singlet at 52.3 ppm. The values for the gold(I) complexes are 49.4
and 30.0, respectively.
Crystal data for 2b: C25H22AuI5P2S, M = 1247.89, orthorhombic, a =
3
˚
˚
˚
˚
10.4495(5) A, b = 14.0201(3) A, c = 21.6335(5) A, V = 3169.37(18) A ,
T = 100(2)K, space group P212121, Z = 4, 80673 reflections measured,
7552 independent reflections (Rint = 0.056). The final wR2 value was 0.0425
(all data), with R1 0.0238 (I > 2s(I)).
The structures of 4a and 4b, which are not isostructural, were
determined by X-ray analysis. Ph3PSeBr+ AuBr4 (4b) crystallizes
-
¯
Crystal data for 2c: C25H22AuI5P2Se, M = 1294.79, orthorhombic, a =
in the triclinic space group P1 with one cation and two half anions
3
˚
˚
˚
˚
21.931(2) A, b = 10.4353(10) A, c = 13.7270(8) A, V = 3141.5(5) A ,
T = 100 K, space group Pna21, Z = 4, 42845 reflections measured, 5548
independent reflections (Rint = 0.157). The final wR2 value was 0.0490 (all
data), with R1 0.0391 (I > 2s(I)).
˚
in the asymmetric unit. The Se–Br bond length is 2.3121(4) A
and the Br ◊ ◊ ◊ Br contact between cation and anion is 3.4009(5)
˚
A. Compound 4b represents the first successful isolation and
structure determination of an R3PSeBr+ cation.
Crystal data for 3: C30.5H25AuBr5ClP2S, M = 1117.47, triclinic, a =
◦
˚
˚
˚
˚
14.948(2) A, b = 16.397(3) ◦A, c = 16.986(3) A, a = 117.927(15) , b =
For phosphane sulfides, which are weaker donors than the
selenides towards dihalogen molecules, no such adducts are known
so far. The crystal structure of the Ph3PSBr+ AuBr4- salt 4a, shown
in Fig. 4, is the first crystal structure of any species with a P–S–
Br unit, according to the Cambridge Structural Database (2010
version). It crystallizes in the monoclinic space group P21/n with
one formula unit in the asymmetric unit. The Br ◊ ◊ ◊ Br contact
◦
3
94.835(12) , g = 108.542(15) , V = 3349.6(10) A , T = 100 K, space group
¯
P1, Z = 4, 94741 reflections measured, 11848 independent reflections (Rint
=
0.204). The final wR2 value was 0.0726 (all data), with R1 0.0467 (I >
2s(I)).
Crystal data for 4a: C18H15AuBr5PS, M = 890.85, monoclinic, a =
◦
˚
˚
˚
13.7340(4) A, b = 12.2533(2) A, c = 14.9748(4) A, b = 114.913(5) , V =
3
˚
2285.56(10) A , T = 100 K, space group P21/n, Z = 4, 58880 reflections
measured, 4661 independent reflections (Rint = 0.045). The final wR2 value
was 0.0462 (all data), with R1 0.0221 (I > 2s(I)).
˚
of 3.151(1) A is very short and is comparable with the value of
Crystal data for 4b: C18H15AuBr5PSe, M = 937.75, t◦riclinic, a = 8.7461(4)
16
˚
◦
3.123(2) A in the adduct Ph3PBr2.
˚
˚
˚
A, b = 9.4386(5) A, c = 16.4508(7) A, a = 84.594(4) , b = 76.871(4) , g =
◦
3
¯
˚
62.835(5) , V = 1176.58(10) A , T = 100 K, space group P1, Z = 2, 86646
reflections measured, 6278 independent reflections (Rint = 0.039). The final
wR2 value was 0.0348 (all data), with R1 0.0170 (I > 2s(I)).
1 See for instance M. S. Hussain, Acta Crystallogr., Sect. C: Cryst. Struct.
Commun., 1987, C43, 450–453; M. S. Hussain, J. Chem. Cryst., 1986,
16, 91–99; P. G. Jones and E. Bembenek, J. Crystallogr. Spectrosc. Res.,
1992, 22, 397–401.
2 M. Preisenberger, A. Bauer and H. Schmidbaur, Chem. Ber., 1997, 130,
955–958.
3 D. H. Brown, R. J. Cross and R. Keat, J. Chem. Soc., Dalton Trans.,
1980, 871–874; S. W. Carr and R. Colton, Aust. J. Chem., 1981, 34,
35–44.
4 H. Schmidbaur, J. Ebner von Eschenbach, O. Krumberger and G.
Mu¨ller, Chem. Ber., 1990, 123, 2261–2265.
