Synthesis, structures, and luminescent properties of d10 group 12 metal complexes with substituted 2,2′-bipyridine ligands

Article abstract of DOI:10.1002/ejic.200600262

Four d¹⁰ group 12 metal complexes, 6-(2-methoxyphenyl)-2, 2′-bipyridinezinc dichloride (2a), -mercury dichloride (2b), 6-[2-(dimethylamino)phenyl]-2,2′-bipyridinezinc dichloride (2c), and -mercury dichloride (2d), were synthesized and the struc

Full text of DOI:10.1002/ejic.200600262

FULL PAPER
DOI: 10.1002/ejic.200600262
Synthesis, Structures, and Luminescent Properties of d10 Group 12 Metal
Complexes with Substituted 2,2Ј-Bipyridine Ligands
Xiao-ming Liu,[a] Xiao-yue Mu,[a] Hong Xia,[a,b] Ling Ye,[a] Wei Gao,[a] Hao-yu Wang,[a] and
Ying Mu*[a]
Keywords: Group 12 metal complexes / 2,2Ј-Bipyridine / Solid-state structures / Luminescence
Four d10 group 12 metal complexes, 6-(2-methoxyphenyl)-
2,2Ј-bipyridinezinc dichloride (2a), -mercury dichloride (2b),
6-[2-(dimethylamino)phenyl]-2,2Ј-bipyridinezinc dichloride
(2c), and -mercury dichloride (2d), were synthesized and the
structures determined by single-crystal X-ray crystallogra-
phy. Complexes 2a and 2b are four-coordinate and adopt a
distorted tetrahedral geometry, while complexes 2c and 2d
are five-coordinate with a distorted trigonal bipyramidal ge-
ometry for the metal center. Luminescent properties of com-
plexes 2a–2d in both solution and the solid state were
studied.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
modified bipyridine ligands that are synthesized by intro-
ducing an aromatic group with a donor at its α position to
the 3-position of 2,2Ј-bipyridine. The ligands were selected
considering that larger conjugating systems can be formed
in their complexes and better luminescent properties might
be expected. We herein report on the preparation, structural
characterization, and photoluminescence of these zinc(II)
and mercury(II) complexes.
Introduction
Luminescent coordination complexes have attracted in-
creasing attention because of their potential application in
areas of optoelectronic devices and chemical sensors.[1] One
of the most important considerations in organic light-emit-
ting diodes (OLEDs) is the design and synthesis of mole-
cules capable of tuning luminescent properties through the
modification of ligands.[2,3] The organic compounds with
aromatic nitrogen heterocycles, which can be receptors for
metal ions, have been studied extensively because they are
capable of performing useful light- and/or redox-induced
tasks. For example, a large number of complexes based on
8-hydroxyquinoline, 7-azaindole, pyridyl-phenol, and
phenyl-pyridine have been investigated during the last dec-
ades.[3–5] Particularly, luminescent complexes of ReI,[6]
RuII,[7] and OsII[8] containing bipyridine type ligands have
attracted much attention because of their high luminescent
efficiency. However, the lower synthetic yields and higher
costs of these complexes are disadvantages for their use as
optoelectronic materials. The lower-cost d10 metal com-
plexes with the nitrogen-containing ligands are of interest
because of their photoluminescent and/or electrolumines-
cent properties.[9–11] To develop new complexes of this type
with improved luminescent performance, we have synthe-
sized four new complexes of zinc(II) and mercury(II) with
Results and Discussion
Synthesis of Compounds
Ligand 1a was prepared according to a known procedure
(Scheme 1)[12] and ligand 1b was synthesized by the reaction
of dry 2,2Ј-bipyridine with the aryllithium reagent, ob-
tained from the treatment of 2-bromo-N,N-dimethylaniline
with nBuLi, in moderate yield after oxidative rearomatiza-
tion. Ligand 1a is a known compound while 1b is a new
compound. The new ligand 1b was characterized by 1H
1
NMR spectroscopy along with elemental analysis. The H
NMR spectrum of 1b exhibits resonance at δ = 2.77 ppm
for the CH3 proton. Compound 1b is soluble in most or-
ganic solvents. Treatment of ZnCl2 and HgCl2 with equiva-
lent free ligands in methanol at ambient temperature af-
forded the corresponding d10 metal complexes 2a–2d in
good yields (Ͼ80%) as light yellow or white crystalline sol-
ids (Scheme 1). Complexes 2a–2d were all characterized by
elemental analyses, 1H NMR spectroscopy, and IR spec-
troscopy, and satisfactory analytic results were obtained on
all compounds. All complexes are moderately soluble in
DMSO, slightly soluble in dichloromethane, methanol,
DMF, and THF, and insoluble in saturated hydrocarbon
solvents.
