Synthesis, characterisation and X-ray structures of diorganotin(IV) and iron(III) complexes of dianionic terdentate Schiff base ligands

Article abstract of DOI:10.1016/j.jorganchem.2005.09.052

Diorganotin(IV) complexes, [SnR₂L] (1)-(4), (R = Me, Ph), of the terdentate Schiff bases N-[(2-pyrroyl)methylidene]-N′-tosylbenzene-1,2- diamine (H₂L¹) and N-[(2-hydroxyphenyl)metylidene]- N′-tosylbenzene-1,2-diamine (H

Full text of DOI:10.1016/j.jorganchem.2005.09.052

Journal of Organometallic Chemistry 691 (2006) 1321–1332
www.elsevier.com/locate/jorganchem
Synthesis, characterisation and X-ray structures of diorganotin(IV)
and iron(III) complexes of dianionic terdentate Schiff base ligands
´
´
Elena Labisbal, Laura Rodrıguez, Antonio Sousa-Pedrares, Monica Alonso, Araceli Vizoso,
*
´
´
´
Jaime Romero, Jose Arturo Garcıa-Vazquez, Antonio Sousa
Departamento de Quı´mica Inorga´nica, Universidad de Santiago de Compostela, Qumica Inorgnica, Campus Sur, Santiago de Compostela 15782, Spain
Received 18 July 2005; received in revised form 12 September 2005; accepted 12 September 2005
Available online 7 February 2006
Abstract
Diorganotin(IV) complexes, [SnR2L] (1)–(4), (R = Me, Ph), of the terdentate Schiff bases N-[(2-pyrroyl)methylidene]-N0-tosylben-
zene-1,2-diamine (H2L1) and N-[(2-hydroxyphenyl)metylidene]-N0-tosylbenzene-1,2-diamine (H2L2) have been synthesised. The com-
plexes were obtained by addition of the appropriate ligand to a methanol suspension of the corresponding diorganotin(IV) dichloride
in the presence of triethylamine. However, the reaction between the precursor [g5-C5H5Fe(CO)2]2SnCl2 and the Schiff bases in the pres-
ence of triethylamine gave ½Et3NHꢀ½FeL12ꢀ (5) and ½Et3NHꢀ½FeL22ꢀ (6), respectively. The crystal structures of the ligands and complexes
have been studied by X-ray diffraction. The structure of [SnR2L] complexes shows the tin to be five-coordinate in a distorted square
pyramidal environment with the dianionic ligand acting in a terdentate manner. In 5 and 6, the iron atom is in a slightly distorted octa-
hedral environment and is meridionally coordinated by two ligands. Spectroscopic data for the ligands and complexes (IR, 1H, 13C and
119Sn NMR and mass spectra) are discussed and related to the structural information.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Organotin(IV) complexes; Iron(III) complexes; Schiff base ligands; Amide ligand; Crystal structure; 119Sn NMR
1. Introduction
reviews dealing with the synthesis, structural behaviour
and biological applications of these materials have been
published [3]. In particular, complexes with Schiff bases
derived from amino acids [4–6] and ONO and NNO dian-
ionic terdentate Schiff bases have been widely reported [6–
12]. Recently, the synthesis and toxicological activity of
organotin(IV) compounds with a sulfonamide imine ligand
have been also described, although crystal structures for
these compounds were not reported [13].
As a continuation of our previous work dealing with
the study of the interaction of tin and diorganotin(IV)
with Schiff bases, we report here the synthesis and
characterisation of new dimethyl-, diphenyl- and di[(cyclo-
pentadienyldicabonyl)iron]tin(IV) complexes with [N-
(pyrroyl)methylidene]-N0-tosylbenzene-1,2-diamine (H2L1)
and [N-(hydoxyphenyl)methylidene]-N0-tosylbenzene-1,2-
diamine (H2L2). These ligands contain, in addition to a
pyrrole N–H or phenolic O–H group, respectively, a
Metal complexes of Schiff base ligands have played an
important role since the early days of Coordination Chem-
istry, not only from an inorganic point of view but also
because of the possible biological interest in such com-
pounds [1]. A great deal of work has been performed on
the synthesis and characterisation of transition metal com-
pounds with these ligands. More recently, organotin com-
plexes with Schiff base ligands have been studied, not
only due to their novel structural features caused by the
multidenticity of these ligands but also in view of their
pharmacological and antitumour activity [2]. Several
*
Corresponding author. Tel.: +34 981563100x14245; fax: +34
81597225.
E-mail address: qiansoal@usc.es (A. Sousa).
0022-328X/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.09.052

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E. Labisbal et al. / Journal of Organometallic Chemistry 691 (2006) 1321–1332
OH
H
H
N
H
N
N
Tos
Tos
N
H
N
H
H2L1
H2L2
Fig. 1. H2L1 and H2L2.
sulfonamide N–H group (Fig. 1). The nature of the groups
bonded to tin was chosen in an effort to assess whether the
steric hindrance produced by them influences the structure
of the complexes formed.
Fig. 2. The molecular structure of H2L1, showing the intra- and
intermolecular hydrogen bonding.
2. Results and discussion
In the case of [g5-C5H5Fe(CO)2]2SnCl2, the reaction
produced crystalline solids of composition ½Et3NHꢀ½FeL12ꢀ
(5) and ½Et3NHꢀ½FeL22ꢀ (6). The structures of both of these
compounds show an iron atom octahedrally coordinated
by two dianionic terdentate ligands in a meriodional way
(vide infra).
2.1. Synthesis
Room temperature reaction between SnR2Cl2 (R = Me,
Ph) and an equimolar amount of the Schiff base ligand,
[H2L], in methanol in the presence of triethylamine, Eq.
(1), led to yellow crystalline compounds 1–4. The analytical
data for these complexes are consistent with the formula
[SnR2L].
2.2. Molecular structures of (H2L1) and (H2L2)
ORTEP views of [H2L1] and [H2L2] are shown in Figs. 2
and 3 along with the atom-labelling scheme. Selected bond
lengths and angles, with the estimated deviations, are given
in Tables 1 and 2.
The structural parameters for both ligands are as
expected, with a relatively short bond distance for the
R2SnCl2 þ H2L þ 2NEt3 ! ½SnR2Lꢀ þ 2HNEt3Cl
ð1Þ
These compounds are stable to air and moderately solu-
ble in methanol and chlorinated solvents. Crystallisation
from the mother liquor afforded crystals of 1–4 that were
suitable for X-ray studies.
Fig. 3. The molecular structure of H2L2, showing the intra- and intermolecular hydrogen bonding.

