Synthesis and Crystal Structure of a New Copper–PMIDA Compound (H4PMIDA=H2O3PCH2N(CH2CO2H)2)

A new Cu(II)PMIDA compound [Cu(H₂PMIDA)(phen)] 3H₂O (1) (H₄PMIDA = H₂O₃PCH₂N (CH₂CO₂H)₂,phen = 1,10-phenanthroline) has been successfully synthesized and structurally characterized. In complex 1, Cu (II) is six coordinated by chelation in a tetradentate fashion by a PMIDA ligand and by two N atoms of a phen ligand. Every phen–Cu(II)–PMIDA group connects with each other via a hydrogen bond and the edge-to-face -stacking interaction. Complex 1 crystallized in triclinic P-1 with cell dimensions of a = 7.5817(6) Å, b = 10.6980(8) Å, c = 13.1852(10) Å, =82.350(2)°, = 84.151(2)°, =78.4250(2), V= 1035.25(14) ų, Z = 2, Dc = 1.677 Mg/m³.     

X-ray Diffraction Structural Study of Acid Pyridinium Hexamolybdochromate(III)

Acid pyridinium hexamolybdochromate(III) (₅₅NH)H₂[CrMo₆O₁₈(OH)₆] · 6H₂O was synthesized and structurally characterized. The crystals are monoclinic, space group P2₁/c, a = 11.400(2) Å, b = 11.165(2) Å, c = 11.665(2) Å, = 104.39(3)°, Z = 2, _calcd = 2.789 g/cm³.     

Complexation with diol host compounds. Part 1. Structures of the 1:2 molecular complexes oftrans-9, 10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene with acetophenone and with 3-methylcyclopentanone

The structures of the 1:2 molecular complexes of trans -9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene with acetophenone (1), (C₂₆H₂₀O₂·2 C₈H₈O) and with 3-methylcyclopentanone (2), (C₂₆H₂₀O₂·2C₆H₁₀O) have been determined by X-ray crystallography. The crystal data are as follows: Compound (1):P ,a =8.979(5) Å,b =9.316(3) Å,c = 11.12(1) Å, =94.40(6)°, = 106.53(6)°, = 109.92(5)°,V = 822.94 ų,Z = 1,R = 0.097 for 2549 unique reflections. Compound (2):P ,a = 8.958(7) Å,b =9.815(4) Å,c = 9.807(4) Å, = 96.88(3)°, = 109.21(8)°, = 103.33(7)°,V = 774.10 ų,Z = 1,R = 0.059 for 2494 unique reflections. The intermolecular arrangements in both structures are characterised by host-to-guest hydrogen bonding interactions. The thermal properties of compound (2) have been characterised by DTA and TGA thermograms.     

Characteristic Features of the Formation of Copper(I) π-Complexes with N-Allyl Derivatives of Piperazinium Sulfamate

The crystals of two copper(I) complexes and piperazinium sulfamate were synthesized by ac electrochemical technique from Cu(NH₂SO₃)₂· xH₂O and N,N-diallylpiperazine, N-allylpiperazine, or piperazine titrated by sulfamic acid in aqueous methanol to pH 4. The crystal structures of the complexes were determined (DARCh diffractometer, MoK radiation, /2 scan mode). The crystal data: [C₃H₅NH(CH₂)₄NHC₃H₅]_0.5[Cu(NH₂SO₃)₂] · H₂O (I), space group P1¯, a = 8.053(1) Å, b = 10.247(2) Å, c = 8.918(2) Å, = 113.03(1)°, = 107.14(2)°, = 95.15(1)°, Z = 2; [NH₂(CH₂)₄NH₂]_0.5NH₂SO₃ (II), space group P2₁/a, a = 8.468(7) Å, b = 5.92(1) Å, c = 10.890(9) Å, = 100.40(9)°, Z = 4; {[C₃H₅NH(CH₂)₄NHC₃H₅][NH₂(CH₂)₄NH₂]}_0.5[Cu(NH₂SO₃)₃] · H₂O (III), space group P1¯, a = 11.729(3) Å, b = 8.266(2) Å, c = 10.611(3) Å, = 82.13(2)°, = 65.73(2)°, = 74.86(2)°, Z = 2. Structure III is a hybrid of elements of structures I and II and contains the -coordinated Cu(I) atom surrounded by three -donor sulfamate nitrogen atoms, which was found for the first time.     

