Syntheses, crystal structures, and quadratic nonlinear optical properties in four push-pull diorganotin derivatives

Article abstract of DOI:10.1016/j.jorganchem.2004.04.012

Four push-pull diorganotin compounds obtained by reaction of methoxysalicylaldehyde or 4-diethylaminosalicylaldehyde, 2-amino-5-nitrophenol and dibutyltin or diphenyltin oxide are reported. The molecular structures for the diphenyl derivatives, in the solid state, show a tin in a distorted trigonal bipyramid geometry with the oxygen atoms in axial positions and the organic moieties and iminic nitrogen in equatorial ones. For the dibutyl derivative, a dimeric structure was favored due to intermolecular interactions between the tin and oxygen atoms, in this case, the tin atom shows a distorted octahedral geometry. A computational study of the diethyl derivatives constructed from the available dibutyl structure, at DFT level, revealed that the main differences between the solid and gas phases are the geometry around the tin atom and the π-conjugated organic backbone which is nearly planar in the solid state and distorted in the gas phase. The electric field induced second-harmonic (EFISH) of the nonlinear optical (NLO) response for the dibutyl derivatives revealed that the change from boron to tin increases 1.5 times the hyperpolarizabilities (β).

Full text of DOI:10.1016/j.jorganchem.2004.04.012

Journal of Organometallic Chemistry 689 (2004) 2303–2310
www.elsevier.com/locate/jorganchem
Syntheses, crystal structures, and quadratic nonlinear
optical properties in four ‘‘push–pull’’ diorganotin derivatives
a,
a
a,
a
*
Horacio Reyes , Concepcion Garcıa , Norberto Farfan *, Rosa Santillan ,
ꢀ
ꢀ
ꢀ
b,
b
c
Pascal G. Lacroix *, Christine Lepetit , Keitaro Nakatani
a
Departamento de Quꢀımica, Centro de Investigaciꢀon y de Estudios Avanzados del IPN, Apdo. Postal 14-740, 07000 Mꢀexico, Mꢀexico
Laboratoire de Chimie de Coordination du CNRS, 205 Route de Narbonne, 31077 Toulouse Cedex, 04, France
b
c
Laboratoire de Photophysique et Photochimie Supramolꢀeculaires et Macromolꢀeculaires (UMR8531 du CNRS),
Ecole Normale Supꢀerieure de Cachan, Avenue du Prꢀesident Wilson, 94235 Cachan, France
Received 24 February 2004; accepted 8 April 2004
Abstract
Four ‘‘push–pull’’ diorganotin compounds obtained by reaction of methoxysalicylaldehyde or 4-diethylaminosalicylaldehyde,
2-amino-5-nitrophenol and dibutyltin or diphenyltin oxide are reported. The molecular structures for the diphenyl derivatives, in the
solid state, show a tin in a distorted trigonal bipyramid geometry with the oxygen atoms in axial positions and the organic moieties
and iminic nitrogen in equatorial ones. For the dibutyl derivative, a dimeric structure was favored due to intermolecular interactions
between the tin and oxygen atoms, in this case, the tin atom shows a distorted octahedral geometry. A computational study of the
diethyl derivatives constructed from the available dibutyl structure, at DFT level, revealed that the main differences between the
solid and gas phases are the geometry around the tin atom and the p-conjugated organic backbone which is nearly planar in the solid
state and distorted in the gas phase. The electric field induced second-harmonic (EFISH) of the nonlinear optical (NLO) response
for the dibutyl derivatives revealed that the change from boron to tin increases 1.5 times the hyperpolarizabilities (b).
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Diorganotin; Multinuclear NMR; X-ray structure; NLO properties; DFT
1. Introduction
Moreover, there has been considerable interest in the
introduction of metal [5] or organometallic [6] fragments
in molecules with nonlinear optical properties (NLO)
with the aim to improve properties such as: increased
thermal stability [7], increased NLO response [8], to in-
troduce chiral moieties which are important for bulk
response [9], or to offer the possibility of switching such
properties [10]. In a previous paper, we reported a series
of ‘‘push–pull’’ boronates (Scheme 1) in which the
possibility of switching NLO properties taking advan-
tage of the rotation of the phenyl ring attached to the
boron atom was studied using a semiempirical approach
[11]. However, the NLO skeleton in the boron deriva-
tives was found to be invariably bent, leading to chro-
mophores with reduced NLO response. In order to
overpass this difficulty and to extend the range of metal
organic NLO materials, we report in the present inves-
tigation on the syntheses of four ‘‘push–pull’’ diorg-
anotin derivatives, their spectroscopic characterization,
Recently, diorganotin (IV) complexes have attracted
considerable attention due to potential application in
homogeneous catalysis [1] and medicinal chemistry, as
anti-cancer agents [2]. In particular, diorganotin (IV)
complexes have shown higher antitumor activity in vitro
and in vivo, as well as lower toxicity than other well-
known drugs like cis-platin [3]. An important class of
diorganotin (IV) complexes are derived from Schiff ba-
ses, in this respect we have reported a series of diorg-
anotin complexes containing aminoacid fragments in
which different correlations were found between the
spectroscopic data and the X-ray structures [4].
