The syntheses and structures of two silver compounds based on Phdat

Article abstract of DOI:10.1134/S107032841303010X

Based on the organic ligand 2,4-diamine-6-phenyl-1,3,5-triazine (Phdat), two Ag(I) compounds, Ag(Phdat)₂(NO₃) (I) and Ag(Phdat)₂(OAc) (II), have been synthesized and characterized by single crystal X-ray diffractions, elem

Full text of DOI:10.1134/S107032841303010X

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2013, Vol. 39, No. 3, pp. 293–296. © Pleiades Publishing, Ltd., 2013.
The Syntheses and Structures of Two Silver Compounds
Based on Phdat1
Y. M. Lia, *, C. Y. Xiaoa, Y. H. Xub, S. B. Wanga, and D. G. Yanga
a Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University,
Kaifeng, Henan, 475004 P.R. China
b Department of Medical Imaging, Bethune Medical NonꢀCommissioned Officer’s, College,
Shijiazhuang, Hebei, 050081 P.R. China
*eꢀmail: liyamin@henu.edu.cn
Received August 8, 2011
Abstract—Based on the organic ligand 2,4ꢀdiamineꢀ6ꢀphenylꢀ1,3,5ꢀtriazine (Phdat), two Ag(I) comꢀ
pounds, Ag(Phdat)2(NO3) (
crystal Xꢀray diffractions, elemental analyses, and IR spectra. Compounds
binuclear structures, respectively, and with the help of N–H⋅⋅⋅O and N–H⋅⋅⋅N hydrogen bonds and π⋅⋅⋅π
I) and Ag(Phdat)2(OAc) (II), have been synthesized and characterized by single
I
and II are mononuclear and
packing interactions, the 3D supramolecular networks are built up.
DOI: 10.1134/S107032841303010X
1
INTRODUCTION
tometer using KBr pellets in the range of 400–
4000 cm–1. Elemental analyses were performed via
Vario EL III Etro Elemental Analyzer. Thermograviꢀ
metric analysis (TGA) was performed under atmoꢀ
In past few decades some coordination compounds
have been synthesized, exhibit diverse structural
motifs, as well as showing potential applications in gas
storage [1], as magnetic [2] and optoelectronic mateꢀ
rials [3]. The key factor that influences the structures
and properties is the choice of the organic ligands.
Good ligands not only provide the donor atoms at speꢀ
cific positions to coordinate the metal ion, but also
provide potential interaction sites to generate noncoꢀ
valent interactions, such as hydrogenꢀbonding and
sphere with a heating rate of 10
TGA/SDTA851e.
°
C min–1 using
Xꢀray crystallography. The colorless block crystals
of compounds and II were selected for Xꢀray diffracꢀ
tion analyses, with dimensions of 0.44 0.37
0.23 mm and 0.20 0.14 0.11 mm. Xꢀray singleꢀ
I
×
×
×
×
crystal data were collected at 296(2) K on a Bruker
ApexꢀII CCD areadetector diffractometer with a
π
⎯
π
stacking interactions. 2,4ꢀDiamineꢀ6ꢀRꢀ1,3,5ꢀ
triazine (R = NH2, Phenyl, CH3) are the desired
ligands [4–8], which contain five nitrogen atoms, two
Mo
K
radiation ( = 0.71073 Å). Data reduction and
λ
α
amino nitrogen atoms considered as perfect Hꢀbond absorption correction were made with empirical
donors, three triazineꢀnitrogen atoms being apt to
coordinate to transition metals especially silver(I) or
as Hꢀbond acceptors. Besides, aromatic rings can proꢀ
methods. The structure was solved by direct methods
and refined by fullꢀmatrix leastꢀsquares techniques
using SHELXLꢀ97 [10]. Anisotropic displacement
parameters were refined for all nonꢀhydrogen atoms,
and all hydrogen atoms were added in the riding model
without refinement. Crystal data and refinement
details are presented in Table 1.
vide potential
π
– stacking interactions.
π
So herein, we used 2,4ꢀdiamineꢀ6ꢀphenylꢀ1,3,5ꢀ
triazine (Phdat) and Ag+ ion as the starting materials,
and synthesized two compounds, Ag(Phdat)2(NO3)
(I) and Ag(Phdat)2(OAc) (II). As far as we know, the
related compounds with Phdat are seldom reported
[9].
Supplementary material for structures of
I and II
has been deposited with the Cambridge Crystalloꢀ
graphic Data Centre (nos. 836177 and 836178;
deposit@ccdc.cam.ac.uk
cam.ac.uk).
or
http://www.ccdc.
EXPERIMENTAL
Materials and physical measurements. AgNO3,
AgOAc are of A.R. grade and used as purchased. Phdat
(99+%) is purchased from ACROS. Infrared spectra
were recorded on a Nicolet 170 FTꢀIR spectrophoꢀ
Synthesis of I. AgNO3 (2 mmol), Phdat (1 mmol)
and H2O (10 mL) were added to a Teflonꢀlined vessel,
with stirring about 20 min. Then the mixture was
sealed in stainlessꢀsteel autoclave and heated to 120
°
C
1
The article is published in the original.
for 72 h, then cooled to room temperature. Colorless
293

