Crystal and molecular structure of diaquobis(1,1′-dimethyl-2,2′-diimidazolylsulfide)copper(II) methylsulfate, (C8H10N4S)2Cu(II)(OH2)2(CH3OS03)2

The crystal and molecular structure of the title complex has been determined. The space group isP2₁/n, witha=8.460(3),b=8.503(3),c=20.341 (8) Å,=98.41(3) andZ=2. The ligand molecules chelate the Cu^II such that the metal has a tetragonally distorted octahedral geometry; four N atoms occupy the equatorial plane and two H₂O molecules occupy the axial positions. The average Cu-N and Cu-O distances are 2.005(6) and 2.47(1) Å, respectively. The novel ligand, 1,1-dimethyl-2,2-diimidazolylsulfide was formedin situ from a methanolic solution of copper(II) sulfate pentahydrate and 1-methylimidazole-2-thiol. The measured spectral parameters (visible, EPR, and photoelectron spectroscopy) correlate well with the molecular structure.     

Structure of dichloroethanolaminecopper(II) and dibromoethanolaminecopper(II)

CuCl₂(NH₂CH₂CH₂OH) is monoclinic, space group C2/c, witha+11.092(2),b+10.012(2),c+6.401(1) Å, =121.71(1)°, andV=604.8(2)ų withZ+4. The structure was refined to a final value ofR+0.27 for 518 unique observed reflections with |F|>3. The ethanolamine and halide ions coordinate to the copper(II) ion forming a pseudoplanar four-coordinate monomeric CuCl₂L² complex (L²+bidentate ligand). The copper ion also interacts with the halides of neighboring complexes through the formation of semi-coordinate Cu-Cl linkages (2.926(1) Å) between oligomers. The copper thus attains a 4+2 elongated octahedral coordination geometry. In this space group, the ligand is statisticallydisordered The Cu-Cl distance is 2.267(1)Å while the Cu-N/O distances are 2.025(2)Å. The dibromide structure is isomorphous with the dichloride structure, with space group C2/c, anda+11.285(2),b+10.218(2),c+6.715(1) Å, =121.65(1)°, andV=659.2(2)ų.     

Transition metal(II) complexes of a biological buffer. Structural and spectroscopic study on Co(II), Ni(II), Cu(II), Zn(II), and Cd(II) complexes of N-[2-hydroxy-1,1-bis-(hydroxymethyl)ethyl]glycine

The structural and spectroscopic properties of complexes of N-[2-hydroxy-1,1-bis-(hydroxymethyl)ethyl]glycine (thmmg) with Co(II), Ni(II), Cu(II), Zn(II), and Cd(II) were investigated. The complex [Zn(thmmg)₂] crystallizes in the space groupP2₁/n, witha=8.796(2),b=9.050(3),c=9.926(2) Å,=97.35(1)° andZ=2; the copper(II) homolog is isomorphous. The complex [Ni(thmmg)₂]·6H₂O crystallizes in the space groupP2₁/n witha=8.432(8),b=8.495(2),c=15.967(1) Å,=95.57(2)° andZ=2; the cobalt(II) homolog is isomorphous. Ni(II) and Zn(II) complexes show an elongated octahedral coordination arising from two symmetry related amino acid molecules acting as a tridentate chelate through the amino nitrogen, one carboxylate oxygen, and one hydroxyl oxygen; the water molecules in the Ni(II) complex are not involved in metal coordination. The same ligand bonding mode may be suggested also for the Cu(II) and Co(II) complexes, while for Cd(II) only the nitrogen atom and the carboxylate oxygens seem to be involved in metal coordination.     

