Syntheses and structural characterization of silver(I) complexes with pyridine and carboxylate derivatives

Article abstract of DOI:10.1134/S107032841101009X

Self-assembly between silver carboxylates with 2-aminopyridine derivatives give two silver(I) complexes, [[Ag(5MP)₂(CNB)] ? NH₃ (I) and [Ag(3MP)₂(HMB)] (II), where 5MP, CNB, 3MP, and HMB represent 2-amin-5-methylpyridine, 5-chloro-2-nitrobenzoate, 2-amino-3-methylpyridine, and 2-hydroxy-3-methoxybenzoate, respectively. The crystal structures of the complexes were investigated. The Ag atom in each complex is coordinated by two pyridine N atoms and weakly coordinated by a carboxylic O atom. The crystal of I is triclinic: space group P 1, a = 7.562(2), b = 11.708(3), c = 12.933(3) A, α = 103.378(4)°, β = 93.910(4)°, γ = 99.001(4)°, V = 1093.7(5) A³, Z = 2. The crystal of II is monoclinic: space group C2/c, a = 25.727(5), b = 10.274(2), c = 19.872(4) A, β = 126.62(3)°, V = 4215.7(15) A³, Z = 4.

Full text of DOI:10.1134/S107032841101009X

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2011, Vol. 37, No. 1, pp. 36–39. © Pleiades Publishing, Ltd., 2011.
Syntheses and Structural Characterization of Silver(I) Complexes
with Pyridine and Carboxylate Derivatives1
J. F. Lu*, H. G. Ge, and S. T. Min
School of Chemistry and Environmental Science, Shaanxi University of Technology, Hanzhong, 723000, P.R. China
*eꢀmail: jiufulu@163. com
Received April 28, 2010
Abstract—Selfꢀassembly between silver carboxylates with 2ꢀaminopyridine derivatives give two silver(I)
complexes, [[Ag(5MP)2(CNB)] ⋅ NH3 (I) and [Ag(3MP)2(HMB)] (II), where 5MP, CNB, 3MP, and HMB
represent 2ꢀaminꢀ5ꢀmethylpyridine, 5ꢀchloroꢀ2ꢀnitrobenzoate, 2ꢀaminoꢀ3ꢀmethylpyridine, and 2ꢀhydꢀ
roxyꢀ3ꢀmethoxybenzoate, respectively. The crystal structures of the complexes were investigated. The Ag
atom in each complex is coordinated by two pyridine N atoms and weakly coordinated by a carboxylic
O atom. The crystal of
103.378(4) = 93.910(4)
2/ = 25.727(5), = 10.274(2),
I
°
is triclinic: space group
a
, Z
= 7.562(2),
= 2. The crystal of II is monoclinic: space group
= 126.62(3) = 4.
= 4215.7(15) Å3
b = 11.708(3), c = 12.933(3) Å, α =
P 1,
= 1093.7(5) Å3
= 19.872(4)
°,
β
,
γ
= 99.001(4)
°,
V
C
c,
a
b
c
Å,
β
°,
V
, Z
DOI: 10.1134/S107032841101009X
1
INTRODUCTION
analyses were preformed with a PerkinElmer elemenꢀ
tal analyzer.
Silver(I) carboxylates with organic amines form an
important class of metal complexes in coordination
chemistry. These complexes have been received much
attention in many fields, and their crystal structures
have widely been investigated [1–5]. Studying the
variety of products in the selfꢀassembly processes
between the silver atoms with nitrogenꢀ and oxygenꢀ
containing ligands is an interesting topic in supramoꢀ
lecular chemistry. The balance between the formation
of different structures is often subtle. Factors that
affect the coordination topology include not only the
highly influential factors of metal and ligand coordiꢀ
nation preferences but also anionꢀbased influences.
The latter factor is particularly notable in the silver
complexes [6, 7]. In the present work, two silver(I)
Synthesis of complex I. Ag2O (0.5 mmol, 0.116 g)
and CNB (1.0 mmol, 0.201 g) were dissolved in a 30%
ammonia solution (50 ml) and stirred for 30 min in
dark to give a colorless solution. Then 5MP
(2.0 mmol, 0.216 g) was added to the solution with
continuous stiring for 30 min in dark at room temperꢀ
ature. Colorless blockꢀshaped crystals of
I were
formed by the slow evaporation of the solution in dark.
The crystals were isolated by filtration, washed with
water and methanol. The yield was 0.370 g (69%).
For C19H22Cl N6O4Ag
anal. calcd., %:
Found, %:
C, 42.1;
C, 42.5;
H, 4.1;
H, 4.2;
N, 15.5.
N, 15.3%.
complexes, [Ag(5MP)2(CNB)]
⋅ NH3 (I) and
[Ag(3MP)2(HMB)] (II , where 5MP, CNB, 3MP, and
)
HMB represent 2ꢀaminoꢀ5ꢀmethylpyridine, 5ꢀchloroꢀ
2ꢀnitrobenzoate, 2ꢀaminoꢀ3ꢀmethylpyridine, and 2ꢀ
hydroxyꢀ3ꢀmethoxybenzoate, respectively, were syntheꢀ
sized and characterized by elemental analyses and sinꢀ
gleꢀcrystal Xꢀray diffraction.
Synthesis of complex II. Ag2O (0.5 mmol, 0.116 g)
and HMB (1.0 mmol, 0.168 g) were dissolved in a 30%
ammonia solution (50 ml), and stirred for 30 min in
dark to give a colorless solution. Then 3MP (2.0 mmol,
0.216 g) was added to the solution with continuous
stiring for 30 min in dark at room temperature. Colorꢀ
less blockꢀshaped crystals of II were formed by the
slow evaporation of the solution in dark. The crystals
were isolated by filtration, and washed with water and
methanol. The yield was 0.610 g (62%).
EXPERIMENTAL
Materials and instruments. The chemicals with AR
grade were used as purchased from Aldrich without
further purification. The silver(I) carboxylates were
prepared by the reaction of Ag2O with carboxylic acids
in 30% ammonia solutions. C, H, and N elemental
For C40H46N8O8Ag2
anal. calcd., %:
Found, %:
C, 48.9;
C, 49.3;
H, 4.7;
H, 4.6;
N, 11.4.
N, 11.7.
1
The article is published in the original.
36

