Synthesis and structural properties of thiapyridinophane and its complex with Ni(II) and Ag(I)

Article abstract of DOI:10.1134/S1070328416060087

The 2,11-dithia[3.3](3,5)pyrdinophane (L¹) has been synthesized by a new method and characterized by ¹H NMR, which is used to form coordination complexes C₁₄H₁₄N₄O₆S₂Ni (I) by addition of Ni²⁺ cation and C₁₄H₁₄N₃O₃S₂Ag (II) by addition of Ag⁺ cation. 2,11,20-Trithia[3.3.3](3,5)pyridinophane (L²) and 2,11,20,29-tetrathia[3.3.3.3](3,5)pyridinophane (L³) have also been synthesized as by-products. Single-crystal X-ray analysis reveals that the conformation of the L¹ is syn(boat-chair), complexes I and II also adopt syn(boat-chair) (CIF files CCDC nos. 1400332 (I) and 700724 (II)). While in I, Ni(II) is coordinated with L¹ with two nitrogen and four oxygen atoms, in II, Ag(^I) is coordinated with L¹ by two nitrogen and two sulfur atoms came from four ligands. In complexes I and II, the formation of three-dimensional structure depends on π???π stacking and hydrogen bonds.

Full text of DOI:10.1134/S1070328416060087

ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2016, Vol. 42, No. 7, pp. 455–460. © Pleiades Publishing, Ltd., 2016.
Synthesis and Structural Properties of Thiapyridinophane
1
and Its Complex with Ni(II) and Ag(I)
a
a
a
b,
c
P. C. Wu , R. Shi , D. Y. Fang , C. C. Jin *, and M. Zhou
a
Department Information Engineering, Liaoning University of Traditional Chinese Medicine, Shengyang, 110000 P.R. China
b
Company of Shenyang Parkerizing, Shengyang, 110042 P.R. China
c
Pnjin Vocational and Technical College, Panjin, 124000 P.R. China
*
e-mail: jinchengcheng58@126.com
Received June 5, 2015
1
Abstract—The 2,11-dithia[3.3](3,5)pyrdinophane (L ) has been synthesized by a new method and character-
1
2+
2
ized by H NMR, which is used to form coordination complexes C H N O S Ni (I) by addition of Ni cat-
14
14
4
6 2
+
ion and C H N O S Ag (II) by addition of Ag cation. 2,11,20-Trithia[3.3.3](3,5)pyridinophane (L ) and
14
14
3
3 2
3
2
,11,20,29-tetrathia[3.3.3.3](3,5)pyridinophane (L ) have also been synthesized as by-products. Single-crys-
1
tal X-ray analysis reveals that the conformation of the L is syn(boat-chair), complexes I and II also adopt
syn(boat-chair) (CIF files CCDC nos. 1400332 (I) and 700724 (II)). While in I, Ni(II) is coordinated with
1
1
L with two nitrogen and four oxygen atoms, in II, Ag(I) is coordinated with L by two nitrogen and two sulfur
atoms came from four ligands. In complexes I and II, the formation of three-dimensional structure depends
on π⋅⋅⋅π stacking and hydrogen bonds.
DOI: 10.1134/S1070328416060087
INTRODUCTION
Since the definition was given by Cram [1], cyclo-
nitrogen atoms, respectively, and its molecular skele-
1
tons are located towards different directions, thus, L
has unique coordination properties. In this paper, we
phanes, which are organic compounds comprising of
aromatic elements as structural units, have been stud-
ied [2–4]. Cyclophanes known as bridged aromatic
compounds have been intensively studied from various
points of view for the last few decades [5, 6]. Among
them large-sized cyclophanes capable of forming an
inner cavity have been playing a central role as syn-
thetic receptors in molecular recognition [7–10]. On
the contrary, small-sized cyclophanes can be charac-
terized by their aromatic components fixed in a forced
proximity and their particular orientation. Consider-
ing their unique three-dimensional structure and con-
formational mobility, the small-sized cyclophanes
1
report the Ni(II) and Ag(I) complexes with L which
show interesting structure. These studies enrich the
knowledge of structure and physical properties of pyr-
idinophane as well as its complexes. To the best of our
knowledge, the formation of dual-core coordination
in complex I is new coordination examples of thiapyr-
idinophane.
EXPERIMENTAL
Materials and methods. Reactions were monitored
by TLC with glass-backed silica gel HF plates and
254
possibly provide the fascinating supramolecular self- visualized under λ = 254 nm or by iodine adsorption as
assembly upon coordination.
appropriate. Flash column chromatography was per-
formed using silica gel neutral alumina (100–
In recent years, many review articles and books on
cyclophanes have been published [11–16]. The aro-
matic units can be interlinked by hydrocarbon units,
heteroatom containing units, or mixed substituents.
Our group is interested in thiapyridinophane [17] and
its complexes. 2,11-Dithia[3.3](3,5)pyrdinophane
1
2
00 mesh). H NMR spectra were obtained with a
Varian Mercury 300 spectrometer. Chemical shift
were reported as δ values (ppm) relative to internal
tetramethylsilane (TMS) in DMSO unless otherwise
noted. Reagents were used without further purifica-
tion from commercial sources unless otherwise stated.
1
2
(
L ), 2,11,20-trithia[3.3.3](3,5)pyridinophane (L )
1
2
3
and 2,11,20,29-tetrathia[3.3.3.3](3,5)pyridinophane
Synthesis of compound L , L , and L . To a solution
3
(
L ) have been synthesized in our lab using Ramberg- of Na
2
S · 9H
2
O (3.68 g, 15.3 mmol) in 95% EtOH
1
Bäcklund reaction. Ligand L contains sulfur and (100 mL) was added dropwise a solution of freshly
prepared 3,5-bis(chloromethyl)pyridine (0.98 g,
2.86 mmol) in EtOH (50 mL) at room temperature
1
The article is published in the original.
455

