Aminobenzonitrile isomers-mediated self-assembly of mixed-ligand silver(I) coordination architectures: Synthesis, structural characterization and properties

Article abstract of DOI:10.1016/j.molstruc.2011.01.035

Three mixed-ligand coordination compounds (CCs) of the formula {[Ag(p-abn)(dnca)]·H₂O}_n (1), {[Ag(o-abn)(dnca)] ·H₂O}_n (2), and {[Ag(m-abn)₄)] ·(dnca)·H₂O} (3) (where p-abn = 4-aminobenzoni

Full text of DOI:10.1016/j.molstruc.2011.01.035

Journal of Molecular Structure 990 (2011) 158–163
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Aminobenzonitrile isomers-mediated self-assembly of mixed-ligand silver(I)
coordination architectures: Synthesis, structural characterization and properties
a
Fu-Jing Liu a, Di Sun a, Yun-Hua Li a, Hong-Jun Hao a, Geng-Geng Luo b, Rong-Bin Huang a, , Lan-Sun Zheng
⇑
a State Key Laboratory for Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen
University, Xiamen, 361005, China
b Institute of Materials Physical Chemistry, Huaqiao University, Xiamen, Fujian 361021, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Three mixed-ligand coordination compounds (CCs) of the formula {[Ag(p-abn)(dnca)]ꢀH2O}n (1), {[Ag(o-
abn)(dnca)]ꢀH2O}n (2), and {[Ag(m-abn)4)]ꢀ(dnca)ꢀH2O} (3) (where p-abn = 4-aminobenzonitrile, o-abn =
2-aminobenzonitrile, m-abn = 3-aminobenzonitrile, Hdnca = 3,5-dinitrobenzoic acid) were synthesized
by reactions of Ag2O and aminobenzonitrile ligands with Hdnca under the ammoniacal condition. All
CCs have been structurally characterized by element analysis, IR and X-ray single-crystal diffraction.
Received 12 January 2011
Received in revised form 20 January 2011
Accepted 20 January 2011
Available online 26 January 2011
The aminobenzonitrile acts as bidentate
l
2-N,N0 ligand in both 1 and 2, and as monodentate ligand in
Keywords:
Silver(I)
Aminobenzonitrile ligand
3,5-Dinitrobenzoic acid
Agꢀ ꢀ ꢀAg interaction
Photoluminescence
3. As the change of the relative position of amino and cyano groups of aminobenzonitrile ligands, the
dimensionality of 1–3 decreases from 2D to 0D mainly due to the steric effect of the substituted groups,
which indicates that aminobenzonitrile isomers play important roles in the formation of the diverse
coordination architectures. The three CCs exhibit photoluminescent emissions in the solid state at room
temperature.
Ó 2011 Elsevier B.V. All rights reserved.
1. Introduction
cussed the influence of the relative position of amino and cyano
groups of aminobenzonitrile ligands on the resulting structures.
The construction of metal–organic CCs is of intense current
interest due to their novel structures and potential applications
in many fields [1–3]. As we know, construction of CCs is mainly
dependent on the metal centers and organic ligands. The Ag(I)
ion with d10 closed-shell electronic configuration is famous for
having pliant coordination geometries including linearity, triangle,
tetrahedron and trigonal-pyramid with occasional instances of
square and octahedron [4]. The structural features of the organic
ligand including the relative angle and orientation of the donor
groups also play an important role in controlling CCs’ structures.
In recent years, although heterocyclic N-donor ligands (such as
pyridine, pyrazine, pyrimidine, and their derivatives) have been
widely used in transition metal CCs as either bridging or chelating
ligands [5–18], aminobenzonitrile ligands are rarely used in Ag(I)
CCs due to their two weak coordinative sites, Namino and Ncyano
[19,20]. On the other hand, influence of relative positions of the do-
nor groups of organic ligands on the assembly process has received
much less attention [21–23], as a consequence, systematical inves-
tigation on this aspect becomes an urgent need. Herein, we utilized
mixed-ligand strategy to construct three new Ag/aminobenzoni-
trile/3,5-dinitrobenzoic acid CCs ranging from 2D to 0D and dis-
2. Experimental
2.1. Materials and physical measurements
All the reagents and solvents employed were commercially
available and used as received without further purification. Infra-
red spectra were recorded on a Nicolet AVATAT FT-IR330 spec-
trometer as KBr pellets in the frequency range 4000–400 cmꢁ1
.