SYNTHESES AND STRUCTURAL CHARACTERIZATION OF SILVER(I) COMPLEXES
37
Table 1. Crystallographic data and structure refinement paꢀ Table 2. Selected bond lengths (
rameters for and II and II
Å) and bond angles (deg) for
I
I
Bond
d,
Å
Bond d, Å
Value
Parameter
I
I
II
Ag(1)–N(1)
Ag(1)–O(1)
2.168(5) Ag(1)–N(3)
2.593(5)
2.181(5)
Formula weight
Space group
541.75
Triclinic
P 1
982.59
II
Monoclinic
Ag(1)–N(1)
Ag(1)–O(1)
2.151(4) Ag(1)–N(3)
2.747(4) Ag(1)···Ag(1
2.149(4)
3.131(2)
Unit cell dimensions:
C2/c
A)
a
,
Å
Å
Å
7.562(2)
11.708(3)
12.933(3)
103.378(4)
93.910(4)
99.001(4)
1093.7(5)
2
25.727(5)
10.274(2)
19.872(4)
90
Angle
ω
, deg
Angle
ω, deg
b
,
I
c
,
N(1)Ag(1)N(3) 153.2(2)
N(3)Ag(1)O(1) 109.2(2)
N(1)Ag(1)O(1) 97.3(2)
N(1)Ag(1)O(1) 89.8(2)
α
, deg
II
β
, deg
126.62(3)
90
N(1)Ag(1)N(3) 169.4(2)
N(3)Ag(1)O(1) 96.8(2)
γ, deg
V
,
Å3
4215.7(15)
4
Z
1.43(2) Å. Other H atoms were placed in calculated
positions and constrained to ride on their parent
atoms. The crystallographic data for the complexes are
summarized in Table 1. Selected bond lengths and
angles are given in Table 2.
ρcalcd, g cm–3
, mm–1
1.645
1.548
μ
1.082
0.989
F
(000)
548
2000
Atomic coordinates and other structural parameters
of the complexes have been deposited with the Camꢀ
θ
range, deg
1.63–27.00
9244
1.97–27.50
17763
4803
bridge Crystallographic Data Centre (nos. 769311 for
and 769312 for II; deposit@ccdc.cam.ac.uk or http://
www.ccdc.cam.ac.uk).
I
Reflections measured
Independent reflections
Observed reflections
Variables
4675
2359
2905
RESULTS AND DISCUSSION
303
278
The carboxylates CNB and HMB contain oxygen
donors, which can react with Ag2O to give silver(I) carꢀ
boxylates. The pyridine derivatives 5MP and 3MP
contain nitrogen donors. Since the silver atom has
been classified as an extremely soft acid, it prefers to
combine with the soft bases such as Nꢀcontaining
ligands [11, 12]. In the present work, the complexes
were prepared by reaction of the silver(I) carboxylates
with pyridine derivatives in 30% ammonia solutions.
The pyridine N atoms are coordinate to the Ag atoms,
however, the carboxylic O atoms are weakly coordiꢀ
nate to the Ag atoms.
Restraints
12
6
R1
(I
≥
2σ
(
I
))
))
0.0581
0.1352
0.1275
0.1642
0.0658
0.1161
0.1193
0.1335
wR2
(
I
≥
2
σ
(
I
R1 (all data)
wR2 (all data)
Xꢀray structure determination. Diffraction intensiꢀ
ties for the complexes were collected at 298(2) K using
a Bruker SMART APEX II area detector with MoKα
The molecular structure of I is shown in Fig. 1. The
radiation (
λ = 0.71073 Å). The collected data
complex consists of a mononuclear silver complex
molecule and an ammonia molecule of crystallization.
The Ag atom in the complex is coordinated by two
pyridine N atoms from two 5MP ligands and by one
carboxylic O atom of the CNB ligand. The amino N
atoms of the 5MP ligands do not participate in the
coordination. The O(1) atom of CNB is weakly coorꢀ
dinated to the Ag(1) atom with an Ag(1)–O(1) disꢀ
tance of 2.593(5) Å, which is longer than the normal
were reduced using the SAINT program [8], and mulꢀ
tiscan absorption corrections were applied using the
SADABS program [9]. The structures were solved by
direct methods and refined against F2 by fullꢀmatrix
leastꢀsquares methods using the SHELXTL package
[10]. All of the nonꢀhydrogen atoms were refined
anisotropically. Amino H atoms were located in differꢀ
ence Fourier maps and refined isotropically with N⎯H
and H···H distances restrained to 0.90(1) and Ag–O bonds [13, 14]. The Ag–N bonds in the comꢀ
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
No. 1
2011

