X-ray structural study of a zinc(II) inclusion complex of a phenolate-pendant cyclam

The molecular structure of phenol-pendant cyclam-zinc(II) complex,4a, has been determined by X-ray structure analysis. Crystals of4a · ClO₄ · CH₃OH (C₁₆H₂₇N₄OZn · ClO₄ · CH₃OH) are monoclinic, space groupP2₁/nn, with four molecules in the unit cell of dimensionsa=31.198(2) Å,b=8.426(1) Å,c=8.214(1) Å, and=93.96(1)°. The structure was solved by the heavy atom method and refined anisotropically toR=0.044,R _w=0.062 for 1551 independent reflections. The complex assumes a five-coordinate, square pyramidal geometry, where zinc(II) is surrounded by the cyclam moiety in a planar fashion with the pendant phenolate anion occupying an axial position. An extremely short Zn-O(phenolate) bond distance of 1.983(5) Å, in conjunction with the 0.288 Å displacement of Zn(II) above the cyclam N₄ plane toward the phenolate, accounts for the extremely low pK _a value of 5.8 for the pendant phenol. These facts about4a, in comparison with the previous findings for the Ni(II) (4b) and Cu(II) complexes (4c) with the same ligand, illustrate well the characteristics of zinc(II) ion coordination properties.This paper is dedicated to the memory of the late Dr C. J. Pedersen.     

Alternative methods of modifying the calixarene conformation. The synthesis and molecular structures oft-butylcalix[4]arene methyl ether complexed with aluminum alkyl species

The configurations of calix[4]arenes may be modified by the formation of donor-acceptor complexes which make use of the basicity of the oxygen atoms of the macrocycle. The complex [t-butylcalix[4]arene methyl ether][AlMe₃]₂,2, exhibits the previously unseen 1,2-alternate geometry, while [t-butylcalix[4]arene methyl ether][MeAlCl₂]₂,3, and [t-butylcalix[4]arene methyl ether][EtAlCl₂]₂,4, show the 1,3-alternate configuration.2 crystallizes in the triclinic space groupPl witha=11.14(1),b=11.60(1),c=12.02(1) Å, =77.32(8), =67.91(8), and =69.34(8)^o withD _c =1.06 g cm^–3 forZ=1. Refinement based on 1270 observed reflections led toR=0.106.3 as the benzene solvate belongs to the monoclinic space groupC2/c witha=12.116(2),b=21.557(7),c=23.470(6) Å, and =104.05(2)^o withD _c =1.13 g cm^–3 forZ=4. Refinement based on 2335 observed reflections led toR=0.075.4 crystallizes in the monoclinic space groupC2/c witha=12.062(4),b=21.175(6),c=21.596(5) Å, and =100.78(4)^o withD _c =1.18 g cm^–3 forZ=4. Refinement based on 2529 observed reflections gaveR=0.082. The Al-O lengths in all three complexes are normal for donor-acceptor interactions. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82053 (45 pages).     

Palladium Clusters Pd4(SEt)4(OAc)4and Pd6(SEt)12: Structure and Properties

Palladium clusters Pd₄(SEt)₄(OAc)₄(I) and Pd₆(SEt)₁₂(II) were synthesized and studied. Their structure was determined by X-ray diffraction analysis. For I, a= 9.774(2) Å, b= 10.821(2) Å, c= 13.061(3) Å, = 92.88(3)°, V= 1379.6(5) ų, (calcd.) = 2.182 g/cm³, space group P2₁/n, Z= 4, N _ref= 1558, and R= 0.031; for II, a= 10.581(1) Å, b= 10.584(2) Å, c= 11.478(2) Å, = 101.62(1)°, = 104.95(1)°, = 106.74(1)°, V= 1135.2(4) ų, (calcd) = 2.007 g/cm³, space group P1, Z= 1, N _ref= 2828, and R= 0.022. In cluster I, four Pd atoms form a planar cycle. The neighboring palladium atoms are bound by two acetate or by two mercaptide bridges, the Pd···Pd distances being 3.036–3.195 Å. In cluster II, Pd atoms form a planar six-membered cycle with Pd···Pd distances of 3.083–3.127 Å. The neighboring palladium atoms are bound by two mercaptide bridges. The formation of analogous clusters in solution was confirmed by IR spectroscopy.     

