On the organoaluminum chemistry of multidentate phosphine ligands. Reaction of trimethylaluminum with bis(diphenylphosphino)methane: Synthesis and molecular structure of [Al(CH3)3]2[(C6H5)2PCH2P(C6H5)2]

Reaction of an excess of trimethylaluminum with bis(diphenylphosphino)-methane in heptane affords the crystalline complex [A1(CH₃)₃]₂[(C₆H₅)₂PCH₂P(C₆H₅)₂]. The title compound crystallizes in the triclinic space group P¯1 with unit cell parametersa=10.053(6),b=11.017(6),c=15.908(8) Å,=85.58(4),=71.80(4), =77.49(4)°,V=1634(1) ų, andD _c=1.07 g cm^–3 forZ=2. Least-squares refinement based on 2924 observed reflection with intensitiesI3I) in the range 2.00245.0° converged atR=0.050 (R _w=0.067). The Al-P distances are 2.585(2) and 2.521(2) Å, and the P-C-P angle is 121.4(2)°.     

Crystal structure ofcis-diaqua bis(2,2′-bipyridyl)chromium(III) nitrate, [Cr(bipy)2(H2O)2] (NO3)3

cis-Diaquabis(2,2-bipyridyl)chromium(III) nitrate crystallizes in the mono-clinic system, space groupP2₁/c, witha=16.102(6),b=10.792(5),c=15.076(6) Å,=112.90(5)°, andZ=4. The saltlike structure was determined from X-ray crystallography and refined toR=7.5% for 3342 observed reflections. The Cr atom is octahedrally surrounded by twocis water molecules and by two chelated 2,2-bypiridyl ligands forming two nearly orthogonal planes. Selected bond distances are: Cr-O, 2.00(1) and 1.98(1) Å, Cr-N, 2.04 Å (mean).     

Study on the crystal and molecular structure of triphenyl tin methacrylate: (C6H5)3SnOCOCCH2CH3

The crystal and molecular structure of (C₆H₅)₃SnOCOCCH₂CH₃ has been determined by a single crystal X-ray diffraction study. The crystal is monoclinic with space group P2₁/c,a=11.902(3),b=10.104(4),c=16.721(2) Å,=97.56(1)°,V=1930.4 ų,Z=4 andD _c =1.495 g/ cm³,F(0,0,0)=872,(CuK)=1.5418 Å. The structure was solved by the heavy-atom method and refined by full-matrix least-squares procedures to anR factor of 0.060 based on 2157 independent reflections. The results showed that the Sn-O bond distance is 2.064(4) Å. The average Sn-C bond distance is 2.126 Å. There is a weak coordination through the O of the CO group of the methacrylate residue (Sn-O(2) 2.774(5) Å) except for four normal coordinations. The coordination number at the Sn⁴⁺ is 5.     

Synthesis,characterization and crystal structure of oxovanadium(IV) complex with tridentate o-van-gly and bidentate phenanthroline

A novel oxovanadium(IV) complex with tridentate schiff base and bidentate phenanthroline ligands, VO(o-van)(phen) 2H₂O[o-van-gly: o-vanillin-glycine; phen: phenanthroline], was synthesized and characterized by elemental analysis, IR and UV-vis spectra. The crystal structure was determined by X-ray single crystal diffraction analysis. The crystal of title complex (C₂₂H₂₁N₃O₇V, M_w = 490.36) belongs to triclinic, space group P-1 with the following crystallographic parameters: a = 9.247(3) Å, b = 10.125(4) Å, c = 13.100(5) Å, = 106.343(6), = 96.042(7), = 101.726(7), V = 1135.0(7) ų, Z = 2, D_c = 1.435 Mg m^–3, (MoK = 0.485 mm^–1, F(000) = 506, and final R₁ = 0.0779, wR₂ = 0.1598 for observed reflections 1606 (I > 2(I)). V(IV) is six-coordinate with three oxygen atoms and three nitrogen atoms in a distorted octahedral geometry. The complex forms a 3-D network via – stacking and hydrogen bonds.     

