Synthesis, spectral characterization, crystal structure and antibacterial studies of diorganotin(IV) complexes with isonicotinoyl hydrazone derivatives

Article abstract of DOI:10.1016/j.poly.2014.04.061

The new diorganotin(IV) complexes R₂SnL (L = L^a: R = Me 1, Ph 2; L = L^b: R = Me 3, Ph 4, L = L^c: R = Me 5, Ph 6, Bu 7) have been synthesized by the reaction of the hydrazone ligands N′-(5-bromo-2-hydroxybenzylid

Full text of DOI:10.1016/j.poly.2014.04.061

Accepted Manuscript
Synthesis, spectral characterization, crystal structure and antibacterial studies
of diorganotin(IV) complexes with isonicotinoyl hydrazone derivatives
Tahereh Sedaghat, Maryam Yousefi, Giuseppe Bruno, Hadi Amiri Rudbari,
Hossein Motamedi, Valiollah Nobakht
PII:
S0277-5387(14)00288-5
DOI:
http://dx.doi.org/10.1016/j.poly.2014.04.061
POLY 10705
Reference:
To appear in:
Polyhedron
Received Date:
Accepted Date:
26 March 2014
27 April 2014
Please cite this article as: T. Sedaghat, M. Yousefi, G. Bruno, H.A. Rudbari, H. Motamedi, V. Nobakht, Synthesis,
spectral characterization, crystal structure and antibacterial studies of diorganotin(IV) complexes with isonicotinoyl
hydrazone derivatives, Polyhedron (2014), doi: http://dx.doi.org/10.1016/j.poly.2014.04.061
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Synthesis, spectral characterization, crystal structure and antibacterial studies of
diorganotin(IV) complexes with isonicotinoyl hydrazone derivatives
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a*
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Tahereh Sedaghat , Maryam Yousefi , Giuseppe Bruno , Hadi Amiri Rudbari , Hossein
d
a
Motamedi , Valiollah Nobakht
a
Department of Chemistry, College of Sciences, Shahid Chamran University, Ahvaz, Iran
b
Dipartimento di Chimica Inorganica, Vill. S. Agata, Salita Sperone 31, Università di Messina,
98166 Messina, Italy
c
Department of Chemistry, University of Isfahan, Isfahan 81746-73441, Iran
d
Department of Biology, College of Sciences, Shahid Chamran University, Ahvaz, Iran
*
corresponding author: tsedaghat@scu.ac.ir , Fax: 98 611 3331042
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Abstract
a
b
The new diorganotin(IV) complexes R SnL (L = L : R = Me 1, Ph 2; L= L : R = Me 3, Ph 4, L=
2
c
L : R = Me 5, Ph 6, Bu 7) have been synthesized by the reaction of the hydrazone ligands N'-(5-
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a
bromo-2-hydroxybenzylidene) isonicotinohydrazide
(H L ), N'-((2-hydroxynaphthalen-1-
2
b
yl)methylene)
isonicotinohydrazide
(H L )
and
N'-(2,4-dihydroxybenzylidene)
2
c
isonicotinohydrazide (H L ) with diorganotin(IV) dichloride. The synthesized compounds have
2
1
119
been investigated by elemental analysis, together with IR, H and Sn NMR spectroscopy. The
a
b
structures of H L , H L and 3 have also been confirmed by X-ray crystallography. On the basis
2
2
a
b
of these data, H
L and H L are present in the keto-amine tautomeric form and intermolecular
2
2
N-H∙∙∙N hydrogen bonds form 1D chain structures. The hydrazone ligands act as tridentate
dibasic in the enol form and are coordinated via the imine nitrogen, phenolate and enolate
oxygen atoms. The in vitro antibacterial activity of the ligands and their complexes has been
evaluated against Gram-positive (Bacillus subtilis and Staphylococcus aureus) and Gram-
negative (Escherichia coli and Pseudomonas aeruginosa) bacteria and compared with standard
c
antibacterial drugs. The R SnL complexes exhibited greater activities than the other compounds.
2
Keywords: Hydrazone, Crystal structure, Organotin(IV), Antibacterial activity, Schiff base
Introduction
The synthesis and structural investigation of hydrazones and their metal complexes have
attracted great and growing interest due to their coordinative properties and versatile
applications. They have been well known to be biologically important and found to have
2

