, a = 9.958(2) Å, b = 11.991(3) Å, c = 13.676(3) Å, α = 73.230(4)°, β = 73.806(4)°, γ = 77.409(4)°, V = 1484.6(6) ų, Z = 2, and d _calc = 1.723 Mg/m³; R = 0.0367, R _w  = 0.0857 for 4253 reflections with I > 2σ(l).     

Synthesis, redox properties, and molecular structure of 4,5-diethylthio-4-cyclopenten-1,3-dione: Cyclic voltammetric evidence for a kinetically stable radical anion

The preparation of the new disulfide compound 4,5-diethylthio-4-cyclopenten-l,3-dione (1) from 4,5-dichloro- 4-cyclopenten-l,3-dione and ethanethiol is described. The title compound has been isolated and characterized in solution by IR and NMR spectroscopies, and the solid-state structure solved by X-ray crystallography. 4,5-Diethylthio-4-cyclopenten-l,3-dione crystallizes in the triclinic space group P-l, a = 7.230(4) Å, b = 8.191(5) Å, c = 10.187(6) Å, α = 108.48(1)°, β = 97.75(1)°, γ = 105.90(1)°, V = 533.8(6) ų, Z = 2, and d _calc = 1.346 Mg/m³; R = 0.0406, R _w = 0.0967 for 1394 reflections with I > 2σ(I). The redox properties of 4,5-diethylthio-4-cyclopenten-l,3-dione have been examined by cyclic voltammetry in CH₂C1₂ solution, where a reversible one-electron reduction was found. The reduction behavior of the diethylthio derivative is discussed relative to the closely related 4,5-bis(p-tolylthio)-4-cyclopenten-l,3-dione, whose radical anion exhibits quasi-reversible reduction behavior due to competitive C(dione ring)–S bond cleavage. The differences in the electrochemical behavior of the two disulfides are discussed with respect to the ancillary R group.     

Group 6 metal carbonyl complexes of a bulky phosphine: The crystal structures of tris(trimethylsilyl)phosphine-M(0)pentacarbonyl, M = chromium, molybdenum, and tungsten

The crystal structures of M(P{Si(CH₃)₃}₃)(CO)₅, M = Cr (1), Mo (2), and W (3), have been determined. Crystal data for 1, trigonal crystal system, space group = P3₁, a, b = 9.2118(6) ?, c = 22.416(3) ?, V = 1647.3(2) ?³, Z = 3; for 2, trigonal crystal system, space group = P3₂, a, b = 9.3394(3) ?, c = 22.7375(12) ?, V = 1717.56(12) ?³, Z = 3; trigonal crystal system, space group = P3₂, a, b = 9.3147(5) ?, c = 22.6955(16) ?, V = 1705.33(18) ?³, Z = 3. All three structures show distorted octahedral coordination environments around the metal center and exhibit especially long M–P bond distances, illustrating the unique steric and electronic properties of this bulky phosphine ligand. The ³¹P{¹H} NMR spectra of the compounds are also reported.     

Organometallic derivatives of N-phenylmaleimidetriazoles and quinonetriazoles

The syntheses, properties, and structures of Mn, Cr, Re, and W organometallic derivatives of N-phenyl-1,2,3-triazoles and quinone-1,2,3-triazoles are described. The X-ray structures of eleven compounds are described. 9, a = 11.588(2), b = 11.904(2), 14.179(2) Å, α = 69.407(3)°, β = 70.879(3)°, γ = 78.627(3)°, P-1, R = 0.0739. 10, a = 7.643(1), 9.375(1), 13.077(2) Å, α = 74.292(2)°, β = 74.763(2)°, γ = 71.694(2)°. P-1, R = 0.0415. 11, a = 14.325(4) Å, b = 17.508(5) Å, c = 15.465(5), β = 99.282(5)°, P2/n, R = 0.0610. 17, a = 7.679(2) Å, b = 9.273(2) Å, c = 13.084(3) Å, α = 75.166(3)°, β = 74.651(3)°, γ = 71.613(3)°, P-1, R = 0.0428. 18, a = 5.757(1), 13.470(3), 23.056(4) Å, P2₁2₁2₁, R = 0.0697. 19, a = 8.118(1) Å, b = 10.471(2), 15.027(2) Å, α = 72.848(2)°, β = 82.237(2)°, γ = 71.829(2)°, P-1, R = 0.0597. 23, a = 7.993(1), 9.302(1) Å. C = 13.318(2) Å, α = 94.471(2)°, β = 105.269(2)°, γ = 109.523(2)°, P-1, R = 0.0271. 24, a = 7.583(4), 9.595(5), 13.030(6) Å, α = 76.389(7)°, β = 74.883(7)°, γ = 71.102(7)°, P-1, R = 0.0502. 26, a = 32.757(5) Å, b = 6.7083(9) Å, c = 26.033(4) Å, β = 128.895(5)°, C2/c, R = 0.0489. 31, a = 8.302(2), 8.347(2), 13.794(4) Å, α = 85.749(4)°, β = 81.176(4)°, γ = 74.849(4)°, P-1, R = 0.0400. 32, a = 11.321(2) Å, b = 12.110(2), 18.179(3) Å, β = 103.951(3)°, P2₁/c, R = 0.0318.     

