Silver(I) and mercury(II) complexes with N,N′-bis(acetylacetone)-1R, 2R-diaminocyclohexane ligands exhibiting three different coordination modes

Article abstract of DOI:10.1016/j.jorganchem.2010.12.006

Treatment of AgNO₃ with one equiv. of N,N′- bis(acetylacetone)-1R,2R-diaminocyclohexane (L) afforded a mononuclear complex [Ag(η²-L)NO₃] (1) in which the central silver(I) atom adopts a distorted trigonal planar geometry by coordinating two carbon atoms of the methane moieties of the ligand and one oxygen atom of the NO ₃^- group. Interaction of CF₃COOAg with one equiv. of L produced a one-dimensional coordination polymer [Ag ₂(μ-L)(CF₃CO₂)₂]_n (2). Each silver(I) in 2 exhibits highly distorted square planar coordination geometry that connects one oxygen atom of L and one neighboring Ag atom with the Ag?Ag interactions. Reaction of HgCl₂ with one equiv. of L resulted in the formation of one-dimensional [{Hg(μ-Cl)Cl} ₂(μ-η¹-L)]_n (3) with a C-coordinated dinuclear mercury(II) chloride moiety being linked by L.

Full text of DOI:10.1016/j.jorganchem.2010.12.006

Journal of Organometallic Chemistry 696 (2011) 2294e2298
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Silver(I) and mercury(II) complexes with N,N0-bis(acetylacetone)-1R,
2R-diaminocyclohexane ligands exhibiting three different coordination modes
,
,
,b,
Yan Li a b, Jian-Gang Wang a b, Taike Duan b, Qun Chen a, Qian-Feng Zhang a
*
a School of Chemistry and Chemical Engineering, Changzhou University, Jiangsu 213164, PR China
b Institute of Molecular Engineering and Applied Chemistry, Anhui University of Technology, 59 Hudong Road, Ma’anshan, Anhui 243002, PR China
a r t i c l e i n f o
a b s t r a c t
Treatment of AgNO3 with one equiv. of N,N0-bis(acetylacetone)-1R,2R-diaminocyclohexane (L) afforded
Article history:
a mononuclear complex [Ag(h
2-L)NO3] (1) in which the central silver(I) atom adopts a distorted trigonal
Received 14 October 2010
Received in revised form
5 December 2010
planar geometry by coordinating two carbon atoms of the methane moieties of the ligand and one
oxygen atom of the NOꢀ3 group. Interaction of CF3COOAg with one equiv. of L produced a one-dimen-
Accepted 6 December 2010
sional coordination polymer [Ag2(m-L)(CF3CO2)2]n (2). Each silver(I) in 2 exhibits highly distorted square
planar coordination geometry that connects one oxygen atom of L and one neighboring Ag atom with the
Ag/Ag interactions. Reaction of HgCl2 with one equiv. of L resulted in the formation of one-dimensional
Keywords:
Silver(I)
Mercury(II)
Schiff base complexes
Coordination polymer
Crystal structure
AgeAg interaction
[{Hg(
m
-Cl)Cl}2(
m
-
h
1-L)]n (3) with a C-coordinated dinuclear mercury(II) chloride moiety being linked
by L.
Ó 2011 Elsevier B.V. All rights reserved.
1. Introduction
It is well known that the chirality of enantiopure ligands may
ensure the formation of chiral MOFs which are of great current
The utilization of metal ions in the self-assembly of organic
molecules as hybrid metal-organic frameworks (MOFs) has attrac-
ted much attention for recent years because metal ions with definite
coordination geometry have a good structural controlling in the
organization of the organic ligands [1]. Actually, the combination of
metal ions and bridging ligands containing rigid and flexible or both
can allow the formation of coordination polymers possessing high
thermal and mechanical stabilities [2]. The coordination geometry
of the metal ion and coordination behavior of organic ligand can be
effectively utilized to produce a series of topological framework
structures with interesting properties [3]. Remarkably, changes in
the types of ancillary ligands and variations due to electronic and
steric effects resulted in numerous ligands having been used for
synthesizing metal-organic complexes [4]. Thus, ligands containing
heteroatoms such as O, N, S, and P have been broadly studied [5]. Of
which the bidentate anionic ligands containing N and/or O atoms
such as Schiff bases and diketiminato ligands have beenwidely used
as ancillary ligands with many types of metals [6].
