Synthesis and structural characterisation of five copper(I) and silver(I) complexes with 2-aminopyridine (2-APy), [Cu(μ-Cl)(2-Apy)(PPh3)]2, [Ag(μ-X)(2-Apy)(PPh3)]2 (X = Cl, Br), [Ag(μ-ONO2)(2-Apy)(EPh

Article abstract of DOI:10.1016/j.poly.2009.06.036

Five new copper(I)/silver(I) complexes containing 2-aminopyridine, [Cu(μ-Cl)(2-Apy)(PPh₃)]₂(1), [Ag(μ-Cl)(2-Apy)(PPh₃)]₂(2), [Ag(μ-Br)(2-Apy)PPh₃)]₂(3), [Ag(μ-ONO₂)(2-Apy)(PPh

Full text of DOI:10.1016/j.poly.2009.06.036

Polyhedron 29 (2010) 441–445
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Synthesis and structural characterisation of five copper(I) and silver(I)
complexes with 2-aminopyridine (2-APy), [Cu(l-Cl)(2-Apy)(PPh3)]2,
[Ag( -X)(2-Apy)(PPh3)]2 (X = Cl, Br), [Ag( -ONO2)(2-Apy)(EPh3)]2 (E = P, As)
l
l
a
a
a
b
a
a,
*
Qiong-Hua Jin a, , Ke-Yi Hu , Li-Li Song , Rong Wang , Cun-Lin Zhang , Xia Zuo , Xiao-Ming Lu
*
a Department of Chemistry, Capital Normal University, Beijing 100048, PR China
b Beijing Key Laboratory for Terahertz Spectroscopy and Imaging, Key Laboratory of Terahertz Optoelectronics, Ministry of Education, Department of Physics,
Capital Normal University, Beijing 100048, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Available online 23 June 2009
Five new copper(I)/silver(I) complexes containing 2-aminopyridine, [Cu(
Cl)(2-Apy)(PPh3)]2(2), [Ag(l-Br)(2-Apy)PPh3)]2(3), [Ag(l-ONO2)(2-Apy)(PPh3)]2(4), [Ag(l-ONO2)(2-
l
-Cl)(2-Apy)(PPh3)]2(1), [Ag(
l-
Apy)(AsPh3)]2(5) have been synthesised for the first time. Complexes 1–5 are obtained by the reactions
of MX (MX = CuCl for 1; M = Ag for 2–5; X = Cl, Br for 2–3; X = NO3 for 4–5) with the monodentate ligands
EPh3 (E = P for 1–4; E = As for 5) and 2-Apy in the molar ratio of 1:1:2 in the mixed solvent of CH2Cl2 and
MeOH. Complexes 1–5 are characterised by IR and X-ray diffraction. In 1–5, chloride, bromide and nitrate
ions bridge two metal atoms to form dinuclear complexes containing the parallelogram cores M2X2
(M = Cu, Ag).
Keywords:
Copper(I) complex
Silver(I) complex
Aminopyridine
Crystal structure, triphenlyphosphine,
triphenlyarsine
Ó 2009 Elsevier Ltd. All rights reserved.
1. Introduction
anions and solvent appear to modulate the stereochemistry of d10
metal complexes [17]. 2-Aminopyridine contains a pyridine ring
Copper(I) and silver(I) complexes containing triphenlyphos-
phine, triphenlyarsine (EPh3, E = P, As), bis(diphenylphosphino)-
alkane (Ph2P(CH2)xPPh2, x = 1–3, i.e. dppm, dppe and dppp) and
heterocyclic nitrogen ligands have been studied well because of
their interesting coordination chemistry and potential applications
in photography, electrochemical processes, antimicrobial and anti-
tumor activities [1–6].