[a] Key Laboratory for Supramolecular Structure and Materials of
Ministry of Education, School of Chemistry, Jilin University,
2699 Qianjin Street, Changchun 130012, People’s Republic of
China
Fax: +86-431-5193421
E-mail: ymu@mail.jlu.edu.cn
[b] State Key Laboratory of Integrated Optoelectronics, College of
Electronic Science and Technology, Jilin University,
Changchun 130012, People’s Republic of China
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FULL PAPER
Scheme 1. Synthetic procedure of ligands 1a and 1b, and of complexes 2a–2d.
Crystal Structure
The molecular structures of complexes 2a, 2b, 2c, and 2d
were determined by X-ray crystallographic analysis. Crys-
tals of all four complexes suitable for X-ray crystal structure
Figure 1. Top: molecular structure of complex 2a; bottom: crystal
packing diagram between two adjacent molecules of 2a showing
the lack of a π–π stacking interaction in the solid state. (Thermal
ellipsoids are drawn at the 30% probability level.)
Figure 2. Top: molecular structure of complex 2b; bottom: the π–
π stacking column structure of complex 2b. (Thermal ellipsoids are
drawn at the 30% probability level.)
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d10 Group 12 Metal Complexes with Substituted 2,2Ј-Bipyridine Ligands
FULL PAPER
determination were grown from dichloromethane or than the one [70.04(10)°] in its mercury analog 2b. The dihe-
CH3CN at room temperature. The ORTEP drawings of the dral angles between the two pyridyl rings are 10.1° for 2a
molecular structures of 2a and 2b are shown in Figure 1 and 2.2° for 2b, and the dihedral angles between the aro-
and Figure 2, respectively. Selected bond lengths and angles matic ring and the adjacent pyridyl ring are 61.0° for 2a
for the two complexes are given in Table 1. The X-ray and 50.7° for 2b. The data of the dihedral angles in two
analysis reveals that both complexes adopt a distorted tetra- complexes indicate that the conjugated extent of 2b is larger
hedral geometry with the metal center chelated by the li- than that of 2a. In addition, there is π–π stacking between
gand 1a through the pyridine nitrogen atoms, and the oxy- the pyridyl rings of two neighboring molecules for complex
gen atom does not coordinate to the metal center in either 2a in the solid state, forming an antiparallel dimeric struc-
complex because of the weak donating ability of the –OMe ture (Figure 1 bottom). The distance between two pyridyl
group. The Zn–N bond lengths in 2a are 2.071 Å (average), planes is 3.51 Å.[15] In contrast, a π–π stacking column
which is close to the values previously reported for similar structure was observed in 2b (Figure 2 bottom). In the col-
tetrahedral zinc complexes.[13] In complex 2b, the two Hg– umn each molecule of 2b forms antiparallel π–π stacking
N bond lengths are slightly different [2.363(3) Å for Hg(1)– with two adjacent molecules. The distances between the
N(1) and 2.356(3) Å for Hg(1)–N(2)]. The values are consis- stacked aromatic planes are 3.46 Å and 3.50 Å, respectively.
tent with bond lengths found in other four-coordinate HgII A similar π–π stacking column structure was also observed
complexes.[13c,14] The average MII–N(pyridyl) bond dis- in HgII complexes.[13c]
tances (2.071 Å for Zn–N Ͻ 2.359 Å for Hg–N) are consis-
The molecular structures of complexes 2c and 2d are
tent with ionic radii. The N–Zn–N bite angle in 2a given in Figure 3 and Figure 4, respectively. Important
[80.27(10)°] is smaller than those found in other pyridyl- bond lengths and angles are listed in Table 1. The crystal
containing four-coordinate ZnII complexes,[13a] but larger structure analysis reveals that complexes 2c and 2d are five-
coordinate and adopt distorted trigonal bipyramidal geom-
etry for the metal center. The ligand 1b binds to the metal
center in tridentate form by three nitrogen atoms, and there-
Table 1. Selected bond lengths (Å) and bond angles (°) for com-
plexes 2a–2d.