5 P. G. Jones and C. Tho¨ne, Acta Crystallogr., Sect. C: Cryst. Struct.
Commun., 1992, 48, 2114–2116.
6 P. G. Jones and B. Ahrens, Chem. Commun., 1998, 2307–2308; P. G.
Jones and B. Ahrens, Z. Naturforsch., 1999, B54, 1474–1477.
7 D. Schneider, A. Schier and H. Schmidbaur, Dalton Trans., 2004, 1995–
2005.
Fig. 4 Crystal structure of Ph3PSBr+AuBr4- (H atoms omitted). Selected
bond lengths [A] and angles [ ]: P–S 2.085(2), Br1–S 2.202(2), Br1 ◊ ◊ ◊ Br2
3.151(1); P–S–Br1 101.31(6), S–Br1 ◊ ◊ ◊ Br2 174.79(4), Br1 ◊ ◊ ◊ Br2–Au
99.41(2).
◦
˚
8 W.-W. du Mont, M. Ba¨tcher, C. Daniliuc, F. A. Devillanova, C.
Druckenbrodt, J. Jeske, P. G. Jones, V. Lippolis, F. Ruthe and E. Seppa¨la¨,
Eur. J. Inorg. Chem., 2008, 4562–4577.
9 S. M. Godfrey, S. L. Jackson, C. A. McAuliffe and R. G. Pritchard, J.
Chem. Soc., Dalton Trans., 1998, 4201–4204.
10 C. G. Hrib, F. Ruthe, E. Seppa¨la¨, M. Ba¨tcher, C. Druckenbrodt, C.
Wismach, P. G. Jones, W.-W. du Mont, V. Lippolis, F. A. Devillanova
and M. Bu¨hl, Eur. J. Inorg. Chem., 2006, 88–100.
More gold(I) complexes with various mono- and diphosphine
chalcogenide ligands are currently being synthesised with a
view to investigating their halogenation products; studies on
gold complexes with diphosphane dichalcogenide ligands are in
progress.
11 S. O. Grim and E. D. Walton, Inorg. Chem., 1980, 19, 1982–1987.
12 A. Karac¸ar, M. Freytag, H. Tho¨nnessen, J. Omelanczuk, P. G. Jones,
R. Bartsch and R. Schmutzler, Z. Anorg. Allg. Chem., 2000, 626, 2361–
2372.
13 H. Schmidbaur, A. Wohlleben, F. Wagner, O. Orama and G. Huttner,
Chem. Ber., 1977, 110, 1748–1754.
14 Only two previous examples of Au2Se2 rings are known, in a gold(III)
polyselenide complex [M. G. Katzanidis and S.-P. Huang, Inorg.
Chem., 1989, 28, 4667–4669] and in the mixed-valence compound
{Ph3PAuSe}2{m-Au(C6F5)3}2; S. Canales, O. Crespo, M. C. Gimeno,
P. G. Jones, A. Laguna and F. Mendizabal, Organometallics, 2001, 20,
4812–4848].
15 Confirmed by X-ray structure determination; details to be published
elsewhere.
16 N. Bricklebank, S. M. Godfrey, A. G. Mackie, C. A. McAuliffe
and R. G. Pritchard, J. Chem. Soc., Chem. Commun., 1992, 355–
356.
Notes and references
‡ X-Ray structure determinations: Data were collected at 100 K on an
Oxford Diffraction Xcalibur E diffractometer using monochromated Mo-
Ka radiation. Structures were refined using the program SHELXL-97 (G.
M. Sheldrick, University of Go¨ttingen, Germany).
Crystal data for 1: C74H58Au2Cl20P4Se2, M = 2331.94, triclinic, a = 9.974(2)
◦
◦
˚
˚
˚
A, b = 13.760(3) A, c = 15.679(3) A, a = 95.70(3) , b = 97.32(3) , g =
◦
3
¯
˚
95.08(3) , V = 2112.5(7) A , T = 100 K, space group P1, Z = 1, 68021
reflections measured, 7450 independent reflections (Rint = 0.186). The final
wR2 value was 0.1695 (all data), with R1 0.0687 (I > 2s(I)).
Crystal data for 2a: C25H22AuBr5P2S, M = 1012.94, monoclini◦c, a =
˚
˚
˚
10.3072(6) A, b = 13.378(2) A, c = 21.0032(16) A, b = 91.302(7) , V =
3
˚
2895.4(5) A , T = 100 K, space group P21/c, Z = 4, 44975 reflections
measured, 5293 independent reflections (Rint = 0.089). The final wR2 value
was 0.0300 (all data), with R1 0.0256 (I > 2s(I)).
This journal is
The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 11687–11689 | 11689
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