Molecular and crystal structure of 1-amino-3,5-diphenyl-2,4,4,6,6-Pentacyano-cyclohex-1-ene and 1-amino-3,5-diphenyl-2,4,4,6-tetracyanocyclohex-1-ene

Molecular and crystal structures of 1-amino-3,5-diphenyl-2,4,4,6,6-pentacyano-cyclohex-1-ene (I) and 1-amino-3,5-diphenyl-2,4,4,6-tetracyanocyclohex-1-ene (II) are studied to examine intermolecular interactions. Crystal data for (I): space group P2₁, a=11.172(3), b=6.561(2), c=16.390(4) Å, β=100.25(2)⁰, V=1182.1 ų, Z=2, R=0.046; for (II): space group P1, a=10.756(3), b=10.890(3), c=12.999(3) Å, α=62.20(2), β=70.73(2), γ=65.42(2)⁰, V=1207.2 ų, Z=2, R=0.074. Intermolecular bonds via the aminonitrile fragment in (I) lead to formation of chains along they axis: N1…N6′ (1?x, ?1/2+y, 1?z) of 3.465(8) Å, N6…N1″ (1?x, 1/2+y, 1?z), and the contact with the solvent (acetone) O1…N1 of 2.984(7) Å. In compound (II), the intermolecular contacts N1…N5′ (?x+1, ?y, ?z+1) of 3.064(7) Å link the molecules into dimeric associates.     

Chemical Transformations of (2,3,9,10-Tetramethyl-1,4,5,7,8,11,12,14-Octa-Azacyclotetradeca-1,3,8,10-Tetraenato)Cobalt(II)Perchlorate

The monomeric octa-aza bis-α-diimine macrocyclic complex [Co^II(C₁₀H₂₀N₈)(H²O)](ClO₄)₂ I, undergoes various reactions on the macrocyclic ligand. Reaction of complex I with triethylamine in double molar proportions, followed by slow aerial oxidation, produces a molecular dimeric complex [Co^II(C₁₀H₁₄N₈)]₂, III, and a novel Co(I) complex [Co^I(C₁₀H₁₉N₈)], IV. Complex III is a staggered cofacial dimer with a cobalt-cobalt bond length 2.86(1) Å. The macrocyclic ligand of the complex contains an a-diimine function in each five-membered chelate ring, and a three-atom N-C-N^? delocalized system in each six-membered chelate ring. Complex IV has the 5-5-6-6 chelate arrangement because one α-diimine moiety is rearranged to a syn-anti configuration. In the structure, the two fused six-membered chelate rings are fully conjugated and the two fused five-membered rings are saturated. However, when complex I reacts with excess triethylamine under the similar conditions, a dimeric complex of another type, [Co^II(C₁₀H_l6N₈)]₂, II, was generated, in which one N-N bond of the macrocyclic ligand is broken. Complex IV can be isolated also from the reaction of complex I with excess hydrazine, followed by slow aerial oxidation. When hydrazine in double molar proportions was used, complex [Co^I(C₁₀H₁₇N₈)(NHNH)] V, which contains a coordinated diazene ligand, was obtained. Only one six-membered chelate ring of complex V is deprotonated and oxidized to form a three-atom N-C-N^? delocalized system. The structures of octa-aza complexes I-V are determined by X-ray crystallography: I, orthorhombic, C mca, a = 11.646(4), b = 17.049(3), c = 10.706(3) Å, Z = 4, R = 0.045, R_w = 0.047, based on 1024 reflections with I > 2σ(I); II, monoclinic, P 2₁/c, a = 9.814(3), b = 22.583(6). c = 14.632(9) Å, β = 98.90(5)°, Z = 4, R = 0.085, R_w = 0.101, based on 2033 reflections with I > 2σ(I); III, tetragonal, P 4/nmm, a = 15.614(3), c = 6.498(2) Å, Z = 4, R = 0.081, R_w = 0.115, based on 340 reflections with I > 2σ(I); IV, orthorhombic, P bca, a = 8.484(1), b = 16.662(3), c = 18.760(2) Å, Z = 8, R = 0.029, R_w = 0.024, based on 1441 reflections with I > 2σ(I); V, monoclinic, P 2₁/m, a = 7.892(3), b = 11.713(6), c = 9.326(4) Å, β = 108.03(3), Z = 2, R = 0.047, R_w = 0.056, based on 948 reflections with I > 2σ(I).     

