Metal-penicillamine interactions. Part 1. Preparation and crystal structure of a 1:1 complex of mercuric chloride with d-penicillamine, 2[μ3-Cl){HgSC(CH3)2CH(NH3)COO}3·3(μ2-Cl)· 2(H3O)·(H2O·Cl)3

A 1:1 complex of mercuric chloride with D-peniccillamine has been isolated and characterised as 2[(μ₃-Cl){HgSC(CH₃)₂CH(NH₃)COO}3]·3(μ₂-Cl)·2(H₃O)·(H₂O·Cl)₃. The compound crystallises in cubic space group P4₁32, with a = 18.679(5) Å and Z = 4. The structure, refined to R_F = 0.086 for 443 observed Mo-Kα diffractometer data, features a triply bridging chloride ion linking three equivalent [HgSC(CH₃)₂CH(NH₃)COO]⁺ units [Hg-Cl = 2.37(1) Å, Hg-Cl-Hg′ = 98.5(9)°]. The carboxylate groups of a pair of adjacent penicillamine ligands are strongly linked via a symmetrical O?H?O hydrogen bond of length 2.24(8) Å, and neighboring pyramidal trinuclear [μ₃-Cl){HgSC(CH₃)₂CH(NH₃)-COO}₃]²⁺ moieties are further connected by symmetrical chloride bridges [Hg-Cl = 3.06(2) Å; HgClHg′' = 79.6(7)°] to form a three-dimensional network. The voids in the lattice are filled by hydronium ions and novel planar cyclic hydrogen-bonded (H₂O·Cl^?)₃ rings of edge O-H?Cl = 2.46(4) Å.     

X-ray structure of a mono(1-methylthyminato) complex of cisplatin,chloro-(1-methylthyminato-N3)-cis-diammineplatinum(II) monohydrate

The crystal structure of chloro-(1-methyltyminato- N3)-cis-diammineplatinum(II) monohydrate, cis- (NH₃)₂Pt(C₆H₇N₂O₂)Cl·H₂O, is reported. The compound crystallizes in space group P$\text{1}$ with a = 6.911(2) Å, b = 8.598(3) Å, c = 11.464(4) Å, α = 100.13(3)°, β = 120.03(3)°, γ = 93.16(3)°, Z = 2. The structure was refined to R = 0.048 and R_w = 0.057. The compound contains the deprotonated 1-methylthymine ligand coordinated to Pt through N3 (1.973(10) Å). This distance represents the shortest Pt-N3(pyrimidine-2.4-dione) bond reported so far. The two PtNH₃ bond lengths differ significantly: PtNH₃ (trans to Cl) is longer (2.052(10) Å) than PtNH₃ (trans to N3 of 1-MeT) (2.002(11) Å). The PtCl distance (2.326(3) Å) is normal, as is the large dihedral angle between the Pt coordination plane and the nucleobase (76.5°).     

Metal complexes of 2,4-diamino-5-(3′,4′,5′-trimethoxybenzyl)pyrimidine, (trimethoprim). Part II. Synthesis,magnetic characterization and X-ray structure of [Cu2(O2CCH3)4(trimethoprim)2]·2C6H6·CH3OH

The reaction of [Cu₂(O₂CCH₃)₄·2H₂O] with trimethoprim is reported. In methanol a green solution was obtained, which, on adding benzene, yielded tetrakis(μ-acetato)bis(trimethoprim)dicopper(II) di-benzene methanol solvate. The compound crystallizes with four molecules per cell in the monoclinic space group C2/c, with a = 24.109(5), b = 15.256(3), c = 16.532(3) Å, β = 116.89(2) for λ(Mo-Kα) = 0.71073 Å. The copper atoms are bridged by four acetate groups to form the binuclear molecule [Cu₂-(O₂CCH₃)₄(TMP)₂]·2C₆H₆·CH₃OH. The TMP ligand acts as a donor molecule through one pyrimidinic nitrogen atom.     

