MOLECULAR STRUCTURES AND SINGLE CRYSTAL ESR SPECTRA OF IMIDAZO-LATE-BRIDGED Co(Ⅲ)-Cu(Ⅱ)-Co(Ⅲ)AND Co(Ⅲ)-Zn(Ⅲ)-Co(Ⅲ) COMPLEXES

The structures of the heterotrinuclear complexes, [(NH_3)_5ColmCu(dien)ImCo(NH_3)_5]-(C10_4)_6·4H_20 and [(NH_3)_5CoImZn(dien)ImCo(NH_3)_5]-(ClO_4)_6·4H_2O, are reported. Co--Cu--Cocrystallizes in the monoclinic space group C2/c with a =32.414(4), b= 9.421(1), c=15.167(5)?,β= 90.91(2)°, Z=4 and Co--Zn--Co in the same space group with a = 32.578(2), b = 9.419(1), c = 15.125(3)?, β=91.10(1)°Z=4. The Cu(Ⅱ) and Zn(Ⅱ) geometriesare intermediate between a trigonal bipyramid and a square pyramid,the Co(Ⅲ) is a-hexagonal coordination and the dien ligand shows a disordered contribution in the respectivestructure.The magnetic properties of Co--Cu--Co are investigated. From the single crystalESR spectra studies, the anisotropic g and A tensors and electronic spin-density of Co--Cu--Co are obtained and the nature of the bonding for Cu~(2+) is discussed.     

The Syntheses and crystal structures of trans-dichlorobis (10-thiabenzo-15-crown-5)-palladium(Ⅱ)and trans-dichlorobis-(10-selenabenzo-15-crown-5)palladium(Ⅱ)

The preparation and X-ray crystal structures of the adducts of 10-thiabenzo-15-crown-5 and 10-selenabenzo-15-crown-5 with PdCl2 are reported. [PdCl2(C14H20O4S)2] (1): or-thorhombic, space group Pbca with cell dimensions of a=17.285(5), 6=8.354(3), c=21.689(4) A, K=3131.9 A3, Z=4;R=0.0330 for 2301 reflections with I > 3o(I), [PdCl2(C14H2oO4Se)2] (2): monoclinic, space group P21/n with cell dimensions of a=18.928(4), b=8.912(3), c=9.813(2) A, β=96.90(2)0, V=1643.4 A3, Z=2; R=0.0289 for 2617 reflections with I> 3σ(I), Both complexes are monomeric, square-planar palladiurn(Ⅱ) compounds with the Pd(Ⅱ) ion situating on a crystal-lographic inversion centre, and the crown ligands all adopt the axial coordination with the Pd-S bond of 2.3233(7) A and the Pd-Se bond of 2.4357(3) A. Their complexing characteristics are discussed in brief.     

CRYSTAL AND MOLECULAR STRUCTURE OF (CYANOETHYLOXY-FERROCENYL)-p-FLUOROPHENYL METHANE

<正> The crystal structure of (Cyanoethyloxy-ferrocenyl)-p-fluoro-phenyl methane (Fc-C(H)OCH2CH2CN, Mr=363.23) belongs to the monoclinic spacegroup P21/c with unit cell parameters: a =9.751(3), b =18.448(4), c =9.891(4)A,β= 105.71(3)°,V= 1712.7A3,Z=4,Dc=1.409g/cm3,μ=8.930cm-1,λ=0.71073A (MoKα),R=0.05. The structure and reactivities of the title compound are compared with those of its isomer.     

CRYSTAL STRUCTURE OF GdCl_3(DIMETHOXYETHANK)_2

<正> C8H2oCl3GdO4,Mr=443.80,monoclinic, space group P21/c, a=11.442 (3),b= 8.849(2), c= 15.575(5)A,β=104.8l(2)° ,V=1521.9(7)A3,Z= 4, DC = 1.94 g/cm3,λ(MoKα) =0.71069A,F(000)=860. The structure was solved by Patterson and Fourier techniques and refined by least-squares nethod to a final conventional lvalue of 0.051 (Rw=0.054). The central ion Gd(III) is bonded to three chlorine atoms and four oxygen atoms froa two dimethoxye-thane molecules to form a distorted pentagonal bipyramid. The Qd-Cl distances are in the range of 2.460-2.628A (average 2.571A). The Gd-O distances are in the range of 2.408-2.493A (average 2.458A).     