Crystal Structures of Mono-, Di-, and Triaminoguanidinium Sulfate,as Well as Azidoformamidinium Sulfate: Important Precursors for Syntheses of Nitrogen Rich Ionic Compounds

Bis(1-aminoguanidinium) sulfate monohydrate (AG₂SO₄ … H₂O, 1), bis(1,3-diamino-guanidinium sulfate (DAG₂SO₄, 2), bis(1,3,5-triaminoguanidinium) sulfate dihydrate (TAG₂SO₄ … 2 H₂O, 3) and bis(azidoformamidinium) sulfate (AF₂SO₄, 5) were synthesized and characterized by multinuclear NMR, IR, and Raman spectroscopy and elemental analysis. In the synthesis of 3, double protonated triaminoguanidinium sulfate (HTAGSO₄, 4) was obtained as a byproduct. The molecular structures of 1–5 in the crystalline state were determined by low-temperature single crystal X-ray diffraction. 1: orthorhombic, Pnma, a = 6.7222 (8) Å, b = 14.153 (2) Å, c = 11.637 (1) Å, V = 1107.1(2) ų, Z = 4, ρ_calc.= 1.586 g cm^?3 R₁ = 0.0442, wR₂ = 0.1007 (all data). 2: hexagonal, P6₁22, a,b = 6.6907 (1) Å, c = 43.4600 (8) Å, γ= 120°, V = 1684.86 (5) ų, Z = 6, ρ_calc.= 1.634 g cm^?3, R₁ = 0.0321, wR² = 0.0714 (all data). 3: monoclinic, C2/c, a = 9.6174 (8) Å, b = 22.858 (1) Å, c = 6.7746 (5) Å, β= 109.49 (1), V = 1404.0 (4) ų, Z = 4, ρ_calc.= 1.620 g cm_?3, R₁ = 0.0292, wR₂ = 0.0781 (all data). 4: monoclini c, P2₁/c, a = 8.9998 (9), b = 6.3953 (6), c = 13.3148(12) Å, β= 99.679 (8), V = 755.44 (13) ų, Z = 4, ρ_calc.= 1.778 g cm^?3, R₁ = 0.0305, wR₂ = 0.0809 (all data); 5: orthorhombic, Pbca, a = 11.3855 (9), b = 7.1032 (6), c = 12.807 (1) Å, V = 1035.74 (14) ų, Z = 4, ρ_calc.= 1.720 g cm^?3, R₁ = 0.0389, wR₂ = 0.0862 (all data).     

Volatile ZnPhen(S2CNEt2)2 and MnPhen(S2CNEt2)2 complexes and the MnZn2Phen3(S2CNEt2)6 phase: Thermal behavior and crystal and molecular structures of two modifications of ZnPhen(S2CNEt2)2

Two crystal modifications, I and II, of the ZnPhen(S₂CNEt₂)₂ complex have been isolated. According to XRD data, the single crystals of I are triclinic with a=9.745(2), b=10.252(2), c=14.331(3) Å, α=99.18(2), β=91.01(2), γ=113.28(2)°, V=1293.2(4) ų, space group P1, Z=2, d_calc=1.401 g/cm³. The crystals of II are monoclinic with a=7.220(6), b=18.095(2), c=19.050(4) Å, β=95.85(2)°, V=2475.8(7) ų, space group C2/c, Z=4, d_calc=1.461 g/cm³. In both modifications, the structure is formed by monomer molecules with a distorted octahedral environment of the zinc atom. All atoms in I are in the general position; in II, the atoms are linked by the twofold rotation axis. It is shown by X-ray phase analysis (XRPA) that the MnPhen(S₂CNEt₂)₂ complexes (III) are isostructural to modification I of the ZnPhen(S₂CNEt₂)₂ complex, which underlies the synthesis of a solid solution of these complexes, MnZn₂Phen₃(S₂CNEt₂)₆ (phase IV). It is found that MPhen(S₂CNEt₂)₂ (M=Zn²⁺, Mn²⁺) and phase IV quantitatively sublime when heated in vacuum. Thermolysis of III in argon yields manganese(II) sulfide of cubic modification; the main product of thermolysis of phase IV is a solid solution of Zn_xMn_1?xS of hexagonal modification.     