interest because of their unique applications in asymmetric catal-
ysis and enantioselective separations [7]. In contrast to well-
documented enantiopure ligands to introduce chirality into
framework complexes, the chiral Schiff bases as monoanionic
ketiminato or linked dianionic ketiminato ligands have received
less attention [8,9]. The typical chiral Schiff base ligand, N,N0-bis
(acetylacetone)-1R,2R-diaminocyclohexane (L), easily formed from
the condensation of trans-1R,2R-diaminocyclohexane with two
equivalents of acetylacetone (acacH) in hot ethanol solution [10]. It
is interesting to note that this chiral Schiff base ligand L is of two
substituted imines, two open ends on the oxygen sites, and higher
acidity of the
[9,10]. It has been reported that the new helical metal coordination
polymer [CdI2( -L)]n was obtained from the 1:1 interaction of the
b-hydrogen atoms due to the ketiminato backbone
m
diastereopure Schiff bases L with CdI2 [11]. In this polymeric
cadmium(II) complex, the two carbonyl oxygen atoms bound to
individual Cd(II) centres arise from two different Schiff base ligand
molecules with the two NH donors of each ligand remaining
unbound. Recently, Zhu and Wei have successfully isolated the
unusual dinuclear coordination polymer [Ag2(L)2(NO3)2]n and the
unique trinuclear discrete complex {[Ag3(L)3(m3-O,O,OeNO3)
(H2O)3]2(NO3)}(NO3)3, obtained from the 1:2 interaction of silver
nitrate with the chiral Schiff base ligand L in ethanol, which
incorporates a symmetrical m3-bridging nitrato group that gives rise
* Corresponding author. School of Chemistry and Chemical Engineering,
Changzhou University, Jiangsu 213164, PR China. Tel./fax.: þ86 519 86330360.
E-mail address: zhangqf@ahut.edu.cn (Q.-F. Zhang).
0022-328X/$ e see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.12.006

Y. Li et al. / Journal of Organometallic Chemistry 696 (2011) 2294e2298
2295
to a C3-symmetric triskelion motif [12]. Both species also feature
g
-
The mixture was stirred for about 3 h at room temperature. After
filtration, the resulting solution was slowly evaporated in air,
colorless block crystals of 3 were obtained within two days in ca.
62% yield (127 mg) based on mercury salt. 1H NMR (300 MHz,
carbon
h
1 aryl-like coordination of neutral bridging acetylacetone-
imine units to the respective Ag(I) centres. These somewhat
surprising characters prompted us to further investigate reaction of
the chiral Schiff base ligand L with d10 metal ions Agþ and Hg2þ
,
acetone-d6):
d
¼
1.50 (br.m, 4H, cyclohexane-1,2-diyl-CH2),
accordingly, the initial results of our efforts including the metale
alkyl complexes [Ag( -Cl)Cl}2(
2-L)NO3] (1) and [{Hg( 1-L)]n (3),
and the one-dimensional polymer [Ag2( -L)(CF3CO2)2]n (2) with
1.84e2.45 (br.m, 4H, cyclohexane-1,2-diyl-CH2), 1.91 (s, 6H, CMe),
1.98 (s, 6H, CMe), 3.46 (br.m, 2H, cyclohexane-1,2-diyl-CHeN), 5.59
(d, J ¼ 14.7 Hz, 2H, NCMeCHCOMe), 10.90 (br.s, 2H, NH) ppm. MS
(FAB): m/z 821 (Mþ), 786 (MþꢀCl), 751 (Mþꢀ2Cl). Selected IR (KBr,
h
m
m-h
m
AgeAg argentophilic interactions are reported in this paper.
cmꢀ1): 3263 (br)
1629 (m)
n
(NeH), 1670 (vs) 1658 (vs)
n
(C]O), 1635 (m)
2. Experimental
n(C]C),1533 (s)
n(CeN). Anal. Calc. for C16H26N2O2Cl4Hg2:
C, 23.4; H, 3.19; N, 3.41. Found: C, 23.2; H, 3.14; N, 3.38%.