Structure of (1,2-diaminoethane) (1-[[2-[(2-aminoethyl)imino]propyl]thio]-2-propanone)nickel(II) nitrate

A single crystal X-ray investigation of the purple nickel (II) complex Ni[L(en)](NO₃)2, produced by condensation of 1,2-diaminoethane (en) with the thiodiketone S(CH₂COCH₃)2 in the presence of nickel (II) nitrate (L is NH₂(CH₂)₂N=C(CH₃)CH₂SCH₂COCH₃), shows that the metal ions are six coordinate. The new ligand L is tetradentate, with the N,N and S donor atoms arranged meridionally, and the coordination shell completed by the carbonyl oxygen atom of L and the nitrogen atoms of 1,2-diaminoethane. Metal-ligand bond distances are Ni-N: 2.08 av. (en), 2.10 and 2.05 (NH₂ and N=C respectively of L); Ni-O, 2.16; Ni-S, 2.45 Å. There is considerable angular distortion from regular octahedral values of the bond angles at nickel. The crystals are monoclinic,P2₁/c (No. 14),a=12.433(2),b=11.709(1),c=13.150(2) Å,=103.93(1)°,V _c=1858.2(4) ų. The structure was solved by the heavy-atom method and refined by full-matrix least squares to anR value of 0.055 for 3633 reflections.     

Crystal structure of dinitratotris(pyridine)nickel(II), Ni(NC5H5)3(NO3)2

Ni(NC₅H₅)₃(NO₃)₂ crystallizes in the triclinic space group P¯1 witha=8.432(2),b=9.993(2),c=12.181(3)Å, =69.78(2),=83.16(2), =67.73(1), andD _c =1.57 g cm^–3 forZ=2. The Ni²⁺ ion is six-coordinate with one bidentate and one monodentate nitrato ligand.     

Crystal and molecular structure of tris-(O-isopropylxanthato)-chromium(III)

The title compound has been synthesized by the reaction of CrCl₃6H₂O with K{S₂COCH(CH₃)₂} in a 13 molar ratio in an aqueous medium. It has been characterized by elemental analysis and IR spectral studies. Crystals of Cr{S₂COCH(CH₃)₂}₃ are monoclinic, space group P2₁/n witha=10.002(2),b=10.973(1),c=18.961(6) Å,=91.78(2)°,V=2079.9 ų,Z=4,D _calc=1.46 g cm^–3, monochromatic radiation (Mo-K), =0.71069 Å,=11.2 cm^–1,F(0 0 0)=948,T=295K, finalR=0.0320 for 2641 reflections. The environment of the chromium atom is based on an octahedral geometry having six sulfur donor atoms from three symmetrically chelated ligands with average distances: Cr-S=2.396(9) Å, C-S=1.690(3) Å and C-O=1.315(3) Å. The bond distance between oxygen atom and the carbon atom of the isopropyl group (O-C_av=1.478(4) Å) suggests that the form –S ₂ ^(–) C=O⁽⁺⁾CH(CH₃)₂ contributes significantly to the structure of the isopropyl group.     

Cobalt(II) and nickel(II) complexes ofN-protected amino acids. Crystal and molecular structure of bis (N-acetylglycinato)tetraaquocobalt(II)

Binary complexes of formula [M(II)(acgly)₂(H₂O)₄] (M(II)=Co(II), Ni(II), acgly=N-acetylglycinate ion) were synthesized, and for the Co(II) complex the crystal and molecular structure was determined. The crystals are monoclinic, space groupP2₁/c,a=4.838(1),b=10.785(2),c=14.340(6) Å,=96.96(2)°,Z=2. The structure was solved by the heavy-atom method and refined through full-matrix least-squares calculations toR=0.0394 for 1069 observed reflections. The coordination around the cobalt atom is slightly elongated octahedral arising from one carboxylate oxygen of each of the two centrosymmetrically related monodentateN-acetylglycinate anions and four water molecules.     

The crystal structure of a N-(2-thiophenyl)-salicylaldiminopiperidino nickel(II) complex

The crystal and molecular structure of the title complex, C₁₈H₁₉N₂OSNi, has been determined by direct methods. The compound crystallizes in monoclinic crystal system witha=11.968(1),b=12.182(1),c=12.399(1) Å, =115.23(1)°, space group P2₁/n. Nickel is in a slightly distorted square-planar environment of two nitrogens [1.881(2) and 1.952(2) Å] and one oxygen [1.856(3) Å] and one sulphur [2.138(2) Å] atom. Ni is 0.005 Å out of the plane of its ligands.     

