X-ray and neutron diffraction studies of the hydridotriruthenium cluster complex (μ-H)Ru3(CO)7(μ-As(C6H5)CH2As(C6H5)2) ((C6H5 2AsCH2As(C6H5)·CH2Cl2: an example of dibridged metal-metal bond M(μ-H)(μ-X)M,involving a heavy bridgehead atom

The title compound is (μ-H)Ru₃(CO)₇(μ-As(C₆H₅)CH₂As(C₆H₅)₂)((C₆H₅)₂ AsCH₂As(C₆H₅)₂)·CH₂C1₂. Crystal data: monoclinic,P2₁/n, cell parameters (X-ray)a=12.82(2) Å,b=22.91(2) Å,c=17.83(2) Å, β=99.1(3)°; (neutron)a=12.94(1) Å, β=22.95(2)Å,c=17.93(3)Å,β=99.55(5)°. The structure was solved from X-ray data. FinalR indices areR(F)=0.051,R _w (F)=0.049 (X-ray);R(F)=0.064,R _w (F)=0.048,R(F ²)=0.072,R _w (F²)=0.088 (neutron). The complex is derived from Ru₃(CO)₈(dpam)₂ through reaction with hydrogen. The structure consists of a triangular array of metal atoms involving three metal-metal bonds[Ru(1)?Ru(2)=2.912(7)Å;Ru(1)?Ru(3)=2.829(3) A; Ru(2)?Ru(3)=2.845(6) Å]. The metal-metal edge Ru(1)?Ru(2) is supported by a bridging bis(diphenylarsino)methane ligand which lies in the equatorial plane. Activation of the second dpam ligand has generated the new face-bridging ligand unit μ-As(C₆H₅)CH₂As(C₆H₅)₂. In this unit, the bridgehead As atom spans over the Ru(1)?Ru(2) bond, while the second As atom is only bonded to Ru(3). The metal environment is achieved by CO ligands. The hydride ligand is bridging the Ru(1)?Ru(2) vector [Ru(1)?H=1.791(10) Å; Ru(2)?H=1.818(8) Å]. Geometric features of the dibridged Ru(μ-H)(μ-As)Ru bond are discussed.     

Structure of (N-(2-hydroxyphenyl)-salicylaldiminopiperidino) Ni(II) complex

The crystal and molecular structure of the title complex, C₁₈H₁₉N₂O₂Ni, has been determined by direct methods. The compound crystallizes in the monoclinic crystal system witha=22.973(1),b=5.212(1),c=27.076(1)Å, β=106.46(1)°, space groupC2/c,V=3109.1(6)ų, Z=8, andD _x=1.51g cm^?3. The nickel atom is in a slightly distorted square-planar environment of two oxygens [Ni(1)?O(1) 1.824(3) and Ni(1)?O(2) 1.856(3)Å] and two nitrogens [Ni(1)?N(1) 1.849(3) and Ni(1)?N(2) 1.932(3)Å] with O?Ni?N angles between 85.7(1) and 97.1(1)°. The nickel atom is 0.006 Å out of the plane of its ligands.     

Crystal structure of NH3(CH2)2NH3(BiI4)2·4H2O

The ethylenediammonium bis tetraiodobismuthate(III) tetrahydrate salt is monoclinic with the following unit cell dimensions:a=7.476(3)Å,b=13.194(3)Å,c=13.916(9)Å, β=95.22(6)°, space groupP2₁ lc withZ=2. The structure consists of disordered ethylenediammonium cations, water molecules and polynuclear anions in which slightly distored [BiI₆]^3? octahedra sharingcis edges are interconnected into chains. The [BiI₄]^? anions are connected through O(W2)?H...I hydrogen bonds, so that infinite two dimensional chains parallel to thea axis with anionic period [BiI₄(H₂O)]^? are formed in the structure. These chains are themselves interconnected by means of the O?H...I and N...O(I) bonds originating respectively from the water molecules and the ethylenediammonium entities, forming a three-dimensional network.     

