A new class of triazepine-ruthenium(II) complexes: Synthesis, crystal structure and NMR spectroscopic properties

Article abstract of DOI:10.1016/S0022-328X(00)00680-X

Two unprecedented three-dimensional ruthenium(II) complexes I and II derived from 2-methyl-5-oxo-7-phenyl-3-thioxo-3,4,5,6-tetrahydro-2H-1,2,4-triazepine (HTAZO) and 2-methyl-7-phenyl-3,5-dithioxo-3,4,5,6-tetrahydro-2H-1,2,4-triazepine (H₂TAZS) have been prepared by the reaction of these triazepines with [Ru(p-cymene)Cl₂]₂ in the presence of triethylamine. NMR spectroscopic and X-ray diffraction studies of the structures of the resulting complexes reveal different behavior of HTAZO and H₂TAZS in the coordination process.

Full text of DOI:10.1016/S0022-328X(00)00680-X

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 619 (2001) 265–270
A new class of triazepine–ruthenium(II) complexes: synthesis,
crystal structure and NMR spectroscopic properties
Mustapha Aitali a, My Youssef Ait Itto* a,1, Aisa Hasnaoui a, Abdelkhalek Riahi b,
Abdellah Karim a, Jean-Claude Daran* c,2
a De´partement de Chimie, Faculte´ des Siences, Semlalia, BP 2390 Marrakech, Morocco
b Laboratoire de Photochimie associe au CNRS, BP. 1039, F-51687 Reims Cedex 2, France
c Laboratoire de Chimie de Coordination, CNRS, 205 route de Narbonne, 31077 Toulouse Cedex 4, France
Received 2 August 2000; accepted 12 September 2000
Abstract
Two unprecedented three-dimensional ruthenium(II) complexes I and II derived from 2-methyl-5-oxo-7-phenyl-3-thioxo-3,4,5,6-
tetrahydro-2H-1,2,4-triazepine (HTAZO) and 2-methyl-7-phenyl-3,5-dithioxo-3,4,5,6-tetrahydro-2H-1,2,4-triazepine (H2TAZS)
have been prepared by the reaction of these triazepines with [Ru(p-cymene)Cl2]2 in the presence of triethylamine. NMR
spectroscopic and X-ray diffraction studies of the structures of the resulting complexes reveal different behavior of HTAZO and
H2TAZS in the coordination process. © 2001 Published by Elsevier Science B.V. All rights reserved.
Keywords: Heterocycles; Triazepine; Ruthenium(II); X-ray analyses; NMR
1. Introduction
complexes by reacting [Ru(p-cymene)Cl2]2 with
HTAZO [10,11] (four equivalents) and H2TAZS [10,11]
(four equivalents) respectively, in the presence of an
excess of triethylamine under 2-propanol reflux
conditions.
We have found that, when HTAZO reacts with
[Ru(p-cymene)Cl2]2, only one chlorine atom is removed
leading productively and cleanly to formation of the
mononuclear complex [RuCl(p-cymene)TAZO] (I) [12].
However, with H2TAZS, the two chlorine atoms are
displaced from the complex precursor to afford readily
a good yield of binuclear [Ru(p-cymene)TAZS]2 (II).
The NMR spectroscopic data (Table 1) of these
complexes suggest that both triazepines HTAZO and
H2TAZS were transformed before complexation, into
the respective triazepinate ligands TAZO− and
In recent years, heterocyclic systems have found wide
application in organometallic chemistry. Thus a large
number of complexes with heterocyclic molecules as
ligands have been prepared [1–4]. These kinds of com-
pounds act predominantly as chelates, giving versatile
mono, bi or polynuclear complexes [5–8] having broad
applicability in a wide range of reactions in organic
synthesis [2,5b,6,7,8]. In spite of the frequent use of
heterocyclic compounds as ligands, mainly with transi-
tion metals, complexes containing 1,2,4-triazepines are
not known. This type of chelate which presents differ-
ent coordination sites, could provide efficient catalysts
with great conformational rigidity (Scheme 1).
2. Results and discussion
As part of our work in this field [9], we have pre-
pared two unprecedented 1,2,4-triazepine-ruthenium(II)
1 *Corresponding author.
