Synthesis and characterization of diaquatetra(3,5-dinitrobenzoato) tetrasilver(I) and polymeric (ethylenediaminesilver(I) di(3,5-dinitrobenzoato) silver(I) dihydrate)

Article abstract of DOI:10.1081/SIM-200037227

Two new silver complexes have been synthesized, diaquatetra(3,5- dinitrobenzoato)-tetrasilver(I) (1) and polymeric (ethylenediaminesilver(I) di(3,5-dinitrobenzoato)silver(I) dihydrate) (2). These two complexes were characterized by elemental analyses and X-ray crystallographic technique. The crystal structure of (1) belongs to the monoclinic system with the space group P2₁/c, a = 5.685(11) A, b = 16.96(3) A, c = 19.67(4) A, α = 90.00°, β = 90.00(3)°, γ = 90.00°, U = 1897(6) A³, Z = 2, Dx = 1.544 g cm^-3. The crystal structure of (2) belongs to the triclinic system with the space group P-1. a = 6.978(2) A, b = 12.919(5) A, c = 15.0291(5) A, α = 84.320(6)°, β = 76.810(5)°, γ = 79.612(6)°, U = 1295.2(8)³, Z = 2, Dx = 1.882 g cm^-3. Copyright

Full text of DOI:10.1081/SIM-200037227

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Synthesis and Reactivity in Inorganic, Metal-Organic,
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Synthesis and Characterization of
Diaquatetra(3,5‐dinitrobenzoato)tetrasilver(I)
and Polymeric (Ethylenediaminesilver(I)
Di(3,5‐dinitrobenzoato)silver(I) Dihydrate)
Xiao‐Yang Qiu a , Ji‐Long Ma a , Lin Sun a , Song Yang a & Hai‐Liang Zhu a
a Department of Chemistry , Fuyang Normal College , Fuyang, P.R. China
Published online: 15 Feb 2007.
To cite this article: Xiao‐Yang Qiu , Ji‐Long Ma , Lin Sun , Song Yang & Hai‐Liang Zhu (2005) Synthesis and Characterization
of Diaquatetra(3,5‐dinitrobenzoato)tetrasilver(I) and Polymeric (Ethylenediaminesilver(I) Di(3,5‐dinitrobenzoato)silver(I)
Dihydrate), Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 35:3, 189-192, DOI: 10.1081/
SIM-200037227
To link to this article: http://dx.doi.org/10.1081/SIM-200037227
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Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry, 35:189–192, 2005
Copyright # 2005 Taylor & Francis, Inc.
ISSN: 0094-5714 print/1532-2440 online
DOI: 10.1081/SIM-200037227
Synthesis and Characterization of
Diaquatetra(3,5-dinitrobenzoato)tetrasilver(I) and Polymeric
(Ethylenediaminesilver(I) Di(3,5-dinitrobenzoato)silver(I)
Dihydrate)
Xiao-Yang Qiu, Ji-Long Ma, Lin Sun, Song Yang, and Hai-Liang Zhu
Department of Chemistry, Fuyang Normal College, Fuyang, P.R. China
et al., 1995). We are interested in the investigation of
Two new silver complexes have been synthesized, silver(I) complexes with various organic ligands containing
diaquatetra(3,5-dinitrobenzoato)-tetrasilver(I) (1) and poly-
meric (ethylenediaminesilver(I) di(3,5-dinitrobenzoato)silver(I)
N and/or O atoms. Here we report two new silver(I) carboxy-
lato complexs, (1) is disquatetra(3,5-dinitrobenzoato)tetrasil-
ver(I) and (2) is polymeric (ethylenediaminesilver(I) di(3,5-
dinitrobenzoato)silver(I) dihydrate).
dihydrate) (2). These two complexes were characterized by
elemental analyses and X-ray crystallographic technique. The
crystal structure of (1) belongs to the monoclinic system with
˚
the space group P21/c, a 5 5.685(11) A, b 5 16.96(3) A,
˚
˚
c 5 19.67(4) A,
a 5 90.008,
b 5 90.00(3)8,
g 5 90.008,
U 5 1897(6) A , Z 5 2, Dx 5 1.544 g cm23. The crystal structure
3
EXPERIMENTAL
˚
of (2) belongs to the triclinic system with the space group
˚
˚
˚
Materials and Measurements
P-1.
a 5 84.320(6)8, b 5 76.810(5)8, g 5 79.612(6)8, U 5 1295.2(8)3,
Z 5 2, Dx 5 1.882 g cm23
a 5 6.978(2) A,
b 5 12.919(5) A,
c 5 15.0291(5) A,
All reagents and solvents were used as obtained without
further purification. C, H and N elemental analyses were
performed with a Perkin-Elmer elemental analyzer. The
X-ray analysis was carried out on a Siemens SMART
Charged Couple Device (CCD) area detector diffractometer.
.
Keywords Silver (I) complexes, silver (I) benzoate, ethylenedi-
aminesilver (I), single crystal structure
Preparation of Diaquatetra(3,5-dinitrobenzoato)
tetrasilver(I) (1)
INTRODUCTION
Ag2O (0.5 mmol, 116 mg) and 3,5-dinitrobenzoic acid
(dnbc), (1 mmol, 167 mg) were dissolved in an aqueous
ammonia solution (30%, 10 mL) and stirred for ca. 10 min.
After keeping the solution in air for two days, large colorless
prismatic crystals were isolated by filtration, washed with
distilled water, and dried in a vacuum desiccator over
anhydrous CaCl2. Anal. Calcd. for C28H16Ag4N8O26 (FW
1311.97): C, 25.63; H, 1.23; N, 8.54%. Found: C, 25.78;
H, 1.25; N, 8.40%. Yield, 0.27 g (83%). Decomposition
point: 2698C.
The coordination chemistry of the coinage metals has been
the subject of interests for decades (Hathaway, 1987). The rich
coordination chemistry of these metals can be utilized in
biomimetics, catalysis and material science (Lehn, 1988).
Historically, interest in this area grew out of the diverse
structural motifs displayed by these superficially simple mono-
valent cations. More recently, interest has been renewed by
practical concerns. Such coinage metal complexes can be
used as potential precursors to metal films via CVD
(chemical vapor deposition) process (Holl, et al., 1994, Xu,
.
Preparation of [Ag(en)Ag(dnbc)2]n 2nH2O (2)
Received 14 July 2003; accepted 11 August 2004.
This work was supported by the Foundation of the Education
Office of Anhui Province, People’s Republic of China, and the grant
Nos. are 2004kj300zd and 2004kj302.
Address correspondence to Hai-Liang Zhu, Department of Chem-
istry, Fuyang Normal College, Fuyang 236032, P.R. China. E-mail:
hailiang_zhu@fync.edu.cn
Ag2O (0.5 mmol, 116 mg) and 3,5-dinitrobenzoic acid,
dnbc, (1 mmol, 212 mg) were dissolved in an aqueous
ammonia solution (30%, 10 mL) and stirred for ca. 10 min.
Then ethylenediamine, en, (1 mmol, 60 mg) was added to the
system with stirring to give a clear colorless solution. After
keeping the solution in air for two days, large colorless prism
189