QSAR and CoMFA Study of Cocaine Analogs: Crystal and Molecular Structure of (–)-Cocaine Hydrochloride and N-Methyl-3β-(p-Fluorophenyl)Tropane-2β-Carboxylic Acid Methyl Ester

A QSAR and CoMFA study including 78 cocaine analogs has been completed. These analogs have varied functional groups on the 2 and 3 positions of the tropane ring and include various stereoisomers. The CoMFA program was used to calculate the steric and electrostatic interaction energies as a probe atom or probe charge interacts with the molecules. Shaded contour maps show regions of the cocaine analogs where an increase in bulky substituents is desirable for increased pharmacological activity. The maps also show that small electronegative substituents on the phenyl ring are favored for enhanced activity. The X-ray crystal structures of (–)-cocaine hydrochloride (1) and N-methyl-3-(p-fluorophenyl)tropane-2-carboxylic acid methyl ester (2) are reported. These molecules are mostly rigid except for some rotational flexibility in the orientation of the phenyl and benzoyl functional groups. Crystallographic data: (1) C₁₇H₂₁NO₄·HCl, orthorhombic space group P2₁2₁2₁, a = 7.622(1)Å, b = 10.285(1)Å, c = 21.428(3)Å, Z = 4, final R = 0.035 for 960 observed reflections (I>3(I)). (2) C₁₆H₂₀FNO₂, monoclinic space group C2, a = 22.572(7)Å, b = 5.810(1)Å, c = 15.752(4)Å, = 133.65(2)°, Z = 4, final R = 0.059 for 1511 observed reflections (I>3(I)).     

Tetracarbonyliron adducts of Cp2Cr2(CO)4(μ-η2-P2). Syntheses and crystal structures of Cp2Cr2(CO)4P2[Fe(CO)4] m (m=1 and 2)

Cp₂Cr₂(CO)₄( - ² - P₂), 1, reacts with one molar equivalent of Fe₂(CO)₉ in THF to yield the mono- and di-iron complexes, Cp₂Cr₂(CO)₄P₂[Fe(CO)₄], 2, (16.5% yield) and Cp₂Cr₂(CO)₄P₂[Fe(CO)₄]₂, 3, (16.9% yield), as dark magenta brown and dark greenish brown crystals, respectively. Both complexes were characterized by single-crystal X-ray diffraction analysis. Crystal data –2: space group =P2₁/c,a=17.024(1) Å,b=8.180(1) Å,c=30.891(2) Å, =100.953(5)°,V=4223.4(7)ų,Z=8, 3743 observed reflections,R _F=0.033; 3: space group P1,a=10.209(2) Å,b=10.212(2) Å,c=15.989(3) Å, =106.93(1)°, =91.87(1)°, =119.50(1)°,V=1356.5(4) ų,Z=2, 3489 observed reflections,R _F=0.029.     

Calixcrown Binding to Caesium – X-Ray Structural Determination of a 1,3-Alternate Calix[4]arenebiscrown-7 Ligand

The crystal structure of calix[4]biscrown-7, 1, (C₅₂H₆₈O₁₄), (triclinic,space group P1, Z = 2, a = 11.115 (5), b = 11.710 (5), c = 18.990 (7)Å, = 85.12 (4), = 93.11 (5), = 91.01 (5)4°,V = 2458.9 ų, Rw = 0.0737 for 4170 observed, I 3 (I),reflections) has been determined. It is suggested that the polyether loopswith a radius of ca. 2.1 Å are too shallow to efficiently complex theCs⁺ cation (radius = 1.69 Å).     