Synthesis and molecular structure of {[Se(CH3)3][(CH3)AlCl3]}n: A novel two-dimensional layered organoaluminum-selenium polymer

The crystalline product {[Se(CH₃)₃][(CH₃)AlCl₃]}_n was prepared from reaction of SeCl₄ with A1(CH₃)₃ in heptane. The organo-main group polymer crystallizes in the monoclinic space group P2₁/c with unit cell parametersa=11.218(3) Å,b=11.119(3) Å,c=9.915(2) Å,=107.82(2)°,V=1177.4(5) ų, andD ^calcd=1.54 g cm^–3 forZ=4. Least-squares refinement based on 1195 observed reflections I>3(I) in the range 3.50°<2<45.0° led to a finalR factor of 0.036 (R ^w=0.047). The asymmetric unit contains one selenonium ion, Se(CH₃) ₃ ⁺ , and one organoaluminum anionic species, (CH₃)AlCl ₃ ^– . Secondary interactions (SeCl) serve to link the ions along two dimensions to form infinite layers. Thus, {[Se(CH₃)₃] [(CH₃)A1C1₃]}_n may be regarded as a layered organoaluminum-selenium polymer. The mean Se-C bond distance is 1.921(5) Å while the mean C-Se-C bond angle is 99.1(4)°. The independent Al-C bond distance is 1.927(8) Å while the mean Al-Cl bond distance is 2.166(7) Å.     

Crystal and molecular structure of OC(CoC5H5)3(CF3CCCF3)

The structure of the title compound has been confirmed by an X-ray diffraction analysis, and refined by full-matrix least squares. The crystals are mono-clinic:a=9.171(3),b=25.176(15)c=9.192(3) Å,=117.08(3)°,Z=4,D _x =1.976g cm^–3,=2.66mm^¯1, space groupP2₁/n (No. 14). The finalR value is 5.7%. Interatomic distances and bond angles are compared with those reported in related molecules.The preferred name of this compound according to the IUPAC rules is ₃-[11–2-bis(trifluoromethyl)vinylene]- ₃-carbonyl-tris (-cyclopentadienyl)-triangulo-tricobalt.     

Crystal and molecular structures of O,O-propan-1,3-dithionobenzoate (2TBZ-A), O,O-2,2-dimethylpropan-1,3-dithionobenzoate (2TBZ-B), and O,O,O,O-pentaerythritoltetrathionobenzoate (4TBZ)

The crystal and molecular structures of three thionobenzoates have been determined: O,O-propan-1,3-dithionobenzoate (2TBZ-A) is tetragonal witha=13.086(2),c=19.048(2) Å, space groupI4₁/a,Z=8; O,O-2,2-dimethylpropan-1,3-dithionobenzoate (2TBZ-B) is monoclinic witha=13.851(5),b=12.428(3),c=10.996(4) Å,=104.01(4)°, space groupP2₁/c,Z=4; and O,O,O,O-pentaerythritol-tetrathionobenzoate (4TBZ) is triclinic witha=15.423(4),b=10.924(3),c=10.698(2) Å,=112.43(2),=100.64(2), =104.57(2)°,Z=2, space groupP¯1. The structures were all solved by direct methods and refined by least squares toR=0.046 for 886 reflections (2TBZ-A),R=0.075 for 1458 reflections (2TBZ-B) andR=0.075 for 2975 reflections (4TBZ),I>3(I) in each case, CuK radiation, =1.5418 Å. The minimum S---CH₂ intramolecular distances in these three structures are significantly larger than the minimum corresponding distance in O,O,O-propan-1,2,3-trithionobenzoate (3TBZ) (Moore and Palmer, 1990), thus providing a possible explanation of why 2TBZ-A, 2TBZ-B, and 4-TBZ are inert with respect to pyrolitic solid-state isomerization; whereas 3TBZ readily undergoes thermally induced rearrangement (Das, 1978; Hedgley, 1981).     