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.     

Further studies of M3(μ3-O)(μ-X)3(μ-O2CCH3)3L3 (M=Mo,W) type clusters with nine core electrons

Four new compounds having nine cluster electrons and cores of the types Mo₃OCl₃, Mo₃OBr₃, and W₃OCl₃ are reported. Compound (1) prepared by reduction of [Bu₄N][Mo₃OCl₆(OAc)₃] in THF with metallic zinc, was shown by X-ray crystallography to be Mo₃OCl₄(OAc)₃ (THF)₂ (1). It forms crystals in space groupP2₁ with unit cell dimensionsa=9.472(2) Å,b=13.546(4) Å,c=9.652(2) Å, =101.70(2)°,V=1201(1) Å₃,Z=2. The [Mo₃(₃-O)(-Cl)₃]⁴⁺ core is surrounded by three -O₂CCH₃ anions, one Cl^–, and two THF and has Mo-Mo distances of 2.620(1) Å, 2.613(1) Å, and 2.530(1) Å, with the shortest bond between the two Mo atoms to which the THF molecules are coordinated. Compounds [Bu₄N]₂ [Mo₃OBr₆(O₂CCH₃)₃] · Me₂CO, (2) and [Mo₃OBr₃(O₂CCH₃)₃(PMe₃)₃]₃ · BF₄, (3) are the first two nine-electron Mo₃ species with a [Mo₃(₃-O) Br₃]⁴⁺ core. Both were obtained by zinc reduction of [Mo₃OBr₆(O₂CCH₃)₃]^– in the presence of (NBu₄) Br (2) or PMe₃ and NaBF₄ (3), and each was characterized crystallographically. Compound (2) crystallized in space group Cc with unit cell dimensionsa=25.037(5) Å,b=12.827(2) Å,c=21.484(4) Å, =122.96(1)⁰,V=5790(3) ų,Z=4. While the anion has no crystallographically required symmetry, its virtual symmetry is C_3v . The Mo-Mo distances are 2.619(2) Å, 2.610(3) Å, 2.644(2) Å, with a mean value of 2.624[14] Å. Compound (3) crystallized in space groupP2₁/c with unit cell dimensionsa=10.846(2) Å,b=25.033(5) Å,c=12.641(5) Å, =94.74(2)⁰,V=3420(2) ų,Z=4. The cation occupies a general position but has virtual C_3v symmetry, with Mo-Mo distances of 2.601(2) Å, 2.610(2) Å, 2.627(2) Å, with a mean value of 2.613[14] Å. Thus the anionic and cationic Mo₃ clusters in (2) and (3), respectively, have average Mo-Mo distances that are equal within experimental error. Compound (4), [NEt₄]₂ [W₃OCl₆(O₂CCH₃)₃] is the first 9-electron compound of this type containing tungsten. It was prepared by reduction of [Et₄N][W₃OCl₆(OAc)₃] in benzene with Na/Hg. It crystallized in space groupP2₁2₁2₁ with unit cell dimensionsa=11.076(2) Å,b=14.345(2) Å,c=21.026(3) Å,V=3574(1) ų,Z=4. The anion resides on a general position but has virtual C_3v symmetry, with W-W distances of 2.577(1) Å, 2.612(1) Å, 2.584(1) Å and a mean value of 2.591[15] Å.     

Hydrogen-bonded urea-anion host lattices. Part 2. Crystal structures of inclusion compounds of urea with tetraalkylammonium bicarbonates

New inclusion complexes (C₂H₅)₄N⁺HCO ₃ ^– ·(NH₂)₂CO·2H₂O (1) and (n-C₄H₉)₄N⁺HCO ₃ ^– ·3(NH₂)₂CO (2) have been prepared and characterized by X-ray crystallography. Crystal data, MoK radiation:1, space groupP2₁/n,Z=8,a=9.356(1),b=29.156(4),c=12.161(1) Å, =90.03(1)°,R _F =0.062 for 2214 observed data;2, space groupP,Z=2,a=8.404(2),b=12.352(2),c=14.377(4) Å,a=88.20(2), =89.56(2), =71.68(1)°,R _F =0.052 for 3092 observed data. In both compounds the tetraalkylammonium ions are sandwiched between puckered layers, which are constructed from [((NH₂)₂CO)₂(HCO ₃ ^– )₂], ribbons, each composed of centrosymmetric hydrogen-bonded urea dimers and bicarbonate dimers, by lateral linkage through water molecules in1, and by direct cross-linkage of an alternate, parallel arrangement of the urea/bicarbonate and complementary urea ribbons in2. Supplementary Data relating to this article have been deposited with the British Library as Supplementary Publication No. SUP 82201 (40 pages).     