294
LI et al.
Table 1. Crystallographic data and details of the experiment
RESULTS AND DISCUSSION
and refinement of complexes
I
and II
The Ag(I) atom of
ring N atoms of two monodentate Phdat ligands,
I
is coordinated by two triazine
Value
forming a broken line with NAgN angle of 145.39(12)
°
Parameter
I
II
(Fig. 1a), smaller than that of the similar mononuclear
compound Ag(melamine)2NO3 [11] as well as that of
the compound [Ag(Phdat)](BF4) [9]. The Ag–N
lengths are about 2.197(3)–2.210(3) Å. Two neighꢀ
bouring Ag+ ions are linked by Ag–O weak interacꢀ
tions with Ag–O bond distances of 2.807 and 2.860 Å,
where Ag+ ion formed in distorted tetrahedron. Simiꢀ
lar interactions are also found in Ag(melamine)2NO3,
[Ag(NO3)(melamine)]n and [Ag(melamine)2]ClO4
[12, 13], where Ag–O distances are 2.7924 and
M
544.30
Monoclinic
21/
541.34
Crystal system
Space group
Orthorhombic
Pnnm
P
n
a
, Å
, Å
12.2311(7)
13.1227(8)
13.4304(7)
93.2730(10)
2152.1(2)
4
12.9113(9)
14.8538(11)
12.0376(9)
90
b
c
, Å
2.569 Å, respectively, shorter than that of I.
β
V
Z
ρ
F
μ
, deg
, Å3
In the Phdat ligand, the triazine rings are practiꢀ
cally perfectly flat (aplanarities 0.0070 and 0.0074 Å),
but the phenyl rings show more aplanar with the root
mean square aplanarities of 0.0108 and 0.0123 Å. The
2308.6(3)
4
, mg/m–3
(000)
, mm–1
1.680
1.558
interplanar angles of two rings in the ligands are 6.2
and 31 . As shown in Fig. 2a, in the structure of the
compound , there are two noticeable motives for
assembly between the elemental building blocksꢀ
namely, triazineꢀphenyl and triazineꢀtriazine
stacking. Obviously the triazineꢀphenyl stacking
°
1096
1096
°
0.983
0.912
I
Reflections measured
9215
12834
π π
–
Independent reflections
3777
2983
π–π
interaction is stronger than that of triazineꢀtriazine,
which can be seen by the vertical planeꢀplane disꢀ
tances between two rings, 3.45 and 3.95 Å, respecꢀ
tively, compared with the reported [14–16]. The cenꢀ
troidꢀcentroid distances are 3.54 and 4.23 Å, with the
Rint
0.0219
0.0641
1.016
GOOF
Ra
Rwb
1.085
0.0392
0.0509
0.1205
0.000/0.000
0.1008
angles between planes of 6.2
°
and 0
°
, respectively. The
Largest and mean
delta/sigma
0.000/0.000
stacking extends along axis direction and leads to the
x
formation of 2D layer structure.
Between the neighbouring layers, the hydrogen
bonds help to construct 3D network, which are
Largestdifferencepeak, 0.708/–0.629 0.790/–0.840
/Å3
e
N⎯H⋅⋅⋅N hydrogen bonds between NH2 and the
uncoordinated triazine–N atoms, N–H⋅⋅⋅O hydrogen
bonds between NH2 and NO–3 (Table 2).
As we know, CH3COO– group is one excellent
bridging ligand, in complex II, both Ag(I) atoms,
besides coordinated by two triazine ring N atoms of
a
b
Note:
R
=
Σ
(||
F
|
–
2
|
F
c||)/
= 1/[
= 0.0502,
Σ
|
F
|,
Rw
=
o
o
2
2
[(F2o – F2c ) ]
/
Σ
w
[(F2o) ]},
w
σ
(Fo) + (aP) +
= 1.6661; II: a =
2
2
{
Σ
w
bP],
P
=
(F2o + 2F2c ) /3].
I
:
a
b
0.0601,
b
= 0.5153.
two monodentate Phdat ligands, are bridged by two
I
μ2:η
:
IꢀCH3COO– groups, forming distorted tetraꢀ
η
block crystals
I were obtained (0.15 g, yield 27.6%
hedron configurations with the bond angles in the
range of 99.87(9) –133.61(15) (Fig. 1b). The Ag–N
lengths are about 2.292(4)–2.347(5) Å, which are
longer than those of . The Ag–O length is 2.372(3) Å.
In Phdat, the triazine ring (C(1), C(2), C(3), C(4),
C(1 ), C(2 )) shows more aplanar (aplanarity of
based on Phdat).
°
°
For C18H18N11O3Ag
I
anal. calcd., %: C, 39.72;
H, 3.33;
H, 3.07;
N, 28.31.
N, 28.01.
Found, %:
C, 39.33;
A
A
0.0493 Å) than other phenyl and triazine rings (aplaꢀ
narities 0.0140, 0.0105 and 0.0165 Å). The interplanar
Synthesis of II. Replacement of AgNO3 (2 mmol)
by AgOAc (2 mmol), a small amount of colorless block
crystals II were obtained.
angles of two rings in the ligands are 0.9
°
and 9.2 ,
°
smaller than that (31 ) of , so more offset π⋅⋅⋅π stackꢀ
°
I
ing interactions are found in II. From Fig. 2b, all of the
aromatic rings of II containing benzene and triazine
rings involves in π⋅⋅⋅π stacking interactions, namely,
benzeneꢀtriazine π⋅⋅⋅π stacking interactions, which
help the dinuclear units forming 2D network. The verꢀ
For C20H21N10O2Ag
anal. calcd., %: C, 44.38;
Found, %: C, 44.08;
H, 3.91;
H, 4.22;
N, 25.88.
N, 25.52.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 39
No. 3
2013