4
56
WU et al.
1
over a period of 5 h, and then the mixture was heated (0.350 g, 15%, R = 0.41); H NMR (300 MHz;
f
to reflux for 24 h. After cooling, the solvent was evap- DMSO; 25°C; δ, ppm): 8.45 (s., 6H, 2,6-PyH), 7.46
orated under reduced pressure. The residue was (s., 3H, 4-PyH), 3.65 (s., 12H, –CH SCH –); MS
2
2
+
extracted with CH Cl . The combined extracts were (LCQ) m/z: 412.1 [M ]. Anal. calcd. for C H N S
2
2
21 21
3 3
3
dried with MgSO and filtered. The filtrate was evap- (412.4). L (0.09 g, 3%, R = 0.21); δ 8.28 (s., 6H, 2,6-
4
f
orated under reduced pressure, and the residue was PyH), 7.45 (s., 3H, 4-PyH), 3.68 (s., 12H,
+
purified by PTLC on silica gel with EtOH to give white ‒CH SCH –); MS (LCQ) m/z: 549.12 [M ]. Anal.
2
2
1
1
power L (0.400 g, 26%, R = 0.57); H NMR (300 MHz; calcd. for C H N S (549.4).
f
28 28
4 4
1
DMSO; 25°C; δ, ppm): 7.94 (s. 4H, 2,6-PyH, 7.62 (s.,
Synthesis of 2,11-dithia[3.3](3,5)pyrdinophane L ,
2
2
3
2
H, 4-PyH), 3.89 (s., 8H, –CH SCH –) and L
L , L are given in Scheme:
Cl Cl
2
2
NCS
BPO
N
N
N
N
S
S
S
S
S
N
N
S
S
Na2S
+
+
N
N
C2H5OH
S
N
S
N
N
3%
26%
15%
(L3)
1
(L2)
(
L )
Synthese of complex I. The solution of CHCl
(nos. 1400332 (I) and 700724 (II); deposit@ccdc.
3
1
cam.ac.uk or http://www.ccdc.cam.ac.uk).
(
5 mL) containing compound
L
(19.7 mg,
0
.07 mmol) was poured into a 6 mm diameter bottom-
sealed glass tube and then layered with CH CN solu-
3
RESULTS AND DISCUSSION
tion (5 mL) of Ni(NO ) ⋅ 6H O (49.4 mg, 0.17 mmol).
3
2
2
1
Although preparation of compound L reported by
The glass tube was sealed. Green block crystals of
complex I, suitable for X-ray diffraction analysis, was
obtained after 10 days. Complex II was obtained by the
similar method.
H.A. Staab et al. via the coupling reaction, we used
1
2
another method to obtain L and L . Comparing to the
1
previous method, the yield of compound L declined,
2
X-ray crystallography. Single-crystal X-ray diffrac- but the yield of compound L increased. We produced
tion measurements were carried out on a Bruker Smart 3,5-bis(chloromethyl)pyridine by direct chlorination
Apex CCD diffractometer at room temperature of 3,5-lutidine with N-chlorosuccinimide. The freshly
(
293(2) K). The data collections were performed with prepared 3,5-bis(chloromethyl)pyridine was reacted
MoK radiation (λ = 0.71073 Å). Unit cell dimensions with Na
S ⋅ 9H
O in EtOH under high dilution condi-
α
2
2
1
2
were obtained with least squares refinements, and all tions to give L (26.0%) and L (15.0%).
structures were solved by direct method. The non-
hydrogen atoms were located in successive difference
Fourier syntheses. The final refinement was per-
formed by full matrix least-squares methods with
anisotropic thermal parameters for nonhydrogen
In the crystal structure of I, Ni(II) was coordinated
by the four oxygen atoms of NO – and two nitrogen
3
atoms which come from different ligands, two ligands
and two Ni(II) formed dual-core complex. Every
Ni(II) adopted a distorted octahedron coordination
geometry. The coordination environment of Ni(1) and
Ni(1A) was same, as well as in crystallography. The
distance between Ni(1) and Ni(1A) was 3.417 Å, which
2
atoms on F [18]. Hydrogen atoms were added theo-
retically and were riding on their parent atoms. Crys-
tallographic data are summarized in table.
Supplementary material has been deposited with was smaller than the van der Waals radius but larger
the Cambridge Crystallographic Data Centre than the metallic radius of Ni···Ni, it indicated that in
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
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SYNTHESIS AND STRUCTURAL PROPERTIES
457
Crystallographic data and structure refinement summary for compounds I and II
Value
Parameter
I
II
Empirical formula
C H N O S Ni
C H N O S Ag
1
4
14
4
6
2
14 14
3
3 2
Formula weight
457.12
444.27
Crystal system; space group
Monoclinic; P2 /n
Monoclinic; P2 /n
1
1
Unit cell dimensions:
a, Å
9.374(2)
18.472(5)
10.341(2)
94.236(19)
15.319(3)
15.456(2)
16.237(3)
90
b, Å
c, Å
β, deg
Volume, Å3
1785.7(7)
3844.3(12)
Z
4
8
ρcalcd, mg/m3
1.700
1.535
μ, mm–1
1.361
1.280
F(000)
936
1776
Crystal size, mm
0.46 × 0.34 × 0.31
2.21 to 26.02
0.37 × 0.32 × 0.27
1.87 to 29.19
θ Range for data collection, deg
Limiting indices
–11 ≤ h ≤ 1, –1 ≤ k ≤ 22, –12 ≤ l ≤ 12 –21 ≤ h ≤ 1, –19 ≤ k ≤ 1, –1 ≤ l ≤ 20
Reflections collected/ unique (Rint)
Completeness to θ = 27.51, %
Max and min transmission
Data/restraints/ parameters
4450/3514 (0.0289)
99.9
2804/2452 (0.0545)
85.3
0.6761 and 0.5757
3514/0/244
0.7254 and 0.6495
2452/1/208
1.179
Goodness-of-fit on F2
Final R indices (I > 2σ(I))
R indices (all data)
1.029
R = 0.0395, wR = 0.1023
R = 0.0508, wR = 0.1589
1
2
1
2
R = 0.0539, wR = 0.1110
R = 0.0822, wR = 0.1821
1
2
1
2
Largest diff. peak and hole, e Å–3
0
.754 and –0.304
1.375 and –0.857
complex Ni(1) and Ni(1A) have some strong interac- complex I is 8.88°, which is smaller than the dihedral
tion, which can be called dual-core complex. The con- angle of ligand by 1.41° as shown in Fig. 1a. The inter-
formation of the ligand in complex I is syn(boat- molecular pyridine rings also have π···π stacking (dis-
chair), which is the same as the ligand (syn(boat- tance between two pyridine rings was 3.419 Å) as
chair)). But the distance of two nitrogens in every pyr- shown in Fig. 2, the distance of N···H was 2.624 Å
idinophane was 3.518, which was smaller than which was smaller than the van der Waals radius of
the ligand. The dihedral angle of pyrazine ring in N···H (2.750 Å). The distance of O···H was 2.355 and
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 42 No. 7 2016