Crystal and molecular structures of binuclear caesium complexes with 1,3-calix[4]-bis-crown-6 and 1,3-calix[4]-bis-benzo-crown-6

The crystal structures of two binuclear complexes between caesium and 1,3-calix[4]-bis-crowns have been determined. Cs₂ Bis-benzoC6(NO₃)₂. 3CHCl₃ (1) in whichBis-benzoC6 is 1,3-calix[4]-bis-benzo-crown-6, crystallizes in the orthorhombic system: space groupPca2 ₁ a=19.513(10),b=15.382(5),c=23.708(9) Å,V=7116(5) ų,Z=4. Refinement led to a final conventionalR value of 0.065 for 2321 reflections. The structure of (1) is analogous to those already reported withBis-C6, (in whichBis-C6 is, 1,3-calix[4]-bis-crown-6) and NO ₃ ^– as a counter-ion. Cs₂ Bis-C6(NCS)₂ (2) crystallizes in the monoclinic system: space, groupC2 a=36.57(2),b=11.47(1),c=13.65(1) Å, =109.03(5)°.,V=5415(6) ų,Z=4. Refinement led to a final conventionalR value of 0.063 for 2227 reflections. Compound (2) is made of dimers bridged by a disordered NCS^– ion. The crown ether chain conformations are discussed. Supplementary data relating to this article (atomic coordinates, anisotropic displacement parameters, bond distances and angles and observed and calculated structure factors) are deposited with the British Library as Supplementary Publication No. SUP 82199 (52 pages).     

A doubly deprotonated form of calix[6]arene: Crystal and molecular structure of (calix[6]arene-2H)2−·(HNEt 3 + )2

The doubly deprotonated form of calix[6]arene, with two protonated triethylamines as counter-ions, crystallizes in the monoclinic system: space groupP2₁/n,a=8.465(4),b=17.822(8),c=15.182(6) Å,=90.18(4)°,V=2291(2) ų,Z=2. Refinement led to a final conventionalR value of 0.063 for 1046 reflections. The macrocycle conformation is not apinched cone, usual for freeR-calix[6]arene, but a distorted 1,2,3-alternate cone, since the molecule lies on a symmetry center. Furthermore, one of the torsion angles defined by the methylene bridges is near to zero, which is unusual in calixarene structures. Supplementary Data relating to this article (atomic coordinates for hydrogen atoms, anisotropic displacement parameters for oxygen and nitrogen atoms, and observed and calculated structure factors) are deposited with the British Library as Supplementary Publication No. SUP 82182 (7 pages).     

The crystal structures ofα,ω-diaminoalkane-cadmium(II) tetracyanonickelate(II) — Aromatic molecule inclusion compounds. VII: Three-dimensional host structures built ofcatena-[cadmium(II) tetra-μ-cyanonickelate(II)] layers and 1,3-diaminopropane, 1,5-diaminopentane or 1,7-diaminoheptane pillar