Complex 2a
Zn(1)–N(1)
Zn(1)–N(2)
Zn(1)–Cl(1)
Zn(1)–Cl(2)
N(2)–C(1)
2.079(2)
2.062(2)
2.2042(10)
2.2104(10)
1.333(4)
1.342(4)
N(1)–Zn(1)–Cl(1)
N(2)–Zn(1)–Cl(2)
N(1)–Zn(1)–Cl(2)
Cl(1)–Zn(1)–Cl(2) 117.18(4)
C(1)–N(2)–Zn(1)
C(5)–N(2)–Zn(1)
123.53(8)
115.07(8)
108.76(7)
125.8(2)
113.69(19)
N(1)–C(10)
N(2)–Zn(1)–N(1) 80.27(10)
N(2)–Zn(1)–Cl(1) 106.30(8)
C(10)–N(1)–Zn(1) 127.7(2)
C(6)–N(1)–Zn(1) 113.09(19)
Complex 2b
Hg(1)–N(1)
Hg(1)–N(2)
Hg(1)–Cl(1)
Hg(1)–Cl(2)
N(1)–C(1)
2.363(3)
2.356(3)
2.3791(14)
2.4140(12)
1.344(5)
1.344(5)
N(1)–Hg(1)–Cl(1) 118.49(9)
N(2)–Hg(1)–Cl(2) 116.07(8)
N(1)–Hg(1)–Cl(2) 100.44(9)
Cl(1)–Hg(1)–Cl(2) 122.98(4)
C(6)–N(2)–Hg(1)
116.8(2)
N(2)–C(10)
C(10)–N(2)–Hg(1) 123.1(2)
N(2)–Hg(1)–N(1) 70.74(10)
N(2)–Hg(1)–Cl(1) 115.30(8)
C(5)–N(1)–Hg(1)
C(1)–N(1)–Hg(1)
116.9(2)
123.6(3)
Complex 2c
Zn(1)–N(1)
Zn(1)–N(2)
Zn(1)–N(3)
Zn(1)–Cl(2)
Zn(1)–Cl(1)
N(1)–Zn(1)–N(2) 76.34(6)
Cl(2)–Zn(1)–Cl(1) 118.74(3)
N(1)–Zn(1)–N(3) 157.87(6)
2.1413(16)
2.1425(16)
2.3076(16)
2.2454(8)
2.3066(7)
N(2)–Zn(1)–N(3)
N(2)–Zn(1)–Cl(2)
N(2)–Zn(1)–Cl(1)
Cl(2)–Zn(1)–N(3)
Cl(1)–Zn(1)–N(3)
Cl(2)–Zn(1)–N(3)
Cl(1)–Zn(1)–N(3)
C(1)–N(1)–Zn(1)
84.17(6)
118.54(5)
122.65(5)
97.37(5)
91.39(4)
97.37(5)
91.39(4)
125.53(14)
Complex 2d
Hg–N(1)
Hg–N(2)
Hg–N(3)
Hg–Cl(1)
2.381(10)
2.440(9)
2.584(10)
2.440(3)
2.406(3)
68.8(3)
N(2)–Hg–N(3)
N(1)–Hg–Cl(2)
Cl(2)–Hg–N(2)
N(1)–Hg–Cl(1)
N(2)–Hg–Cl(1)
Cl(2)–Hg–N(3)
Cl(1)–Hg–N(3)
C(1)–N(1)–Hg
76.9(3)
112.4(2)
113.2(2)
91.4(2)
121.9(2)
99.1(2)
89.9(2)
121.3(9)
Hg–Cl(2)
N(1)–Hg–N(2)
Cl(1)–Hg–Cl(2)
N(1)–Hg–N(3)
Figure 3. Top: molecular structure of complex 2c; bottom: the π–
π stacking dimer structure of complex 2c. (Thermal ellipsoids are
drawn at the 30% probability level.)