Synthesis and characterization of carboxylate-bridged copper(II) dinuclear complex

The dinuclear copper(II) complex {[Cu(pmea)Cl][Cu(H₂O)₃Cl]}(Cl)·H₂O (1) (pmea =bis(2-pyridylmethyl)amino-2-ethanoic acid) has been synthesized and characterized. It crystallizes in the monoclinic system P2₁/c, a = 9.0057(11), b = 28.031(3), c = 8.5669(10) Å, β = 104.267(2)°, V = 2095.9(4) ų, Z = 4. Crystal structure of 1 reveals a syn-anti carboxylate-bridged dinuclear complex, in which the coordination environment around each copper atom exhibits a distorted square-pyramid. Magnetic susceptibility measurement for 1 exhibits a weak intermolecular antiferromagnetic exchange interaction with 2J = −1.17(9) cm⁻¹. The cyclic voltammogram of 1 gives one oxidation and two reduction processes.     

Synthesis and characterization of Bis(μ-sulfido)bis[{O,O-dimethyldithiophosphato}oxomolybdenum(V)]. Crystal structure of Mo2O2(Φ-S2)[S2P(OMe)2]2.C6H6

Bis(μ-sulfido)bis[{O,O-dimethyldithiophosphato}oxomolybdenum(V) was prepared by dropwise addition of an ethanolic solution of the ammonium salt of O,O-dimethyldithio-phosphoric acid to a hot aqueous solution of MoCl₅. The X-ray structure of Mo₂O₂(Φ-S₂)[S₂P(OMe)₂]₂.C₆H₆ was determined. Crystal data: Monoclinic, P2₁/n, a = 6.9788(6), b = 22.616(3), c = 14.633(1) Å, β = 101.193(9)°, V = 2265.5(4) Å⁻³, Z = 4. The immediate environment around the two molybdenum atoms is essentially square pyramidal if the Mo—Mo interaction is ignored. The terminal oxygen atoms are in the syn conformation.     

Crystal structure of cis-[Rh(biq)2Cl2]Cl·3H2O: Solid-state characterization and crystal packing analysis

The title compound, cis-[Rh(biq)₂Cl₂]Cl·3H₂O (biq = 2,2′-biquinoline) crystallized in the monoclinic space group P2 ₁ /n with a = 11.231(2) Å, b = 20.895(4) Å, c = 14.081(3) Å, β = 94.76(3)°, V = 3293.0(11) ų, D _c = 1.565 g cm⁻³, μ = 0.806 mm⁻¹, F(000) = 1576 and Z = 4. It contains a monomeric [Rh(biq)₂Cl₂]⁺ cation, a chloride ion and three molecules of H₂O. The rhodium(III) ion is hexa coordinated forming a distorted octahedral arrangement. The mean Rh(III)–N distance for the four Rh(III)–N bonds is 2.0625 Å. The two chloride atoms are bonded in a cis configuration [Rh(III)–Cl bond distances are 2.329(3) and 2.341(4) Å]. The structure shows a curling stacks of cationic complexes interacting via offset-face-to-face (OFF) π–π aryl interaction motif. Water molecules and chloride ions are hydrogen bonded (H₂O···H–OH and Cl···H–OH) and links the curling stacks by hydrogen bonding via Rh–Cl···H–OH interactions.     

