PREPARATION AND CRYSTAL AND MOLECULAR-STRUCTURE OF A TRIS(THIOBENZOYLDIAZENE)MOLYBDENUM COMPLEX - EXAMPLE OF DISTORTED TRIGONAL-PRISMATIC COORDINATION

被引:59
作者
DILWORTH, JR [1 ]
HYDE, J [1 ]
LYFORD, P [1 ]
VELLA, P [1 ]
VENKATASUBRAMAMAN, K [1 ]
ZUBIETA, JA [1 ]
机构
[1] SUNY ALBANY,DEPT CHEM,ALBANY,NY 12222
关键词
D O I
10.1021/ic50192a012
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Molybdenum dioxobis(acetylacetonate), [Mo02(acac)2], or sodium molybdate reacts with the thioaroylhydrazines RNHNHCSR' (R = H, R' = C6H5, p-MeC6H4, p-MeOC6H4; R = Ph, R' = PhCH2, 1-C10H7, p-MeC6H4, p-MeOC6H4) to give the dark green or black complexes [Mo(RN2CSR')3]. The structure of tris(thiobenzoyldiazene)molybdenum-(Vl)-dimethylformamide, [Mo(C6H5CSN2H)3KCH3)2NCHO, has been determined in a single-crystal X-ray diffraction study. The coordination geometry of the molybdenum is a distorted trigonal prism of sulfur and nitrogen donor atoms contributed by three chelating diazene ligands disposed in a facial configuration. The distortion may be expressed in terms of an average twist angle of 7°, compared to the value of a - 0° for a regular trigonal prism. The average molybdenum-sulfur bond distance is 2.400 (5) A and the average molybdenum-nitrogen bond distance is 2.03 (1) A. The bond lengths in the chelate ring systems Mo-N-N-C-S- are intermediate between single- and double-bond distances, suggesting considerable derealization of charge: N-N(av) = 1.32 (2), N-C(av) = 1.35 (2) A, C-S(av) = 1.69 (2) A. The complex crystallizes in the orthorhombic system, space group Pbca, with a = 17.458 (8) A, b = 17.541 (9) A, and c = 17.896 (9) A. The measured density of 1.51 ± 0.03 g/cm3 requires eight molecules per unit cell (pcaic(1 = 1.50 g/cm3). The structure was solved by conventional Patterson and Fourier synthesis methods from 1456 independent reflections with I > 2.58<r(/). Full-matrix least-squares refinement of all atoms, excluding hydrogens, converged at values for Rt = 0.071 and R2 = 0.077. © 1979, American Chemical Society. All rights reserved.
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页码:268 / 274
页数:7
相关论文
共 36 条
[1]   HYDROGEN BONDING IN THIOSEMICARBAZIDE [J].
ANDREETT.GD ;
DOMIANO, P ;
GASPARRI, GF ;
NARDELLI, M ;
SGARABOT.P .
ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL CRYSTALLOGRAPHY AND CRYSTAL CHEMISTRY, 1970, B 26 :1005-&
[2]  
BAKER RJ, 1971, INORG CHEM, V10, P138
[3]   TRIGONAL PRISMATIC AND ANTIPRISMATIC COORDINATION IN AN ISOELECTRONIC SERIES OF TRIS(BENZENEDITHIOLATO) COMPLEXES [J].
BENNETT, MJ ;
COWIE, M ;
MARTIN, JL ;
TAKATS, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (22) :7504-7505
[4]   SYNTHESIS, STRUCTURE, AND PROPERTIES OF ASYMMETRIC BENZOYLDIAZENIDO AND THIOBENZOYLDIAZENIDO COMPLEXES OF MOLYBDENUM [J].
BISHOP, MW ;
CHATT, J ;
DILWORTH, JR ;
HYDE, JR ;
KIM, S ;
VENKATASUBRAMANIAN, K ;
ZUBIETA, J .
INORGANIC CHEMISTRY, 1978, 17 (10) :2917-2928
[5]   NOVEL ASYMMETRIC BENZOYLDIAZENIDO-BRIDGED COMPLEX OF MOLYBDENUM - X-RAY CRYSTAL-STRUCTURE OF [MO2O(PHCON2)2(S2CNET2)2] [J].
BISHOP, MW ;
CHATT, J ;
DILWORTH, JR ;
KAUFMAN, G ;
KIM, S ;
ZUBIETA, J .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1977, (02) :70-71
[6]   CRYSTAL AND MOLECULAR-STRUCTURES OF BIS(TETRAPHENYLARSONIUM) TRIS(1,2-DICYANOETHYLENEDITHIOLATO)MOLYBDENATE(IV), [(C6H5)4AS]2[MO(MNT)3], AND ITS TUNGSTEN ANALOG [(C6H5)4AS]2[W(MNT)3] [J].
BROWN, GF ;
STIEFEL, EI .
INORGANIC CHEMISTRY, 1973, 12 (09) :2140-2147
[7]  
BUTLER GW, UNPUBLISHED
[8]   CRYSTAL AND MOLECULAR STRUCTURE OF BIS-THIOSEMICARBAZIDATO-NICKEL(II), (RED CRYSTALS) [J].
CAVALCA, L ;
FAVA, G ;
NARDELLI, M .
ACTA CRYSTALLOGRAPHICA, 1962, 15 (NOV) :1139-&
[9]  
CHATT J, 1974, J LESS COMMON METALS, P36
[10]   TRIGONAL-PRISMATIC VS OCTAHEDRAL COORDINATION IN A SERIES OF TRIS(BENZENE-1,2-DITHIOLATO) COMPLEXES .2. CRYSTAL AND MOLECULAR-STRUCTURE OF TETRAPHENYLARSONIUM TRIS(BENZENE-1,2-DITHIOLATO)NIOBATE(V), [(C6H5)4AS][NB(S2C6H4)3] [J].
COWIE, M ;
BENNETT, MJ .
INORGANIC CHEMISTRY, 1976, 15 (07) :1589-1595