2.1. General
2.5. X-ray crystallography
All chemicals employed for syntheses were purchased from
commercial sources and used without further purification. The
ligand N,N0-bis(acetylacetone)-1R,2R-diaminocyclohexane (L) was
synthesized according to the literature procedure [10]. NMR spectra
were recorded on a Bruker ALX 300 spectrometer operating at
A summary of crystallographic data and experimental details for
[Ag(
1-L)]n (3) are summarized in Table 1. Intensity data were collected
on a Bruker SMART APEX 2000 CCD diffractometer using graphite-
monochromated Mo-K radiation (
¼ 0.71073 Å) at 293(2) K. The
h m-L)(CF3CO2)2]n (2) and [{Hg(m-Cl)Cl}2(m-
2-L)NO3] (1), [Ag2(
h
300 MHz for 1H. Chemical shifts (
d, ppm) were reported with
a
l
reference to SiMe4 (1H). Infrared spectra (KBr) were recorded on
a PerkineElmer 16 PC FT-IR spectrophotometer with use of pressed
KBr pellets and positive FAB mass spectra were recorded on a Fin-
nigan TSQ 7000 spectrometer. Elemental analyses were carried out
using a PerkineElmer 2400 CHN analyzer.
collected frames were processed with the software SAINT [13]. The
data were corrected for absorption using the program SADABS [14].
Structures were solved by the direct methods and refined by full-
matrix least-squares on F2 using the SHELXTL software package
[15]. All non-hydrogen atoms were refined anisotropically. The
positions of all hydrogen atoms were generated geometrically
(Csp3eH ¼ 0.96 and Csp2eH ¼ 0.93 Å), assigned isotropic thermal
parameters, and allowed to ride on their respective parent carbon
atoms before the final cycle of least-squares refinement.
2.2. Synthesis of [Ag(h
2-L)NO3] (1)
To a stirred solution of L (139 mg, 0.50 mmol) in ethanol (5 mL)
was dropwise added AgNO3 (85 mg, 0.50 mmol) in water (2 mL).
The mixture was stirred for about 4 h at room temperature. After
filtration, the resulting solution was slowly evaporated in air,
colorless block crystals of 1 were obtained within three days in ca.
74% yield (166 mg) based on silver salt. 1H NMR (300 MHz, acetone-
3. Results and discussion
Scheme 1 illustrates synthetic reactions of N,N0-bis(acetylace-
tone)-1R,2R-diaminocyclohexane (L) with AgNO3, CF3COOAg and
d6):
d
¼ 1.43 (br.m, 4H, cyclohexane-1,2-diyl-CH2), 1.68e2.10 (br.m,
4H, cyclohexane-1,2-diyl-CH2), 1.89 (s, 6H, CMe), 1.93 (s, 6H, CMe),
3.49 (br.m, 2H, cyclohexane-1,2-diyl-CHeN), 5.27 (d, J ¼ 12.4 Hz,
2H, NCMeCHCOMe), 10.90 (br.s, 2H, NH) ppm. MS (FAB): m/z 448
Table 1
Crystallographic data and experimental details for [Ag(
h
2-L)NO3] (1), [Ag2(
m-L)
(Mþ), 386 (MþꢀNO3). Selected IR (KBr, cmꢀ1): 3264 (br)
n(NeH),
(CF3CO2)2]n (2) and [{Hg(
m-Cl)Cl}2(
m
-h
1-L)]n (3).
1672 (vs) 1664 (vs) n(C]O), 1643 (m) 1630 (m) n(C]C), 1542 (s) n
Compound
1
2
3
(CeN), 1345 (vs) 1315 (s)
42.9; H, 5.85; N, 9.37. Found: C, 42.5; H, 5.81; N, 9.33%.
