Stereoselective synthesis of vinylic (Z)-vic-bis(arylchalcogenides)

Article abstract of DOI:10.1016/j.jorganchem.2006.09.054

Alkyne-titanium complexes 3, readily prepared in situ by the reaction of alkynes with Ti(O-i-Pr)₄/2 i-PrMgCl, react with electrophilic chalcogen species under mild conditions to provide the corresponding addition products in fair to good yields

Full text of DOI:10.1016/j.jorganchem.2006.09.054

Journal of Organometallic Chemistry 691 (2006) 5873–5886
www.elsevier.com/locate/jorganchem
Self-assembly of triorganotin(IV) moieties with
2,3,4,5-tetrafluorobenzoic acid and 4,40-bipy, triphenylphosphine oxide
or phen: Syntheses, characterizations and supramolecular structures
a,b,
a
a
Chunlin Ma
*, Junshan Sun , Rufen Zhang
a
Department of Chemistry, Liaocheng University, Liaocheng 252059, PR China
b
Taishan University, Taian 271021, PR China
Received 29 July 2006; received in revised form 16 September 2006; accepted 21 September 2006
Available online 5 October 2006
Abstract
A series of triorganotin (IV) complexes with 2,3,4,5-tetrafluorobenzoic acid and mixed-ligands of the types: R3Sn(O2CC6HF4)m Æ L
(m = 1, L = 0, R = Ph 1; m = 1, L = Ph3PO, R = Ph 4, Me 5), [R3Sn(O2CC6HF4)]m Æ L (m = 2, L = 4,40-bipy, R = Ph 2, Me 3;
m = n, L = 0, R = Me 6), and [R3Sn(O2CC6HF4) Æ (H2O)]m Æ L Æ C2H5OH (m = 2, L = Phen, R = Ph 7, Me 8), (4,40-bipy = 4,40-bipyr-
idyl; Phen = 1,10-phenanthroline), have been synthesized by the reaction of triorganotin chloride and 2,3,4,5-tetrafluorobenzoic acid
in the presence of mixed-ligands: 4,40-bipy, triphenylphosphine oxide, or phen. All complexes were characterized by elemental anal-
ysis, IR, 1H, 13C, 119Sn NMR spectroscopy analysis. Except for 5 and 8, all the complexes were also characterized by X-ray
crystallography.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: 2,3,4,5-Tetrafluorobenzoic acid; Self-assembly; Supramolecular structures; Triorganotin
1. Introduction
properties for potential practical applications [4]. A biolog-
ically interesting donor is the carboxyl group, which coex-
ists with the nitrogen atom in several relevant species. In
our previous work, we have reported on the chemical,
structural, polymer properties of a series of similar organo-
tin(IV) carboxylate complexes [5]. As a extension of this
research, we are interested in utilizing the organic ligand
with non-coordinated functional groups such as N and O
atoms in conjunction with aromatic carboxylate groups is
considered for the creation of supramolecular assemblies
by non-covalent bonds (hydrogen bonds or p–p and
C–Hꢀ ꢀ ꢀp stacking interaction). To evaluate some of these
features of coordination complexes, we have considered
2,3,4,5-tetrafluorobenzoic acid to form complexes with
triorganotin. In this process, mixed-ligands (4,40-bipy, tri-
phenylphosphine oxide or phen) have been chosen as a
co-ligand [6], because they are well known for their
Supramolecular chemistry has increasingly emerged as a
powerful field for construction of molecular-based devices
with advanced functions and well-defined structures [1].
A number of supramolecular architectures had been suc-
cessfully designed and synthesized through metal-directed
self-assembly of organic ligands and metal ions or molecu-
lar hydrogen bonds and p–p or C–Hꢀ ꢀ ꢀp stacking interac-
tions [2,3]. In recent years, organotin(IV) derivatives have
received much attention, owing to the enormous variety
of intriguing structural topologies and their unexpected
*
Corresponding author. Address: Department of Chemistry, Liaocheng
University, Liaocheng 252059, PR China. Tel.: +86 635 8230660; fax: +86
538 6715521.
E-mail address: macl@lcu.edu.cn (C. Ma).
0022-328X/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.09.054

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C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 5873–5886
robustness to act as a spacer to unsaturated metal ion,
which may facilitate the coordination between the metal
ion and bulky organic moleculars due to the minimization
of crowding. In addition, these mixed ligands also have the
ability to assemble into supramolecular framework with
carboxyl group via intermolecular hydrogen bonds, p–p
and C–Hꢀ ꢀ ꢀp stacking interaction.
2.2. IR spectra
The stretching frequencies of interest are those associ-
ated with the C(O)O, Sn–C, Sn–O and Sn–N groups. The
strong absorption in the region 468–496 cmꢁ1, which is
absent in the spectrum of the free ligand, is assigned to
the Sn–O stretching mode. All these values are consistent
with those detected in number of organotin(IV)–oxygen
derivatives [8].
In organotin carboxylate complexes, IR spectroscopy
can provide useful information concerning the coordina-
tion mode of the carboxylate group. It was possible to dis-
tinguish the coordination mode of the –CO2 group. In
complex 6, the magnitude of Dm (Dm = mas (COO)- ms(COO))
of about 140 cmꢁ1, compared with those for the corre-
sponding sodium salts, reveals that the carboxylate ligands
function as bidentate ligands under the conditions
employed [9]. While in other complexes, the value of Dm
of about 220–272 cmꢁ1, showing the carboxylate ligands
are in a monodentate manner [10]. The m(C@N) band,
occurring at about 1523 cmꢁ1, is considerably shifted
towards lower frequencies with respect to that of the free
ligand, confirming the coordination of the heterocyclic N
to the tin. This is also consistent with the X-ray diffraction
study.
Herein, we synthesized several new triorganotin (IV)
complexes with 2,3,4,5-tetrafluorobenzoic acid and
mixed-ligands of the type: R3Sn(O2CC6HF4)m Æ L (m = 1,
L = 0, R = Ph 1; m = 1, L = Ph3PO, R = Ph 4, Me 5),
[R3Sn(O2CC6HF4)]m Æ L (m = 2, L = 4,40-bipy, R = Ph 2,
Me 3; m = n, L = 0, R = Me 6), and [R3Sn(O2CC6H-
F4) Æ (H2O)]m Æ L Æ C2H5OH (m = 2, L = Phen, R = Ph 7,
Me 8). All complexes were characterized by elemental,
IR, 1H, 13C and 119Sn NMR spectra analyses. Except
for 5 and 8, all the complexes were also characterized
by X-ray crystallography. All of these complexes show
an intricate supramolecular organization in the solid state
that results from a cumulative effect of intermolecular sec-
ondary interactions. The hydrogen bonds and aromatic
interactions (p–p and C–Hꢀ ꢀ ꢀp) have been well docu-
mented [7].
2. Results and discussion
2.1. Syntheses
2.3. NMR spectra
Reactions of triorganotin(IV) chloride and 2,3,4,5-tetra-
fluorobenzoic acid with the presence of mixed ligand of
4,40-bipy, triphenylphosphine oxide or phen were carried
out. The syntheses procedures are shown in Scheme 1.
The 1H NMR spectra show the expected integration and
peak multiplicities. In the spectrum of the free ligand, the
resonance observed at about 10.11 ppm, which is absent
in the spectra of the complexes, indicates the replacement
F
R
F
Sn
R
O
O
1
R = Ph
F
C6H6
R
F
R
R
F
F
R= Ph
2
3
C=
4,4'-Bipy
Sn
O
N
R= Me
C2H5OH
F
2
O
R
F
R
R
F
F
4
5
R= Ph
C=
EtONa
Ph3P=O
O
Sn
O
PPh3
C
A
B
+
+
F
R= Me
C2H5OH
O
R
F
R
R
Sn
O
O
R= Me
6
C6H6
R
F
n
F
F
F
R
R
F
F
H
C=
Phen
7
8
R= Ph
Sn
O
O
C2H5OH
Phen
¡¤
¡¤
F
C2H5OH
R= Me
H
O
R
F
Scheme 1. A=2,3,4,5-Tetrafluorobenzoic acid; B= Triorganotin(IV) chlorides.