190
X.-Y. QIU ET AL.
crystals formed at the bottom of the vessel on slow evaporation
of the solvent. The crystals were isolated by filtration, washed
three times with distilled water, and dried in a vacuum desicca-
tor over anhydrous CaCl2. Anal. Calcd. for C16H18Ag2N6O14
(FW 734.10): C, 26.18; H, 2.47; N, 11.45%. Found: C,
26.45; H, 2.55; N, 11.26%. Yield, 0.27 g (73%). Decompo-
sition point: 2088C.
TABLE 1
Crystallographic and experimental data for
complexes (1) and (2)
Complex
(1)
(2)
Crystal shape/color
Prism/
colorless
Prism/
colorless
0.26 ꢁ 0.13
ꢁ 0.08
Crystal size (mm)
0.30 ꢁ 0.15
ꢁ 0.06
Monoclinic
P21/c
RESULTS AND DISCUSSION
Crystal system
Space group
Triclinic
P-1
Preparation of the Complexes
˚
a (A)
5.685(11)
16.96(3)
19.67(4)
90.00
6.978(2)
12.919(5)
15.0291(5)
84.320(6)
76.810(5)
79.612(6)
1295.2(8)
2
It is necessary to avoid light throughout the synthesis and
crystallization. Ag2O does dissolve in 30% ammonia
solution. Additionally, the ammonia solution is helpful to
prevent the target products from precipitating too fast. For
the complex (1), in order to obtain pure 3,5-dinitrobenzoato
compounds with silver(I), it is important to keep the proportion
at 2:1 for dnbc and silver oxide. If the silver oxide is in excess,
mixtures of products would be obtained. Excess of dnbc will
decrease the yield of the target compound. For the complex
(2), the molar ratio of en: Agþ must be less than 1:2. When
the molar ratio of en: Agþ is equal to 1:1, the yield of (2)
will be reduced to ca. 15%. When the molar ratio of en: Agþ
is larger than 2:1, no crystal is isolated.
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
90.00(3)
90.00
3
˚
U (A )
1897(6)
2
298(2)
Z
T (K)
298(2)
1.589
m (mm21) (Mo-Ka)
2.148
2.297
2593/306
dx (g cm23
)
1.882
4780/359
Reflections/
parameter
F(000)
1272
724
The formation of (1) and (2) can be expressed as the follow-
ing two equations, respectively:
Tmax
0.8819
0.5650
0.635
0.8834
0.6828
0.741
Tmin
Goodness of fit on F2
R1, wR2 [I ꢄ 2s(I)]a
R1, wR2 (all data)a
4½3;5-ðO2NÞ2C6H3COOHꢀ þ 2Ag2O
NH3ð30%aqÞ
0.0603, 0.1309
0.0687
0.2676
P
0.0631, 0.0885
0.0666
0.1580
½3;5-ðO2NÞ C6H3COOAgꢀ4
ð1Þ
ð2Þ
4n½3;5-ðO2NÞ C6H3COOHꢀ2þ 2nAg O
2
2
P
P
P
NH3ð30%aqÞ
H2NCH2CH2NH2
w(Fo2 2 Fc2)2/ w(F2o)2
,
1/2
]
fAgðH2NCH2CH2NH2Þ
aR1 ¼ jjFoj 2 jFcjj/ jFoj,wR2 ¼
[
w ¼ s2(Fo)2 þ (0.1(max(0,Fo2) þ 2Fc2)/3)2
.
21
]
[
ꢁ Ag½OOCC6H3ðNO2Þ2 ꢂ 3;5ꢀ2gn ꢃ 2nH2O
˚
which is coordinated by two (Ag ꢃ ꢃ ꢃ O ¼ 2.875(6) A) between
the dnbc nitro groups and the silver ions (Ag(1)ꢃ ꢃ ꢃ O(1) and
Ag(2) ꢃ ꢃ ꢃ O(2)) join the tetranuclear complexes along the bc
direction to form a plane. Surprisingly, the Ag(2)–O (water
Structure Description of (1)
The crystallographic experimental data, as well as selected
bond parameters for complexes (1) and (2) are listed in
Tables 1 and 2, respectively. As shown in Figure 1, complex
(1) crystallizes in a tetranuclear form in which there are two
kinds of silver atoms, Ag(1) and Ag(2). Ag(1) is five-
coordinated by three oxygen atoms from three different 3,5-
dinitrobenzoate anion ligands and by two neighboring
silver(I) atoms, foming a severely distorted square-pyramidal
geometry of the Ag(1) atom. O(1), O(7), O(8A) and Ag(1A)
˚
molecule) bond length, 2.050(16) A, is very short. The weak
(Ag ꢃ ꢃ ꢃ Ag interactions between the layers link the planes to
form a three-dimensional network structure.
Structure Description of (2)
Complex (2) crystallizes in the triclinic space group P-1, and
constitute the basal plane of the square-pyramid with the the asymmetric unit consists of two Ag ions, two 3,5-dinitro-
˚
mean deviation of 0.176(6) A, and the Ag(1) atom is located benzoate anions, one ethylenediamine molecule, and two
˚
0.121(6) A above the plane towards the axial Ag(2) atom. crystal lattice water molecules, which is displayed in
˚
The Ag(1)–O(1) bond length, 2.524(14) A, is significantly Figure 2. The Ag(1) ion has a linear coordination geometry,
longer than other similar distances of Ag–O in the complex, being coordinated by two nitrogen atoms from the different
indicating a weaker interaction. The Ag(2) atom is in a ends of a non-chelating ethylenediamine ligand. The Ag–N
˚
slightly distorted linear geometry (O–Ag–O ¼ 175.9(6)8), bond lengths are 2.149(5) and 2.168(5) A, and the N–Ag–N

