Copper(II) and cadmium(II) complexes based on N,N-Bis(3, 5-dimethyl-2-hydroxybenzyl)-N-(2-pyridylmethyl)amine ligand: Syntheses, structures, magnetic, and luminescent properties

Article abstract of DOI:10.1002/zaac.201200244

The reaction of the aryl-oxide ligand H₂L [H₂L = N,N-bis(3, 5-dimethyl-2-hydroxybenzyl)-N-(2-pyridylmethyl)amine] with CuSO ₄·5H₂O, CuCl₂·2H₂O, CuBr₂, CdCl₂·2.5H₂O, and Cd(OAc) ₂·2H₂O, respectively, under hydrothermal conditions gave the complexes [Cu(H₂L¹)₂]·SO ₄·3CH₃OH (1), [Cu₂(H₂L ²)₂Cl₄] (2), [Cu₂(H ₂L²)₂Br₄] (3), [Cd ₂(HL)₂Cl₂] (4), and [Cd₂(L) ₂(CH₃COOH)₂]·H₂L (5), where H₂L¹ [H₂L¹ = 2, 4-dimethyl-6- ((pyridin-2-ylmethylamino)methyl)phenol] and H₂L² [H ₂L² = 2-(2, 4-dimethyl-6-((pyridin-2-ylmethylamino)methyl) phenoxy)-4, 6-dimethylphenol] were derived from the solvothermal in situ metal/ligand reactions. These complexes were characterized by IR spectroscopy, elementary analysis, and X-ray diffraction. A low-temperature magnetic susceptibility measurement for the solid sample of 2 revealed antiferromagnetic interactions between two central copper(II) atoms. The emission property studies for complexes 4 and 5 indicated strong luminescence emission. Copyright

Full text of DOI:10.1002/zaac.201200244

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ARTICLE
DOI: 10.1002/zaac.201200244
Copper(II) and Cadmium(II) Complexes Based on N,N-Bis(3,5-dimethyl-2-
hydroxybenzyl)-N-(2-pyridylmethyl)amine Ligand: Syntheses, Structures,
Magnetic, and Luminescent Properties
Lijuan Yang,[a] Wenqian Chen,[a] Yanmei Chen,[a] Wei Liu,[a] Tao Lei,[b] Lei Li,[a]
Miaoshui Lin,[a] Jian Wu,[a] Yanyuan Cao,[a] Wu Li,[b] and Yahong Li*[a,c]
Keywords: Aryl-oxide ligand; In situ metal/ligand reaction; Coordination complexes; Luminescence; Magnetic properties
Abstract. The reaction of the aryl-oxide ligand H2L [H2L = N,N- methyl)phenoxy)-4,6-dimethylphenol] were derived from the solvo-
bis(3,5-dimethyl-2-hydroxybenzyl)-N-(2-pyridylmethyl)amine] with thermal in situ metal/ligand reactions. These complexes were charac-
CuSO4·5H2O, CuCl2·2H2O, CuBr2, CdCl2·2.5H2O, and Cd(OAc)2·
2H2O, respectively, under hydrothermal conditions gave the complexes
terized by IR spectroscopy, elementary analysis, and X-ray diffraction.
A low-temperature magnetic susceptibility measurement for the solid
[Cu(H2L1)2]·SO4·3CH3OH (1), [Cu2(H2L2)2Cl4] (2), [Cu2(H2L2)2Br4] sample of 2 revealed antiferromagnetic interactions between two cen-
(3), [Cd2(HL)2Cl2] (4), and [Cd2(L)2(CH3COOH)2]·H2L (5), where tral copper(II) atoms. The emission property studies for complexes 4
H2L1 [H2L1 = 2,4-dimethyl-6-((pyridin-2-ylmethylamino)methyl)phe-
nol] and H2L2 [H2L2 = 2-(2,4-dimethyl-6-((pyridin-2-ylmethylamino)
and 5 indicated strong luminescence emission.
while, the phenol oxygen atom of the ligand can serve as a
bridging atom [bis(μ-phenoxo) bridging motif], generating di-
nuclear iron[17] and scandium[15] complexes. There is only one
polymeric 1D chain complex ([Cu(H2L)(SO4)]·CH3OH) re-
ported.[18]
However, all of the reported mononuclear and dinuclear
complexes were synthesized by traditional coordination chem-
istry techniques, and the above-mentioned 1D chain com-
plex[18] can only be generated under the solvothermal condi-
tions. We envisioned that a number of new polynuclear com-
plexes with aesthetically pleasing structures and fascinating
properties might be prepared under solvothermal conditions.