STRUCTURE OF 5-(N-METHYL-β-NAPHTHYLAMINO)-PENTA-2,4-DIENAL,C_(16)H_(15)NO

<正> M=237.31, orthorhombic, Pbca, a=8.342(2), b=15.675(3), c=19.779 (4)A3, Z=8, Dx=1.21 g/cm3, λ(MoKα)=0.71069A, μ=0.71 cm-1, F(000)=1008, room temperture, R=0.046. The planes of the formyl butadienyl group and the naph-thyl ring are tilted with respect to the plane of the nitrogen frame N by 2.8° and 31.4° , respectively. The O atom and the methyl group are in Z position.     

CRYSTAL AND MOLECULAR STRUCTURE OF μ-ACYL Fe-S COMPLEX (μ-C_2H_5S)[μ-CO-C(CH_3 )=CH_2]Fe_2(CO)_6

<正> The crystal and molecular structure of(u-C2H5S)[μ-CO-C(CH3)-CH2]Fe2(CO)6, Mr = 409.958 has been determined by X-ray diffraction method. Crystals of this complex are monoclinic, belonging to space group P21/c, and the cell parameters are a = 9.191(1), b = 9.666(1), c = 18.47(2)A,β=98.71(1)° V= 1621.9A3,Z=4,Dc=1.68g/cm3.Thg final R and Rw equal 0.058 and 0.089 for 1948 observed unique reflections. The acyl and ethyl-thio groups are bridged to two iron atoms to form an envelope type of structure. The bond lengths of Fe(1)-0(1), Fe(2)-C(1), Fe(l)-S, Fe(2)-S, Fe(l)-Fe(2) involved in the envelope structure are 1.992, 1.980, 2.260, 2.242 and 2.552A, respectively.     

THE CRYSTAL STRUCTURE OF COMPLEX OF DIBENZO-30-CROWN-10 (DB-30C-10) WITH THALLIUM(I) PERCHLORATE

<正> The title complex T1[DB-30C-10]ClO4(Mr=840. 45) crystallizes in the monoclinic,space group P21/n with a=12. 383(3),b= 18. 785(6),c= 14. 081(2) A and B=100.56(2) , Z=4, V= 3220.0A,Dx=1.734g/cm3,F(000) = 1672. The final refinement converged with R=0. 045 and Rw=0.053 for 2218 observed independent reflections. Ten oxygen atoms coordinated to thallium (I) are arranged in a hexadecahe-dron with quasi-D2h symmetry. Bond lengths and angles in the complexed and free crown-ethers are essentially the same but their conformations are different. Four of the C-O-C-C angles in (DB-30C-10) change from trans in the free to gauche in the complex;the remaining torsion angles are of the same type in both forms.     

CRYSTAL AND MOLECULAR STRUCTURE OF TETRAAQUA TRIM TRATO SAMARIUM(Ⅲ) DIHYDRATE [Sm(H_2O)_4(NO3)_3] ·2H_2O

<正> [Sm(H2O)4(NO3)3]·2H2O,Mr=444. 46,triclinic,space group P1 ,a = 6.747(1),b=9. 156(1),c=11.673(l) A ,α= 69. 90(1),β=88. 88(1),γ=69. 29 (1)°,V = 629.0A3,Z=2,λ(MoKa) = 0. 7107A,F(000) = 430,Dx=2. 346/cm3,final R=0. 032. The Sm atom in the title complex has bicapped square antiprismtic coordination of oxygen atoms from four water molecules and three NO3 groups. The Sm -O(nitrato) and Sm-O(aqua) distances are in the ranges of 2. 517-2. 716 and 2. 407-2. 432A , respectively. The N-O bond lengths vary between 1. 209 and 1. 265 A with the shortest distances being those involving noncoordinated oxygen atoms. The two lattice water molecules are outside the coordination sphere of the Sm atom but participate in the network of intermolecular hydrogen bonds.     