124.77(13)
140.1(3)
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X.-M. Liu, X.-Y. Mu, H. Xia, L. Ye, W. Gao, H.-Y. Wang, Y. Mu
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fore a five-membered metallacycle and a six-membered solution and the solid state. In solution, the free ligands
metallacycle are constructed. The N(1)–Zn(1)–N(2), N(2)– 1a and 1b have emission bands at λmax = 431 and 396 nm,
Zn(1)–N(3), and Cl(1)–Zn(1)–Cl(2) angles are 76.34(6), respectively. In comparison with the free ligand 1a, com-
84.17(6), and 118.74(3)° in 2c, respectively. The Zn–N bond plexes 2a and 2b in solution give a broad emission band
lengths, ranging from 2.1413(16) Å [Zn(1)–N(1)] to (bandwidth at half-height = 80–95 nm) with λmax = 447 nm
2.3076(16) Å [Zn(1)–N(3)], are within the range of 2.098– and 452 nm, respectively, as shown in Figure 5. The emis-
2.321 Å observed for similar complexes,[16] while they are sion maxima of the two complexes are slightly red-shifted
longer than those (2.079 and 2.062 Å) in the four-coordi- compared to that of the free ligand. In contrast to com-
nate complex 2a. The dihedral angles between the two pyr- plexes 2a and 2b, the emission maxima of 2c and 2d in solu-
idyl rings, and between the pyridyl ring and the adjacent tion are almost the same as that of the free ligand 1b (see
aromatic ring are 18.0° and 47.7° for 2c and 19.1° and 56.3° Figure 6). The luminescence of these complexes should be
for 2d, respectively. In solid state, molecules of 2c are paired attributed to the transition from π* to π of their ligands. In
up through intermolecular π–π stacking of the ligand, re- solution, complex 2a shows a strongly solvent-dependent
sulting in the formation of a dimeric structure (Figure 3, emission band and its emission maximum shifts toward a
bottom). The distance between the planes of the π–π shorter wavelength with the increase in polarity of the sol-
stacked ligand is 3.53 Å. Similar to complex 2b, a π–π vent. As shown in Figure 7, the emission maximum of 2a is
stacking column structure was also observed in the mercury 461 nm in dichloromethane, while it becomes 358 nm in the
complex 2d (Figure 4, bottom). The distances between the polar solvent DMF. This is a rare case, as a red-shift of the
stacked aromatic planes are 3.42 and 3.65 Å, respectively. emission maximum would be expected for most compounds
The intermolecular π–π interactions suggest that complexes when solvent polarity increases. The observed blue-shift
2a–2d can possess charge transport property, which is essen- phenomenon might be attributed to the presence of a highly
tial for electroluminescent material.[17]
polarized ground state.[18] The quantum yields of all com-
pounds have been determined in solution. It was found that
the quantum yields of the ZnII complexes 2a and 2c are
slightly higher than those of their free ligands, while the
quantum yields of the HgII complexes 2b and 2d are lower
than those of their free ligands. These results can be easily
understood considering the following factors: the ligand be-
comes more rigid after coordination with a metal atom,
which can reduce the loss of energy by vibrational motions
and therefore increase the emission efficiency. On the other
hand, the HgII cation and the chloride anions can quench
the fluorescence and result in luminescence decay. The
quantum yields of complexes 2a and 2b are similar to those
of four-coordinate zinc(II) complexes.[13b] The efficiency of
1a and its corresponding complexes is about 20 times higher
than that of 1b and its corresponding complexes, probably
because, in comparison with the –OMe group, the bulkier
–NMe2 group reduces the conjugated length and increases
vibrational motion in 1b, 2c, and 2d. The emission spectra
of compounds 1a, 1b, 2a, 2b, and 2c in the solid state are
Table 2. Photoluminescent data for ligands 1a and 1b and com-
plexes 2a–2d.
Abs. λ (nm) Ex λ (nm)
Em λ
(nm)
Quantum
yields[a]
Conditions
1a
1b
2a
2b
2c
2d
273, 313
275, 310
340, 356
339, 353
309, 343
305, 340
374
340
374
374
340
340
431
458, 536
394
444
447
397
452
410
395
0.108
0.005
0.113
0.083
0.006
0.003
CHCl3, 298 K
solid, 298 K
CHCl3, 298 K
solid, 298 K
CHCl3, 298 K
solid, 298 K
CHCl3, 298 K
solid, 298 K
CHCl3, 298 K
solid, 298 K
CHCl3, 298 K
Figure 4. Top: molecular structure of complex 2d; bottom: the π–
π stacking column structure of complex 2d. (Thermal ellipsoids are
drawn at the 30% probability level.)