Hydrogen bonding in 2-hydroxy((di)thio)benzoates. I. X-ray structures of 2,6-dimethylpiperidinium salts

X-ray structural data are reported for 2,6-dimethyl-piperidinium-2-hydroxybenzoate (C₁₄H₂₁NO₃, orthorhombic,P2₁2₁,2₁, (19);a=7.983(1)Å,b=12.680(2)Å,c=13.838(2)Å;Z=4;R=0.042) and for two polymorphs of 2,6-dimethylpiperidinium-2-hydroxythiobenzoate (C₁₄H₂₁NO₂S), an-form (monoclinic,P2₁/n (14);a=8.005(4)Å,b=22.150(2)Å,c=8.672(4)Å,=101.91(6)°;Z=4;R=0.059) with an intramolecular O-HS hydrogen bond, and a-form (orthorhombic,P2₁2₁2₁ (19);a=8.188(1)Å,b=14.781(2)Å,c=24.163(4)Å;Z=8;R=0.15) with an intramolecular O-HO hydrogen bond. The intra-and intermolecular hydrogen bond patterns are discussed, including the literature data of 2,6-dimethylpiperidinium-2-hydroxydithiobenzoate.     

Synthesis and structure of 1-(2-amino)phenyl-2-phenyl-12H-indolo[3,2-c]carbazole ethylacetate solvate,a new indolocarbazole compound

The structure of a new indolo-carbazole compound, unique in having two indole rings with NH groupstrans-fused to a phenyl ring, has been determined by X-ray crystallography. The crystals are monoclinic, space groupP2₁/n,a=25.548(7),b=8.532(3),c=12.594(4) Å,=93.50(2)°,V _c=2740.1(2) ų,Z=4,D _k=1.240 g cm^–3, (CuK)=1.54178 Å,=5.79 cm^–1,F(000)=1080,R=0.071,R _w=0.080 for 2939 unique significant reflections measured at 298 K. The crystals retain one mole of ethyl acetate per molecule, which shows disorder. Restricted rotation of the phenyl and aminophenyl groups was detected by¹³C nmr. The title Indolo-carbazoles are easily obtained by reaction of 3-bromoindoles with 2,3-biindolyls and show an interesting planar structure which could be investigated for anticancer properties.     

Structure of (Z)-1-p-methoxyphenyltelluro-1,4-diphenyl but-1-en-3-yne

C₂₃H₁₈TeO,M _r=437.97, ,a=9.940(2),b=13.664(3),c=7.895(2) Å, =80.60(1), =69.71(2), =75.95(1)°,V=972.0(4) ų,Z=2,R=0.041 for 2668 observed reflections. The Te–C bond distances are 2.109(5)Å and the C–Te–C angle is 96.0(2)°. The phenyl rings are planar to within experimental accuracy, making dihedral angles of 64.6(2), 65.3(2) and 31.1(3)°.     

Molecular structure and some reactivity aspects of 2,6-diamino-4(3H)-pyrimidinone monohydrate

Crystals of C₄H₆N₄O·H₂O are orthorhombic:Pbca,a=16.721(2),b=4.242(1),c=18.293(2)Å,Z=8. The structure has been solved by direct methods and refined by full-matrix least-squares techniques toR=0.046 for 1252 unique reflections. The structure consists of approximately planar molecules of the 3(H)4-one tautomer. Delocalization of the ring and the C=O-electrons, and conjugation of the lone-pair electrons of the amine groups with the pyrimidinone nucleus are observed. The molecules are connected by O-HO, N-HN, and N-HO hydrogen bonds. The molecular structure clarifies the chemical properties of the compound.     

Crystal and molecular structure of the rutheniumcarbene-tetraborohydrate complex [Ru(BH4)(LAr)(PPh3)2]; (LAr=CN(C6H4Me-4)CH2CH2NC6H3Me-4)

The structure of the title compound has been determined by single crystal X-ray diffraction analysis:P2₁/c,M _r=889.9,a=15.940(1),b=23.357(2),c=18.767(2) Å,=132.62(1)°,V _c=5141.6 ų,Z=4,D _x=1.150 mg m^–3,F(000)=1848; finalR _f=0.074 (R _w=0.085). The BH ₄ ^– ligand in the complex is bidentate. A comparative study indicates that the lengths of the Ru-carbene carbon bond and other bonds to the Ru atom are determined by a combination of several factors, and not just by a purely - or -bonding interaction.     