E. Labisbal et al. / Journal of Organometallic Chemistry 691 (2006) 1321–1332
1323
Table 1
1
˚
Selected bond distances (A) and angles (ꢁ) for [H2L ]
S(1)–O(1)
S(1)–O(2)
S(1)–N(3)
S(1)–C(12)
1.4269(16)
1.4329(16)
1.620(2)
N(1)–C(4)
N(2)–C(5)
N(2)–C(6)
N(3)–C(11)
1.358(3)
1.272(3)
1.410(3)
1.427(3)
1.758(2)
N(1)–C(1)
1.348(3)
O(1)–S(1)–O(2)
O(1)–S(1)–N(3)
O(2)–S(1)–N(3)
O(1)–S(1)–C(12)
O(2)–S(1)–C(12)
118.64(10)
108.89(11)
104.90(11)
107.85(10)
108.26(11)
N(3)–S(1)–C(12)
N(1)–C(4)–C(5)
N(2)–C(5)–C(4)
C(5)–N(2)–C(6)
C(11)–N(3)–S(1)
107.86(10)
122.5(2)
122.5(2)
121.10(19)
123.03(16)
1
˚
Hydrogen bonds for [H2L ] (A and deg)
D–Hꢁ ꢁ ꢁA
d(D–H)
d(Hꢁ ꢁ ꢁA)
d(Dꢁ ꢁ ꢁA)
\(DHA)
N(1)–H(1)ꢁ ꢁ ꢁO(2)#1
N(3)–H(3)ꢁ ꢁ ꢁN(2)
N(3)–H(3)ꢁ ꢁ ꢁO(2)#1
0.85(2)
0.81(2)
0.81(2)
2.16(3)
2.25(2)
2.41(2)
3.004(3)
2.677(3)
3.147(3)
176(2)
113.0(19)
152(2)
Symmetry transformations used to generate equivalent atoms: #1 ꢂx + 1/2, ꢂy + 1/2, ꢂz + 2.
Table 2
cules is shown in Fig. 4 along with the atomic numbering
scheme adopted. The asymmetric unit of 2 contains one
complex molecule and a methanol molecule. The molecular
structure is shown in Fig. 5 together with the atomic
2
˚
Selected bond distances (A) and angles (ꢁ) for [H2L ]
S(1)–O(3)
S(1)–O(2)
S(1)–N(2)
S(1)–C(14)
1.416(3)
1.442(3)
1.625(3)
1.765(4)
N(1)–C(7)
N(1)–C(8)
N(2)–C(9)
O(1)–C(1)
1.277(5)
1.412(4)
1.447(5)
1.342(4)
O(3)–S(1)–O(2)
O(3)–S(1)–N(2)
O(2)–S(1)–N(2)
O(3)–S(1)–C(14)
O(2)–S(1)–C(14)
N(2)–S(1)–C(14)
C(7)–N(1)–C(8)
120.0(2)
108.3(2)
O(1)–C(1)–C(6)
N(1)–C(7)–C(6)
C(9)–C(8)–N(1)
C(13)–C(8)–N(1)
C(10)–C(9)–N(2)
C(8)–C(9)–N(2)
C(9)–N(2)–S(1)
121.3(3)
123.5(3)
119.1(3)
122.2(3)
119.8(4)
119.8(3)
120.8(2)
104.69(16)
107.60(18)
108.39(18)
107.35(15)
118.6(3)
Hydrogen bonds for H2L2 (A and deg)
˚
D–Hꢁ ꢁ ꢁA
d(D–H)
d(Hꢁ ꢁ ꢁA)
d(Dꢁ ꢁ ꢁA)
\(DHA)
O(1)–H(1)ꢁ ꢁ ꢁN(1)
0.90(7)
1.89(6)
2.32(5)
2.649(4)
3.030(4)
141(5)
143(4)
N(2)–H(2)ꢁ ꢁ ꢁO(2)#1 0.83(5)
Symmetry transformations used to generate equivalent atoms: #1 ꢂx + 1,
y, ꢂz.
Fig. 4. The molecular structure of [L1SnMe2].
˚
imine group; 1.272(3) and 1.277(5) A, respectively, for
[H2L1] and [H2L2], which confirms the multiple nature of
this bond [14]. The structural resolution confirms the pres-
ence, in both compounds, of intra- and intermolecular
hydrogen bonds. In [H2L1], the intramolecular hydrogen
bond is established between the NH(amide) and the imine
˚
˚
nitrogen [N(3)–H 0.81(2) A, N(2)ꢁ ꢁ ꢁH 2.25(2) A] (Table 1)
and in H2L2 between the hydoxyl group and the imine
˚
˚
group [O–H 0.90(7) A, Nꢁ ꢁ ꢁH 1.89(6) A] (Table 2). In
addition, in both ligands intermolecular hydrogen bonds
are observed involving the N–H groups and the oxygen
atoms of the sulfonyl group.
2.3. Molecular structures of [SnMe2L1] Æ 1/2(MeOH) (1)
and [SnPh2L1] Æ MeOH (2)
The asymmetric unit of 1 contains two independent mol-
ecules that are chemically identical and two half molecules
of MeOH. For the sake of clarity, only one of these mole-
Fig. 5. The molecular structure of [L1SnPh2].

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E. Labisbal et al. / Journal of Organometallic Chemistry 691 (2006) 1321–1332
numbering scheme adopted. A selection of bond distances
and angles for these two complexes is given in Tables 3 and
4.
for pentacoordinated organotin(IV) compounds with Schiff
base ligands [11].
In the coordinated ligands, the rings that contain the
donor atoms are planar, as are the C–C–N–C atoms across
the imine double bond (rms 0.023 for 1 and 0.014 for 2).
This arrangement means that this part of the ligand as a
whole can be considered planar, with the tin centre also
located in this plane. Coordination of the ligand to the
metal leads to an increase in the bond distance to the imine
group; this is a consequence of the loss of multiple bond
character due to coordination of the nitrogen to the metal.
In 1, the methanol solvent molecules are located in holes
within the network and there are no noteworthy intermo-
lecular contacts. However, in 2 the solvent molecules are
involved in hydrogen bonding with an oxygen atom of a
sulfonyl group.
In both compounds, the metal centre is coordinated to
the carbon atoms of the two organic groups and by a tri-
dentate ligand that is bonded to the metal through the
three nitrogen atoms. The metal environment is highly dis-
torted, with the coordination polyhedron around the tin
having a distorted square pyramidal geometry, s = 0.22
and s = 0.23 for 1 and 2, respectively [15]. In this arrange-
ment, the imine N is located at the vertex of the pyramid
and the carbon atoms and the other two nitrogens form
the base. The low values of the N–Sn–N chelate angles,
˚
which are in the range 72.77(6)–74.72(6) A for both com-
pounds, are significantly different to those expected for a
regular geometry and this deviation is the main cause of
distortion in both structures.