38
LU et al.
C(2)
C(3)
C(6)
C(1)
C(4)
C(5)
N(2)
N(1)
O(3)
N(5)
O(4)
O(1)
C(11)
Ag(1)
N(3)
C(14)
C(10)
C(9)
C(15)
C(19)
C(13)
C(12)
O(2)
N(6)
C(16)
N(4)
C(18)
C(17)
C(7)
C(8)
Cl(1)
Fig. 1. Molecular structure of
I
showing 30% probability thermal ellipsoids.
C(12)
C(8)
C(9)
N(4)
C(10)
C(7)
C(11)
N(3)
C(17)
C(18)
C(13)
C(16)
O(4)
Ag(1)
O(1)
C(15)
C(14)
O(3)
C(19)
O(2)
N(1)
C(5)
Ag(1A)
C(20)
N(2)
C(4)
C(1)
C(2)
C(3)
C(6)
Fig. 2. Molecular structure of II showing 30% probability thermal ellipsoids; H atoms are omitted for clarity. Unlabelled atoms
are at the symmetry position – , 1 – , –
x
y
z.
plex are typical and comparable with those observed in cent two mononuclear silver complex molecules are
other silver complexes [15–17]. The C(13)–C(18)
benzene ring forms dihedral angles of 57.4(6) and
46.1(6) , respectively, with the two pyridine rings.
linked via Ag···Ag interactions (3.131(2) Å), forming a
dimer. The Ag atom in the complex is coordinated by
two pyridine N atoms from two 3MP ligands and by
one carboxylic O atom of the HMB ligand. The amino
°
°
The crystal structure of II is shown in Fig. 2. The
compound is a mononuclear silver complex. The adjaꢀ N atoms of the 3MP ligands do not participate in the
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
No. 1
2011