* Corresponding authors. Tel.: +52-55-57-47-37-25; fax: +52-55-57-
47-71-13.
ꢀ
E-mail addresses: jfarfan@mail.cinvestav.mx (N. Farfan), pas-
cal@lcc-toulouse.fr (P.G. Lacroix).
0022-328X/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.04.012

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H. Reyes et al. / Journal of Organometallic Chemistry 689 (2004) 2303–2310
(H-7) between 8.29 and 8.58 ppm confirms formation of
the product, in general, complexes with a Et2N group
appear at higher frequencies than CH3O derivatives.
NO2
N
B
O
R
O
3
The iminic signal shows a J(Sn–H) coupling with the
117Sn and 119Sn nuclei in the range between 45 and 60
Hz, this fact is indicative of Sn–N coordination, as
shown in the solid state. The individual rings in the
complexes were differentiated based on their COSY
spectra which allow correlation between the protons in
the ring containing the electron-withdrawing group and
those of the ring with the electron-donating group. The
COSY spectra were necessary because the multiplicity
and chemical shifts of some signals are almost identical.
In the case of the diphenyl derivatives, correct assign-
ment of the signals to a particular ring is not trivial due
to the presence of three different aromatic rings.
R
1a OCH3
2a NEt2
Scheme 1.
X-ray diffraction studies as well as DFT calculations of
geometry and NLO response in solution.
2. Results and discussion
An important data that allows to estimate the C–Sn–
1
C angle in solution is the J(119Sn–13C), which in the
2.1. Synthetic aspects
case of dibutyl derivatives shows values of 600 and 621
Hz for 1b and 2b, respectively. These values allowed to
calculate the C–Sn–C angle using the equation proposed
The most common route for the synthesis of this kind
of complexes is the reaction of SnX2R2 (X ¼ halogen,
R ¼ alkyl, phenyl) with a tridentate ligand in the pres-
ence of a strong base, a procedure which requires two
steps. In a recent paper, a one step synthesis of tin
complexes from Schiff bases that involves the reaction of
salicylaldehyde, an aminoacid and a diorganotin oxide,
under reflux of an adequate solvent was reported [4]. In
this case the Schiff base is formed in situ and then re-
acted with tin to form the complex. The previous
methodology was followed for the preparation of the
derivatives reported herein (1b, 1c, 2b and 2c). Thus,
SnOR2 (R ¼ Ph, Bu) was reacted with 2-amino-5-nitro-
phenol and the corresponding salicylaldehyde in aceto-
nitrile under reflux, as shown in Scheme 2. The reactions
were considered completed when all the diorganotin
oxide was dissolved (3 h for dibutyltin oxide and 48 h
for diphenyltin oxide).
ꢁ
by Holecek et al. [12] (134.8° for 1b and 136.8° for 2b).
For the diphenyl derivatives, the coupling constants
were 1007 Hz for 1c and 1022 Hz for 2c while the Ph–
Sn–Ph angle were 122.5° and 127.0°, respectively [4].
The 119Sn NMR spectra for the four compounds
show a single sharp signal at )176.6 and )178.0 ppm for
the dibutyl derivatives (1b, 2b) and )320.6 and )319.3
ppm for the diphenyl derivatives (1c, 2c), characteristic
for diorganotin complexes with a pentacoordinated ge-
ometry. It is well known also that the 119Sn signals shift
to lower frequencies upon substitution of a butyl for a
phenyl group [13].
The experimental UV–Vis data for the tin and boron
derivatives are summarized in Table 1. In addition to the
well-documented shift to higher wavelengths and in-
tensities as the donor–acceptor strength is increased, it is
important to notice that an additional red shift and in-
creased intensity is achieved on going from boron to tin.
This observation is consistent with an increased pla-
narity in the tin compounds, as discussed in the next
section.
2.2. Spectroscopic properties
1
The H NMR data for all compounds is reported in
Section 4, the presence of a signal for the iminic proton
12
13
O
7
11
6
8
NO2
NH2
1
2
5
H
SnOR2
CH3CN, reflux
N
+
10
1
9
1
Sn
R
OH
O2N
OH
O
R2
4
R
O
3
R2
R1
R2
1b
1c
2b
2c
OCH3
OCH3
NEt2
n-Bu
Ph
n-Bu
Ph
NEt2
Scheme 2.