Complexation of the 2, 4, 6‐Triallyloxy‐1, 3, 5‐triazine with Copper(I,II) Chlorides. Syntheses and Crystal Structures of [CuCl2·2C3N3(OC3H5)3], [Cu7Cl8·2C3N3(OC3H5)3], and [Cu8Cl8·2C3N3(OC3H5)3]·2C2H5OH

Interaction of copper(II) chloride with 2, 4, 6‐triallyloxy‐1, 3, 5‐triazine leads to formation of copper(II) complex [CuCl₂·2C₃N₃(OC₃H₅)₃] ( I ). Electrochemical reduction of I produces the mixed‐valence Cu^{I, II} π, σ‐complex of [Cu₇Cl₈·2C₃N₃(OC₃H₅)₃] ( II ). Final reduction produces [Cu₈Cl₈·2C₃N₃(OC₃H₅)₃]·2C₂H₅OH copper(I) π‐complex ( III ). Low‐temperature X‐ray structure investigation of all three compounds has been performed: I : space group P1¯, a = 8.9565(6), b = 9.0114(6), c = 9.7291(7) Å, α = 64.873(7), β = 80.661(6), γ = 89.131(6)°, V = 700.2(2) ų, Z = 1, R = 0.0302 for 2893 reflections. II : space group P1¯, a = 11.698(2), b = 11.162(1), c = 8.106(1) Å, α = 93.635(9), β = 84.24(1), γ = 89.395(8)°, V = 962.0(5) ų, Z = 1, R = 0.0465 for 6111 reflections. III : space group P1¯, a = 8.7853(9), b = 10.3602(9), c = 12.851(1) Å, α = 99.351(8), β = 105.516(9), γ = 89.395(8), V = 1111.4(4) ų, Z = 1, R = 0.0454 for 4470 reflections. Structure of I contains isolated [CuCl₂·2C₃N₃(OC₃H₅)₃] units. The isolated fragment of I fulfils in the structure of II bridging function connecting two hexagonal prismatic‐like cores Cu₆Cl₆, whereas isolated Cu₆Cl₆(CuCl)₂ prismatic derivative appears in III . Coordination behaviour of the 2, 4, 6‐triallyloxy‐1, 3, 5‐triazine moiety is different in all the compounds. In I ligand moiety binds to the only copper(II) atom through the nitrogen atom of the triazine ring. In II ligand is coordinated to the Cu^II‐atom through the N atom and to two Cu^I ones through the two allylic groups. In III all allylic groups and nitrogen atom are coordinated by four metal centers. The presence of three allyl arms promotes an acting in II and III structures the bridging function of the ligand moiety. On the other hand, space separation of allyl groups enables a formation of large complicated inorganic clusters.     

Synthesis and structure of trinuclear clusters (Et4N)2[(μ3-Se)]Fe3(CO)9, [(μ-H)2Fe3(μ3-Se)(CO)9], and [(μ3-Se)FeMo2(η5-C5H5)2(CO)7]

The cluster anion [Fe₃(μ₃-Se)(CO)₉]^2- (I) was isolated as a salt (Et₄N)₂[I] by the reaction of Fe(CO)₅ with Na₂Se in isopropanol. The protonated form, (μ-H)₂Fe₃(μ₃-Se)(CO)₉ (II), was obtained by acidifying the reaction mixture and used for the synthesis of the heterometallic cluster FeMo₂(μ₃-Se)(CO)₇Cp₂ (III), CP=η⁵-C₅H₅. The structure of I and III was established by X-ray diffraction analysis. Crystals I are monoclinic, a=14.210(3), b=11.547(3), c=19.831(2), Å, β=90.92(2)°, V_cell=3254(1) ų, space group P2/c, Z=4, d_calc=1.550 g/cm³, Syntex P2₁, λCuK_α, R(F)=0.1333 for 1264 F_hkl>6σ(F_hkl). Crystals III are monoclinic, a=20.440(5), b=12.771(3), c=16.342(4) Å, β=113.80(2)°, V_cell=3903(2) ų, space group P2₁/c, Z=8, d_calc=2.222 g/cm³, Syntex P2₁, λCuK_α, R(F)=0.0734 for 1116 F_hkl>4σ(F_hkl). The structure of II was inferred from the Mössbauer, IR, and¹H and⁷⁷Se NMR spectroscopy data.     