Coordination chemistry of lanthanides with cryptands. An X-ray and spectroscopic study of the complex Nd2(NO3)6 [C18H36O6N2]·H2O

By reacting neodymium nitrate hexahydrate with the cryptand 〈222〉 in methanol, the complex Nd₂-(NO₃)₆[C₁₈H₃₆O₆N₂]·H₂O was obtained and analyzed by single-crystal X-ray diffraction. The cell is triclinic P$\text{1}$ with a = 14.870(2) Å, b = 13.261(2) Å, c = 8.832(1) Å, α = 91.2(1)°, β = 93.4(1)°, γ = 87.6(1)°, Z = 2 and U = 1736.6 ų. The structure was refined by least-squares methods to the conventional R = 0.039 for 6177 observed reflections. The compound contains the cations [Nd〈222〉(NO₃)]²⁺ and the anions [Nd(NO₃)₅·H₂O]^2?, and is isostructural with the samarium analogue. Solid state fluorescence spectra of the title complex were measured at room and liquid nitrogen temperature, and the transitions ⁴F_3/2 → ⁴I_9/2 and ⁴F_3/2 → ⁴I_11/2 analyzed.     

Nickel—nitrosyl Complexes: structure of nitrosyltris(trimethylphosphine)nickel hexafluorophosphate, {Ni(NO)(PMe3)3} PF6

The crystal and molecular structure of nitrosyltris-(trimethylphosphine)nickel(O) hexafluorophosphate, {Ni(NO)(PMe₃)₃}PF₆, has been determined from three dimensional single crystal X-ray analysis. The compound crystallizes in the orthorhombic space group Pnma with Z = 4 and a unit cell of dimensions: a = 16.253(3), b = 10.536(1) and c = 12.228(2) Å. The structure was solved by conventional heavy atom techniques and refined by least-squares methods to R₁ = 0.036 and R₂ = 0.048 respectively for 1085. independent reflections. The coordination geometry around the nickel is a slightly distorted tetrahedron with an average PNiP angle of 105.63° and PNiN angle 113.03°. The nickel nitrosyl group is slightly bent with an NiNO angle of 175.4(5)°. The bending occurs in the ClPlNiNO plane toward Pl. The structure is compared with other tetrahedral {MNO}¹⁰ phosphine complexes and the MNO bonding is discussed.     

Synthesis and characterization of uranyl(VI) and thorium(IV) complexes with phosphine oxides. The crystal structure of UO2(NO3)2(NO2-C6H4Ph2PO)2

Uranyl(VI) and thorium(IV) complexes of the type UO₂(NO₃)₂(L¹)₂, UO₂(NO₃)₂(L²)₂, UO₂(CH₃COO)₂L¹, UO₂(CH₃COO)₂L², Th(NO₃)₄(L¹)₂ and Th(NO₃)₄(L²)₂ (L¹ = (2-nitro)phenyl-bis-phenyl phosphine oxide, L² = triferrocenylphosphine oxide) are reported, together with their physico-chemical properties.The crystal structure of UO₂(NO₃)₂(L¹)₂ is also reported. The crystals are monoclinic, space group P2₁/n with a = 17.78(1), b = 13.88(1), c = 17.37(1) Å, β = 114.8(1)° for Z = 4. The uranium atom is 8-coordinated, the uranyl(VI) group being equatorially surrounded by an irregular hexagon of six oxygen atoms from two trans neutral ligands and two nitrato groups.     