H. Reyes et al. / Journal of Organometallic Chemistry 689 (2004) 2303–2310
2305
Table 1
The change in coordination geometry when the boron
atom is substituted by tin is indicative that the p-con-
jugated organic backbone is changed from a bent system
in boron chromophores to nearly planar in the tin de-
rivatives, as evidenced by the crystal structures of 1b, 1c
and 2c (Figs. 1–3). This increased planarity would be
expected to increase considerably the intramolecular
charge transfer properties, and hence the hyper-
polarizability. However, recent combined theoretical-
crystallographic studies have shown differences in
conformational and geometrical parameters for diorg-
anotin systems in the solid and gas phases which can be
attributed to crystal packing effects [15]. This observa-
tion raises the issue of whether the planarity of the
molecule is due to packing factors or to an intrinsic
stability of the molecular geometry. To clarify this
question, a theoretical study at the DFT level was per-
formed. Initially calculations were run on the butyl de-
rivative, however, they showed no minimum. Thus, the
gas-phase structures of the analogous diethyl derivatives
constructed from the available X-ray data for the di-
butyl complex were calculated within the framework of
DFT theory, to avoid the effect of the environment. An
important difference between the solid and gas phase
structures is a sizeable reduction of the C–Sn–C angle,
as illustrated in Fig. 4. This difference is consistent with
the presence of intermolecular Sn–O interactions with a
neighbouring molecule, which pushes the hydrocarbon
chains apart from one another. It is important to notice
that the angles in the gas phase are significantly smaller
than those based on coupling constant values deter-
mined in solution. More importantly, the crystal struc-
Comparison of the experimental low lying intense transitions (kmax in
nm) and intensities (e in dm3 molꢀ1 cmꢀ1) for organotin and boron
chromophores
kmax
e
1a [11]
1b
1c
452
464
459
475
486
477
16 400
27 700
24 800
43 300
55 700
48 200
2a [11]
2b
2c
2.3. Molecular structure of tin derivatives
An important issue when comparing the NLO re-
sponse of the tin and boron chromophores is related to
the change in molecular geometry. We reported previ-
ously that boron-based chromophores are strongly bent
as a result of the tetrahedral coordination sphere around
the boron atom, leading to reduced NLO responses
when compared to the related and well-known stilbene-
based chromophores. In the case of the diphenyl tin
chromophores, the tin atom shows a distorted trigonal
bipyramid geometry, the axial positions being occupied
by the oxygen atoms and the equatorial ones by organic
moieties and the iminic nitrogen, in the solid state. The
distances and angles around the tin atom are shown in
Table 2. The distances are comparable with those pre-
viously reported in similar complexes [14]. However, in
dibutyl derivative 1b, the compound is a dimer with Sn–
O intermolecular interactions. This fact modifies the
coordination around the tin atom which show a dis-
torted octahedral geometry with Sn–O interaction dis-
ꢂ
tances of 3.033(4) A. The dimeric structure is assembled
through the formation of a four-membered Sn–O(2)–
Sn–O(2) ring.
Table 2
ꢂ
Selected bond lengths (A) and angles (°) around the tin atom for 1b, 1c,
2c (e.s.d’s are in parentheses)
1b
1c
2c
C(14)–Sn(1)
C(14a)–Sn(1)
N(1)–Sn(1)
O(2)–Sn(1)
O(1)–Sn(1)
2.122(4)
2.146(5)
2.208(3)
2.119(3)
2.137(3)
2.118(3)
2.110(3)
2.125(6)
2.119(6)
2.155(5)
2.106(4)
2.079(4)
2.180(2)
2.0943(18)
2.0879(19)
O(2)–Sn(1)–C(14)
O(2)–Sn(1)–O(1)
C(14)–Sn(1)–O(1)
O(2)–Sn(1)–C(14a)
C(14)–Sn(1)–C(14a)
O(1)–Sn(1)–C(14a)
O(2)–Sn(1)–N(1)
C(14)–Sn(1)–N(1)
O(1)–Sn(1)–N(1)
C(14a)–Sn(1)–N(1)
95.76(15)
156.29(12)
86.86(15)
96.30(19)
140.8(2)
96.03(9)
160.66(7)
94.53(10)
95.32(9)
93.4(2)
162.21(16)
93.4(2)
94.6(2)
125.7(2)
94.7(2)
122.01(10)
92.74(9)
77.24(7)
96.4(2)
76.03(10)
115.12(13)
81.52(11)
104.00(18)
76.84(18)
123.64(19)
85.71(18)
110.43(19)
114.35(9)
83.66(8)
114.35(9)
Fig. 1. Dimeric structure of 1b. H atoms were omitted for clarity
(thermal ellipsoids at 30%).

2306
H. Reyes et al. / Journal of Organometallic Chemistry 689 (2004) 2303–2310
O3
which is expected to red shift the electronic transitions,
and finally to enhance the NLO response.
