The crystal and molecular structure of the enol form of 3,3'-dithiobis-(2,4-pentanedione)

Abstract

The crystal structure of the enol form of 3,3'-dithiobis-(2,4-pentanedione), C10H~404S2, has been determined using three-dimensional X-ray diffraction data (Mo K0c radiation) collected by counter methods.A report [Power & Jones, Inorg. Nucl. Chem. Lett. (1971), 7, 887-890] outlining what is now known to be the incorrect structure, has previously been published. The compound crystallizes in the orthorhombic space group Pna21 and has cell dimensions a= 14-852 (5), b= 12.264 (4) and c=6.935 (2) A; at,,= 1.36, de= 1-38 g cm -a for Z=4. The structure was refined, on F, by full-matrix, least-squares methods to an R value of 0.053 and wR of 0.038 for 1297 measured reflexions. The molecule exists as the enol tautomer and the short, intramolecular hydrogen bonds formed [O..-O contacts of 2.418 (6) and 2.444 (7) A] are asymmetric. There is evidence for alternating single and double bonds in the enol ring. The S-S distance is 2.082 (2) A and the C-S distances are 1.744 (5) and 1-743 (4) ~. From comparison with other organic sulphides, a dependence of the C-S bond length on the state of hybridization of the carbon atom is indicated. The C-S-S-C torsion angle is 68-6 °.

Chemistry of .eta.2-CS2 - metal complexes: synthesis of dithiolene complexes of iron via acetylene additions to Fe(.eta.2-CS2)(CO)2(PR3)2. X-ray structure of Fe[S2C(COMe)C(C6H4NO2)](CO)[P(OMe)3]2

“…Comparison of the Fe-S bond lengths (average 2.175 Á) in 3g with the sum of covalent radii for iron (~1.26 Á) and sulfur (1.04 Á) suggests that the Fe-S bonds are slightly shortened single bonds. The C(3)-S(2) and C(3)-S(l)dis- tances (1.722 (3) and 1.736 (5) Á), which are marginally different, compare favorably with corresponding distances in other dithiolate complexes24 and are close to the expected value of 1.75 Á for a C(sp2)-S single bond 25. The C(2)-C(3) bond length (1.355 (5) Á) corresponds to that expected for a double bond differing from the sp2-sp2 single bond length found in the related dithiolate derivative (C5H5)Co[S2C2(CF3)2] (C-C = 1.48 Á)26 but being rather similar to the corresponding distance (1.364 (10) Á) in (C5H5)[CoS2C2(CN)2].27 There…”

“…18(2) C( 7) 1131 ( 44) 31 (2) 176 ( 9) 101 ( 7) 297 ( 18) 25 (3) C( 8) 319(15) 29( 1) 164 (8) -47 ( 4) 18( 9) 16(3) C( 9) 229 ( 13) 35 (2) 232 ( 11) 15 (4) 81 ( 9) 28 (3) C( 10) 264 (12) 16.0( 8) 152( 7) 3( 3) 56( 7) 20 (2)…”

Studies on tellurium–carbon bonded compounds. III. The crystal structure of acetylacetone tellurium(II)

“…The only anomalous examples so far reported are with Pt Ii, Pt TM and S (Figgis, Lewis, Long, Mason, Nyholm, Pauling & Robertson, 1962;Hazell, Swallow & Truter, 1959;Jones & Power, 1976;Mason, Robertson & Pauling, 1969;Swallow & Truter, 1960. In these cases the ligand can be either uni-or trifunctional.…”