C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 5873–5886
5875
of the carboxylic acid proton on complex formation. The
chemical shifts of the signal for the methyl groups
(d = 0.61–1.21 ppm) and the phenyl group (d = 7.21–
7.76 ppm) appear at almost the same position as in the
ligands. In addition, the resonance at 7.86–8.74 ppm are
attributed to the protons of 4,40-bipy and the resonance
at 7.26–7.81 ppm are signed to the protons of phen [11].
In 13C NMR spectra, the position of the carboxylate
carbon moved to the lower field in all the complexes shifts,
as compared with the ligand acid, indicating participation
of the carboxylic group in coordination to tin(IV) [12].
Although at least two different types of carboxylate groups
are present, only single resonances are observed for the
COO group in the 13C NMR spectra. These findings are
interpreted by a fast equilibrium between bidentate and
monodentate mode of COO groups of the complexes in
CDCl3. It is noted that such an equilibrium explains that
all carboxylate resonances are averaged out on the 13C
NMR time scales [13]. Complementary information for
several complexes is given by the values of the coupling
constant.
Sn atom is best described as distorted tetrahedral geometry
defined by three ipso-C atoms of the phenyl groups and
O(1) atom of the ligand. The bond length of Sn(1)–O(1)
˚
˚
is 2.060(4) A, which lies in the range of 2.038–2.115 A that
has been reported as the Sn–O covalent bond length [19],
which proves that the oxygen atoms are coordinated to
the tin atoms by a strong chemical bond. The relatively
close interaction between O(2) and Sn(1) [Sn(1)ꢀ ꢀ ꢀO(2) =
˚
˚
2.891(6) A], which is in the range 2.634–2.916 A. Although
this distance is considerably longer than the normal Sn–O
covalent bond length, they lie in range of Sn–O distances
˚
of 2.61-3.02 A which have been confidently reported for
intramolecular bonds [15]. The monodentate mode of coor-
dination of the ligand is reflected in the disparate O(1)–C(1)
˚
and O(2)–C(1) bond distances of 1.302(8) and 1.200(9) A,
Table 1
Selected bond lengths and angles for the complexes 1 and 2
Complex 1
Complex 2
˚
˚
Bond
Distance (A)
Bond
Distance (A)
The 119Sn NMR spectra of complex 1 show only one sig-
nal (d = 86.3 ppm), typical of a four-coordinate mode.
However, the chemical shift for 2–8 (d = ꢁ134.2, ꢁ96.8,
ꢁ128.6, ꢁ98.1, ꢁ94.9, ꢁ121.4, ꢁ90.3 ppm, respectively),
which are within the range corresponding to a typical
five-coordinated species (ꢁ90 to ꢁ190), which is in accor-
dance with their structures in the solid state [14].
Sn(1)–C(14)
Sn(1)–C(20)
Sn(1)–C(8)
Sn(1)–O(1)
O(1)–C(1)
O(2)–C(1)
2.104(6)
2.122(7)
2.124(6)
2.060(4)
1.302(8)
1.200(9)
Sn(1)–C(20)
Sn(1)–C(8)
Sn(1)–C(14)
Sn(1)–O(1)
Sn(1)–N(1)
2.119(4)
2.130(4)
2.130(4)
2.136(3)
2.555(3)
Angle
Amplitude (ꢁ) Angle
116.3(2) C(20)–Sn(1)–C(8)
Amplitude (ꢁ)
C(14)–Sn(1)–C(8)
113.63(18)
C(14)–Sn(1)–C(20) 111.1(3)
C(20)–Sn(1)–C(14 ) 122.68(18)
2.4. Description of crystal structures
C(20)–Sn(1)–C(8)
C(14)–Sn(1)–O(1)
C(8)–Sn(1)–O(1)
C(20)–Sn(1)–O(1)
C(1)–O(1)–Sn(1)
O(2)–C(1)–O(1)
112.2(3)
114.1(2)
106.6(2)
94. 4(3)
112.1(5)
123.7(7)
C(8)–Sn(1)–C(14)
C(20)–Sn(1)–O(1)
C(14)–Sn(1)–O(1)
C(20)–Sn(1)–N(1 )
C(8)–Sn(1)–N(1 )
C(14)–Sn(1)–N(1)
C(20)–Sn(1)–N(1)
O(1)–Sn(1)–N(1)
121.17(17)
101.37(14)
94.95(14)
84.29(13)
85.27 (14)
84.62(13)
158.45(15)
173.44(12)
2.4.1. [Ph3Sn(O2CC6HF4)] (1)
The molecular structure is illustrated in Fig. 1, selected
bond distances and angles are listed in Table 1. The struc-
ture is in agreement with the result obtained from infrared
spectroscopy and the lattice is comprised of discrete mole-
cule of the complex. The coordination geometry about the
Fig. 2. Supramolecular structure of complex 1, showing 2D framework
via intermolecular C–Hꢀ ꢀ ꢀp stacking interaction.
Fig. 1. Molecular structure of complex 1.