THE CRYSTAL STRUCTURE OF TR1S (μ-SULFJDO)-(U3-SULFJDO)-TETRAKTS (O,O-DIETHYLPHOSPHORODITHIOATO-S,S)-OXAZOLE-TRI-MOLYBDENUM-ANTIMONOUSCHLORID {Mo_3(U3-S)[u-S)_3·SbCl_3][S_2P(OEt)_2]_4·(C_3H_3ON)}

<正> Mr = 1445.67, triclinic. The space group is P1 with the unit cell parameters: a = 10.342(3), b = 11.994(3), c = 21.352(4) A; (?)= 76.27(2), β - 88.55(2)°, r = 73.26(2)°; V = 246lA3, Z = 2, DC = 1.959 g.cm-3. The final R factor is 0.068 based on 4053 reflectioons with I≥3(?)(Ⅰ). The title compound may be regarded as the result of that a molecule of trinuclear Mo cluster {Mo3S4[S2P(OEt)2]4·(C3H3ON)}[1] connects with a molecule of SbCl3 by three bridging S atoms. The skeleton {Mo3SbS4} is a distorted cube. The distances of Mo-Mo bonds are 2.728(2), 2,743(2) and 2.751(2) A, respectively, and the distances between Sb and Mo atoms are 3.814(2), 3.815(2) and 3.847(2) A, respectively.     

SYNTHESIS AND STRUCTURE OF THE FIRST TUNGSTEN-IRON-SULFUR CUBANE-LIKE CLUSTER [WFe_3S_4(S_2CNC_4H_8)s]·2DMF CONTAINING DITHIOCARBAMATO LIGANDS

<正> The title compound (Mr =1236.54) crystallizes in monoclinic space group C2/c with a =12.553(4),b=20.121(6),c=19.659(2)A,β=102.96(2)°,V=4839.1A3, Z = 4 and DC -1.697g/cm3. The structure was solved by direct methods.A full matrix least-squares refinement for 2197 reflections with I>3σ(I) gave final R and Rw of 0.064 and 0.076,respectively. The [WFe3S4] core of the cluster can be considered to be a [WFe3] tetrahedron capped by a sulfur atom on each face to fora a distorted cubane. The 57Fe Mossbauer spectrum indicates that there are two types of Fe atoms of ratio 2:1 in the cluster.     

CRYSTAL AND MOLECULAR STRUCTURES OF SCHIFF BASE COM-PLEXES WITH TRANSITION METAL IONS Ⅱ . BIS-( N-( 4-CHLQRO-PHENYL)-SALICYLALDIMINATO)COBALT (Ⅱ)

<正> The crystal and molecular structure of the title compound was determined by means of Patterson and Fourier synthesis based on three-dimensional X-ray data. The crystallographic parameters are as follows; (C13H8NOCl)2Co, monoclinic, space group A2/a,a = 11. 722 (8) , b = 8. 726 (5) , c = 21. 810 (8) A ,β= 95. 90 (6)°, V = 2219. OA3,Z= 4, Dc=1.55g/cm3,μ= 10. 71cm-1, F(000) = 1052, R= 0.042, Rw = 0. 051. Two iminato ligands are attached to the center atom Co through their donor atoms N(1),O(1),N(1)* ,and O(1)* to form a distorted tetrahedral configuration. The bond lengths of Co-O and Co-N are 1. 891 and 1. 988 A , respectively.     

CRYSTAL AND MOLECULAR STRUCTURE OF 1,10-PHENANTHROLINE TETRACARBONYL CHROMIUM AND -MOLYBDENUM COMPLEXES, (C_(12)H_8N_2)M(GO)_4 (M=Cr and Mo)

<正> The crystal and molecular structures of (C12H8N2)Mo(CO)4 and (C12H8N2)Cr(CO)4 are reported. They crystallize in the space group C2/m and are isomorphous with each other. The unit cell dimensions for (C12H8N2 Cr(CO)4 are a=15.404(2), b=12.091(2), c=8.223(2) A, 3=108.70(2)0, and V=1450.6(9) A3, while for (C12H8N2)Mo(CO)4 are a=15.546(6), b=12.086(4), c=8.269(1.) A, β= 107.37(2)0 and V=1482.9(l.5) A3, and both Z=4. Final R=0.040 Rw=0.050 for (C12H8N2)Cr(CO)4 and R=0.034 Rw=0.053 for (C12H8N2)Mo(CO)4.     