2 *Corresponding author.
Scheme 1.
0022-328X/01/$ - see front matter © 2001 Published by Elsevier Science B.V. All rights reserved.
PII: S0022-328X(00)00680-X

266
M. Aitali et al. / Journal of Organometallic Chemistry 619 (2001) 265–270
Table 1
Some pertinent 1H (300 MHz) and 13C-NMR (75 MHz) assignments (TMS standard, CDCl3 solvent, l in ppm) of HTAZO, H2TAZS and the
corresponding complexes
HTAZO
Ru-TAZO (I)
H2TAZS
Ru-TAZS (II)
H–S
H–C(6)
8.62, br s, 1H
4.02, s, 2H
10.01, br s, 1H
4.28, s, 2H
3.82, d 12.5 Hz, 1H
3.48, d 12.5 Hz, 1H
3.52, s, 3H
180.55
164.73
41.31
7.04, s, 1H
H–CN(2)
C(3)
C(5)
3.75, s, 3H
173.78
163.74
39.62
3.81, s, 3H
172.59
195.28
46.45
3.13, s, 3H
178.86
170.64
120.11
160.40
38.72
C(6)
C(7)
C–N(2)
159.47
46.17
154.66
43.66
160.99
47.66
Scheme 2.
Scheme 3.
TAZS2− via the pathways shown in Schemes 2 and 3.
This behavior is similar to that we described for the
alkylation of these trazepines with mono and di-
haloalkanes [11].

M. Aitali et al. / Journal of Organometallic Chemistry 619 (2001) 265–270
267
The 1H-NMR spectra of HTAZO and H2TAZS show
respectively a broad singlet at 8.62 ppm and 10.01 ppm
corresponding to the SH group. Signals for the H2C(6)
methylene group at 4.02 ppm (for HTAZO) and 4.28
ppm (for H2TAZS) are also observed (Table 1). This
reveals that both HTAZO and H2TAZS exist in solu-
tion as the tautomeric form B (in solid state form A has
been demonstrated [10]) (Schemes 2 and 3).
is confirmed by the X-ray structural analyses: the S(5)–
,
C(5) bond length is 1.748(7) A (1.753(6) for molecule b)
,
and the C(5)–C(6) bond length is 1.377(9) A (1.354(9)
for molecule b). Moreover the angles around C(5) are
close to 120°: S(5)–C(5)–C(6) 121.7(5)° (120.8(5)°),
S(5)–C(5)–N(4) 117.3(5)° (117.8(5)°), C(6)–C(5)–N(4)
120.4(6)° (121.0(6)°).
In view of all these facts, we can state that while both
sulfur atoms of H2TAZS at C(3) and C(5) positions are
coordinated to the metal, only that of HTAZO at C(3)
position participates in the coordination. It is notewor-
thy to emphasize that the HTAZO C(5) oxo group is
not involved.
Upon binding of HTAZO to the metal, a typical AB
system and a geminal coupling are observed in the
1H-NMR spectrum for the H2C(6) group (Table 1).
This indicates a rigid structure of the Ru-TAZO com-
plex with less conformational flexibility compared to
the free HTAZO triazepine (Table 1).
1
On the other hand, comparison of H-NMR spectra
of HTAZO, H2TAZS and their corresponding ruthe-
nium complexes shows that coordination led to depro-
tonation of the ligands, as indicated by loss of the SH
signal. Moreover, we observed for the complex II the
disappearance of the H2C(6) methylene group signal
and the appearance of a singlet at 7.04 ppm due to an
ethylenic proton. This shows an additional deprotona-
tion of the H2TAZS triazepine leading to a coordina-
tion of the other sulfur atom in position 5 (Schemes 2
and 3).