Crystal Structures of the Inclusion Complexes of β-Cyclodextrin with Aliphatic Monoacids Tridecanoic Acid and (Z)-Tetradec-7-enoic Acid. Formation of [3]Pseudorotaxanes

The structures of the inclusion complexes of beta cyclodextrin with the aliphatic mono-acids tridecanoic acid (1) and (Z)-tetradec-7-enoic acid (2) have been determined at room temperature. Both compounds crystallise in P1, a = 15.654(6) Å, b = 15.650(6) Å, c = 15.937(6) Å, = 101.58(1)°, = 101.59(1)°, = 103.58(1)°, Z = 1, for 1 and a = 15.6259(9) Å, b = 15.623(1) Å, c = 15.935(1) Å, = 101.547(2)°, = 101.555(2)°, = 103.642(2)°, Z = 1, for 2. One molecule of the monoacids threads through two cyclodextrin macrocycles arranged in dimers thus forming [3]pseudorotaxanes. The host dimers are aligned along a channel in order to create a hydrophobic environment for the terminal methyl group of the guest and isolate it from the aqueous environment that surrounds the cyclodextrin dimeric units. The guests exhibit disorder over two orientations resulting in hydrogen bonding between the carboxyl groups of adjacent guest molecules along the channel and formation of carboxylic dimers. This crystal packing differs from that of -CD complexes of homologous dicarboxylic acids.     

Antimony(III) Oxofluorides α-Sb3O2F5 and β-Sb3O2F5: Synthesis and Crystal Structures

The conditions for the synthesis of two polymorphous forms of antimony(III) oxofluoride Sb₃O₂F₅ from aqueous solutions are established. The crystal structure of a new polymorphous modification -Sb₃O₂F₅ is determined (monoclinic crystals with a = 6.9548(6) Å, b = 9.1043(7) Å, c = 20.336(2) Å, = 94.167(2)°, V = 1284.2(2) ų, Z = 8, (calcd) = 5.092 g/cm³, F(000) = 1712, space group P2₁/n) and the structure of -Sb₃O₂F₅ is refined. The geometric characteristics of crystal structures of antimony(III) oxofluorides SbOF (L- and -forms) are compared with those of Sb₃O₂F₅ (- and -forms).     

Synthesis and Crystal Structures of Copper(I) Complexes with N-Allylhexamethylenetetraminium Chloride Obtained in Different Acidic Media

The crystals of [(CH₂)₆N₄(C₃H₅)]Cu₂Cl₃ (I), [(CH₂)₆N₄(C₃H₅)]Cu₂Cl₃ (II), and [(CH₂)₆N₄(C₃H₅)]CuCl₂ (III) complexes were electrochemically synthesized (ac) from CuCl₂ · 2H₂O and N-allylhexamethylenetetraminium chloride in ethanol solutions at pH 6, 4.5, and 3. Their structures were determined using X-ray diffraction analysis (DARCh diffractometer, MoK radiation, /2 scan mode). Complex Icrystallizes in the monoclinic system: space group A2/a, a = 24.812(6) Å, b = 8.855(3) Å, c = 12.080(2) Å, = 89.21(3)°, and Z = 8. Complex II crystallizes in the triclinic system: space group P , a = 7.618(2) Å, b = 7.048(2) Å, c = 13.150(3) Å, = 97.50(2)°, = 92.70(2)°, = 100.74(2)°, and Z = 2. The crystals of complex III are orthorhombic: space group Pmn2₁, a = 7.478(2) Å, b = 8.827(2) Å, c = 9.662(3) Å, Z = 2. The organic cation in complex I acts as a tridentate ,,-ligand; that in complex II, as a bidentate ,-ligand. In complex III, the organic cation is involved in coordination with the copper(I) atom only through one nitrogen atom.     

Syntheses,crystal structures,and characterizations of two novel cubane-like and double cubane-like molybdenum-copper-sulphur clusters {MoCu3S3(S2COEt)}(O)(Ph3P)3 and {Mo2Cu6S6(SCMe3)2}(O)2(Ph3P)4

