Construction of Mononuclear Copper(II) and Trinuclear Cobalt(II) Complexes Based on Asymmetric Salamo-Type Ligands

Article abstract of DOI:10.1002/zaac.201500751

Mononuclear copper(II) and trinuclear cobalt(II) complexes, namely [Cu(L¹)]₂·CH₂Cl₂ and [{Co(L²)(EtOH)}₂Co(H₂O)]·EtOH {H₂L¹ = 4,6-dichloro-6′-methyoxy-2,2′-

Full text of DOI:10.1002/zaac.201500751

Journal of Inorganic and General Chemistry
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ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
DOI: 10.1002/zaac.201500751
Construction of Mononuclear Copper(II) and Trinuclear Cobalt(II)
Complexes Based on Asymmetric Salamo-Type Ligands
Wen-Kui Dong,*[DEFAULT] Jin-Tong Zhang, Yin-Juan Dong, Yang Zhang,
[a]
[a]
[a]
and Zheng-Kun Wang[
a]
Keywords: Salamo-type ligand; Copper; Cobalt; Synthesis; Crystal structure
Abstract. Mononuclear copper(II) and trinuclear cobalt(II) complexes, is four-coordinate, with a N
2
O
2
coordination sphere, and has a slightly
1
2
namely [Cu(L )]
2
·CH
2
Cl
2
and [{Co(L )(EtOH)} Co(H O)]·EtOH distorted square-planar arrangement. Interestingly, the obtained tri-
2 2
1
II
{
H
2
L = 4,6-dichloro-6Ј-methyoxy-2,2Ј-[1,1Ј-(ethylenedioxydinitrilo)- nuclear Co complex is different from the common reported 2:3
2
II
II
dimethylidyne]diphenol and H
3
L = 6-ethyoxy-6Ј-hydroxy-2,2Ј-[1,1Ј-
(L:Co ) salamo-type Co complexes. Infinite 2D layer supramolecular
(
ethylenedioxydinitrilo)dimethylidyne]diphenol}, were synthesized structures are formed via abundant intermolecular hydrogen bonding
II
II
and characterized by elemental analyses, IR and UV/Vis spectroscopy,
and single-crystal X-ray diffraction. In the Cu complex, the Cu atom
and π···π stacking interactions in the Cu and Co complexes.
II
II
Introduction
to the parent salen and are useful for the construction of helical
metalloarchitectures.[
16–20]
Salen-type ligand is a kind of tetradentate chelate ligand
The aim of the presented work is the construction of supra-
consisting of two N and two O donors, capable of forming molecular metal complexes based on asymmetric salamo-type
II
II
stable metal complexes. Various functional salen-metal com- ligands. Herein, mononuclear Cu and trinuclear Co com-
1
2
plexes have been synthesized by complexation with the appro- plexes with H
priate metal sources. It is important to introduce suitable func- Furthermore, the crystal structures, supramolecular features,
L
and H
L
were prepared successfully.
2
3
II
II
tional groups into the organic moiety of metal complexes in and spectral properties of the Cu and Co complexes are dis-
order to improve or tune the properties of these metal com- cussed.
plexes.[ The introduction of functional groups is crucial for
1]
the electron-donating and -withdrawing groups are utilized to
II
Experimental Section
finely tune the nonlinear optical properties of the Cu com-
plexes of the salen analogues.[ Such functional groups are Materials and Physical Measurements: 3-Ethoxysalicylaldehyde,
2]
mainly introduced into the benzene rings of salicylaldimine. 3,5-dichlorosalicylaldehyde, and 3-hydroxysalicylaldehyde were pur-
chased from Alfa Aesar and used without further purification. The
Salen-type metal complexes are used in various organic reac-
[3–5]
other reagents and solvents were analytical grade reagents from Tianjin
Chemical Reagent Factory. Elemental analyses for Cu and Co were
detected with an IRIS ER/S·WP-1 ICP atomic emission spectrometer.
C, H and N analyses were carried out with a GmbH VarioEL V3.00
tion processes as catalysts,
models of reaction centers of
metalloenzymes,[
6,7]
[8,9]
nonlinear optical materials,
and so on.
