Synthesis and characterization of triphenylphosphine stabilized silver α,β-unsaturated carboxylate: Crystal structure of [Ag(O 2CCH=C(CH3)2)(PPh3)2]

Article abstract of DOI:10.1016/j.ica.2005.10.002

A series of triphenylphosphine coordinated silver α,β- unsaturated carboxylates of type [Ag(O₂CR)(PPh₃) _n: n = 1, R = CH₃CH=CH (2a), (CH₃) ₂C=CH (2b), CH₃CH₂CH=CH (2c), CH ₃CH₂CH₂CH=CH (2d), PhCH=CH (2e), CH ₂CH (2f); n = 2, CH₃CH=CH (3a), (CH₃) ₂C=CH (3b), CH₃CH₂CH=CH (3c), CH ₃CH₂CH₂CH=CH (3d)] were prepared by reaction of relative silver carboxylates (1a-1f) with triphenylphosphine in chloroform. These complexes were obtained in high yields and characterized by elemental analysis, ¹H NMR, ¹³C NMR, ³¹P NMR and IR spectroscopy. Thermal stability of the complexes has been determined by TG analysis. The molecular structure of [Ag((O₂CCH=C(CH ₃)₂))(PPh₃)₂] (3b) shows that the senecioato ligand is chelated with silver atom and generate, a distorted tetrahedron.

Full text of DOI:10.1016/j.ica.2005.10.002

Inorganica Chimica Acta 358 (2005) 4417–4422
www.elsevier.com/locate/ica
Synthesis and characterization of triphenylphosphine stabilized silver
a,b-unsaturated carboxylate: Crystal structure
of [Ag(O2CCH@C(CH3)2)(PPh3)2]
a
a
a
a
a,b,
*
Jianlin Han , Yingzhong Shen , Chunxiang Li , Yizhi Li , Yi Pan
a
State Key Lab of Coordination, School of Chemistry and Chemical Engineering, Nanjing University, 22 Hankou Road, Nanjing 210093, PR China
b
Key Lab of Fine PetroChemical Technology, Jiangsu Industrial Institute, Changzhou, Jiangsu Province, PR China
Received 3 January 2005; received in revised form 18 August 2005; accepted 6 October 2005
Available online 8 November 2005
Abstract
A series of triphenylphosphine coordinated silver a,b-unsaturated carboxylates of type [Ag(O2CR)(PPh3)n: n = 1, R = CH3CH@CH
(2a), (CH3)2C@CH (2b), CH3CH2CH@CH (2c), CH3CH2CH2CH@CH (2d), PhCH@CH (2e), CH2@CH (2f); n = 2, CH3CH@CH (3a),
(CH3)2C@CH (3b), CH3CH2CH@CH (3c), CH3CH2CH2CH@CH (3d)] were prepared by reaction of relative silver carboxylates (1a–1f)
with triphenylphosphine in chloroform. These complexes were obtained in high yields and characterized by elemental analysis, 1H NMR,
13C NMR, 31P NMR and IR spectroscopy. Thermal stability of the complexes has been determined by TG analysis. The molecular struc-
ture of [Ag((O2CCH@C(CH3)2))(PPh3)2] (3b) shows that the senecioato ligand is chelated with silver atom and generate, a distorted
tetrahedron.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Silver; CVD; Carboxylates; Triphenylphosphine; X-ray crystallography
1. Introduction
Monophosphine coordinated silver complexes are
expected to have better volatility, which is essential for
CVD growth of silver film. But to our knowledge, only a
few monophosphine ligand coordinated silver carboxylates
were reported, mostly because of their low thermal stability
[16,17,19].
Nomiya et al. [20] reported, a mercapto group adjacent
to the carboxylic species could form intramolecular mer-
capto-coordinated complexes. So we believe that introduc-
ing a conjugating double bond to carboxyl group of
carboxylic species should vary the interaction between car-
boxyl and silver metal center and have some influence on
the stability of the complexes.
In this paper, we report a series of monotriphenyl-
phosphine and bistriphenylphosphine coordinated silver
a,b-unsaturated carboxylates. We note that monotriphe-
nylphosphine coordinated silver carboxylates decompose
at lower temperature compared to bistriphenylphosphine
coordinated ones. And as we expected, the decomposition
Silver compounds have recently attracted many inter-
ests, mostly because of their application as precursors in
the growth of metal thin films via MOCVD techniques.