The crystal structures of four novel Hofmann-diam-type clathrates [Cd(tn)Ni(CN)₄]·1.72(o-MeC₆H₄NH₂),3-o, [Cd(tn)Ni(CN)₄]·0.5(m-ClC₆H₄NH₂),3-m, [Cd(daptn)Ni(CN)₄]·1.5(p-MeC₆H₄NH₂),5-p and [Cd(dahpn)Ni(CN)₄]·1.5(2-MeC₉H₆N),7-q have been determined by single crystal X-ray diffraction method [tn:n=3, daptn:n=5, dahpn:n=7 for NH₂(CH₂) _n NH₂.3-o crystallizes in the monoclinic space groupP2/m,a=7.538(2),b=9.314(5),c=7.670(2) Å, =91.03(2)°,Z=1,R=0.047 for 1252 reflections;3-m: orthorhombicPbam,a=12.1714(7),b=15.798(1),c=7.737(1) Å,Z=4,R=0.044 for 1871;5-p: monoclinicP2₁/a,a=13.736(3),b=22.014(4),c=7.762(3) Å, =91.04(3)°,Z=4,R=0.047 for 5281; and7-q: orthorhombicPbam,a=13.599(2),b=27.938(4),c=7.619(2) Å,Z=4,R=0.054 for 3098. Their host structures are topologically the same to those of the previously reported Hofmann-diam-type clathrates: the two-dimensional [CdNi(CN)₄] networks are spanned by NH₂(CH₂) _n NH₂ at every Cd atom to build up the three-dimensional hosts. The number of cavities available for the guest is regulated by the deformation of the 2D networks and the diamine ligand in the host structure. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82192 (37 pages).     

Synthesis and X-ray structural characterization of cobalt(II), copper(II), and silver(I) complexes of triphenylphosphoniopropionate

Four transition-metal carboxylate-like complexes have been synthesized from the reaction of the tertiary phosphine betaine triphenylphosphoniopropionate, Ph₃P⁺(CH₂)₂CO ₂ ^– , with Co(ClO₄)₂· 6H₂O, Cu(ClO₄)₂·6H₂O, Cu(BF₄)₂·xH₂O, and AgClO₄, respectively, and fully characterized by single-crystal X-ray analysis. [CoPh₃P(CH₂)₂CO_{2 4}(H₂O)₂](ClO₄)₂·2H₂O, 1, space groupP¯ l witha=9.195(2),b=13.000(2),c=18.795(3) Å,=102.52(1),=90.12(1),=109.28(2)° andZ=1; [CuPh₃P(CH₂)₂CO_{2 4}][Cu₂ -Ph₃P(CH₂)₂CO₂ -O,O ₄(H₂O)₂] (ClO₄)₆· 4H₂O, 2, space groupP2_l/c witha=14.225(3),b=24.624(6),c=24.297(5) Å,=94.18(1)°, andZ=2; [CuPh₃,P(CH₂)₂CO₂Me₂N(CH₂)₂NMe₂(H₂O)₂](BF₄)₂,3, space groupP2_l/c witha=17.668(2),b=13.454(3),c=15.876(2) Å,=116.45(1)°, andZ=4; [Ag₂Ph₃P(CH₂)₂CO_{2 2}(ClO₄)]₂(ClO₄)₂,4, space groupP¯ l witha=10.925(2),b=13.110(3),c=18.795(3) Å,=82.93(3),=87.45(3),=67.49(3)°, andZ=2. In complex1, the cobalt(II) atom is located in an inversion center and coordinated by four unidentate betaine ligands and a pair oftrans aqua ligands, and strong hydrogen bonds are formed between the aqua ligands and the pendant oxygen atoms of the betaine ligands. In complex2, mononuclear and dinuclear cations coexist in the asymmetric unit. In the mixed-ligand complex3 the betaine ligand acts in the unidentate coordination mode andN,N,N,N-tetramethylethylenediamine (tmen) in the chelate mode. Complex4 contains a discrete centrosymmetric tetranuclear cations in which one pair of betaine ligands act in the bidentate bridging mode and the other in both bidentate and one-atom bridging modes.     

Preparation and structural characterization of the isomorphous compounds: [Bu4N][Mo3(μ3-O)(μ-X)3(μ-OAc)3 X 3]·(CH3)2CO,X=Cl,Br