Molecular and crystal structure of Bis(η5-cyclopentadienyl)titanium(IV) Dibromide,Ti(η5-C5H5)2Br2

The crystal and molecular structure of Bis(η⁵-cyclopentadienyl)titanium(IV) dibromide, Ti(η⁵?C₅H₅)₂Br₂, has been investigated by an X-ray structure determination. Crystal data: triclinic, a = 7.872(5), b = 11.807(5), c = 12.310(3) Å, α = 107.62(3), β = 100.83(4), γ = 90.69(4)°, V = 1 068(14) ų, T = 293, space group P1 , Z = 4 (there are two crystallographically independent molecules in the asymmetric unit cell and their conformations are similar). Final R and R_w values are 0.068 and 0.073, respectively. The structural results are compared to those for similar type molecules.     

A Revised Structure Model for the UCl6 Structure Type,Novel Modifications of UCl6 and UBr5, and a Comment on the Modifications of Protactinium Pentabromides

The redetermination of the crystal structure of trigonal UCl₆, which is the eponym for the UCl₆ structure type, showed that certain atomic coordinates had been incorrectly reported. This led to noticeably different U−Cl distances within the octahedral UCl₆ molecule (2.41 and 2.51 Å). Within the revised structure model presented here, which is based on single crystal data as well as quantum chemical calculations, all U−Cl distances are essentially equal within standard uncertainty (2.431(5), 2.437(5), and 2.439(6) Å). This room temperature modification, called rt-UCl₆, crystallizes in the trigonal space group P m1, No. 164, hP21, with a=10.907(2), c=5.9883(12) Å, V=616.9(2) ų, Z=3 at T=253 K. A new low-temperature (lt) modification of UCl₆ is also presented that was obtained by cooling a single crystal of rt-UCl_6. The phase change occurs between 150 and 175 K. lt-UCl₆ crystallizes isotypic to a low-temperature modification of SF₆ in the monoclinic crystal system, space group C2/m, No. 12, mS42, with a=17.847(4), b=10.8347(18), c=6.2670(17) Å, β=96.68(2)°, V=1203.6(5) ų, Z=6 at 100 K. The Cl anions form a close-packed structure corresponding to the α-Sm type with uranium atoms in the octahedral voids. During the synthesis of UBr₅ a new modification was obtained that crystallizes in the triclinic crystal system, space group P , No. 2, aP36, with a=10.4021(6), b=11.1620(6), c=12.2942(7) Å, α=68.3340(10)°, β=69.6410(10)° and γ=89.5290(10)°, V=1231.84(12) ų, Z=3 at T=100 K. In this structure the UBr₅ units are dimerized to U₂Br₁₀ molecules. The Br anions also form a close-packed structure of the α-Sm type with adjacent uranium atoms in the octahedral voids. Comparisons of the crystal structures of the compounds MX₅ (M=Pa, U; X=Cl, Br) show that the crystal structure of monoclinic α-PaBr₅ is probably not correct.     