The Sn–C bond distances in both compounds are in the
2.4. Molecular structure of [SnMe2L2] (3) and [SnPh2L2]
(4)
˚
range 2.105(2)–2.139(4) A and these are very similar to
those found in other organotin(IV) compounds with the
same coordination number [16]. The Sn–N(imine) distances
The molecular structure of 3 is shown in Fig. 6 and one
of the two independent molecules of 4 in the asymmetric
unit is shown in Fig. 7. Selected bond distances and angles
for the two compounds are given in Tables 5 and 6.
˚
˚
have average values of 2.1814(16) A for 1 and 2.174(3) A
for 2, and these are slightly shorter than the corresponding
Sn–N(pyrrolato) and Sn–N(amidato) bonds, which are in
˚
the range 2.210(4)–2.2374(17) A. However, these bond dis-
tances are consistent with those found in complexes 3 and 4
(vide infra) as well as with those reported in the literature
Table 3
1
˚
Selected bond distances (A) and angles (ꢁ) for [SnMe2L ] Æ 1/2(MeOH) (1)
Molecule A
Molecule B
Sn(1)–C(19)
2.116(2)
Sn(2)–C(39)
2.105(2)
Sn(1)–C(20)
2.116(2)
Sn(2)–C(40)
2.107(2)
Sn(1)–N(2)
Sn(1)–N(1)
Sn(1)–N(3)
N(2)–C(5)
2.1727(15)
2.2111(18)
2.2183(18)
1.317(2)
Sn(2)–N(5)
Sn(2)–N(4)
Sn(2)–N(6)
N(5)–C(25)
2.1902(16)
2.2247(18)
2.2374(17)
1.309(3)
Fig. 6. The molecular structure of [L2SnMe2].
C(19)–Sn(1)–C(20)
C(19)–Sn(1)–N(2)
C(20)–Sn(1)–N(2)
C(19)–Sn(1)–N(1)
C(20)–Sn(1)–N(1)
N(2)–Sn(1)–N(1)
C(19)–Sn(1)–N(3)
C(20)–Sn(1)–N(3)
N(2)–Sn(1)–N(3)
N(1)–Sn(1)–N(3)
134.05(9)
C(39)–Sn(2)–C(40)
C(39)–Sn(2)–N(5)
C(40)–Sn(2)–N(5)
C(39)–Sn(2)–N(4)
C(40)–Sn(2)–N(4)
N(5)–Sn(2)–N(4)
C(39)–Sn(2)–N(6)
C(40)–Sn(2)–N(6)
N(5)–Sn(2)–N(6)
N(4)–Sn(2)–N(6)
144.46(9)
108.81(7)
117.10(8)
95.86(8)
94.12(8)
74.72(6)
96.05(8)
98.95(8)
72.93(6)
147.60(6)
106.17(8)
109.30(8)
95.10(8)
92.11(8)
74.48(7)
95.36(8)
97.14(8)
72.77(6)
147.21(6)
Table 4
1
˚
Selected bond distances (A) and angles (ꢁ) for [SnPh2L ] Æ MeOH (2)
Sn(1)–C(25)
Sn(1)–C(19)
Sn(1)–N(2)
2.132(4)
2.139(4)
2.174(3)
Sn(1)–N(1)
N(3)–C(11)
N(2)–C(5)
2.222(4)
1.413(4)
1.315(4)
Sn(1)–N(3)
2.210(4)
C(25)–Sn(1)–C(19)
C(25)–Sn(1)–N(2)
C(19)–Sn(1)–N(2)
C(25)–Sn(1)–N(3)
C(19)–Sn(1)–N(3)
133.51(13)
114.90(11)
111.22(13)
98.86(12)
99.57(13)
N(2)–Sn(1)–N(3)
C(25)–Sn(1)–N(1)
C(19)–Sn(1)–N(1)
N(2)–Sn(1)–N(1)
N(3)–Sn(1)–N(1)
73.13(10)
91.36(13)
95.38(14)
74.48(13)
147.41(11)
Fig. 7. The molecular structure of [L2SnPh2].

E. Labisbal et al. / Journal of Organometallic Chemistry 691 (2006) 1321–1332
1325
Table 5
Selected bond distances (A) and angles (ꢁ) for [SnMe2L ] (3)
The distortion is mainly due to the rigidity of the five-mem-
bered N(1)–Sn(1)–N(2) chelate rings, with angles of
73.15(12)ꢁ and 73.43(9)ꢁ (average value) in 3 and 4,
respectively.
2
˚
Sn(1)–C(22)
Sn(1)–C(21)
Sn(1)–N(2)
Sn(1)–N(1)
2.105(5)
2.111(5)
2.173(3)
2.224(3)
S(1)–N(1)
Sn(1)–O(1)
N(2)–C(7)
1.597(3)
2.120(3)
1.305(5)
˚
The Sn–C bond distances [average values of 2.108(5) A
˚
in 3 and 2.116(3) A in 4] are very similar to one another
C(21)–Sn(1)–C(22)
C(21)–Sn(1)–O(1)
C(21)–Sn(1)–N(1)
C(21)–Sn(1)–N(2)
C(22)–Sn(1)–N(1)
133.0(2)
C(22)–Sn(1)–N(2)
O(1)–Sn(1)–N(2)
O(1)–Sn(1)–N(1)
N(1)–Sn(1)–N(2)
C(22)–Sn(1)–O(1)
110.11(17)
81.95(12)
154.82(12)
73.15(12)
94.36(18)
and are comparable to those described above for com-
plexes 1 and 2 as well as those generally found in organotin
complexes with the same coordination number. In terms of
89.42(18)
98.31(18)
116.79(17)
97.62(18)
˚
˚
the Sn–N(imine) [2.173(3) and 2.183(2) A (average value)]
and Sn–N(amide) [2.224(3) and 2.196(3) A (average value)]
bond distances for 3 and 4, these are again very similar to
one another and to those described for the complexes
above. The Sn–O bond distances are 2.120(2) and
Table 6
2
˚
Selected bond distances (A) and angles (ꢁ) for [SnPh2L ] (4)
Molecule A
Molecule B
˚
2.126(3) A (average value), respectively, for 3 and 4 and
Sn(1)–C(21)
Sn(1)–C(27)
Sn(1)–O(1)
Sn(1)–N(1)
2.112(3)
2.115(3)
2.139(2)
Sn(2)–C(53)
Sn(2)–C(59)
Sn(2)–O(4)
Sn(2)–N(3)
2.114(3)
2.125(3)
2.114(2)
are similar to those found in other organotin complexes
with Schiff base ligands containing oxygen donor atoms
[8,9].