Preparation and crystal structure of diaquabis(1,8-naphthyridine-N-monoxide)nickel(II)nitrate

The title compound [Ni(napyo)₂(H₂O)₂](NO₃)₂ was formed by the reaction of nickel(II) nitrate with 1,8-naphthyridine-N-monoxide (napyo) in ethanol medium. The complex crystallizes in the monoclinic, space groupP2₁/n withZ=2. Lattice parameters are:a=7.160(2),b=11.713(3),c=11.830(2) Å,=95.11(3)°. The structure was determined from 1399 observed reflections and refined toR=0.061. The Ni atom shows a slightly distorted octahedral coordination, being bonded to two oxygen atoms and two nitrogen atoms of two napyo ligands and to two oxygen atoms of two water molecules.     

Crystal structure of trans-C2SnO5 pentagonal bipyramidal dibutylbis(phenylacetato)tin(IV) hydrate

The Lewis acidity of tin in a diorganotin dicarboxylate is demonstrated in this first example of a 1/1 adduct of the ester with a neutral ligand. The structure of dibutyltin bisphenylacetate hydrate [(C₄H₉)₂Sn(O₂CCH₂C₆H₅)₂·H₂O] has been determined from 1211 F ₀6F _c MoK reflections and refined to anR _F of 0.061 [space groupP2/a witha=8.416(2),b=10.391(5),c=14.28(1) Å,=98.42(4)° andZ=2]. TheC atoms [Sn-C 2.101(8) Å; C-Sn-C 169.9(5)°] make up the apices and the O_carboxylate [Sn-O 2.234(5), 2.439(7) Å; O-Sn-O 55.7(2)°] and O_water [Sn-O 2.342(8) Å] atoms the equatorial points of thetrans-C₂SnO₅ pentagonal bipyramid around the Sn atom. The molecular symmetry isC ₂, and the Sn and O_water atoms lie along a crystallographic twofold axis. The aqua ligand forms donor H-bonds with neighboring carboxylato groups to link the molecules into a double zigzag chain running parallel toa.     

Crystal and molecular structure of trans-(tricarbonyl)bis(trans-2,2,3,4,4-pentamethyl-1-phenylphosphetane)iron

The title compound crystallizes in the monoclinic space groupP2₁/a witha=13.092(2) Å,b=15.853(2) Å,c=15.406(3) Å,=103.00(1)°,V=3116(1) ų, andD _calc=1.237 g cm^–3 forZ=4. The structure was solved by direct methods, and refined to a finalR value of 0.057. The phosphetane ligands adopt a nonlinear trans relationship. The four-membered rings are non-planar and have different flap angles of 6.1 and 20.3°. Virtual coupling is evident in the¹³C NMR spectrum of the title compound. Comparison of the¹³C NMR spectral data of this molecule with the parent phosphine ligand, the ligand oxide, and the mono-phosphine iron complex is provided.     

Polymeric and mixed carboxylate compounds: Crystal structure of [Zn(tiglate)0.54 (benzoate)1.46]x

The crystal structure of [Zn(O₂CC(CH₃)CHCH₃)_0.54(O₂CC₆H₅)_1.46]_x has been determined by single crystal X-ray diffraction. The compound crystallizes in the monoclinic system, space group P2₁/c witha=10.311(1),b=13.170(1),c=19.000(2) Å,=91.895(7)°,V=2578.7 ų,Z=4,D _x=1.525g cm^–3, (Mo K)=0.71073 Å,=1–95 mm^–1, F(000)=1206,T=295K,R=0.046 for 4548 unique reflections. The two different carboxylates are randomly scrambled along a one dimensional polymer, made up of binuclear units connected by a syn-anti carboxylate bridge. Each binuclear unit contains three syn-syn carboxylates which bridge two zinc atoms. Vibrational data indicate that [Zn(O₂CC(CH₃)CHCH₃)₂]_x has the same polymeric structure; orientation of tiglate is the same as for the mixed ligand compound. Recrystallization of mixed carboxylate species produces either an alteration in carboxylate ligand ratio, or a total separation of the two carboxylates, giving two different compounds.     