Two novel heterometallic cubane-like and double cubane-like clusters, {MoCu₃S₃(S₂COEt)}(O)(Ph₃P)₃ I and {Mo₂Cu₆S₆(SCMe₃)₂}(O)₂(Ph₃P)₄ II, were synthesized by reaction of {MoCu₂S₃}(O)(Ph₃P)₃ with CuS₂COEt and CuSCMe₃, respectively. ClusterI crystallized in the triclinic space group (2) witha=12.766(6) Å,b=22.904(5) Å,c=10.522(3) Å, =99.86(2)°, =109.68(2)°, =86.84(3)°,V=2854(2) ų,Z=2,R=0.049 for 6622 observed reflections (I>5(I)) and 410 variables. ClusterII crystallized in the triclinic space group (2) with dimensionsa=14.212(4) Å,b=14.725(5) Å,c=12.396(8) Å, =110.32(4)°, =90.40(5)°, =62.88(2)°,V=2129(2) ų,Z=1,R=0.039 for 6020 observed reflections (I>3(I)) and 461 variables. ClusterI consists of a neutral cubane-like molecule with the core {MoCu₃S₃(S₂COEt)}²⁺, in which one corner of the cubane-like core is a novel triply bridging bidentate 1,1-dithiolato (xanthate, S₂COEt^–) ligand. ClusterII is a double cubane-like one, in which two cubane-like cores {MoCu₃S₃(SCMe₃)}²⁺ are connected by two Cu-S bonds of the triply bridging monothiolato (SCMe ₃ ^– ) ligand. Two different pathways of unit construction from a small heterometallic cluster {MoCu₂S₃}(O)(Ph₃P)₃ have been outlined. Comparisons of the selected bond lengths and bond angles for the cubane-like core {MoCu₃S₃ X} (X=Cl^–, Br^–, S₂COEt^–, SCMe ₃ ^– ) are given. Spectroscopic properties of the title clusters are also reported.     

Synthesis and Structural Features of Copper(I) Chloride and Bromide Complexes with the N,N,N′,N′-Tetraallylpiperasinium Cation (L2+) of Compositions L2+[CuCl2]– 2 and L2+[CuBr3]2–

Crystals of the -complex [C₄H₈N₂(C₃H₅)₄]²⁺[CuCl₂]^– ₂ (I) were prepared by ac electrochemical synthesis from copper and N,N,N,N-tetraallylpiperasinium chlorides in alcohol solution. Similar synthesis with the use of the metal and N,N,N,N-tetraallylpiperasinium bromides yielded the complex [C₄H₈N₂(C₃H₅)₄]²⁺[CuBr₃]^2– (II). Structures I and II were studied by X-ray diffraction (DARCh automated single-crystal diffractometer, MoK radiation). Crystals of I are triclinic, space group P1¯, a = 8.650(3) Å, b = 7.572(2) Å, c = 8.095(3) Å, = 100.45(2)°, = 83.91(2)°, = 99.89(2)°, V = 512.1(6) ų, Z = 1. Crystals of II are orthorhombic, space group Pn2₁ a, a = 17.673(3) Å, b = 14.369(6) Å, c = 8.244(2) Å, V = 2093(2) ų, Z = 4. In structure I, the potentially tetradentate N,N,N,N-tetraallylpiperasinium cation uses two centrosymmetric allyl groups for bonding with copper atoms, whose environment is completed to the trigonal-planar coordination with the chlorine atoms. The [C₄H₈N₂(C₃H₅)₄]²⁺[CuCl₂]^– ₂ groups are joined into a three-dimensional framework by weak hydrogen bonds. The inorganic fragment CuCl^– ₂ is partially disordered, which appears as splitting of the positions of the copper atom and one of the chlorine atom. In compound II, the inorganic fragment occurs as an unusual trigonal-planar CuBr^2– ₃ anion; the N,N,N,N-tetraallylpiperasinium cation is not involved in metal coordination.     

Reactions of ReH3(CO)(PMe2Ph)3 with Metallic Lewis Acids. Synthesis and Structural Characterization of Hydrido-Bridged Heterometallic Rhenium-Gold, Rhenium-Silver, and Rhenium-Copper Complexes