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C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 5873–5886
Fig. 3. Molecular structure of complex 2.
respectively, with the longer separation being associated
with the stronger Sn(1)–O(1) interaction. These bond dis-
tances and angles are in agreement with the corresponding
values found for similar Sn complexes contained in the
Cambridge Structure Database [16]. The major distortion
from the ideal geometry is found in the O(1)–Sn(1)–C(20)
angle of 94.4(3)ꢁ, and the O(1)–Sn(1)–C(8) and O(1)–
Sn(1)–C(14) are 106.6(2)ꢁ and 114.1(2)ꢁ, respectively. How-
ever, it is noteworthy that the C(8)–Sn(1)–C(14) angle of
116.3(2)ꢁ is the next major distortion from the ideal
geometry.
cule, the remainder being generated by an inversion center
at the midpoint of the co-crystallized 4,40-bipy ligand. The
structure contains two R3Sn(O2CC6HF4) (R = Ph2, Me 3)
units associated through a bridging 4,40-bipy moiety. The
coordination environment around tin is five-coordinated
distorted trigonal bipyramidal geometry with trans-
NOSnR3. The axial position was occupied by the carboxyl
O atom of 2,3,4,5-tetrafluorobenzoic acid and the ring N
atom of the neutral bipyridyl donor. The Sn(1)–O(1) bond
˚
˚
length [2.136(3) A] for 2 and [2.157(3) A] for 3 is at the
longer end of the range of Sn–O distances measured for
monomeric triorganotin carboxylate.[17] The Sn–N bond
The supramolecular structure of complex 1 is shown in
Fig. 2, showing 2D framework by C–Hꢀ ꢀ ꢀp stacking inter-
action along a and b axis. It has been clearly established
that this weak molecular force has a directional preference
with the C–H pointing towards the center of the aromatic
ring. The C(23)–H(23) atom is directed towards the sym-
metry related (1.5 ꢁ x, 0.5 + y, z) aromatic ring containing
the C(8)A–C(13)A atoms. The closest contact of 2.843
˚
˚
length [2.555(3) A] for 2 and [2.570(3) A] for 3, closely to
the Sn–N distance in [Me3Sn(PhN2C2S3)]2 Æ (4,40-bipy)
˚
[2.613(2) A] ,[18] is longer than those found in organotin
˚
A occurs between the H(23)–C(8)A atoms. The distance
˚
˚
of C(23)ꢀ ꢀ ꢀCg and H(23)ꢀ ꢀ ꢀCg are 3.598 A and 2.673 A,
respectively. The angle of C(21)–H(21)ꢀ ꢀ ꢀCg is 135.53ꢁ.
Another is the C(21)–H(21) atom, which is directed
towards the symmetry related (0.5 + x, y, 1.5 ꢁ z) aromatic
ring containing C(8)B–C(13)B atoms. The closest contact
˚
of 2.900 A is H(21)–C(8)B atoms. The distance of
˚
˚
C(21)ꢀ ꢀ ꢀCg and H(21)ꢀ ꢀ ꢀCg are 3.581 A and 2.692 A,
respectively. The angle of C(21)–H(21)ꢀ ꢀ ꢀCg is 159.99ꢁ.
These weak but significant stacking interactions stabilize
these crystal structures.
2.4.2. [Ph3Sn(O2CC6HF4)]2 Æ (4,40-bipy) (2) and
[(CH3)3Sn(O2CC6HF4)2] Æ (4,40-bipy)
The molecular structures of complexes 2 and 3 are
shown in Figs. 3–5 selected bond distances and angles are
listed in Tables 1 and 2. The asymmetric units of 2 and 3
are found to consist of one-half of the mononuclear mole-
Fig. 4. Supramolecular structure of complex 2, showing 2D head-to-tail
zigzag framework via intermolecular C–Hꢀ ꢀ ꢀp stacking interaction.

C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 5873–5886
5877
Fig. 5. Molecular structure of complex 3.
Table 2
to-face C–Hꢀ ꢀ ꢀp stacking interaction. Every pair of adja-
Selected bond lengths and angles for the complexes 3 and 4
cent C–H atom are directed towards the symmetry
˚
Complex 3
Complex 4
related (C(11)–H(11)ꢀ ꢀ ꢀCg = 3.808 A, C(12)–H(12)ꢀ ꢀ ꢀCg
˚
˚
˚
= 4.062 A, symmetry operation: 1 ꢁ x, ꢁ0.5 + y, 0.5 ꢁ z)
Bond
Distance (A)
Bond
Distance (A)
aromatic rings and formed head-to-tail zigzag chain
structure, which are further connected by C–Hꢀ ꢀ ꢀp stack-
ing interaction into a 2D structure.
Sn(1)–C(15)
Sn(1)–C(14)
Sn(1)–C(13)
Sn(1)–O(1)
Sn(1)–N(1)
O(1)–C(1)
2.121(4)
2.123 (4)
2.129(4)
2.157(3)
2.570(3)
1.295(4)
1.213(4)
1.476(6)
Sn(1)–C(14)
Sn(1)–C(20)
Sn(1)–C(8)
Sn(1)–O(1)
Sn(1)–O(3)
2.118(4)
2.123(4)
2.125(4)
2.146(3)
2.386(3)
The supramolecular frameworks of complex 3 are
shown in Fig. 6a,b. The 1D ladder-like chain structures
and alternation of moleculars are easily recognized, which
were assembled by two distinct intermolecular C–Hꢀ ꢀ ꢀO
and C–Hꢀ ꢀ ꢀF hydrogen bonds with the distances of
O(2)–C(1)
C(10)–C(10)#1
Angle
Amplitude (ꢁ) Angle
Amplitude (ꢁ)
˚
˚
2.462 A and 2.648 A and angles of 149.90ꢁ and 126.67ꢁ,
which are consistent with what have been reported in the
Cambridge database [20]. The ladders are hydrogen-
bonded into continuous parallelogram lattices, which form
two infinite 1D chains with the bipyridyl rings along a-axis.
C(15)–Sn(1)–C(14) 118.70(18)
C(15)–Sn(1)–C(13 ) 122.95(17)
C(14)–Sn(1)–C(13) 117.24(18)
C(15)–Sn(1)–O(1)
C(14)–Sn(1)–O(1)
C(13)–Sn(1)–O(1)
C(15) –Sn(1)–N(1 )
C(14)–Sn(1)–N(1)
C(13)–Sn(1)–N(1)
O(1)–Sn(1)–N(1)
C(14)–Sn(1)–C(8)
C(14)–Sn(1)–C(20) 127.04(16)
116.97(16)
101.37(14)
96.65(15)
87.49(14)
85.52 (15)
90.20(14)
83.96(13)
170.92(9)
C(20)–Sn(1)–C(8)
C(14)–Sn(1)–O(1)
C(8)–Sn(1)–O(1)
C(20)–Sn(1)–O(3)
C(20)–Sn(1)–O(1)
C(8)–Sn(1)–O(3)
O(1)–Sn(1)–O(3)
P(1)–O(3)–Sn(1)
113.62(16)
98.91(13)
89.54(14)
85. 24(13)
96. 09(14)
88. 60(13)
178. 03(11)
172. 35(18)
2.4.3. [Ph3Sn(O2CC6HF4)] Æ OPPh3 (4)
The molecular structure is shown in Fig. 7, selected
bond distances and angles are listed in Table 2. The geom-
etry at central Sn atoms is slightly distorted trigonal bipyr-
amid with Ph3PO coordinated in a trans position to the oxo
ligand, in which three C atoms of phenyl groups form the
equatorial plane, the sum of the trigonal plane angle is
357.63(16)ꢁ, while two oxygen atoms from the carboxyl
groups and Ph3PO ligand occupy the axial apical position.
The Sn(IV) atom is displaced from the equatorial plane of
˚
tetrazoles [2.27–2.43 A] [18]. It is noteworthy that a weak
intramolecular Snꢀ ꢀ ꢀO interaction is recognized between
the Sn(1) and O(2) derived from the monodentate carboxyl
˚
group. The Sn(1)ꢀ ꢀ ꢀO(2) distances of 2 and 3 are 3.086(3) A
˚
and 3.058(3) A, respectively, which are considerably less
˚
˚
than the sum of the van der Waals radii (3.68 A) [20]. Thus,
the coplanar atoms toward the oxo atom O(3) by 0.0707 A
if the weak Sn(1)ꢀ ꢀ ꢀO(2) interaction is considered, the
geometry of Sn(1) is best described as distorted octahe-
dron. Furthermore, owing to the coordination of N atom,
the angles of O–Sn–C [94.95(14)–101.37(14)ꢁ] for 2 and
[87.49(14)–96.65(15)ꢁ] for 3, is smaller than those of
[Ph3Sn(O2CC6HF4)] [94.95(3)–14.1(2)ꢁ] in complex 1. The
angle of O–Sn–N and C–Sn–C are 173.44(12)ꢁ and
[113.63(18)–122.68(18)ꢁ] in complex 2 and 170.92(9)ꢁ and
[117.24(18)–122.95(17)ꢁ] in complex 3, which reflect this
coordination geometry.
and the slightly distortion lies the angle of O(1)–Sn(1)–O(3)
[178.03(11)ꢁ]. Moreover, the bond distance of O(1)–Sn(1) is
˚
˚
2.146(3) A, larger than the O(1)–Sn(1) [2.060(4) A] in
complex 1 owing to electrostatic repulsion of the phenyl
groups to O(1) atom. The geometry of the Ph3PO ligand
˚
shows no usual features. The P–O bond, 1.460(1) A in free
Ph3PO [21], is only slightly affected by the coordination to
˚
Sn atom (1.486(3) A). The phosphorus atoms show tetrahe-
dral coordination, being surrounded by the atoms C(32),
C(38), C(26) and O(3). The tetrahedral angles vary from
106.67(19)ꢁ to 107.91(19)ꢁ. The P–C bond lengths are basal
In Fig. 4, the supramolecular structure of complex 2
exhibits a 2D zigzag structure via intermolecular edge-
˚
the same [(1.798 0.004) A].