n
(NOꢀ3 ). Anal. Calc. for C16H26N3O5Ag: C,
Empirical
formula
Formula
weight
C16H26N3O5Ag
C20H26N2O6F6Ag2
C16H26N2O2Cl4Hg2
448.27
720.17
821.37
2.3. Synthesis of [Ag2(m-L)(CF3CO2)2]n (2)
Crystal system
a (Å)
b (Å)
Monoclinic
23.4662(3)
7.8386(1)
21.9702(3)
109.899(1)
3809.65(9)
C2/c
Orthorhombic
18.4310(6)
8.4494(2)
Monoclinic
9.0998(6)
15.3611(12)
17.2062(13)
104.624(5)
2327.2(3)
C2/c
To a stirred solution of L (139 mg, 0.50 mmol) in methanol
(8 mL) was dropwise added CF3COOAg (110 mg, 0.50 mmol) in
methanol (5 mL). The mixture was stirred for about 40 min at room
temperature. After filtration, the resulting solution was slowly
evaporated in air, colorless block crystals of 2 were obtained within
three days in ca. 65% yield (112 mg) based on silver salt. 1H NMR
c (Å)
16.8376(5)
b
(ꢁ)
V (Å3)
2622.13(13)
Pcca
4
1.824
296(2)
1424
Space group
Z
4
4
Dcalc (g cmꢀ3
)
1.563
296(2)
1840
1.088
2.344
296(2)
1520
13.650
(300 MHz, acetone-d6):
d
¼ 1.44 (br.m, 4H, cyclohexane-1,2-diyl-
Temperature (K)
F(000)
CH2), 1.68e2.11 (br.m, 4H, cyclohexane-1,2-diyl-CH2), 1.89 (s, 6H,
CMe), 1.94 (s, 6H, CMe), 3.48 (br.m, 2H, cyclohexane-1,2-diyl-
CHeN), 4.93 (s, 2H, NCMeCHCOMe), 10.89 (br.s, 2H, NH) ppm. MS
(FAB): m/z 720 (Mþ), 607 (MþꢀCF3CO2), 494 (Mþꢀ2CF3CO2).
m
(Mo-K
a
)
1.573
(mmꢀ1
)
Total refln
Independent
refln
17949
4344
20430
2979
10737
2675
Selected IR (KBr, cmꢀ1): 3268 (br)
n
(NeH), 1736 (vs)
(C]O), 1636 (m) 1628 (m) (C]C), 1539 (s)
1246 (s) 1058 (m) (CF3). Anal. Calc. for C20H26N2O6F6Ag2: C, 33.4; H,
3.64; N, 3.89. Found: C, 33.1; H, 3.63; N, 3.85%.
n
(CO2), 1675
(vs) 1661 (vs)
n
n
n
(CeN),
Rint
0.0194
0.0318, 0.0825
0.0360
0.0499, 0.1306
0.0276
0.0286, 0.0614
R1,a wR2b
n
(I > 2s(I))
R1, wR2
0.0375, 0.0871
0.0640, 0.1410
1.084
0.0386, 0.0656
1.035
(all data)
2.4. Synthesis of [{Hg(m-Cl)Cl}2(m-h
1-L)]n (3)
GoFc
1.028
P
P
a
b
c
R1 ¼
jjFoj ꢀ jFcjj= jFoj.
P
P
P
wR2 ¼ ½ wðjFo2 ꢀ Fc2jÞ2= wjFo2j2ꢂ1=2
.
To a stirred solution of L (139 mg, 0.50 mmol) in ethanol (6 mL)
was dropwise added HgCl2 (136 mg, 0.50 mmol) in ethanol (4 mL).
GoF ¼ ½ wðjFo ꢀ FcjÞ2=ðNobs ꢀ NparamÞꢂ1=2
.