This contribution presents a study of the reactions of ReH₃(CO)(PMe₂Ph)₃ (1) with a variety of metallic Lewis acids of the coinage metals to form hydrido-bridged heterometallic rhenium-gold, rhenium-silver, and rhenium-copper complexes. The reaction of 1 with AuCl(PPh₃) proceeds with elimination of hydrogen to give the hydrido-bridged heterobinuclear rhenium-gold complex (PMe₂Ph)₃(CO)ClRe(-H)Au(PPh₃) (2). In contrast, the reactions of 1 with AgPF₆, [Cu(CH₃CN)₄]PF₆ or CuCl proceed without elimination of hydrogen to give the hydrido-bridged heterotrinuclear rhenium-silver and rhenium-copper complexes [(PMe₂Ph)₃(CO)HRe(-H)₂M(-H)₂ReH(CO)(PMe₂Ph)₃]PF₆ (M=Ag (3), Cu (4)) and the hydrido-bridged heterotetranuclear rhenium-copper complex (PMe₂Ph)₃(CO)HRe(-H)₂Cu(-Cl)₂Cu(-H)₂ReH(CO)(PMe₂Ph)₃ (5), respectively. The molecular structures of compounds 2 and 3 have been determined by single-crystal X-ray diffraction studies. Crystallographic data for 2: monoclinic, space group P2₁2₁2₁, a=12.804(2) Å, b=13.512(2) Å, c=24.312(3) Å, V=4206(1) ų, Z=4, and R=0.042. Crystallographic data for 3: monoclinic, space group C2/c, a=24.212(6) Å, b=13.098(3) Å, c=20.177(5) Å, b=116.40(2)°, V=5732(2) ų, Z=4, and R=0.044. The X-ray crystal structure of 2 exhibits a short contact (2.798(12) Å) between the gold atom and the CO ligand that is primarily bound to the adjacent rhenium atom, suggesting an incipient semibridging relationship.     

Clusters containing ynamine ligands. 4. The synthesis and characterizations of ReMn(CO)8 [μ-MeC2NMe2] and ReMn(CO)7 [μ-MeCC(NMe2)C(NMe2)CMe] and the development of a bonding model for the coordination of ynamines to M2(CO)8 clusters

The compound ReMn(CO)₈ (-MeC₂NMe₂),2 was obtained in 11% yield by the decarbonylation of ReMn(CO)₁₀ with Me₃NO followed by reaction MeC₂NMe₂. Compound2 will add one equivalent of MeC₂NMe₂ at 25°C to yield the mixed metal complex ReMn(CO)₇ [-C(Me) C(NMe₂) C(NMe₂) C(Me)],3 in 7% yield. Compounds2 and3 were characterized by IR,¹H NMR, and single crystal x-ray diffraction analyses. Compound2 exists as two isomers. Each isomer contains an asymmetric bridging ynamine ligand. The principal isomer has the amine-substituted carbon atom coordinated to the manganese atom. The minor isomer has the amine-substituted carbon atom coordinated to the rhenium atom. In compound3 the two ynamines have been coupled in a head-to-head fashion to produce a ferrole-like structure in which the coupled ligands are -bonded to the manganese atom. Extended Hückel molecular orbital calculations were performed on the parent complex Re₂(CO)₈ (-MeC₂NMe₂),1 to try to understand the reasons for the preferred asymmetric coordination of the ynamine ligand in1 and2. It was found that the asymmetric coordination permits a strong stabilizing interaction between the one of the * orbitals of the ligand and the metallic orbital that is principally responsible for the formation of the metal-metal bond. Crystal Data: for2: space group=P2₁/c,a=9.740(1)Å,b=11.293(2)Å,c=15.483(3)Å, =97.46(1)°,Z=4, 1876 reflections,R=0.026; for3: space group=Pca2₁,a=17.541(2)Å,b=8.441(1)Å,c=14.033(3)Å,Z=4, 1335 reflections,R=0.022.     

VUV-Photolyse von Methanol bei 1236 Å

Zusammenfassung Es wird über die indirekte und die direkte VUV-Photolyse von luftfreiem Methanol in flüssiger Phase bei 1236 Å berichtet. Bei der Bestrahlung von wäßr. 0,01m-Methanol wurden folgende Produkte und Ausbeuten erhalten: (H₂)=1,00, (HCHO)=0,27, (CH₂OH)₂=0,12, (CH₂OH·CHO)=0,04 und (HCOOH)=0,02. Die Photolyse von flüssigem Methanol lieferte die gleichen Produkte, jedoch mit höheren Ausbeuten: (H₂)=1,50, (HCHO)=0,98, (CH₂OH)₂=0,28 und (CH₂OH·CHO)=0,06. Unter Anwendung von Methanol als Radikalfänger konnte auch die Quantenausbeute der Wasserphotolyse bei 1236 Å, (H,OH)=1,025 verifiziert werden. Wahrscheinliche Reaktionsmechanismen werden diskutiert.