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C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 5873–5886
Fig. 6. Supramolecular frameworks of complex 3, showing 1D infinite chain structures by C–Hꢀ ꢀ ꢀO (a) and C–Hꢀ ꢀ ꢀF hydrogen bonds (b).
Fig. 7. Molecular structure of complex 4.
The supramolecular structure unit of complex 4 exists
center, which is generated by the bidentate bridging car-
boxylate ligands and the Sn center. The Sn atom exists in
a distorted trigonal bipyramidal environment with two O
atoms and three methyl groups, which exhibits a trans-
R3SnO2 geometry. The axial positions are occupied by
O(1) and O(3) and axial angle is 173.98(13)ꢁ. The sum of
C–Sn–C is 357.3(3)ꢁ, which illustrates the three methyl
groups and Sn atom are nearly coplanar.
two distinct C–Hꢀ ꢀ ꢀF hydrogen bonds [C(11)–
˚
H(11B)ꢀ ꢀ ꢀF(2AA), 2.657, 3.152 A and 121.77ꢁ; C(29)–
0
˚
H(29)ꢀ ꢀ ꢀF(1 B), 2.595, 3.465 A and 156.01ꢁ] and formed a
box-like ring structure (Fig. 8). Further, these rings were
assembled into 2D network structure.
2.4.4. [(CH3)3Sn(O2CC6 HF4)]n (6)
The molecular structure of complex 6 is shown in Fig. 9,
selected bond lengths and angles are listed in Table 3. In
the crystalline state, complex 6 adopts an infinite zigzag
1D polymeric chain structure with a five-coordinated tin
The deviation only slightly from regular distorted geom-
etry, mean deviation from plane is 0.0746(3) A. A evident
twist is shown between this COO group and the aromatic
ring [O(1)/C(1)/C(2)/C(3) is ꢁ44.51ꢁ and O(2)/C(1)/C(2)/
˚

C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 5873–5886
5879
Table 3
Selected bond lengths and angles for the complexes 6 and 7
Complex 6
Complex 7
˚
˚
Bond
Distance (A)
Bond
Distance (A)
Sn(1)–C(15)
Sn(1)–C(17)
Sn(1)–C(16)
Sn(1)–O(3)
Sn(2)–C(20)
Sn(2)–C(19)
Sn(2)–C(18)
Sn(2)–O(2)
2.096(6)
2.098(6)
2.109(6)
2.161(3)
2.099(6)
2.107(6)
2.117(6)
2.170(4)
2.587(4)
2.587(4)
Sn(1)–C(14)
Sn(1)–C(20)
Sn(1)–C(8)
Sn(1)–O(1)
Sn(1)–O(3)
2.123(4)
2.127(5)
2.129(5)
2.187(3)
2.351(3)
Sn(2)–O(4)#1
O(4) –Sn(2) #2
Angle
Amplitude (ꢁ) Angle
Amplitude (ꢁ)
C(15)–Sn(1)–C(17) 117.9(3)
C(15)–Sn(1)–C(16) 116.3(3)
C(17)–Sn(1)–C(16) 123.1(3)
C(20)–Sn(1)–C(8)
C(20)–Sn(1)–C(14) 120.24(18)
115.62(19)
C(8)–Sn(1)–C(14)
C(20)–Sn(1)–O(1)
C(14)–Sn(1)–O(1)
C(20)–Sn(1)–O(3)
C(8) –Sn(1)–O(3)
O(3)–Sn(1)–O(1)
C(14)–Sn(1)–O(3)
123.32(18)
95.48(15)
96.60(15)
90.05(15)
86.07 (15)
172.42(12)
85.01(14)
C(15)–Sn(1)–O(3)
C(17)–Sn(1)–O(3)
90.5(2)
98.6(2)
C(20)–Sn(2)–C(19) 124.8(3)
C(20)–Sn(2)–C(19) 115.8(3)
C(19)–Sn(2)–C(18) 117.2(3)
O(2)–Sn(2)–O(4)#1 175.0(15)
Fig. 8. 2D network structure of complex 4, formed through intermolec-
ular C–Hꢀ ꢀ ꢀF hydrogen bonds.
C(7) is ꢁ43.54ꢁ]. The disparity in the Sn–O distance is
reflected in the associated C–O distances, the longer C–O
bond involving the O(1) atom with the shorter Sn–O inter-
action. The unit cell (Fig. 10 and 11) exhibits a elliptic mac-
rocycle in every layer of the supramolecular structure. An
elliptic channel was formed via the stacking interaction
along c-axis direction.
In Fig. 12a, one-dimensional polymeric chain structure
are interconnected by means of p–p stacking interactions
between the parallel phenyl groups (dihedral angle is 0ꢁ)
to form a paratactic double-chain structure. The two phenyl
rings involved in this p–p stacking are staggered with an
interplanar distance of 3.700 A (symmetry operation
˚
2 ꢁ x, 1 ꢁ y, 1 ꢁ z) and departure angle of phenyl–phenyl
is 15.6ꢁ. The polymeric chain are further p-stacked to form
a two-dimensional framework.
In Fig. 12b, the supramolecular structure exhibits a 2D
network structure. The resultant C–Hꢀ ꢀ ꢀF contacts allow
the molecular to arrange into a staircase type of one-
dimensional polymeric chain array in the solid state. The
distances of paratactic two C–Hꢀ ꢀ ꢀF interactions are
Fig. 9. Molecular structure of complex 6.