Several inorganic and organometallic species including sil-
ver complexes have been used as CVD precursors [1–13].
However, these complexes mentioned above are usually
light-sensitive, and with low thermal stability, which limit
their application in the CVD process. In recent years, many
researches are focused on sliver carboxylates, especially
their Lewis-base stabilized complexes. Up to now, most
of the complexes reported are bisphosphine coordinated
silver carboxylates [14–18].
*
Corresponding author. Tel.: +86 25 83593153; fax: +86 25 83686218.
E-mail addresses: yipan@netra.nju.edu.cn, yipan@nju.edu.cn (Y. Pan).
0020-1693/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2005.10.002

4418
J. Han et al. / Inorganica Chimica Acta 358 (2005) 4417–4422
temperature of a,b-unsaturated silver carboxylates is
lower than the reported saturated silver carboxylates
[14].
2.2.3. Preparation of Ag(O2CCH@CHCH2CH3)(PPh3)
(2c)
Yield of 82%, 0769 g. Anal. Calc. for C23H22O2PAg
(469.0): C, 58.87; H, 4.73. Found: C, 58.66; H, 4.76%.
1
2. Experimental
M.p. 166 ꢁC. H NMR (CDCl3): 7.26–7.48 (m, 15H, Ph–H),
6.85–6.91 (m, 1H, CH@), 5.96–6.01 (m, 1H, @CH), 2.20–
2.24 (m, 2H, CH2), 1.05–1.10 (m, 3H, CH3). 13C NMR
(CDCl3): 176.2 (CO), 147.6 (CH@), 134.4 (PPh3), 134.2
(PPh3), 131.6 (PPh3), 130.6 (PPh3), 130.0 (PPh3), 129.7
(PPh3), 129.6 (PPh3), 124.6 (@CH), 25.5 (CH2), 13.1
(CH3). 31P NMR (+25 ꢁC): 21.9, 18.6. IR data (cmꢀ1):
3047 (m), 2961 (m), 1650 (s) (mC@C), 1563 (vs) (CO, asym.),
1480 (s) (CO, sym.), 1434 (vs), 1347 (s), 1095 (s), 996 (s),
864 (m), 743 (s), 693 (vs), 519 (s).
2.1. General procedure
All operations were carried out under an atmosphere of
purified nitrogen using standard Schlenk techniques. The
solvents were dried before use. Elemental analyses were
performed on a Perkin–Elmer 240 elemental analysis
instrument. 1H NMR, 13C NMR (TMS internal standard),
and 31P NMR (85% H3PO4 reference) spectra were
recorded on a Bruker ARX-300 spectrometer and CDCl3
was used as a solvent. Infrared spectra were collected on
Bruker Vector 22 in KBr pellets. TG was recorded on
LABSYS TG/DSC under a nitrogen atmosphere at a ramp
rate of 10 K/min and the sample amount used in TG anal-
ysis is about 2.00 mg.
2.2.4. Preparation of Ag(O2CCH@CHCH2CH2CH3)-
(PPh3) (2d)
Yield of 70%, 0.676 g. Anal. Calc. for C24H24O2PAg
(483.1): C, 59.65; H, 5.01. Found: C, 59.43; H, 5.01%.
1
M.p. 158 ꢁC. H NMR (CDCl3): 7.42–7.51 (m, 15H, Ph–H),
6.80–6.85 (m, 1H, CH@), 5.96–6.02 (m, 1H, @CH), 2.13–
2.20 (m, 2H, CH2C@), 1.45–1.53 (m, 2H, CH2), 0.91–0.96
(m, 3H, CH3). 13C NMR (CDCl3): 176.0 (CO), 145.4
(CH@), 134.4 (PPh3), 134.1 (PPh3), 131.5 (PPh3), 130.7
(PPh3), 130.2 (PPh3), 129.7 (PPh3), 129.5 (PPh3), 125.8
(@CH), 34.5 (CH2C@), 22.0 (CH2), 14.1 (CH3). 31P
NMR (+25 ꢁC): 22.1, 18.7. IR data (cmꢀ1): 3058 (m),
2955 (m), 1650 (s) (mC@C), 1580 (vs) (CO, asym.), 1480 (s)
(CO, sym.), 1436 (vs), 1337 (s), 1097 (s), 975 (s), 752 (s),
695 (s), 520 (s).