With this consideration in mind, we performed the reactions
between metal salts and H2L ligand under solvothermal condi-
Introduction
The study of complexes with tetradentate amine-bis(phen-
olate) ligands is of unabated interest to inorganic chemists. The
efforts of several research groups are driven by a number of
considerations. These include the development of the structural
models for mimicking the active site of galactose oxidase,[1–3]
the employment of the tetradentate amine-bis(phenolate) li-
gands in the synthesis of coordination complexes with interest-
ing magnetic properties,[4–8] and the application of metal ion/
tetradentate amine-bis(phenolate) systems as efficient catalysts
for the polymerization of olefins and lactides.[9–11] As a sub-
class of the tetradentate amine-bis(phenolate) ligands, N,N-
bis(3,5-dimethyl-2-hydroxybenzyl)-N-(2-pyridylmethyl)amine
(H2L)[12] is currently popular ligand because of several as-
pects. It is a tripodal ligand featuring a N2O2 donor site and
forms mononuclear complexes with various transition metals,
such as indium,[13] rhodium,[14] and titanium.[15–16] Mean-
* Prof. Dr. Y. Li
Fax: +86-512-65880089
E-Mail: liyahong@suda.edu.cn
[a] Key Laboratory of Organic Synthesis of Jiangsu Province
College of Chemistry
Chemical Engineering and Materials Science, Soochow University
Suzhou, 215123, P. R. China
[b] Key Laboratory of Salt Lake Resources and Chemistry
Qinghai Institute of Salt Lakes
Chinese Academy of Sciences
Xining, 810008, P. R. China
[c] State Key Laboratory of Applied Organic Chemistry
Lanzhou University
Lanzhou, 730000, P. R. China
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201200244 or from the au-
thor.
Scheme 1. The structures of the H2L, H2L1, and H2L2 ligands, and the
reaction scheme for the H2L ligand.
Z. Anorg. Allg. Chem. 0000, ᭿,(᭿), 0–0
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tions. Our investigations led to five complexes of compositions vibrations of the aromatic rings and deformation vibrations
[Cu(H2L1)2]·SO4·3CH3OH
(1),
[Cu2(H2L2)2Cl4]
(2), of –OH groups in 1–5, appear in the 1612–1446 cm–1 range.
[Cu2(H2L2)2Br4] (3), [Cd2(HL)2Cl2] (4), and [Cd2(L)2(CH3- The out-plane deformation of the aromatic ring in 1–5 was
COOH)2]·H2L (5), where H2L1 [H2L1 = 2,4-dimethyl-6-((pyr- found in the 788–659 cm–1 range.
idin-2-ylmethylamino)methyl)phenol] and H2L2 [H2L2 = 2-
(2,4-dimethyl-6-((pyridin-2-ylmethylamino)methyl)phenoxy)-
Structure Descriptions of Complexes 1–5
4,6-dimethylphenol] were derived from solvothermal in situ
metal/ligand reactions (Scheme 1). Herein, we report the syn-
theses, structures, and properties of these complexes.
Partially labeled plots of complexes 1–5 are shown in Fig-
ure 1, Figure 2, Figure 3, and Figure 4. The crystallographic
data of the complexes are listed in Table 1.
Results and Discussion
Synthesis and IR Spectra
Complexes 1–5 were prepared under solvothermal condi-
tions in methanol in sealed reaction vessels (Scheme 2).
Scheme 2. Syntheses of complexes 1–5.