Cu3SbS3: Zur Kristallstruktur und Polymorphie

Cu₃SbS₃: Crystal Structure and Polymorphism The hitherto unknown crystal structure of β-Cu₃SbS₃ at room temperature could be determined from a twinned crystal. The compound crystallizes in the monoclinic system, space group P2₁/c (No. 14), with a = 7.808(1), b = 10.233(2) and c = 13.268(2) Å, β = 90.31(1)°, V = 1 060.1(2) ų, Z = 8. An Extended-Hückel-Calculation shows weak bonding interactions between copper atoms which are coordinated trigonal planar. At ?9°C a first order phase transition occurs and the crystals disintegrate. The low-temperature modification (γ) crystallizes in the orthorhombic system with a = 7.884(2), b = 10.219(2) and c = 6.623(2) Å, V = 533.6(2) ų (?100°C). At 121°C a phase transition of higher order is observed. The high-temperature polymorph (α) of Cu₃SbS₃ is orthorhombic again. From high-temperature precession photographs the space groups Pnma (No. 62) or Pna2₁ (No. 33) can be derived. The lattice constants at 200°C are a = 7.828(3), b = 10.276(4) and c = 6.604(3) Å, V = 531.2(2) ų.     

Novel W(CO)6-Promoted C-S Bond Cleavage Reactions of Dithianes. X-Ray Structure of 9,9′:9,9′-Terfluorene

The reactions of dithianes with W(CO)₆ in refluxing chlorobenzene give dimeric alkenes and their reduced products; fluorenone derivative yielding trimer 8. A radical mechanism is suggested. The structure of 8 has been determined by a single-crystal X-ray diffraction study. Crystal data: P2₁/n; a = 11.948(5), b = 16.8795(14), c = 13.491(6) Å, β = 105.03(3)°, Z = 4, V = 2628(2) ų; R_F = 0.061, R_WF = 0.051 for 2142 reflections and 353 variables.     

CuSeTeCl,CuSeTeBr und CuSeTeI: Verbindungen mit geordneten [SeTe]-Schrauben

CuSeTeCl, CuSeTeBr, and CuSeTeI: Compounds with ordered [SeTe] Screws The hitherto unknown copper(I) chalcogen halides CuSeTeCl, CuSeTeBr and CuSeTeI have been prepared and their crystal structures were determined. The compounds of general composition CuSeTeX crystallize in the monoclinic system, space group P2₁/n (No. 14), Z = 4, a = 7.9796(9), b = 4.7645(8), c = 10.843(3) Å, β = 104.12(1)°, V = 399.8(1) ų (X = Cl), a = 8.155(3), b = 4.765(2), c = 11.286(4) Å, β = 104.21(3)°, V = 425.1(3) ų (X = Br) and a = 8.4370(9) b = 4.7652(5), c = 11.996(2) Å, β = 103.178(9)°, V = 469.6(1) ų (X = I). The crystal structures show infinite onedimensional screws YY′ of chalcogen atoms, with Y = Se and Y′ = Te alternately. The coordinations of Se and Te in these compounds are quite different.     

2D HETCOR NMR Spectrum and Structure of Dicarbonyl(η5‐N,N‐dimethylcarbamoylcyclopentadienyl)nitrosylchromium [η5‐C5H4CON(CH3)2)]Cr(CO)2(NO)

Dicarbonyl(η⁵‐N,N‐dimethylcarbamoylcyclopentadienyl)nitrosylchromium ( 5 ) was prepared by the reaction of the corresponding acid chloride with dimethylamine. The structure of 5 has been determined by X‐ray diffraction studies: space group, P‐1; monoclinic; a=6.406(7), b=8.805(8), c=10.710(10) Å, α=91.73(8), β=93.67(8), γ=101.96(8)°; Z=2. The exocyclic carbon is bent away from the chromium atom with a θ angle of ?0.27°. The nitrosyl group is cisoid to the exocyclic carbonyl carbon of the Cp(Cr) ring with a twist angle of 63.27°. The chemical shifts of C(2,5) and C(3,4) on the Cp ring has been assigned using two‐dimensional HETCOR NMR spectroscopy.     