SYNTHESES AND STRUCTURAL CHARACTERIZATION OF SILVER(I) COMPLEXES
39
5. Kokunov, Y.V., Kovalev, W., and Gorbunova, Y.E.,
Russ. J. Inorg. Chem., 2008, vol. 53, no. 12, p. 1893.
6. Erxleben, A., Inorg. Chem., 2001, vol. 40, no. 12,
coordination. The O(1) atom of HMB is weakly coorꢀ
dinated to the Ag(1) atom with Ag–O distance of
2.747(4) Å, which is also longer than the normal
Ag⎯O bonds [13, 14]. The Ag–N bonds in II are a litꢀ
tle shorter than those in I, which might be caused by
p. 2928.
7. Khlobystov, A.N., Blake, A.J., Champness, N.R., et al.,
Coord. Chem. Rev., 2001, vol. 222, p. 155.
the weaker interaction of the Ag–O bond in II than
that in
dral angles of 83.1(5)
the two pyridine rings.
The stronger interaction between the Ag(1) and
O(1) atoms in than that in II can also be observed by
the N(1)Ag(1)N(3) bond angles (153.2(2) in
169.4(2) in II).
I. The C(13)–C(18) benzene ring forms diheꢀ
8. SMART & SAINT, Software Reference Manuals, Version
6.22, Madison (WI, USA): Bruker AXS Analytic Xꢀray
Systems Inc., 2000.
9. Sheldrick, G.M., SADABS, Software for Empirical
Absorption Correction, Göttingen (Germany): Univ. of
Göttingen, 2000.
10. Sheldrick, G.M., SHELXTL, Reference Manual, Verꢀ
sion 5.1, Madison (WI, USA): Bruker AXS, Analytic Xꢀ
Ray Systems Inc., 1997.
°
and 75.1(5)°, respectively, with
I
°
I,
°
11. Zhao, Y.J., Hong, M.C., Liang, Y.C., et al., Polyheꢀ
dron, 2001, vol. 20, no. 20, p. 2619.
12. Wei, Y.J., Wang, F.W., and Zhu, C.G., Russ. J. Coord.
Chem., 2010, vol. 36, no. 3, p. 170.
13. Schultheiss, N., Powell, D.R., Bosch, E., and Krisꢀ
tiansson, O., Inorg. Chem., 2001, vol. 40, no. 20,
p. 5058.
ACKNOWLEDGMENTS
The authors thank the Scientific Research Founꢀ
dation of the Shaanxi University of Technology for
financial support (project no. SLGQD0708).
REFERENCES
14. Kaoo, P.O., Grins, J., Fahlman, M., et al., Polyhedron
2001, vol. 20, no. 21, p. 2747.
,
1. Della Pergola, R., Sironi, A., Manassero, C., et al., Eur.
J. Inorg. Chem., 2009, vol. 31, p. 4618.
15. Schultheiss, N., Powell, D.R., and Bosch, E., Inorg.
Chem., 2003, vol. 42, no. 17, p. 5304.
16. Jian, F.F., Zheng, G.X., and Xiao, H.L., Russ. J. Coord.
Chem., 2004, vol. 30, no. 11, p. 800.
17. Omary, M.A., RawashdehꢀOmary, M.A., Diyabalꢀ
anage, H.V.K., et al., Inorg. Chem., 2003, vol. 42,
no. 26, p. 8612.
2. Wei, M.L., Sun, R.P., Zhuang, P.F., et al., Russ. J.
Coord. Chem., 2009, vol. 35, no. 12, p. 885.
3. Kandaiah, S., Halasz, I., Dinnebier, R.E., et al., Inorg.
Chim. Acta, 2009, vol. 362, no. 11, p. 4009.
4. Ruan, B.F., Tian, Y.P., Zhou, H.P., et al., J. Organomet.
Chem., 2009, vol. 694, no. 18, p. 2883.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
No. 1
2011