Treatment of CuSO4·5H2O with two equiv. of the H2L li-
gand led to [Cu(H2L1)2]·SO4·3CH3OH (1), where H2L1 was
believed to be obtained by the in situ metal ligand reaction
between CuSO4·5H2O and the H2L ligand.[2] Complex 1 was
readily isolated as purple crystals with moderate yield.
The reactions of the H2L ligand with one equiv. of
CuCl2·2H2O and two equiv. of CuBr2, respectively, generated
[Cu2(H2L2)2Cl4] (2) and [Cu2(H2L2)2Br4] (3), in which the
H2L2 ligand was assumed to be formed by the in situ metal/
ligand reaction of CuII and the H2L ligand.[2]
Figure 1. (a) Solid state structure of 1 showing the atom labeling
scheme. Hydrogen atoms and solvent molecules are omitted for clarity.
(b) Crystal packing diagram of complex 1. Hydrogen contacts are rep-
resented by dotted lines.
Treatment of the H2L ligand with one equiv. of
CdCl2·2.5H2O and Cd(OAc)2·2H2O, respectively, gave
[Cd2(HL)2Cl2] (4) and [Cd2L2(CH3COOH)2]·H2L (5). They
were both directly obtained as colorless crystals in moderate
yields.
We have explored the preparation of 1–5 by “conventional”
coordination chemistry. The synthetic investigation of the
metal salts and the H2L ligand in MeOH under atmospheric
and ambient or reflux conditions resulted in solutions from
which we failed to crystallize any product. It seems that solvo-
thermal technique is a good method to prepare 1–5.
The presence of –OH groups in 1–5 is manifested by a broad
IR band of medium intensity at 3421–3441 cm–1. The strong
intensity band in the 3135–3202 cm–1 range, which was ob-
served in 1–3 but was not found in 4–5, was assigned to the
ν(N–H) mode. The presence of the ν(N–H) mode confirms the
decomposition of the ligand H2L in 1–3. The band in the range
of 2912–2919 cm–1 in 1–5 was ascribed to the νas(C–H) vi-
Figure 2. Solid state structure of 2 (X = Cl–) and 3 (X = Br–) showing
bration. Several bands, which are assigned as the stretching the atom labeling scheme. Hydrogen atoms are omitted for clarity.
2
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CuII and CdII Complexes Based on N,N-Bis(3,5-dimethyl-2-hydroxybenzyl)-N-(2-pyridylmethyl)amine
2–
of SO4 ion (acceptor). These hydrogen contacts connect the
molecules to generate an infinite 1D chain structure (Fig-
ure 1b).
Structures of [Cu2(H2L2)2Cl4] (2) and [Cu2(H2L2)2Br4] (3)
Complex 2 has a centrosymmetrical dimeric structure. The
two CuII ions are linked by a pair of chloride bridges and have
a similar pentacoordinate environment. The arrangement
around each central CuII atom is best described as a distorted
square-pyramid (τ = 0.13, the parameter τ is used to describe
the geometry; τ is zero for an ideal square pyramid and one
for an ideal trigonal bipyramid[23]). The CuII ion is bound to
one amine nitrogen atom, one pyridine nitrogen atom, a ter-
minal Cl– ion and two bridging Cl– ions. The Cu–N distances
[2.100(3) and 2.013(2) Å] are slightly shorter than those in
previously reported complexes containing Cu–N bonds
[2.156(3)–2.1982(14) Å[19–20] for Cu–N(amine) bonds and
2.066(4)–2.119(4) Å[21,22] for Cu–N(pyridyl) bonds]. The Cu–
Cl distances are concurrent with the published values.[24]
Complex 3 is isostructural with complex 2; therefore the
structure of complex 3 is not described herein in detail.
Figure 3. Solid state structure of 4 showing the atom labeling scheme.
Hydrogen atoms are omitted for clarity.