The reaction of MoCl₃(H₂O)₃ with a mixture of acetic acid and acetic anhydride in the presence of [N(C₄H₉)₄][BF₄] followed by crystallization from acetone/hexane gives a 77% yield of dark purple [NBu₄][Mo₃OCl₆(OAc)₃]·Me₂CO (1). A similar reaction employing MoBr₃(H₂O)₃ gives purple [NBu₄][Mo₃OBr₆(OAc)₃]·Me₂CO (2) in 50% yield. Also produced in this reaction in low (10–20%) yields are [NBu₄]₂[Mo₄OBr₁₂] · 0.5Me₂CO and [NBu₄]₂[Mo₃OBr₆(OAc)₃] · Me₂CO which will be discussed elsewhere Compounds (1) and (2) are isomorphous, space groupP2₁/n,Z=4 with the following unit cell dimensions, where the values for (1) and (2) are given in that order for each one:a=13.406(4), 13.726(5) Å;b=15.701(4), 15.839(5) Å;c=19.250(5), 19.831(6) Å; =101.61(2), 102.92(3)°. Both (1) and (2) are eight-electron species in which the mean Mo-Mo distances are 2.578(1) Å and 2.597(1) Å, respectively.     

Metal carbonyl derivatives of lanthanides. CpLuCl2-induced synthesis of the trinuclear tungsten cluster [Na(DME)3]2[W3(CO)14]

The cluster [Na(DME)₃]₂[W₃(CO)₁₄] (1) was prepared by treating CpLuCl₂ with an equimolar mixture of Na₂W(CO)₅ and Na₂W₂(CO)₁₀ in DME and characterized by X-ray analysis (MoK radiation, 653 reflections,R = 0.125). The crystals are rhombic,a=18.749(4) Å,b=15.074(3) Å,c=9.505(3) Å,Z = 2, space groupC _mmm. The W-W distance in the W-W-W chain is 2.79 Å. The carbonyl ligands at the tungsten atoms are eclipsed. Compound 1 is the first example of a homometallic carbonyl cluster of an early transition metal. It is suggested that CpLuCl₂ interacts with Na₂W(CO)₅ to afford the highly reactive species CpLu (CO)₅ which further reacts with Na₂W₂(CO)₁₀ to form1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 582–585, March, 1993.     

Cluster synthesis 37—Platinum-ruthenium carbido-cluster complexes: The syntheses and structural characterizations of PtRu5(C)(CO)16, Pt2Ru5(C)(CO)13(COD)2, and Pt3Ru5(C)(CO)14(COD)2

From the reaction of [Ru₅(C)(CO)₁₄]^2– with Pt(COD)Cl₂, COD=1, 5 cyclooctadiene, the new platinum-ruthenium carbido cluster complex PtRu₅ (C)(CO)₁₄(COD),1, was obtained in 41% yield. When1 was allowed to react with carbon monoxide (25°C/1 atm), the new complex PtRu₅(C)(CO)₁₆,2, was obtained almost quantitatively (97% yield). Compound2 was characterized by IR and single-crystal X-ray diffraction analysis. The six metal atoms are arranged in the form of an octahedron with the carbide ligand located in the center. Compound1 is believed to have a similar structure to2 except for a COD ligand coordinated to the platinum atom. When activated by treatment with Me₃NO, compound2 reacts with Pt(COD)₂ at 25°C to yield two higher nuclearity cluster complexes, Pt₂Ru₅C(CO)₁₃(COD)₂.3, and Pt₃Ru₅C(CO)₁₄(COD)₂,4. The structure of3 is similar to that of1, but contains a Pt(COD) grouping capping one Ru₃ triangle of the PtRu₅ octahedron. The structure of4 consists of a PtRu₅ octahedron with two Pt(COD) capping groups, one on an Ru₃ triangle and the other on a PtRu₂ triangle of the octahedron. Crystal data: for2, space group=P2₁/n,a=9.341 (2) Å,b=14.957 (3) Å,c=36.80 (1) Å, =90.38 (2) °,Z=8, 4034 reflections,R=0.030, for3, space group=P2₁/c,a=14.998 (3) Å,b=10.288 (3) Å,c=26.581 (7) Å, =102.75 (2) °,Z=4, 2917 reflections,R=0.028. for4, space group=P2₁/n,a=13.412 (4) Å,b=16.252 (4) Å,c=20.107 (4) Å, =106.13 (2) °,Z=4, 2745 reflections,R=0.032.     