Anhydrous Nitrates and Nitrosonium Nitratometallates of Manganese and Cobalt,M(NO3)2, NO[Mn(NO3)3], and (NO)2[Co(NO3)4]: Synthesis and Crystal Structure

Crystalline NO[Mn(NO₃)₃] ( I ) and (NO)₂[Co(NO₃)₄] ( II ) were synthesized by reaction of the corresponding metal and a liquid N₂O₄/ethylacetate mixture. I is orthorhombic, Pca2₁, a = 9.414(2), b = 15.929(3), c = 10.180(2) Å, Z = 4, R₁ = 0.0286. II is monoclinic, C2/c, a = 14.463(3), b = 19.154(4), c = 13.724(3) Å, β = 120.90(3), Z = 12, R₁ = 0.0890. Structure I consists of [Mn(NO₃)₃]^– sheets with NO⁺ cations between them. Two types of Mn atoms have CN_Mn = 7 and 8. Structure II is ionic containing isolated [Co(NO₃)₄]‐anions and NO⁺ cations with CN_Co = 8. Crystals of Mn(NO₃)₂ ( III ) and Co(NO₃)₂ ( IV ) were obtained by concentration of metal nitrate hydrate solutions in 100% HNO₃ in a desiccator with P₂O₅. III is cubic, Pa 3, a = 7.527(2) Å, Z = 4, R₁ = 0.0987. IV is trigonal, R 3, a = 10.500(2), c = 12.837(3) Å, Z = 12, R₁ = 0.0354. The three dimensional structure III is isotypic to the strontium and barium dinitrates. Structure IV contains a three dimensional network of interconnected Co(NO₃)_6/3 units with a distorted octahedral coordination environment of Co atoms. General correlations between central atom coordination and coordination modes of NO₃ groups are discussed.     

The Crystal Structures of α- and β-F2 Revisited

The crystal structures of α-F₂ and β-F₂ have been reinvestigated using neutron powder diffraction. For the low-temperature phase α-F₂, which is stable below circa 45.6 K, the monoclinic space group C2/c with lattice parameters a=5.4780(12), b=3.2701(7), c=7.2651(17) Å, β=102.088(18)°, V=127.26(5) ų, mS8, Z=4 at 10 K can now be confirmed. The structure model was significantly improved, allowed for the anisotropic refinement of the F atom, and an F−F bond length of 1.404(12) Å was obtained, which is in excellent agreement with spectroscopic data and high-level quantum chemical predictions. The high-temperature phase β-F₂, stable between circa 45.6 K and the melting point of 53.53 K, crystallizes in the cubic primitive space group Pm n with the lattice parameter a=6.5314(15) Å, V=278.62(11) ų, cP16, Z=8, at 48 K. β-F₂ is isotypic to γ-O₂ and δ-N₂. The centres of gravity of the F₂ molecules are arranged like the atoms in the Cr₃Si structure type.     

Neue Oxometallate vom BaCuSm2O6-Typ: BaCoHo2O5, BaCoYb2O5 und vom BaNiLn2O5-Typ: BaCoEr2O5

Inhaltsübersicht. (I) BaCoHo₂O₅, (II) BaCoYb₂O₅ und (III) BaCoEr₂O₅ wurden neu dargestellt und an Einkristallen mit Röntgenbeugungsmethoden die Kristallstruktur bestimmt. (I) und (II) gehören zum BaCuSm₂O₅-Typ mit (I): A = 12,267; b = 5,714; c = 7,064 Å; Z = 4; (II): A = 12,138; b = 5,662; c = 7,004 Å; Z = 4. Beide kristallisieren in der Raumgruppe D¹⁶_2h–Pnma. (III) kristallisiert im BaNiLn₂O₅-Typ, Raumgruppe D²⁵_2h–Immm mit a = 3,734; b = 5,770; c = 11,421 Å; Z = 2. Die Koordination um Co²⁺ wechselt von (I, II) nach (III) von tetragonal pyramidal nach oktaedrisch. New Oxides of the BaCuSm₂O₅-Type: BaCoHo₂O₅, BaCoYb₂O₅, and of the BaNiLn₂O₅ Type: BaCoEr₂O₅ (I) BaCoHo₂O₅, (II) BaCoYb₂O₅, and (III) BaCoEr₂O₅ are new compounds prepared by high temperature reactions. X-ray single crystal work show: (I) and (II) belong to the BaCuSm₂O₅-type (space group D¹⁶_2h-Pnma, Z = 4). (I): A = 12.267; b = 5.714; c = 7.064 Å; (II): A = 12.138; b = 5.662; c = 7,004 Å. (III) crystallizes with BaNiLn₂O₅-structure, space group D²⁵_2h-Immm; Z = 2; a = 3.734; b = 5.770; c = 11.421 Å; within (I) and (II) Co²⁺ has a tetragonal pyramidal coordination by oxygen. The coordination changes in (III) to a compressed octehedral O^2– surrounding.     