Structure of [Cd2(HL)2Cl2] (4)
X-ray crystallographic analysis reveals that complex 4 is a
dinuclear compound. It contains two CdII ions, two HL– li-
gands and two Cl– anions. The complex has a crystallographi-
cally-imposed C2 symmetry. The result is that there is one
crystallographically independent CdII site. The two cadmium
atoms are bridged by two endogenous μ-phenoxo oxygen
atoms, with the Cd···Cd distance being 3.4811(12) Å. Each
cadmium atom was five-coordinate, with τ value being 0.167,
indicating an arrangement closer to a regular square pyramid
(τ = 0) than to a regular trigonal bipyramid (τ = 1).[23] The
basal plane contains one terminal Cl– ion, one μ-phenoxo oxy-
gen atom, one nitrogen atom of amine, and one nitrogen atom
from pyridine ring. The oxygen atom from the other HL– li-
gand (μ-phenoxo oxygen) occupies the apical position.
Figure 4. Solid state structure of 5 showing the atom labeling scheme.
Hydrogen atoms and one free ligand molecule are omitted for clarity.
Structure of [Cu(H2L1)2]·SO4·3CH3OH (1)
Structure of [Cd2L2(CH3COOH)2]·H2L (5)
X-ray crystallographic analysis reveals that 1 crystallizes in
the triclinic P1 space group. It consists of one Cu ion, two
II
¯
X-ray crystallographic analysis reveals that complex 5 is di-
H2L1 ligands, which were assumed to be derived from the de- nuclear and has a crystallographically-imposed C2 symmetry,
2–
composition of the H2L ligand, one SO4 ion, and three solv- too. The complex is composed of two CdII ions, two L2– li-
ate methanol molecules (Figure 1a). The central CuII atom dis- gands, two acetic acids, and one free H2L ligand. The two CdII
plays a square planar arrangement and is coordinated by two atoms are bridged by two phenoxo oxygen atoms from two
pyridine nitrogen atoms (N1 and N1Ј), and two amine nitrogen L2– ligands. Each central CdII atom is coordinated by two ni-
atoms (N2 and N2Ј) from two H2L1 ligands, with Cu–N bond trogen atoms and one bridging phenoxo oxygen atom from one
lengths being 1.999(4) Å (N1, N1Ј) and 2.050(4) Å (N2, N2Ј). L2– ligand, one bridging phenoxo oxygen atom from the other
The Cu–N bond lengths within 1 are slightly shorter than those L2– ligand, and one oxygen atom from one acetic acid mole-
in previously reported amine-containing CuII complexes cule. The environment of the central metal could be described
[2.156(3)–2.1982(14) Å[19–20] for Cu–N(amine) bonds, and as a distorted octahedron. The Cd–O(μ-phenoxo) bond lengths
2.066(4)–2.119(4) Å[21–22] for Cu–N(pyridyl) bonds].
are 2.231(2) and 2.374(2) Å, which are in the range of Cd–
Noticeable intermolecular N–H···O contacts are presented O bond lengths observed in other CdII complexes [2.213(3)–
from NH group of the H2L1 ligand (donor) to the oxygen atom 2.455(5) Å].[25–26]
Z. Anorg. Allg. Chem. 0000, 0–0
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A number of coordination complexes of transition metals Luminescence Properties of 4 and 5
supported by the tetradentate amine-bis(phenolate) ligands
Many previous studies have shown that coordination com-
pounds including CdII and ZnII ions, which have d10 arrange-
ment exhibit luminescence properties.[27–29] Thus we investi-
gated the luminescent properties of the ligand H2L and com-
plexes 4 and 5 (Figure 7). In the solid state H2L emits at a
maximum 448 nm upon excitation around 360 nm. The spectra
of compounds 4 and 5 show strong luminescence emission
have been documented,[1–11] but no coordination complex of
CdII ion was reported. Complexes 4 and 5 are the first two
coordination complexes based on the tetradentate amine-bis(-
phenolate) ligands.
Magnetic Property of 2
bands. Blue-shifted maxima at approximately 392 nm (λex
=
305 nm) for 4 and red-shifted maxima at approximately
484 nm (λex = 335 nm) for 5 were observed.