The heterocyclic nitrogen ligands such as pyrazine (pyz), 2-ami-
nopyrimidine (2-AMP) and pyridine (py) have been known as co-li-
gands to form di- or poly-nuclear or supramolecular Cu(I)/
Ag(I)-EPh3/Ph2P(CH2)xPPh2 complexes. Some examples for such
and an amino group, so its pyridine ring is capable of coordinating
to metal atom, similar to pyridine; its amino group may form
hydrogen bonds with other acceptors, similar to 2-aminopyrimi-
dine(2-AMP). For example, in [Cu(2-AMP)2 (H2O)2(CF3SO3)2]
(2-AMP)2 (2-AMP)2, four hydrogen bonds were formed by the
amino groups of the 2-AMP with the coordinated ligand, triflate
and water [18]. So 2-Apy may be used as a building block to form
di-, poly-nuclear or supramolecular complexes.
We focus our attention on di-, poly-nuclear or supramolecular
Cu(I)/Ag(I) complexes of EPh3 or Ph2P(CH2)xPPh2 with different
heterocyclic nitrogen co-ligands and anions. In the present work,
we selected 2-aminopyridine as a nitrogen-containing co-ligand,
compounds are {[Cu3(dppm)3(l3-Br)2][Cu2(dppm)(pyz)Br2] Br(CH3
OH)2}n, {[Cu2(dppm)2(NO3)2(pyz)](pyz)}n (dppm = bis(diphenyl-
five new dinuclear complexes [Cu(
-Cl)(2-Apy)(PPh3)]2(2), [Ag( -Br)(2-Apy)(PPh3)]2(3), [Ag(
(2-Apy)(PPh3)]2(4), [Ag( -ONO2)(2-Apy)(AsPh3)]2(5) were isolated
and characterised by IR, elemental analyses and X-ray diffraction.
2. Experimental
l
-Cl)(2-Apy)(PPh3)]2(1), [Ag
phosphino)methane) [3] and [Ag2X2(PPh3)2(2-AMP)] (X = Cl, Br,
(l
l
l-ONO2)
1
I) [7–9] as well as dinuclear complexes [AgX(PPh3)(Py)]2 (X = Cl,
Br) [10] and [CuI(PPh3)(Py)]2 [11]. The halide and nitrate ions act
as bridging ligands in the above complexes and in some Cu(I)/
Ag(I)-PPh3 complexes such as [X2Ag3(dppm)3]X and [X2Cu3
(dppm)3](CuX2) (X = Cl, Br, I) [4], [Ag2Cl2(PPh3)4] [12], [Cu2 (PPh3)4
(NO3)2] [13], [Ag2Br2(PPh3)2] [14], [AgClPPh3]4 [15] and [AgIPPh3]4
[16] .
l
2.1. Materials and physical measurements
All reagents were supplied by J&K Chemical Ltd. and were used
as received without further purification. All experiments were per-
formed at ambient temperature. Elemental analyses (C, H, N) were
performed on a Flash EA 1112 analyzer. IR spectra were recorded
from KBr pellets on a Brucker EQUINOX 55 FT-spectrometer.
However, to our best knowledge, the Cu(I)/Ag(I) complex with
2-aminopyridine has not been reported. The nature of the ligands,
* Corresponding authors.
E-mail address: jinqh@mail.cnu.edu.cn (Q.-H. Jin).
0277-5387/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2009.06.036

442
Q.-H. Jin et al. / Polyhedron 29 (2010) 441–445
2.2. Preparation of the complexes
2.2.5. Preparation of [Ag(l-ONO2)(2-Apy)(AsPh3)] (5)
Compound 5 was prepared in a manner similar to that de-
scribed for 1, using AgNO3 (0.034 g, 0.2 mmol), AsPh3 (0.0612 g,
0.2 mmol) and 2-Apy (0.0376 g, 0.4 mmol) as starting materials.
Yield: 74%. Anal. Calc. for C23H20O3N3AsAg: C, 47.69; H, 3.49; N,
7.26. Found: C, 47.53; H, 3.40; N, 7.14%. IR data (cmꢀ1, KBr pellets):
3416w, 3316w, 3057w, 2426w, 1624m, 1567w, 1485m, 1435m,
1384s, 1326w, 1185w, 1156w, 1078w, 1023w, 999w, 839w,
769w, 738m, 695m, 671w, 469w, 412w.