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therapeutic activity. This activity is due to the potential ability of hydrazones to form stable
chelate complexes with metal ions. For example, in an attempt to develop novel Fe chelators for
the treatment of Fe overload disease, some hydrazone ligands were synthesized and their
structure-activity relationships were investigated [1-3]. The chemistry of hydrazones and their
complexes have also received considerable attention due to their activity against various bacteria
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[
4-6]. Of interest to structural chemists is the facile keto-enol tautomerization and the
coordination ability through several potential donor sites in these ligands allows a structural
variety in their complexes [7]. Hydrazone organotin(IV) complexes are of interest in view of
their chemical properties, biological significance, industrial importance and structural variety.
According to the literature, the biocidal properties of organotin(IV) compounds are dependent on
the structure and coordination number of the tin atom, the number and nature of the organic
groups and also the nature of the donor ligand attached to the tin atom [8,9]. A judicious choice
of the ligand coordinated to the organotin(IV) fragment can modulate the activity of the complex
or minimize its drawbacks [8]. In the field of bioorganotin chemistry, one of the interesting work
areas is the introduction of bioactive ligands, coordinating to the organotin fragment [10,11].
Among these, hydrazones have received much attention because of their potential biological
applications. It has been found earlier that pyridine containing hydrazones show antibacterial
activity [12], also some organotin(IV) complexes of Schiff bases containing a pyridine moiety
show appreciable antimicrobial activities [13-15]. As a part of our investigation dealing with the
study of organotin(IV) complexes of Schiff bases, herein we have synthesized and studied the
structural, spectral and antibacterial properties of some diorganotin(IV) complexes with three
a
b
c
hydrazones, H L , H L and H L , derived from isonicotinohydrazide (Figure 1).
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. Experimental
2
.1. Materials and methods
All starting materials were purchased from Merck, while diphenyltin dichloride was supplied
from Alfa Aesar Company, and were all used as received. All solvents were of reagent grade and
used without further purification. IR spectra were obtained using a FT BOMEM MB102
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spectrophotometer. The H and Sn NMR spectra were recorded with a Bruker 400 MHz
Avance Ultrashield spectrometer. The C, H and N analyses were performed with a CHN
analyzer, Thermo Finigan Flash EA 1120.
2
.2. Synthesis of the ligands
a
b
c
H L , H L and H L have been prepared by a general procedure: equimolar amounts of
2
2
2
isonicotinohydrazide (4-pyridine carboxylic acid hydrazide) and the corresponding aldehyde, 5-
bromo-2-hydroxybenzaldehyde, 2-hydroxynaphthaldehyde and 2,4-dihydroxybenzaldehyde
respectively, were refluxed in ethanol for 3 h and then cooled to ambient temperature. Crystals
suitable for X-ray crystallography were obtained by slow evaporation of a dilute ethanolic
solution of the compounds.
a
H L . Yield: 86.5 %. M.p. 258-260 C. Anal. Calcd. For C H BrN O : C, 48.8; H, 3.1; N, 13.1
2
13 10
3
2
-1
%. Found: C, 48.4; H, 3.4; N, 13.4 %. FT-IR (KBr, cm ): (OH), 3000 br; (NH), 3180;
1

(C=O), 1675; (C=N), 1617; H NMR (DMSO) δ: 12.37 (s, 1H, OH), 11.14 (s , 1H, NH/OH),
3
3
8
.79 (d, 2H, H , J = 5.6 Hz), 8.65 (s, 1H, HC=N), 7.84 (d, 2H, H , J = 5.6 Hz), 7.82 (d, 1H,
a HH b HH
4
3
4
3
H , J = 2.4 Hz), 7.42 (dd, 1H, H , J = 8.7, J = 2.4 Hz), 6.90 (d, 1H, H , J = 8.7 Hz).
3
HH
2
HH
HH
1
HH
b
H L . Yield: 84 %. M.p. 260-262 C. Anal. Calcd. For C H N O : C, 70.0; H, 4.5; N, 14.4 %.
2
17 13
3
2
-1
Found: C, 69.8; H, 4.3; N, 14.7 %. FT-IR (KBr, cm ): (OH), 3000 br; (NH), 3242; (C=O),
4

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790; (C=N), 1624; H NMR (DMSO) δ: 12.54 (s, 1H, OH), 12.43 (s, 1H, NH/OH), 9.48 (s,
3
4
3
1H, HC=N), 8.85 (dd, 2H, H
, JHH = 4.5, JHH = 1.5 Hz), 8.34 (d, 1H, H , JHH = 8.6 Hz), 7.95
6
a
3
(
d, 1H, H , J = 9.0 Hz), 7.89-7.92 (m, 3H, H ), 7.60-7.65 (m, 1H, H ), 7.40-7.45 (m, 1H, H ),
2
HH
3,b
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.25 (d, 1H, H , J = 9.0 Hz).
1 HH
c
H L . Yield: 81.6 %. M.p. 268-270 C. Anal. Calcd. For C H N O : C, 60.7; H, 4.3; N, 16.3 %.
2
13 11
3
2
-1
Found: C, 60.4; H, 4.6; N, 16.5 %. FT-IR (KBr, cm ): (OH), 3226, 3000 br; (NH), 3089;
1

(C=O), 1646; (C=N), 1632; H NMR (DMSO) δ: 12.15 (s , 1H, OH), 11.29 (s, 1H, NH/OH),
3
3
10.05 (s , 1H, OH), 8.77 (d, 2H, H , J = 5.6 Hz), 8.54 (s, 1H, HC=N), 7.82 (d, 2H, H , J =
HH
a
HH
b
3
3
4
5
.6 Hz), 7.36 (d, 1H, H , J = 8.4 Hz), 6.36 (dd, 1H, H , J = 8.5, J = 2.0 Hz), 6.34 (d,
3 HH 2 HH HH
4
1H, H
, JHH = 2.0 Hz).
1
2
2
.3. Synthesis of the complexes
a
.3.1. Synthesis of Me SnL (1)
2
a
Triethylamine (0.5 mmol) was added to a stirring solution of H L (0.064 g, 0.25 mmol) in
2
methanol (10 mL). This solution was stirred for 15 min, then a solution of Me SnCl (0.055 g,
2
2
0
.25 mmol) in methanol (5 mL) was added. The resulting solution was refluxed for 3 h. Yellow
crystals were produced after reducing the solution volume at room temperature. The crystals
were filtered off, washed with methanol and dried in vacuum over CaCl . Yield: 0.053 g (45 %).
2
M.p. 224-226 C. Anal. Calcd. For C15H14BrN O Sn: C, 38.6; H, 3.0; N, 9.0 %. Found: C, 38.8;
3 2
-1
H, 2.7; N, 9.2 %. FT-IR (KBr, cm ): (C=N), 1611;  (Sn-C), 646;  (Sn-C), 570; (Sn-O),
as
s
1
3
5
50; (Sn-N), 470. H NMR (CDCl ) δ: 8.82 (d, 2H, H , J = 5.7 Hz), 8.70 [s, 1H, HC=N,
3
a
HH
3
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1
3
3
4
J( Sn- H) = 43.2 Hz], 8.00 (d, 2H, H , J = 5.7 Hz), 7.42 (dd, 1H, H , J = 9.0, J = 2.0
b
HH
2
HH
HH
5

