Inorganic Chemistry Communications 70 (2016) 75–78

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Inorganic Chemistry Communications

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Short communication

Schiff pentadentate ligands based on an [ON2O2] core displaying

structural isomerism and their coordination to dibutyltin moieties
Jovana Pérez-Pérez a, José G. Alvarado-Rodríguez a,⁎, Noemí Andrade-López a, Julián Cruz Borbolla a,
Diego Martínez-Otero b, José Manuel Vásquez-Pérez a
a
Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Hidalgo, km. 4.5 Carretera Pachuca-Tulancingo, Col. Carboneras, C.P. 42184 Mineral de la Reforma, Hidalgo, México
b
Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM, km 14.5 Carretera Toluca-Atlacomulco, Unidad San Cayetano, C.P. 50200 Toluca, Edo. de México, México

a r t i c l e i n f o a b s t r a c t

Article history: Two tin compounds [Sn(nBu)2(Ln)], where L1_{O(C6H4-2-N_C(H)C6H4-2′-O)2}2− and L2_{O(C6H4-2-
Received 3 January 2016 C(H)_NC6H4-2′-O)2}2− enclosing five electron donors in an [ON2O2] core, were synthesized and structurally
Accepted 16 May 2016 characterized by infrared and NMR spectroscopy and by single crystal X-ray crystallographic studies at room
Available online 18 May 2016
temperature. The hepta-coordinate geometry around the Sn centers is achieved through the bonding of two
monodentate n-butyl groups and the coordination of the pentadentate Ln ligands, where the [ON2O2] core is
Keywords:
Tin compounds
forming a pentagonal base. The two types of oxygen atoms displayed different bonding situations around the
Schiff ligands Sn atom. DFT calculations with Gaussian 09 using PBEPBE/6-31G**/SDD level were carried out for both com-
DFT pounds. The topological analysis indicated that bond critical points are present along the Sn\\Oether direction.
© 2016 Elsevier B.V. All rights reserved.

Tin compounds containing ligands based on mono- and bis-
aldimines [1] are of interest because of their photophysical properties
[2], activity in catalysis [3], and biological properties [4]. Most of these
compounds have ligands with [NO] or [N2O2] electron donating cores.
In contrast, compounds having ligands with higher open cores such as
[DN2O2] have not received much attention. For example, for cores
enclosing five donor atoms, the reports have mainly addressed to com-
pounds where D = N, yielding [N3O2] cores [5,6,7,8]. When a D donor
such as an oxygen atom is included in the core, the number of studies
fall dramatically down and these reports almost exclusively consider
transition metals [9]. Herein we report the experimental and theoretical
studies of two tin compounds having pentadentate ligands where the
H2L1 and H2L2 ligands are structural isomers.
The ligand H2L1 was prepared by reacting two equivalents of
salicylaldehyde with one equivalent of bis-(2-aminophenyl)ether [10];
H2L2 was synthetized by condensing two equivalents of 2-aminophenol
with one of bis-(2-formylphenyl)ether [11]. The NOESY NMR experi-
ments in CDCl3 solution of both ligands let us to stablish the orientation
of the hydrogen atoms of the iminic groups in both magnetically equiv-
alent halves as anti (H2L1) or syn (H2L2) respect to the oxygen atom act-
ing as a bridge.
The reaction of either H2L1 [12] or H2L2 [13] with di-n-butyltin oxide
in a 1:1 ratio in a toluene-methanol mixture yielded hepta-coordinate
tin compounds of general formula [Sn(nBu)2(Ln)] (See Scheme 1) [14].
The electroneutrality of these compounds was achieved by the coordi-
nation of the corresponding dianionic ligand {Ln}2 − to the
⁎ Corresponding author.
E-mail address: jgar@uaeh.edu.mx (J.G. Alvarado-Rodríguez).
{Sn(nBu)2}2 + moiety; the twofold deprotonation was enhanced be-
cause of the basicity of the oxide anion. Both isomeric compounds
displayed a peak at m/z = 641.00 that corresponds to the M+1 molec-
ular ion.
The 1H and 13C{1H} spectra of tin compounds indicated that, in CDCl3
solution, both halves are magnetically equivalent. The 119Sn{1H} NMR
spectra of compounds 1 and 2 displayed only one sharp resonance at
− 427.0 and − 313.4 ppm, respectively, confirming the existence of
one tin species. The first chemical shift falls within the range of hepta-
coordinate tin species [15] and is closely related to those observed in
tin compounds having pentadentate Schiff-type ligands with [N3O2]
core [5,6]. The second one is more related with hexa-coordinate species;
we attributed this difference to the higher flexibility caused by the six-
membered chelate ring present in 2 in comparison with the more fa-
vored five-membered ring in 1, where a Sn\\O interaction is weak in
solution.
We carried out single crystal X-ray diffraction studies at room tem-
perature for both compounds. [16] The molecular structures displayed
hepta-coordinate tin atoms in a pentagonal-bipyramidal local geometry
in both cases (See Fig. 1). In each case the ligands are pentacoordinated
to the tin central atom, with the n-butyl groups located on the axial po-
sitions and the [ON2O2] core occupying the pentagonal base. The bond
angles sum around Sn is 360.1° in both cases and the pentagonal
mean plane deviation is 0.0398 and 0.0487 Å for 1 and 2, respectively.
The covalent bonds Sn\\O(2) and Sn\\O(3)—hereinafter named as
Sn\\Ophenolate bonds—are significantly equal and similar to the covalent
radii sum [Σrcov(Sn, O) = 2.14 Å] [17]. The Sn\\Niminic bond distances
(Table 1) are shorter for compound 1 where five-membered chelate
rings were formed in comparison with the longer distances observed