Crystal structure of platinum(II) chloro(1,1,1-trifluoro-4-imino-2-pentanononate(Hydrate)) [PtCl(ktf)H2O]

This paper reports on our study of the mixedligand βiminoketonate complex [PtCl(ktf)H₂O] including 1,1,1-trifluoro-4-imino-2-pentanone as a ligand. An X-ray diffraction analysis was performed on a CAD-4 diffractometer (MoK_α radiation, ω/2θ scan mode). Crystal data ofPtClF₃O₂NC₅H₇: a = 26.264(5), b = 4.750(1), c = 15.955(3) Å, β = 108.16(3)°, V = 1891.3ų, space group C2/c, Z = 8, d_calc = 2.82 g/cm³. The Pt atom has a distorted square planar environment. The Pt-Cl, Pt-O(H₂O), Pt-N, and Pt-O bonds are 2.29, 2.07, 1.97, and 1.98 Å in length, respectively. The chelate angle is 93.7°. The environment of Pt is completed to pyramidal due to interactions with the C_γ atom of the neighboring molecule at a distance of 3.57 Å. The compound has a molecular structure. The molecules of the complex are stacked along the Y direction.     

New examples of mixed-ligand bis(hexafluoroacetylacenonato)copper(II) complexes with 3-imidazoline nitroxide radicals at a Cu(C5HF6O2)2∶L=3∶2 ratio (L2=C14H19N2O,L3=C13H17N2O3)

The crystal structures of two (hexafluoroacetylacetonato)copper(II) complexes with 3-imidazoline nitroxide radicals, [Cu(C₅HF₆O₂)₂]₃ (C₁₄H₁₉N₂O)₂ (I) and [Cu(C₅HF₆O₂)₂]₃ (C₁₃H₁₇N₂O₃)₂ (II), have been determined. The compounds are triclinic (PI, Z=1) with a=8.730(2), b=10.357(2), c=21.996(5) Å, α=103.24(2), β=94.03(2), γ=95.04(2)⁰, V=1920(1) ų for I and a=8.679(2), b=14.769(4), c=15.368(4) Å, α=85.58(2), β=96.25(1), γ=104.60(1)⁰, V=1893(1) ų for II. Complexes I and II are molecular. The trinuclear molecules are centrosymmetric relative to the Cu(1) atom. The coordination polyhedron of Cu(1) is a square bipyramid formed by the O atoms of the hfac anions and nitroxide radicals (average Cu?O_hfac 1.92(1) for I and 1.93(1) Å for II; Cu?O_N?O 2.47(1) for I and 2.56(1) Å for II). The coordination polyhedron of Cu(2) is a trigonal bipyramid formed by the O atoms of the hfac anions (Cu?O_hfac 1.91(1)–2.12(1) for I and 1.91(1)–2.09(1) Å for II) and an imine N atom of the radical (Cu(2)?N(2) 2.00(1) for I and 2.03(1) Å for II). The molecules are linked by van der Waals forces.     

Synthetic,spectroscopic, and structural Studies on Lanthanide Complexes of Diphosphazane Dioxide Ligands