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Hz), 7.35 (d, 1H, H , J = 2.0 Hz), 6.69 (d, 1H, H , J = 9.0 Hz), 0.89 [s, 6H, SnMe2,
3
HH
1
HH
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J( Sn- H) = 77.1 Hz]. Sn NMR (CDCl ) δ: -248.
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a
2
.3.2. Synthesis of Ph SnL (2)
2
Complex 2 was synthesized as described for compound 1, but using Ph SnCl (0.086 g, 0.25
2
2
mmol). The mixture was refluxed for about 3h. During this time, a yellow solid was formed. The
resulting product was filtered, washed with methanol and dried in vacuum over CaCl . Yield:
2
0
.10 g (75.8%). M.p. 240-242 C. Anal. Calcd. For C H BrN O Sn: C, 50.8; H, 3.0; N, 7.1 %.
2
5
18
3
2
-1
Found: C, 51.0; H, 2.8; N, 7.4 %. FT-IR (KBr, cm ): (C=N), 1595; (Sn-O), 564; (Sn-N),
1
3
3
119
1
4
37. H NMR (CDCl ) δ: 8.80 (d, 2H, H , J = 5.9 Hz), 8.70 [s, 1H, HC=N, J( Sn- H) =
3 a HH
3
3
4
48.6 Hz], 8.15 (d, 2H, H , J = 5.9 Hz), 7.85 [dd, 4H, H (Ph Sn) J = 6.4, J = 2.5 Hz,
b
HH
o
2
,
HH
HH
3
119
1
3
4
J( Sn- H) = 87.4 Hz], 7.53 (dd, 1H, H , J = 9.0, J = 2.5 Hz), 7.46-7.48 [m, 6H, Hm, p
2
HH
HH
4
3
119
(Ph
Sn)], 7.35 (d, 1H, H
, JHH = 2.5 Hz), 7.04 (d, 1H, H
, JHH = 9.0 Hz). Sn NMR (CDCl
) δ:
2
3
1
3
-327.
b
2
.3.3. Synthesis of Me SnL (3)
2
b
Complex 3 was synthesized as described for compound 1, but using H L (0.072 g, 0.25 mmol).
2
The solution was refluxed for 3 h and yellow irregular crystals suitable for X-ray crystallography
were obtained after slow evaporation of this solution at room temperature. Yield: 0.049 g (93.0
%). M.p. 218-220 °C. Anal. Calcd. For C H N O Sn: C, 52.0; H, 3.9; N, 9.6 %. Found: C, 52.2;
1
9
17
3
2
-1
H, 3.8; N, 9.8 %. FT-IR (KBr, cm ): (C=N), 1618; υ (Sn-C), 652; υ (Sn-C), 575; (Sn-O),
as
s
1
3
119
1
563; (Sn-N), 455. H NMR (CDCl ) δ: 9.72 [s, 1H, HC=N, J( Sn- H) = 40.6 Hz], 8.74 (dd,
3
3
4
3
3
2
H, H , J = 4.7, J =1.5 Hz), 8.08 (d, 1H, H , J = 8.5 Hz), 7.99 (dd, 1H, H , J = 4.7,
a HH HH 6 HH b HH
6

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JHH = 1.5 Hz), 7.82 (d, 1H, H , J = 9.1 Hz), 7.73 (d, 1H, H , J = 7.9 Hz), 7.55-7.59 (m, 1H,
2
HH
3
HH
3
2
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1
H ), 7.36-7.38 (m, 1H, H ), 6.94 (d, 1H, H , J = 9.1 Hz), 0.90 [s, 6H, SnMe , J(
Sn- H) =
5
4
1
HH
2
119
7
8.3/75.4 Hz]. Sn NMR (CDCl ) δ: -227.
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b
2.3.4. Synthesis of Ph SnL (4)
2
b
Complex 4 was synthesized as described for compound 2, but using H L . Yield: 0.093 g (66.4
2
%). M.p. 240-242 °C. Anal. Calcd. For C H N O Sn: C, 62.0; H, 3.7; N, 7.5 %. Found: C, 62.2;
2
9
21
3
2
-1
1
H, 3.3; N, 7.8 %. FT-IR (KBr, cm ): (C=N), 1618; (Sn-O), 531; (Sn-N), 456. H NMR
3
119
1
(CDCl ) δ: 9.75 [s, 1H, HC=N, J( Sn- H) = 53.9 Hz], 8.79 (d, 2H, H , J = 5.6 Hz), 8.20 (dd,
3
a
HH
3
4
3
3
1
H, H , J = 4.9, J =1.4 Hz), 8.06 (d, 1H, H , J = 8.7 Hz), 7.93 (d, 1H, H , J = 9.0 Hz),
b
HH
HH
6
HH
2
HH
3
7.87-7.90 [m, 4H, H
(Ph
o
Sn)], 7.76 (d, 1H, H
, JHH = 8.0 Hz), 7.54-7.59 (m, 1H, H
), 7.46-7.48
2
3
5
3
119
[
(
m, 7H, Hm, p (Ph Sn)], 7.36-7.40 (m, 1H, H ), 7.28 (d, 1H, H , J = 9.0 Hz). Sn NMR
2
4
1
HH
CDCl ) δ: -328.
3
c
2
.3.5. Synthesis of Me SnL (5)
2
c
Complex 5 was synthesized as described for compound 1, but using H L (0.064 g, 0.25 mmol).
2
Yield: 0.093 g (89.4 %). M.p. 275-277 °C. Anal. Calcd. For C H N O Sn: C, 44.6; H, 3.7; N,
1
5
15
3
3
-
1
10.4 %. Found: C, 44.8; H, 3.6; N, 10.7 %. FT-IR (KBr, cm ): (C=N), 1592; υ (Sn-C), 636;
as
1
υ (Sn-C), 567; (Sn-O), 534; (Sn-N), 436. H NMR (DMSO) δ: 10.23 (s , 1H, OH), 8.74 (s, 1H,
s
3
4
3
4
HC=N), 8.67 (dd, 2H, H , J = 4.5, J = 1.5 Hz), 7.82 (dd, 2H, H , J = 4.5, J = 1.5 Hz),
a
HH
HH
b
HH
HH
3
3
4
4
7
.25 (d, 1H, H , J = 8.7 Hz), 6.21 (dd, 1H, H , J = 8.7, J = 2.2 Hz), 6.04 (d, 1H, H , J
3 HH 2 HH HH 1 HH
2
119
1
119
= 2.2 Hz), 0.70 [s, 6H, SnMe , J( Sn- H) = 86.7 Hz]. Sn NMR (DMSO) δ: -207.
2
7