2.2.1. Preparation of [Cu(l-Cl)(2-Apy)(PPh3)]2(1)
A mixture of CuCl (0.0198 g, 0.2 mmol), triphenylphosphine
(PPh3) (0.0525 g, 0.2 mmol) and 2-aminopyridine(2-Apy)
(0.0376 g, 0.4 mmol) were dissolved in a mixture of 5 ml dichloro-
methane and 5 ml methanol, stirred for 1 h and filtered. Colorless
crystal 1 was obtained from the filtrate after standing at the room
temperature for several days. Yield: 65%. Anal. Calc. for
C46H40N4P2Cl2Cu2: C, 60.53; H, 4.43; N, 6.14. Found: C, 60.40; H,
4.31; N, 6.02%. IR (cmꢀ1, KBr pellets): 3341m, 3310w, 3045w,
1623s, 1566w, 1488m, 1445s, 1435m,1385w, 1095w, 1027w,
999w, 851w, 700w, 749m, 696m, 440w, 418w.
2.3. X-ray crystallography
Single-crystal X-ray diffraction studies of complexes 1–5 were
performed on a Bruker SMART diffractometer equipped with CCD
area detector with a graphite monochromator situated in the inci-
dent beam for data collection. The determination of unit cell
2.2.2. Preparation of [Ag(l-Cl)(2-Apy)(PPh3)]2(2)
Compound 2 was prepared in a manner similar to that de-
scribed for 1, using AgCl (0.0287 g, 0.2 mmol), PPh3 (0.0525 g,
0.2 mmol) and 2-Apy (0.0376 g, 0.4 mmol) as starting materials.
Yield: 57%. Anal. Calc. for C46H40N4P2Cl2Ag2: C, 55.36; H, 4.05; N,
5.62. Found: C, 55.21; H, 3.92; N, 5.57%. IR (cmꢀ1, KBr pellets):
3408m, 3309w, 3045m, 1625s, 1566w, 1485m, 1435s, 1385w,
1327w, 1263w, 1182w, 1156w, 1096s, 1027w, 746s, 695s, 516w,
439w.
parameters and data collections were performed with Mo K
a radi-
ation (k = 0.71073 Å) by scan mode. All data were corrected by
x
semi-empirical method using SADABS program. The program SAINT
was used for integration of the diffraction Profiles.
All structures were solved by direct methods using SHELXS pro-
gram of the SHELXTL-97 [19] package and refined with SHELXL-97
[20]. Metal atom centers were located from the E-maps and other
non-hydrogen atoms were located in successive difference Fourier
syntheses. The final refinements were performed by full-matrix
least-squares methods with anisotropic thermal parameters for
non-hydrogen atoms on F2. All the hydrogen atoms were first
found in difference electron density maps, and then placed in the
calculated sites and included in the final refinement in the riding
model approximation with displacement parameters derived from
the parent atoms to which they were bonded. Further crystallo-
graphic data and experimental details for structural analyses of
all complexes are summarised in Table 1.
2.2.3. Preparation of [Ag(l-Br)(2-Apy)(PPh3)]2(3)
Compound 3 was prepared in a manner similar to that de-
scribed for 1, using AgBr (0.047 g, 0.2 mmol), PPh3 (0.0525 g,
0.2 mmol) and 2-Apy (0.0376 g, 0.4 mmol) as starting materials.
Yield: 62%. Anal. Calc. for C46H40N4P2Br2Ag2: C, 50.85; H, 3.72; N,
5.16. Found: C, 50.71; H, 3.66; N, 5.10%. IR (cmꢀ1, KBr pellets):
3441m, 3311w, 3051w, 1623m, 1566w, 1486m, 1443s, 1435s,
1385w, 1096w, 1027w, 998w, 849w, 770w, 746m, 695m, 516w,
412w.
3. Results and discussion
2.2.4. Preparation of [Ag(l-ONO2)(2-Apy)(PPh3)] (4)
3.1. Synthesis
Compound 4 was prepared in a manner similar to that de-
scribed for 1, using AgNO3 (0.034 g, 0.2 mmol), PPh3 (0.0525 g,
0.2 mmol) and 2-Apy (0.0376 g, 0.4 mmol) as starting materials.