564
394
Luminescence Properties
Table 2 summarizes the UV/Vis and fluorescent proper-
[a] Determined using quinine sulfate in sulfuric acid (0.1 ⁾ as a
ties of compounds 1a, 1b and 2a–2d determined in both standard in DMF at ambient temperature.
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d10 Group 12 Metal Complexes with Substituted 2,2Ј-Bipyridine Ligands
FULL PAPER
shown in Figure 8. Except for 2d, all compounds in solid and 410 nm, respectively. The emission maxima of 2a and
state emit bright fluorescence when irradiated by exciting 2b in the solid state are blue-shifted compared to emission
light. The emission maxima of 1a, 2a, and 2b are 536, 397, maximum of their ligand 1a, while the emission maximum
of complex 2c (λmax = 564 nm) in the solid state is red-
shifted compared to that (λmax = 444 nm) of its correspond-
ing ligand 1b. These properties are probably a result of their
π-stacking structures in the solid state.
Figure 5. Excitation and emission spectra of compounds 1a, 2a,
and 2b in chloroform (ca. 1×10–5 M).
Figure 8. Emission spectra of compounds 1a, 1b, 2a, 2b, and 2c in
the solid state.
Conclusions
We have described the syntheses and X-ray structures of
a number of d10 group 12 metal complexes supported by
two substituted 2,2Ј-bipyridine ligands. Crystal structure
analysis reveals crystal structures of these complexes are
different from each other. It was found that antiparallel di-
meric structures are formed for complexes 2a and 2c while
one-dimensional supramolecular structures are constructed
for complexes 2b and 2d by π–π stacking in the solid state.
These complexes produce fluorescence in both solution and
the solid state, and the emission color in the solid state is
dramatically affected by their packing structures.
Figure 6. Excitation and emission spectra of compounds 1b, 2c,
and 2d in chloroform (ca. 1×10–5 M).
Experimental Section
All reactions were performed using standard Schlenk techniques in
high-purity nitrogen or glovebox techniques. Toluene and diethyl
ether were dried by refluxing over sodium and benzophenone and
distilled under nitrogen prior to use. CDCl3 was dried with CaH2
for 48 h and vacuum-transferred to an air-free flask. ZnCl2, HgCl2,
and nBuLi were purchased from Aldrich and used as received.
NMR spectra were measured using a Varian Mercury-300 NMR
spectrometer. The elemental analysis was performed with a Perkin–
Elmer 2400 analyzer. UV/Vis absorption spectra were recorded
with a UV-3100 spectrophotometer. Fluorescence measurements
were carried out on an RF-5301PC.
6-[2-(Dimethylamino)phenyl]-2,2Ј-bipyridine (1b):
A solution of
nBuLi (30.32 mL, 48.5 mmol) in hexanes was added to a solution
of 2-bromo-N,N-dimethylaniline (9.7 g, 48.5 mmol) in Et2O
(30 mL) under nitrogen at –78 °C. The mixture was allowed to
warm to room temperature and stirred overnight. The resulting
Figure 7. Emission spectra of complex 2a in various solvents (ca.
1×10–5 M).
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mixture was added dropwise to an ice-cooled solution of 2,2Ј-bipyr- filtering, the light yellow precipitate was collected and washed with
idine (7.57 g, 48.5 mmol) in degassed Et2O (30 mL), and a wine- cold methanol. Pure product was obtained in 83% yield (0.34 g) by
red solution was obtained immediately. The resultant mixture was recrystallization from CH3CN. C17H14Cl2HgN2O (533.80): calcd.