Synthesis, Crystal Structure and Magnetic Property of a Cyano-Bridged Two-Dimensional Heterometallic Assembly [Mn(salen)]2[Fe(CN)5NO]·2H2O

Abstract  

A cyano-bridged bimetallic assembly, [Mn^III(salen)]₂[Fe^II(CN)₅NO]·2H₂O [salen = N,N′-1,2-ethylenebis(salicylideneiminato)dianion], has been prepared and characterized structurally and magnetically. It crystallizes in the tetragonal space group P4/ncc with a = b = 14.813(2) ?, c = 17.093(5) ?, V = 3750.6(13) ?³, Z = 4. In this complex, each [Fe(CN)₅NO]²⁻ unit connects four [Mn(salen)]⁺ units with its four co-planar cyanide groups, and each [Mn(salen)]⁺ unit is linked to two [Fe(CN)₅NO]²⁻ ions in trans-form, which results in a two-dimensional (2-D) network consisting of pillow-like octanuclear [–Fe^II–CN–Mn^III–NC–]₄ units with dimensions: Fe–C = 1.943(3) ?, C≡N– = 1.139(4) ?, Mn–N = 2.326(3) ?, Fe–C≡N = 178.0(3)°, Mn–N≡C = 161.7(3)°. The NO group of [Fe(CN)₅NO]²⁻ remains monodentate and the bond angle of Fe–N–O is linear (180.0°). The variable temperature magnetic susceptibilities, measured in the 1.8–300 K range, show a weak Mn^III···Mn^III antiferromagnetic interaction through the diamagnetic –NC–Fe^II–CN– bridges.     

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 a new dysprosium(III) complex with 2-fluorobenzoato and 1,10-phenanthroline

The dysprosium complex with 2-fluorobenzoato (2-FBA) and 1,10-phenanthroline (phen) was synthesized and characterized by X-ray diffraction. The complex crystallizes in the triclinic system with space group , lattice parameters: a = 11.233(7)  Å, b = 12.598(8)  Å, c = 22.718(14)  Å, α = 81.045(13)°, β = 78.213(12)°, γ = 80.506(11)°, V = 3079(3) ų, Z= 2, Dcalc = 1.689 Mg/m³. The complex contains two independent binuclear molecules, namely, [Dy(2-FBA)₃·phen·CH₃CH₂OH]₂ (I) and [Dy(2-FBA)₃·phen]₂ (II). In molecule (I), Dy1³⁺ ion is coordinated by eight atoms, five O atoms from five 2-FBA groups, one O atom from an ethanol molecule and two N atoms from the phen ligand. The 2-FBA groups adopt monodentate and bridging two-coordination modes. In molecule (II), the Dy2³⁺ ion is coordinated by nine atoms, seven O atoms from five 2-FBA groups and two N atoms from the phen ligand. The 2-FBA groups adopt chelating, bridging and chelating-bridging three-coordination modes.Supplementary material CCDC-257186 for the compound contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK; fax: (44(0) 1223-336033; email: deposit@ccdc.cam.ac.uk.     

Crystal structure of bis 4-benzyl piperidinium bis dihydrogenmonophosphate trihydrogenmonophosphate

The salt bis 4-benzyl piperidinium bis dihydrogenmonophosphate trihydrogenmonophosphate (bis 4-BPP bis DPT) is monoclinic with the following unit cell dimensions: a = 13.132(2) Å, b = 8.755(2) Å, c = 13.643(2) Å, β = 92.40(2)°, space group P2₁ with Z = 2. The structure was solved by the Patterson method and refined to final R value of 0.0430. The structure consists of infinite parallel two-dimensional planes built of mutually H₂PO₄ ⁻, H₃PO₄ tetrahedra and cations connected by strong O–H···O and N–H···O hydrogen bonding. There are no contacts other than van der Waals interactions between the layers.     