SILVER(I) COMPLEXES
191
TABLE 2
˚
Selected bond (A) distances and angles (8)
(1) C28H16Ag4N8O26
Ag(1)–O(8)
Ag(1)–O(7)
2.215(9)
2.253(13)
2.525(14)
3.054(5)
3.328(5)
Ag(2)–O(13)
Ag(2)–O(2)
2.050(16)
2.0556(15)
Ag(1)–O(1)
Ag(1)–Ag(2)
Ag(1)–Ag(1A)
O(8)–Ag(1)–O(7)
O(8)–Ag(1)–O(1)
O(1)–Ag(1)–O(7)
O(1)–Ag(1) –Ag(1A)
Ag(1A)–Ag(1)–Ag(1)
O(13)–Ag(2)–O(2)
O(13)–Ag(2)–Ag(1)
O(2)–Ag(2)–Ag(1)
148.8(4)
117.5(4)
93.7(5)
165.8(4)
99.33(3)
175.9(6)
89.2(6)
90.8(5)
O(8)–Ag(1)–Ag(2)
Ag(2)–Ag(1)–O(7)
O(1)–Ag(1)–Ag(2)
O(8)–Ag(1)–Ag(1A)
O(7)–Ag(1)–Ag(1A)
103.2(3)
87.1(4)
68.0(5)
70.5(3)
78.8(3)
(2) C16H18Ag2N6O14
Ag(1)–N(1)
Ag(1)–Ag(2)
2.149(5)
3.1770(13)
2.168(5)
Ag(2)–O(1)
2.147(5)
N(2)–Ag(1)–Ag(2)
N(1)–Ag(1)–Ag(2)
N(1)–Ag(1)–N(2)
O(1)–Ag(2)–O(3)
91.27(17)
91.27(16)
175.9(2)
Ag(1)–N(2)
Ag(2)–O(3)
2.091(5)
100.06(18)
74.84(17)
O(3)–Ag(2)–Ag(1)
O(1)–Ag(2)–Ag(1)
174.4(3)
FIG. 1. Molecular structure of diaquatetra(3,5-dinitrobenzoato)tetrasilver(I) (1).

192
X.-Y. QIU ET AL.
.
FIG. 2. Molecular structure of [Ag(en)Ag(dnbc)2]n 2nH2O (2).
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