C12
C13
C8
C6
C5
C11
N2
2.4. NLO response
C7
C1
C4
O5
N1
O4
Analysis of the spectroscopic data, in particular the
UV and the molecular structures, reveals that one can
expect almost the same NLO response for dibutyl or
diphenyl-based chromophores. Since the dibutyl deriv-
atives are more soluble in common organic solvents they
were selected for the NLO studies. The electric field in-
duced second-harmonic (EFISH) data for 1b and 2b are
summarized in Table 3 and compared to those of the
boron derivatives previously investigated. Before dis-
cussing the NLO response for both families of organo-
metallic chromophores, it is important to observe that
the agreement between experimental and calculated data
is satisfactory, within the formalism of the DFT meth-
od. On the other hand, the ZINDO (Zerner intermediate
neglect of differential overlap) method [16], which has
been successfully used in connection with the sum-
over-state (SOS) formalism [17] for the description of
numerous organometallic chromophores cannot be
employed in the present case since tin is not parame-
trized in the ZINDO releases commercially available. As
a major consequence, it is not possible to establish
precisely the relationship between the NLO responses,
and the optical spectra for the tin derivatives. Never-
theless, the effect of the experimental red shift and in-
creased intensity evidenced on the electronic spectra on
going from boron to tin derivatives may tentatively be
analysed within the framework of the two-level quan-
tum description of the NLO response.
C10
C9
C2
O1
C3
Sn1
C20
O2
C15
C14
C14a
C19a
C18a
C16
C19
C15a
C16a
C17a
C17
C18
Fig. 2. Molecular structure of 1c. H atoms were omitted for clarity
(thermal ellipsoids at 30%).
O4
C12
C13
C6
C21
C5
C11
N2
O3
C20
C7
C8
C1
N1
N3
C9
O2
C4
C10
C22
C2
O1
C14
Sn1
C3
C19a
C14a
C15
C19
C15a
C18a
C23
C16
C18
C16a
C17a
C17
Fig. 3. Molecular structure of 2c. H atoms and one disorder molecule
of CHCl3 were omitted for clarity (thermal ellipsoids at 30%).
Table 3
Experimental EFISH data (b in cm5 esuꢀ1 and l in D) for 1b, 2b
recorded at 1.907 lm, and DFT calculated values
ture shows an angle of 8.1° between the methoxyphenyl
and the nitrophenyl moieties, as a result of a nearly
planar geometry. By comparison, the calculated struc-
tures reveal angles of 22.8° and 22.0° between the phenyl
rings in 1b and 2b, respectively. Therefore, even if the
planarity is partially explained by crystal packing effects,
the large torsion angle observed in the boron derivatives
is undoubtedly reduced in the tin analogues. This ten-
dency will favour a better charge transfer delocalization,
Experimental data
DFT calculated values
b
l
b
l
1a [11]
1b
27.0
48.9
46.4
63.5
10.2
10.2
13.6
12.6
40.2
9.64
12.8
2a [11]
2b
73.8
The NLO responses of the boron-based chromophores 1a, 2a are
shown for reference.
O
O
156.4˚
C
158.7˚
O
158.1˚
C
C
Sn
Sn
Sn
140.7˚
O
126.3˚
O
127.0˚
O
C
C
C
1b
X-ray structure
1b
2b
diethyl derivative analogue
gas phase
diethyl derivative analogue
gas phase
Fig. 4. Gas-phase coordination sphere of the tin atom compared to that of the available crystal structure data.

H. Reyes et al. / Journal of Organometallic Chemistry 689 (2004) 2303–2310
2307
In ‘‘push–pull’’ stilbene-based chromophores, a sim-
ple two-level model is a widely used guideline, this as-
sumes that the low-lying electronic transition is
responsible for most of the NLO response. In this
model, b is described in terms of a ground and a first
excited-state having a charge-transfer character and re-
lated to the energy of the optical transition (E), its os-
cillator strength (f), and the difference between the
ground and excited state dipole moment (Dl) through
the relation [18]
atom. The results show that metal organic tin deriva-
tives, which up to now have not been investigated that
much in molecular electronics might be envisioned as
good candidates for NLO due to excellent planarity. In
this respect, chiral tin-based Schiff bases complexes have
recently been reported [4]. This route could allow to
engineer tin-based chromophores in various acentric
environments, which is an requisite for a bulk NLO
response.
3e2ꢃh2f ðDlÞz
2mE3
E4
2
4. Experimental
ꢀ
ꢁꢀ
ꢁ
bzzz
¼
:
ð1Þ
2
E2 ꢀ ð2ꢃhxÞ
E2 ꢀ ðꢃhxÞ
All starting materials were commercially available.