Synthesis and molecular structure of [Al(CH3)2]2[C10H22N4] [Al(CH3)3]2: Condensation product of trimethylaluminum and a multidentate open-chain amine

The crystalline condensation product [Al(CH₃)₂]₂[C₁₀H₂₂N₄][Al(CH₃)₃]₂ is prepared from reaction of the multidentate open-chain amine 1,4-bis(3-aminopropyl)piperazine with trimethylaluminum in methylene chloride. The compound crystallized in the monoclinic space groupC2/c with unit cell parametersa=25.166(12),b=7.268(4),c=17.316(4) Å,=115.3(4)°, andD _c =1.06 g cm^–3 forZ=4. Least-squares refinement based on 1054 observed reflections with intensitiesI 3(I) in the range 2<2<45° led to a finalR factor of 0.053 (R _w =0.064). The title compound resides on a crystallographic center of symmetry with independent Al-N distances of 1.889(5), 2.058(5), and 2.030(5) Å.     

Crystal and molecular structure of 3-(4-chlorobenzoylimino)-5,6-dihydro-3H-imidazo[2,1-c]-1,2,4-dithiazole

Crystal structure of the title compound belonging to the group of-acylimino derivatives of sulfur(II) compounds has been determined by X-ray structure analysis. The crystals are monoclinic, P2₁/c,a=11.210(2),b=8.197(1),c=13.659(2) Å,=102.36(2)°,V=1226.0(3) ų,Z=4,D _x =1.61 g cm^–3, (MoK)=0.71069 Å,=6.3 cm^–1. The structure has been refined to a finalR value of 0.035 for 1401 observed reflexions.The molecule is nearly planar with symmetrym. The title compound contains a very short intramolecular C=OS contact of 2.328(3) Å, suggesting a bond-non-bond resonance interaction.     

A new monoclinic crystal phase of [Bu4N][Ni(dmit)2]

The crystal structure of the title compound, tetrabutylammonium bis(2-thioxo-1,3-dithiole-4,5-dithiolato)nickelate(III), [N(C₄H₉)₄][Ni(C₃S₅)₂], is the fourth known phase of this polymorphous compound. It is monoclinic space group P2₁/c, with a = 20.040(2) Å, b = 13.1151(17) Å, c = 12.1093(15) Å, = 105.456(15)°, and V = 3067.5(6) ų with Z = 4, for D _calc = 1.503 g cm^–3. The [Ni(dmit)₂] anion packing arrangement consists of arrays of side-on touching anions and these arrays are connected via head-to-tail close S S contacts.     

Crystal and molecular structure of palladium(II), copper(II) and zinc(II) complexes of 1-methyl-3-(4-methyl)phenyltriazen-1-oxide

The structures of palladium(II), copper(II) and zinc(II) bis(chelates) of 1-methyl-3-(4-methyl)phenyltriazen-1-oxide have been determined by single-crystal X-ray methods. The crystals of [Pd(OMeN₃C₆H₄Me-4)₂] (I) are triclinic witha=7.410(3),b=7.806(3),c=8.371(2) Å, =65.80(2), =88.73(3), =81.04(3)°,Z=1, space group . The crystals of [Cu(OMeN₃C₆H₄Me-4)₂] (II) are monoclinic,a=14.934(5),b=10.111(4),c=11.762(3) Å, =96.00(2)°,Z=4, space group P2₁/c. The crystals of [Zn(OMeN₃C₆H₄Me-4)₂] (III) are triclinic witha=7.912(2),b=10.056(2),c=11.600(2) Å, =87.31(3), =74.96(3), =74.02(3)°,Z=2, space group . The structures of (I), (II), and (III) were solved to final values ofR=0.029, 0.043 and 0.034, respectively. A planar structure has been found for (I), (II) exhibits a tetrahedrally distorted square planar structure, whereas (III) is tetrahedral. The crystals of all three complexes are held by networks of stacking interactions.     

Structures of Z-(nitrostilbene)chromium tricarbonyl complexes: The effect of metal coordination on the nonplanarity of the stilbene system