Complexation with diol host compounds. Part 36: inclusion compounds of 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol with benzene, toluene and mesitylene

The title compound 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol (H) forms inclusion compounds with benzene, toluene and mesitylene. H·C₆H₆ (1) and H·C₇H₈ (2) crystallize in the triclinic space group P(-1) with unit cell dimensions for 1: a = 13.001(3) ?, b = 15.284(3) ?, c = 16.744(3) ?, α = 99.26(3)°, β = 74.78(3)°, γ = 64.96(3)°, Z = 4 and for 2: a = 12.922(3) ?, b = 15.159(3) ?, c = 16.562(3) ?, α = 68.12(3)°, β = 73.99(3)°, γ = 66.00(3)°, Z = 4. The hydroxyl groups of adjacent host molecules are involved in hydrogen bonding. H·C₉H₁₂ (3) exhibits a different packing arrangement with weak hydrogen bonding between the hydroxyl hydrogen of the host and the phenyl ring of the guest. The crystal system of compound 3 is monoclinic with space group C2/c, a = 23.750(5) ?, b = 8.4746(17) ?, c = 17.760(4) ?, α = 90°, β = 123.40(3)°, γ = 90°, Z = 4. The thermal behaviour of these compounds has also been studied.     

Aquadifluoro(1,10-phenanthroline)copper(II) dihydrate: X-ray crystal structure reveals strong hydrogen bonds between ligand fluoride and lattice water molecules

C₁₂H₁₄CuF₂N₂O₃,M=335.797, monoclinic, space groupP2₁/n,a=6.985(2),b=17.406(2),c=10.581(2) Å,=92.41(2)°,V=1285(1) ų,D _c =1.736 g cm^–3,Z=4,F(000)=684,(CuK)=27.0 cm^–1, =1.5418 Å,T=20°C, crystal dimensions=0.75×0.45×0.30 mm. The structure of the title compound shows it to be [Cu(phen)F₂(H₂O)]·2H₂O with pentacoordinate-square pyramidal Cu(II), short Cu-F bonds [1.890(4) and 1.891(4) Å], and short FH-O hydrogen bonds (ca. 2.68 Å) between the complex and lattice water molecule.     

Syntheses and crystal structures of two N-substituted thio-imidazoles

The syntheses and structures of two N-substituted thio-imidazoles are reported. The geometrical parameters for both compounds, including essentially planar imidazole rings, are consistent with previous structural studies of related materials. The only possible non-van der Waals’ interactions influencing the molecular packing are weak C–H⋯π bonds. Crystal data: C₁₂H₁₄N₂S (N-methyl-N′-2-phenylethyl-imidazol-2-thione), M _r = 218.31, monoclinic, P2₁/n, (No. 14), a = 6.8441(2) ?, b = 12.9960(4) ?, c = 13.4703(4) ?, β = 97.7729(16)°, V = 1187.12(6) ?³, Z = 4, R(F) = 0.039, wR(F ²) = 0.104. C₁₉H₂₀N₂S (N,N′-bis((s)-1-phenylethyl)imidazol-2-thione), M _r = 308.43, orthorhombic, P2₁2₁2₁ (No. 19), a = 10.4060(3) ?, b = 10.6712(3) ?, c = 14.8932(3) ?, V = 1653.81(7) ?³, Z = 4, R(F) = 0.038, wR(F ²) = 0.085.     

Absence of Platinophilic Interactions in a Series of Tetracyanoplatinates Incorporating Cyclic Amines

Abstract  

Three novel compounds have been synthesized and structurally characterized: [1,10-Hphen]₂Pt(CN)₄·2H₂O (1a) space group P2₁/n, a = 8.73070(17) ?, b = 15.4609(2) ?, c = 9.82661(19) ?, β = 103.252(2)°; [2,2′-Hbipy]₂Pt(CN)₄·2H₂O (1b) space group P2₁/n, a = 7.0859(14) ?, b = 12.940(2) ?, c = 13.7486(19) ?, β = 100.708(16)°; K₂[Pt(CN)₄]·2phen (phen = 1,10-phenanthroline) (2) space group P2₁/c, a = 8.1393(4) ?, b = 20.4050(9) ?, c = 8.4085(4) ?, β = 105.284°. All three structures contain isolated [Pt(CN)₄]²⁻ ions and they all illustrate the absence of Pt⋯Pt interactions due to the presence of bulky cyclic amines or ammoniums. The structures of 1a and 1b contain large organic cations, 2,2′-bipyridinium and 1,10-phenanthrolinium, respectively while compound 2 contains neutral 1,10-phenanthroline molecules co-crystallized between the potassium tetracyanoplatinate framework.