THE CRYSTAL STRUCTURE OF A NOVEL TETRANUCLEAR SILVER CLUSTER COMPLEX Ag_4(α-C_(10)H_7CS_2)_4(Py)_4·2Py

The title compound has been synthesized by the reaction of α-dithionaphthoic acidwith AgNO_3 in an organic solvent. The single crystals were obtained by recrystallizingfrom pyridine. We obtained two kinds of crystal with different colours (A and B), usingdifferent ratios of silver nitrate and α-dithionaphthoic acid (1:2,1:4) in the reactions. The structures of the two kinds of crystal were determined by a single-crystal X-raydiffraction analysis. The crystal (A) belongs to monoclinic space group C_(2h)~5-P2_1/a withunit cell parameters: a = 22.822(4) A, b = 12.803 (4) A, c = 24.444 (7) A, β = 103.90 (2)°V = 6933.14 A~3, Z = 4. The crystal (B) belongs to monoclinic space group C_(2h)~6-C2/c witha = 29.150 (2) A, b = 12.799 (3) A, c = 24.413 (2) A, β = 130.56 (4)°, V = 6914.38 A~3,Z = 4. Both crystals (A) and (B) have the same molecular configuration, but they havedifferent symmetry. In crystal (B), the molecule possesses a C_2 symmetry. This paperreports the structure determination and parameters o     

CRYSTAL STRUCTURE OF (Et_4N)_2[Mo_6O(μ-O)_(12)O_5]

<正> Mr= 1140.4, tetragonal,P4/mnc,a=10.726(2), c=14.208(3)A, Z=2,Dc=2.316 g.cm-3,V=1634.5(9)A3,final R=0.050 for 1457 independent reflections. The anion [Mo6O19]2- has its No atoas in octahedral configuration with one oxygen atom situated in the center of the octahedron, twelve bridging oxygen atoms,and six terminal oxygen atoms. The average bond lengths of the three types of Mo-O bonds are 1.678 A (Mo=0), 1.919A [Mo-(μ-O)], and 2.310 A [Mo-(μs-O)], respectively.     

CRYSTAL AND MOLECULAR STRUCTURE OF Th(TPPO)_2(DBM)(NO_3)_3 (TPPO=Ph_3PO, HDBM=PhCOCH_2COPh)

<正> Mr=1196.89, orthorhombic, P212121,a=15.592(4), b=17.419(6), c= 17.982(5)A, V=4883.8A3, Z=4. The structure was solved by direct methods and Fourier synthesis and refined by block-diagonal and full matrix Least-squares method to a .final R of 0.027 for 3916 independent observable reflections I>3 (I). The ten donor oxygen atoms are coordinated to centre metal ion Th(IV) forming a irregular coordination polyhedron. The three nitrate groups and the OBM anion are all bidentate ligands and the average bond lengths of Th-O(NO3) and Th-O(DBM) are 2.60A and 2.37A, respectively. The average coordination bond length of Th-O(TPPO) is 2.37A.     

CRYSTAL STRUCTURES OF COPPER (Ⅱ) AND COBALT (Ⅲ) COM- PLEXES OF o-HYDROXYBENZYLGLYCINATE (HBG)

<正> The structures of two complexes C(CuOC6H4CH2NHCH2COO)2 (H2 O)]·H2P(1) and [Co(NH3)6[Co(OC6H4CH2NHCH2COO)2]2[C1]·10H2O (2) were determined by X-ray analyses. Compound (1) crystallizes in the orthorhombic space group P212121 with a=11. 357(1),b= 24. 304(2),c=7.317(4) A,Z= 4;While compound (2) in the monoclinic space group A2/a(C2/c) with a=23. 486(9) ,b=26. 605(6) ,c= 10. 542(1) A,γ= 128. 42(4)°,Z= 4. In compound (1),two Cu(Ⅱ) ions are bonded together by the phenolic oxygen atoms of two tridentate chelating ligands and each of them is separately coordinated by the carboxyl oxygen,amino nitrogen of each chelate ligand and by the fifth oxygen atom as well (from aqua or the carbonyl group in adjacent molecule). Thus the coordination of each Cu(Ⅱ) is a square pyramid with distances of 1. 93- 1. 97A to the four corner atoms and 2. 30 and 2. 32 A to the apex atoms. The whole molecule has an approximately planar configuratioir with the two pyramid apexes pointing towards one side. Compound (2) consists of     