2.2. Syntheses
2.2.1. Preparation of Ag(O2CCH@CHCH3)(PPh3) (2a)
Triphenylphosphine (0.512 g, 2.0 mmol) dissolved in
20 mL CHCl3 was added dropwise into a stirred solution
of (CH3CH@CHCO2)Ag (1a) (0.386 g, 2.0 mmol) sus-
pended in 20 mL CHCl3 at 0 ꢁC. After stirring the mixture
for 3 h, filtration through a pad of celite, removal of all vol-
atile materials in vacuo produces a white solid (2a) in yield
of 80%, 0.728 g. Anal. Calc. for C22H20O2PAg (455.0): C,
58.04; H, 4.43. Found: C, 58.03; H, 4.43%. 1H NMR
(CDCl3): 7.40–7.52 (m, 15H, Ph–H), 6.82 (m, 1H, CH@),
6.02 (m, 1H, @CH), 1.85 (qd, 3H, J = 6.79, 1.56 Hz,
CH3). 13C NMR (CDCl3): 175.9 (CO), 140.3 (CH@),
134.4 (PPh3), 134.2 (PPh3), 131.5 (PPh3), 130.8 (PPh3),
130.3 (PPh3), 129.7 (PPh3), 129.5 (PPh3), 127.3 (@CH),
18.1 (CH3). 31P NMR (+25 ꢁC): 22.1, 18.7. IR data
(cmꢀ1): 3052 (m), 2971 (m), 1658 (s) (mC@C), 1558 (vs)
(CO, asym.), 1478 (s) (CO, sym.), 1434 (s), 1380 (s), 1097
(s), 997 (s), 745 (s), 694 (vs), 522 (s), 505 (s).
2.2.5. Preparation of Ag(O2CCH@CHPh)(PPh3) (2e)
Yield of 95%, 0.982 g. Anal. Calc. for C27H22O2PAg
(517.3): C, 62.67; H, 4.25. Found: C, 62.63; H, 4.34%.
M.p. 142 ꢁC. 1H NMR (CDCl3): 7.61 (d, 1H,
J = 15.9 Hz, CH@), 7.29–7.55 (m, 20H, Ph–H), 6.66 (d,
1H, J = 15.9 Hz, @CH). 13C NMR(CDCl3): 176.0 (CO),
141.5 (CH@), 136.4 (C–Ph), 134.4 (PPh3), 134.2 (PPh3),
131.5 (PPh3), 130.9 (PPh3), 130.3 (PPh3), 129.7 (PPh3),
129.5 (PPh3), 129.3 (C–Ph), 129.0 (C–Ph), 128.0 (C–Ph),
123.8 (@CH). 31P NMR (+25 ꢁC): 22.1, 18.7. IR data
(cmꢀ1): 3057 (m), 1636 (s) (mC@C), 1588 (vs) (CO, asym.),
1480 (s) (CO, sym.), 1435 (s), 1337 (vs), 1096 (s), 979 (m),
746 (s), 694 (s), 521 (s).
Complexes 2b–2f were also prepared by the same
method of 2a.
2.2.2. Preparation of Ag(O2CCH@C(CH3)2)(PPh3) (2b)
Yield of 90%, 0.844 g. Anal. Calc. for C23H22O2PAg
(469.0): C, 58.85; H, 4.65. Found: C, 58.70; H, 4.65%. H
2.2.6. Preparation of Ag(O2CCH@CH2)(PPh3) (2f)
Yield of 75%, 0.661 g. Anal. Calc. for C21H18O2PAg
(440.9): C, 57.14; H, 4.08. Found: C, 57.23; H, 4.73%.
1
NMR (CDCl3): 7.41–7.52 (m, 15H, Ph–H), 5.87 (s, 1H,
CH), 2.17 (d, J = 0.85 Hz, 3H, CH3), 1.85 (d,
J = 0.74 Hz, 3H, CH3). 13C NMR (CDCl3): 176.7 (CO),
148.7 (C@), 134.4 (PPh3), 134.2 (PPh3), 131.5 (PPh3),
130.7 (PPh3), 130.2 (PPh3), 129.6 (PPh3), 129.5 (PPh3),
121.2 (@CH), 27.3 (CH3), 20.2 (CH3). 31P NMR
(+25 ꢁC): 21.0, 19.0. IR data (cmꢀ1): 3047 (m), 2906 (m),
1644 (s) (mC@C), 1585 (vs) (CO, asym.), 1483 (s) (CO,
sym.), 1429 (s), 1345 (s), 1086 (s), 852 (s), 748 (s), 690
(vs), 504 (s).