2.184(2)
2.181(2)
In the ligand, the bond distances and angles are as one
would expect and are similar to those found in the free
ligand – for this reason these values do not warrant further
Sn(1)–N(2)
N(1)–C(7)
2.195(3)
1.306(4)
Sn(2)–N(4)
N(3)–C(39)
2.197(2)
1.305(4)
C(21)–Sn(1)–C(27)
C(21)–Sn(1)–O(1)
C(27)–Sn(1)–O(1)
C(21)–Sn(1)–N(1)
C(27)–Sn(1)–N(1)
O(1)–Sn(1)–N(1)
C(21)–Sn(1)–N(2)
C(27)–Sn(1)–N(2)
O(1)–Sn(1)–N(2)
N(1)–Sn(1)–N(2)
130.48(12)
91.88(10)
90.57(10)
114.16(10)
114.97(10)
80.10(9)
97.82(11)
101.63(11)
153.25(9)
73.18(9)
O(4)–Sn(2)–C(53)
O(4)–Sn(2)–C(59)
C(53)–Sn(2)–C(59)
O(4)–Sn(2)–N(3)
C(53)–Sn(2)–N(3)
C(59)–Sn(2)–N(3)
O(4)–Sn(2)–N(4)
C(53)–Sn(2)–N(4)
C(59)–Sn(2)–N(4)
N(3)–Sn(2)–N(4)
93.37(10)
88.12(10)
131.02(11)
81.80(8)
109.48(10)
119.14(10)
154.97(8)
99.37(10)
99.32(11)
73.68(8)
˚
discussion. The C–N(imine) bond distance is 1.305(5) A in
both compounds and is again slightly longer that the corre-
˚
sponding distance in the free ligand [1.277(5) A].
2.5. Molecular structure of [Et3NH][FeL12] ꢁ 1=2(H2O) (5)
and [Et3NH][FeL22] (6)
The asymmetric unit in 5 contains one complex molecule
and half a water molecule. The molecular structures of the
two compounds are shown in Figs. 8 and 9 along with the
atomic numbering scheme adopted. Selected bond dis-
tances and angles are given in Tables 7 and 8.
Structural analysis of the compounds showed that both
complexes consist of a complex anion, ½FeL12ꢀꢂ or ½FeL22ꢀꢂ,
and the counterion [Et3NH]+ formed by protonation of the
triethylamine.
In the anion, the iron is coordinated to two dianionic
ligands, which in 5 are bonded to the metal through the
three nitrogen atoms and in 6 through the nitrogen atoms
and the oxygen. In both cases, the environment around the
metal is a highly distorted octahedron, where a major cause
of distortion is the low vale of the five-membered chelate
angle formed by two nitrogen atoms of the same ligand –
this angle has values of 74.57(13)ꢁ and 77.18(12)ꢁ in 5
and 6, respectively. This small angle in turn leads to the
bond angles involving donor atoms in the trans position
to have values in the range 150.58(14)–174.70(12)ꢁ, which
is significantly different to the theoretical value expected
for a regular geometry.
Fig. 8. The molecular structure of ½Et3NHꢀ½FeL12ꢀ.
Both compounds consist of molecular units in which the
metal atom is pentacoordinated by the two carbon atoms
of the two organic substituents as well as by the phenolate
oxygen, the imine nitrogen and the amidate nitrogen of the
dianionic ligand.
The coordination polyhedron around the tin is a dis-
torted square-based pyramid (s = 0.38 and 0.36 for 3 and
4, respectively), with the carbon atoms, the phenolate oxy-
gen and the amide nitrogen forming the plane at the base of
the pyramid and the imine nitrogen in the apical position.
In both complexes, the three donor atoms of the ligands
are arranged in the metal environment in such a way that
the meridional isomers are formed, with the two oxygen
atoms in 6 in the cis positions.
The Fe–N bond lengths are in the range 2.090(4)–
˚
2.146(3) A and the Fe–O bond lengths are between
˚
1.953(3) and 1.958(4) A in compound 6. These values are

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E. Labisbal et al. / Journal of Organometallic Chemistry 691 (2006) 1321–1332
Fig. 9. The molecular structure of ½Et3NHꢀ½FeL22ꢀ.
Table 7
bonding interaction with one of the oxygen atoms of the
sulfonyl group in the complex.
1
˚
Selected bond distances (A) and angles (ꢁ) for ½Et3NHꢀ½FeL2ꢀ ꢁ 1=2ðH2OÞ
(5)
Fe(1)–N(4)
Fe(1)–N(1)
2.090(4)
2.099(4)
Fe(1)–N(6)
Fe(1)–N(2)
2.094(3)
2.107(3)
2.6. Spectroscopy studies
Fe(1)–N(5)
2.112(3)
Fe(1)–N(3)
2.146(3)
N(2)–C(5)
1.295(5)
N(5)–C(23)
1.302(5)
The IR spectra of the ligands (experimental part) are
consistent with the formation of the Schiff bases. Both
ligands show the band corresponding to m(N–H) from the
amide group (3230 and 3274 cmꢂ1, respectively). A band
at 3353 cmꢂ1 for H2L1 is assigned to m(N–H) pyrrole and
weak bands in the range 3100–2900 cmꢂ1 for H2L2 are
assigned to m(OH) involved in intramolecular hydrogen
bonding (vide supra). The spectra also show strong bands
at 1618 and 1612 cmꢂ1, which are attributed to m(C@N).
The spectra of the complexes do not contain bands corre-
sponding to m(OH) and m(N–H), confirming the presence
of the dianionic form of the ligand in the complexes. The
IR spectra of the complexes also show a sharp band in
the region 1609–1580 cmꢂ1, attributed to m(C@N), which
is shifted to lower frequency on going from the free ligand
to the complexes. This is indicative of the coordination of
the azomethine nitrogen to the metal [18] and is consistent
with the X-ray diffraction studies (vide supra).