1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
c
2
.3.6. Synthesis of Ph SnL (6)
2
c
Complex 6 was synthesized as described for compound 2, but using H L . Yield: 0.105 g (80.0
2
%
). M.p. 280-282 °C. Anal. Calcd. For C H N O Sn: C, 56.8; H, 3.6; N, 8.0 %. Found: C, 57.0;
25 19 2 3
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
-1
1
H, 3.3; N, 8.3 %. FT-IR (KBr, cm ): (C=N), 1557; (Sn-O), 489; (Sn-N), 445. H NMR
3
3
119
1
(
DMSO) δ: 10.33 (s , 1H, OH), 8.72 (d, 2H, H , J = 5.3 Hz), 8.70 [s, 1H, HC=N, J( Sn- H)
a HH
3
4
3
119
=
53.8 Hz], 7.95 (dd, 2H, H , J = 4.7, J = 1.5 Hz), 7.62-7.64 [m, 4H, H (Ph Sn), J( Sn-
b HH HH o 2
1
3
H) = 80.4 Hz], 7.32-7.39 [m, 7H, Hm, p (Ph Sn)], 7.30 (d, 1H, H , J = 8.4 Hz), 6.25-6.27 (m,
2
3
HH
119
2
H, H ). Sn NMR (DMSO) δ: -405.
1,2
c
2
.3.7. Synthesis of Bu SnL (7)
2
Complex 7 was synthesized as described for compound 1, but using Bu
SnCl (0.0755 g, 0.25
2
2
c
mmol) and H L . Yield: 0.069 g (58.5 %). M.p. 277-279 °C; Anal. Calcd. For C H N O Sn: C,
2
21 27
3
3
-
1
5
1.6; H, 5.5; N, 8.6 %. Found: C, 51.4; H, 5.7; N, 8.9 %. FT-IR (KBr, cm ): (C=N), 1589;
1

(Sn-O), 533; (Sn-N), 488. H NMR (DMSO) δ: 10.23 (s, 1H, OH), 8.82 [s, 1H, HC=N,
3
119
1
3
3
4
J( Sn- H) = 36.4 Hz], 8.65 (d, 2H, H
, JHH = 5.3 Hz), 7.81 (dd, 2H, H , JHH = 4.6, JHH = 1.3
b
a
3
4
Hz), 7.24 (d, 1H, H , J = 8.1 Hz), 6.6.19-6.22 (m, 1H, H ), 6.05 (d, 1H, H , J = 2.2 Hz),
3
HH
2
1
HH
1
.40-1.53 (m, 8H, H ), 1.23(t, 1H, Hᵧ ,J = 7.2 Hz), 1.22 (sextet, 1H, Hᵧ ,JHH = 8.1 Hz), 0.74
α,β HH
1
19
(
t, 1H, H , J = 7.4Hz). Sn NMR (DMSO) δ: -229.
δ HH
2
.4. X-ray crystal structure determination
Data were collected at room temperature with a Bruker APEX II CCD area-detector
diffractometer using MoK radiation (= 0.71073 Å). Data collection, cell refinement, data
reduction and absorption corrections were performed using multiscan methods with Bruker
8

1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
software [16]. The structures were solved by direct methods using SIR2004 [17]. The non-
2
hydrogen atoms were refined anisotropically by the full matrix least squares method on F using
SHELXL [18]. All the hydrogen (H) atoms were placed at calculated positions and constrained
to ride on their parent atoms. Details concerning collection and analysis are reported in Table 1.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
2
.5. Antibacterial tests
The in vitro antibacterial activity of the ligands and their corresponding organotin(IV) complexes
was investigated against the standard strains of two Gram-positive (Bacillus Subtilis ATCC 6638
and Staphylococcus aureus ATCC 6538) and two Gram-negative (Escherichia coli ATCC 25922
and Pseudomonas aeruginosa ATCC 9027) bacteria. In order to compare the results,
Vancomycin (30 mg/disc), Streptomycin (10 mg/disc), penicillin (10 mg/disc), Nalidixic acid (30
mg/disc) and Gentamicin (10 mg/disc) were used as standard antibacterial drugs. Determination
of the antibacterial activity was carried out by the paper-disc diffusion method. The compounds
were dissolved in DMSO at 10 and 40 mg/ml concentrations. Muller Hinton broth was used for
preparing basal media for the bioassay of the organisms. A lawn culture from 0.5 MacFarland
suspension of each strain was prepared on Muller Hinton agar. Blank paper discs (6.4 mm
diameter) were saturated with a solution of the test compounds (40 L) and placed on the surface
of the agar plates. On one paper disc only DMSO was poured as a control. The plates were
incubated at 37 C for 24 h. The inhibition zone diameters around each disc were measured in
mm.
3. Results and discussion
9