Preparation and structural characterization of di-μ-azido-bis[azido(2-aminopyridine)aquo]dicopper(II), [Cu(2-ampy)(N3)2(H2O)]2

Di-μ-azido-bis[azido(2-aminopyridine)aquo]dicopper(II), [Cu(2-ampy)(N₃)₂(H₂O)]₂, was synthesized and characterized by X-ray crystallography. The crystals are triclinic, space group P$\text{1}$, with a = 7.142(1), b = 7.812(1), c = 9.727(1) Å, a = 96.52(1), β = 95.52(1), γ = 113.47(1)°, and Z = 1. The structure was refined to R_F = 0.030 for 1960 observed MoKα diffractometer data. The dimeric molecule, which possesses a crystallographic inversion center, contains both terminal and μ(1)-bridging azido groups. Each copper(II) atom is further coordinated by a 2-aminopyridine ligand (via its ring N atom) and a water molecule to give a distorted square pyramid, with the metal atom raised by 0.17 Å above the N₄ basal plane [CuN (ring) = 2.001(2), CuN (azide) = 1.962(3)–2.018(2) Å] towards the apical aquo ligand [CuO = 2.371(2) Å]. Each water molecule forms an intramolecular O?HN (amine) acceptor hydrogen bond, and is linked by two OH?N (terminal azide) intermolecular donor hydrogen bonds to adjacent dimeric complexes to yield a layer structure parallel to (001). Infrared and electronic spectral data are presented and discussed.     

Synthesis and crystal structure of (pipzH2)2Mo2Cl8·4H2O (pipz = piperazine)

The title compound (pipzH₂)₂Mo₂Cl₈·4H₂O (pipz = piperazine),was isolated from the solution of (morphH)₂Mo₂Cl₆(H₂O)₂ in HCl 1:1 by addition of (pipzH₂)Cl₂. This reaction indicates the reversibility of the substitution of chloride ions in Mo₂Cl₈^4? by water molecules. (pipzH₂)₂Mo₂Cl₈·4H₂O crystallizes in the Pbca space group, with a = 15.154(2), b = 13.170(2), c = 12.208(2) Å and Z = 4. The structure was solved by the Patterson method and refined to the unweighted and weighted residuals of 0.050 and 0.048. The crystal structure is built form Mo₂Cl₈^4?, (pipzH₂)²⁺ and H₂O. The MoMo distance of 2.129(3) Å is the shortest one found in all structurally-characterised Mo₂X₈^4? (X = Cl, Br) anions. Four independent MoCl distances are 2.456(3), 2.445(3), 2.463(4) and 2.455(4) Å. The (pipzH₂²⁺ exists in a usual chair conformation. There is a network of hydrogen bonds of the type NH?Cl, NH?O, OH?Cl and OH?O between the ions and water molecules.     

Spectroscopy and crystal structure of neodymium coordination compound with glycine: Nd2(Gly)6·(ClO4)6·9H2O

Neodymium complex compound with glycine: Nd₂(Gly)₆·(ClO₄₆·9H₂O was synthesized and obtained in the form of monocrystals. Absorption spectra recorded in the region of 8000–35 000 cm^-1 were measured along the crystallographic axes. Intensities of the f-f transitions were analysed on the basis of the Judd theory. The X-ray crystal structure determination of the complex is reported. Crystals are triclinic, space group P$\text{I}$, with a = 11.554(4) Å, b = 14.108(1) Å, c = 15.660(3) Å, α = 97.14(1)°, β = 102.82(2)°, γ = 105.28(1)°, V = 2355.25 ų Z = 2, M.W. = 1495.4, D_c = 2.129)(3) g cm^-3, D^m = 2.103(1) g cm^-3. The structure was solved by Patterson's method and successive Fourier syntheses giving the locations of all nonhydrogen atoms. The final R factor was 0.062 and R_w = 0.073 for 12869 reflections with |F_o| > 5σ|(F_o)|. The asymmetric unit consists of a dimeric formula unit. The coordination polyhedron of Nd atoms comprises seven oxygen atoms from glycine and two from water molecules. The neodymium-glycine bonding mode is compared with that of the calcium-glycine complex.     