3. Description of the structure
For the Ru-TAZS complex, the asymmetric unit is
built up from two halves of the molecule and a CHCl3
solvent molecule. Each half is linked through the S(5)
(or S(105)) atom to its related centrosymmetry counter-
part thus resulting in the occurrence of two dinuclear
complexes in the unit cell. The molecular structure of
one of these dinuclear ruthenium complexes is shown
with atoms labeling scheme in Fig. 1. Important bond
lengths and angles are reported in Table 2. The
TAZS2− ligand exhibits an unprecedented m-kS, k2N,S
coordination mode: the two sulfur atoms S(3) and S(5)
and the nitrogen N(4) are indeed engaged in coordina-
tion with the Ru atoms. The nitrogen and S(3) form a
four-membered chelate ring containing the ruthenium
Ru(1) whereas the second sulfur atom S(5) is coordi-
nated to the centrosymmetric related Ru(1)%. The m-kS,
k2N,S coordination mode has been previously observed
in some di- and trinuclear (h6-arene)ruthenium(II) com-
plexes containing bridging heterocyclic thioamide [13]
and in the polymeric cadmium(II) complex [Cd(mbt2]n
[14]. However, in these cases, the three donating N,S,S
atoms belong to two different ligands whereas in the
title complex the two sulfur and the nitrogen atoms
arise from the same TAZS2− ligand. The bridging
sulfur atoms (S(5) or S(105)) lead to the formation of
an eight-membered ring Ru(1)–N(4)–C(5)–S(5)–
Ru(1)%–N(4)%–C(5)%–S(5)% which has a chair conforma-
tion (or a step like structure). It is indeed formed of
three planes Ru(1)–S(5)–S(5)%–Ru(1)%, Ru(1)–N(4)–
C(5)–S(5) and its centrosymmetric related one, with
dihedral angle between them of 79.6(2)°. Although,
such eight-membered (M–N–C–S–M–N–C–S) rings
are rather commonly observed with chelating N,S con-
taining ligands [15], the preferred conformation is boat-
shaped. To the best of our knowledge, only one
example of a chair conformation for such a ring has
been reported for bis(benzoylmethylthiopyridinium)-
bis(triphenylphosphine)-di-silver(I) [16].
In the 13C-NMR, participation of both triazepines
S–C(3)–N(4) moiety is shown furthermore by
downfield shift (average Dlꢀ6 ppm) of the C(3) car-
bon atom. A shielding of C(7) and C(2) carbon atoms
is also observed (Table 1).
After coordination of HTAZO, the changes in chem-
ical shift of C(5) and C(6) carbon atoms are less
pronounced (Dlꢀ1–4 ppm). Remarkably, the
H2TAZS C(5) carbon atom is hardly shielded by about
24.64 ppm, while the C(6) signal is observed in the
H–Csp2 area (l=120.11 ppm). These data reveal great
modification in the electronic charge distribution of the
H2TAZS S–C(5)–C(6) fragment which evolute from
SꢀC(5)–C(6) towards S–C(5)ꢀC(6) configuration. This
Fig. 1. Molecular structure of the dinuclear complex (Ru-TAZS)2
with atom labeling. Ellipsoids represent 50% probability.

268
M. Aitali et al. / Journal of Organometallic Chemistry 619 (2001) 265–270
Table 2
4. Experimental
,
Important bond lengths (A) and angles (°); e.s.d.s in parentheses refer
to the last significant digit
2-Propanol (Aldrich) was distilled over magnesium
under nitrogen atmosphere, triethylamine (Aldrich) was
Molecule a
Molecule b
,
distilled over molecular sieve (4 A). [Ru(p-cymene)Cl2]2
Ru(1)–N(4)
Ru(1)–C(12)
Ru(1)–C(13)
Ru(1)–C(15)
Ru(1)–C(16)
Ru(1)–C(11)
Ru(1)–C(14)
Ru(1)–S(5)c1 a
Ru(1)–S(3)
S(3)–C(3)
2.112(5) Ru(2)–N(104)
2.177(6) Ru(2)–C(22)
2.177(8) Ru(2)–C(23)
2.189(7) Ru(2)–C(25)
2.193(7) Ru(2)–C(26)
2.206(7) Ru(2)–C(21)
2.208(7) Ru(2)–C(24)
2.402(2) Ru(2)–S(105)c2
2.4343(19)Ru(2)–S(103)
1.722(6) S(103)–C(103)
1.748(7) S(105)–C(105)
2.402(2) S(105)–Ru(2)c2
1.303(9) N(101)–C(107)
1.464(8) N(101)–N(102)
1.414(8) N(102)–C(103)
1.438(9) N(102)–C(102)
1.307(8) N(104)–C(103)
1.403(8) N(104)–C(105)
1.377(9) C(105)–C(106)
1.427(10) C(106)–C(107)
1.507(10) C(107)–C(171)
2.116(5)
2.179(7)
2.182(7)
2.179(8)
2.162(7)
2.203(7)
2.198(7)
2.400(2)
2.4227(19)
1.705(7)
1.753(6)
2.400(2)
1.278(9)
1.458(8)
1.421(8)
1.446(9)
1.298(8)
1.413(8)
1.354(9)
1.462(10)
1.498(11)
complex was prepared according to literature proce-
dures [17]. Elemental analyses were performed by Laure
Donnadieu-Noe´ on a Perkin–Elmer 2400 se´rie II in the
Laboratoire de Chimie de Coordination. HTAZO and
H2TAZS triazepines were synthesized by published
methods [10,18].