1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
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5
6
7
8
9
0
1
2
3
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5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
a
b
c
The hydrazone ligands H L , H L and H L were synthesized by the condensation reaction of
2
2
2
isonicotinohydrazide with 5-bromo-2-hydroxybenzaldehyde, 2-hydroxynaphthaldehyde and 2,4-
dihydroxybenzaldehyde, respectively. Owing to the existence of a ketoamide group (NH-C=O)
in the structure of the ligands, two tautomerizations, keto-amine and enol-imine, are possible for
the hydrazinic moiety. On the other hand, aldimine Schiff base ligands may exhibit tautomerism
between the phenol-imine and the keto-amine forms and have two types of intramolecular
hydrogen bonds (N–HO or NH–O), so two tautomeric forms are also predicted for the
aldehydic moiety of these molecules. Herein, we report the crystal structure and the nature of the
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
a
b
intramolecular hydrogen bonds for H L and H L .
2
2
The new complexes 1-7 were prepared by the reaction of R SnCl (R = Me, Ph or Bu)
2
2
a
b
c
with the hydrazone ligands H
L , H L and H L in methanol in the presence of triethylamine to
2 2
2
force the deprotonation of the ligand. The new complexes were characterized by elemental
1
119
b
analysis and IR, H and Sn NMR spectroscopy. The structure of SnMe L has been also
2
determined by X-ray diffraction.
3.1. Spectroscopic studies
The infrared spectra of the free ligands display the characteristic bands associated with the N-H
and C=O bonds of the amide functionality. The absence of ν(C=O) in the complexes confirms
that the ligands coordinate with tin in the enol form [19]. The ν(C=N) band of the ligands (1632-
-1
1
617 cm ) shifts to a lower wavenumber in the spectra of complexes. These shifts support the
participation of the azomethine group of the ligands in binding to the tin atom. In the IR spectra
of the complexes, the disappearance of bands attributed to ν(O-H) and ν(N-H) in the free ligands
shows complete deprotonation of the hydrazone ligands and their subsequent coordination to the
1
0

1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
tin atom. The appearance of new bands in the IR spectra of the synthesized complexes assigned
to (Sn-N) and (Sn-O) supports the bonding of nitrogen and oxygen atoms to the tin atom [20-
2
2]. The presence of both  (Sn-C) and  (Sn-C) in the IR spectra of 1 and 3 is consistent with a
s
as
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
non-linear Me-Sn-Me configuration.
1
In the H NMR spectra of the complexes, the absence of both phenolic and hydrazinic
signals suggests deprotonation and coordination of the dianionic ligands to tin. The signal
attributable to the imine proton of the free ligands is shifted downfield and is accompanied by
3
119
satellites in the complexes due to J( Sn-H) coupling. This is an indication that the imine
1
nitrogen atoms are coordinated to tin(IV). The H NMR spectra of 1, 3 and 5 shows a singlet for
2
119
1
the SnMe protons, accompanied by satellites with J( Sn- H) larger than uncomplexed
2
SnMe Cl (68.7 Hz), indicating the higher coordination number of tin [23]. Substitution of
2
2
2
119
1
J( Sn- H) in the Lockhart-Manders equation [24], gives values of 127.33, 128.75 and 139.98 °
for the Me-Sn-Me angles in 1, 3 and 5, respectively.
119
1
The Sn{ H}NMR spectra of all the complexes show one sharp singlet at a significantly
lower frequency than that of the original SnMe Cl (+137 ppm), SnPh Cl (-32 ppm) and
2
2
2
2
SnBu Cl (+122 ppm) [23]. This large up-field shift is because of the increase in the
2
2
coordination number of tin. On the basis of the chemical shifts observed for organotin(IV)
derivatives [21,22,25-29], the coordination number of tin is five for all the complexes.
3.2. X-ray structures
a
b
The molecular structures of H L and H L are shown in Figures 2 and 3, respectively.
2
2
Selected bond lengths and angles are listed in Table 2. For both compounds, the monoclinic unit
cell contains four molecules. These molecules show a trans -C=N-N-C conformation, with
1
1

1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
intramolecular hydrogen bonding from the phenolic OH to the azomethine nitrogen atom.
According to the crystal structures, both hydrazones are in the keto-amine tautomeric form in
hydrazinic moiety and in the phenol-imine form in the aldehydic moiety. In these compounds,
one dimensional chains form by intermolecular N-H∙∙∙N hydrogen bonds between the pyridinic
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
nitrogen of one molecule and the hydrazinic hydrogen from an adjacent molecule (Figure 4a, 5a).
a
In the case of H L , intermolecular N-H∙∙∙N hydrogen bonds form a V-shaped 1D chain structure,
2
~13.95 Å in width and ~153.86 angle, that stacks in an ABAB fashion (Figure 4b). The
b
intermolecular hydrogen-bonding in the structure of H L also results in the formation of infinite,
2
1-D chains extending along the crystallographic b axis with an ABAB packing mode (Figure 5b).
Two neighboring 1D chains run in opposite directions and show π-π interactions between the
aromatic rings of the pyridine and one of naphthalene rings with a centroid∙∙∙centroid distance of
3
.941 Ǻ (Figure 5c). This relatively large stack contact is commonly observed with N-
heteroaromatic rings [30]. The angle between two ligands in a polymeric chain is 83.20. The
hydrogen bond distances and angles are listed in Table 3.
b
Figure 6 shows the molecular structure, with atomic numbering scheme, of SnMe L .
2
Selected bond distances and angles are given in Table 4. Complex 3 crystallizes in the triclinic
space group, P-1 and the unit cell contains two molecules. The hydrazone ligand acts as
tridentate dibasic in the enol form and is coordinated via the imine nitrogen, phenolate and
enolate oxygen atoms. The coordination sphere is completed by two carbon atoms of methyl
groups. Therefore the coordination number of tin is five and the extent of distortion from either
ideal square pyramid (SP) or trigonal bipyramid (TBP), is determined from the trigonality index,
τ, [31]. The τ value is calculated from τ = (α  )/60, where α and  are the two largest bond
angles around the metal atom in the five-coordinated environment. The τ value obtained for 3 is
1
2