1
M.p. 136 ꢁC. H NMR (CDCl3): 7.44–7.54 (m, 15H, Ph–
H), 6.29 (qd, 2H, J = 8.52, 3.75 Hz, CH2@), 5.66 (qd,
1H, J = 8.52, 3.75 Hz, @CH). 13C NMR (CDCl3): 175.4
(CO), 134.4 (CH2@), 134.2 (PPh3), 133.1 (PPh3), 131.7
(PPh3), 130.5 (PPh3), 130.0 (PPh3), 129.7 (PPh3), 129.6
(PPh3), 127.2 (@CH).31P NMR (+25 ꢁC): 22.1, 18.6. IR
data (cmꢀ1): 3051 (m), 1633 (s) (mC@C), 1566 (vs) (CO,
asym.), 1479 (s) (CO, sym.), 1435 (vs), 1306 (s), 1096 (s),
985 (s), 745 (s), 693 (vs), 520 (s), 503 (s).

J. Han et al. / Inorganica Chimica Acta 358 (2005) 4417–4422
4419
2.2.7. Preparation of Ag(O2CCH@CHCH3)(PPh3)2 (3a)
Triphenylphosphine (1.024 g, 4.0 mmol) dissolved in
30 mL CHCl3 was added dropwise into a stirred solution
of (CH3CH@CHCOO)Ag (1a) (0.386 g, 2.0 mmol) sus-
pended in 20 mL CHCl3 at 0 ꢁC. After stirring the mixture
for 1 h, filtration through a pad of celite, removal of all vol-
atile materials in vacuo produces a white solid (3a) in yield
of 93%, 1.33 g. Anal. Calc. for C40H35O2P2Ag (717.5): C,
66.94; H, 4.88. Found: C, 66.83; H, 4.68%. 1H NMR
(CDCl3): 7.26–7.43 (m, 30H, Ph–H), 6.69 (m, 1H, CH@),
6.02 (m, 1H, @CH), 1.81 (qd, 3H, J = 6.79, 1.56 Hz,
CH3). 13C NMR (CDCl3): 174.4 (CO), 136.8 (CH@),
134.4 (PPh3), 134.2 (PPh3), 133.1 (PPh3), 132.8 (PPh3),
130.4 (PPh3), 129.9 (@CH), 129.2 (PPh3), 129.1 (PPh3),
17.9 (CH3). 31P NMR (+25 ꢁC): 11.01. IR data (cmꢀ1):
3055 (m), 2948 (m), 1653 (s) (mC@C), 1535 (vs) (CO, asym.),
1478 (s) (CO, sym.), 1429 (s), 1382 (s), 1091 (s), 975 (m),
746 (vs), 691 (s), 501 (s).
141.6 (CH@), 134.5 (PPh3), 134.2 (PPh3), 133.1 (PPh3),
132.7 (PPh3), 130.4 (PPh3), 129.2 (PPh3), 129.1 (PPh3),
128.5 (@CH), 34.5 (CH2C@), 22.3 (CH2), 14.2 (CH3). 31P
NMR (+25 ꢁC): 10.93. IR data (cmꢀ1): 3057 (m), 2955
(m), 1650 (s) (mC@C), 1540 (vs) (CO, asym.), 1478 (s) (CO,
sym.), 1434 (vs), 1391 (s), 1094 (s), 983 (m), 746 (s), 695
(vs).
2.3. Single crystal structure of
[Ag(O2CCH@C(CH3)2)(PPh3)2] (3b)
Single crystal of compound 3b was obtained by recrys-
tallization from chloroform–ether solution. A single crystal
suitable for X-ray determination was packed in glue for it is
sensitive to air. X-ray structure measurement was per-
formed on a BRUKER SMART Apex CCD detector
equipped with graphite monochromator. The unit cell
was determined with the program SMART [21]. For data
integration and refinement of the unit cell, the program
SAINT [21] was used. The space group was determined
using the program ABSEN [22]. All data were corrected
for absorption using SADABS [23]. The structure was sol-
ved using direct methods (SHELX-97 [24]), refined using
least square methods (SHELX-97 [24]) and drawn using
ZORTEP [25]. All of the non-hydrogen atoms were refined
anisotropically. Positions of the hydrogen atoms were
determined from a difference Fourier map and were refined
isotropically.