Yield: 70%. Anal. Calc. for C23H20O3N3PAg: C, 53.16; H, 3.85; N,
8.00. Found: C, 52.09; H, 3.77; N, 7.92%. IR (cmꢀ1, KBr pellets):
3411w, 3054w, 1766w, 1626s, 1566m, 1489s, 1436m, 1385s,
1327w, 1295m, 1096m, 819w, 774s, 746s, 695s, 618w, 519m,
503m, 438w.
Five compounds 1–5 are synthesised by the reactions of cop-
per(I) salt and silver(I) salt with 2-Apy and PPh3 in the mixed sol-
vent of dichloromethane and methanol. Complexes 1–5 are
insoluble in diethyl ether but soluble in ethanol, methanol, aꢀceto-
nitrile, DMF and DMSO. In 1–5, the anions Brꢀ, Clꢀ and NO3 be-
have as the bridging ligands. The molar ratio of M:EPh3:2-Apy
(1:1:2) is very important for the generation of [MX(PPh3)2
Table 1
Crystallographic data for compounds 1–5.
Compound
1
2
3
4
5
Empirical formula
Formula weight
Crystal system
Space group
C46H42Cl2–Cu2N2P2
910.78
monoclinic
C2/c
C46H42Ag2–Cl2N4P2
999.42
monoclinic
P2(1)/c
C44H44Ag2–Br2N4P2
1066.33
monoclinic
C2/m
C46H44Ag2–N6O6P2
1054.56
triclinic
C46H42Ag2–As2N6O6
114 .44
triclinic
P1
P1
a (Å)
b (Å)
c (Å)
26.230(3)
14.3697(17)
11.1794(16)
95.104(2)
4197.1(9)
4
14.3615(18)
14.3334(17)
11.1168(12)
107.907(2)
2177.5(4)
2
11.3020(10)
14.5681(15)
14.1369(16)
108.3740
2209.0(4)
2
9.6910(7)
14.1873(9)
18.6174(13)
76.909(4)
2274.2(3)
4
9.7719(4)
14.3587(5)
18.6036(7)
77.222(10)
2318.99(15)
2
b (°)
V (Å3)
Z
Dcalc(g/cm3)
1.313
1.154
1.524
1.132
1.603
2.802
1.540
0.986
1.633
2.314
l
(mm-1
)
T (K)
298(2)
0.1042
0.1633
298(2)
0.0820
0.0949
298(2)
0.0667
0.1471
293(2)
0.0636
0.1117
296(2)
0.1089
0.2043
Ra
b
wR2
P
P
a
R = (||F0|ꢀ|Fc||)/ |Fo|.
P
P
b
wR2 = [ w(|F0|2ꢀ|Fc|2)2/ w(F02)]1/2
.

Q.-H. Jin et al. / Polyhedron 29 (2010) 441–445
443
(2-Apy)]2(M = Ag, Cu). If the molar ratio of 1:1:1 was employed, we
cannot obtain the single-crystals. The excess of 2-Apy facilitates its
coordination to Ag atom because the coordination ability of 2-Apy
is weaker than that of EPh3 and anions.
The anion and metal ion also play important roles in the synthe-
sis of complexes of [M(l-X)(2-Apy)EPh3]2. To obtain a full series
complexes, we studied the reactions of MX (M = Cu, Ag; X = I, Br,
Cl, NO3) with 2-Apy and EPh3 (E = P, As) in the molar ratio
(1:1:2) in the mixed solvent of CH2Cl2 and MeOH. But only five
reactions were successful and gave rise to 1–5. All of the rest reac-
tions were failed and most of them only produced the adducts
MX:EPh3 (1:3). The possible reason is that Iꢀ and Brꢀ induce AsPh3
substitutes 2-Apy in the Ag(I) complexes and EPh3 (E = P, As) sub-
stitutes 2-Apy in the Cu(I) complexes. When CuNO3 reacted with 2-
APy and EPh3, the yellow filtrate turned blue in two days, which
means the Cu(I) product was oxidised to the Cu(II) product by
ꢀ
the air induced by NO3
.
Fig. 1. Perspective view of 1 with 50% thermal ellipsoids. All the hydrogen atoms
are omitted for clarity.