N(4)–Fe(1)–N(6)
N(6)–Fe(1)–N(1)
N(6)–Fe(1)–N(2)
N(4)–Fe(1)–N(5)
N(1)–Fe(1)–N(5)
N(4)–Fe(1)–N(3)
N(1)–Fe(1)–N(3)
N(5)–Fe(1)–N(3)
150.68(14)
91.78(14)
119.06(13)
75.95(14)
95.57(14)
92.18(14)
150.59(14)
116.80(13)
N(4)–Fe(1)–N(1)
N(4)–Fe(1)–N(2)
N(1)–Fe(1)–N(2)
N(6)–Fe(1)–N(5)
N(2)–Fe(1)–N(5)
N(6)–Fe(1)–N(3)
N(2)–Fe(1)–N(3)
93.56(14)
90.21(14)
76.58(14)
75.02(14)
161.98(14)
97.16(13)
74.57(13)
Table 8
2
˚
Selected bond distances (A) and angles (ꢁ) for ½Et3NHꢀ½FeL2ꢀ (6)
Fe(1)–O(1)
Fe(1)–N(1)
Fe(1)–N(3)
O(1)–C(1)
N(3)–C(27)
O(1)–Fe(1)–O(4)
O(1)–Fe(1)–N(1)
O(4)–Fe(1)–N(1)
N(1)–Fe(1)–N(4)
O(1)–Fe(1)–N(3)
O(4)–Fe(1)–N(2)
N(3)–Fe(1)–N(4)
N(3)–Fe(1)–N(2)
1.953(3)
2.128(3)
2.133(3)
1.321(4)
Fe(1)–O(4)
Fe(1)–N(4)
Fe(1)–N(2)
O(4)–C(21)
1.959(4)
2.133(3)
2.141(3)
1.310(4)
1.291(5)
88.07(11)
88.07(11)
163.87(11)
86.69(11)
161.96(10)
76.12(11)
92.20(11)
1.303(5)
N(1)–C(7)
93.11(10)
86.65(10)
88.02(10)
108.11(11)
93.91(10)
91.61(11)
77.18(12)
103.74(11)
O(4)–Fe(1)–N(4)
O(1)–Fe(1)–N(4)
O(4)–Fe(1)–N(4)
O(4)–Fe(1)–N(3)
O(1)–Fe(1)–N(2)
N(1)–Fe(1)–N(2)
N(4)–Fe(1)–N(2)
The ligands and tin complexes were also studied in solu-
1
tion by H and 13C NMR spectroscopy and, in the case of
the tin complexes, by 119Sn NMR spectroscopy.
1
The H NMR spectra of the complexes do not contain
peaks corresponding to –NH and –OH groups of the
ligands, again confirming deprotonation in the synthetic
procedure. The imine proton peaks appear in the range
8.7–8.6 ppm for the different tin complexes and are shifted
downfield with respect to the corresponding signals in the
free ligands. In all cases, these signals show satellite peaks
as expected, i.e., similar to those found in other octahedral
Fe(III) complexes with Schiff base ligands [17], and do not
warrant further discussion. In both complexes the NH
group of the cation [Et3NH]+ is involved in a hydrogen

E. Labisbal et al. / Journal of Organometallic Chemistry 691 (2006) 1321–1332
1327
due to coupling of the proton with 117Sn and 119Sn nuclei.
[M+ ꢂ Ph] and [M+ ꢂ Ph2] are also observed in the spectra
of 2 and 4.
3
The J(117/119Sn–1H) values are in the range 43.3–69.4 Hz
for the four complexes. The presence of these satellites
indicates that the Sn–N bond is retained in solution. The
spectra also show signals due to the aromatic and pyrrole
ring protons. The signal at 7.9 ppm in the diphenyltin
derivatives 2 and 4 is assigned to the ortho protons in the
phenyl rings of the organometallic fragment and these sig-
nals also have satellites due to coupling with the tin atom
[3J(117/119Sn–1H) of 89.1 and 86.0 Hz for each of these com-
plexes]. The highfield regions in the spectra of dimethyltin
derivatives 1 and 3 show signals at 1.1 ppm for both
complexes and these are due to the methyl groups in the
organometallic fragment. These signals once again have
satellites due to coupling with tin [2J(117/119Sn–1H) 79.9
and 80.1 Hz]. The data described above are all consistent
with those observed for other pentacoordinated diorgano-
tin complexes containing Schiff base ligands [11]. Substitu-
tion of these values into the Lockhart–Manders equation,
h = 0.0161|2J|2 ꢂ 1.32|2J| + 133.4 [19] (an empirical rela-
tionship between the coupling constant and C–Sn–C bond
angle), affords values of 130.7ꢁ and 131.0ꢁ for the C–Sn–C
angle in the two complexes. These values are in agreement
with those determined in the solid state (Tables 3 and 5),
confirming that the coordination polyhedron present in
the solid state persists in chloroform solution.
3. Conclusions
In this report, we have described the products obtained
by reacting a series of diorganotin(IV) dichloride R2SnCl2
(R = Me, Ph, g5-C5H5Fe(CO)2) and the ligands N-[(2-pyr-
royl)methylidene]-N0-tosylbenzene-1,2-diamine (H2L1) and
N-[(2-hydroxyphenyl)metylidene]-N0-tosylbenzene-1,2-di-
amine (H2L2) in methanol in presence of triethylamine.
When R is Me or Ph, diorganotin(IV) complexes of the
general formula R2SnL have been synthesised, in which
the tin atom is five-coordinated in a distorted square pyra-
midal environment with the ligands acting in a terdentate
manner. However, in the case of the [g5-C5H5Fe-
(CO)2]2SnCl2 compounds of composition [Et3N][FeL2]
are isolated. These results are summarised in Scheme 1.
4. Experimental
4.1. General considerations
Dimethyltin dichloride (Aldrich), diphenyltin dichloride
(Aldrich) di(cyclopentadienyldicarbonyl)iron (Aldrich) and
all other reagents were used without further purification.
N-tosyl-1,2-diaminobenzene was prepared by the reaction
of 1,2-phenylenediamine and toluenesulfonyl chloride in
pyridine as described in [22]. Di[(cyclopentadienyldica-
bonyl)iron]tindichloride was synthesised by reaction of
SnCl2 Æ 2H2O and di(cyclopentadienyldicarbonyl)iron in
MeOH and AcOEt as described in [23].
The 13C NMR spectra of the complexes contain the sig-
nals for the different carbon atoms. The signal due to the
azomethine is observed at low field (145.8–165.8 ppm)
and this is shifted slightly on going from ligands to com-
plexes. A group of signals can be observed in the region
142–113 ppm and these correspond to the carbon atoms
of the rings in the ligand. The complexity of these signals
precludes their unambiguous assignment. For this reason,
and also due to solubility issues, it was not possible to
determine values for the Sn–C coupling constants in these
compounds.
4.2. Synthesis of ligands
4.2.1. Synthesis of [N-(pyrroyl)methylidene]-N0-
tosylbenzene-1,2-diamine (H2L1)
The 119Sn NMR spectra of these complexes were also
recorded at room temperature in Cl3CD using SnMe4 as
an external standard. The spectra of the complexes show
a singlet at ꢂ188.4 and ꢂ195.5 ppm for 1 and 3, respec-
tively, and at ꢂ332.9 and ꢂ357.8 ppm for 2 and 4, respec-
tively. It is well known that 119Sn chemical shifts are very
sensitive to changes in the coordination number of tin
and to the nature of the groups directly attached to the
tin atom [20]. The chemical shifts for the complexes
reported here are within the expected range for dimethyl-
and diphenyltin(IV) complexes with a coordination num-
ber of five [21].