Complexes 3b–3d were also prepared by the same
method of 3a.
2.2.8. Preparation of Ag(O2CCH@C(CH3)2)(PPh3)2 (3b)
Yield of 95%, 1.38 g. Anal. Calc. for C41H37O2P2Ag
(731.6): C, 67.30; H, 5.06. Found: C, 67.35; H, 5.15%.
1
M.p. 189 ꢁC. H NMR (CDCl3): 7.26–7.44 (m, 30H, Ph–
H), 5.86 (s, 1H, CH), 2.05 (s, 3H, CH3), 1.79 (s, 3H,
CH3). 13C NMR (CDCl3): 175.4 (CO), 143.1 (C@), 134.4
(PPh3), 134.2 (PPh3), 133.2 (PPh3), 132.8 (PPh3), 130.4
(PPh3), 129.2 (PPh3), 129.1 (PPh3), 124.1 (@CH), 26.8
(CH3), 20.0 (CH3). 31P NMR (+25 ꢁC): 10.93. IR data
(cmꢀ1): 3054 (m), 2914 (m), 1647 (s) (mC@C), 1532 (vs)
(CO, asym.), 1477 (s) (CO, sym.), 1431 (s), 1390 (s), 1091
(s), 994 (m), 749 (s), 693 (s), 504 (s).
3. Results and discussion
3.1. Synthesis and characterization
Triphenylphosphine coordinated silver a,b-unsaturated
carboxylates: [Ag(O2CR)(PPh3)n] [n = 1, 2a–2f, n = 2, 3a–
3d] were prepared by adding stoichiometry triphenylphos-
phine to the silver carboxylates (1a–1f) in chloroform at
0 ꢁC under inert atmosphere. The yields are good to excel-
lent varying from 70% to 95%. The preparation is fairly
simple, as the phosphine ligand is soluble in petroleum
ether, but the adducts formed are nearly insoluble, separa-
tion and purification of the products are easy to handle.
The compounds are stable at ambient temperature as we
expected. All products obtained gave satisfactory elemental
analysis results and have been characterized by IR, 1H
NMR, 13C NMR, 31P NMR and TG, respectively.
2.2.9. Preparation of Ag(O2CCH@CHCH2CH3)(PPh3)2
(3c)
Yield of 93%, 1.36 g. Anal. Calc. for C41H37O2P2Ag
1
(731.6): C, 67.30; H, 5.06. Found: C, 67.14; H, 5.12%. H
NMR (CDCl3): 7.26–7.43 (m, 30H, Ph–H), 6.71–6.77 (m,
1H, CH@), 5.96–6.01 (m, 1H, @CH), 2.15–2.20 (m, 2H,
CH2), 1.04–1.09 (m, 3H, CH3). 13C NMR (CDCl3):
174.62 (CO), 143.5 (CH@), 134.4 (PPh3), 134.2 (PPh3),
133.2 (PPh3), 132.8 (PPh3), 130.3 (PPh3), 129.2 (PPh3),
129.0 (PPh3), 127.3 (@CH), 25.4 (CH2), 13.3 (CH3). 31P
NMR (+25 ꢁC): 11.29. IR data (cmꢀ1): 3057 (w), 2939
(m), 1647 (s) (mC@C), 1537 (vs) (CO, asym.), 1479 (s) (CO,
sym.), 1434 (vs), 1393 (s), 1095 (s), 9983 (m), 746 (vs),
695 (vs), 514 (s).
The IR spectra of 1:1 adducts (2a–2f) show strong
absorptions in the region of 1558–1588 cꢀm1ꢀ1 for asymmet-
ric stretches, masðCO2ꢀÞ, 1478–1483 cm
for symmetric
2.2.10. Preparation of Ag(O2CCH@CHCH2CH2CH3)-
(PPh3)2 (3d)
stretches, msðCO2ꢀÞ, while that of 1:2 adducts (3a–3d) show
strong absorptions within the region of 1532–1540 cmꢀ1
for asymmetric stretches, masðCO2ꢀÞ, 1478–1479 cmꢀ1 for
symmetric stretches, msðCO2ꢀÞ. The asymmetric vibration
bands of 1:1 adducts are higher than those of 1:2 adducts,
which implies different modes between silver metal and car-
boxylic group; bridge mode for 1:1 adducts and chelating
mode for 1:2 adducts [14]. For carbon–carbon double bond
Yield of 85%, 1.26 g. Anal. Calc. for C42H39O2P2Ag
(745.6): C, 67.65; H, 5.23. Found: C, 67.60; H, 5.12%.