Crystal structure of chloro[1-hydroxyethane-1,1-diphosphonato(3−)]ditin(II) monohydrate Sn2(HL)Cl · H2O

The synthesis and X-ray structure analysis of Sn₂(HL)Cl · H₂O, where HL ^3? is the anion of 1-hydroxyethane-1,1-diphosphonic acid, are reported. The coordination polyhedra of two independent tin(II) atoms are the Sn(1)O₂Cl and Sn(2)O₃ trigonal pyramids, in which one of the vertices is occupied by a lone electron pair (Sn-O, 2.144–2.218 Å and Sn-Cl, 2.573 Å). The pyramids are complemented by weaker Sn?O and Sn?Cl contacts to form severely distorted (3 + 3) octahedra. The SnO₂Cl and SnO₃ pyramids are linked by the HL ^3? bridging ligands into the [Sn₂(HL)Cl]₆ cyclic molecules, which, in turn, are joined by additional Sn?O, Sn?Cl, O(H₂O)?O(L), and O(H₂O)?Cl contacts with each other and with crystallization water molecules into a three-dimensional framework.     

The crystal and molecular structure of SnBr[N(SiMe3)2]3

The crystal structure of SnBr[N(SiMe₃)₂]₃ has been determined from three-dimensional X-ray diffraction data collected by counter methods. This compound crystallizes in the rhombohedral space groupR3c witha=11.970(3) Å, α=99.06(3)°, andZ=2forD _c> =1.37 g cm^?3. The finalR value was 0.027 based on 608 independent observed reflections. The molecule lies on a crystallographic three-fold axis which contains the Sn and Br atoms. The bromine atom is covalently coordinated to the tin atom at a Sn-Br separation of 2.519(2) Å. The three nitrogen atoms complete the bonding to tin with an Sn-N bond length of 2.056(7) Å.     

Structural and spectroscopic study of a five-coordinate rhodium(I) complex (η-1,5-cyclooctadiene)(η-2, 6-diallylpyridine,N)rhodium (1+) with two different and unusual di-μ-chloro-bis[dichlorodimethylstannate](2−) anions. Crystal structures of [Rh(C8H12)-(C11H13N)]2[{SnCl3(CH3)2}2] · 2CH2C12 and [Rh(C8H12)-(C11H13N)]2[{SnCl3(CH3)2}2]

The preparation and structures of a five-coordinate rhodium(I) complex with 2,6-diallylpyridine (DAP) and cyclooctadiene (COD) ligands with two different [{SnCl₃(CH₃)₂}₂]^2? anions are described, including IR and¹H NMR data. The crystals of the title compounds are both triclinic P¯1: C₄₂H₆₂Cl₆N₂Rh₂Sn₂·2CH₂Cl₂ (1)a=12.200(4),b=13.016(4),c=9.402(2) Å,α=93.92(1),β=100.67(1), γ=115.03(2)°,V _c =1311.2(7) ų,Z= 1,R=0.0312 for 3321 independent observed reflections; C₄₂H₆₂Cl₆N₂Rh₂Sn₂ (2)a=12.187(3),b=12.851(3),c=7.752(2) Å,α=90.15(1),β=101.22(1), γ=73.29(1)°,V _c =1138.8(5) ų,Z=1,R=0.0429 for 4117 independent observed reflections. In both structures the cationic rhodium has a trigonal-bipyramidal environment with theN-pyridine and one double bond of the COD ligand in axial positions and the two allylic double bonds together with the other double COD bond in equatorial positions. Much more interesting are the structures of the anionic parts, which show a different unsymmetrical dimerization through two chlorine bridges. The tin coordination polyhedra, which assume a distorted trigonal-bipyramidal geometry in the monomeric units, achieve an octahedral shape. There is a simple correlation between the Me-Sn-Me angle value and the longest Sn-Cl bond distance.     

The 1:1 crystal complex of salicylic acid and urea

The 1∶1 crystal complex of salicylic acid (C₇H₆O₃) and urea (CH₄N₂O), mp 121° C, is monoclinic, with space groupC2/c (C ₂ ⁶ h, No. 15) and unit cell dimensionsa=22.206(3),b=5.108(1),c=17.177(2) Å,β=106.18(1)°.d _calc=1.407 g cm^?3,d _meas=1.41 g cm^?3 forZ=8. The structure was determined by direct methods and refined by a full-matrix least-squares procedure to giveR=0.057 andR _w =0.050 for 1652 integrated intensities above 2σ(I). The structure contains a strong OH?O hydrogen bond with O?O distance 2.54 Å in which the carboxyl OH group is donor and urea oxygen atom is acceptor. There are two NH?O intermolecular hydrogen bonds with N?O distances of 2.90 and 2.96 Å. Additionally, the salicyclic acid contains an intramolecular OH?O hydrogen bond of 2.56 Å.     