Solvents were used without further purification. Melting
points were recorded on a Gallenkamp MFB-595 ap-
paratus and are uncorrected. Infrared spectra were
measured on a Perkin–Elmer 16F-PC FT-IR spectrom-
In this equation, ꢃhx is the energy of the incident laser
beam. Owing to the pseudo-stilbene type of the organic
skeleton, and ‘‘push–pull’’ character of the molecules,
we will assume that, to a large extend, the two-level
model can lead to a rationale for the origin of the NLO
response. For the methoxy-containing chromophores,
the red shift and increased intensity obtained on going
from boron to tin (Table 1) leads to a b value 1.8 time
larger for 1b than for the parent boron derivative,
through the estimation provided by Eq. (1). In the case
of 2b, there is an enhancement of 1.4 times. Both esti-
mations are fully consistent with the experimentally
determined b value summarized in Table 3, providing a
satisfactory understanding for the modulation of
the NLO properties in these organometallic NLO
chromophores.
1
eter. H, 119Sn and 13C-NMR spectra were recorded on
a Bruker avance DPX 300 spectrometer. Chemical shifts
1
(ppm) are relative to (CH3)4Si for H and 13C and to
Sn(CH3)4 for 119Sn. UV spectra were obtained with a
Perkin–Elmer Lambda 12 UV/Vis spectrophotometer.
Mass spectra were recorded on a HP 5989A spectrom-
eter. Elemental analyses were carried out on a Thermo
Finnigan Flash 1112 elemental microanalizer.
4.1. Syntheses
The following procedure was used in the syntheses of
the four compounds studied herein. Equimolecular
amounts of 4-diethylaminosalicylaldehyde (or 4-meth-
oxysalicylaldehyde), 2-amino-5-nitrophenol and dibu-
tyltin oxide (or diphenyltin oxide) were refluxed in
acetonitrile for 3 h for the dibutyl derivatives and 48 h
for the diphenyl derivatives. The solvent was removed
under vacuo and the products recrystallized from chlo-
roform–hexane to yield the products.
3. Conclusion
The work described herein shows that this kind of
‘‘push–pull’’ diorganotin complexes can be easily pre-
pared and have better NLO properties than the boron
derivatives previously reported. The increase in b is in
the order of 1.5 times and can be attributed to the fact
that the tin derivatives are more planar than the corre-
sponding boron complexes, as established by X-ray
diffraction studies. However, crystal packing effects are
partially responsible for this planarity, as shown by
DFT calculations, which revealed that in the gas phase
the structure of the organic p backbone is less planar
than in the solid state. Moreover, in the solid state, the
geometry of the tin atom in the dibutyl derivatives is
affected by neighboring molecules due to formation of
Sn–O intermolecular interaction. These interactions are
not present in the gas phase and the most important
consequence is the modification in the C–Sn–C angle,
which is close to 13°. In our opinion, the fact that diethyl
derivatives were used for geometry optimizations in-
stead of the dibutyl derivative, which did not show a
minimum, should have no effect in the planarity of the
molecule in the gas phase or the geometry around the tin
4.1.1. 2,2-Di-n-butyl-6-aza-1,3-dioxa-11-methoxy-16-ni-
tro-2-stannabenzocyclononene (1b)
Compound 1b was obtained from 0.30 g (2.0 mmol)
of methoxysalicylaldehyde, 0.30 g (2.0 mmol) of 2-ami-
no-5-nitrophenol and 0.49 g (2.0 mmol) of dibutyltin
oxide. The product was obtained as a red solid (0.90 g,
1
1.7 mmol), m.p. 102–103 °C, yield: 86%. H NMR (300
MHz, CDCl3): d, 0.86 (t, J ¼ 7.3, 6H, H-17), 1.32 (sx,
J ¼ 7.3, 4H, H-16), 1.53 (m, 4H, H-14), 1.67 (m, 4H, H-
15), 3.86 (s, 3H, OCH3), 6.23 (d, J ¼ 2.4, 1H, H-3), 6.39
(dd, J ¼ 2.4, 8.9, 1H, H-5), 7.17 (d, J ¼ 8.9, 1H, H-6),
7.33 (d, J ¼ 8.9, 1H, H-13), 7.56 (dd, J ¼ 2.5, 8.9, 1H, H-
12), 7.62 (d, J ¼ 2.5, 1H, H-10), 8.56 (s, 3J119=117Sn–
1H ¼ 45.3 Hz, 1H, H-7); 13C NMR (75.4 MHz, CDCl3):
d, 13.6 (C-17), 22.3 (1J119Sn–13C ¼ 600.0, C-14), 26.6
(C-16), 26.9 (C-15), 55.7 (OCH3), 103.5 (C-3), 109.5 (C-
5), 111.4 (C-12), 112.5 (C-1), 112.6 (C-10), 114.2 (C-13),

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H. Reyes et al. / Journal of Organometallic Chemistry 689 (2004) 2303–2310
137.5 (C-6), 138.4 (C-11), 147.5 (C-8), 159.0 (C-9), 162.6
(C-7), 168.9 (C-4), 173.7 (C-2); 119Sn NMR (111.9 MHz,
CDCl3): d, )176.6 ppm; IR (KBr): m, 2956, 2920, 1614,
(C@N), 1588, 1564, 1514, 1486, 1308, 1256, 1210, 1174;
MS m=z (%): 520 (58) [Mþ, (120Sn)], 518 (42) [Mþ,
CDCl3): d, )320.6 ppm; IR (KBr): m, 3051, 1733, 1613
(C@N), 1514, 1487, 1438, 1410, 1380, 1334, 1305, 1075,
863; MS m=z (%): 560 (94) [Mþ, (120Sn)], 558 (71) [Mþ,
(
118Sn)], 556 (40) [Mþ, (116Sn)], 483 (100), 437 (15), 406
(26), 255 (22), 240 (23), 212 (63). Elemental Anal. Calc.