1
M.p. 189 ꢁC. H NMR (CDCl3): 7.25–7.43 (m, 30H, Ph–
H), 6.66–6.71 (m, 1H, CH@), 5.96–6.03 (m, 1H, @CH),
2.10–2.18 (m, 2H, CH2C@), 1.45–1.53 (m, 2H, CH2),
0.82–0.97 (m, 3H, CH3). 13C NMR (CDCl3): 174.6 (CO),

4420
J. Han et al. / Inorganica Chimica Acta 358 (2005) 4417–4422
of unsaturated carboxylic species, the absorption appeared
in the range 1630–1660 cmꢀ1
of the relative 1:1 adducts, which may imply that they
are stable than the relative 1:1 ones. However, the thermal
decomposition of the 1:2 adducts 3a and 3c is different
from that of 1:1 complexes; they are divided into two evi-
dent decomposition stages in TG curves. The first decom-
position temperature begins at low temperature (about
75 ꢁC) with quantitative detachment of carboxylate, and
the second decomposition begins at about 199 ꢁC with
quantitative detachment of triphenylphosphine. A similar
decomposition mechanism was observed for bis-phosphine
coordinated silver carboxylates complexes [14].
The residue which remained after decomposition of the
complexes is almost pure metallic silver, whose content
agreed well with the silver percentage in the complexes
(2a–2f, 3a–3d).
CVD growth of silver thin film from the obtained com-
plexes is underway in our laboratory.
.
1H and 13C NMR results confirm the stoichiometry of
the adducts. The 31P NMR spectra of the compounds were
recorded at room temperature. It shows two broad peaks in
the region 18.0–22.5 ppm for 2a–2f, and one broad peak
in the region 9.0–11.0 ppm for 3a–3d. The absence of
1J(Ag–P) shows the rapid coordination/dissociation pro-
cess or intermolecular exchange. This is in consistence with
most of such previous NMR studies [14,26–28]. The varia-
tions of 31P chemical shifts (Dd) from free triphenylphos-
phine to complexes are largely correlative with the
number of phosphine ligands and not carboxyl species.
This is similar to the reported literature [14]. The Dd for
1:1 and 1:2 adducts were about 26 ppm and about
16 ppm downfield, respectively.
The results of the thermal analysis are summarized in
Table 3. The decomposition of complexes 2a–2f starts
between 161 and 197 ꢁC and finishes between 297 and
311 ꢁC, while the decomposition of complexes 3a–3d starts
between 75 and 195 ꢁC and finishes between 288 and
317 ꢁC. All of the 1:1 complexes show a single thermal
decomposition stage in TG curves, but the DTG curves
analysis shows that all these complexes dissociate in two
overlap decomposition processes, and no individual
decomposition stages were evident. The decomposition
mechanism is similar to that of reported silver complexes
[29]. The decomposition fashion of 1:2 adducts 3b and 3d
is similar that of 1:1 adducts. The initial decomposition
temperature of 1:2 adducts 3b and 3d is higher than those
3.2. Single crystal structure of 3b
In order to establish the molecular structure of the com-
plex in the solid state, a single-crystal X-ray diffraction
analysis was carried out on 3b. The structure of 3b is illus-
trated in Fig. 1. Crystallographic data of 3b in Table 1 and
selected bond distances and angles are listed in Table 2.
Complex 3b exists as a monomer in crystal structure. Sil-
ver atom is in distorted tetrahedron geometry. Silver atom
is bonded to two oxygen atoms of the carboxyl at the same
time (see Table 3). The angle of P1–Ag1–P2 is 130.62(3)ꢁ,
which is similar to the angle reported in the previous
Fig. 1. A view of the complex 3b with atom labels. Displacement ellipsoids shown at the 30% probability level. H-atoms on calculated positions are
omitted for clarity.