The structures of the nitrostilbene complexes Z-(4-R–C₆H₄–CH=CH–C₆H₄-4-NO₂)Cr(CO)₃ (R=Me₂N,1; H,2; F₃C,3), are reported. The copounds were prepared as part of a study of the synthesis of organometallic complexes with potential nonlinear optics applications. For Z-(4-Me₂N–C₆H₄–CH=CH–C₆H₄-4-NO₂)Cr(CO)₃,1, triclinic, ,a=7.214 (3) Å,b=7.340 (3) Å,c=17.238 (9)Å, =88.23 (5)°, =88.76 (4)°, =87.66 (3) °,Z=2. For Z-(C₆H₅–CH=CH–C₆H₄-4-NO₂)Cr(CO)₃,2, monoclinic, P2₁/C,a=12.255 (3) Å,b=9.415 (1) Å,c=13.579 (4) Å, =105.60 (2)°,Z=4. For Z-(4-F₃C–C₆H₄–CH=CH–C₆H₄-4-NO₂)Cr(CO)₃,3, triclinic, ,a=7.094 (2) Å,b=8.057 (5) Å,c=17.295 (9) Å, =87.95 (5)° =85.94 (4)°, =64.24 (5)°,Z=2. The structural data show that the Z isomers exhibit bond lengths and angles similar to those observed in the E isomers, but the stilbene fragment is considerably more nonplanar. As a consequence, these molecules are unlikely to behave as NLO materials.     

Crystal structures of 4-amino-1,2,4-triazolidine-3,5-dione (urazine) (C2H4N4O2) and dichlorobis (4-amino-1,2,4-triazolidine-3,5-dione-N,O) copper (II) (C4H8Cl2CuN8O4)

Crystal structure analyses of urazine and of its adduct with CuCl₂ show that this ligand can exchange interactions of stacking that cannot be defined as simple - interactions. The copper atoms are octahedrally coordinated by two oxygen atoms and two aminic nitrogen from chelating uraxines and two chlorine atoms. The crystals of urazine are monoclinicP2₁ c:a=6.741(1),b=5.815(1),c=11.141(2) Å,/gb=92.13(1)°,V _c=436.4(1) ų,Z=4,R=0.0402 for 714 independent observed reflections; the crystals of [CuCl₂(urazine)₂] are triclinicP¯1:a=5.236(1),b=6.662(1),c=8.411(1) Å,=93.00(1),=104.87(1), =105.69(1)°,V _c=270.66(8) ų,Z=1,R=0.0380 for 875 independent observed reflections.     

Interaction of aromatic hydrocarbons with organometallic compounds of the main group elements: VI. Synthesis and crystal structure of cesium diiododimethylaluminatep-xylene solvate,Cs[Al(CH3)2I2]·C6H4(CH3)2

The crystal structure of thep-xylene solvate of cesium diiododimethylaluminate has been determined from counter data, and refined by full-matrix least-squares techniques. The crystals belong to the orthorhombic space groupC222₁ witha = 12.577(4),b = 9.311(3),c = 14.256(4) Å, andD _x = 2.19 g cm^–3 forZ = 4. The finalR value for 481 observed reflections is 0.036. The anion resides on a two-fold axis; the Al-I bond length is 2.647(4) Å, and the Al-C distance, 1.98(2) Å. Important bond angles include I-Al-I, 102.3(2) °; C-Al-C, 115(1) °; I-Al-C, 114(3) °; and I-Al-C, 106(3) °. The cesium ion also lies on the two-fold axis. Throughout the crystal the cesium ions are separated byp-xylene molecules. The Cs C distances average 3.84 Å. In the lattice the iodine atoms reside on thea,b face diagonals (and symmetry-related positions) and are situated almost exactly between the cesium ions. The Cs I contact, 3.925(1) Å, is consistent with a significant bonding interaction.For Part V see Atwood et al. (1978).     

Molecular structures of two conjugated ene-ynes derived from thiophene

The crystal structures of two conjugated ene-yne derivatives of thiophene are described, 2,5-di-(trimethylsilylethynyl)-3,4-dibromothiophene (1), is triclinic P witha=6.3281(4)Å,b=9.7421(6)Å,c=16.3669(9)Å; =80.516(5)°, =84.810(5)°, =74.072(5)°,Z=2,R=0.054; 2,3,4,5-tetra(trimethylsilylethynyl)thiophene (2), is monoclinic, P2₁/c with a=20.928(2)Å b=5.852(1)Å,c=23.907(2)Å; =100.245(6)°,Z=4,R=0.049. The ethynylic C atoms of both compounds lie near the thiophene plane, with deviations in the range 0.010(3)–0.455(4)Å. The phenyl groups of2 form a dihedral angle of 13.0(4)°.