http://dx.doi.org/10.1016/j.inoche.2016.05.015
1387-7003/© 2016 Elsevier B.V. All rights reserved.
76 J. Pérez-Pérez et al. / Inorganic Chemistry Communications 70 (2016) 75–78

Scheme 1. Synthesis of hepta-coordinate tin compounds [Sn(nBu)2(Ln)].

in 2 that displayed two six-membered rings. This situation agreed with
the data observed in solution as noted by 119Sn{1H} NMR. In these struc-
tures an interaction Sn\\Oether is present whose interatomic distances
are 2.737(12) Å for 1 and 2.758(3) Å for 2; they are evidently longer
than the covalent radii sum but shorter than the van der Waals radii
sum [ΣrvdW (Sn, O) = 3.69 Å17]. This bonding situation used to be relat-
ed to the presence of secondary bonding that has an influence on the
local geometry of a given central atom that, in our case, was Sn. In con-
nection with this, the wider N\\Sn\\N angle was observed for com-
pound 2 where the Sn\\Oether and Sn\\Niminic bond distances are also
the longer distances. The C\\O\\C ether-type bridge displayed values
quite different (125.6° in 1 and 115.5° in 2), indicating the high flexibil-
ity and adaptability of a dicoordinated oxygen atom to easily modify its
COC bond angle and, therefore, to change its hybridization, when it co-
ordinates to central atoms such as Sn.
The nature of the chemical bonds in both tin compounds was stud-
ied by computational methods on the basis of the Atoms in Molecules
Theory. Starting geometry of complex 2 was obtained from crystallogra-
phy coordinates while starting geometry of complex 1 was guessed
from geometries of complex 2. Both geometries were optimized at the
DFT PBEPBE/6-31G**/SDD level of theory with the Gaussian09 software
[18]. The SDD pseudopotential was used only for tin atoms. Empirical
dispersion corrections were also included in the calculation. In order
to perform the AIM analysis of the electron density, single point calcula-
tions at the DFT PBEPBE/6-311++G**/Def2TZVPP were performed. The
Def2TZVPP basis set was used only for tin atoms. These large basis sets
were used in order to avoid artifacts in the AIM analysis due to its finite
size. AIM calculations were performed with the Multiwfn software [19].
In Fig. 2, bond and ring critical points along with bond paths are shown.
Only critical points with electron density values larger than 0.001 a.u.
are plotted. (See Fig. 2).
In order to characterize covalent and non-covalent interactions
[20,21], electron density, electron density laplacian, kinetic energy
density, potential energy density, and total energy density were cal-
culated at the bond critical points. Table 1 lists these parameters for
the Sn\\O and Sn\\N interactions corresponding to the three bond
critical points of both complexes shown in Fig. 2. The critical points
of the Sn\\Ophenolate bonds have negative total energy densities, indi-
cating covalent bonding. On the other hand, Sn\\Niminic bonds fea-
ture small total energy densities indicating a dative bonding. In
contrast, Sn\\O interaction has a larger positive total energy density,
which is related to closed shell interactions. In addition, O\\N critical
points display the smallest set of values (0.0106 a.u.), indicating a
very weak interaction; actually, O\\N critical points are accompa-
nied by near ring critical points (not displayed) with density value
of 0.0097 whose effects cancel each other. The electron density
[ρ(r)] on the tin environment decreases according to the different
bonding situation as follows: Sn\\Ophenolate NSn\\Niminic N Sn\\Oether.
Another interesting result is that the laplacian of the electron density
is positive for all critical points, indicating that they do not represent
traditional covalent interactions. The electron localization function
(ELF) for both compounds was also calculated from the same elec-
tron density obtained at the level of theory above mentioned, by
using the Multiwfn software. The resulting isosurfaces plotted at a
value of 0.75 are shown in Fig. 3. The graphs revealed the presence
of the lone pairs of the Oether and Niminic atoms with their ELFs direct-
ed towards the central tin atom, supporting the existence of dative
bonds between them.