4.1. HTAZO
S(5)–C(5)
1
S(5)–Ru(1)c1
M.p. 177–178°C (ethanol). H-NMR (CDCl3): l=
N(1)–C(7)
8.62 [s, 1H, SH], 7.54–7.82 [m, 5H, C6H5], 4.02 [s, 2H,
H2C(6)], 3.75 [s, 3H, H3CN(2)]. 13C-NMR (CDCl3):
l=173.78 [C(3)], 163.74 [C(5)], 159.47 [C(7)], 132.84,
132.02, 129.19 and 127.34 [C–Ar], 46.17 [C–N(2)],
39.62 [C(6)]. Anal. Found (calc. for C11H11N3OS): H
4.54 (calc. 4.6), C 56.63 (calc. 56.6), N 18.08 (calc.
18.08).
N(1)–N(2)
N(2)–C(3)
N(2)–C(2)
N(4)–C(3)
N(4)–C(5)
C(5)–C(6)
C(6)–C(7)
C(7)–C(71)
N(4)–Ru(1)–S(5)c1 89.11(16)N(104)–Ru(2)–S(105)c2 87.03(16)
N(4)–Ru(1)–S(3) 66.88(16)N(104)–Ru(2)–S(103) 66.48(16)
S(5)c1–Ru(1)–S(3) 81.05(7) S(105)c2–Ru(2)–S(103) 82.57(7)
C(3)–S(3)–Ru(1) 79.2(2) C(103)–S(103)–Ru(2) 79.6(2)
C(5)–S(5)–Ru(1)c1 107.4(2) C(105)–S(105)–Ru(2)c2 107.4(2)
4.2. H2TAZS
1
M.p. 180–181°C (ethanol). H-NMR (CDCl3): l=
10.01 [br s, 1H, SH], 7.94–7.43 [m, 5H, C6H5], 4.28 [s,
2H, H2C(6)], 3.81 [s, 3H, H3CN(2)]. 13C-NMR
(CDCl3): l=195.28 [C(5)], 172.59 [C(3)], 160.99 [C(7)],
132.44, 132.12, 129.00 and 127.32 [C–Ar], 47.66 [C–
N(2)], 46.45 [C(6)]. Anal. Found (Calc. for
C11H11N3S2): H 3.74 (calc. 4.4), C 53.01 (calc. 53.0), N
16.85 (calc. 16.8).