Generally, the copper(I) or silver(I) complexes of halides with
triphenylphosphine are prepared in acetonitrile or dichꢀlorometh-
ꢀ
ane, and that of oxy-anions such as NO3 and CH3CO2 are pre-
pared in MeOH or EtOH [1]. In our work, we prepared five new
complexes in the mixed solvent of dichloromethane and methanol.
The choice of the solvent has great influence on the experimental
productions. When only one solvent, such as MeCN, MeOH, EtOH
or CH2Cl2, is used in the synthesis reaction, the crystal of good
quality could not be obtained. The synthesis of compounds 1–5
was shown in Scheme 1.
Table 2
Selected bond lengths (Å) and angles (°) for complex 1.
Cu(1)–N(1)
Cu(1)–P(1)
Cu(1)–Cl(2)
Cu(1)–Cl(1)
Cu(1)–Cu(1)#
Cl(1)–Cu(1)#
Cl(2)–Cu(1) #
P(1)–Cu(1)–Cl(2)
2.048(4)
N(1)–Cu(1)–P(1)
N(1)–Cu(1)–Cl(1)
Cl(2)–Cu(1)–Cl(1)
Cu(1)–Cl(2)–Cu(1)#
N(1)–Cu(1)–Cl(2)
P(1)–Cu(1)–Cl(1)
Cu(1)–Cl(1)–Cu(1)#
120.77(13)
104.34(14)
102.29(4)
77.87(6)
102.85(14)
112.43(4)
77.55(6)
2.2102(13)
2.4343(15)
2.4429(15)
3.0597(13)
2.4429(15)
2.4343(15)
112.17(4)
3.2. Single crystal X-ray studies
3.2.1. Crystal structure of complex 1
Complex 1 is monoclinic in C2/c space group. The perspective
view of 1 is shown in Fig. 1 and its selected bond lengths and an-
gles are given in Table 2. The metal center is bonded to the N atom
in the 2-Apy ligand and P atom in the PPh3 ligand and the two Cu
atoms are bridged by the Cl atom. The angles around Cu are in the
range 102.29(4)–120.77(13)°, which indicates that the geometry
around the CuCl2NP core is approximately tetrahedral. Geometrical
distortion from ideal angles can be attributed to the need to
accommodate the bulky triphenylphosphine groups and the four-
member ring. The Cuꢁ ꢁ ꢁCu distance of 3.0597 Å is longer than the
sum of two Van der Waals radii for copper (2.8 Å), which indicates
that the copper atoms in complex 1 are not involved in metal–me-
tal bonding interaction. The mean bond distances of Cu–N and Cu–
Cl are 2.048(4) and 2.4429(15) Å, respectively. The average length
of Cu–P is 2.2102(13) Å, which is in good agreement with the sum
of the covalent radii (2.27 Å), but much more shorter than the va-
lue found in the complex [Cu(H2L)(PPh3)2]NO3ꢁ0.5H2O(2.325 Å) [2].
The angles of Cu1A–Cl1–Cu1 [77.55(6)°] and Cu1–Cl2–Cu1A
[77.87(6)°] are almost equal and the angle Cl1–Cu1–Cl2 and Cl1–
Cu1A–Cl2 are the same [102.29(4)°], the sum of the internal angles
of the four-member ring [–Cu–Cl–Cu–Cl–] in the Cu2Cl2 core are
3.2.2. Crystal structures of complexes 2 and 3
Complexes 2 and 3 are monoclinic in P2(1)/c and C2/m space
group, respectively. The perspective views of compounds 2 and 3
are shown in Figs. 2 and 3 and their selected bond lengths and an-
gles are given in Tables 3 and 4. The crystal structures of complexes
2 and 3 are similar to that of complex 1. Each structure contains a
center of symmetry and features a di-nuclear unit in which the two
Ag atoms are bridged by two Br and Cl atoms. The coordination
geometry of Ag atom in 2 and 3 is a distorted tetrahedron with
the four vertexes occupied by the N atom from 2-Apy ligand, the
P atom from PPh3 ligand and two halide atoms (Cl atoms for 2
and Br atoms for 3). Both the Agꢁ ꢁ ꢁAg distances in 2 [3.1184(7) Å]
and 3 [3.1240(7) Å], are longer than the sum of the covalent radii
(2.88 Å) [21], show that there is no Ag–Ag bond in the complexes.