Moreover, some of these complexes possess interesting mag-
netic properties.[
10–13]
1
13
automatic elemental analyzer. H and C NMR spectra were deter-
mined with a German Bruker AVANCE DRX-400 spectrometer. Infra-
red (IR) spectra were recorded with a VERTEX-70 FT-IR spectropho-
To improve such functions, replacement of some atoms on
the ligands with other elements changes usually their proper-
ties drastically.[
14,15]
Recently, a reported oxime-type salen li- tometer, with samples prepared as KBr (500–4000 cm–1) or CsI (100–
–
1
gand “salamo”, which is an analogue of salen; i.e., the imine 500 cm ) pellets. UV/Vis absorption spectra were recorded with a Shi-
C=N-C moieties of salen are replaced by C=N–O oxime madzu UV-2550 spectrometer. X-ray single crystal structures were de-
bonds.[ These salamo-type ligands exhibited a very high sta-
16]
termined with a Bruker Smart 1000 CCD area detector. Melting points
were measured by the use of a microscopic melting point apparatus
bility that resisted recombination of the C=N bonds compared
made in Beijing Taike Instrument Limited Company, and the thermo-
meter was uncorrected.
*
Prof. Dr. W.-K. Dong
2 2 2
L : Synthesis of H
L1 is shown in Scheme 1. H L1
1
Preparation of H
was synthesized according to an analogous method reported ear-
E-Mail: dongwk@126.com
[
a] School of Chemical and Biological Engineering
Lanzhou Jiaotong University
Lanzhou 730070, P. R. China
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201500751 or from the au-
thor.
[17,19]
lier.
1.14; H 4.04, N 7.02%; found: C 51.01; H 3.95; N 7.09%. H NMR
400 MHz, CDCl ): δ = 3.93 (s, 3 H, -CH ), 4.50–4.53 (m, 4 H, -CH
–), 6.84 (dd, J = 7.70, 1.81 Hz, 1 H, Ar–H), 6.88 (t, J = 7.72,
2 2 5
Yield, 60.0%. M.p. 145–146 °C. C17H16Cl N O : calcd. C
1
5
(
3
3
2
–
CH
2
Z. Anorg. Allg. Chem. 2016, 642, (2), 189–196
189
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1
Scheme 1. Synthesis of H
2
L .
2
Scheme 2. Synthesis of H
3
L .
7
(
(
.72 Hz, 1 H, Ar–H), 6.94 (dd, J = 7.73, 1.60 Hz, 1 H, Ar–H), 7.09
d, J = 2.45 Hz, 1 H, Ar–H), 7.37 (d, J = 2.43 Hz, 1 H, Ar–H), 8.18 area detector. The diffraction data were collected using graphite mono-
s, 1 H, N=C–H), 8.27 (s, 1 H, N=C–H), 9.70 (s, 1 H, O–H), 10.40 (s, chromated Mo-K radiation (λ = 0.71073 Å) at 298(2) K. The struc-
H, O–H) ppm.
0.40ϫ0.22ϫ0.11 mm3 were placed on a Bruker Smart 1000 CCD
α
1
tures were solved by using SHELXL-97 and Fourier difference tech-
2
niques, and refined by full-matrix least-squares on F . All hydrogen
atoms were added in the calculated positions.
Preparation of the CuII Complex [Cu(L )]
Cu(OAc) ·H O (1.99 mg, 0.01 mmol) in ethanol (2 mL) was added
dropwise to a solution of H
ane (4 mL) at room temperature. The color of the obtained solution
turned to green immediately, then it was allowed to volatilize at room
1
2
2 2
·CH Cl : A solution of
2
2
1
2
L (3.99 mg, 0.01 mmol) in dichlorometh-
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
temperature. After several weeks, the solvent was partially evaporated of the data can be obtained free of charge on quoting the depository
II
II
and green prismatic single crystals were obtained, which were suitable numbers CCDC-1434636 (Cu complex) and CCDC-1434637 (Co
1
for X-ray crystallographic analysis. C35
H30Cl
6
Cu
2
N
4
O
10 ([Cu(L )]
2
·
complex) (Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk,
CH Cl
2
2
): calcd. C 41.77; H 3.00; N 5.57; Cu 12.63%; found: C 41.52;
http://www.ccdc.cam.ac.uk).
H 2.86; N 5.69; Cu 12.85%.
Supporting Information (see footnote on the first page of this article):
Characterization of the ligands and the supramolecular features of the
complexes.
2
L2 is shown in
Preparation of H
3
L : Synthesis of the ligand H
3
2
Scheme 2. H
reported earlier.
calcd. C 59.99; H 5.59, N 7.77%; found: C 59.90; H 5.50; N 7.88%.