1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
0
.497 and this value indicates the geometry of the complex is completely between square-
pyramidal and trigonal-bipyramidal ( = 0.0 and 1.0 for SP or TBP geometries, respectively).
The slight difference between the C-Sn-C angle from the X-ray data, 123.87(7)°, and the
empirical estimation in solution (128.75°) may be related to removing the crystal network
pressure in solution. The increase of the C-O and decrease of the C-N bond lengths in the amide
functionality upon complexation indicates enolization and charge delocalization in the hydrazinic
moiety upon deprotonation and coordination. Therefore, C-O goes from a carbonyl bond in the
ligand to an enolate bond in the complex and C-N goes from a single bond in the ligand to a
double bond in the complex. The lengthening of the C-N(imine) bond from 1.278(2) Å in the
free ligand to 1.3026(14) Å in the complex is a consequence of the involvement of the nitrogen
atom of the imine in the coordination to the tin atom. The Sn-N2 (2.1532 Å), Sn-O1 (2.1435 Å)
and Sn-O2 (2.0897 Å) bond lengths are very similar to the sum of the covalent radii of Sn-N
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
(2.15 Å) and Sn-O (2.10 Å), indicating very strong covalent bonds between the tin atom and the
oxygen and nitrogen atoms. The Sn-O(phenolate) bond length is shorter than the Sn-O(enolate)
bond length.
In absence of both amine and hydroxyl groups, the interactions that stabilize the crystal
arrangement are weak hydrogen bonds (C-H∙∙∙C, C-H∙∙∙N) and π-π interactions. The π-π
interactions between the pyridine ring and one of naphthalene rings have centroid-centroid
distances of 3.670 and 3.743 Ǻ (Figure 7).
3
.3. Antibacterial studies
The in vitro antibacterial activities of the Schiff bases and their organotin(IV) complexes were
studied along with five standard antibacterial drugs, viz Vancomycin, Streptomycin, penicillin,
1
3

1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
Nalidixic acid and Gentamycin. The microorganisms used in this work include Bacillus subtilis
and Staphylococcus aureus (as Gram-positive bacteria) and Escherichia coli and Pseudomonas
aeruginosa (as Gram-negative bacteria). The results are presented in Table 5. The antibacterial
activity and inhibition zone around the tested compounds can be caused by their bactericide
effects (killing the bacteria) or from their bacteriostatic effects (inhibiting multiplication of
bacteria by blocking their active sites on the surface or inside bacterial cells). A comparison of
the biological activity of the ligands, organotin(IV) complexes and standard drugs indicates that
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
some of synthesized compounds have good activity against the studied bacteria. The results show
c
that 5, 6 and 7 exhibit more inhibitory effects than both the parent ligand (H
L ) and the other
2
complexes towards B. subtilis, S. aureus and P. aeruginosa. The greater activity of these three
complexes relative to the other complexes may be attributed to the OH group inside the ligand,
which can play an important role in the antibacterial activity [32], and the greater inhibitory
effects than the parent ligand may be explained based on chelation theory (increasing the
lipophilic character and efficient diffusion into bacterial cells upon complexation [22,29,33-35]).
In fact, these three complexes profit both from the hydrogen bonding ability of the ligands,
which interact with active biological centers impairing normal cellular processes, and also from
intrinsic biocidal effects and lipophilicity of organotin moiety, which facilitates permeability
across the bacterial cells.
It is remarkable that the bacteria of the genus Pseudomonas are a group of resistant
microorganism against which many standard drugs were found to have no activity [36,37].
Therefore it is interesting that P. aeruginosa was inhibited by some of the synthesized
compounds.
1
4

1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
4
. Conclusion
On the basis of spectral and structural data, in their tin complexes, the newly synthesised
hydrazones are completely deprotonated and coordinate as tridentate ligands through imine
nitrogen, and phenolic and enolic oxygen atoms, and the coordination number of the tin atom is
five. The synthesized organotin complexes show different activities against the studied Gram-
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
positive (B. subtilis and S. aureus) and Gram-negative (E. coli and P. aeruginosa) bacterial
c
species and R SnL exhibits greater inhibitory effects. This research shows that the substituents
2
on the donor ligand (L) can change the biological activity of organotin derivatives.
Acknowledgment
Support of this work by Shahid Chamran University, Ahvaz, Iran (Grant 1391) is gratefully
acknowledged.
Appendix A. Supplementary data
CCDC 879076, 879077 and 879079 contain the supplementary crystallographic data for
b
a
b
SnMe L , H L and H L , respectively. These data can be obtained free of charge via
2 2 2
http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
References
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1] D. S. Kalinowski, P. C. Sharpe, P. V. Bernhardt, D. R. Richardson, J. Med. Chem. 50 (2007)
6212-6225.
1
5