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V.U.V.-Photolysis of methanol at 1236 Å

The indirect and the direct v.u.v.-photolysis of air free methanol in liquid phase at 1236 Å is reported. After irradiation of aqueous 0.01M-methanol the following products were obtained: (H₂)=1.00, (HCHO)=0.27, (CH₂OH)₂=0.12, (CH₂OH·CHO)=0.04 and (HCOOH)=0.02. The photolysis of liquid methanol yielded the same compounds, however with higher amount as follows: (H₂)=1.50, (HCHO)=0.98, (CH₂OH)₂=0.28 and (CH₂OH·CHO)=0.06. Using methanol as a scavenger for the H and OH radicals the quantum yield of the water photolysis at 1236 Å could be verified to be (H,OH)=1.025. Probable reaction mechanisms are discussed.

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Mit 3 Abbildungen

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Herrn Prof. Dr.E. Broda zum 60. Geburtstag gewidmet.     

Synthesis and Structure of Acetonitrile Solvates of Copper(II) Monofluoroacetate and Silver(I) Trifluoroacetate, [Cu2(CH2FCOO)4· 2CH3CN](CH3CN) and Ag3(CF3COO)3(CH3CN)2

Compounds [Cu₂(CH₂FCOO)₄· 2CH₃CN](CH₃CN) (I) and Ag₃(CF₃COO)₃(CH₃CN)₂(II) were synthesized and studied by X-ray structural analysis. Crystals Iare monoclinic, space group C2/c, a= 27.854(6), b= 8.286(2), c= 19.428(4) Å, = 106.82(3)°, V= 4292(2) ų, Z= 8, R ₁= 0.0426; crystals IIare triclinic, space group , a= 8.676(2), b= 9.819(2), c= 11.961(2) Å, = 95.27(3), = 109.59(3)°, = 104.60(3)°, V= 911.4(3) ų, Z= 2, R ₁= 0.0252. Structure Iis composed of the structural units (lanterns) typical of copper(II) carboxylates. The presence of an additional acetonitrile molecule noncoordinated by the copper atoms makes it possible to consider compound Ias a lattice clathrate. Structure IIhas no analogs among the silver carboxylates. It simultaneously contains silver atoms with coordination numbers varying from 2 to 4.     

Cluster assisted formation of carbon-carbon bonds: Synthesis and crystal structures of two trinuclear heterometallic complexes CpWRu2(CO)7(μ-H)[OC(NMe2)CCHCHEt] and CpWRu2(CO)6(μ-H)[OC(NMe2)CCH(μ-η2-C6H4)]

Treatment of the carbamoyl cluster Ru₃(CO)₁₀(-H)(-²-OC(NMe₂)] with a two molar excess of CpW(CO)₃CCⁿ Pr in refluxing toluene produced a heterometallic cluster complex CpWRu₂(CO)₇(-H)[OC(NMe₂) CCHCHEt] (II), whereas the heterometallic clusters CpWRu₂(CO)₆(-H)[OC(NMe₂)CCH(-²-C₆H₃X)] (IVb, X=H;IVc, X=Me;IVd, X=F) were isolated from the reactions with CpW(CO)₃CCC₆H₄X under similar conditions. Both complexesII andIV were generated via a complicated sequence involving hydride migration to the acetylide, fragmentation of the cluster via removal of a Ru(CO)_n unit, coupling with the carbamoyl ligand and C-H bond activation at the substituent. Crystal data forII: space group R ;a=26.605(3),c=17.934(2) Å,Z=18; finalR _F =0.032,R _w =0.034 for 2720 reflections withI>2(I). Crystal data forIVb: space group C 2/c;a=16.120(6),b=14.972(2),c=18.872(4) Å, =95.46(2)°,Z=8; finalR _F =0.0375,R _w =0.0375 for 2074 reflections withI>3(I).     

Thiourea N- and S-Derivatives as Ligands: Synthesis and Crystal Structure of 4CuCl · 6All–NHCSNH2 and [(All–NH)2C–SC2H5]Cu2ClxBr3 – x (x = 0.765, All is Allyl)