Lanthanide nitrate complexes of diphosphazane dioxides Ph₂P(O)N(Prⁱ)P(O)Ph₂ ( 1 ) and (PhO)₂P(O)N(Me)P(O)(OPh)₂ ( 2 ) have been synthesised and studied by conductometry, IR, multinuclear NMR spectroscopic methods and X-ray diffraction. Ligand 2 is accessible by two different methods, viz., by direct oxidation of the phosp(III)azane ligand or by starting from phosph(V)azane chloro precursor. The structure of 2 is confirmed by X-ray diffraction. Crystallographic data for 2 : Triclinic, Space group P1 , a = 10.078(1), b = 10.575(3), c = 12.364(4) Å, α = 75.70(2)°, α = 75.56(1)°, γ = 77.68(1)°, Z = 2, V = 1 220 ų; structure refined to R_F = 0.0459 on 3 495 data with F > 3σ(F). The diphosphazane dioxide ligand exhibits trans geometry in the solid state. The structure of a lanthanide complex, [Pr(NO₃)₃( 2 )₂] ( 14 ) is also determined by X-ray diffraction. Crystallographic data for 14 : Trigonal, Space group P3₂, a = b = 15.710(2), c = 40.067(2) Å, Z = 6, V = 8 564 ų; structure refined to R_F = 0.0430 on 8 077 data with F > 5σ(F). The two diphosphazane dioxide ligands and the nitrate groups are coordinated to praseodymium in a bidentate chelate fashion. The geometry around the ten coordinated metal is distorted bicapped square antiprism.     

Preparation and Characterization of a Heteronuclear μ-Alkyne Complex; X-Ray Crystal Structure of MoCo(CO)4(PPh3){μ-HCCSiMe3)(η5-C5H5)

Reaction of MoCo(CO)₅(PPh₃)₂(η⁵-C₅H₅) (1a) with trimethylsilylacetylene in tetrahydrofuran at 58° C yielded two acetylene bridged heterobimetallic compounds, MoCo(CO)₄(PPh₃){μ-HC?CSiMe₃}(η⁵-C₅H₅) (4) and MoCo (CO)₅{μ-HC?CSiMe₃}(η⁵-C₅H₅)(5). (4) was characterized by mass, infrared, ¹H, ¹³C and ³¹P NMR spectra. The X-ray crystal structure of (4) was determined:triclinic, P-1, a=8.821(1) Å, b=11.315(3) Å, c=17.029(2) Å, α=70.73(1)°, β=78 .72(1)°, γ=86.10(2)°,V =1573.4(6) ų, Z=2, R = 3.92%,R_w = 6.06% for 4285 (F > 4σ (F)) observed reflections. The core of this molecule is a quasi-tetrahedron containing Mo, Co and two carbons of acetylene. The triphenylphosphine ligand is attached to cobalt rather than molybdenum center.     

Die Reaktionen von M[BF4] (M = Li,K) und (C2H5)2O·BF3 mit (CH3)3SiCN. Bildung von M[BFx>(CN)4—x] (M = Li,K; x = 1, 2) und (CH3)3SiNCBFx(CN)3—x, (x = 0, 1)

The Reactions of M[BF₄] (M = Li, K) and (C₂H₅)₂O·BF₃ with (CH₃)₃SiCN. Formation of M[BF_x(CN)_4—x] (M = Li, K; x = 1, 2) and (CH₃)₃SiNCBF_x(CN)_3—x, (x = 0, 1) The reaction of M[BF₄] (M = Li, K) with (CH₃)₃SiCN leads selectively, depending on the reaction time and temperature, to the mixed cyanofluoroborates M[BF_x(CN)_4—x] (x = 1, 2; M = Li, K). By using (C₂H₅)₂O·BF₃ the synthesis yields the compounds (CH₃)₃SiNCBF_x(CN)_3—x x = 0, 1. The products are characterized by vibrational and NMR‐spectroscopy, as well as by X‐ray diffraction of single‐crystals: Li[BF₂(CN)₂]·2Me₃SiCN Cmc2₁, a = 24.0851(5), b = 12.8829(3), c = 18.9139(5) Å V = 5868.7(2) ų, Z = 12, R₁ = 4.7%; K[BF₂(CN)₂] P4₁2₁2, a = 13.1596(3), c = 38.4183(8) Å, V = 6653.1(3) ų, Z = 48, R₁ = 2.5%; K[BF(CN)₃] P1¯, a = 6.519(1), b = 7.319(1), c = 7.633(2) Å, α = 68.02(3), β = 74.70(3), γ = 89.09(3)°, V = 324.3(1) ų, Z = 2, R₁ = 3.6%; Me₃SiNCBF(CN)₂ Pbca, a = 9.1838(6), b = 13.3094(8), c = 16.840(1) Å, V = 2058.4(2) ų, Z = 8, R₁ = 4.4%