Table 1
Relevant structural and electronic parameters for tin compounds 1 and 2. Bond distances in Å. Electron density (ρ), electron density laplacian (∇2ρ), kinetic energy density (G), potential
energy density (V), and total energy density (H) calculated at the bond critical points. All values are given in atomic units.

Compound Bond distance ρ ∇2ρ G V H

\Ophenolate
Sn\ 2.108(13) 0.1261 0.4441 0.1422 −0.1733 −0.0311
\Ophenolate
Sn\ 2.115(14) 0.1256 0.4431 0.1417 −0.1727 −0.0310
1 \Niminic
Sn\ 2.471(19) 0.0567 0.2377 0.0577 −0.0559 0.0017
\Niminic
Sn\ 2.519(18) 0.0541 0.2322 0.0555 −0.0530 0.0025
\Oether
Sn\ 2.737(12) 0.0248 0.1859 0.0378 −0.0292 0.0086
\Ophenolate
Sn\ 2.102(3) 0.1394 0.4409 0.1526 −0.1950 −0.0424
\Ophenolate
Sn\ 2.087(3) 0.1394 0.4409 0.1526 −0.1950 −0.0424
2 \Niminic
Sn\ 2.543(5) 0.0570 0.2479 0.0603 −0.0586 0.0017
\Niminic
Sn\ 2.533(4) 0.0570 0.2479 0.0603 −0.0587 0.0016
\Oether
Sn\ 2.758(3) 0.0215 0.1723 0.0347 −0.0263 0.0084
 J. Pérez-Pérez et al. / Inorganic Chemistry Communications 70 (2016) 75–78 77

Fig. 1. Molecular structures of 1 (left) and 2 (right). (ORTEP 50%; toluene solvent molecule in 2 has been omitted for the sake of clarity).