5880
C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 5873–5886
Fig. 10. Cell packing of complex 6, showing a multi-membered elliptic macrocycle in every layer and a channel-like framework via Oꢀ ꢀ ꢀSn and non-
bonded Fꢀ ꢀ ꢀSn interaction.
Fig. 11. Supramolecular structure of complex 6, showing 1D zigzag chain via intermolecular O ! Sn coordinating.
˚
equivalent of 2.589 A (symmetry operation 1 ꢁ x, 2 ꢁ y,
ꢁz). These interactions together with the polymeric chain
assemble into a macrocycle quadrate lattice unit [the angle
O(1)–Sn(1)/ O(2)–Sn(2) is 91.5ꢁ].
intermolecular tin–oxygen bonds and close in length to
the sum of covalent radii of tin and oxygen (2.13 A), which
is recognized as strongly coordinative bonds. Worth men-
tioning here is that bond length of O(1) and Sn(1) is
˚
˚
˚
2.187(3) A, which is larger than that of O(1)–Sn(1)
2.4.5. [Ph3Sn(O2CC6HF4) Æ (OH2)2]2 Æ (phen)2 (7)
(2.060(4) A) in the complex 1, owing to electrostatic repul-
For complex 7, co-crystallized phen and two monomers
of the main component, [Ph3Sn(O2CC6HF4)] Æ H2O, are
found in the crystal in Fig. 13, selected bond lengths and
angles are listed in Table 3. In the two monomers, the
geometries at Sn(1) is distorted trigonal bipyramidal with
O(3) from the water molecular and O(1) from carboxyl
group coordinating to Sn atom and occupying the axial
apical position. The sum of the trigonal plane angles is
359.18ꢁ, which illustrates Sn(1), C(8), C(14) and C(20) are
almost coplanar with the tin atom slightly deviating from
sion of the phenyl groups to O(1) atom.
In Fig. 14, the dimer of complex 7 with centrosymmetric
14-membered ring and trans carboxyl ligand is formed
through the hydrogen bonds from the water molecular to
˚
the nitrogen atom of its heterocycle (Oꢀ ꢀ ꢀN = 2.785(5) A),
˚
and another (Oꢀ ꢀ ꢀN = 2.797(5) A) to the nitrogen atom of
the symmetrical o-phenanthroline molecular. The two pairs
of hydrogen bonds hold together the flat heterocyclic bases
[22], which are twisted with respect to each other in a pro-
peller-like conformation. The hydrogen bonding distances
exceed those found in aquachlorotriphenyl tin 3,4,7,8-tet-
˚
the ideal plane by 0.0420 A. Distortion from strict trigonal
˚
bipyramidal coordination lies to the angle of O(1)–Sn(1)–
O(3) [172.42(12)ꢁ]. There is only one monodentate type of
carboxyl group in the monomers. The guest water molecu-
lar is also found in the coordination sphere, with Sn–O
ramethyl-O-phenanthroline (Oꢀ ꢀ ꢀN = 2.661(3), 2.767(3) A;
Nꢀ ꢀ ꢀOꢀ ꢀ ꢀN = 60.9(1)ꢁ), whose five-membered C–Nꢀ ꢀ ꢀO
P
waterꢀ ꢀ ꢀN–C ring is planar ( angles = 540(1)ꢁ) [23]. The
packing appears to be less efficient compared with that of
the title complex, as suggested by its density (1.475 g cmꢁ1).
˚
bond lengths of 2.351(3) A, comparable in strength to the

C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 5873–5886
5881
Fig. 12. Supramolecular structure of complex 6: (a) showing 1D framework via interchain p–p stacking interaction and (b) showing a staircase type of
one-dimentional polymer chain array via interchain C–Hꢀ ꢀ ꢀF hydrogen bonds.
In this complex, hydrogen bonding involves only the two
outer pyridyl groups of the non-planar terpyridyl ligand
[24].
As shown in Fig. 15, these dimer structure units are
assembled by intermolecular C–Hꢀ ꢀ ꢀF hydrogen bond
and formed a linear 1D chain structure with multi-mem-
bered squareness parallelogrammical organotin rings in
the defined plane. The distance of C–H36Aꢀ ꢀ ꢀF2AB and
˚
C–H36Dꢀ ꢀ ꢀF2 is 2.633 A, which is somewhat smaller than
˚
the sum of van der Waals radii (2.67 A) [20]. The corre-
sponding angle is 142.64ꢁ, which is consistent with those
reported by Dautel [25]. These adjacent 1D chain struc-
tures are further self-assembled via p–p (face-to-face)
stacking interaction and formed a 2D network framework
(Fig. 16). The average separation between the two ring is
˚
3.60 A and the dihedral angle is 0ꢁ, which illustrated two
completely parallel aromatic rings. The angle between cen-
tric linkage and the perpendicular of phenyl rings is 3.2ꢁ,
showing the slightly derivation between phenyl rings.
Fig. 13. Molecular structure of complex 7.

5882
C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 5873–5886
Fig. 14. The dimer structure of complex 7 (a) showing a 14-membered ring (b) via O–Hꢀ ꢀ ꢀN hydrogen bond.
Fig. 15. The one-dimentional chain structure of complex 7 with multi-membered squareness ring via C–Hꢀ ꢀ ꢀF hydrogen bond.
2.5. Conclusion
atom or a discrete four- or five-coordinate form. The
supramolecular chemistry showed intriguing structural
topologies and their 1D or 2D framework was formed
through the self-assembly based on covalent interactions
or supramolecular contacts (such as hydrogen bonding
or stacking interactions).
In summary, a series of triorganotin (IV) complexes
based on 2,3,4,5-tetrafluorobenzoic acid have been syn-
thesized and characterized. In general, trimethyltin ben-
zoates mainly assume one-dimensional associated
arrangements (such as complex 6), and triphenyltin ben-
zoates generally exist in a discrete five-coordinate form
(complexes 2, 4, and 7). However, complexes 1 and 3
are different with1 containing a four-coordinated tetrahe-
3. Experimental details
3.1. Materials and measurements
dron geometry and
3 containing two mononuclear
molecular units associated through a bridging 4,40-bipy.
Furthermore, these structures are able to assemble into
supramolecular framework through hydrogen bonds
and p–p or C–Hꢀ ꢀ ꢀp stacking interaction. In general, in
the crystalline state these complexes generally adopted
either a polymeric structure with a five-coordinate tin
Trimethyltin chloride, triphenyltin chloride, 2,3,4,5-tet-
rafluorobenzoic acid, 4,40-bipy, triphenylphosphine oxide
and phen are commercially available and were used with-
out further purification. The melting points were obtained
with Kofler micro-melting point apparatus and are uncor-
rected. IR spectra were recorded on a Nicolet-460 spectro-