The elemental analyses (C, H, N contents) were determined on a
CE instruments EA 1110 analyzer. Photoluminescence measure-
ments were performed on a Hitachi F-7000 fluorescence spectro-
photometer with solid powder on a 1 cm quartz round plate.
2.2. Synthesis of compound {[Ag(p-abn)(dnca)]ꢀH2O}n (1)
A mixture of Ag2O (23 mg, 0.1 mmol), p-abn (24 mg, 0.2 mmol)
and Hdnca (42 mg, 0.2 mmol) was stirred in methanol-ethanol
mixed solvent (6 mL, v/v: 1/1). Then aqueous NH3 solution (25%,
1 mL) was dropped into the mixture to give a clear solution under
ultrasonic treatment. The resultant solution was allowed to evapo-
rate slowly in darkness at room temperature for several days to
give yellow crystals of 1 (Yield: 46%, based on silver). Anal. Calc.
(found) for AgC14H11N4O7: C, 36.95 (36.94); H, 2.44 (2.34); N,
⇑
Corresponding author.
E-mail address: rbhuang@xmu.edu.cn (R.-B. Huang).
0022-2860/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2011.01.035

F.-J. Liu et al. / Journal of Molecular Structure 990 (2011) 158–163
159
12.31 (12.25)%. IR (KBr):
m
(cmꢁ1) = 3477 (m), 3372 (s), 3213 (w),
Mo Karadiation source (k = 0.71073 Å) for 2 and 3. The crystal struc-
3101 (w), 3082 (w), 2214 (m), 1624 (s), 1603 (m), 1581 (m),
1533 (s), 1451 (w), 1382 (m), 1344 (s), 1326 (m), 1176 (m), 1073
(w), 918 (w), 839 (w), 830 (w), 798 (w), 733 (m), 721 (s), 547 (w).
tures were solved by direct methods and refined with the full-matrix
least-squares technique on F2 using the SHELXS-97 and SHEXL-97
programs [24,25]. The positions of the water H atoms were refined
with the OAH bond length restrained to 0.85 Å. The crystallographic
details of 1–3 are summarized in Table 1. Selected bond lengths and
angles for 1–3 are collected in Table 2. The hydrogen bond geome-
tries for 1–3 are shown in Table 3.
2.3. Synthesis of compound {[Ag(o-abn)(dnca)]ꢀH2O}n (2)
The synthesis of 2 was similar to that of 1, but with o-abn
(24 mg, 0.2 mmol) in place of p-abn. Yellow crystals of 2 were ob-
tained in 53% yield (based on silver). They were washed with a
small volume of cold ethanol. Anal. Calc. (found) for AgC14H11N4O7:
C, 36.95 (36.52); H, 2.44 (2.44); N, 12.31 (12.20)%. IR (KBr):
4. Results and discussion
4.1. Syntheses and IR
m
(cmꢁ1) = 3459 (m), 3367 (m), 3102 (m), 3091 (m), 2209 (m),
1623 (s), 1581 (m), 1569 (m), 1534 (s), 1494 (m), 1456 (m), 1381
(s), 1344 (s), 1265 (m), 1161 (w), 1073 (m), 935 (w), 918 (m),
798 (m), 747 (m), 733 (s), 721 (s), 521 (w), 494 (m).
The syntheses of compounds 1–3 were carried out in the dark-
ness to avoid photodecomposition. The infrared spectra and
Table 2
2.4. Synthesis of compound {[Ag(m-abn)4)]ꢀ(dnca)ꢀH2O}n (3)
Selected bond distances (Å) and angles (°) for 1–3.