Magnetic property studies on polynuclear metal complexes
are of continuing interest for coordination chemists. The dc
magnetic property for 2 was measured in the temperature range
of 2–300 K at the applied magnetic field of 1000 Oe (Fig-
ure 5). At 300 K, the χMT product value is measured to be
0.76 cm3·mol–1·K, which is close to the theoretical value for
the two isolated magnetic centers per formula unit
(0.75 cm3·mol–1·K). Upon cooling, the value is almost un-
changeable (around 0.8 cm3·mol–1·K) at the temperature range
of 300–20 K, below which it decreases rapidly to a value of
0.16 at 2 K. This behavior indicates the antiferromagnetic in-
teractions between the magnetic centers.
Figure 7. Normalized emission spectra of H2L, 4, and 5 in the solid
state at room temperature.
Figure 5. Temperature dependence of magnetic susceptibilities in the
form of χMT vs. T for 2 at 1 kOe.
Conclusions
The Curie-Weiss fitting of the magnetic data (200–4 K)
yields C = 0.83 cm3·mol–1·K and θ = –0.70 K (Figure 6), indi-
cating the presence of very weak antiferromagnetic exchange
coupling interactions between the central metal atoms.
Five complexes of compositions [Cu(H2L1)2]·SO4·3CH3OH
(1), [Cu2(H2L2)2Cl4] (2), [Cu2(H2L2)2Br4] (3), [Cd2(HL)2Cl2]
(4), and [Cd2(L)2(CH3COOH)2]·H2L (5) were prepared and
characterized, where the ligands H2L1 and H2L2 were gener-
ated via solvothermal in situ metal/ligand reactions. Magnetic
property measurement indicates that there exist weak antiferro-
magnetic interactions between the magnetic centers in 2. The
emission property studies reveal strong luminescence emission
for complexes 4 and 5. Blue-shift maxima at approximately
392 nm (λex = 305 nm) for 4 and red-shift maxima at approxi-
mately 484 nm (λex = 335 nm) for 5 were observed. The in-
depth researches to produce polynuclear complexes, which
may exhibit SMMs behavior, by adding other paramagnetic
transition metals are under investigation in our lab. Our stud-
ies, already well advanced, will be reported soon.
Experimental Section
Materials and Instruments: All reagents used in the synthesis were
of analytical grade. Elemental analyses for carbon, hydrogen, and ni-
trogen atoms were performed with a Carlo-Erba EA1110 CHNO-S
microanalyzer. Infrared spectra (4000–400 cm–1) were recorded by
using KBr pellets with a Nicolet MagNa-IR500 FT-IR spectrometer.
Figure 6. Temperature dependence of magnetic susceptibilities in the
form of χM vs. T for 2 at 1 kOe. The solid line corresponds to the
best fit from 200 K to 4 K.
–1
4
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CuII and CdII Complexes Based on N,N-Bis(3,5-dimethyl-2-hydroxybenzyl)-N-(2-pyridylmethyl)amine
Crystal determination was performed with a Bruker SMART APEX II
8 mL Pyrex-tube, which was heated at 70 °C for 3 days and cooled to
CCD diffractometer equipped with graphite-mono-chromatized Mo-Kα room temperature at a rate of 5 K·h–1. Blue crystals of 2 were collected
radiation (λ = 0.71073 Å). Variable-temperature magnetic susceptibilit- in a yield of 65% (0.0322 g). Elemental analysis: C46H52Cl4Cu2N4O4
ies were measured with a Quantum Design MPMS-7 SQUID magne-
(993.8): calcd. C 55.59, H 5.27, N 5.64%; found: C 55.27, H 5.205,
tometer. Diamagnetic corrections were made with Pascal’s constants N 5.745%. IR (KBr, selected data): ν˜ = 3421 (s), 3211 (s), 1607 (m),
for all constituent atoms. The solid-state luminescence emission/exci-
tation spectra were recorded on a FLS920 fluorescence spectrophotom-
eter equipped with a continuous Xe-900 xenon lamp and a μF900
microsecond flash lamp.