J. Han et al. / Inorganica Chimica Acta 358 (2005) 4417–4422
4421
Calc
Table 1
Crystal data, collection parameters, and refinements for 3b
Table 3
Thermogravimetric data for 2a–2f and 3a–3d
Formula
Formula weight
Space group
C41H37AgO2P2
Decompostion
Weight loss (%)
Found
731.52
temperature (ꢁC)
P2(1)/c
0.3 · 0.2 · 0.2
monoclinic
16.766(2)
10.7193(13)
21.026(3)
107.892(2)
3596.0(8)
4
1.351
0.683
(k = 0.71073)
293(2)
2.0–27.0
7830
Tinitial
Tfinal
Crystal dimensions (mm)
Crystal system
2a
2b
2c
2d
2e
2f
161
168
197
181
183
187
75
199
191
79
307
307
301
297
311
297
126
317
293
120
288
293
76.1
75.2
76.5
77.1
80.5
75.8
76.2
76.9
76.9
77.6
79.1
75.5
˚
a (A)
˚
b (A)
˚
c (A)
b (ꢁ)
3
˚
V (A )
3a
Z value
Dcalc (g/cm3)
85.2
81.0
84.9
85.2
l (Mo Ka) (mmꢀ1
)
3b
3c
˚
Radiation Mo Ka (A)
Temperature (K)
h Range (ꢁ)
201
195
83.1
81.4
85.2
85.5
3d
Number of reflections measured
Independent reflections observed [(I) > 2.00 (r(I))]
R1 [I P 2r(I)]/alla
5372
0.0473
0.1123
wR2 [I P 2r(I)]/allb
4. Supplementary material
Goodness-of-fit on F2c
0.99
P
P
a
Crystallographic data (comprising hydrogen atom coor-
dinates, thermal parameters and full tables of bond lengths
and angles) for the structural analysis have been deposited
with the Cambridge Crystallographic Data Center (Depo-
sition No. CCDC 258194). Copies of this information
may be obtained free of charge from The Director, CCDC,
12 Union Road, Cambridge, CB2 1EZ, UK (fax: +44-
1223-336033; e-mail: deposit@ccdc.cam.ac. Uk or www:
http://www.ccdc.cam.ac.uk).
R1 ¼ ðkF oj ꢀ jF ckÞ= jF oj.
P
P
2
1=2
2
b
wR2 ¼ ½ ðwðF 2o ꢀ F c2Þ Þ= ðwF 4oÞꢁ
;
w ¼ 1=½r2ðF 2oÞ þ ð0:0490PÞ ꢁ;
P ¼ ðF 2o þ 2F 2c Þ=3.
P
c
S ¼ ½ wðF 2o ꢀ F 2c Þ ꢁ=ðn ꢀ pÞ1=2, n = number of reflections, p = parameters
2
used.
Table 2
˚
Selected bond distances [A] and angles [ꢁ] for 3b
Bond distances
Ag(1)–P(1)
Ag(1)–O(2)
Ag(1)–O(1)
Ag(1)–P(2)
C(1)–O(1)
2.406(10)
2.418(3)
2.431(3)
2.448(10)
1.244(4)
C(1)–O(2)
C(1)–C(2)
C(2)–C(3)
C(3)–C(5)
C(3)–C(4)
1.256(4)
1.484(5)
1.311(5)
1.488(5)
1.506(6)
Acknowledgments
We gratefully acknowledge the National Natural Sci-
ence Foundation of China, Science Foundation of Jiangsu
Province and the 863 High Technology Program for their
financial support. The research funds for Y. Pan from
Qing-Lan program of Jiangsu Province and Kua-Shi-Ji
program of Education Ministry of China are also
acknowledged.
Bond angles
P(1)–Ag(1)–O(2)
P(1)–Ag(1)–O(1)
O(2)–Ag(1)–O(1)
P(1)–Ag(1)–P(2)
O(2)–Ag(1)–P(2)
O(1)–Ag(1)–P(2)
O(1)–C(1)–O(2)
113.33(7)
C(1)–O(1)–Ag(1)
C(1)–O(2)–Ag(1)
C(3)–C(2)–C(1)
C(2)–C(3)–C(5)
C(2)–C(3)–C(4)
C(5)–C(3)–C(4)
91.2(2)
91.5(2)
128.3(4)
124.1(4)
121.5(4)
114.3(4)
120.10(6)
53.94(8)
130.62(3)
104.16(7)
107.60(6)
123.2(4)
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