The Ag–P bond distances in 2 [2.406(9) Å] and 3 [2.424(2) Å]
are close to those in compounds [Ag2Cl2(
l-S-pySH)2(PPh3)2]
(2.435 Å) and [Ag2Br2( -S-pySH)2(PPh3)2] (2.441 Å) [22]. The Ag–
l
N bond distances in 2 [2.296(3) Å] and 3 [2.302(8) Å] are much
more shorter than the sum of the Van der Waals radii of silver
approximately 360°, which indicates that the ring is
a
parallelogram.
Fig. 2. Perspective view of 2 with 50% thermal ellipsoids. All the hydrogen atoms
Scheme 1. The routine of synthesis for compounds 1–5.
and phenyl groups are omitted for clarity.

444
Q.-H. Jin et al. / Polyhedron 29 (2010) 441–445
Fig. 3. Perspective view of 3 with 50% thermal ellipsoids. All the hydrogen atoms
and phenyl groups are omitted for clarity.
Table 3
Fig. 4. Perspective view of 4 with 50% thermal ellipsoids. All the hydrogen atoms
and phenyl groups are omitted for clarity.
Selected bond lengths (Å) and angles (°) for complex 2.
Ag(1)–N(1)
Ag(1)–P(1)
Ag(1)–Cl(1)
Cl(1)#–Ag(1)#
Ag(1)–Cl(1)#
Ag(1)–Ag(1)#
N(1)–Ag(1)–Cl(1)
P(1)–Ag(1)–Cl(1)
2.296(3)
N(1)–Ag(1)–Cl(1)
P(1)–Ag(1)–Cl(1)
Cl(1)–Ag(1)–Cl(1)#
Ag(1)–Cl(1)–Ag(1)#
N(1)–Ag(1)–P(1)
96.23(10)
114.62(4)
108.67(3)
71.33(3)
125.02(9)
108.67(3)
71.33(3)
2.4069(11)
2.6730(12)
2.6760(12)
2.6755(13)
3.1184(7)
99.14(10)
110.90(4)
Cl(1)–Ag(1)#–Cl(1)#
Ag(1)–Cl(1)#–Ag(1)#
Table 4
Selected bond lengths (Å) and angles (°) for complex 3.
Ag(1)–N(1)
Ag(1)–P(1)
Ag(1)–Br(1)
Ag(1)–Br(1)#
Ag(1)–Ag(1)#
Br(1A)–Ag(1)#
N(1)–Ag(1)–P(1)
Br(1)–Ag(1)–Br(1)#
2.302(8)
2.424(2)
N(1)–Ag(1)–Br(1)
P(1)–Ag(1)–Br(1)
100.86(10)
109.87(3)
100.86(11)
109.87(3)
68.81(3)
2.7644(9)
2.7644(9)
3.1240(15)
2.7644(9)
123.6(2)
N(1)–Ag(1)–Br(1)#
P(1)–Ag(1)–Br(1)#
Ag(1)–Br(1)#–Ag(1)#
Ag(1)–Br(1)–Ag(1)#
Br(1)–Ag(1)#–Br(1)#
68.81(3)
111.19(3)
111.19(3)
and nitrogen (1.55 + 1.70 = 3.25 ppm) [2]. The mean bond length of
Ag–Cl in 2 is 2.674 Å and that of Ag–Br in 3 is 2.764 Å. The Ag–Br
Fig. 5. Perspective view of 5 with 50% thermal ellipsoids. All the hydrogen atoms
are omitted for clarity.
bond length in
[2.7350(6)–2.8241(5)] [23] and [Ag(
3
agrees to that in [Ag(PPh3)(pymtH)Br]2
2-Br)(dppbz)]2 (2.6932 Å)
l
[24]. The angles around Ag atoms are in the range 108.67(3)–
125.02(9)° in 2 and 100.86(11)–123.6(2)° in 3. The sum of the
internal angles of the Ag2X2 (X = Cl for 2 and Br for 3) core is
360°, so the four-member ring [–Ag–X–Ag–X–] is of co-plane.