3
L was synthesized according to an analogous method
[17,19]
20 2 6
Yield, 84.7%. M.p. 131–132 °C. C18H N O :
1
H NMR (400 MHz, CDCl
.14 (q, J = 6.99 Hz, 2 H, –CH
s, 1 H, O–H), 6.75 (dd, J = 7.79, 1.42 Hz, 1 H, Ar–H), 6.85 (m, 3 H,
Ar–H), 6.94 (dd, J = 6.18, 3.37 Hz, 1 H, Ar–H), 6.98 (dd, J = 7.91, type ligands H L and H L were synthesized from an ethanol/
3
): δ = 1.50 (t, J = 6.99 Hz, 3 H, –CH
3
), Results and Discussion
4
(
2
–), 4.50 (m, 4 H, –CH –CH –), 5.66
2
2
II
II
The Cu and Co complexes with the asymmetric salamo-
1
2
2
3
1
.39 Hz, 1H, Ar–H), 8.24 (s, 1H, N=C–H), 8.28 (s, 1H, N=C–H), 9.67 dichloromethane solution, and characterized by molar conduc-
(s, 1H, O–H), 9.94 (s, 1H, O–H) ppm.
tance, IR and UV/Vis spectroscopy and single-crystal X-ray
diffraction. Both complexes are soluble in DMF, DMSO and
CH Cl , slightly soluble in EtOH and MeOH, but not soluble
Preparation of the CoII Complex [{Co(L )(EtOH)}
2
2
2
Co(H O)]·
2
2
EtOH: A solution of Co(OAc) ·4H O (7.47 mg, 0.03 mmol) in ethanol
2 mL) was added dropwise to a solution of H
2
2
2
in MeCN, THF, acetone, and ethyl acetate, which are similar
(
3
L
(7.21 mg,
[19–22]
to those of the previously reported salamo-type complexes.
0.02 mmol) in dichloromethane (4 mL) at room temperature. The color
1
2 3
2
of the obtained solution immediately turned brown. The solution was Meanwhile, the free ligands H L and H L are soluble in all of
allowed to stand at room temperature for about two weeks. The solvent the aforementioned solvents. Noticeably, only the Cu complex
was partially evaporated and brown prismatic single crystals suitable displays good stability in air at room temperature but the Co
3 4 16
for X-ray crystallographic analysis were obtained. C42H54Co N O
II
II
complex is markedly unstable. The molar conductance values
2
([{Co(L )(EtOH)}
2
Co(H
2
O)]·EtOH): calcd. C 48.15; H, 5.20; N, 5.35;
II
II
–3
–3
of the Cu and Co complexes in 1.0ϫ10 mol·dm
Co, 16.88%; found: C 48.06; H, 5.13; N, 5.49; Co, 16.97%.
2
–1
DMF solutions are 10.4 and 12.8 S·cm ·mol , respectively.
Compared with the molar conductivity in different types of
electrolytes in organic solvents reported by Geary, it can be
X-ray Structure Determinations of the CuII and Co Complexes:
The crystal data and structure refinement of the Cu and Co com-
plexes are given in Table 1. Single crystals of the Cu and Co com- assumed that the Cu and Co complexes are non-electro-
plexes with approximate dimensions of 0.42ϫ0.40ϫ0.12 mm and lytes.
II
II
II
II
II
II
II
3
[23]
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Table 1. Crystal data and structure refinement for the CuII and CoII complexes.