Acknowledgments
JPP fully acknowledges the scholarship from CONACYT. This research
was partially supported by PROFOCIE 2014.
Appendix A. Supplementary material
CCDC-1441036 and CCDC-1441037 contain the supplementary crys-
tallographic data for 1 and 2, respectively. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associated
with this article can be found in the online version, at http://dx.doi.
org/10.1016/j.inoche.2016.05.015.
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Fig. 2. Bond and ring critical points found in 1 (left) and 2 (right). Only critical points with electron density values larger than 0.001 a.u. are plotted.
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[12] Compound H2L1: In 25 mL of toluene were added bis-(2-aminophenyl)ether
(500 mg, 2.50 mmol), salicylaldehyde (0.5 mL, 5.00 mmol) and anhydrous sodium
sulfate (900 mg). The mixture was refluxed by 24 h. Then, it was let to reach room
temperature and the sodium sulfate was filtered off. The solution was evaporated
and orange powder was obtained (94%). 1H NMR (400 MHz, CDCl3) δ ppm: 13.15
(s, 2H, OH) 8.67 (s, 2H, H7), 7.31 (td, J = 7.6 Hz, J = 2.1 Hz, 2H, H11), 7.30 (d,
J = 7.3 Hz, 2H, H13), 7.26 (dd, J = 7.5 Hz, J = 2.1 Hz, 2H, H3), 7.20 (td, 7.5 Hz,
J = 2.1 Hz, 2H, H5), 7.16 (dd, J = 7.5 Hz, J = 1.8 Hz, 2H, H4), 6.98 (dd, J =
7.5 Hz, J = 1.8 Hz, 2H, H6), 6.94 (m, 2H, H10), 6.85 (ddd, J = 7.6 Hz, J =
7.3 Hz J = 1.2 Hz, 2H, H12). 13C{1H} NMR (100 MHz, CDCl3) δ ppm: 164.1 (C7),
161.4 (C9), 149.7 (C1), 139.7 (C2), 133.2(C11), 132.5(C13), 127.8 (C5), 124.4(C4),
121.0 (C3), 119.5 (C6), 119.4(C8), 119.0 (C12), 117.4(C10). Anal. Calc. For.
C26H20N2O3: C, 76.45; H, 4.94. Found: C, 76.25; H, 4.91%. M.p. 178–179 °C.
[13] Compound H2L2: In 25 mL of toluene were added bis-(2-formylphenyl)ether
(500 mg, 2.21 mmol), 2-aminophenol (530 mg, 4.87 mmol) and anhydrous sodium
sulfate (900 mg). After some minutes were added two drops of sulfuric acid con-
centrated. The mixture was refluxed by 24 h. Then, it was let to reach room temper-
ature and the sodium sulfate was filtered off. The solution was evaporated and
extracted with dichloromethane (3 × 5 mL). This organic phase was dried with an-
hydrous sodium sulfate and vacuum evaporated, yielding an orange powder (85%)
1
H NMR (400 MHz, CDCl3) δ ppm: 9.19 (s, 2H, H7), 8.31 (dd, J = 7.6 Hz, J = 1.8 Hz,
2H, H3), 7.47 (ddd, J = 8.3 Hz, J = 7.6 Hz, J = 1.8 Hz, 2H, H5), 7.29 (td, J = 7.6 Hz,
J = 1.0 Hz, 2H, H4), 7.28 (dd, 8.0 Hz, J = 1.3 Hz, 2H, H13), 7.20 (ddd, J = 8.1 Hz, J =
7.4 Hz, J = 1.3 Hz, 2H, H11), 7.02 (dd, J = 8.1 Hz, J = 1.8 Hz, 2H, H10), 6.93 (dd, J =
8.3 Hz, 1.0 Hz, 2H, H6), 6.87 (m, 2H, H12). 13C{1H} NMR (100 MHz, CDCl3) δ ppm:
157.3 (C1), 152.55(C9), 151.82 (C7), 135.72(C8), 133.3(C5), 129.4(C11), 128.1 (C3),
127.2(C2), 124.5(C13), 120.3(C12), 119.1(C6), 116.2(C4), 115.6(C10). Anal. Calc.
For. C26H20N2O3: C, 76.45; H, 4.94. Found: C, 76.77; H, 5.02%. M.p. 168–169 °C.
[14] Compound 1. To a solution containing H2L1 (100 mg, 0.24 mmol) dissolved in 25 mL
of toluene/methanol in a 1:1 ratio was added di-n-butyltin oxide (60 mg,
0.24 mmol). The resulting yellow solution was refluxed by 30 h. The mixture was
slowly evaporated and by fractional crystallization yellow crystals of compound 1
