(N,N-diisopropyldithiocarbamato-S,S′)bis(triphenylphosphine-P)gold(I) butane solvate

Article abstract of DOI:10.1107/S0108270100007319

The synthesis and crystal structure of the novel gold(I) (N,N-diisopropyldithiocarbamato-S,S′)bis(triphenylphosphine-P)gold(I) butane solvate complex are examined. The Au atom is in a distorted tetrahedral environment consisting of two P atoms of the triphenylphosphine ligands and the two S atoms of the diisopropylthiocarbamate ligand. The molecular structure and packing are stabilized by van der Waals interactions.

Full text of DOI:10.1107/S0108270100007319

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
through the two S atoms, forming a four-membered chelate
ring. The other positions of the tetrahedron are occupied by
the P atoms of two triphenylphosphine ligands.
ISSN 0108-2701
The four-membered AuS2C ring is planar, with a maximum
Ê
deviation of 0.047 (6) A for C37. The Au1ÐS2 bond length
Ê
Ê
[2.714 (2) A] is longer than that of Au1ÐS1 [2.681 (2) A] as
the former is a coordination bond. Only a small variation in
the CÐS bond distance is observed. The AuÐP distances are
almost equal and are slightly longer than those found in
(N,N-Diisopropyldithiocarbamato-
S,S0)bis(triphenylphosphine-P)gold(I)
butane solvate
Ê
(AuSC2H4PEt2)2 [2.27 (2) A; Crane & Beall, 1978] and
Ê
C14H38Au3Cl3O12P6Á2.5H2O [2.296 (7) A; Yam et al., 1990].
Ê
The C37ÐN1 distance [1.350 (7) A] has double-bond char-
Fangfang Jian,a Lude Lu,a Xin Wang,a S. Shanmuga
Sundara Raj,b Ibrahim Abdul Razakb and Hoong-Kun
Funb*
acter, but is a little longer than those observed in related
structures (Sharma et al., 1991; Gimeno et al., 1996; Jian et al.,
1999). The PÐC and CÐC bond distances are in good
agreement with values reported for similar structures (Zheng
et al., 1997; Razak et al., 2000).
The smallest angle, S1ÐAu1ÐS2 of 65.71 (5)ꢀ, is restricted
by the bite angle of the ligand (Crespo et al., 1997; Jones et al.,
1994; Gimeno et al., 1994), whereas the largest angle, P1Ð
Au1ÐP2 of 132.15 (5)ꢀ, is at the open side opposite the
chelate ring. A possible explanation for this large value is
minimization of the steric interaction between the PPh3
groups. The other PÐAuÐS angles deviate slightly from the
tetrahedral value of 109.47ꢀ.
A non-crystallographic twofold axis passes through atoms
N1, C17 and Au1. The diisopropyl group is twisted by 7.5 (2)ꢀ
with respect to the AuS2C group. The isopropyl groups are at
anticlinal (C38, C39 and C40) and synclinal (C41, C42 and
C43) orientations with respect to the N1ÐC38 and N1ÐC41
bonds, respectively. The N1ÐC37 bond act as an ethylene
bond with S atoms and isopropyl groups on either side. The
aMaterial Chemistry Research Centre, School of Chemical Engineering, Nanjing
University of Science and Technology, Nanjing 210094, People's Republic of China,
and bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800
USM, Penang, Malaysia
Correspondence e-mail: hkfun@usm.my
Received 3 May 2000
Accepted 15 May 2000
In the crystal structure of the title complex, [Au(C7H14NS2)-
(C18H15P)2]ÁC4H10, the Au atom is in a distorted tetrahedral
environment consisting of the two P atoms of the triphenyl-
phosphine ligands and the two S atoms of the diisopropyl-
thiocarbamate ligand. The molecular structure and packing
are stablized by van der Waals interactions.
Comment
There has been growing interest in the study of d10 metal
complexes, which exhibit rich photophysical and photo-
chemical properties (Harvey & Gray, 1988; Vogler & Kunkely,
1988). Of particular interest is the nature of the lowest elec-
tronic excited states, which serve to develop a better under-
standing of the luminescent properties of d10±d10 systems
(Yam et al., 1990). Also, it has been found that gold(I) di-
alkyldithiocarbamates exist in discrete dimeric units which
stack in the solid state to form linear gold chains (Hesse &
Jennische, 1972). The number of gold(I) complexes of this type
is limited in the literature. As part of our work on this type of
complex, we present here the synthesis and crystal structure of
the novel gold(I) complex (N,N-diisopropyldithiocarbamato-
S,S0)bis(triphenylphosphine-P)gold(I) butane solvate, (I).
The crystal structure of (I) consists of mononuclear [Au-
(PPh3)2{S2CN(iPr)2}] units and butane molecules in a 1:1 ratio.
As shown in Fig. 1, the AuI ion in (I) is four-coordinated,
forming a distorted tetrahedron. The diisopropyldithio-
carbamate ligand acts as a bidentate ligand coordinating
Figure 1
The molecular structure of (I) showing 50% probability displacement
ellipsoids and the atom-numbering scheme; the butane solvent molecule
has been omitted for clarity.
ꢁ
Acta Cryst. (2000). C56, 939±940
# 2000 International Union of Crystallography
Printed in Great Britain ± all rights reserved 939