Crystal structures of thecis andtrans isomers of dithiahexahydro[3.3]metacyclophane

Structures of both thecis andtrans isomers of dithiahexahydro[3.3]metacyclophane, ?C₆H₄?CH₂SCH₂?C₆H₁₀?CH₂SCH₂?, have been determined, wherecis andtrans refer to the attachments to the cyclohexane ring. Thecis form crystallizes in the monoclinic space groupP2₁/c witha=8.4299(11)Å,b=21.772(2)Å,c=8.9724(13)Å, β=116.574(11)^o, andZ=4. Thetrans isomer packs into the monoclinic space groupP2₁ witha=8.159(16)Å,b=10.185(5)Å,c=9.558(2)Å, β=112.435(18)^o, andZ=2. The cyclohexane ring of thecis isomer is in the chair conformation, while the cyclohexane of thetrans isomer is found in a twisted boat conformation.     

Ether cleavage of [2.2.2]cryptand: synthesis and X-ray crystal structure of [NH(CH2CH2I)3][I5]

Treatment of [2.2.2]cryptand1 in toluene with HI(g) has resulted in the formation of a twophase liquid clathrate solution from which the complex [NH(CH₂CH₂I)₃][I₅]2 has been isolated and crystallographically characterized. Crystal data for2: triclinic, space group $P\bar 1$ ,a=9.301(3) Å,b=10.419(3) Å,c=11.078(3) Å, α=90.20(2)^o, β=103.28(2)^o γ=96.50(2)^o,D _c =3.57g/cm³,Z=2,R _f =0.054,R _w =0.054. The salt is a product of an ether cleavage of the macrobicycle. The crystal structure of2 contains [NH(CH₂CH₂I)₃]⁺ ions and zigzag chains of [I₅]^? ions which self-assemble to form alternating layers, of cations and anions.     

Molecular structure of (tBu)3AlP(nPr)3

The crystal and molecular structure of (^tBu)₃AlP(ⁿPr)₃ has been determined. The Al(1)?P(1) bond distance [2.594(3) Å] is slightly longer than other aluminum-phosphine complexes; however, the geometry about aluminum is similar to that of the [AlCl(^tBu)₃]^? anion, suggesting that the geometry about the aluminum in tri-tert-butylaluminum complexes is defined by the size of thetert-butyl ligands and not as a consequence of the steric bulk of the Lewis base. Crystal data: Monoclinic,P2_t,a=8.932(2),b=16.832(3),c=9.328(2), Å, β=114.36(3)°,V=1277.6(6) ų,Z=4,R.=0.055,R _w =0.053.     

Crystal Structures of 6-methyl-3-phenylsulfonylchroman-4-one andtrans-6-methyl-3-phenylsulfonylchroman-4-ol

The crystal structures of (i) CH₃(C₉H₆O₂)SO₂C₆H₅ and (ii) CH₃(C₈H₈O₂)SO₂?C₆H₅ have been determined by X-ray diffraction. (i) crystallizes in the monoclinic space groupP2₁/c with unit cell parametersa=8.814(1)Å,b=10.310(1)Å,c=15.841(4)Å, β=98.17(1)^o, andZ=4, and (ii) crystallizes in the orthorhombic space groupP2₁2₁2₁ with unit cell parametersa=6.206(1)Å,b=11.752(5)Å,c=19.865(3)Å, andZ=4. The pyran ring in both of them is in the distorted half-chair conformation with differeing degrees of distortion from the ideal.     

Interaction of mercury(II) halides with tertiary phosphine betaines: synthesis and structural characterization of [HgX2{Ph3P(CH2)2CO2}] (X=Cl, I) and [HgCl(μ-Cl)-{Ph3P(CH2)3CO2}]2