4
58
WU et al.
a)
(
S(1)
C(1)
C(11)
C(4)
C(7)
C(14)
C(8)
C(5)
C(2)
C(3)
C(9)
S(2)
C(12)
C(6)
C(13)
C(10)
N(1)
N(4A)
O(6A)
N(2)
O(5A)
O(3A)
O(4A)
O(2)
O(1A)
Ni(1A)
N(3A)
O(2A)
O(4)
O(1)
Ni(1)
N(3)
O(3)
N(2A)
O(5) N(4)
O(6)
C(13A)
C(3A)
N(1A)
C(10A)
C(9A)
C(6A)
C(14A)
S(2A)
C(12A)
C(11A)
C(8A)
C(5A)
C(2A)
C(7A)
C(4A)
C(1A)
S(1A)
(b)
S(2)
C(7)
C(8)
C(9)
C(4)
C(5)
C(3)
C(13)
N(1)
C(2)
C(10)
C(11)
C(14)
C(1)
S(1)
N(1A)
C(6)
N(2)
N(2A)
Ag(1)
C(12)
S(2A)
Fig. 1. Coordination environment of the nickel and silver atoms in complexes I (a) and II (b).
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
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SYNTHESIS AND STRUCTURAL PROPERTIES
459
(a)
2.355
2.624
2.688
(b)
3.027
3.236
Fig. 2. Fragment of the chain in complex I.
(a)
(b)
z
y
0
x
Fig. 3. Perspective view of the 3D structures of I along the x axis (a) and II along the z axis (b).
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 42 No. 7 2016