1
refluxed for 24 h and cooled in an ice bath, then deionized water C 38.25, H 2.64, N 5.25; found C 38.44, H 2.86, N 5.03. H NMR
(25 mL) was added to hydrolyze the products. The yellow organic (300 MHz, [D6]DMSO, 293 K): δ = 3.35 (s, 3 H, CH3), 7.20 (t, 1
phase was separated and stirred with MnO2 for 24 h, then filtered H), 7.23 (d, 1 H), 7.44–7.51 (m, 2 H), 7.91–7.98 (m, 4 H), 8.31 (d,
and dried with MgSO4. The solid was obtained upon concentration 1 H), 8.47 (d, 1 H), 8.73 (d, 1 H) ppm. IR (KBr): ν = 3075 w, 3023
˜
of the solution, and chromatography on silica gel with dichloro- w, 2980 w, 2933 w, 2828 w, 1588 s, 1571 m, 1485 s, 1440 s, 1386 m,
methane as eluent afforded a light yellow solid. Yield: 6.7 g (50%). 1283 m, 1262 s, 1238 s, 1179 m, 1159 m, 1109 m, 1055 w, 1017 s,
C18H17N3 (275.35): calcd. C 78.52, H 6.22, N 15.26; found C 78.32, 1000 s, 946 w, 894 w, 859 w, 824 w, 779 s, 754 s, 734 m, 633 m, 577
1
H 6.41, N 15.10. H NMR (300 MHz, CDCl3, 293 K): δ = 2.77 (s, w, 616 w.
6 H, CH3), 7.17 (d, 1 H), 7.32–7.40 (m, 2 H), 7.76–7.84 (m, 4 H),
6-[2-(Dimethylamino)phenyl]-2,2Ј-bipyridinezinc Dichloride (2c): A
7.99 (d, 1 H, J = 7.8 Hz), 8.30 (d, 1 H, J = 7.8 Hz), 8.49 (d, 1 H,
methanol solution (10 mL) of 1b (0.2 g, 0.73 mmol) was added to
J = 5.4 Hz), 8.71 (d, 1 H, J = 4.8 Hz) ppm.
a methanol solution (15 mL) of ZnCl2 (0.11g, 0.74 mmol). The re-
6-(2-Methoxyphenyl)-2,2Ј-bipyridinezinc Dichloride (2a): A meth- action mixture was stirred for 4 h at room temperature. After filter-
anol solution (10 mL) of 1a (0.2 g, 0.76 mmol) was added to a ing, the light yellow precipitate was collected and washed with cold
methanol solution (10 mL) of ZnCl2 (0.11 g, 0.77 mmol). The reac- methanol. Pure product was obtained in 82% yield (0.25 g) by
tion mixture was stirred for 4 h at room temperature. After filter- recrystallization from CH3CN/CH2Cl2. C18H17Cl2N3Zn (411.64):
ing, the light yellow precipitate was collected and washed with cold calcd. C 52.52, H 4.16, N 10.21; found C 52.71, H 4.26, N 10.03.
methanol. Pure product was obtained in 81% yield (0.25 g) by 1H NMR (300 MHz, [D6]DMSO, 293 K): δ = 2.59 (s, 6 H, CH3),
recrystallization from CH3CN/CH2Cl2. C17H14Cl2N2OZn (398.60): 7.13–7.20 (m, 2 H), 7.39 (t, 1 H), 7.52 (s, 1 H), 7.61 (d, 1 H), 7.95–
1
calcd. C 51.22, H 3.54, N 7.03; found C 51.40, H 3.67, N 7.15. H 8.13 (m, 3 H), 8.36 (s, 1 H), 8.50 (d, 1 H), 8.71 (d, 1 H) ppm. IR
NMR (300 MHz, [D6]DMSO, 293 K): δ = 3.34 (s, 3 H, CH3), 7.13 (KBr): ν = 3061 w, 3015 w, 2984 w, 2928 w, 2873 w, 2833 w, 2362
˜
(t, 1 H), 7.21 (d, 1 H), 7.41–7.52 (m, 2 H), 7.91–7.99 (m, 4 H), 8.30 m, 1601 s, 1568 s, 1446 s, 1401 m, 1298 m, 1262 m, 1246 m, 1156
(d, 1 H), 8.48 (d, 1 H), 8.72 (d, 1 H) ppm. IR (KBr): ν = 3072 w, m, 1130 w, 1104 w, 1053 w, 1021 m, 926 m, 833 m, 783 s, 742 m,
˜
3007 w, 2959 w, 2850 w, 1600 s, 1569 m, 1484 s, 1459 s, 1441 s, 700 w, 655 w, 634 m, 549 w.
1401 w, 1299 m, 1260 s, 1248 m, 1179 w, 1162 m, 1119 m, 1055 w,
1023 s, 829 w, 784 s, 755 s, 643 w, 561 w.