Three new mercury(II) complexes containing tertiary phosphine betaine ligands Ph₃P⁺(CH₂)₂CO₂ ^? and Ph₃P⁺(CH₂)₃CO₂ ^? have been synthesized and fully characterized by single-crystal X-ray analysis: [HgCl₂{Ph₃(CH₂)₂CO₂}],1, space groupP2₁/n,a=9.819(2),b=14.966(4),c=14.973(5) Å, β=105.67(2)° andZ=4; [HgI₂{Ph₃(CH₂)₂CO₂}],2,P2₁/n,a=10.206(2),b=14.807(3),c=15.557(3) Å, β=107.11(2)° andZ=4; [HgCl(μ-Cl){Ph₃P(CH₂)₃CO₂}]₂,3, $P\bar 1$ ,a=10.813(2),b=11.975(3),c=11.180(2) Å, α=87.04(2), β=75.14(1), γ=81.95(1)° andZ=1. The isomorphous complexes1 and2 contain discrete mononuclear molecules in which the mercury(II) atom is unsymmetrically chelated by a Ph₃P⁺(CH₂)₂CO ₂ ^? ligand and coordinated by a pair of terminal halo ligands in a distorted tetrahedral environment, while3 consists of discrete centrosymmetric dinuclear molecules in which the betaine ligand Ph₂P⁺(CH₂)₃CO ₂ ^? acts in the chelate mode and the mercury(II) atoms are unsymmetrically bridged by a pair of chloro ligands.     

Structure of chlorohydroxonitrosyl(terpyridine)ruthenium(II) hexafluorophosphate

The title complex has the NO grouptrans to the hydroxyl ligand and the chloride ion in the plane of the tripyridyl ligand. The Ru?O and Ru?N(O) distances are 1.939(5) Å and 1.764(6) Å, respectively; the Ru?N?O bond angle is 171.7(6)⁰. These values are consistent with previously reported shortening of Ru?O distances whentrans to a linear NO ligand. The space group of the structure isP2₁/c, witha=9.7213(9) Å,b=13.9318(11) Å,c=14.523(4) Å, and β=105.820(13)⁰.     

Direct and outer-sphere coordination of the magnesium ions in the crystal structures of complexes with 2-furancarboxylic acid (I) and 3-furancarboxylic acid (II)

(I) Mg₂C₂₀H₂₄O₁₈ monoclinic,PT,a=10.760(2) Å,b=11.052(2) Å,c=12.822(3) Å, α=105.31(3)^o, β=98.18(3)^o, γ=91.59(3)^o,Z=2. (II) MgC₁₀H₁₄O₁₀, monoclinic,C2/c,a=30.817(6)Å,b=10.499(2)Å,c=9.000(2)Å, β=91.31(3)^o,Z=8. Magnesium in complexes with furoic acids reveals two ways of coordination: direct, when furoic anions are bonded to Mg²⁺ in an ionic fashion and outer-sphere, when cations bind water in the first coordination sphere and furancarboxylic ligands are hydrogen bonded to the water molecules. This results in the formation of three bridging systems: ?Mg?O_carboxyl?C?O_carboxyl?Mg?, ?Mg?O_water ?O_carboxyl?C?O_carboxyl?C?O_carboxyl?Mg?, and ?Mg?O_water?O_carboxyl?C?O_carboxyl?O_water?Mg?. Magnesium 2-furancarboxylate (I) is dimeric, while magnesium 3-furancarboxylate (II) exhibits a polymeric structure.     

Formation of thesyn-isomer of [Cp*MoO(μ−S)]2

The structure of the title compound,syn-[Cp^*MoO(μ?S)]₂,1, has been determined.1 crystallized in the monoclinic space groupC2/c with dimensionsa=11.758(2),b=12.243(2), c = 15.585(3)Å, β=104.63(3)°. The reaction of Cp^* ₂Mo₂(S₂)(S)(S₂O₃) with Me₂PhP producessyn-[Cp^*MoO(μ?S)]₂ and Me₂PhPO. The compounds [Cp′MoO(μ?S)]₂ [Cp′=Cp, CpMe, Cp^*] can exist as either thesyn- oranti-isomers. The present structure,syn-[Cp^*MoO(μ?S)]₂ is compared with the structure of theanti-isomer and with the previously determined structure ofsyn-[Cp^*MoO(μ?S)]₂ in a different space group.     

Crystal structure of a silver(I) complex with the 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid)

The reaction between freshly precipitated silver oxide Ag₂O and an aqueous solution of tetrabenzenecarboxylic acid H₄L leads to the anhydrous Ag₂H₂L complex. It crystallizes in the space groupP2₁/c, witha=6.457(1),b=8.180(1),c=9.982(1) Å, β=97.83(1)°,V=522.3(1) ų,Z=2,d=2.976 g cm^?3. This structure is a three dimensional polymeric network polymer without any silver...silver interaction. The silver environment is a bipyramid trigonal polyhedron with three short bond distances in the equatorial plane (Ag?O=2.255(2), 2.295(2), and 2.499(2) Å) and two longer bond distances in axial positions (Ag?O=2.558(2) and 2.617(2) Å). Thus, the silver polyhedron involves five different ligands. It is noteworthy that the (H₂L₂)^2? ligand is located around an inversion centre.     