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7
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6
7
8
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6
7
8
9
0
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2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
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2
3
4
5
6
7
8
9
0
1
2
3
4
5
[
2] D. S. Kalinowski, P. C. Sharpe, P. V. Bernhardt, D. R. Richardson, J. Med. Chem. 51 (2008)
31-344
3] P. V. Bernhardt, P. Chin, P. C. Sharpe, J. Y. C. Wang, D. R. Richardson, J. Biol Inorg. Chem
0 (2005) 761-777
3
[
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
1
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6

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2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
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7
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1
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1
1
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2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
[
[
[
[
[
[
[
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1
[
1
[
[
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7

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8
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1
2
3
4
5
6
7
8
9
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2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
[
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1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
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[
37] D. M. Livermore. Clin. Infect. Dis., 34 (2002) 634-640.
1
8

1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
Fig. 1. Structures of the hydrazone ligands with the numbering for NMR assignments
a
Fig. 2. ORTEP view of H L . Non H-atoms, represented as displacement ellipsoids, are plotted at
2
the 50% probability level, while H atoms are shown as small spheres of arbitrary radius. The
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
dotted lines represent intramolecular hydrogen bonding interactions.
b
Fig. 3. ORTEP view of H L . Non H-atoms, represented as displacement ellipsoids, are plotted
2
at the 50% probability level, while H atoms are shown as small spheres of arbitrary radius. The
dotted line represents intramolecular hydrogen bonding interactions.
Fig. 4. (a) Part of the infinite 1D chain formed by intermolecular N-H∙∙∙N interactions. (b)
a
ABAB packing mode in H
L .
2
b
Fig. 5. Intermolecular interactions in H L , (a) showing the 1D chain formed by intermolecular
2
N-H…N hydrogen bonds (b) showing the angle between two ligands in one chain and the ABAB
packing mode (c) showing π∙∙∙∙π stacking interactions.
Fig. 6. ORTEP view of 3. Non H-atoms, represented as displacement ellipsoids, are plotted at the
50% probability level, while H atoms are shown as small spheres of arbitrary radius.
Fig. 7. Aromatic π…π stacking interactions in 3
a
b
Table 1 Crystallographic and structure refinement data for H L , H L and 3
2
2
a
b
Table 2 Selected bond lengths (Å) and bond angles () for H
L and H L
2
2
a
b
Table 3. Hydrogen bond lengths (Å) and angles (°) for H L and H L
2
2
Table 4 Selected bond lengths (Å) and bond angles () for 3
Table 5 Antibacterial activity data of the ligands and their organotin(IV) complexes
1
9

1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
a
b
Table 1 Crystallographic and structure refinement data for H L , H L and 3
2
2
b
2
a
H2L
H
2
L
3
C H N O
Empirical formula
Formula weight
T (K)
C H BrN O
17 13
3
C H N O Sn
1
3
10
3
2
19
17
3
2
291.30
320.15
296(2)
438.05
293(2)
0.71073
Triclinic
P -1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
296(2)
0.71073
Wavelength, λ (Å)
Crystal system
Space group
a (Å)
0.71073
Monoclinic
Monoclinic
P 2 /n
P 2 /n
.7853(7)
1
1
8
8.57500(10)
15.8908(3)
9.3816(2)
7.4785(2)
9.8391(2)
10.2410(7)
5.8133(10)
b (Å)
c (Å)
1
1
12.7833(2)
95.7710(10)
101.3790(10)
105.6750(10)
875.96(3)
2
1.661
2.51 to 32.74
436

β (˚)
(˚)
99.407(3)
100.4390(10)
γ (˚)
3
403.59(17)
4
V (Å )
1257.21(4)
4
Z
-3
1
.379
.61 to 27.60
08
0.093
Dcalc. (Mg m )
1.691
2
θ Ranges for data collection (˚)
F(000)
Absorption coefficient (mm )
Index ranges
2.73 to 30.10
640
3.271
-12 ≤ h ≤ 12
6
-1
1.476
-11 ≤ h ≤ 10
-13 ≤ k ≤ 13
-18 ≤ l ≤ 20
-11 ≤ h ≤ 11
-14 ≤ k ≤ 14
-19 ≤ l ≤ 19
24705
-22 ≤ k ≤ 22
-13 ≤ l ≤ 13
1
2583
263
R(int) = 0.0293]
263/0/200
.999
.0464
0.1141
Reflections collected
Independent reflections
36060
3694
3
6434
[
[R(int) = 0.0280]
3694/0/176
0.963
[R(int) = 0.0149]
6434/0/226
1.048
3
Data / restraints / parameters
2
0
Goodness-of-fit on F
0
Final R indices [I>2(I)]
R1 = 0.0271
R = 0.0174
1
wR = 0.0664
wR = 0.0525
R = 0.0190
2
2
0
0
.0957
.1353
R indices (all data)
R = 0.0436
1
1
wR
0.510 and -0.350
= 0.0729
wR
= 0.0542
2
0.476 and -0.436
2
-3
0.155 and -0.169
Largest diff. peak and hole (e A )
2
0