Crystal structure oftrans-tetrachlorobis[2-(2-1H-imidazolyl)-1H-imidazolium]cadmium(II), [Cd(H3biim)2Cl4]

The reaction between cadmium(II) chloride and 2,2'-bi-1H-imidazole (H₂biim) in an acidic solution affords [Cd(H₃biim)₂Cl₄] (H₃biim=2-(2-1H-imidazolyl)-1H-imidazolium) in 63% yield. The compound crystallizes in the triclinic space groupP1, wherea=8.072(2),b=8.100(2),c=8.593(2) Å, =75.89(2), =62.94(2), =63.29(1)°,V=446.4(2) ų, andZ=1. The central Cd atom exhibits an octahedral geometry composed of a Cl₄N₂ core. The Cd-N bond distance is 2.392(2) Å. Cd–Cl distances are 2.5919(9) and 2.671(1) Å.     

Schiff bases and their complexes with metal ions. Part II. Structures of N-n-butyl-2-hydroxy-1-naphthaldimine and bis[N-n-pentyl-2-hydroxy-1-naphthaldiminato]nickel(II)

The Schiff base ligand (1), [C₁₅H₁₇NO] crystallizes in the monoclinic space group P2₁/c witha=10.054(3),b=10.313(3), c=13.173(4)Å, =107.42(4)°,V=1303.2(7)ų,Z=4,Dx=1.159 g cm^–3, and (MoK)=0.674 cm^–1. The C2-O[1.23(1)Å] and C3–C4 [1.33(2)Å] bond lengths are short, due to its quinoidal structure. In the Schiff base nickel complex (2), [Ni(C₁₆H₁₈NO)₂] the asymmetric unit is comprised of two half-complexes. It crystallizes in the triclinic space group witha=5.124(3),b=16.227(3),c=16.886(4)Å, =95.47(8), =96.00(1), =90.71(4)°,V=1389.6(9) ų,Z=2,Dx=1.289 g cm^–3, and (MoK) =12.1 cm^–1. The coordination of the Ni(II) ions are square planar with bond angles between 87.9(1) and 92.1(1)°. The Ni–O and Ni–N distances are 1.819(2), 1.922(2) and 1.823(2), 1.914(3)Å in these two complexes.     

Structure oftrans-dichlorooxobis(triphenylphosphine)rhenium(V), ReCl2O(OEt)(Ph3P)2

C₃₈H₃₅Cl₂O₂P₂Re,M _r=842, triclinic,P¯1,a=17.71(2),b=11.33(1),c=9.82(1) Å,=114.60(3),=90.84(3), =78.05(3),V=1747(2) ų,D _m(flotation)=1.60,D _x=1.60 Mg m^–3 forZ=2, MoK, =0.7107 Å,=41.6 cm^–1,F(000)=836, room temperature. The structure was solved by standard methods from diffractometer data and refined to a conventionalR of 3.4% for 5412 observed reflections. The Re atom is six coordinate octahedral withtrans-Cl atoms andtrans-Ph₃P groups. Relevant bond distances are: Re-P 2.533(1) and 2.535(1) Å, Re-O(ethoxo) 1.888(4) Å, and Re-O(oxide) 1.699(4) Å. The ethyl chain is partially disordered.     

Crystal and molecular structure of the ethanol adduct of tris(oxinato)indium(III)

The ethanol adduct of tris(oxinato)indium(III), prepared in aqueous ethanol, crystallizes in the monoclinic space groupP2₁/n (Nr.14) witha=11.343(2),b=13.477(3),c=16.845(2)Å, -94.71(1)°,V=2566.4(8)ų andZ=4. The structure was solved by direct methods and refined by full-matrix least-squares methods toR=0.032 for 3374 observed reflections withI>2 (I). Three bidentate oxinato ligands (or 8-quinolinolato) coordinate to indium atom leading to an approximately octahedral coordination of the metal(III) ion. One ethanol molecule per mole of metal complex is occluded in the crystal lattice and forms a hydrogen bond with the O(3) oxygen atom of one oxinato ligand [O(3) ... O(4) =2.715(3) Å]. The two other oxinato ligands of the same unit are not involved in hydrogen bonding.     