2296
Y. Li et al. / Journal of Organometallic Chemistry 696 (2011) 2294e2298
HgCl2 in the alcohol solvents at room temperature. Treatment of
Interaction of CF3COOAg with one equiv. of the ligand L in
methanol produced colorless crystalline solid of [Ag2( -L)
(CF3CO2)2]n (2) in a yield of 65% that gave mircoanalytical data
AgNO3 with one equiv. of ligand L in ethanolewater (2.5:1) affor-
a
m
ded a clear solution from which colorless block crystals of [Ag(
h
2-L)
NO3] (1) were isolated in a yield of 74%. Microanalytical data were
consistent with the solid having a 1:1 of Ag:L ratio. The typically
consistent with a 2:1 CF3COOAg-to-ligand ratio. The peaks at
1732 cmꢀ1 for
n
(CO2) and 1246 and 1058 cmꢀ1 for
n
(CF3) in the IR
spectrum indicated the presence of the CF3COꢀ2 in complex 2. Also
present peaks at 3268 cmꢀ1 for (NeH), 1675 and 1661 cmꢀ1 for
(C]O), and 1539 cmꢀ1 for
(CeN) indicative of the ligand L. The
absorption peak of 1H NMR spectrum of 2 shows the methane
proton resonances at
¼ 4.93 ppm in a singlet, which is very close
characteristic peaks at 3264 cmꢀ1 for (NeH), 1664 and 1672 cmꢀ1
n
for
n
(C]O), and 1542 cmꢀ1 for
n
(CeN) in the IR spectrum indicated
n
n
the presence of the ligand L in complex 1. The IR spectrum showed
one feature in the NOꢀ3 stretching region, two strong peaks at 1345
and 1315 cmꢀ1, a suggestive of the coordination of the NOꢀ3 anion to
the silver atom. The 1H NMR spectrum of 1 shows the methane
n
d
to those of the free ligand L, indicating that the carbon atoms of the
methane moieties non-coordinate with the silver atoms. The FABþ
mass spectrum of 2 exhibits molecular ions corresponding to Mþ,
(MþꢀCF3CO2) and (Mþꢀ2CF3CO2) with the characteristic isotopic
distribution patterns. X-ray structural analysis revealed that
complex 2 formed a one-dimensional (1D) coordination network,
which crystallized in the orthorhombic space group Pcca. The
molecule of the neutral polymeric complex 2 has an imposed
centrosymmetry. Each silver(I) exhibits highly distorted square
planar coordination geometry that connected three oxygen atoms
and one neighboring Ag atom (see Fig. 2). The N,N0-bis(acetylace-
tone)-1R,2R-diaminocyclohexane ligand acts as 1,12-bridging in the
structure, it is coordinated by the oxygen atom of each of its acet-
amide groups to the neighboring silver atom with AgeO bond
length of 2.399(3) Å. Pairs of CF3COꢀ2 groups bridge the edge of Ag2
in an opposite direction. The distance of the Ag/Ag separation
proton resonances at
expected downfield shift for the CH protons with relative to the free
ligand (
d
¼ 5.27 ppm in a sharp doublet which is
d
¼ 4.92 ppm), an indicative of the coordination of the
carbon through the methane groups. The FABþ mass spectrum of 1
exhibits molecular ions corresponding to Mþ and (MþꢀNO3) with
the characteristic isotopic distribution patterns. X-ray structural
analysis revealed that 1 is a mononuclear silver(I) complex and
crystallized in the monoclinic space group C2/c. The central silver(I)
atom adopts a distorted trigonal planar geometry by coordinating
two carbon atoms of the methane moieties of the ligand and one
oxygen of the NOꢀ3 group, as shown in Fig. 1, indicted by the angles
around the silver atom ranging from 89.59(10)ꢁ to 141.94(10)ꢁ. The
average AgeC bond length in 1 (av. 2.492(2) Å) is compared with
those in {[Ag3(L)3(m3-O,O,OeNO3)(H2O)3]2(NO3)}(NO3)3 (av. 2.411
(2) Å) [12], [Pd2Ag2(m2-dmpz-k k -
N,N0)2(m3-dmpz- N,N0,C4)4Ag2(m2
ClO4)2] (Hdmpz ¼ dimethylpyrazole) (av. 2.412(6) Å) [16] and
[Ag4(pcp)(C2F4(CO2)2)2] (pcp ¼ [2.2]paracyclophane) (av. 2.416
(3) Å) [17]. The AgeO bond length of 2.571(4) Å in 1 is normal [12].
bridged by
bridged by the same groups in [Ag4(
m
-CF3COꢀ2 groups in 2 (3.0556(8) Å) is shorter than that
-dppa)2(m4-O2PPh2)2(m-
m
CF3CO2)2] (dppa ¼ bis(diphenylphosphino)amide) (av. 3.491(1) Å)
H
N
H
N
O
AgNO3
O
Ag
O
O
N
O
1
CF3
C
N
O
H
O
Ag
O
O
H N
O
n
H
N
CF3COOAg
N
N
H
O
H
O
Ag
O
O
N
H
O
C
F3C
2
Cl
N
N
H
O
HgCl2
O
H
Cl
Hg
O
O
H H
N
Hg
Cl
n
Cl
N
3
Scheme 1.