Synthesis and crystal structure of bis(tetramethylammonium) aquotetra-fluorodioxouranate(VI) dihydrate, [(CI3)4 N]2[UO2 F4(H2 O)]·2H2O

The title compound has been synthesized and subjected to crystal structure analysis. M_r = 548.50, m.p. 108.1 °C (decom.), orthorhombic, Im2m,a = 7.006(2), b = 8.938(2), c = 13.619(2) Å V = 852.8(3) ų, Z = 2, D_x = 2.136, D_m, (flotation in CCl₄/CH₂I₂) = 2.128 g cm^?3, λ(Mo-Kα) = 0.71069 Å, μ = 90.79 cm^?1, F(000) = 519.89, T = 295 K, final R_F = 0.036 and R_G = 0.044 for 566 observed reflections. The discrete [UO₂F₄(H₂0)]^2? anion has site symmetry m2m, its virtually linear uranyl moiety being surrounded by fluoro and aquo ligands occupying the vertices of a pentagon in the equatorial plane. Watet molecules serve to link the complex anions by hydrogen bonds into layers, between which the organic cations are accommodated.     

Crystal structure of nonaquasamarium(III)bromide-l,4-dioxan adduct (1:3:2), Sm(H2O)9·Br3(C4H8O2)2

The title compound has been found to consist of tricapped trigonal prismatic Sm(H₂O)₉³⁺ ions in C_2v symmetry, sandwiched between expanded ‘close packed’ layers of bromide ions, with 1,4-dioxan molecules in chair conformation hydrogen bonding between the equatorial water molecules of adjacent cations.Orthorhombic, Amm2, a = 8.010(3), b = 19.848(4), c = 7.388(3) Å, R = 0.022 for 992 unique reflexions.     

New preparations and molecular structures of cis-MCl2(Ph2PCH2PPh2)2, M = Ru,Os and trans-RuCl2(Ph2PCH2PPh2)2

The title compounds were made by reacting bis(diphenylphosphino)methane (dppm) with reduced solutions of OsCl₆^4? and Ru₂OCl₁₀^4?. The crystal and molecular structures of these compounds have been determined form three-dimensional X-ray study. The cis-isomers crystallize with one CHCl₃ per molecule of the complex. All three compounds crystallize in the monoclinic space group P2₁/n with unit cell dimensions as follows: Cis-OsCl₂(dppm)₂·CHCl₃: a = 13.415(4) Å, b = 22.859(4) Å, c = 16.693(3) Å, β = 105.77(3)°, V = 4926(3) ų, Z = 4. cis-RuCl₂(dppm)₂·CHCl₃: a = 13.442(3) Å, b = 22.833(7) Å, c = 16.750(4) Å, β = 105.53(2)°, V = 4953(3) ų, Z = 4. trans-RuCl₂(dppm)₂: a = 11.368(7) Å, b = 10.656(6) Å, c = 18.832(12) Å; β = 103.90(6)°, V = 2213(7) ų; Z = 2. The structures were refined to R = 0.044 (R_w = 0.055) for cis-OsCl₂(dppm)₂·CHCl₃; R = 0.065 (R_w = 0.079) for cis-RuCl₂(dppm)₂·CHCl₃ and R = 0.028 (R_w = 0.038) for trans-RuCl₂(dppm)₂. The complexes are six coordinate with stable four-membered chelate rings. The PMP angle in the chelate rings is ca. 71° in each case.     

The crystal and molecular structure of [Co(NH3)5PO4]·3H2O,a Na+-K+ ATPase probe

The title compound, Co(NH₃)₅PO₄, prepared by a modified literature procedure, was used to study the inhibition of Na⁺-K⁺ ATPase and to serve as a structural model for ML₄(nucleotide) complexes. The structure was determined by single crystal X-ray diffraction techniques. The crystals are monoclinic, space group P2₁/n, a = 8.638(3), b = 14.517(2), c = 9.145(2) Å, and β = 112.71(2)°. The structure, solved by the heavy atom method to an R value of 3.3% for 1924 reflections, consists of a slightly distorted octahedron with the cobalt bound to the five amines and a monodentate phosphate. Solution structural data is taken from ³¹P NMR measurements. From comparison with other metal phosphate complexes it is concluded that multiple monodentate coordination of a di- or triphosphate closely resembles the coordination of a monophosphate This is based on the similarity of the MO bond angle which is 129.6° in the present example.     