C(7)–N(1)–N(2)
C(3)–N(2)–C(2)
C(3)–N(2)–N(1)
C(2)–N(2)–N(1)
C(3)–N(4)–C(5)
C(3)–N(4)–Ru(1)
C(5)–N(4)–Ru(1)
N(4)–C(3)–N(2)
N(4)–C(3)–S(3)
N(2)–C(3)–S(3)
C(6)–C(5)–N(4)
C(6)–C(5)–S(5)
N(4)–C(5)–S(5)
C(5)–C(6)–C(7)
N(1)–C(7)–C(6)
N(1)–C(7)–C(71)
C(6)–C(7)–C(71)
113.4(6) C(107)–N(101)–N(102)
115.4(5) C(103)–N(102)–C(102)
108.0(5) C(103)–N(102)–N(101)
108.7(5) C(102)–N(102)–N(101)
122.9(5) C(103)–N(104)–C(105)
102.0(4) C(103)–N(104)–Ru(2)
134.2(4) C(105)–N(104)–Ru(2)
121.5(6) N(104)–C(103)–N(102)
111.9(5) N(104)–C(103)–S(103)
126.6(5) N(102)–C(103)–S(103)
120.4(6) C(106)–C(105)–N(104)
121.7(5) C(106)–C(105)–S(105)
117.3(5) N(104)–C(105)–S(105)
125.8(6) C(105)–C(106)–C(107)
127.1(7) N(101)–C(107)–C(106)
114.3(6) N(101)–C(107)–C(171)
118.6(6) C(106)–C(107)–C(171)
114.4(6)
114.0(6)
110.2(5)
107.9(6)
125.3(5)
101.8(4)
132.5(4)
121.8(6)
112.1(5)
126.1(5)
121.0(6)
120.8(5)
117.8(5)
125.6(6)
127.9(7)
117.3(6)
114.7(7)
4.3. General procedure for the synthesis of
[Ru–triazepine] complexes
A mixture of [Ru(p-cymene)Cl2]2, 1,2,4-triazepine
and triethylamine (molar ratio 1:4:8) in 2-propanol was
heated at 80°C for 1 h under nitrogen atmosphere using
standard Schlenk-type glassware. The orange–red solu-
tion was then concentrated to dryness and the resulting
solid was treated with absolute ethanol. After filtration,
from the resulting solution crystals of the product were
obtained. X-ray measurements and NMR spectral data
were performed on the crystalline product so obtained.
a Symmetry transformations used to generate equivalent atoms:
c1 −x, −y −z+1; c2 −x+1, −y+1, −z+1.
The geometry observed for the four-membered
chelate ring compares well with the similar ring in the
Ru-TZAO mononuclear complex (Fig. 2) and in some
other related k2N,S ruthenium chelates (Table 3). It is
worth pointing out that the triazepine rings in com-
plexes I and II present different conformations as
shown by comparison of their torsional angles and
bond distances (Table 4). The C(5)–C(6) and C(6)–
4.4. [RuCl(p-cymene)TAZO] (I)
1
70% yield. H-NMR (CDCl3): l=7.34–7.85 [m, 5H,
C6H5 triazepine], 5.58 [d 6.1 Hz, 1H, C6H4 p-cymene],
5.55 [d 6.1 Hz, 1H, C6H4–p-cymene], 5.40 [d 6.2 Hz,
1H, C6H4–p-cymene], 5.19 [d 6.2 Hz, 1H, C6H4–p-
cymene], 3.82 [d 12.5 Hz, 1H, H–C(6)], 3.48 [d 12.5 Hz,
1H, H–C(6)], 3.52 [s, 3H, H3CN(2)], 2.83 [m, 1H, H–C
p-cymene], 2.21 [s, 3H, H3C p-cymene], 1.22 [d 7.1 Hz,
,
C(7) bond lengths of 1.522 and 1.491 A respectively,
clearly indicate that the C(6) atom remains a methylene
group as suggested by the NMR studies.

M. Aitali et al. / Journal of Organometallic Chemistry 619 (2001) 265–270
269
3H, H3C p-cymene], 1.18 [d 7.0 Hz, 3H, H3C p-
cymene]. 13C-NMR (CDCl3): l=180.55 [C(3)], 164.73
[C(5)], 154.66 [C(7)], 133.67, 131.25, 128.81 and 127.32
[C–Ar triazepine], 102.68, 97.65, 81.89, 81.45, 80.81
and 80.14 [C–Ar p-cymene], 43.66 [C–N(2)], 41.31
[C(6)], 31.62 [C–Me2 p-cymene], 22.54, 22.31 and 19.21
[H3C
p-cymene].
Anal.
Found
(calc.
for
C21H24ClN3ORuS): H 4.74 (calc. 4.8), C 50.01 (calc.
50.1), N 8.26 (calc. 8.4).