Formation of copper(II) coordination polymers by a flexible double betaine: [{Cu(L)X2(H2O)} n ]·2nH2O [X=Cl,Br] and [{Cu(L)(H2O)4} n ](ClO4)2n ·2nH2O [L=−O2CCH (Me3N+)CH2CH2CH(Me3N+)CO 2 − ]

Three polymeric copper(II) complexes of a flexible double betaine, namely, [{Cu(L)Cl₂(H₂O)} _n ]·2 _n H₂O (1), [{Cu(L)Br₂(H₂O)} _n ]·2nH₂O (2), and [{Cu(L)(H₂O)₄} _n ](ClO₄)_2n ·2nH₂O (3) [L=?O₂CCH(Me₃N⁺)CH₂CH₂CH(Me₃N⁺CO₂], have been prepared and characterized by singlecrystal X-ray analysis. Isomorphous complexes (1) and (2) crystallize in space groupC2/c (No. 15) witha=17.725(3),b=5.958(2),c=19.077(3) Å, β=110.70(1)^o,V=1881.4(4) ų, Z=4 anda=18.268(4),b=5.948(3),c=19.166(5) Å, β=109.08(2)^o,V=1964.7(9) ų, Z=4, respectively. Complex (3) belongs to space groupPī (No. 2) witha=6.203(1),b=9.293(2),c=12.035(2) Å, α=86.56(2), β=87.33(3), γ=71.23(2)^o,V=655.4(2) ų and Z=1. The crystal structure of (1) and (2) features an infinite zigzag chain composed of an alternate arrangement of metal atoms and double betaines ligands, with each Cu(II) atom in a distorted CuX₂O₃ [X-Cl, Br] square-pyramidal geometry, and hydrogen bonding between adjacent chains leads to a layer structure concentrated the (200) family of planes. Complex (3) exhibits a layer structure corresponding to the (001) family of planes, in which neighboring chains constructed from the metal atoms and the double betaine ligands are cross-linked by hydrogen bonding between the aqua ligands. The Cu(II) atom is coordinated in a CuO₆ octahedral geometry with Jahn-Teller distortion.     

Interaction of cystamine with palladium(II) monoethanolaminate complex: Crystal structure of [Pd(NH2CH2CH2OH)4][Pd6(NH2CH2CH2S)8]Cl6 · 5H2O

The new compound [Pd(NH₂CH₂CH₂OH)₄][Pd₆(NH₂CH₂CH₂S)₈]Cl₆ · 5H₂O (I) is synthesized and its crystal structure is determined. The crystals are monoclinic, a = 25.625(6) Å, b = 9.633(5) Å, c = 24.847(7) Å, β = 91.47(2)°, Z = 4, and space group C2/c. The structural units of crystals I are the centrosymmetric hexanuclear [Pd₆(NH₂CH₂CH₂S)₈]⁴⁺ cations, the mononuclear [Pd(NH₂CH₂CH₂OH)4]²⁺ cations with C ₂ symmetry, the Cl^? anions, and crystallization water molecules. In the hexanuclear cation, the interaction between the Pd atoms occurs through the S atoms of the mercaptoethylaminate ligands. The Pd(2) and Pd(3) atoms and the ligands form two metallochelate fragments in which the N and S atoms are located in cis positions. The average lengths of the Pd-S and Pd-N bonds are equal to 2.274(1) and 2.074(6) Å, respectively. The metallochelate fragments are joined to each other and to their centrosymmetric analogues through the Pd(1) atom, which coordinates four S atoms [the average Pd-S_av bond length is 2.332(1) Å]. In the mononuclear cation, the Pd(4) atom coordinates four N atoms of the monoethylaminate ligands [the Pd-N bond lengths are 2.045(6) and 2.056(6) Å]. The shortest Pd?Pd distance is equal to 3.207(1) Å. The bonding in the structure is provided by numerous hydrogen bonds with the participation of all the H₂O molecules, NH₂ groups, and Cl^? anions.