STRUCTURE OF PENTAAQUO PYROMEL DIZINE (Ⅱ)-DIHYDROUS [C_6H_2(COO)_4Zn_2(H_2O)_5]·2H_2O

Crystal and molecular structure of [C6H2(COO)4Zn2(H2O)5]·2H2O has been determined by X-ray diffraction technique, Mr = 507. 0,monoclinic,space group P21/n,a = 5. 925(1), 6 = 23. 613(9) ,c= 11. 790(5) A ,β= 96. 36 (3)°, V=1639. 3 (1. 0) A3,Z=4,DC = 2. 05g/cm3,λ=0. 71069 A,μ(MoKa) = 30. 9/cm-1,F(000) = 1024e. The structure was solved by Patterson and Fourier techniques and refined by least-squares method to a final conventional R value of 0. 055(Re = 0. 059)for 1557(I>3σ(I))reflections. Both atoms Zn(1) and Zn(2) are bridged by the Z,E-type of the car-boxyl group, in addition, Zn (1) is monodentate-bonded to the three remaining carboxyl and Zn(2) is bonded to five water molecules. The crystal structure shows a 2-dimensional polymeric network along(010)face. The Zn(l) -O distances are in the range of 1. 94~ 2. 01 A (average 1. 98 A ). The Zn(2) -O distances are in the range of 2. 06~2. 21 A (average 2. 12A).     

The preparation, structure and spectra properties of dual μ3-oxo bridged tetranuclear complexes containing the [CrnFe4-nO2]8+ core(n=0,2,4)

The preparation and characterization of [CrnFe4-nO2(O2CMe)7(bipy)2]Cl (1, n=0; 2, n=2; 3, n=4, bipy=2,2'-bipyridine) are described. The three complexes (1, 2 and 3) are obtained by tipyridine-mediated conversion of trinuclear [CrnFe3-nO(O2CMe)6(H2O)3]+(1, n=0; 2, n=1;3, n=3), and crystallized as three of approximate isomorphs. Crystal 2 is monoclinic with space group C2/c, a=27.454(5)A, b=11.789(1)A, c=16.570(3)A, B=118.78(1), V=4700.8A, z=4, u(MoKa)=11.64cm-1, F(000)=2056, final R=0.058 and Rw=0.066 for 3479 reflections with I > 3o(I). The Fe and Cr atoms in the cation are all +3 oxide state and disordered in the lattice, which is also supported by its Mossbauer studies. The [Cr2Fe2O2]8+ core can be thought of as being derived from two edge-sharing M3O units (M=Fe or Cr), and as a butterfly-like structure. The cations' structure of all three crystals are similar to each other and have C2 symmetry. The species are characterized by IR spectra and magnetic techniques, with particular emphasis on different     

SYNTHESIS AND STRUCTURE OF (Ph_4P)_2[Ni_3(μ-SC_3H_6S)_4]·2CH_3CN

<正> (Ph4P)2[Ni3(u-SC3H6S)4].2CH3CN was obtained from the reaction of NiCl2.6H2O,Na2(1,2-pdt)(pdtH2=CH3CH(SH)CH2SH) and Ph4PBr.Mr=1361. 80, P21/c,a=10.802(2),b=30.111 (7),c=9. 907(3) A ,B=93. 60(3) ;V= 3216. 0 A3;Z=2,Dc=1. 41g/cm3. The three Ni atoms of the anion are linearly arranged and bridged by four sulfur atoms from the four 1 ,2-propyldithiolato ligands.     

SYNTHESIS AND STRUCTURE OF HEXAKIS CDI-μ-(4-CHLORO-BENZYLTHIO ) NICKEL ] TRITETRACHLOROMETHANE SOL-VATE, [Ni(SCH_2C_6H_4Cl-p)_2]_6 · 3CC1_4

<正> C_(86)H_(72)Cl_(20)Ni_6S_(12) , Mr = 2551. 62, monoclinic, space group C2/c, crystal data: a = 30. 322(5), b=14. 168(3), c=26. 453(4) A ,β=101. 00(4)°, V = 11155. 6 A3, Z=4, Dx=1. 519 g/cm3, λ(MoKα) = 0. 71069 A ,μ=17. 370 cm-1, F(000) = 5152, T = 293 K, final R = 0. 078, Rw = 0. 086 for 5610 (I>3σ(I)) reflections. The crystal is composed of discrete [Ni (SCH2C6H4Cl-p)2]6 and CCl4 solvent molecules. The coordination geometries of the Ni atoms are perfect planes sharing S...S edges. The six NiS4 squares are linked with each other forming a hexagonal prism. The p-ClC6H4CH2S- side chains in the molecule are arranged in the axial and equatorial positions alternately with respect to the pseudo-hexagonal axis of the molecule.