Caffeine complexes of platinum(II): crystal structure of cis-[Pt(C8H10N4O2)2Cl2]·0.4H2O

The preparations are reported of cis[Pt(caffeine)₂Cl₂]·0.4H₂O, Pd(caffeine)₂Cl₂, the methanol adduct of the previously known compound K[Pt(caffeine)Cl₃], and Pt(caffeine)(cytidine)Cl₂. Crystals of [Pt(caffeine)₂Cl₂]·0.4H₂O are tetragonal P4₂/n with a = 13.156(2) 0?, c = 12.734(2) 0?, Z = 4. The structure was refined on 945 reflections to R = 0.025. The molecule is cis with a crystallographic two-fold axis bisecting the ClPtCl and NPtN angles. The Pt is square planar with PtN and PtCl bonds of 2.029(5) Å and 2.271(2) Å respectively. There is a 5.4° dihedral angle between the imidazole and pyrimidine rings, and the imidazole ring is rotated away from the coordination plane by 86.4°. Symmetry related caffeine units pack parallel to each other with an inter-ring separation of 3.45 Å.     

Structural comparison of (CuICH3CN4·dibenzo-18-crown-6 (I) and (CuICH3CN)x (II) fluorescent copper(I) materials

The single crystal X-ray structures of (CuICH₃CN₄·dibenzo-18-crown-6 (I) and (CuICH₃CN) (II) have been determined at room temperature [(I) C₂₈H₃₆Cu₄I₄N₄o₆, monoclinic space group P2₁/n, a = 10.116(4), b = 18.092(8), c = 22.211(9) Å, β = 98.66(3)°, Z = 4; (II) C₂H₃CuIN, orthorhombic pBN2₁, a = 13.618(8), b =8.742(2), c = 4.298(2), Z = 4]. (I) exists as a distorted cube with copper and iodine at alternate corners, the fourth coordination site copper occupied by an acetonitrile molecule coordinated through nitrogen. The cluster contains no crystallographic symmetry element and CuCu distances average 2.770(5) Å. The dibenzo-18-crown-6 displays only second sphere type interactions with cluster. (II) displays a pleated double chain type structure with distorted rectangles of alternating Cu and I atoms sharing opposite edges in infinite array. Copper displays tetrahedral geometry by coordination to three iodine atoms and a nitrogen bound acetonitrile molecule.     

New precursors in the chemistry of IVB transition metal alkoxides V. Synthesis and molecular structure of Zr3Fe(μ4-O)(μ2-OC3H7)6-(OC3H7)4(acac)3

The reaction of iron(III) acetylacetonate with zirconium(IV) n-propanolate in n-propanol leads to a tetranuclear species Zr₃FeO(OC₃H₇)₁₀(acac)₃. This compound crystallizes in the triclinic system (space group P ): a = 12.426(2), b = 12.977(2), c = 20.129(4) Å, α = 91.55(1), β = 97.90(1), γ = 100.53(1)°. The structure consists of discrete tetranuclear molecules. The metal atoms design an almost perfect tetrahedron around a four-fold coordinated oxygen atom. The zirconium atoms are in a seven-fold coordination and the iron atom in a five-fold coordination.     

Metal complexes of virus inhibitors. Part III. Coordination properties of 1-n-propyl-2-α-hydroxybenzylbenzimidazole and the X-ray crystal structure of Ni(C17H18N2O)2(C17H17N2O)1(ClO4)1

Complexes are described of Cobalt(II) and Nickel- (II) salts with the title ligand L. The X-ray crystal structure is described of NiL₂L′₁(ClO₄)₁. One ligand molecule (L′) in this complex is deprotonated and the structure involves strongly hydrogen bonded dimers with OHO bonds = 2.56 Å and 2.62 Å and a NiNi bond = 4.77 Å. The corresponding Cobalt complex is thought to be similar but no other compounds containing L′ were obtained.     