6-[2-(Dimethylamino)phenyl]-2,2Ј-bipyridinemercury Dichloride (2d):
A methanol solution (10 mL) of 1b (0.2 g, 0.73 mmol) was added
6-(2-Methoxyphenyl)-2,2Ј-bipyridinemercury Dichloride (2b):
A
to a methanol solution (15 mL) of HgCl2 (0.21 g, 0.74 mmol). The
methanol solution (10 mL) of 1a (0.2 g, 0.76 mmol) was added to reaction mixture was stirred for 4 h at room temperature. After
a methanol solution (10 mL) of HgCl2 (0.21 g, 0.77 mmol). The filtering, the light yellow precipitate was collected and washed with
reaction mixture was stirred for 4 h at room temperature. After cold methanol. Pure product was obtained in 85% yield (0.34 g) by
Table 3. Crystal data and structural refinements details for 2a, 2b, 2c, and 2d.
2a
2b
2c
2d
Empirical formula
Formula mass
Temp. [K]
Wavelength [Å]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
C17H14Cl2N2OZn
398.57
293(2)
0.71073
monoclinic
P2(1)/n
8.2680(17)
13.037(3)
15.433(3)
90
C17H14Cl2HgN2O
533.79
293(2)
0.71073
monoclinic
P2(1)/c
7.5130(15)
16.718(3)
13.403(3)
90
C18H17Cl2N3Zn
411.62
293(2)
0.71073
monoclinic
P2(1)/n
10.236(2)
13.145(3)
12.916(3)
90
C18H17Cl2HgN3
546.84
293(2)
0.71073
triclinic
¯
P1
8.3858(17)
8.6676(17)
13.173(3)
82.56(3)
β [°]
95.03(3)
90
1657.1(6)
4
0.799
404
97.02(3)
90
1670.8(6)
4
1.061
504
90.08(3)
90
1737.9(6)
2
0.787
420
89.46(3)
73.93(3)
912.0(3)
2
1.991
520
γ [°]
V [Å3]
Z
Dcalcd. [Mgm–3]
F(000)
Crystal size (mm)
θ range for data collection [°] 3.08–27.47
Limiting indices
0.23×0.17×0.16
0.34×0.15×0.12
2.99–27.45
–8 Յ h Յ 9
–21 Յ k Յ 21
–17 Յ l Յ 17
3746/0/264
1.004
0.20×0.17×0.11
3.10–27.46
–13 Յ h Յ 11
–17 Յ k Յ 17
–16 Յ l Յ 16
3973/0/285
1.055
0.28×0.19×0.13
3.00–27.48
–9 Յ h Յ 10
–10 Յ k Յ 11
–17 Յ l Յ 17
3979/0/217
1.102
–10 Յ h Յ 10
–16 Յ k Յ 16
–20 Յ l Յ 17
3774/0/208
1.079
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I Ͼ 2σ(I)]
[a]
[a]
[a]
[a]
R1 = 0.0414
R1 = 0.0260
R1 = 0.0280
R1 = 0.0663
[b]
[b]
[b]
[b]
wR2 = 0.1193
wR2 = 0.0580
wR2 = 0.0670
wR2 = 0.1439
[a]
[a]
[a]
[a]
R indices (all data)
R1 = 0.0487
R1 = 0.0342
R1 = 0.0371
R1 = 0.0823
[b]
[b]
[b]
[b]
wR2 = 0.1222
wR2 = 0.0614
wR2 = 0.0707
wR2 = 0.1517
Largest diff. peak/hole [eÅ–3] 0.665, –0.261
0.917, –1.172
0.315, –0.231
2.854, –1.997
[a] R1 = ∑||Fo| – |Fc||/∑|Fo|. [b] wR2 = [∑[w(Fo – Fc ) ]/∑[w(Fo2)2]]1/2
.
2
2 2
4322
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Eur. J. Inorg. Chem. 2006, 4317–4323

d10 Group 12 Metal Complexes with Substituted 2,2Ј-Bipyridine Ligands
FULL PAPER
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7.21 (m, 2 H), 7.41 (s, 1 H), 7.58 (m, 2 H), 7.98–8.09 (m, 3 H), 8.41
1
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be attributed to additional atomic sites.
CCDC-602363 (for 2a), -602364 (for 2b), -602365 (for 2c), and
-602366 (for 2d) contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
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This work was supported by the National Natural Science Founda-
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Received: March 25, 2006
Published Online: August 24, 2006
Eur. J. Inorg. Chem. 2006, 4317–4323
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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4323