for C26H20N2O5Sn: C, 55.89; H, 3.60; N, 5.01. Found:
C, 56.07; H, 3.60; N, 5.10%.
(
118Sn)], 516 (23) [Mþ, (116Sn)], 463 (100), 461 (86), 459
(48), 407 (74), 405 (65), 403 (40), 361 (8), 359 (7), 357 (5).
Elemental Anal. Calc. for C22H28N2O5Sn: C, 50.90; H,
5.44; N, 5.40. Found: C, 51.08; H, 5.44; N, 5.63%.
4.1.4. 2,2-Diphenyl-6-aza-1,3-dioxa-11-diethylamino-16-
nitro-2-stannabenzocyclononene (2c)
4.1.2. 2,2-Di-n-butyl-6-aza-1,3-dioxa-11-diethylamino-
16-nitro-2-stannabenzocyclononene (2b)
Compound 2c was obtained from 0.38 g (2.0 mmol)
of diethylaminosalicylaldehyde, 0.30 g (2.0 mmol) of 2-
amino-5-nitrophenol and 0.56 g (2.0 mmol) of diphe-
nyltin oxide. The product was obtained as a red solid
(0.98 g, 1.6 mmol), m.p. 281–282 °C, yield: 82%. 1H
NMR (300 MHz,): d, 1.31 (t, J ¼ 7.0, 6H, CH3), 3.50 (q,
J ¼ 7.0, 4H, CH2), 6.21 (d, J ¼ 2.2, 1H, H-3), 6.26 (dd,
J ¼ 2.2, 9.2, 1H, H-5), 7.02 (d, J ¼ 9.2, 1H, H-6), 7.23 (d,
J ¼ 8.8, 1H, H-13), 7.36–7.44 (m, 6H, Hmeta Hpara), 7.55
(dd, J ¼ 2.2, 8.8, 1H, H-12), 7.84 (d, J ¼ 2.2, 1H, H-10),
7.91–7.93 (m, 4H, Hortho), 8.29 (s, 3J119=117Sn–1H ¼ 59.7,
1H, H-7); 13C NMR (75.4 MHz, CDCl3): d, 13.3 (CH3),
45.5 (CH2), 100.8 (C-3), 106.7 (C-5), 110.4 (C-1), 112.4
(C-12), 112.7 (C-10), 113.3 (C-13), 129.1 (Cmeta), 130.7
(Cpara), 136.9 (Cortho), 138.7 (C-6), 139.3 (1J119Sn–
13C ¼ 1022.1, Cipso), 140.4 (C-11), 146.5 (C-8), 156.6 (C-
9), 157.9 (C-4), 158.9 (C-7), 172.4 (C-2); 119Sn NMR
(111.9 MHz, CDCl3): d, )319.3; IR (KBr): m, 3052, 2972,
2927, 1615 (C@N), 1588, 1558, 1491, 1432, 1328, 1242,
1070, 732; MS m=z (%): 601 (100) [Mþ, (120Sn)], 599 (77)
[Mþ, (118Sn)], 597 (41) [Mþ, (116Sn)], 586 (21), 524 (53),
432 (27), 312 (16), 253 (42), 209 (42); Elemental Anal.
Calc. for C29H27N3O4Sn: C, 58.02; H, 4.53; N, 7.00.
Found: C, 57.73; H, 4.51; N, 6.85%.