The synthesis and structural analysis of Pt2Ru4(CO)18 and the products obtained from its reactions with 1, 2-bis(diphenylphosphino)ethane

From the reaction of Ru(CO)₅ and Pt(COD)₂, COD = 1, 5-cyclooctadiene, the new platinum-ruthenium heteronuclear cluster complex Pt₂Ru₄(CO)₁₈,1, was obtained in 60% yield.1 has a folded ladder-like structure with alternating pairs of ruthenium atoms and platinum atoms. The cluster of1 can be split to yield the known compound PtRu₂(CO)₈(²-dppe),2, (54% yield) by reaction with 1, 2-bis(diphenylphosphino)ethane, dppe, at 25°C. When1 was treated with excess dppe at 40°C, thebis-diphos compound3, PtRu₂(CO)₆(-²-dppe)₂ was obtained (39% yield). Under the similar reaction conditions,2 was converted to3 in 44% yield. All these complexes were characterized by single crystal X-ray diffraction analyses. Compounds2 and3 both contain a triangular cluster of one platinum and two ruthenium atoms, but in2 the bidentate ligand, dppe, chelates the platinum atom and in3 the two dppe ligands bridge the two Pt-Ru metal-metal bonds. Crystal data for1: space group C2/c,a=12.542(2)Å,b=15.350(4)Å,c=15.252(3)Å, =105.32(2)°,Z=4, 2192 reflections,R=0.025. For2: space group P2₁/c,a=14.351(2)Å,b=13.486(3)Å,c=19.218(3)Å, =108.48(1)°,Z=4, 3029 reflections,R=0.027. For3: space group P2₁/c,a=18.836(6)Å,b=15.559(5)Å,c=23.259(7)Å, =111.26(2)°,Z=4, 4204 reflections,R=0.038.     

Synthesis and crystal structures of heterobimetallic Fe-Cd,Fe-Zn,and Fe-In complexes containing hemilabile phosphorus/oxygen and silicon/oxygen bridging ligands

The reactions of K[Fe{Si(OMe)₃}(CO)₃(PY)][PY=Ph₂PCH₂C(O)Ph, Ph₂PCH₂C(O)[(-C₅H₄)FeCp] (Cp=⁵-C₅H₅), Ph₂P(CH₂)₂CN] with CdCl₂·2.5H₂O, ZnX ₂ (X=Cl, I) or InCl₃ afforded Fe-Cd-Fe or Fe-M(-X)₂ M-Fe (M=Cd, Zn, In;X=Cl, I) and Fe-InCl₂ complexes. Some of them contain an unusual and labile -²-SiO alkoxysilyl bridge which may be associated with a bridging mode for the ketophosphine ligand (first such example structurally established), thus providing original results in bimetallic chemistry on the intramolecular coordination of oxygendonor functions ofchemically different hemilabile ligands firmly attached to a neighboring metal center. The structures of the trinuclear complex (3), of the chlorobenzene solvate of the tetranuclear complex (4a·C₆H₅Cl) and of [mer-(OC)₃{(EtO)₃Si} (4e) have been determined by X-ray diffraction. Crystals of 3 are orthorhombic, space groupPbcn, witha=19.010(4),b=11.766(5),c=26.998(7)Å, andZ=4. Crystals of4a·C₆H₅Cl are monoclinic, space groupC2/c witha=22.455(3),b=17.680(2),c=16.627(4)Å, =90.80(4)°, andZ=4. Crystals of4e are monoclinic, space groupC2/c witha=25.392(5),b=18.554(6),c=16.28(1)Å, =120.73(3)°, andZ=4. The structures were solved using direct methods and Fourier difference techniques and refined by blocked full-matrix least squares toR=0.035 (R _w =0.049) for 2719 observed reflections, toR=0.042 (R _w =0.056) for 3082 observed reflections, and toR=0.057 (R _w =0.075) for 1850 observed reflections for3, 4a·C₆H₅Cl and4e, respectively. The Fe-Zn complexes (9a), (9b) and (9c) were prepared and characterized by spectroscopic methods.Part 21 in the Series: Complexes with Functional Phosphines. Part 20: P. Braunstein, S. Coco Cea, A. DeCian, and J. Fischer (1992).Inorg. Chem. 31, 4203.     