Table 5
Selected bond lengths (Å) and angles (°) for complex 4.
Ag(1)–N(1)
Ag(1)–P(1)
Ag(1)–O(1)
Ag(1)–O(1)#
N(1)–Ag(1)–P(1)
2.254(2)
N(1)–Ag(1)–O(1)
P(1)–Ag(1)–O(1)
O(1)–Ag(1)–O(1)#
O(1)–Ag(1)#–O(1)#
Ag(1)–O(1)–Ag(1)#
105.90(7)
115.46(5)
114.62(4)
96.23(10)
110.90(4)
2.3833(6)
2.4947(19)
2.6755(13)
138.43(5)
3.2.3. Crystal structures of complexes 4 and 5
Compounds 4 and 5 are both triclinic in P1 space group. The
perspective views of compounds 4 and 5 are shown in Figs. 4
and 5 and their selected bond lengths and angles are given in Ta-
bles 5 and 6. In complexes 4 and 5 the coordination spheres around
the metal center are occupied by two O atoms from NO3ꢀ, one N
atom from 2-APy ligand and one E (E = P for 4; E = As for 5) from
EPh3. The angles around Ag atom are in the range 96.69(10)–
138.43(5)° in 4 and 67.79(18)–137.18(13)° in 5. The distorted tet-
rahedral coordination for Ag atoms in 4 and 5 is similar to that in
compounds 1–3. The mean bond length of Ag–O in 4 is 2.5851 Å,
which is slightly longer than that of Ag–O in 5 (2.527 Å). The dis-
tance of Ag–P is 2.3833(6) Å, which is slightly longer than that of
[Ag(Phen)(PPh3)(ONO2)] (2.354 Å) [24], but is significantly shorter
than the distance of Ag–As (2.4855 Å) in complex 5. The mean Ag–
N bond lengths are 2.254(2) and 2.247(6) Å in 4 and 5, respectively,
which are shorter than those found in 2 [2.296(3) Å] and 3
[2.302(8) Å].
Table 6
Selected bond lengths (Å) and angles (°) for complex 5.
Ag(1)–N(1)
Ag(1)–O(1)
Ag(1)–As(1)
Ag(1)–O(1)#
N(1)–Ag(1)–O(1)
2.247(6)
2.482(5)
2.4855(8)
2.572(5)
110.19(19)
N(1)–Ag(1)–As(1)
Ag(1)–O(1)–Ag(1)#
N(1)–Ag(1)–O(1)
O(1)–Ag(1)–O(1)#
As(1)–Ag(1)–O(1)
137.18(13)
112.21(19)
91.4(2)
67.79(18)
109.18(14)
3.3. Infrared spectra
The infrared spectra are consistent with the typical absorption
of the organic N-donors and phosphine or arsine ligands [25].

Q.-H. Jin et al. / Polyhedron 29 (2010) 441–445
445
The typical absorptions around 515 cmꢀ1 in complex 1 are due to the
Cu–P bonds and around 510 cmꢀ1 in the other four complexes are
due to the Ag–P bonds. The strong band at 1385 cmꢀ1 and the med-
gram (973 Program) under Grant no. 2007CB310408, no.
2006CB302901, State Key Laboratory of Functional Materials for
Informatics, Shanghai Institute of Microsystem and Information
Technology, Chinese Academy of Sciences.
ium band around 819 cmꢀ1 are assigned to the characteristic
m(N–O)
vibration of the nitrate (NO3ꢀ) in compounds 4 and 5. The absorption
peaks at ca. 1097 and 1483 cmꢀ1 are caused by the vibration of phe-
nyl. The absorptions around 3049 cmꢀ1 are caused by the C–H
stretching vibration of the phenyl ring in all the complexes.
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respectively. These data can be obtained free of charge via 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.
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This work has been supported by the National Science Founda-
tion of China (Grant no. 20871085), the Committee of Education of
Beijing Foundation of China (Grant no. KM200610028006), the Pro-
ject-sponsored by SRF for ROCS and SEM, the subsidy of
Beijing Personnel Bureau, National Keystone Basic Research Pro-