The diorganotin compounds were also characterised by
mass spectrometry using electrospray or FAB(m/z) tech-
niques. The molecular ion peak is observed at m/z 487,
515, 611 and 638 for 1–4, respectively. Other peaks corre-
sponding to fragments of the parent ions due to loss of dif-
ferent groups from the compounds are also observed. For
example, a peak at m/z 302 is observed in the spectrum
of 3 due to [M+ ꢂ Ts] and fragments associated with
This Schiff base was prepared by heating under reflux an
ethanolic solution of equimolar amounts of pyrrol-2-alde-
hyde (0.95 g, 10 mmol) and N-tosyl-1,2-diaminobenzene
(2.63 g, 10 mmol) using a Dean–Stark trap. The water pro-
duced in the reaction was removed and the solution was
concentrated. The resulting solid was filtered off, washed
with ether and dried under vacuum. Yield 70%. Anal. Calc.
for C18H17N3O2S: C, 63.7; H, 5.0; N, 12.4; S, 9.4. Found:
C, 63.2; H, 5.0; N, 12.4; S, 9.2%. IR (KBr, cmꢂ1): 3353
(s); 3230 (m), 1618 (s), 1587 (m), 1466 (m), 1421 (s), 1334
(s), 1159 (s), 1127 (m), 1091 (m), 761 (s). 1H NMR (CD3Cl,
ppm): d, 10.2 [s, 1H, NH(pyrrole)], 9.3 [s, 1H, NH(amide)],
8.4 (s, 1H, HC@N), 7.8–6.2 (m, 11H, aromatic), 2.1 (s, 3H,
CH3). 13C NMR (CD3Cl, ppm): d , 147.8 (s, C@N), 143.5–
117.2 (s, phenyl rings), 126.4, 116.4, 110.6 (s, pyrrole ring),
21.5 (s, CH3-tolyl). FAB MS: m/z: 340 (M+); 184
(M+ ꢂ {O2S-tolyl}).
Crystallisation from ethanol gave yellow crystals suit-
able for X-ray studies.

1328
E. Labisbal et al. / Journal of Organometallic Chemistry 691 (2006) 1321–1332
a
NTs
R
N
Sn
R2SnCl2 (R = Me, Ph)
MeOH, Et3N
N
R
N
NHTs
_
NH
N
NTs
N
η5
Fe
[
-C5H5Fe(CO)2]2SnCl2
N
N
MeOH, Et3N
TsN
b
NTs
R
N
Sn
R
R2SnL (R = Me, Ph)
MeOH, Et3N
O
NHTs
N
_
OH
O
NTs
N
N
Fe
[η5-C5H5Fe(CO)2]2SnCl2
O
MeOH, Et3N
TsN
Scheme 1. General syntheses of compounds with (a) H2L1, (b) H2L2.
4.2.2. Synthesis of [N-(hydroxyphenyl)methylidene]-N0-
tosylbenzene-1,2-diamine (H2L2)
4.3. Synthesis of complexes
This compound was prepared in an analogous manner
to the previous ligand, using N-tosyl-1,2-diaminobenzene
(1.0 g, 3.82 mmol) and salicylaldehyde (0.4 mL, 3.82 mmol)
in refluxing ethanol using a Dean–Stark apparatus. The
resulting solid was washed with ether and dried under vac-
uum. Yield 75%. Anal. Calc. for C20H18N2O3S: C, 65.6; H,
4.9; N, 7.6; S, 8.7. Found: C, 65.3; H, 4.9; N, 7.8; S, 8.4. IR
(KBr, cmꢂ1): 3274 (s), 3100–2900 (w), 1612 (s), 1595 (s),
1570 (s), 1481 (s), 1326 (s); 1275 (s), 1151 (s), 909 (m),
4.3.1. [SnMe2L1] (1)
To a stirred suspension of H2L1 (0.20 g, 0.60 mmol) in
MeOH (15 mL) at room temperature was added Et3N
(1.2 mL, 1.29 mmol) and, subsequently, SnMe2Cl2
(0.065 g, 0.30 mmol) in methanol (5 mL). The reaction mix-
ture was concentrated and the resulting crystalline yellow
solid was filtered off, washed with ether and dried under
vacuum. Yield 68%. Anal. Calc. for C20H21N3O2SSn: C,
49.1; H, 4.3; N, 8.6; S, 6.5. Found: C, 49.1; H, 4.5; N,
8.8; S, 6.2%.
1
755 (s), 684 (m). H NMR (CD3Cl, ppm): d, 11.8 (s, 1H,
OH), 8.1 (s, 1H, HC@N), 7.7–6.5 (m, 12H, aromatic), 2.3
(s, 3H, CH3). 13C NMR (CD3Cl, ppm): d, 165.0 (s, CO),
160.3 (s, C@N), 143.3–117.3 (s, phenyl rings) 21.6 (s,
CH3-tolyl). MS (ES): m/z: (MH+): 367 (M+); 211
(M+ ꢂ {O2S-tolyl}).
IR (KBr, cmꢂ1): 1585 (s), 1562 (s), 1455 (m), 1422 (m),
1337 (s), 1305 (s); 1140 (s), 1045 (s), 840 (m), 766 (m),
741 (m), 707 (m), 633 (m), 566 (s), 546 (m).
1H NMR (CD3Cl, ppm): d, 8.6 [s, 1H, 3J(119/117Sn–
1H) = 56 Hz, HC@N], 7.9–6.2 (m, 11H, aromatic), 2.3
(s, 3H, CH3), 1.1 [s, 6H, 2J(119/117Sn–1H) = 79.9 Hz,
Sn–CH3]. 13C NMR (CD3Cl, ppm): d, 145.8 (s, C@N),
Crystallisation from ethanol gave yellow crystals suit-
able for X-ray studies.

E. Labisbal et al. / Journal of Organometallic Chemistry 691 (2006) 1321–1332
1329
142.4–117.3 (s, phenyl rings) 130.8, 120.1, 113.3, (s, pyrrole
3J(119/117Sn = 50.2 Hz),
HC@N],
7.9
[dd,
4H,
ring), 21.4 (s, CH3-tolyl); 4.8 (s, Sn–CH3). 119Sn NMR
(CD3Cl, ppm): d, ꢂ188.4.
3J(119,117Sn = 86.0 Hz) Sn–C6H2H3], 7.7–6.6 (m, 12H, aro-
matic), 2.2 (s, 3H, CH3). 13C NMR (CD3Cl, ppm): d, 170.8
(CO), 165.8 (s, C@N), 142.5–116.5 (s, phenyl rings), 21.3
(CH3-tolyl). 119Sn NMR(CD3Cl, ppm): d, ꢂ357.8. MS (ES):
m/z: (MH+): 638 (M+); 561 (M+ ꢂ Ph); 483 (M+ ꢂ Ph2).
From the mother liquor, white crystals suitable for X-
ray studies were obtained.
FAB MS: m/z: 487 (M+); 302 (M+ ꢂ {O2S-tolyl}).