1
2
[
Cu(L )]
2
·CH
2
Cl
2
2 2
[{Co(L )(EtOH)} Co(H O)]·EtOH
Empirical formula
Formula weight
Temperature /K
Wavelength /Å
Crystal system
Space group
C
35
H
30Cl
6
Cu
2
N
4
O
10
42 3 4 16
C H54Co N O
1047.68
298(2)
0.71073
monoclinic
P2(1)/n
1006.40
298(2)
0.71073
orthorhombic
P2
1 1
2 2
a /Å
b /Å
c /Å
15.1589(15)
10.6415(12)
12.1786(13)
13.8354(14)
17.7149(16)
19.5607(17)
98.9710(10)
4735.5(8)
4
1.469
1.110
2.27 to 25.02
2172
β /°
Volume /Å3
1964.6(4)
2
1.701
1.553
2.34 to 25.02
1016
Z
Calcd. density /g·cm–3
Absorption coefficient /mm–1
θ range for data collection /°
F(000)
h/k/l(min, max)
Crystal size /mm
Reflections collected
Independent reflection
Max, min Δρ /e·Å–3
Refinement method
Data / restraints / parameters
–13, 17 / –12, 11 / –14, 14
0.42ϫ0.40ϫ0.12
9878 / 3459 [Rint = 0.0570]
3459
0.8356 and 0.5616
Full-matrix least-squares on F
3459 / 0 / 259
–15, 16 / –21, 18 / –23, 23
0.40ϫ0.22ϫ0.11
23643 / 8353 [Rint = 0.0839]
8353
0.8876 and 0.6650
Full-matrix least-squares on F
8353 / 0 / 591
2
2
a)
Final R indices [I Ͼ 2σ (I)]
R
1
= 0.0451, wR
= 0.0787, wR
2
= 0.0919
= 0.1090
R
1
= 0.0669, wR
= 0.0752, wR
2
= 0.1695
= 0.1707
b)
R indices (all data)
R
1
2
R
1
2
2c)
Goodness-of-fit for F
1.073
0.445 and –0.325
1.110
0.844 and –0.551
Max, min Δρ /e·Å–3
= [Σw(F 2
–F
c
2)2/Σw(F
2 2 1/2
) ] , w = [σ (F
2
2
)+(0.0784P) +1.3233P] , where P = (F
2
–1
2+2F 2)/3. c) GOF = [Σw(F 2–
c o
a) R
1
= Σ||F
o
|–|F
c
||/Σ|F
o
|. b) wR
2
o
o
o
o
2
2
1/2
F
c
) /nobs–nparam)]
.
14,17,26]
FT-IR Spectroscopy
The most important FT-IR spectroscopic data (Figures S3
nated water molecule.[
The O–H stretching frequency
II
–1
of the Co complex appears at 3478 cm , indicating the pres-
[14,27]
ence of coordinated ethanol molecules.
1
2
and S4, Supporting Information) of the ligands H L and H L
1
2
2
3
Both the free ligands H L and H L exhibit characteristic
2
3
II
II
and their corresponding Cu and Co complexes is given in
Table 2. The O–H stretching vibration frequency of salen-type
ligands is expected in the range of 3300–3800 cm , however,
the frequencies of H L and H L are displaced to 3436 and
429 cm , which could be caused by the internal hydrogen
–1
C=N stretching bands at 1607 cm , while the C=N stretching
II
II
bands of the Cu and Co complexes are observed at 1602
–
1
–1
and 1589 cm , respectively. The C=N stretching frequencies
are shifted to lower frequencies by ca. 5 and 18 cm upon
complexation, which show a decrease in the C=N bond order
1
2
2
3
–1
–
1
3
[24]
bond OH···N=C.
Thus, each unit of the polymeric ligands
II
II
due to the coordinated bonds of Cu and Co atoms with the
behaves as a dibasic tetradentate ONNO donor. As the
hydrogen bond becomes stronger, the bandwidth increases, and
this band sometimes is not detected. Electron-donating groups
on the phenolic ring increase the electron density on the hy-
droxyl oxygen making the H–O bond stronger, the absorption
usually appears as a broad band in the FT-IR spectrum. For
[28]
oxime nitrogen lone pair.
The Ar–O stretching frequency appears as a strong band
–1
within 1263–1213 cm range as reported for similar salen-
[29–31]
–1
type ligands.
These bands occur at 1252 and 1244 cm
1
2
for H L and H L , respectively, which are observed at 1242
2
3
–1
II
II
and 1206 cm for the Cu and Co complexes. The Ar–O
stretching frequencies are shifted to lower frequencies, indicat-
II
the Cu complex, the disappearance of this band is expected
II
II
II
due to the substitution of hydrogen for the Cu atom on the ing that the M–O (M = Cu , Co ) bonds are formed between
complex formation.[ Infrared spectra of the Co complex the metal atoms and oxygen atoms of the phenolic
25]
II
show the expected absorptions due to the stretching, bending groups.[28,32]
and wagging modes of water molecule at 3478, 1663, and
The ν(Cu–O) and ν(Cu–N) frequencies are observed at 432
–
1
–1
556 cm , respectively, which indicate the presence of coordi- and 475 cm , while the ν(Co–O) and ν(Co–N) frequencies are
Table 2. Main IR bands /cm–1 for the ligands H L1, H L2 and their CuII and CoII complexes.