Crystals of the compounds 4CuCl · 6CH₂=CH–CH₂–NHCSNH₂ (I) and [(CH₂=CH–CH₂–NH)₂C–SC₂H₅]Cu₂Cl _x Br_{3 – x} (x = 0.765) (II) were synthesized by the ac electrochemical method, and their crystal structures were determined (CuK and MoK radiation, 2575 and 1090 unique reflections with F 4(F), R = 0.050 and 0.028 for I and II, respectively). Complex I crystallizes in space group C2/c, a = 17.230(7) Å, b = 12.258(5) Å, c = 42.95(2) Å, = 97.48(4)°, V = 8994(7) ų, Z = 8. The structure of -complex II is described by space group P2₁/n, a = 10.633(5) Å, b = 9.280(5) Å, c = 16.024(4) Å, = 102.16(3)°, V = 1546(1) ų, Z = 4. Complex I is built from isolated units of the aforementioned composition; every allylthiourea molecule coordinates two metal atoms through the sulfur atom. The distorted tetrahedral surrounding of every Cu(I) atom involves three S atoms and one Cl atom. The N,N"-diallyl-S-ethylisotiouronium cation coordinates two copper atoms through the C=C bonds, 1.32(1) and 1.35(1)Å, uniting the cuprohalide chains in layers. The structure of complex II is very close to the structure of the previously studied -complex of diallylammonium [H⁺L]Cu₂Cl₃.     

Substituted metal carbonyls. Part 25: Unidentate,intramolecular, and intermolecular bridging modes of 1,1′-bis(diphenylphosphino)ferrocene inM 3S2(CO)9 (M = Fe,Ru) cluster derivatives

Carbonyl exchange of Fe₃(₃-S)₂(CO)₉ wioth1,1-bis(diphenylphosphino)ferrocene (dppf) in refluxing THF gives a cluster ligand with a pendant phosphine moiety, Fe₃(₃-S)₂(CO)₈ (gn¹-Ph₂PlC₅H₄)Fe(C₅H₄)P⁴ MePh₂)]1 ^–,4. Addition of 1 to AuCl(SMe₂) gives ClAu(-dppf) Fe₄(₃-S)₂(CO)₈,8 (45%). Spectroscopic evidence is also obtained for (OC)₈ (₃-S)₂Fe₃(-dppf) Os₃(CO)₁₁,7 and PdCl₂[(-dppf)Fe₃(₃-D)₂(CO)₈]₂,9, from1 and Os₃(CO)₁₁(CH₃CN) and PdCl₂CN)₂, respectively. Crystal data dor3: space group P2₁/n,a = 10.891(3) Å,b = 19.939(3) Å,c = 20.443(2) Å, 100.17(2)°.Z = 4, 3917 reflections,R = 0.049.     

Superacid Univalent Metal Phosphites (MH2PO3)2· H3PO3 (M = Rb,Tl(I)) and MH2PO3· H3PO3(M = K,Cs): Synthesis and Structure

By reacting the K, Rb, Cs, or Tl carbonates with excess phosphoric acid, crystals of superacid phosphites, namely, (RbH₂PO₃)₂· H₃PO₃(I), (TlH₂PO₃)₂· H₃PO₃(II), KH₂PO₃· H₃PO₃(III), -CsH₂PO₃· H₃PO₃(IV), and -CsH₂PO₃· H₃PO₃(V), were synthesized. Their structures were determined by single-crystal X-ray diffraction analysis at 150 K. Crystals I: triclinic system, space group , a= 7.713(2) Å, b= 8.679(3) Å, c= 9.235(3) Å, = 79.36(3)°, = 67.60(2)°, = 88.13(3)°, R ₁= 0.0252; crystals II: triclinic system, space group , a= 7.690(3) Å, b= 8.494(3) Å, c= 9.292(4) Å, = 79.48(3)°, = 66.72(3)°, = 85.45(3)°, R ₁= 0.0485; crystals III: monoclinic system, space group P2₁/c, a= 8.726(3) Å, b= 12.182(4) Å, c= 6.354(2) Å, = 104.14(3)°, R ₁= 0.0241; crystals IV: orthorhombic system, space group P2₁2₁2₁, a= 6.033(1) Å, b= 6.444(1) Å, c= 18.345(4) Å, R ₁= 0.0172; crystals Vare monoclinic, space group C2/c, a= 9.990(3) Å, b= 12.197(4) Å, c= 6.866(2) Å. = 118.14(3)°, R ₁= 0.0181. The hydrogen bonding systems form corrugated bands (Iand II), bent layers (III), individual tubes with rectangular cross sections (V), or a three-dimensional framework (IV). A comparative analysis of the crystal structures of acid phosphites with different compositions was performed.