Synthesis and characterisation of a trinuclear uranyl complex: Crystal structure of (CN3H6)5[(UO2)3O(OH)2(CH3COO)(C2O4)3]

The reaction of uranyl oxalate trihydrate with guanidinium acetate at room temperature in water yields known uranyl complex with composition (CN₃H₆)₂[UO₂(C₂O₄)₂(H₂O)]·H₂O as a first phase and a novel complex (CN₃H₆)₅[(UO₂)₃O(OH)₂(CH₃COO)(C₂O₄)₃] as a second. The second phase was investigated by means of IR spectroscopy and X-ray diffraction. The trinuclear discrete complex contains two symmetrically independent uranyl ions with a pentagonal bipyramid structure and has a nonplanar geometry. The distortion of its equatorial plane is caused by substitution of a monodentate bridge hydroxide anion by a bidentate bridge acetate-anion. The acidic ligands found in the complex are usually in competition for a place in coordination sphere of an uranyl ion, thus peculiarities of the complex formation are discussed in terms of ‘crystallochemical analysis’.     

Crystal structures of MoCl2(O)(O2)(OPMePh2)2 and mixtures of MoCl2(O2)(OPPh3)2 and MoCl2(O)(O2)(OPPh3)2: allylic alcohol isomerization studies using MoCl2(O)(O2)(OPMePh2)2

Adding one equivalent of H₂O₂ to compounds of stoichiometry MoCl₂(O)₂(OPR₃)₂, OPR₃ = OPMePh₂ or OPPh₃, leads to the formation of oxo-peroxo compounds MoCl₂(O)(O₂)(OPR₃)₂. The compound MoCl₂(O)(O₂)(OPMePh₂)₂ crystallized with an unequal disorder, 63%:37%, between the oxo and peroxo ligands, as verified by single-crystal X-ray diffractometry, and can be isolated in reasonable yields. MoCl₂(O)(O₂)(OPPh₃)₂, was not isolated in pure form, co-crystallized with MoCl₂(O)₂(OPPh₃)₂ in two ratios, 18%:82% and 12%:88%, respectively, and did not contain any disorder in the arrangement of the oxo and peroxo groups. These complexes accomplish the isomerization of various allylic alcohols. A mechanism of this reaction has been constructed based on ¹⁸O isotopic studies and involves exchange between the alcohol and metal bonded O atoms.     

31P and 195Pt NMR studies on the clusters [Pt4(μ2-CO)5L4]. L = PEt3, PMe2Ph,PMePh2, PEt2But. The molecular structure of a monoclinic modification of [Pt4(μ2-CO)5(PMe2Ph)4].

Several clusters complexes of composition [Pt₄(μ₂-CO)₅L₄] have been synthesized and characterized, using ³¹P and ¹⁹⁵Pt NMR. L = PEt₃, PMe₂Ph, PMePh₂, PEt₂Bu^t. The molecular structure of a new monoclinic modification of the PMe₂Ph derivative has been determined: space group P2₁/n with a = 19.698(4), b = 10.9440(20), and c = 21.360(6) Å, β = 112.432(18)°, Z = 4. Using 4751 reflections measured at 290 ± 1 K on a four-circle diffractometer the structure has been refined to R = 0.0846. The molecule has no imposed symmetry, but the central Pt₄(CO)₅P₄ core has the approximate C₂v architecture established for the previously known orthorhombic modification. The Pt₄ unit is thus a highly distorted, edge-opened (3.3347 Å) tetrahedron, with five edge-bridging carbonyl and four terminal phosphine ligands. In contrast to the crystallographic results ³¹P and ¹⁹⁵Pt NMR spectra reveal equivalent ³¹P and ¹⁹⁵Pt spins, which can be interpreted in terms of a tetrahedral arrangement of platinum atoms. It is suggested that this equivalence arises from time-averaging of all possible isomeric edge-opened tetrahedra.