Compound 2b was obtained from 0.38 g (2.0 mmol)
of 4-diethylaminosalicylaldehyde, 0.30 g (2.0 mmol) of
2-amino-5-nitrophenol and 0.49 g (2.0 mmol) of dibu-
tyltin oxide. The product was obtained as a red solid
(1.00 g, 1.9 mmol), m.p. 127–129 °C, yield: 90%. 1H
NMR (300 MHz, CDCl3): d, 0.84 (t, J ¼ 7.3, 6H, H-17),
1.23 (t, J ¼ 7.3, 6H, CH3), 1.33 (sx, J ¼ 7.3, 4H, H-16),
1.47 (m, 4H, H-14), 1.64 (m, 4H, H-15), 3.42 (q, 4H,
NCH2), 5.90 (d, J ¼ 2.4, 1H, H-3), 6.24 (dd, J ¼ 2.4, 9.0,
1H, H-5), 7.03 (d, J ¼ 9.0, 1H, H-6), 7.23 (d, J ¼ 8.9, 1H,
H-13), 7.53 (dd, J ¼ 2.5, 8.9, 1H, H-12), 7.58 (d, J ¼ 2.5,
3
1H, H-10), 8.30 (s, J119=117Sn–1H ¼ 48.7, 1H, H-7); 13C
NMR (75.4 MHz, CDCl3): d, 13.1 (CH3), 13.8 (C-17),
22.1 (1J119Sn–13C ¼ 621.7, C-14), 26.8 (C-16), 27.1 (C-
15), 45.1 (NCH2), 100.3 (C-3), 106.1 (C-5), 110.2 (C-12),
111.6 (C-10), 111.9 (C-1), 113.3 (C-13), 138.4 (C-6),
139.8 (C-11), 146.5 (C-8), 156.1 (C-9), 158.6 (C-4), 159.3
(C-7), 172.2 (C-2); 119Sn NMR (111.9 MHz, CDCl3): d,
)178.0 ppm; IR (KBr): m, 2956, 2920, 2870, 1614
(C@N), 1586, 1560, 1492, 1306, 1142, 828; MS m=z (%):
561 (41) [Mþ, (120Sn), 559 (30) [Mþ, (118Sn)], 557 (17)
[Mþ, (116Sn)], 504 (81), 502 (60), 500 (32), 447 (100), 445
(74), 443(38). Elemental Anal. Calc. for C25H35N3O4Sn:
C, 53.60; H, 6.30; N,7.50. Found: C, 53.30; H, 6.17; N,
7.95%.
4.2. X-ray data collection and structure determination
X-ray diffraction studies were determined on an En-
raf Nonius-CAD4 area detector diffractometer (Mo Ka;
k ¼ 0:71073 A, graphite monochromator, T ¼ 293 K,
4.1.3. 2,2-Diphenyl-6-aza-1,3-dioxa-11-methoxy-16-ni-
tro-2-stannabenzocyclononene (1c)
ꢂ
Compound 1c was obtained from 0.30 g (2.0 mmol)
of methoxysalicylaldehyde, 0.30 g (2.0 mmol) of 2-ami-
no-5-nitrophenol and 0.56 g (2.0 mmol) of diphenyltin
oxide. The product was obtained as orange solid (1.06 g,
x=2h scan mode) the crystals were mounted in LIND-
EMAN tubes. Absorption correction was performed
with SHELX-A procedure [19]. Corrections were made
for Lorentz and polarization effects. Solution and re-
finement: direct methods (SHELXS-97) for structure so-
lution and SHELXL-97 ver. 34 for refinement and data
output [19] were applied using the WIN-GX program set
[20], the corresponding images were prepared with the
ORTEP 3 program [21]. Hydrogen atoms were deter-
mined by difference Fourier maps and systematically
model situation and calculation, as well as one overall
isotropic thermal parameter for refinement, the other
nonhydrogen atoms were refined anisotropically.
Crystallographic data for the four diorganotin com-
plexes are summarized in Table 4.