Complex 1
The synthesis of 3 was similar to that of 1, but with m-abn
(24 mg, 0.2 mmol) in place of p-abn. Yellow crystals of 3 were ob-
tained in 68% yield (based on silver). They were washed with a
small volume of cold ethanol. Anal. Calc. (found) for AgC35H29-
N10O7: C, 51.93(49.11); H, 3.61 (3.29); N, 17.30 (16.52)%. IR
Ag1AO1
2.214 (2)
2.216 (2)
2.435 (3)
154.24 (9)
95.49 (10)
95.33 (9)
Ag1AN1
2.545 (3)
2.9262 (6)
Ag1AO2i
Ag1AAg1i
Ag1AN2ii
O1AAg1AO2i
O1AAg1AN2ii
O2iAAg1AN2ii
O1AAg1AN1
O2iAAg1AN1
N2iiAAAg1AN1
115.19 (9)
87.10 (9)
94.68 (10)
(KBr):m
(cmꢁ1) = 3401 (s), 3332 (m), 3226 (m), 3102 (m), 3092
Symmetry codes: (i) ꢁx + 1, ꢁy + 2, ꢁz + 1; (ii) ꢁx + 1, y + 1/2, ꢁz + 1/2.
Complex 2
(m), 2233 (m), 1624 (s), 1599 (s), 1581 (s), 1532 (s), 1591 (m),
1478 (w), 1447 (m), 1381 (m), 1345 (s), 1323 (m), 1294 (m),
1168 (w), 1157 (w), 1073 (m), 993 (w), 935 (w), 918 (m), 863
(m), 789 (m), 733 (m), 722 (s), 686 (m), 523 (m), 477 (m).
Ag1AO2i
2.258 (2)
2.287 (3)
2.338 (3)
154.17 (11)
109.07 (13)
89.26 (13)
Ag1AN1
2.532 (3)
2.9441 (8)
Ag1AO1
Ag1AAg1i
Ag1AN2ii
O2iAAg1AO1
O2iAAg1AN2ii
O1AAg1AN2ii
O2iAAg1AN1
O1AAg1AN1
N2iiAAg1AN1
100.39 (11)
95.95 (11)
94.60 (13)
3. X-ray crystallography
Symmetry codes: (i) ꢁx + 1, ꢁy + 1, ꢁz; (ii) x + 1, y, z.
Complex 3
Single crystals of the compounds 1–3 with appropriate dimen-
sions were mounted on a glass fiber and used for data collection.
Data were collected on a Bruker-AXS CCD diffractometer equipped
Ag1AN5
2.327 (3)
Ag1AN1
2.372 (3)
2.452 (3)
Ag1AN3
2.338 (3)
Ag1AN8
N5AAg1AN3
N5AAg1AN1
N3AAg1AN1
123.18 (10)
107.35 (9)
122.21 (9)
N5AAg1AN8
N3AAg1AN8
N1AAg1AN8
107.74 (10)
97.31 (11)
91.78 (11)
with a graphite-monochromated Mo K
a radiation source (k =
0.71073 Å) for 1, and a Rigaku R-AXIS RAPID Imaging Plate single-
crystal diffractometer equipped with a graphite-monochromated
Table 1
Crystallographic data for complexes 1–3.
Complexes
1
2
3
Formula
Mr
AgC14H11N4O7
455.14
AgC14H11N4O7
455.14
AgC35H29N10O7
809.55
Crystal system
Space group
a (Å)
b (Å)
c (Å)
Monoclinic
P2(1)/c
10.2297 (18)
6.5434 (11)
22.729 (4)
90.00
99.639 (3)
90.00
4
Monoclinic
P2(1)/n
6.6015 (13)
7.5135 (15)
32.483 (7)
90.00
91.03 (3)
90.00
4
triclinic
P-1
7.6256 (15)
14.919 (3)
17.290 (3)
114.89 (3)
96.42 (3)
96.94 (3)
2
1742.1 (6)
1.543
0.643
a
(deg)
b (deg)
c
(deg)
Z
V (Å3)
1499.9 (5)
2.016
1.396
1610.9 (6)
1.877
1.300
Dc (g cmꢁ3
)
l
(mmꢁ1
)
F (0 0 0)
904
904
824
No. of unique reflns
No. of obsd reflns [I > 2
Parameters
2619
2542
235
2821
2471
235
6091
5355
482
r(I)]
GOF
1.158
1.131
1.163
Final R indices [I > 2
R indices (all data)
r
(I)]a,b
R1 = 0.0303
wR2 = 0.0826
R1 = 0.0318
wR2 = 0. 0837
0.522 and ꢁ0.547
R1 = 0.0301
wR2 = 0.0761
R1 = 0.0365
wR2 = 0.0838
0.851 and ꢁ0.497
R1 = 0.0324
wR2 = 0.0786
R1 = 0.0397
wR2 = 0.1004
0.701 and ꢁ0.790
Largest difference peak and hole (e Åꢁ3
)
a
R1
wR2 ¼ ½
¼
R
jjFoj ꢁ jFcjj= jFoj.