C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 5873–5886
5883
Fig. 16. Supramolecular structure of complex 7, showing 2D planar framework via intermolecular C–Hꢀ ꢀ ꢀF hydrogen bonding and C–Hꢀ ꢀ ꢀp stacking
interaction.
photometer using KBr discs and sodium chloride optics.
1H and 13C NMR spectra were recorded on Varian Mer-
cury Plus 400 spectrometer operating at 400, 100.6, and
149.2 MHz, respectively. The spectra were acquired at
room temperature (298 K) unless otherwise specified; 13C
spectra are broadband proton decoupled. Elemental analy-
ses were performed with a PE-2400II apparatus.
Ph–H), d 7.41–7.79 (m, 30H), 8.70–8.73 (d, JH,H = 9.6 Hz,
8H). 13C NMR (CDCl3, ppm): d 150.9, 145.8, 137.4, 136.9,
130.7, 129.3, 128.9, 121.6, 113.3. 119Sn NMR (CDCl3):
ꢁ134.2 ppm.
3.2.3. [(CH3)3Sn(O2CC6HF4)2] (4,40-bipy) (3)
Complex 3 was prepared in the same way as that of
complex 1 except that excess 4,40-bipy was added to the
mixture. The solid was then recrystallized from ether/
petroleum. Yield: 76%; m.p. 134–136 ꢁC. Anal. Calc. for
C30H10F8N2O4Sn2: C, 42.30; H, 1.18. N, 2.25. Found: C,
42.53; H, 1.26; N, 2.08%. IR (KBr, cmꢁ1): masym(COO)
1656; msym(COO) 1384; m(Sn–C) 528; m(Sn–O) 498; m(Sn–
3.2. Syntheses
3.2.1. [Ph3Sn(O2CC6HF4)] (1)
The reaction was carried out under nitrogen atmo-
sphere. 2,3,4,5-Tetrafluorobenzoic acid (0.194 g, 1 mmol)
and sodium ethoxide (0.276 g, 1.2 mmol) were added to
the solution of dry benzene in a Schlenk flask and stirred
for 0.5 h. Triphenyltin chloride (0.385 g, 1 mmol) was then
added to the reactor and the reaction mixture was stirred
for 12 h at 40 ꢁC. After filtration, the solvent was evapo-
rated in vacuo. The solid was recrystallized from ether/
petroleum. Colorless crystal was obtained. Yield: 76%;
m.p. 102–104 ꢁC (dec.). Anal. Calc. for C25H16F4O2Sn:
C, 55.29; H, 2.97. Found: C, 55.48; H, 2.76%. IR (KBr,
cmꢁ1): masym(COO) 1641, msym(COO) 1382, m(Sn–C), 559,
1
N) 454. H NMR (CDCl3, ppm): 7.48–7.62 (m, 2H, Ph–
H). 8.73–8.75 (m, 8H, N–H). 0.61–0.76 (m, 9H). 13C
NMR (CDCl3, ppm): 152.1, 148.9, 146.6, 144.3, 143.8,
141.4. 15.3 (CH3). 119Sn NMR (CDCl3): ꢁ96.8 ppm.
3.2.4. Ph3Sn(O2CC6HF4)] Æ OPPh3 (4)
Complex 4 was prepared in the same way as that of
complex 1, except that excess triphenylphosphine oxide
was added to the mixture. The solid was then recrystallized
from ether/petroleum. Yield: 75%; m.p. 161–163 ꢁC. Anal.
Calc. for C43H31F4O3PSn: C, 62.88; H, 3.80. Found: C,
1
m(Sn–O), 449. H NMR (CDCl3, ppm): d 7. 50–7.71 (m,
1H), d 7.48–7.82 (m, 15H). 13C NMR (CDCl3, ppm): d
167.2, 137.5, 136.5, 130.6, 129.4, 114.3. 119Sn NMR
(CDCl3): ꢁ86.3 ppm.
62.65; H 3.98%. IR (KBr, cmꢁ1): masym(COO) 1662, msym
-
(COO) 1437, m(Sn–C) 540, m(Sn–O) 454. 1H NMR (CDCl3,
ppm): d 7.47–7.68 (m, 1Ph–H), d 7.42–7.80 (m, 15H), 8.70–
8.72 (m, 8N–H). 13C NMR (CDCl3, ppm): d 138.0, 137.6,
136.5, 132.9, 132.0, 131.8, 129.0, 128.6, 113.8. 119Sn
NMR (CDCl3): ꢁ128.6 ppm.
3.2.2. [Ph3Sn(O2CC6HF4)]2 Æ (4,40-bipy) (2)
Complex 2 was prepared in the same way as that of
complex 1 except that excess 4,40-bipy was added to the
mixture. The solid was then recrystallized from ether/
petroleum. Yield: 81%; m.p. 140–142 ꢁC. Anal. Calc. for
C60H40F8N2O4Sn2: C, 58.01; H, 3.24; N, 2.35. Found: C,
58.38; H, 3.08; N, 2.16%. IR (KBr,cmꢁ1): masym(COO)
1648, msym(COO) 1428, m(Sn–C) 557, m(Sn–O) 533, m(Sn–
N) 456. 1H NMR (CDCl3, ppm): d 7.53–7.72 (m, 2H,
3.2.5. [(CH3)3Sn(O2CC6HF4)] Æ OPPh3 (5)
Complex 5 was prepared in the same way as that of
complex 1 except that excess 4,40-bipy was added to the
mixture. The solid was then recrystallized from ether/
petroleum. Yield: 81%; m.p. 140–142 ꢁC. Anal. Calc. for
C28H25F4O3PSn: C, 52.95; H, 3.97. Found: C, 52.69; H,

