2,4,6-Trinitrophenylgold(I) complexes. X-Ray crystal structures of [Au(SbPh3)4][Au{C6H2(NO2)3-2,4,6}2]·Et2O and [Au{C6H2(NO2)3-2,4,6}(dmphen)](dmphen = 2,9-dimethyl-1,10-phenanthroline)

Abstract
The reaction of [PPh3(CH2Ph)][AuCl2] in refluxing acetone with [Hg{C6H2(NO2)3-2,4,6}2](1 : 0.55) and excess of NMe4Cl affords NMe4[HgCl3] and [PPh3(CH2Ph)][Au{C6H2(NO2)3-2,4,6}Cl](1). Complex (1) reacts with excess of both NaClO4·H2O and tetrahydrothiophene (tht) at room temperature to give [Au{C6H2(NO2)3-2,4,6}(tht)](2) which reacts with SbPh3(1 : 2) or with excess of 2,9-dimethyl-1,10-phenanthroline (dmphen) to give [Au(SbPh3)4][Au{C6H2(NO2)3-2,4,6}2](3) or [Au{C6H2(NO2)3-2,4,6}(dmphen)](4), respectively. Crystal structures were determined for complexes (3) and (4). That of (3)[space group P21/n, a= 12.320 5(18), b= 35.802(6), c= 19.759(3)Å, β= 102.24(2)°, and Z= 4; R= 0.053, R′= 0.051] consists of tetrahedral [Au(SbPh3)4]+ cations (mean Au–Sb bond length 2.651 Å), linear [Au{C6H2(NO2)3-2,4,6}2] anions (Au–C 2.015 and 2.041 Å), and diethyl ether of crystallization. The nitro groups display high thermal motion or disorder. The crystal structure of complex (4)[space group P21/c, a= 7.165 8(8), b= 16.976 3(18), c= 16.471 8(24)Å, β= 99.80(2)°, and Z= 4; R=R′= 0.023] consists of neutral molecules with geometry intermediate between two- and three-co-ordination (Au–C 2.000, Au–N 2.136, 2.573 Å; C–Au–N 168.4°). Both complexes show ipso C–C–C angles much less than the ideal 120°.

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