4.5. [Ru(p-cymene)TAZS]2 (II)
1
85% yield. H-NMR (CDCl3): l=7.35–7.77 [m, 5H,
C6H5 triazepine], 7.04 [s, 1H, H–C(6)], 5.60 [d 5.8 Hz,
1H, C6H4 p-cymene], 5.35 [d 5.8 Hz, 1H, C6H4–p-
cymene], 5.31 [d 5.9 Hz, 1H, C6H4–p-cymene], 5.27 [d
5.9 Hz, 1H, C6H4–p-cymene], 3.13 [s, 3H, H3CN(2)],
2.85 [m, 1H, H–C p-cymene], 2.19 [s, 3H, H3C p-
cymene], 1.18 [d 6.9 Hz, 3H, H3C p-cymene], 1.05 [d 6.8
Hz, 3H, H3C p-cymene]. 13C-NMR (CDCl3): l=
178.86 [C(3)], 170.64 [C(5)], 160.40 [C(7)], 136.16,
129.87, 128.43 and 128.10 [C–Ar triazepine], 120.11
[C(6)], 102.05, 95.54, 88.45, 87.86, 82.84 and 82.53
[C–Ar p-cymene], 38.72 [C–N(2)], 30.57 [C–Me2 p-
cymene], 23.20, 22.52 and 17.94 [H3C p-cymene]. Anal.
Found (calc. for C43H47Cl3N6Ru2S4): H 3.15 (calc. 4.5),
C 45.26 (calc. 47.8), N 8.12 (calc. 7.7).
Fig. 2. Molecular structure of the mononuclear complex (Ru-TAZO)
with atom labeling.Ellipsoids represent 50% probability.
Table 3
Comparison of geometry for different k2N,S ruthenium chelate rings
4.6. X-ray crystallographic study
Ru-TAZO
(Ru-TAZS)2
[13]
Suitable crystals were obtained by slow diffusion in a
mixture of CHCl3–EtOH. Data were collected on a
Stoe IPDS diffractometer. The final unit cell parameters
were obtained by the least-squares refinement of 5000
reflections. Only statistical fluctuations were observed
in the intensity monitors over the course of the data
collections.
The structure was solved by direct methods (SIR97
[19]) and refined by least-squares procedures on F2. All
H atoms attached to carbon were introduced in calcula-
Ru–S
Ru–N
S–C
2.446(3) (2.429(3)) 2.434(2) (2.423(2)) 2.427(3)
2.099(8) (2.095(8)) 2.112(5) (2.116(5)) 2.090(11)
1.731(10)
(1.724(10))
1.342(13)
(1.310(13))
1.722(6) (1.705(7)) 1.772(12)
N–C
1.307(8) (1.298(8)) 1.280(15)
S–Ru–N
Ru–S–C
S–C–N
66.5(2) (67.2(2))
80.2(3) (79.0(3))
66.9(2) (66.5(2))
79.2(2) (79.6(2)
66.9(3)
78.7(4)
108.9(7) (111.5(7)) 111.9(5) (112.1(5)) 109.2(10)
Ru–N–C 103.8(6) (102.3(6)) 102.0(4) (101.8(4)) 104.5(8)
,
tions in idealized positions [d(CH)=0.96 A] and
Table 4
treated as riding models. One of the phenyl rings is
disordered, the ring is oscillating between two positions
roughly distributed around the axis going through
C(71) to C(74). This disordered ring was treated using
the available tools in SHELXL-97 [20]. Least-squares
refinements were carried out by minimizing the function
ꢀw(F2o−F2c)2, where Fo and Fc are the observed and
calculated structure factors. The weighting scheme used
in the last refinement cycles was w=1/[|2(Fo2)+
(aP)2+bP] where P=(Fo2 +2F2c)/3. Models reached
convergence with R=ꢀ(ꢁꢁFoꢁ−ꢁFcꢁꢁ)/ꢀ(ꢁFoꢁ) and wR2=
,
Comparison of the torsional angles (°) and bond distances (A) within
the triazepine rings for complexes I and II
II (Ru-TAZS)
I (Ru-TAZO)
N1–N2–C3–N4
N2–C3–N4–C5
C3–N4–C5–C6
N4–C5–C6–C7
C5–C6–C7–N1
C6–C7–N1–N2
C7–N1–N2–C3
−76.77
4.67
37.81
−1.51
−38.09
−2.47
71.11
−25.325
−26.030
0.647
62.909
−75.192
4.914
53.584
N(1)–C(7)
N(1)–N(2)
N(2)–C(3)
N(4)–C(3)
N(4)–C(5)
C(5)–C(6)
C(6)–C(7)
1.303(9)
1.464(8)
1.414(8)
1.307(8)
1.403(8)
1.377(9)
1.427(10)
1.257(12)
1.406(12)
1.354(14)
1.342(13)
1.364(12)
1.522(14)
1.492(14)
{ꢀw(Fo2 −Fc2)2/ꢀw(Fo2)2}1/2
, having values listed in
Table 5.