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C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 5873–5886
4.08%. IR (KBr, cmꢁ1): masym(COO) 1621; msym(COO)
1376; m(P@O) 1168; m(Sn–C) 535; m(Sn–O) 452. H NMR
(CDCl3, ppm): d 7.47–7.80 (m, 1H, Ph–H), d 7.41–7.78
(m, 15H). 13C NMR (CDCl3, ppm): d 137.8, 136.7, 136.4,
132.6, 132.0, 131.7, 130.2, 129.5, 113.6, 14.8 (CH3). 119Sn
NMR (CDCl3): ꢁ98.1 ppm.
NMR (CDCl3, ppm): d 9.20 (s, C10H8N2), d 8.26 (d,
JH,H = 5.8 Hz, 4H, C10H8N2), d 7.47–7.70 (m, 1H, Ph–
H), d 7.41–7.87 (m, 15H). 13C NMR (CDCl3, ppm): d
150.3, 145.8, 137.4, 136.9, 130.5, 129.4, 128.7, 126.5,
123.0, 114.1. 119Sn NMR (CDCl3): ꢁ121.4 ppm.
1
3.2.8. [(CH3)3Sn(O2CC6HF4) Æ (OH2)]2 Æ (1,10-
phen)2C2H5OH (8)
3.2.6. [(CH3)3Sn(O2CC6HF4)2]n (6)
Complex 6 was prepared in the same way as that of
complex 1, the solid was recrystallized from ethanol. Yield:
81%; m.p. 108–110 ꢁC. Anal. Calc. For C20H20F8O4Sn2: C,
33.65; H, 2.82. Found: C 33.32, H 2.97%. IR (KBr, cmꢁ1):
mas(C@O) 1615, ms(C–O) 1475, mas(Sn–C) 555, ms(Sn–C) 524,
m(Sn–O) 483. 1H NMR (CDCl3, ppm): d 7.56–7.67 (m, 2H,
Ph–H), d 0.50–1.26 (m, 18H). 13C NMR (CDCl3, ppm):
166.1, 149.2, 147.4, 146.7, 144.9, 142.4, 140.0, 139.7, 14.6
(CH3). 119Sn NMR (CDCl3): ꢁ94.9 ppm.
Complex 8 was prepared in the same way as that of
complex 1 except that excess 1,10-phen was added to the
mixture. The solid was then recrystallized from ether/
petroleum. Yield: 81%; m.p. 140–142 ꢁC. Anal. Calc. for
C46H46F8N2O4Sn2: C, 51.14; H, 4.29; N, 2.59. Found: C,
51.38; H, 4.36; N, 2.42%. IR (KBr,cmꢁ1): masym(COO)
1659, msym(COO) 1392, m(Sn–C) 542, m(Sn–O) 461. 1H
NMR (CDCl3, ppm): d 7.48–7.71 (m, 1H, Ph–H), d 7.45–
7.81 (m, 15H),
d 9.12 (s, C10H8N2), d 8.42 (d,
JH,H = 6.4 Hz, 4H, C10H8N2). 13C NMR (CDCl3, ppm):
d 150.8, 145.8, 137.4, 136.9, 130.6, 129.6, 128.9, 121.7,
113.5, 113.3, 14.2 (CH3). 119Sn NMR (CDCl3): ꢁ90.3 ppm.
3.2.7. [Ph3Sn(O2CC6HF4) Æ (OH2)]2 Æ (1,10-
Phen)2 Æ C2H5OH (7)
Complex 7 was prepared in the same way as that of
complex 1 except that excess 1,10-Phen was added to the
mixture. The solid was then recrystallized from ether/
petroleum. Yield: 81%; m.p. 140–142 ꢁC. Anal. Calc. for
C76H58F8N4O7Sn2: C, 59.71; H, 3.82; N, 3.66. Found: C,
59.42; H, 3.67; N, 3.82%. IR (KBr, cmꢁ1): masym(COO)
1664, msym(COO) 1425, m(Sn–C) 523, m(Sn–O) 454. 1H
3.3. X-ray crystallography
Crystals were mounted in Lindemann capillaries under
nitrogen. Diffraction data were collected on a Smart-1000
CCD area-detector with graphite monochromated Mo
˚
Ka radiation (k = 0.71073 A). A semi-empirical absorption
Table 4
Crystal, data collection and structure refinement parameters of complexes 1–3
Complexes
1
2
3
Empirical formula
Formula weight
Wavelength (A)
Crystal system
Space group
Unit cell dimensions
C
543.07
0.71073
Orthorhombic
Pbca
25H16F4O2Sn
C60H40F8N2O4Sn2
1242.32
0.71073
Monoclinic
P2(1)/c
C30H10F8N2O4Sn2
851.78
0.71073
˚
Triclinic
ꢀ
P1
˚
a (A)
10.845(2)
10.388(2)
7.003(6)
˚
b (A)
18.442(4)
22.301(5)
13.809(3)
18.865(4)
8.945(8)
13.410(11)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
90
90
90
90
96.952
90
90.090(11)
98.876(11)
96.183(11)
825.0(12)
3
˚
V (A )
4460.3(17)
2686.0(11)
Z
8
2
1
Dcalc (Mg mꢁ3
F(000)
)
1.617
2144
1.198
1.536
1236
1.006
1.715
408
1.594
l (mmꢁ1
)
Crystal size (mm)
h Range
0.45 · 0.38 · 0.29
1.83–25.00
0.48 · 0.46 · 0.40
2.18–25.01
0.48 · 0.40 · 0.36
2.74–28.26
Index ranges
ꢁ12 6 h 6 12
ꢁ15 6 k 6 21
ꢁ26 6 l 6 26
22,046
3925 (0.0671)
Semi-empirical from equivalents
0.7227, 0.6147
3925, 0, 289
1.004
ꢁ11 6 h 6 12
ꢁ15 6 k 6 16
ꢁ22 6 l 6 22
13,842
4729 (0.0387)
Semi-empirical from equivalents
0.6890, 0.6437
4729, 0, 343
1.002
ꢁ6 6 h 6 9
ꢁ11 6 k 6 11
ꢁ17 6 l 6 17
5131
3722 (0.0195)
Semi-empirical from equivalents
0.5976, 0.5149
3722, 0, 208
1.000
Reflections collected
Unique reflections (Rint
Absorbtion correction
Max/min transmission
Data, restraints, parameters
GOF
)
Final R indices [I > 2r(I)]
R indices (all data)
R1 = 0.0419, wR2 = 0.0966
R1 = 0.0929, wR2 = 0.1297
R1 = 0.0345, wR2 = 0.0828
R1 = 0.0596, wR2 = 0.1012
R1 = 0.0318, wR2=0.0777
R1 = 0.0398, wR2 = 0.0843

