ISSN:
0044-2313
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Triorganoantimony and Triorganobismuth Derivatives of 2-Pyridinecarboxylic Acid and 2-Pyridylacetic Acid. Crystal and Molecular Structures of (C6H5)3Sb(O2C-2-C5H4N)2 and (CH3)3Sb(O2CCH2-2-C5H4N)2Triorganoantimony and triorganobismuth dicarboxylates R3M(O2C-2-C5H4N)2 (M = Sb, R = CH3, C6H5, 4-CH3OC6H4; M = Bi, R = C6H5, 4-CH3C6H4) and (CH3)3Sb(O2CCH2-2-C5H4N)2 have been prepared from (CH3)3Sb(OH)2, R3SbO (R = C6H5, 4-CH3OC6H4), or R3BiCO3 (R = C6H5, 4-CH3C6H4) and the appropriate heterocyclic carboxylic acid. Vibrational spectroscopic data indicate a trigonal bipyramidal environment of M the O(—C)-atoms of the carboxylate ligands being in the apical and three C atoms (of R) in the equatorial positions; in addition coordinative interaction occurs in the 2-pyridinecarboxylates between M and O(=C) of one and N of the other carboxylate ligand and in (CH3)3)Sb(O2CCH2-2-C5H4N)2 between Sb and O(=C) of both carboxylate ligands.(C6H5)3Sb(O2C-2-C5H4N)2/(CH3)3Sb(O2CCH2-2-C5H4N)2 crystallize monoclinic [space group P21/c/P21/n; a = 892.6(9)/1043.4(6), b = 1326.9(6)/3166.2(18), c = 2233.1(9)/1147.5(7) pm, β = 99.74(8)°/97.67(5)° Z = 4/8; d(calc.) = 1.522/1.553 × Mg m-3; Vcell = 2606.7 × 106/3757.0 × 106pm3, structure determination from 3798/4965 independent reflexions (F ≥ 4.0 σ(F))/(I ≥ 1.96 σ(I), R(unweighted) = 0.024/0.036]. Sb is bonding to three C6H5/CH3 groups in the equatorial plane [mean distances Sb—C: 212.2(3)/208.7(6) pm] and two carboxylate ligands via O in the apical positions [Sb—O distances: 218.5(2), 209.9(2)/212.1(3), 213.2(3) pm]. In (C6H5)3Sb(O2C-2-C5H4N)2 there is a short Sb—O(=C) and a short Sb—N contact [Sb—O: 272.1(2), Sb—N: 260.2(2) pm] and distoritions of the equatorial angles [C—Sb—C: 99.2(1)°, 158.2(1)°, 102.0(1).] and of the axial angle [O—Sb—O: 169.9(1)°], and in (CH3)3Sb(O2CCH2-2-C5H4N)2, which contains two different molecules in the asym-metric unit, there are two Sb—O(=C) contacts [Sb—O, mean: 302.2(4), and 310.7(4)pm, respectively] and distortions of the equatorial angles [C—Sb—C: 114.5(2)°, 132.4(3)° 113.1(2)°, and 123.9(3)° 115.5(2)°, 120.6(3)°, respectively] and of the axial angles [O—Sb—O: 174,9(1)°, 177.9(1)°, respectively].
Notes:
Triorganoantimon- und Triorganobismutdicarboxylate R3M(O2C-2-C5H4N)2 (M = Sb, R = CH3, C6H5, 4-CH3OC6H4; M = Bi, R = C6H5, 4-CH3C6H4) und (CH3)3Sb(O2CCH2-2-C5H4N)2 wurden aus (CH3)3Sb(OH)2, R3SbO (R = C6H5, 4-CH3OC6H4) bzw. R3BiCO3 (R = C6H5, 4-CH3C6H4) und den entsprechenden heterocyclischen Carbonsäuren dargestellt. Aufgrund schwingungsspektroskopischer Daten hat M eine trigonal bipyramidale Umgebung mit den O(—C)-Atomen der Carboxylatliganden in den apikalen und den drei C-Atomen (von R) in den äquatorialen Positionen; zusätzlich erfolgt koordinative Wechselwirkung in den 2-Pyridincarboxylaten zwischen M und O(=C) des einen und N des anderen Carboxylatliganden und in (CH3)3Sb(O2CCH2-2-C5H4N)2 zwischen Sb und O(=C) beider Carboxylatliganden.(C6H5)3Sb(O2C-2-C5H4N)2/(CH3)3Sb(O2CCH2-2-C5H4N)2 kristallisieren monoklin [Raumgruppe P21/c/P21/n; a = 892,6(9)/1043,4(6), b = 1326,9(6)/3 166,2(18), c = 2233,1(9)/1 147,5(7) pm, β = 99,74(8)°/97,67(5)°; Z = 4/8; d(ber.) = 1,522/1,553 · Mg m-3; VZelle = 2606,7 · 106/3757,0 · 106 pm3; Strukturbestimmung anhand von 3 798/4 965 unabhängigen Reflexen (F ≥ 4,0 σ(F))/(I ≥ 1,96 σ(I)), R(ungewichtet) = 0,024/0,036]. Sb bindet drei C6H5-/CH3-Gruppen in der äquatorialen Ebene [mittlere Abstände Sb—C: 212,2(3)/208,7(6) pm] und zwei Carboxylatliganden über O in den apikalen Positionen [Abstände Sb—O: 218,5(2), 209,9(2)/212,1(3), 213,2(3) pm]. In (C6H5)3Sb(O2C-2-C5H4N)2 finden sich ein kurzer Sb—O(=C)- und ein kurzer Sb—N-Kontaktabstand [Sb—O: 272,1(2), Sb—N: 260,2(2) pm] sowie Verzerrungen der äquatorialen Winkel [C—Sb—C: 99,2(1)°, 158,2(1)°, 102,0(1)°] und des axialen Winkels [O—Sb—O: 169,9(1)°] und in (CH3)3Sb(O2CCH2-2-C5H4N)2, in dem sich in der asymmetrischen Einheit des Kristalls zwei unterschiedliche Moleküle befinden, z wei Sb—O(=C)-Kontaktabstände [Sb—O, im Mittel 302,2(4) bzw. 310,7(4) pm] sowie Verzerrungen, der äquatorialen Winkel [C—Sb—C: 114,5(2)°, 132,4(3)°, 113,1(2)° bzw. 123,9(3)°, 115,5(2)°, 120,6(3)°] und des axialen Winkels [O—Sb—O: 174,9(1)° bzw. 177,9(1)°].
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19905820107
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