From the mother liquor, white crystals of [SnMe2L1] Æ
1/2(CH3OH) suitable for X-ray studies were obtained.
4.3.2. [SnPh2L1] (2)
A similar procedure to that described above was fol-
lowed, starting from H2L1 (0.20 g, 0.60 mmol) in methanol
(15 ml), Et3N (1.2 mL, 1.29 mmol) and SnPh2Cl2 (0.10 g,
0.30 mmol) in methanol (5 mL). Yield 72%. Anal. Calc.
for C30H25N3O2SSn: C, 58.9; H, 4.1; N, 6.9; S, 5.2. Found:
C, 58.7; H, 4.2; N, 6.8; S, 5.1%. IR (KBr, cmꢂ1): 1585 (s),
1561 (s), 1389 (m), 1293 (s), 1163 (m), 1143 (s), 965 (m), 696
(m). 1H NMR (CD3Cl, ppm): d, 8.7 [s, 1H,
3J(119/117Sn–1H = 69.4 Hz), HC@N]; 7.9 [dd, 4H,
3J(119/117Sn–1H = 89.1 Hz) Sn–C6H2H3] 7.7–6.3 (m, 12H,
aromatic); 2.3 (s, 3H, CH3). 13C NMR (CD3Cl, ppm): d,
145.8 (s, C@N), 142.2–117.2 (s, phenyl rings), 130.0, 118,
117.2, 113.2, (s, pyrrole ring), 21.4 (CH3-tolyl). 119Sn
NMR (CD3Cl, ppm): d, ꢂ332.9. FAB MS: m/z: 611
(M+); 534 (M+ ꢂ Ph); 456 (M+ ꢂ 2Ph).
4.3.5. [Et3NH][FeL12] (5)
To a solution of H2L1 (0.20 g, 0.60 mmol) in methanol
(15 ml) was added Et3N (1.2 ml, 1.29 mmol) and [g5-
C5H5Fe(CO)2]2SnCl2 (0.32 g, 0.059 mmol) in ethanol
(15 ml). The solution turned red and a black solid subse-
quently precipitated. The solid was filtered off, washed with
ether and dried. Yield 35%. Anal. Calc. for C42H48-
N7O4S2Fe (806.2): C, 60.4; H, 5.8; N, 11.7; S, 7.7. Found:
C, 59.1; H, 5.8; N, 11.7; S, 7.3%. IR (KBr, cmꢂ1): 1580 (s),
1551 (s), 1472 (s), 1384 (s), 1298 (s); 1282 (s), 1249 (m),
1180 (m), 1130 (m), 960 (s), 744 (m), 658 (m), 561 (m).
FAB MS: m/z: 833 (M+).
Air concentration of the mother liquor gave red-brown
crystals of ½Et3NHꢀ½FeL12ꢀ1=2ðH2OÞ suitable for X-ray
studies.
From the mother liquor white crystals of [SnPh2L1] Æ
CH3OH suitable for X-ray studies were obtained.
4.3.6. [Et3NH][FeL22] (6)
4.3.3. [SnMe2L2] (3)
To a solution of H2L2 (0.03 g, 0.082 mmol) in ethanol
(15 ml) was added Et3N (0.6 mL, 0.65 mmol) and [g5-
C5H5Fe(CO)2]2SnCl2 (0.039 g, 0.072 mmol) in ethanol
(20 ml). The resulting red-brown solid was filtered off,
washed with ether and dried. Yield 29%. Anal. Calc. for
C46H48N5O6S2Fe (886.8): C, 62.2; H, 5.4; N, 7.9; S, 7.2.
Found: C, 62.1; H, 5.4; N, 7.9; S, 7.2%. IR (KBr, cmꢂ1):
1638 (s), 1442 (s), 1409 (s), 1323 (m), 1139 (s); 1034 (s),
1022 (m), 780 (s), 607 (m). MS (ES): m/z: 888 (MH+);
522 (MH+ ꢂ L); 367 (LH+).
To a solution of H2L2 (0.1 g, 0.27 mmol) in ethanol
(5 mL) was added Et3N (0.60 ml, 0.65 mmol) and
SnMe2Cl2 (0.06 g, 0.27 mmol) in ethanol (5 ml). The mix-
ture was stirred for 1 h and the resulting yellow solid was
filtered off, washed with ether and dried under vacuum.
Yield 77%. Anal. Calc. for C22H22N2O3SSn: C, 51.4; H,
4.3; N, 5.5; S, 6.2. Found: C, 51.5; H, 4.5; N, 5.6; S,
6.0%. IR (KBr, cmꢂ1): 1609 (s), 1587 (s), 1531 (s), 1486
(s), 1325 (s), 1262 (s), 1149 (s), 883 (m), 759 (s), 671 (s),
1
563 (s), 550 (m). H NMR (CD3Cl, ppm): d, 8.6 [s, 1H,
From the mother liquor, red-brown crystals suitable for
X-ray studies were obtained.
3J(119/117Sn–1H = 43.3 Hz), HC@N], 7.7–6.6 (m, 11H, aro-
matic), 2.3 (s, 3H, CH3), 1.1 [s, 6H, 2J(119/117Sn–1H =
80.1 Hz), Sn–CH3]. 13C NMR (CD3Cl, ppm): d, 170.0 (s,
CO), 165.8 (s, C@N), 142.5–116.8, (s, phenyl rings), 21.4
(s, CH3-tolyl), 3.4 (s, Sn–CH3). 119Sn NMR (CD3Cl,
ppm): d, ꢂ195.5. FAB MS: m/z: 515 (M+).
4.4. Physical measurements
Elemental analyses were performed in a Carlo-Erba EA
1112 microanalyser. IR spectra were recorded on KBr
disks using a Bruker IFS 66 V spectrophotometer. 1H
and 13C spectra were recorded on a Bruker AMX350
MHz instrument using CDCl3 as solvent and chemical
shifts were determined against TMS. 119Sn NMR spectra
were recorded in a Bruker AMX500 spectrometer and
referred to Me4Sn as external reference. The FAB mass
spectra of the complexes were recorded on a Micromass
Autospec instrument and the Electrospray mass spectra
in a Hewlett Packard 1100 spectrometer.
From the mother liquor crystals suitable for X-ray stud-
ies were obtained.
4.3.4. [SnPh2L2] (4)
To a solution of H2L2 (0.2 g, 0.55 mmol) in methanol
(15 ml) was added Et3N (1.2 ml, 1.29 mmol) and SnPh2Cl2
(0.10 g, 0.30 mmol) in methanol (5 ml). The resulting yel-
low solid formed was filtered off, washed with ether and
dried. Yield 60%. Anal. Calc. for C32H26N2O3SSn: C,
60.3; H, 4.1; N, 4.4; S, 5.0. Found: C, 59.9; H, 4.2; N,
4.5; S, 4.9%.