C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 5873–5886
5885
Table 5
Crystal data collection and structure refinement parameters of complexes 4, 6 and 7
Complexes
4
6
7
Empirical formula
Formula weight
Wavelength (A)
C43H31F4O3PSn
821.34
0.71073
C20H20F8O4Sn
713.74
0.71073
C38H29F4N2O3.5Sn
764.32
0.71073
˚
Crystal system
Space group
Unit cell dimensions
Triclinic
Triclinic
Triclinic
ꢀ
ꢀ
ꢀ
P1
P1
P1
˚
a (A)
12.178(3)
12.210(3)
13.528(3)
85.800(3)
71.632(4)
75.559(3)
1848.8(8)
2
6.8849(17)
9.689(2)
20.087(5)
92.768(3)
96.930(3)
106.223(3)
1272.5(5)
2
9.0937(18)
12.383(3)
15.671(3)
88.772(3)
77.385(3)
88.877(3)
1721.5(6)
2
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
V (A )
Z
Dcalc (Mg mꢁ3
F(000)
l (mmꢁ1
)
1.475
828
0.794
1.863
688
2.044
1.475
770
0.804
)
Crystal size (mm)
h Range
Index ranges
0.44 · 0.23 · 0.12
1.72–25.01
ꢁ7 6 h 6 14
ꢁ12 6 k 6 14
ꢁ15 6 l 6 16
9768
6443 (0.0235)
Semi-empirical from equivalents
0.9108, 0.7215
6443, 0, 478
0.988
0.56 · 0.49 · 0.42
2.05–25.00
ꢁ8 6 h 6 5
ꢁ11 6 k 6 11
ꢁ23 6 l 6 23
6618
4400 (0.0179)
Semi-empirical from equivalents
0.4806, 0.3940
4400, 0, 307
0.998
0.47 · 0.45 · 0.26
2.10–25.01
ꢁ10 6 h 6 10
ꢁ14 6 k 6 10
ꢁ17 6 l 6 18
9079
5996 (0.0283)
Semi-empirical from equivalents
0.8181, 0.7036
Reflections collected
Unique reflections (Rint
Absorbtion correction
Max/min transmission
Data, restraints, parameters
GOF
)
5996, 327, 458
1.003
Final R indices [I > 2r(I)]
R indices (all data)
R1 = 0.0398, wR2 = 0.0866
R1 = 0.0662, wR2 = 0.1032
R1 = 0.0361, wR2 = 0.0962
R1 = 0.0457, wR2 = 0.1031
R1 = 0.0465, wR2 = 0.1106
R1 = 0.0674, wR2 = 0.1255
(b) C.N.R. Rao, S. Natarajan, R. Vaidhyanathan, Angew. Chem.,
Int. Ed. 43 (2004) 1466.
[2] (a) S.I. Stupp, P.V. Braun, Science 277 (1997) 1242;
(b) U.B. Sleytr, P. Messner, D. Pum, M. Sara, Angew. Chem., Int.
Ed. 38 (1999) 1034.
[3] W.L. Jorgensen, D.L. Severance, J. Am. Chem. Soc. 112 (1990)
4768.
[4] (a) J.P. Ashmore, T. Chivers, K.A. Kerr, J.H.G. Van Roode, Inorg.
Chem. 16 (1977) 191;
correction was applied to the data. The structure was
solved by direct methods using SHELXLS-97 and refined
against F2 by full matrix least squares using SHELXL-97.
Hydrogen atoms were placed in calculated positions. Crys-
tal data and experimental details of the structure determi-
nations are listed in Tables 4 and 5.
4. Supplementary material
(b) J.H. Wengrovius, M.F. Garbauskas, Organometallics 11 (1992)
1334.
CCDC 609762, 609764, 609765, 609766, 609763 and
609767 contain the supplementary crystallographic data
for 1, 2, 3, 4, 6 and 7. These data can be obtained free of
charge via http://www.ccdc.cam.ac.uk/conts/retrieving.
html, or from the Cambridge Crystallographic Data Cen-
tre, 12 Union Road, Cambridge CB2 1EZ, UK; fax:
(+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
[5] (a) C.L. Ma, Y.F. Han, R.F. Zhang, Daqi Wang, J. Chem. Soc.,
Dalton Trans. (2004) 1832;
(b) C.L. Ma, J.F. Sun, J. Chem. Soc., Dalton Trans. (2004) 1785.
[6] C.L. Ma, J.K. Li, R.F. Zhang, D.Q. Wang, Inorg. Chim. Acta 359
(2006) 2407.
[7] Biradha Kumar, Michael J. Zaworotko, J. Am. Chem. Soc. 120
(1998) 6431.
[8] R.R. Holmes, C.G. Schmid, V. Chandrasekhar, R.O. Day, J.M.
Homels, J. Am. Chem. Soc. 109 (1987) 1408.
[9] H.A. Cruse, N.E. Leadbeater, Inorg. Chem. 38 (1999) 4149.
[10] (a) G.K. Saudhu, R. Gupta, S.S. Sandhu, R.V. Parish, Polyhedron 4
(1985) 81;
Acknowledgement
(b) G.K. Saudhu, R. Gupta, S.S. Sandhu, R.V. Parish, K. Brown, J.
Organomet. Chem. 279 (1985) 373.
[11] I. Lange, E. Wieland, P.G. Jones, A. Blaschette, J. Organomet.
Chem. 458 (1993) 57.
We thank the National Nature Science Foundation of
China (20271025) for financial support.
[12] J. Holecek, A. Lycka, Inorg. Chim. Acta 118 (1986) 15.
[13] F. Ribot, C. Sanchez, A. Meddour, M. Gielen, E.R.T. Tiekink, M.
Biesemans, R. Willem, J. Organomet. Chem. 552 (1998) 177.
References
´
´
´
[14] J. Holee˘ek, A. Lye˘ka, K. Handllr, M. Nadvornlk, Collect. Czech.
[1] (a) P.J. Hagrman, D. Hagrman, J. Zubieta, Angew. Chem., Int. Ed.
38 (1999) 2638;
Chem. Commun. 55 (1990) 1193.

5886
C. Ma et al. / Journal of Organometallic Chemistry 691 (2006) 5873–5886
[15] A.R. Forrester, S.J. Garden, R.A. Howie, J.L. Wardell, J. Chem.
Soc., Dalton Trans. (1992) 2615.
[16] F.H. Allen, J.E. Davies, J.J. Galloy, O. Johnson, O. Kennard, C.F.
Macrae, E.M. Mitchell, G.F. Mitchell, J.M. Smith, D.G. Watson, J.
Chem. Inf. Comp. Sci. 31 (1991) 187.
[20] A. Bondi, J. Phys. Chem. 68 (1964) 441.
[21] G. Bandoli, G. Bortolozzo, D.A. Clemente, U. Croatto, C. Panattoni,
J. Chem. Soc. A (1970) 2778.
[22] o-Phenanthroline crystallizes as a monohydrate in the trigonal P31
or P32 space group but no structural details were given in S.
[17] (a) R.G. Swisher, J.F. Vollano, V. Chandrasekhar, R.R. Holmes,
Inorg. Chem. 23 (1984) 3147;
Nishigaki, H. Yoshioka, K. Nakatsu, Acta Crystallogr.
(1975) 1220;
B 31
(b) J.F. Vollano, R.O. Day, D.N. Rau, V. Chandrasekhar, R.R.
Holmes, Inorg. Chem. 23 (1984) 3153.
G. Thevenet, P. Toffoli, R. Ceolin, N. Rodier, C.R. Hebd, Sci.,
Ser. C 283 (1976) 671.
[18] V. Berceanc, C. Crainic, I. Haiduc, M.F. Mahon, K.C. Molloy,
M.M. Venter, P.J. Wilson, J. Chem. Soc., Dalton Trans. (2002) 1036.
[19] (a) M. Hill, M.F. Mahon, K.C. Molloy, J. Chem. Soc., Dalton
Trans. (1996) 1857;
[23] Seik Weng Ng, V.G. Kumar Das, J. Organomet. Chem. 513 (1996)
105.
[24] L. Prasad, F.L. Lee, Ye Page, F.E. Smith, Acta Crystallogr. B38
(1982) 259.
(b) S. Bhandari, M.F. Mahon, K.C. Molloy, J. Chem. Soc., Dalton
Trans. (1999) 1951.
[25] O.J. Dautel, M.F. Ourmigue, J. Org. Chem. 65 (2000)
6479.