R
2
2
0:5
R
wðF2o ꢁ F2c Þ =
R
wðF2o Þ ꢂ
.
b

160
F.-J. Liu et al. / Journal of Molecular Structure 990 (2011) 158–163
Table 3
The hydrogen bond geometries for 1–3.
Complex 1
DAHꢀ ꢀ ꢀA
DAH
0.92
0.92
Hꢀ ꢀ ꢀA
2.17
2.29
Dꢀ ꢀ ꢀA
DAHꢀ ꢀ ꢀA
155
149
N1AH1Aꢀ ꢀ ꢀO5iii
3.027 (4)
3.118 (4)
N1AH1Bꢀ ꢀ ꢀO6iv
Symmetry codes: (iii) x + 1, y, z; (iv) ꢁx, ꢁy + 1, ꢁz + 1.
Complex 2
DAHꢀ ꢀ ꢀA
DAH
0.92
0.85
Hꢀ ꢀ ꢀA
2.31
1.92
Dꢀ ꢀ ꢀA
DAHꢀ ꢀ ꢀA
153
167
N1AH1Aꢀ ꢀ ꢀO1Wiii
O1WAH1WAꢀ ꢀ ꢀO1
Symmetry code: (iii) x, y + 1, z.
3.151 (9)
2.758 (7)
Complex 3
DAHꢀ ꢀ ꢀA
DAH
0.92
0.92
0.92
0.92
0.85
0.85
Hꢀ ꢀ ꢀA
2.08
2.03
2.17
2.06
2.04
1.90
Dꢀ ꢀ ꢀA
DAHꢀ ꢀ ꢀA
170
172
149
155
N1AH1Bꢀ ꢀ ꢀO2i
N3AH3Aꢀ ꢀ ꢀO2iii
N5AH5Aꢀ ꢀ ꢀO1Wiii
N5AH5Bꢀ ꢀ ꢀO1Wii
O1WAH1WAꢀ ꢀ ꢀO2iv
O1WAH1WBꢀ ꢀ ꢀO1
2.988 (3)
2.942 (3)
2.989 (4)
2.913 (4)
2.866 (3)
2.738 (3)
165
169
Symmetry codes: (i) x + 1, y + 1, z; (ii) ꢁx + 1, ꢁy + 2, ꢁz; (iii) x, y + 1, z; (iv) ꢁx, ꢁy + 1, ꢁz.
elemental analyses of 1–3 are fully consistent with their forma-
tions. Their IR spectra exhibit strong absorptions centered at
ꢃ3400 to ꢃ3100 cmꢁ1 corresponding to asymmetric and symmet-
ric NAH stretching bands of amino group as well as the OAH
stretching vibration of the water molecule. The peak at
ꢃ2200 cmꢁ1 can be assigned to the characteristic vibrations of
C„N of the cyano group. Strong characteristic bands of carboxylic
group are observed in the range of ꢃ1620–1580 cmꢁ1 for asym-
metric vibrations and ꢃ1480 cmꢁ1 for symmetric vibrations,
respectively.