1512 (s), 1301 (m), 1150 (m), 1138 (m), 1025 (s), 959 (m), 771 (m)
cm–1.
[Cu2(HL2)2Br4] (3): A mixture of CuBr2 (0.0223 g, 0.1 mmol), H2L
(0.0189 g, 0.05 mmol), and methanol (1.2 mL) was sealed in a 8 mL
Pyrex-tube, which was heated at 70 °C for 3 days and cooled to room
temperature at a rate of 5 K·h–1. Green crystals of 3 were collected in a
yield of 48% (0.014g). Elemental analysis: C23H23Br2CuN2O2 (582.7):
calcd. C 47.48, H 3.81, N 4.82%; found: C 47.60, H 4.25, N 4.70%.
IR (KBr, selected data): ν˜ = 3438 (s), 3202 (s), 1607 (s), 1502 (s),
1300 (m), 1183 (m), 1151(m), 1138 (m), 1025 (s), 858 (m), 769 (m)
cm–1.
X-ray Crystallography: The single crystals were placed in a Bruker
SMART APEX II CCD. The diffraction data were obtained by using
graphite monochromated Mo-Kα radiation with an ω–2θ scan tech-
nique at room temperature. The structure was solved by direct methods
with SHELX-97. A full-matrix least-squares refinement on F2 was car-
ried out by using SHELXL-97. The collected crystal data for the five
structures are shown in Table 1.
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
of the data can be obtained free of charge on quoting the depository
numbers CCDC-842644 (1), -821013 (2), -838312 (3), -838313 (4),
and -805584 (5) (Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam-
.ac.uk, http://www.ccdc.cam.ac.uk).
[Cd2(HL)2Cl2] (4):
A
mixture of CdCl2·2.5H2O (0.0114 g,
0.05 mmol), H2L (0.0189 g, 0.05 mmol), and methanol (1.2 mL) was
sealed in a 8 mL Pyrex-tube, which was heated at 70 °C for 3 days
and cooled to room temperature at a rate of 5 K·h–1. Colorless crystals
of 4 were collected in a yield of 30% (0.087 g). Elemental analysis:
C48H50Cd2Cl2N4O4 (1042.7): calcd. C 55.29, H 4.83, N 5.37%; found:
C 54.89, H 5.21, N 5.16%. IR (KBr, selected data): ν˜ = 3393 (s), 2912
(m), 1605 (s), 1488 (s), 1385 (m), 1296 (s), 1248 (s), 1198 (m), 1154
(s), 1071 (m), 863 (m), 788 (s), 762 (m), 480 (m) cm–1.
[Cu(H2L1)2]·SO4·3CH3OH (1): A mixture of CuSO4·5H2O (0.0125 g,
0.05 mmol), H2L (0.0377 g, 0.1 mmol), and methanol (1.2 mL) was
sealed in a 8 mL Pyrex-tube, which was heated at 70 °C for 3 days
and cooled to room temperature at a rate of 5 K·h–1. Purple crystals of
1 were collected in a yield of 36% (0.0133 g). Elemental analysis:
C33H48CuN4O9S (740.4): calcd. C 53.53, H 6.53, N 7.57%; found: C
54.19, H 5.20, N 7.69%. IR (KBr, selected data): ν˜ = 3441 (m), 3135
(m), 1612 (s), 1498 (s), 1438 (m), 1256 (s), 1220 (m), 1161 (m), 1139
(m), 1049 (m), 859 (m), 768 (m), 618 (m) cm–1.
[Cd2(L)2(CH3COOH)2]·H2L (5): A mixture of Cd(OAc)2·2H2O
(0.0133 g, 0.05 mmol), H2L (0.0189 g, 0.05 mmol), and methanol
(1.2 mL) was sealed in a 8 mL Pyrex-tube, which was heated at 70 °C
for 3 days and cooled to room temperature at a rate of 5 K·h–1. Color-
less crystals of 5 were collected in a yield of 38% (0.0342 g). Elemen-
tal analysis: C52H60Cd2N4O8 (1798.5): calcd. C 57.20, H 5.35, N
5.13%; found: C 56.99, H 5.52, N 5.18%. IR (KBr, selected data): ν˜
= 3441 (m), 2916 (m), 1603 (s), 1570 (m), 1486 (s), 1432 (m), 1255
(s), 1157 (m), 1005 (m), 856 (s), 788 (m), 755 (m), 660 (m) cm–1.