THE SYNTHESES AND STRUCTURES OF TWO SILVER COMPOUNDS
(a)
(a)
295
O(3)
N(11)
O(2)
O(1)
N(5)
C(8)
3.45 Å
N(9)
C(17)
N(8)
C(13)
C(14)
N(2)
C(7)
C(12)
C(11)
C(16)
C(5)
Ag(1)
N(6)
C(18)
N(7)
N(3)
C(4)
C(3)
C(2)
C(9)
C(15)
C(10)
C(6)
N(1)
N(4)
3.95 Å
3.95 Å
N(10)
C(1)
(b)
3.45 Å
C(7)
C(8)
C(9)
C(11)
N(3)
C(12)
N(4)
C(10)
y
z
N(1)
(b)
Ag(1)
C(13)
O(1)
N(2)
C(14)
N(5)
C(5)
C(6)
N(6)
C(4)
3.49 Å
3.49 Å
3.77 Å
C(1)
C(2)
3.77 Å
C(3)
3.77 Å
3.49 Å
3.77 Å
Fig. 1. The ellipsoid diagram at 30% of compounds
and II (b).
I (a)
3.49 Å
y
tical planeꢀplane distances between triazine and pheꢀ
nyl are 3.49 and 3.77 Å and the centroidꢀplane disꢀ
tances are 3.61 and 3.84 Å, with angles between planes
x
of 9.2
°
and 0.9 .
°
Between the neighbouring 2D layers, there are sevꢀ
eral hydrogen bonds containing N–H⋅⋅⋅N hydrogen
bonds between NH2 and the uncoordinated triazine–N
atoms, N–H⋅⋅⋅O hydrogen bonds between NH2 and
CH3COO–, resulting in the formation of 3D hydrogen
bonds network (Table 2).
Fig. 2.
π
–π
diagram in compound
I
(a) and II (b).
Weight, %
100
IR spectra of I and II are similar for their structural
80
60
40
similarity. The stretching vibrations of N–H and C–H
are found ranging from 3500 to 3100 cm–1. The peaks
at about 1650–1500 cm–1 are attributed to the aroꢀ
matic rings stretching, 820–700 cm–1 for the rings
C
⎯
H inꢀplane vibration and outꢀofꢀplane vibration.
TGA was performed for from Fig. 3, at approxiꢀ
mately 200 C, the compound started a first sharp
mass loss of 40%, which suggested the compound
doesn’t contain small solvent molecules, correspondꢀ
ing to the structure. In succession, from 300 to 550 C,
I
°
I
I
20
0
°
200
400
600
800
two mass reductions were observed and finally 20.1%
of the remnants were left, which should be Ag (19.8%
calculated).
Temperature, °C
Fig. 3. TGA diagram for the compound
I.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 39
No. 3 2013

296
LI et al.
Table 2. Important hydrogenꢀbonding interactions present
in compounds and II
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RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 39
No. 3
2013