4.2. Crystal structures
4.2.1. Crystal structure of {[Ag(p-abn)(dnca)]ꢀH2O}n (1)
X-ray single-crystal analysis reveals that 1 crystallizes in the
monoclinic space group P2(1)/c whose asymmetric unit contains
one Ag(I) ion, one p-abn ligand, one dnca anion and one lattice
water molecule. As shown in Fig. 1a, the center silver ion is coordi-
nated by two nitrogen atoms (one Namino and one Ncyano) from two
different p-abn ligands and two oxygen atoms from two carboxyl-
ate groups to form a distorted tetrahedral coordination geometry
Fig. 1. (a) The coordination environment of the Ag(I) ion and the linkage modes of ligands in 1 with 50% thermal ellipsoid probability. Water molecule and hydrogen atoms
are omitted for clarity. (b) The 2D network viewed along a axis. (c) Simplified 2D stair-shaped network. (d) The hydrogen bonds of adjacent network. (Symmetry codes: (i)
ꢁx + 1, ꢁy + 2, ꢁz + 1; (ii) ꢁx + 1, y + 1/2, ꢁz + 1/2.).

F.-J. Liu et al. / Journal of Molecular Structure 990 (2011) 158–163
161
[Ag1AN1 = 2.545(3), Ag1AN2ii = 2.435(3), Ag1AO1 = 2.214(2),
Ag1AO2i = 2.216(2) Å] without consideration of Agꢀ ꢀ ꢀAg interac-
tion. Notably, the AgAN bond lengths in 1 are obviously longer
than other reported AgANheterocycle bond [26–36] suggesting Namino
and Ncyano atoms are both weaker electron donor compared to
Nheterocycle atoms. The distortion of the tetrahedron can be indi-
cated by the calculated value of the s4 parameter introduced by
Houser [37] to describe the geometry of a four-coordinate metal
system, which is 0.64 for Ag1 (for perfect tetrahedral geometry,
4.2.2. Crystal structure of {[Ag(o-abn)(dnca)]ꢀH2O}n (2)
When p-abn is replaced by its isomer o-abn and react with Ag2O
and dnca ligand under the similar synthetic condition, a 1D chain
structure is produced, which crystallizes in the monoclinic space
group P2(1)/n. As shown in Fig. 2a, the asymmetric unit of 2
consists of one Ag(I) ion, one o-abn ligand, one dnca anion and
one lattice water molecule. The crystallographically independent
Ag1 ion is coordinated by two nitrogen atoms from two o-abn
ligands and two oxygen atoms from two dnca anions to form a
distorted tetrahedral coordination geometry [Ag1AN1 = 2.532(3),
Ag1AN2ii = 2.338(3), Ag1AO1 = 2.287(3), Ag1AO2i = 2.258(2) Å]
s
4 = 1). It is noteworthy that a pair of oppositely arranged l2-dnca
ligands bind two Ag(I) ions (average Ag-O = 2.215(4) Å) with a syn-
syn mode to form a [Ag2(dnca)2] eight-membered ring subunit. The
intra-subunit shortest Agꢀ ꢀ ꢀAg contact is 2.9262(6) Å, which is
obviously shorter than the twice the van der Waals radius of
Ag(I) [38] and indicates so-called argentophilic interaction [39–
43]. This distance is shorter than those (3.116(1) and 3.286(2) Å)
found in two reported infinite molecular ladders ([Ag(bipy)X],
without consideration of AgꢀꢀꢀAg interaction, then the
s4 parameter
is 0.69 for Ag1. Similarly, a pair of 2-dnca ligands with opposite
l
arrangement bind two Ag(I) ions (average AgAO = 2.273(5) Å) with
a syn-syn mode to form a [Ag2(dnca)2] eight-membered ring sub-
unit. The intra-subunit shortest Agꢀ ꢀ ꢀAg contact is 2.9441(8) Å
which is comparable to that in compound 1. On the other hand,
X ¼ H2POꢁ and MeCOꢁ2 Þ [44] and those (2.970(2)–3.312(1) Å)
two oppositely arranged l2-o-abn ligands linked four Ag(I) ions
4
found in other Ag(I) coordination polymers with pyridyl ligands
[45,46]. On the other hand, the binuclear Ag(I) units were linked
to form an infinite 2D network by p-abn ligands with opposite
from two subunits to form a [Ag4(o-abn)2] fourteen-membered
ring subunit incorporating Agꢀ ꢀ ꢀAg interaction. Those two kinds
of subunits interlock with each other to form a 1D infinite chain
(Fig. 2b and c).