metal-organic compounds
parent atoms. The maximum and minimum electron densities (1.31
3
orientations of the isopropyl groups are limited by intramo-
lecular CÁ Á ÁS interactions. The butane solvent is not involved
in any interaction as there is no potential acceptor atom.
It is quite interesting to note that the molecular structure is
stabilized by intramolecular CÐHÁ Á Áꢀ interactions between
the aromatic H atoms of the PPh3 groups and the centroid
(Cg) of the chelate ring (atoms Au1, S1, C37 and S2)
Ê
Ê
and 1.46 e A ) were observed at distances of 1.05 and 0.89 A,
respectively, from the Au1 atom.
Data collection: SMART (Siemens, 1996); cell re®nement: SAINT
(Siemens, 1996); data reduction: SAINT; program(s) used to solve
structure: SHELXTL (Sheldrick, 1997); program(s) used to re®ne
structure: SHELXTL; molecular graphics: SHELXTL; software used
to prepare material for publication: SHELXTL and PLATON (Spek,
1990).
Ê
[C2Á Á ÁCg = 3.48, H2AÁ Á ÁCg = 2.68 A and C2ÐH2AÁ Á ÁCg =
ꢀ
Ê
145 ; C36Á Á ÁCg = 3.43, H36AÁ Á ÁCg = 2.72 A and C36Ð
H36AÁ Á ÁCg = 133ꢀ].
The authors would like to thank the Malaysian Government
and Universiti Sains Malaysia for research grant R&D No.
305/p®zik/610942. SSSR thanks the Universiti Sains Malaysia
for a Visiting Postdoctoral Fellowship. The authors thank
Professor A. L. Spek for valuable help in resolving the space-
group ambiguity.
Experimental
Sodium N,N0-diisopropyldithiocarbamate, Na(S2CNiPr2), dissolved in
H2O was added to gold trichloride at room temperature with stirring.
The brown reaction mixture was ®ltered and the ®ltrate was washed
with water and dried overnight in a vacuum. The brown solid
obtained was dissolved in butane. Triphenylphosphine was added at
353±363 K with stirring and the solution was re¯uxed for 4±5 h before
cooling. Single crystals of (I) suitable for X-ray analysis were grown
by slow evaporation at room temperature over a period of two weeks.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK1392). Services for accessing these data are
described at the back of the journal.
Crystal data
3
[Au(C7H14NS2)(C18H15P)2]ÁC4H10
Dx = 1.376 Mg m
Mo Kꢂ radiation
Cell parameters from 8192
re¯ections
Mr = 955.94
Monoclinic, P21=c
References
Ê
Ê
a = 12.0927 (2) A
Crane, W. S. & Beall, H. (1978). Inorg. Chim. Acta, 31, L469±470.
Crespo, O., Gimeno, M. C., Jones, P. G. & Laguna, A. (1997). J. Chem. Soc.
Dalton Trans. pp. 1099±1102.
b = 25.2129 (5) A
ꢃ = 1.57±28.35ꢀ
ꢄ = 3.378 mm
T = 293 (2) K
1
Ê
c = 15.4999 (3) A
ꢁ = 102.392 (1)ꢀ
V = 4615.70 (15) A
Z = 4
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Terroba, R. (1996). Inorg. Chim. Acta, 249, 69±77.
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3
Ê
Slab, colourless
0.42 Â 0.28 Â 0.12 mm
Data collection
Siemens SMART CCD area-
detector diffractometer
! scans
Absorption correction: empirical
(SADABS; Sheldrick, 1996)
Tmin = 0.331, Tmax = 0.687
31 290 measured re¯ections
11 360 independent re¯ections
5735 re¯ections with I > 2ꢅ(I)
Rint = 0.072
ꢃ
max = 28.26ꢀ
h = 16 ! 16
k = 29 ! 33
l = 20 ! 17
Re®nement
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.052
wR(F2) = 0.119
S = 0.988
11 360 re¯ections
478 parameters
H-atom parameters constrained
w = 1/[ꢅ2(Fo2) + (0.0331P)2]
where P = (Fo2 + 2Fc2)/3
(Á/ꢅ)max = 0.001
Sheldrick, G. M. (1996). SADABS. University of GoÈttingen, Germany.
Sheldrick, G. M. (1997). SHELXTL Software Reference Manual. Version 5.1.
Bruker AXS Inc., Madison, Wisconsin, USA.
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments
Inc., Madison, Wisconsin, USA.
Spek, A. L. (1990). Acta Cryst. A46, C-34.
3
Ê
Áꢆmax = 1.31 e A
3
Ê
1.46 e A
Áꢆmin
=
Vogler, A. & Kunkely, H. (1988). Chem. Phys. Lett. 150, 135±137.
Yam, V. W. W., Lai, T. F. & Che, C. M. (1990). J. Chem. Soc. Dalton Trans. pp.
3747±3752.
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3499±3503.
The butane solvent is disordered and so some atoms have a higher
atomic displacement parameter ratio. All H atoms were ®xed
geometrically at calculated distances and allowed to ride on their
ꢁ
940 Fangfang Jian et al. [Au(C7H14NS2)(C18H15P)2]ÁC4H10
Acta Cryst. (2000). C56, 939±940