Y. Li et al. / Journal of Organometallic Chemistry 696 (2011) 2294e2298
2297
Fig. 1. Molecular structure of [Ag(h
2-L)NO3] 1 (ORTEP, 40% probability, hydrogen
atoms excluded for clarity). Selected bond lengths (Å) and angles (ꢁ): Ag(1)ꢀC(9) 2.487
(2), Ag(1)ꢀC(14) 2.498(2), Ag(1)ꢀO(3) 2.571(4); C(9)ꢀAg(1)ꢀC(14) 117.03(7), C(9)ꢀAg
(1)ꢀO(3) 141.94(10), C(14)ꢀAg(1)ꢀO(3) 89.59(10), N(3)ꢀO(3)ꢀAg(1) 101.4(2).
[18], indicative of the weak Ag/Ag interactions existing in 2. The
two carboxylate groups in the equatorial planar are coordinated to
the metalemetal bond bimetallic core with the average AgeO bond
length of 2.234(4) Å. Fig. 3 displays the packing view of ribbon-like
polymer 2 in the ac plane. Both types of independent ribbon run
parallel to the b-axis.
Fig. 3. Packing diagram for [Ag2(m-L)(CF3CO2)2]n 2.
for the methane proton resonances at
d
¼ 5.59 ppm in a sharp
Reaction of HgCl2 with one equiv. of the ligand L in ethanol
doublet, indicating the coordination of the carbon through the
methane groups. The FABþ mass spectrum of 3 exhibits molecular
ions corresponding to Mþ, (MþꢀCl) and (Mþꢀ2Cl) with the char-
acteristic isotopic distribution patterns. X-ray structural analysis
revealed that 3 is a 1D coordination polymer (see Fig. 4), crystal-
lized in the monoclinic space group C2/c, and straddles the
solution afforded colorless block crystals of [{Hg(
(3) in 62% yield. Mircoanalytical data clearly gave the consistent
with a 2:1 HgCl2-to-ligand ratio. The peaks at 3263 cmꢀ1 for
(NeH), 1670 and 1658 cmꢀ1 for (C]O), and 1533 cmꢀ1 for
(CeN)
m-Cl)Cl}2(m-h
1-L)]n
n
n
n
in the IR spectrum indicated the presence of the ligand in complex
3. The 1H NMR spectrum of 3 shows the expected downfield shift
Fig. 4. Perspective view of a fragment of the polymeric chain of [{Hg(m-Cl)Cl}2(m- -
h1
Fig. 2. Perspective view of a fragment of the polymeric chain of [Ag2(
m
-L)(CF3CO2)2]n
2
L)]n 3 with bridging ligands (ORTEP, 40% probability, hydrogen atoms excluded for
clarity). Symmetry related atoms are shown for completeness. Selected bond lengths
(Å) and angles (ꢁ): Hg(1)ꢀC(6) 2.365(5), Hg(1)ꢀCl(1) 2.8915(13), Hg(1)ꢀCl(1A) 2.4562
(14), Hg(1)ꢀCl(2) 2.3808(15); C(6)ꢀHg(1)ꢀCl(1) 96.37(12), C(6)ꢀHg(1)ꢀCl(1A) 108.07
(12), C(6)ꢀHg(1)ꢀCl(2) 118.33(13), Cl(1)ꢀHg(1)ꢀCl(2) 96.24(5), Cl(1)ꢀHg(1)ꢀCl(1A)
86.10(4), Cl(1A)ꢀHg(1)ꢀCl(2) 132.86(6), Hg(1)ꢀCl(1)ꢀHg(1A) 93.90(4). Symmetry
code: a) ꢀx, ꢀy, ꢀz þ 1; b) ꢀx þ 1, y, ꢀz þ 3/2.
with bridging ligands (ORTEP, 40% probability, hydrogen atoms excluded for clarity).