As shown in Fig. 2d, the lattice water molecules (acceptor and
donor) interact with the amino (donor) and carboxylate (acceptor)
groups through hydrogen bonds which extend the 1D chain into
2D supramolecular sheet. (Symmetry codes: (i) ꢁx + 1, ꢁy + 1,
ꢁz; (ii) x + 1, y, z.).
arrangement in a l2
as nodes are connected via four
contacts to form a ladder-like hexagon, then the 2D structure can
be simplified into a stair-shaped network constructed by this kind
of hexagon (Fig. 1c).
- :
g1 g1 bridging mode (Fig. 1b). Six Ag(I) ions
l2-p-abn ligands and two Agꢀ ꢀ ꢀAg
As shown in Fig. 1d, between the adjacent networks, the amino
group (donor) of p-abn is hydrogen bonded to two oxygen atoms of
two different nitro groups with the Naminoꢀ ꢀ ꢀOnitro distances of
0
3.027(4) and 3.118(4) ÅA to form a R44(12) hydrogen bond motif
4.2.3. Crystal structure of {[Ag(m-abn)4)]ꢀ(dnca)ꢀH2O}n (3)
When using m-abn as N-donor ligand, a three-foothold shaped
0D compound 3 is obtained. It crystallizes in the triclinic space
group P-1. The asymmetric unit of 3 consists of one Ag(I) ion, four
[47]. This kind of hydrogen bond motif extends the 2D network
into
a 3D supramolecular framework. (Symmetry codes: (i)
ꢁx + 1, ꢁy + 2, ꢁz + 1; (ii) ꢁx + 1, y + 1/2, ꢁz + 1/2.).
Fig. 2. (a) The coordination environment of the Ag(I) ion and the linkage modes of ligands in 2 with 30% thermal ellipsoid probability. Water molecule and hydrogen atoms
are omitted for clarity. (b) The 1D chain structure viewed along b axis. (c) The 1D chain structure viewed along a axis. (d) The hydrogen bonds of adjacent chains. (Symmetry
codes: (i) ꢁx + 1, ꢁy + 1, ꢁz; (ii) x + 1, y, z.).

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F.-J. Liu et al. / Journal of Molecular Structure 990 (2011) 158–163
m-abn ligands, one dnca anion and one lattice water molecule. As
shown in Fig. 3a, Ag(I) ion adopts distorted [AgN4] tetrahedral
geometry where one N atom comes from cyano group of a m-abn
ligand and the rest N atoms are from the amino group of three
m-abn ligands. The AgANcyano bond length is 2.452(3) and the
AgANamino bond length fall in the range 2.327(3)–2.338(3) Å. The
the amino and cyano groups is turned from 180 to 60°, that is, p-
abn is replaced by o-abn, the hindrance effect between these two
groups has increased obviously, as a result, the similar [Ag2(dnca)2]
subunit of 2 cannot be extended to the 2D sheet, but only can form
a 1D chain structure by coordinating with o-abn ligand in a N,N0-
bidentate bridging fashion. The bond length of AgANamino and
AgANcyano decreases from 2.545(3) and 2.435(3) to 2.532(3) and
2.338(3) Å. When the h is modified to 120°, that is, o-abn is re-
placed by m-abn, the resulting structure of 3 is a 0D CC, at the same
time, dnca only acts as guest counteranion and does not interact
with the metal center. In all, different relative positions of amino
and cyano groups of aminobenzonitrile ligands bring different ste-
ric effects which intensely influence their coordination modes, as a
result, diverse structural motifs were formed.
s4 parameter is 0.81 for Ag1. Different from 1 and 2, the dnca anion
does not participate in the coordination with metal center and just
acts as guest counteranion in 3.