1
1.7 mmol), m.p. 259–262 °C, yield: 94%. H NMR (300
MHz, CDCl3): d, 3.96 (s, 3H, OCH3), 6.45 (dd, J ¼ 2.4,
8.9, 1H, H-5), 6.56 (d, J ¼ 2.4, 1H, H-3), 7.17 (d, J ¼ 8.9,
1H, H-6), 7.34 (d, J ¼ 9.0, 1H, H-13), 7.43-7.48 (m, 6H,
H
meta, Hpara), 7.58 (dd, J ¼ 2.6, 9.0, 1H, H-12), 7.89–7.94
(m, 5H, H-10, Hortho), 8.58 (s, 3J119=117Sn–1H ¼ 56.2, 1H,
H-7); 13C NMR (75.4 MHz, CDCl3): d, 56.1 (OCH3),
104.3 (C-3), 110.2 (C-5), 112.3 (C-12), 112.9 (C-1), 113.6
(C-10), 114.5 (C-13), 129.3 (Cmeta), 131.07 (Cpara), 136.8
(Cortho), 137.7 (C-11), 137.9 (C-6), 139.3 (1J119Sn–
13C ¼ 1007.0, Cipso), 147.8 (C-8), 158.5 (C-9), 162.3 (C-
7), 169.3 (C-4), 173.8 (C-2); 119Sn NMR (111.9 MHz,

H. Reyes et al. / Journal of Organometallic Chemistry 689 (2004) 2303–2310
2309
Table 4
Crystal data for 1b, 1c and 2c
1b
1c
2c
Chemical formula
Formula weight
Crystal system
Space group
C22H28N2O5Sn
519.15
Triclinic
C26H20N2O5Sn
559.15
Monoclinic
C29H27N3O4Sn Æ CHCl3
719.59
Orthorhombic
Pbca
ꢃ
P1
P21=a
ꢂ
a (A)
10.5496(12)
10.7909(18)
11.535(2)
81.477(15)
74.103(12)
63.567(11)
1130.4(3)
293(2)
8.79270(10)
25.8907(4)
10.1291(2)
90
13.6099(2)
16.1739(3)
28.1345(6)
90
ꢂ
b (A)
ꢂ
c (A)
a (°)
b (°)
c (°)
91.7840(10)
90
90
90
3
ꢂ
V (A )
2304.76(6)
293(2)
6193.1(2)
293(2)
8
T (K)
Z
2
4195
4
5224
Collected reflections
Independent reflections
Ra
11 144
6066
3693
0.0367
5224
0.0322
0.0637
0.1913
407
b
Rw
Variables
0.0413
323
0.0475
388
P
P
a R ¼ jjFoj ꢀ jFcjj= jFoj.
P
P
2
2
1=2
b RwðFoÞ ¼ ½ wðFo2 ꢀ Fc2Þ = w Fo4ꢁ
.
4.3. Computational details
dipolar orientation with a high voltage pulse (6 kV)
synchronized with the laser pulse. The SHG signal was
selected through a suitable interference filter, detected
by a photomultiplier, and recorded on an ultrafast
Tektronic TDS 620 B oscilloscope. With the NLO
response being induced by dipolar orientation of the
chromophores, the EFISH signal is therefore propor-
tional to the dipole moment (l) and to bvec, the vector
component of b along the dipole moment direction.
Due to the pseudo-one-dimensional character of the
charge transfer process, b and l are nearly parallel
and, therefore b and bvec are assumed to be equivalent.
The dipole moments were measured independently by
a classical method based on the Guggenheim theory
[25].
All geometries for diethyl analogues of 1b and 2b
were fully optimized using the GAUSSIAN-98 program
package within the framework of DFT at the
B3PW91/6-31G*/LANL2DZ(Sn) level [22], in which
relativistic effects are included for Sn. In addition, we
checked that the geometry calculated using an all
electron basis set for Sn (B2PW91/6-31G*/DZVP(Sn))
[23] is very similar to the one obtained with the
pseudo-potential basis set LANL2DZ(Sn). The starting
point for DFT calculations was derived from the
crystal structure of 1b, by substituting butyl moieties
by ethyl groups, and eventually MeO– by Me2N–.
Vibrational analysis was performed at the same level in
order to establish the presence of a minimum on the
potential energy surface. Static hyperpolarizabilities
(b0) of the calculated structures were evaluated at the
B3PW91/6-31G*/LANL2DZ(Sn) level, using the nu-
5. Supplementary material
Crystallographic data for 1b, 1c and 2c have been
deposited at the Cambridge Crystallographic Data
Centre with deposition numbers CCDC 229405 for 1b,
CCDC 229406 for 1c and CCDC 229407 for 2c, re-
spectively. Copies of the information may be obtained
free of charge from The Director, CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK (fax: +44-1223-
336033; e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).
merical finite field procedures included in GAUSSIAN
98. A field strength (E) of 0.001 au was chosen for the
calculation of b0.
-
4.4. NLO properties
The principle of the EFISH technique is reported
elsewhere [24]. The data were recorded using a pico-
second Nd:YAG pulsed (10 Hz) laser operating at
k ¼ 1:064 lm. The outcoming Stokes-shifted radiation
at 1.907 lm generated by Raman effect in a hydrogen
cell (1 m long, 50 atm.) was used as the fundamental
beam for second harmonic generation. The compounds
were dissolved in chloroform at various concentration
and the centrosymmetry of the solution was broken by
Acknowledgements
The authors acknowledge Consejo Nacional de
ꢀ
Ciencia y Tecnologıa (CONACYT), Mexico and CNRS,
France for financial support.
ꢀ

2310
H. Reyes et al. / Journal of Organometallic Chemistry 689 (2004) 2303–2310
[13] B. Wrackmeyer, Ann. Rep. NMR Spectrosc. 16 (1985)
73.
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