Synthesis and characterization of the new mixed-metal,mixed-chalcogen clusters Fe2 M(CO)10(μ3-S)(μ3-Te) (M=W,Mo). crystal structure of Fe2W(CO)10(μ3-S)(μ3-Te)

The new clusters Fe₂ M(CO)₁₀(µ₃-S)(µ₃-Te), I (M=W) and 2 (M=Mo) have been isolated from the room temperature reaction of Fe₂(CO)₆(µ-STe) andM(CO)₅(THF) (M=W, Mo), respectively. Compounds1 and2 have been characterized by IR, 125 Te NMR spectroscopy, and elemental analysis. The structure of compound1 has been established by X-ray crystallography. It belongs to the triclinic space groupP witha=6.844(2) Å,b=9.397(2) Å,c=13.681(10) Å, =81.64(2)°,=81360r,=812(2)°,V=861.2(3) ų,Z=2,D _e =2.835 g cm^–3. Full-matrix least-squares refinement of1 converged to R=0.043, andR _w .=0.115. The structure consists of a Fe₂ WSTe square pyramid and the W atom occupies the apical site of the square pyramid.     

The preparation and structural characterization of ruthenium carbonyl cluster complexes containing 3,3 dimethylthietane ligands

The reaction of Ru₃(CO)₁₂ with 3,3 dimethylthietane (DMT) at 68°C yielded the new tetraruthenium cluster complex Ru₄(CO)₁₂(-SCH₂CMe₂CH₂)₂,1 in 23% yield. Compound1 was characterized crystallographically and was shown to consist of a puckered square of four ruthenium atoms with two DMT ligands bridging opposite sides of the cluster via the sulfur atoms. Compound1 reacts with CO (98°C/1 atm) to yield the new tetraruthenium complex Ru₄(CO)₁₃ (-SCH₂CMe₂CH₂),2 in 69% yield. Compound2 consists of a butterfly tetrahedral cluster of four ruthenium atoms with a DMT ligand bridging the wing-tip metal atoms. Addition of DMT to2 regenerates1 in 67% yield. Crystal data—1: space group = ,a=17.490(2) Å,b=18.899(3) Å,c=9.781(1) Å, =93.06(1)°, =91.06(1)°, =105.239(9)°,Z=4, 5799 reflections,R=0.026; for2: space group = P2₁/n,a=15.430(3) Å,b=18.285(4) Å,c=9.850(2) Å, =90.05(2)°,Z=4, 2111 reflections,R=0.036.     

Inclusion compounds of thiourea and peralkylated ammonium salts. Part II. Hydrogen-bonded host lattices built of thiourea and cyclic dimeric bicarbonate moieties

New inclusion complexes R₄N⁺HCO ₃ ^– ·x(NH₂)₂CS·yH₂O (1, R=C₂H₅,x=1,y=1;2, R=n–C₃H₇,x=2,y=0;3, R=n–C₄H₉,x=3,y=0) have been prepared and characterized by X-ray crystallography. Crystal data, MoK radiation:1, space groupPbca,Z=8,a=8.839(2),b=14.930(3),c=24.852(5) Å, andR _F=0.063 for 1419 observed data;2, space groupC222₁,Z=8,a=8.521(3),b=16.941(4),c=32.022(7) Å,R _F=0.054 for 1689 observed data;3, space group ,Z=2,a=9.553(2),b=12.313(3),c=14.228(4) Å, =90.44(2),=103.11(2), =110.12(2)°,R _F=0.044 for 3925 observed data. In the crystal structure of1, the thiourea molecules form hydrogen-bonded zigzag ribbons running parallel to thea axis, and the cyclic dimeric bicarbonate moieties (HCO ₃ ^– )₂ together with water molecules behave likewise. A puckered layer is formed by further lateral hydrogen bonding between these two types of ribbons, and the (C₂H₅)₄N⁺ cations occupy the space between adjacent layers. In the crystal structure of2, the thiourea ribbons are cross-linked orthogonally by (HCO ₃ ^– )₂ unitsvia N–H...O hydrogen bonds to form a composite double layer. Half of the cations are enclosed within and the other half sandwiched between these double layers. In the crystal structure of3, the thiourea molecules form puckered double ribbons running in the [110] direction. The host framework is constructed by cross-linking the double ribbons with bridging bicarbonate dimers, yielding two channel systems aligned parallel to [100] and [111] that accommodate the cationic guests. The structural relationship between the present complexes and the classical thiourea channel adducts is discussed. Supplementary Data relating to this article have been deposited with the British Library as Supplementary Publication No. SUP 82178 (44 pages).     