Two symmetry-related lattice water molecules act as acceptors
and are hydrogen-bonded to two amino groups to form a R24(8) mo-
tif (Fig. 3b). On the other hand, two symmetry-related lattice water
molecules also act as donors and are hydrogen-bonded to two nitro
groups to form a R44(12) motif. These two kinds of hydrogen bond
motifs share the edges to extend the 0D complex into a 1D supra-
molecular chain. The average NAHꢀ ꢀ ꢀO and OAHꢀ ꢀ ꢀO distances are
4.4. Photoluminescence properties
2.958(12) and 2.802(6) Å. The
p
ꢀ ꢀ ꢀ
p
and CAHꢀ ꢀ ꢀ
p interactions (as
shown in Table 4, average centroidꢀ ꢀ ꢀcentroid distance and dihe-
Emissive CCs are of great current interest because of their
various applications in chemical sensors, photochemistry and
electroluminescent display [49,50]. Thus, the photoluminescence
properties of 1–3 as well as free ligands were examined in the solid
state at room temperature (Fig. 4). The p-abn, o-abn and m-abn li-
gands display photoluminescent emissions at 339, 408 and 375 nm
respectively under 300 nm radiation which are probably attributed
dral angle are 3.867(2) Å and 4.3°, respectively, Fig. S1 and S2, Sup-
porting Information.
dCꢀ ꢀ ꢀCg = 3.547(3) Å, h = 163°, Fig. S3,
Supporting Information) also enhance the stability of the resulting
1D.
4.3. Influence of the relative position of amino and cyano groups of
aminobenzonitrile ligands
to the pꢄ
? p transition [51–53]. The intense emission bands at
336 nm (kex = 250 nm) for 1, 382 nm (kex = 300 nm) for 2 and
397 nm (kex = 300 nm) for 3 are observed at room temperature
which are similar to that of the corresponding aminobenzonitrile
ligands. Consideration of weak emissive essence of Hdnca ligand
[54], the photoluminescence of compound 1–3 should originate
from the transitions between the energy levels of N-donor ligands
[55].
Based on above analysis, the structural diversity of compounds
1 and 2 should be arisen from the different relative orientations of
amino and cyano groups situated in the benzene ring. In 1, p-abn
ligand, with an angle h [48] between the two groups of 180°,
adopts N,N’-bidentate bridging mode to extend the [Ag2(dnca)2]
subunit to a 2D network. However, when the angle h between
Fig. 3. (a) The coordination environment of the Ag(I) ion and the linkage modes of ligands in 3 with 50% thermal ellipsoid probability. Water molecule and hydrogen atoms
are omitted for clarity. (b) The 1D chain structure.
Table 4
pꢀ ꢀ ꢀp and CAHꢀ ꢀ ꢀp interactions in 3.
ring (i) ? ring (j)
Cgꢀ ꢀ ꢀCg(Å)
Dihedral angle (i,j) (°)
Cg(i) ? ring (j) (Å)
Cg(j) ? ring (i) (Å)
b [°]
Cg1ꢀ ꢀ ꢀCg2
3.877 (2)
3.764 (2)
3.974 (2)
3.853 (2)
Hꢀ ꢀ ꢀCg(Å)
2.63
7.30
7.30
1.30
1.30
3.6759 (13)
3.6712 (13)
3.4273 (14)
3.3675 (14)
Xꢀ ꢀ ꢀCg(Å)
3.5505 (14)
3.6035 (14)
3.4669 (13)
3.4044 (13)
23.67
16.80
29.26
27.92
Cg1ꢀ ꢀ ꢀCg2v
Cg4ꢀ ꢀ ꢀCg5iii
Cg4ꢀ ꢀ ꢀCg5i
X-H(i) ? Cg(j)
X-Hꢀ ꢀ ꢀCg[°]
C31-H71A ? Cg3vi
163
3.547(3)
Cg1: C1/C2/C3/C4/C5/C6; Cg2: C11/C12/C13/C14/C15/C16; Cg3: C21/C22/C23/C24/C25/C26; Cg4: C31/C32/C33/C34/C35/C36; Cg5: C41/C42/C43/C44/C45/C46.
Symmetry codes: (i) x + 1, y + 1, z; (iii) x, y + 1, z; (v) x + 1, y, z; (vi) ꢁx + 1, ꢁy + 3, ꢁz. b = Angle Cg(i) ? Cg(j) or Cg(i) ? Me vector and normal to ring (i).

F.-J. Liu et al. / Journal of Molecular Structure 990 (2011) 158–163
163
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This work was financially supported by the National Natural
Science Foundation of China (Nos. 21021061 and 21071118), 973
Project (Grant 2007CB815301) from MSTC. Dr. G.-G. Luo also
thanks the Startup Package Funding of Huaqiao University (No.
10BS210) for supporting.
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