4.5. X-ray structure analysis
IR (KBr, cmꢂ1): 1607 (s), 1586 (s), 1533 (s), 1482 (m), 1463
(m), 1438 (m), 1384 (m), 1322 (s), 1286 (m), 1148 (s), 956 (s),
751 (m). 1H NMR (CD3Cl, ppm): d, 8.7 [s, 1H,
Intensity data sets for all compounds except H2L2 and 6
were collected with a Smart-CCD-1000 Bruker diffractometer

Table 9
Summary of crystal data and structure refinement for ligands and tin compounds
Compound
[H2L1]
[H2L2]
1
2
3
4
Empirical formula
Formula weight
Crystal size (mm)
Temperature (K)
Wavelength
C
339.41
18H17N3O2S
C20H18N2O3S
366.42
0.80 · 0.24 · 0.16
293(2)
1.54180
Orthorhombic
Cc2a
C41H46N6O5S2Sn2
1004.34
0.99 · 0.30 · 0.10
150(2)
0.71073
Triclinic
C31H29N3O3SSn
642.32
0.25 · 0.20 · 0.10
293(2)
0.71073
Triclinic
C22H22N2O3SSn
513.17
0.29 · 0.21 · 0.08
293(2)
0.71073
Monoclinic
P21/n
C64H52N4O6S2Sn2
1274.60
0.65 · 0.25 · 0.20
293(2)
0.71073
Triclinic
0.52 · 0.31 · 0.07
293(2)
0.71073
Monoclinic
C2/c
Crystal system
Space group
ꢀ
ꢀ
ꢀ
P1
P1
P1
Unit cell dimensions
˚
a (A)
24.331(4)
14.485(2)
11.1892(17)
90.00
116.195(2)
90.00
3538.5(9)
8
0.197
9.4196(10)
20.320(3)
18.884(2)
90.00
90.00
90.00
3614.5(8)
8
1.779
8.4699(15)
16.234(3)
16.932(3)
101.669(3)
99.908(3)
104.810(3)
2141.9(7)
2
10.011(13)
11.937(15)
12.576(16)
94.67(2)
103.79(2)
90.46(2)
1454(5)
2
8.4110(11)
23.461(3)
11.0574(14)
90.00
96.202(2)
90.00
2169.2(5)
4
1.299
10.3938(17)
10.6023(17)
25.592(4)
88.055(3)
87.791(3)
84.468(3)
2803.7(8)
2
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
Volume (A )
Z
l (mmꢂ1
)
1.313
0.987
1.022
Number of reflections
collected
15091
1861
26812
16397
18671
32074
Number of independent
3614 [0.0365]
1861 [0.0000]
10130 [0.0199]
5914 [0.0665]
4439 [0.0465]
11403 [0.0307]
reflections [Rint
Data/restraints/parameters 3614/0/225
]
1861/1/244
1.001
10130/0/527
1.059
5914/0/357
1.035
4439/0/262
1.001
11403/0/703
1036
Goodness-of-fit
1.045
Final R indices [I > 2r(I)]
Ra = 0.0397; Rwb = 0.0892 R = 0.0552; Rw = 0.1246 R = 0.0216; Rw = 0.0535 R = 0.0352; Rw = 0.0834 R = 0.0331; Rw = 0.0605 R = 0.0304; Rw = 0.0702
P
P
a
R = [|Fo| ꢂ |Fc|]/ [|Fo|].
P
P
1=2
b
Rw ¼ ½ ðF 2o ꢂ F c2Þ= ðF 2oÞꢀ
.

E. Labisbal et al. / Journal of Organometallic Chemistry 691 (2006) 1321–1332
1331
˚
(Mo Ka radiation, k = 0.71073 A) equipped with a graph-
ite monochromator. Intensity data for H2L2 were collected
using a MACH3 Enraf Nonius diffractometer (Cu Ka
structures non-hydrogen atoms were anisotropically
refined, and in the last cycles of refinement a weighting
scheme was used, where weights are calculated from the
2
following formula w ¼ 1=½r2ðF o2Þ þ ðaPÞ þ bPꢀ, where
˚
radiation, k = 1.54180 A) equipped with a graphite mono-
chromator. Intensity data for compound 6 were collected
using a FR591-KappaCCD2000 Bruker-Nonius diffrac-
tometer (Cu Ka radiation, k = 1.54180 A) equipped with
P ¼ ðF 2o þ 2F 2cÞ=3.
Pertinent details of the data collections and structure
refinements are summarised in Tables 9 and 10, while
important geometrical data for all compounds are listed
in Tables 1–8. Further details regarding the data collec-
tions, structure solutions and refinements are included in
the Supporting Information. ORTEP3 [27] drawings with
the numbering scheme used are shown in Figs. 2–9.
˚
a graphite monochromator. All crystals were measured at
293 K – except compound 1, which was measured at
150 K. The x scan technique was employed to measure
intensities in all crystals. Decomposition of the crystals
did not occur during data collection. The intensities of all
data sets were corrected for Lorentz and polarisation
effects. Absorption effects in all compounds except H2L2
and 6 were corrected using the program SADABS [24];
absorption in H2L2 was corrected using semiempirical w
scans; absorption in 6 was corrected using the program
SORTAV [25]. The crystal structures of all compounds were
solved by direct methods. Crystallographic programs used
for structure solution and refinement were those in SHELX97
[26] installed on a PC clone. Scattering factors were those
provided with the SHELX program system. Missing atoms
were located in the difference Fourier map and included
in subsequent refinement cycles. The structures were
refined by full-matrix least-squares refinement on F2.
Hydrogen atoms not involved in hydrogen bonding were
placed geometrically and refined using a riding model with
Uiso constrained at 1.2 (for non-methyl groups) and 1.5 (for
methyl groups) times Ueq of the carrier C atom. For all
5. Supplementary material
Crystallographic data for the structures have been depos-
ited with Cambridge Crystallographic Data Centre CCDC
numbers 272628–277635. Copies of the data can be obtained
free of charge on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK, fax: int. code +44 1223 336
033; e-mail for inquiry: fileserv@ccdc.cam.ac.uk; e-mail for
deposition: deposit@ccdc.cam.ac.uk
Acknowledgments
This work was supported by Ministerio de Ciencia y
Tecnologia (Spain) (Grant BQU2002-01819) and by the
Xunta de Galicia (Grant PGIDT00P-XI20305PR).
References
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841.84
0.24 · 0.19 · 0.11
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0.71073
42H47N7O4.5S2Fe C46H48N5O6S2Fe
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4
l (mmꢂ1
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12829
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reflections collected
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30247
6971 [0.0815]
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1.034
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1.084
R = 0.0584;
Rw = 0.1560
Final R indices
[I > 2r(I)]
P
P
a
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P
P
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