were obtained. (34%) 1H NMR (400 MHz, CDCl3) δ ppm: 8.40 (s, 2H, H-7), 7.43
(m, 2H, H13), 7.36 (m, 2H, H11), 7.29 (m, 6H, H3, H4, H5), 7.24 (m, 2H, H6), 7.10
(d, J = 7.3 Hz, 2H, H10), 6.71 (t, J = 7.3 Hz, 2H, H12), 1.25 (m, 8H, H14, H15),
0.85 (m, 4H, H16), 0.41 (t, J = 7.3 Hz, 6H, H17). 13C{1H} RMN (100 MHz, CDCl3) δ
ppm: 167.9 (C7), 163.8 (C9), 147.3 (C1), 140.0 (C2), 135.8(C11), 135.2(C13),
127.0 (C5), 125.0(C4), 121.0 (C3), 119.4 (C6), 119.0(C8), 118.8 (C12), 117.5(C10),
28.0 (C14), 26.8(C15), 25.9(C16), 13.29 (C17). 119Sn{1H} NMR (149 MHz, CDCl3) δ
ppm: −427.0. Anal. Calc. For C34H36N2O3Sn: C, 63.87; H, 5.68, Found: C, 63.92; H
5.93%. M.p. 196–197 °C.Compound 2 (toluene solvate). To a solution containing
H2L2 (100 mg, 0.24 mmol) dissolved in 25 mL of toluene/methanol in a 1:1 ratio
was added di-n-butyltin oxide (60 mg, 0.24 mmol). The resulting orange solution
was refluxed by 30 h. The mixture was slowly evaporated and the resulting orange
crystals were washed with cold toluene (4 mL; 0 °C). (60%) 1H NMR (400 MHz,
CDCl3) δ ppm: 8.56 (s, 2H, H7), 7.62 (dd, J = 7.5 Hz, J = 1.7 Hz, 2H, H3), 7.40
(ddd, J = 8.3 Hz, J = 7.5 Hz, J = 1.7 Hz, 2H, H5), 7.31 (td, J = 7.5 Hz, J = 1.7 Hz,
2H, H4), 7.24 (m, 4H, H11, H13), 7.10 (dd, J = 8.3 Hz, J = 1.4 Hz, 2H, H10), 6.79
(dd, J = 7.5 Hz, J = 1.7 Hz, 2H, H6), 6.70 (ddd, J = 8.5 Hz, J = 7.1 Hz, J = 1.4 Hz,
2H, H12), 1.37 (m, 2H, H14A), 1.08 (m, 6H, H14B, H15), 0.87 (m, 2H, H16A), 0.77
(m, 2H, H16B), 0.39 (t, J = 7.3 Hz, 6H, H17). 13C{1H} NMR (100 MHz, CDCl3) δ
ppm: 161.8 (C9), 155.7 (C1), 153.4 (C7), 137.2 (C8), 134.9 (C3), 133.1 (C5),
130.8(C11), 126.9 (C2), 125.1 (C4), 122.5 (C6), 121.9 (C10), 116.53(C13),
115.9(C12), 27.4(C14), 27.1(C15), 26.0(C16), 13.22 (C17). 119Sn{1H} NMR (CDCl3,
149 MHz, 25°) δ ppm: −313.4. Anal. Calc. For C34H36N2O3Sn·C7H8: 67.32; H, 6.06,
Found: C, 67.37; H 6.11%. M.p. 158–159 °C.
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monochromated MoKα (λ = 1.54184 Å) and CuKα radiation. Data were integrated,
scaled, sorted, and averaged using the CrysAlis software package. All non-hydrogen
atoms were refined anisotropically by full-matrix least squares on F2. Twinned data
refinement for 1 with scales 0.783(2):0.217(2). The disorder was treated rigid bond
restraints by using instructions such as SAME, SIMU, DELU, RIGU and SADI. Crystal
data for 1 (MoKα): C34H36N2O3Sn, M = 639.34, yellow block, monoclinic, space
group Ia, a = 10.6950(6), b = 25.4630(13), c = 10.9368(6) Å, β = 91.400(5)°,
V = 2977.5(3)Å3, Z = 4, μ(Mo-Kα) = 0.895 mm−1. Total 12832 reflections. Refine-
ment of 12832 reflections (439 parameters) with I N 2σ (I) converged at final R1 =
0.0699 (R1 all data = 0.1216), wR2 = 0.1945 (wR2 all data = 0.2229), GOF = 1.07,
Flack parameter −0.02(2). For 2 (CuKα): C41H44N2O3Sn, M = 731.47, orange block,
orthorhombic, space group P212121, a = 10.79755(10), b = 17.24175(18), c =
19.27390(19) Å, V = 3588.20(6) Å3, Z = 4, μ(Mo-Kα) = 5.972 mm−1. Total
60243 reflections. Refinement of 7607 reflections (492 parameters) with I N 2σ (I)
converged at final R1 = 0.0335 (R1 all data = 0.0391), wR2 = 0.0825 (wR2 all
data = 0.0864), GOF = 1.051, Flack parameter −0.029(3).
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