Crystal and molecular structure of bromo-bis(bis-diphenylphosphino-ethylene)-nickel(II)-tetraphenylborate

The Ni(II) complex of the ligandcis-1,2[bis(diphenylphosphino)ethylene] (VPP), [Ni(VPP)₂Br]BPh₄, crystallizes in the orthorhombic space groupP2₁2₁,2, witha=25.971(6),b=24.508 (6),c=19.642(5) Å,Z=8. The structure was determined by the procedure DIRDIF from Cu K automatic diffractometer X-ray data and refined by block-diagonal least-squares toR=11% for 5572 reflections. A question on the space group assignment betweenP2₁2₁2 andP2₁2₁2₁ was resolved only after the complete structure had been determined. The detailed crystal and molecular structure is presented.     

An oxovanadium(IV) complex containing a pentacoordinate Schiff-base ligand: synthesis and crystal and molecular structure of N,N′-(3,3′-dipropylamine)bis (3-methoxysalicylideneiminato)oxovanadium(IV) dihydrate

Crystals ofN,N-(3,3-dipropylamine)bis(3-methoxysalicylideneiminato) oxovanadium(IV) dihydrate are monoclinic, space groupP2₁/n (No. 14) with four molecules in the unit cell of dimensionsa=8.667(4),b=20.617(4),c=12.744(3) Å,=91.48(3)°. The structure was solved by the heavy-atom method and refined by block diagonal least-squares calculations with anisotropic thermal parameters for nonhydrogen atoms.R=0.038 for 1457 reflections withI>3(I). This structure is the first reported for an oxovanadium(IV) complex involving complexation of a pentacoordinate Schiff-base ligand. The coordination polyhedron is based on a distorted octahedron. Three nitrogen and one oxygen atom from the ligand form an equatorial plane around vanadium with V-N(1) 2.096(4), V-N(2) 2.180(4), V-N(3) 2.088(4), V-O(2) 1.961(3) Å, and octahedral coordination is completed by the vanadyl oxygen [V-O(1) 1.617(3) Å] and the remaining ligand oxygen [V-O(3) 2,098(3) Å]. The relatively long V-O(1) distance correlates well with the low value ofv(V=O) of 919 cm^–1. The molecules of the complex are linked by water molecules of crystallization to form infinite hydrogen-bonded chains parallel toa.     

Crystal and molecular structures of 1-phenyl-4,6-dimethylpyrimidine-2-thionetetraaquacobalt(II) dinitrate complex and of two pyrimidine thiones

The crystal structures of 1-phenyl-4,6-dimethylpyrimidine-2-thionetetraaquacobalt(II) dinitrate (I)a=9.032(2),b=12.458(2),c=18.067(3)Å,=103.25(3)°,Z=4;P2₁/c,R=0.049; 1-phenyl-4,6-dimethylpyrimidine-2-thione (II)a=12.005(3),b=10.090(2),c=9.649(2)Å,=104.4(1)°,Z=4;P2₁/n,R=0.038; and 4,6-dimethylpyrimidine-2-thione (III)a=15.485(3),b=13.255(3),c=7.127(2)Å,=104.3(1)°,Z=8,C2/c,R=0.041 are reported. In (I) the coordination around the cobalt(II) is distorted octahedral involving one ligand moleculevia sulphur and nitrogen atoms and four water molecules. It is relevant that the parameters in the complexed ligand are not different from those found in the uncomplexed one (II), excepting the distances on the nitrogen atom directly involved in the coordination. Bond distances and angles in compound (III) agree with those found in (II).     

Crystal and molecular structure of bis(tetrathiafulvalene) bis(maleonitrile-1,2-dithiolato)nickelate(II)

The crystal and molecular structure of the title compound, C₂₀H₈N₄S₁₂Ni, is reported. Crystals are triclinic, space groupP¯1 (No. 2) withz=1 in a cell of dimensionsa=8;482(2),b=7.950(2),c=9.976(2) Å,=95.64(2),=98.60(2), and =87.65(2)°. The structure was solved by Fourier methods and refined by the method of least squares toR=0.033 for 2027 unique reflections. The Ni atom has an approximate square-planar configuration with Ni-S(1)=2.179(1), Ni-S(2)=2.175(1) Å, and the S(1)-Ni-S(2) bite angle of 91.89(4)°. The anions and the cations form a mixed stack (DAD-DAD-) along the diagonal of theab plane, showing the possibility of unusual electrical behavior.