4
60
WU et al.
2
.688 Å which were smaller than the van der Waals
4. Cram, D.J. and Cram, J.M., Acc. Chem. Res., 1971,
vol. 4, p. 204.
radius of O···H (2.720 Å). We think the N···H, O···H
have some weak interaction. In addition, the distance
between S and O was 3.027 Å which was smaller than
the van der Waals radius of O···S (3.320 Å). Due to all
of above, complexes between molecules formed in lay-
ered structure as shown in Fig. 3a.
5. Vögtle, F., Cyclophane Chemistry, Chichester: Wiley,
1989.
6
. Diederich, F., Cyclophanes, Cambridge: The Royal
Society of Chemistry, 1991.
7
. Vögtle, F., Supramolecular Chemistry, Chichester:
In the crystal structure of II, Ag(I) was coordinated
with two nitrogen and two sulfur atoms came from
four ligands, respectively, as shown in Fig. 1b, and
form a near square cyclic structure by Ag(I) which fur-
ther extend in one dimension. The size of cavity was
Wiley, 1989.
8. Lehn, J.M., Pure Appl. Chem., 1994, vol. 66, p. 1961.
9
. Lehn, J.M., Supramolecular Chemistry, Weinheim:
VCH, 1995.
1
0. Steed, J.W. and Atwood, J.F., Supramolecular Chemis-
8
.133 × 7.953 Å as shown in Fig. 3b. The conformation
try, Chichester: Wiley, 2000.
of the ligand in complex II is also syn(boat-chair). But
the dihedral angle of pyrazine ring in complex is 11.3°, 11. Thilgen, C. and Vögtle, F., Chem. Ber., 1990, vol. 123,
p. 2445.
which was warped as the coordination between Ag(I)
and nitrogen in the pyrazine ring.
12. Cyclophanes, Keehn, R.M. and Rosenfeld, S.M., Eds.,
New York: Academic, 1983.
1
3. Takemura, H., Shinmyozu, T., and Inazu, T., Coord.
ACKNOWLEDGMENTS
We are grateful to G.X. Zhang for his discussion
and suggestions.
Chem. Rev., 1996, vol. 156, p. 183.
14. Cyclophane Chemistry for the 21st Century,
Takemura, H., Ed., India: Research Signpost, 2002.
1
5. Modern Cyclophane Chemistry, Gleiter, R. and
Hopf, H., Eds., Weinheim: Wiley-VCH, 2004.
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1
2
3
(England): Wiley, 1993.
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No. 7
2016