1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
a
b
Table 2 Selected bond lengths (Å) and bond angles () for H L and H L
2
2
a
H2L
C6-C5
C5-O2
C5-N2
N2-N1
N1-C4
C4-C3
C11-O1
1.499(2)
1.212(2)
1.3584(19)
1.3666(18)
1.277(2)
C6-C5-O2
O2-C5-N2
C5-N2-N1
N2-N1-C4
N1-C4-C3
C4-C3-C11
C3-C11-O1
121.19(14)
122.24(15)
115.26(13)
119.69(13)
118.85(14)
122.06(14)
122.48(14)
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
1.452(2)
1.3545(19)
b
H2L
C13-C1
C1-O1
C1-N1
N1-N2
N2-C2
C2-C3
C4-O2
1.502(2)
1.2159(19)
1.352(2)
1.3704(18)
1.278(2)
1.453(2)
1.350(2)
C13-C1-O1
O1-C1-N1
C1-N1-N2
N1-N2-C2
N2-C2-C3
C2-C3-C4
C3-C4-O2
121.54(17)
123.11(16)
118.68(13)
117.37(14)
120.28(15)
120.38(16)
122.85(15)
a
b
Table 3. Hydrogen bond lengths (Å) and angles (°) for H L and H L
2
2
Compound
DH—A
d(DH)
d(H…A) d(D…A) DH…A
Symmetry Code
a
H
L
O1 —H1…N1
N2—H2…N3
O2—H2…N2
N1—H1…N3
0.848(2)
1.823(2)
2.584(2)
3.034(2)
2.549(2)
3.112(2)
148.43( 2)
163.55( 1)
146.16(1)
157.66(9)
x,y,z
2
0.860 (1) 2.199(1)
x+1/2,-y+1/2+1,+z+1/2
x,y,z
b
H2L
0.820(1)
0.860(1)
1.827(1)
2.299(2)
-x+1,+y-1/2,-z+1/2+1
2
1

1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
Table 4 Selected bond lengths (Å) and bond angles () for 3
C13-C1
C1-O1
C1-N1
N1-N2
N2-C2
C2-C3
C4-O2
Sn1-C18
Sn1-C19
Sn1-O1
Sn1-N2
Sn1-O2
1.4821(15)
1.2915(15)
1.3065(14)
1.3948(13)
1.3026(14)
1.4210(15)
1.3116(15)
2.1066(15)
2.1009(14)
2.1435(10)
2.1532(10)
2.0897(9)
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
O1-C1-N1
C1-N1-N2
N2-C2-C3
C2-C3-C4
C3-C4-O2
O2-Sn1-C19
O2-Sn1-C18
C19-Sn1-C18
O2-Sn1-O1
C19-Sn1-O1
C18-Sn-O1
O2-Sn-N2
124.61(10)
111.30(10)
127.95(11)
121.90(10)
124.34(10)
93.65(6)
99.33(6)
123.87(7)
153.70(4)
93.55(6)
97.52(6)
83.48(4)
C19-Sn1-N2
C18-Sn1-N2
O1-Sn1-N2
C4-O2-Sn1
C2-N2-Sn1
N1-N2-Sn1
C1-O1-Sn1
127.25(6)
108.58(6)
73.06(4)
133.46(8)
128.27(8)
116.55(7)
114.22(7)
2
2

1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
Table 5 Antibacterial activity data of the ligands and their organotin(IV) complexes
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
Conc.
mg/mL)
40
Inhibition zone (mm)
Compound
(
E. Coli
P. aeruginosa
S. aureus B. subtilis
a
H2L
8
18
11
n.a.
18
8
n.a.
n.a
10
n.a.
12
8
n.a.
n.a.
n.a.
n.a.
16
15
17
15
10
8
11
n.a.
15
10
8
n.a.
15
8
16
12
11
n.a.
n.a.
n.a.
15
9
16
14
13
12
24
22
13
23
21
1
0
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
12
12
12
n.a.
12
n.a.
13
10
12
8
15
b
H2L
40
1
0
c
H
2
L
40
10
40
a
SnMe L (1)
2
1
0
a
SnPh L (2)
40
2
1
0
b
SnMe L (3)
40
2
1
0
10
b
SnPh L (4)
40
10
40
n.a.
n.a.
17
12
16
2
c
SnMe L (5)
2
1
0
c
SnPh L (6)
40
2
1
0
12
c
SnBu L (7)
40
n.a.
n.a.
14
16
12
15
8
2
1
0
Vancomycin
Streptomycin
penicilin
Nalidixic acid
Gentamicin
n.a.
n.a.
n.a.
n.a.
20
17
12
26
12
16
25
20
n.a. = no activity
2
3

a
a
5
a
b
6
4
3
b
b
N
N
N
H
N
3
H
H
N
3
1
Br
N
2
N
N
N
O
2
O
2
O
HO
HO
HO
OH
1
1
H2La
H2Lb
H2Lc
Fig. 1. Structures of the hydrazone ligands with the numbering for NMR assignments

a
Fig. 2. ORTEP view of H L . Non H-atoms, represented as displacement ellipsoids, are plotted at
2
the 50% probability level, while H atoms are shown as small spheres of arbitrary radius. The
dotted lines represent intramolecular hydrogen bonding interactions.

b
Fig. 3. ORTEP view of H L . Non H-atoms, represented as displacement ellipsoids, are plotted
2
at the 50% probability level, while H atoms are shown as small spheres of arbitrary radius. The
dotted line represents intramolecular hydrogen bonding interactions.

(
a)
(
b)
Fig. 4. (a) Part of the infinite 1D chain formed by intermolecular N-H∙∙∙N interactions. (b)
a
ABAB packing mode in H L .
2

(
a)
(
b)
(
c)
b
Fig. 5. Intermolecular interactions in H L , (a) showing the 1D chain formed by intermolecular N-H…N
2
hydrogen bonds (b) showing the angle between two ligands in one chain and the ABAB packing mode
(
c) showing π····π stacking interactions.

Fig. 6. ORTEP view of 3. Non H-atoms, represented as displacement ellipsoids, are plotted at the
0% probability level, while H atoms are shown as small spheres of arbitrary radius.
5