[Cu2(HL2)2Cl4] (2): A mixture of CuCl2·2H2O (0.0085 g, 0.05 mmol),
H2L(0.0189 g, 0.05 mmol), and methanol (1.2 mL) was sealed in a
Table 1. Crystal data and structure refinements for 1–5.
1
2
3
4
5
Empirical formula
Formula weight
Temperature /K
Wavelength /Å
Crystal system
Space group
a /Å
b /Å
c /Å
α /°
C33H48CuN4O9S
740.35
296(2)
C46H52Cl4Cu2N4O4
993.80
293(2)
0.71073
monoclinic
P21/c
17.150(3) A
8.2165(16) A
17.882(4) A
90
C23H23Br2CuN2O2
582.78
293(2)
0.71073
monoclinic
P21/c
18.043(4)
8.3890(17)
17.357(3)
90
C48H50Cd2Cl2N4O4
1042.62
293(2)
0.71073
monoclinic
P21/n
8.6348(17)
23.306(5)
11.969(2)
90
C100H68Cd2N8O12
1798.44
296(2)
0.71073
0.71073
triclinic
triclinic
¯
¯
P1
P1
8.4981(17)
11.403(2)
18.144(4)
82.10(3)
11.767(2)
11.871(2)
17.263(3)
90.38(3)
β /°
γ /°
85.57(3)
88.29(3)
1736.0(6)
2
115.83(3)
90
2268.0(8)
2
115.74(3)
90
2366.5(8)
4
105.33(3)
90
2323.0(8)
2
90.94(3)
110.63(3)
2256.3(7)
1
Volume /Å3
Z
F(000)
782
1028
1160
1056
916
Crystal size /mm
Theta range /°
Reflections col-
lected / unique
GooF on F2
0.37ϫ0.28ϫ0.21
1.14 to28.37
30882 / 8618
0.41ϫ0.35ϫ0.28
1.32 to 25.00
17012 / 4000
0.37ϫ0.29ϫ 0.27
2.51to 28.31
21247/ 5882
0.31ϫ0.26ϫ0.20
1.75 to 28.50
21081 / 5836
0.34ϫ0.28ϫ0.21
1.18 to 26.00
34651 / 8876
1.062
1.162
0.995
1.164
1.085
R1, wR2 [I Ͼ 2σ(I)] 0.0813, 0.2482
0.0349, 0.1050
0.0449, 0.1166
0.393,-0.682
0.0439, 0.1100
0.0863, 0.1278
0.694, –0.713
0.0808, 0.2349
0.1086, 0.2465
2.03, –0.787
0.0434, 0.1314
0.0629, 0.1511
0.580, –0.350
R1, wR2 (all data)
Largest residual
peaks /e·Å–3
0.1117,0.2656
2.034,-0.647
Z. Anorg. Allg. Chem. 0000, 0–0
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Date: 02-08-12 16:38:28
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Y. Li et al.
ARTICLE
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Received: May 30, 2012
Published Online: ᭿
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Pages: 7
CuII and CdII Complexes Based on N,N-Bis(3,5-dimethyl-2-hydroxybenzyl)-N-(2-pyridylmethyl)amine
L. Yang, W. Chen, Y. Chen, W. Liu, T. Lei, L. Li, M. Lin,
J. Wu, Y. Cao, W. Li, Y. Li* .............................................. 1–7
Copper(II) and Cadmium(II) Complexes Based on N,N-
Bis(3,5-dimethyl-2-hydroxybenzyl)-N-(2-pyridylmethyl)amine
Ligand: Syntheses, Structures, Magnetic, and Luminescent
Properties
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
7