Symmetry related atoms are shown for completeness. Selected bond lengths (Å) and
angles (ꢁ): Ag(1)ꢀO(1) 2.399(3), Ag(1)ꢀO(2) 2.247(4), Ag(1)ꢀO(3) 2.222(3), Ag(1)/Ag
(1A) 3.0556(8); O(1)ꢀAg(1)ꢀO(2) 82.59(15), O(1)ꢀAg(1)ꢀO(3) 111.13(13), O(2)ꢀAg(1)ꢀ
O(3) 157.74(15), O(1)ꢀAg(1)/Ag(1A) 132.50(8), O(2)ꢀAg(1)/Ag(1A) 77.54(11), O(3)ꢀ
Ag(1)/Ag(1A) 80.35(10). Symmetry code: a) ꢀx þ 1, ꢀy þ 1, ꢀz þ 2; b) ꢀx þ 3/2, ꢀy, z.

2298
Y. Li et al. / Journal of Organometallic Chemistry 696 (2011) 2294e2298
Appendix A. Supplementary material
CCDC 795165, 795166 and 795167 contain the supplementary
crystallographic data for [Ag( -L)(CF3CO2)2]n
2-L)NO3] (1), [Ag2(
(2) and [{Hg( -Cl)Cl}2(
1-L)]n (3). These data can be obtained free
h
m
m
m-h
of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
References
[1] (a) J.W. Steed, J.L. Atwood, Supramolecular Chemistry. VCH, New York, 2000;
(b) S.L. James, Chem. Soc. Rev. 32 (2003) 276e288;
Fig. 5. Packing view of complex 3 in the bc plane.
(c) K. Biradha, CrystEngComm 5 (2003) 374e384.
[2] (a) A.G. Wong-Foy, A.J. Matzger, O.M. Yaghi, J. Am. Chem. Soc. 128 (2006)
3494e3495;
crystallographic inversion centre. The N,N0-bis(acetylacetone)-
1R,2R-diaminocyclohexane ligand L acts as 1,8-bridging to coordi-
nate with mercury atoms by the carbon atoms of the methane
moieties of the ligand L, leading to a C-coordinated dinuclear
mercury(II) chloride complex linked by the ligand L. The Hg(II)
centre has a four-coordinate environment with one short HgeCl
bond of 2.3808(15) Å, one HgeC bond of 2.365(5) Å and two
asymmetric bridging HgeCl bonds at distances of 2.4562(14) and
2.8915(13) Å in 3. The HgeC bond length in 3 is slightly longer than
those in [(MBPPY)HgX2]2 (MBPPY ¼ (C6H5)3PCHCO-C6H4OCH3))
(X ¼ Cl: 2.215(4) Å, X ¼ Br: 2.218(11) Å, X ¼ I: 2.213(13) Å) [19],
which suggests that the overlap of the hybrid orbital with high s
character for the methyl carbon being less than the ylidic carbon.
The terminal Hg(1)eCl(2) bond length 2.3808(15) Å in 3 is
comparable to 2.418(14) Å observed in the case of [(MBPPY)HgCl2]2
[19], which has a tetrahedral coordination environment around
mercury with a bridging structure. The two bridged HgeCl bonds
fall within the range 2.4562(14)e2.8915(13) Å reported for other
structures containing chloro bridged mercury. The angles around
mercury vary from 86.10(4)ꢁ to 132.86(6)ꢁ in 3, a very distorted
tetrahedral environment. Fig. 5 displays the packing view of wave-
like polymer 2 in the bc plane. Both types of independent polymer
run parallel to the a-axis.
In summary, the present study describes the synthesis and
characterization of silver(I) and mercury(II) complexes with N,N0-
bis(acetylacetone)-1R,2R-diaminocyclohexane ligands exhibiting
three different coordination modes. The crystal structures of three
complexes indicate that the ligand acts as the bridging ligands
through the coordination of the oxygen atoms of the acetamide
groups and the carbon atoms of the methane moieties, accordingly,
the formation of the presented 1D coordination polymer networks
results from the ligands via oxygen atoms bridging the silver atoms
through connection of the AgeAg argentophilic interactions and
via carbon atoms bridging the mercury atoms through C-coordi-
nated dinuclear mercury(II) chloride fragments. Such organome-
tallic supramolecular assembly in the topology of the poly-
dimensional networks is in active study in this laboratory.
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Acknowledgements
This project was supported by the Natural Science Foundation of
China (20771003) and the Program for New Century Excellent
Talents in University of China (NCET-08-0618).
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