The calculations were carried out with the SHELXL-97
program [20] using the integrated system WINGX(1.63)
[21]. Molecular views were realized with the help of
ORTEP [22]

270
M. Aitali et al. / Journal of Organometallic Chemistry 619 (2001) 265–270
Table 5
Chem. (2000) 83. (b) H. Brunner, B. Nuber, T. Tracht, Tetrahe-
dron: Asymmetry 9 (1998) 3763. (c) M. Shi, G.-X. Lei, Y.
Masaki, Tetrahedron Asymmetry 10 (1999) 2071. (d) D. Enders,
H. Gielen, J. Runsuik, K. Breuer, S. Brode, K. Boehn, Eur. J.
Inorg. Chem. (1998) 913.
Crystal data and structure refinement for Ru-TAZS
Empirical formula
Formula weight
Temperature (K)
Wavelength (A)
Crystal system
Space group
C42H46N6Ru2S4·CHCl3
1084.60
160(2)
0.71073
Triclinic
[6] (a) Y. Carcia, P.J.V. Konnigsbruggen, H. Kooijman, A.L. Spek,
J.G. Haasnoot, O. Kahn, Eur. J. Inorg. Chem. (2000) 307. (b)
R.H. Bode, J.E. Bol, W.L. Driessen, F.B. Hulsbergen, J. Reed-
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(e) D. Pfeiffer, M.J. Heeg, C.H. Winter, Angew. Chem. Int. Ed.
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Estuelas, F.J. Lahoz, L.A. Oro, J. Chem. Soc. Chem. Commun.
(1988) 793.
,
(
P1
Unit cell dimensions
,
a (A)
10.742(2)
14.595(3)
14.842(3)
99.88(3)
96.48(3)
90.97(3)
2276.2(8)
2
0.15×0.16×0.08
1.81–24.22
−125h512, −165k516,
−175l517
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
Volume (A )
Z
3
,
Crystal size (mm3)
q range for data collection (°)
Index ranges
[7] R.H. Bode, W.L. Driessen, F.B. Hulsbergen, J. Reedijk, A.L.
Spek, Eur. J. Inorg. Chem. (1999) 505.
[8] For a recent review, see: (a) R. Kempe, Angew. Chem. Int. Ed.
Engl. 39 (2000) 468. (b) D. Lucet, T. Legall, C. Mioskowski,
Angew. Chem. Int. Ed. Engl. 37 (1998) 2580.
Reflections collected
18423
Independent reflections
Completeness to q=24.22° (%)
Refinement method
6794 [Rint=0.1097]
92.7
[9] (a) B. Abouhamza, L. El Firdoussi, S. Allaoud, A. Karim, A.F.
Barrero, M. Quiros, Acta Crystallogr. Sect. C 55 (1999) 361. (b)
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Main Group Met. Chem. 18 (1995) 21. (d) A. Chiaroni, C.
Riche, L. El Firdoussi, A. Benharref, A. Karim, Acta Crystal-
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Full-matrix least-squares on
F2
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I\2|(I)]
R indices (all data)
6794/414/576
0.850
R1=0.0457, wR2=0.0752
R1=0.1077, wR2=0.0889
Largest difference peak and hole 0.653 and −0.796
−3
,
(e A
)
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Garcia-Granda, A. Gutierres-Rodriguez, Acta Crystallogr. Sect.
5. Supplementary material
Crystallographic data (excluding structure factors)
for the structure reported in this paper have been
deposited with the Cambridge Crystallographic Data
Centre as supplementary publication no. CCDC-
147735. Copies of the data can be obtained free of
charge on application to The Director, CCDC, 12
Union Road, Cambridge CB2 IEZ, UK (Fax: +44-
1223-336033; e-mail: deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk).
C
(2000) electronic paper, Data Validation Number
IUC0000163.
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