Behavior of M[Al2Me6N3] (M=K,Rb, Cs) with aromatic solvents and the crystal structures of Cs[Al2Me6N3]·2p-xylene and [K·dibenzo-18-crown-6] [Al2Me6N3]· 1.5(1-methylnaphthalene)

The title compounds were synthesized by the addition of AlMe₃ to the corresponding azide suspended in an aromatic solvent. Both products were obtained as air-sensitive colorless crystals. Cs[Al₂Me₆N₃]·2p-xylene crystallizes in the monoclinic space groupC2/m witha=19.143(6),b=16.227(6),c=10.392(5) Å, =114.06(2)^o, and _calc = 1.20 g cm^–3 forZ=4. Refinement led to a conventionalR value of 0.037 for 2179 observed reflections. The cesium atom resides on a mirror plane, and the anion is disordered about a twofold axis. Thep-xylene molecules sandwich the cesium ion.[K·dibenzo-18-crown-6] [Al_Me6N₃]·1.5(1-methylnaphthalene) crystallizes in the monoclinic space groupP2₁/c witha=14.176(5),b=13.021(5),c=25.324(8) Å, =98.23(4)⁰, and _calc = 1.08 g cm^–3 forZ=4. The finalR value was 0.132 for 1402 observed reflections. One of the 1-methylnaphthalene molecules is disordered about a center of inversion and interacts with the potassium ion. The other solvent molecule is found roughly in layers in the lattice and also exhibits disorder of the methyl substituent. For both title compounds the AlMe₃ groups of the anion exhibit a staggered (C _s) conformation. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82015 (32 pages).     

Novel butterfly tungsten-osmium carbido cluster Complexes from the reaction of Os3(CO)10(NCME)2 CPW(CO)3(CH2SMe)

Condensation of be triosmium acetonitrile complex Os₃(CO)₁₀(NCMe)₂ with the sulfido complex CpW(CO)₃(CH₂SMe) in refluxing THF solution produced three sulfur-containing compounds Os₃(C0)₁₀)(µ-H)(µ-SMe) (1), Os₃(CO)₁₁ [S(Me)CH₂W(CO)₃Cp] (2) and CpWOs₃(CO)₁₂(µ-CH₂)(µ-SMe) (3). Clusters 2 and 3 were products involving a 1:1 combination of starting materials and were characterized by X-ray diffraction studies. Crystals of 2 belongs to monoclinic space group P 2₁ /c witha=8.418(2),b = 11.912(2),c = 28.288 Å,=97.64(2)°,Z=4;R _F=0.044,R _W,=0.044. Crystal dara far 3: space group P 2₁/e,a 18.156(4).b=9.255(6),c = 15.347(4) Å. = 103.49(2)°,Z = 4;R _F -=0.047,R _W = 0.045. Upon thermolysis in toluene, the methylene cluster 3 released CO and induced C-H bond activation to afford two tetrametallic carbido clusters with formula CPWOS₃(CO)₉(µ₄-C)(µ-H)₂(µ-SMe) (4) and CPWOs₃(CO)₁₁(µ₄-C)(µ-SMe) (5) as the principle products. The first complex possesses a butterfly framework encapsulating a µ₄-C ligmd and a µ-SMe ligand linking a W-Os edge, whereas the second product adopts a puckered, cyclic arrangement of WOs₃ metal atoms with µ-SMe ligand located on a nonbonding Os-Os vector. Complex4 crystallizes in monoclinic space group P 2₁ /c witha=15.633(4) Å,b = 8.699 (3) Å,c=15.422(4) Å,=93.12(2)=°, Z=4,R=0.036,R _W =0.034 for 2780 observed reflections. Crystal data for5: space groupP nma,a=14.542(3),b=13.710(6),c=11.758(3) Å.Z=4,R _F =0.038,R _W = 0.037 for 1826 observed reflections. A variable temperature¹H NMR study was also presented to demonstrate the solution fluxionality of5.