2 3
ν(O–H)
ν(C=N)
ν(Ar–O)
ν(M–O)
ν(M–N)
ν(C=C) benzene ring skeleton
1
H
2
L
3436
–
3429
3478
1607
1602
1607
1589
1252
1242
1244
1206
–
432
–
–
475
–
1576, 1522, 1473
1537, 1484, 1438
1576, 1484, 1421
1544, 1454, 1367
II
Cu 2complex
H
3
L
II
Co complex
460
514
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–
1
[17,33]
observed at 460 and 514 cm , respectively.
As pointed attributed to the intra-ligand π–π* transition of the oxime
out by Percy and Thornton,[ the metal-oxygen and metal- group.
32]
[34]
nitrogen frequency assignments are at times difficult.
The absorption peaks of the CuII and CoII complexes are
1
obviously different from those of the free ligands H L and
2
2
H L upon complexation. Compared with the absorption peaks
3
UV/Vis Spectroscopy
of the free ligands, the corresponding absorption peaks at 287
II
II
1
and 279 nm are observed in the Cu and Co complexes,
which are bathochromically shifted by ca. 17 and 7 nm, respec-
tively. Upon coordination of the ligand, the absorption bands
at about 326 and 321 nm disappear from the UV/Vis spectra
UV/Vis absorption spectra of the ligand H L and its corre-
sponding Cu complex are shown in Figure 1, whereas UV/Vis
absorption spectra of the ligand H L and its corresponding Co
complex are shown in Figure 2. UV/Vis absorption spectra of the
free ligands H L , H L , and their corresponding Cu and Co
complexes were determined in 3.0ϫ10 mol·L DMF solu-
tion. The UV/Vis spectrum of the free ligand H L exhibits
two absorption peaks at approximately 270 and 326 nm, while
2
II
2
II
3
II
II
1
2
II
II
of the Cu and Co complexes, which indicates that the oxime
2
3
II
II
–
5
–1
nitrogen atoms are involved in coordination to Cu and Co
atoms.[ The new bands are observed at ca. 387 and 367 nm
for the Cu and Co complexes, and assigned to those of
35]
1
2
II
II
2
LǞM charge-transfer transition, which are characteristic of the
the other ligand H L exhibits two absorption peaks at approxi-
3
[
14]
transition metal complexes with N O coordination spheres.
2 2
mately 272 and 321 nm. The former absorption peaks at 270
and 272 nm can be assigned to the π–π* transition of the benz-
ene rings, meanwhile, the latter at 326 and 321 nm can be
Description of the Crystal Structure of the CuII Complex
II
The single crystal structure of the Cu complex was deter-
mined by X-ray crystallography. The molecule crystallizes in
the orthorhombic system, space group P2 2 2, with two crys-
1
1
tallographically independent molecules in the unit cell. The
II
molecular structure of the Cu complex is shown in Figure 3.
All bond lengths and angles are in normal ranges, selected
bond lengths and angles are listed in Table 3.
Figure 1. UV/Vis absorption spectra of H
Cu complex.
2
L1 and its corresponding
II
Figure 3. Molecular structure and atom numberings of the CuII com-
plex. Thermal ellipsoids are plotted at 30% probability level.
(
hydrogen atoms are omitted for clarity).
II
The Cu atom is four-coordinate, has a N O coordination
2
2
sphere, and has a slightly distorted square-planar arrangement
which distorted tetrahedrally by 29.84(20)° (defined by the
angle between two sets of N–Cu–O planes). Similar distortions
were also observed for [Cu(3-MeOSalamo)][ [41.05(17)°]
16]
[
36]
and tetramethylene analogue [Cu(salbn)]
(42.8°),
(20.1°) and
although shorter analogue [Cu(saltn)][
37,38]
[39]
[
Cu(4-HOSalamo)]·2H O
[16.6(8)°] showed less distor-
2
tions. The distances of Cu–N and Cu–O bonds are in the range
observed for similar systems.[
16,39]
It is noteworthy that the
L2 and its corresponding
3
Figure 2. UV/Vis absorption spectra of H
Co complex.
II
Cu–N bond lengths, 1.991(5) and 1.934(4) Å, are considerably
Z. Anorg. Allg. Chem. 2016, 189–196
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Table 3. Selected bond lengths /Å and angles /° for the CuII complex.
Bond lengths
Cu1–O3
1.896(3)
Cu1–O4
1.902(4)
Cu1–N1
1.991(5) Cu1–N2
1.934(4)
Bond angles
O3–Cu1–O4
O4–Cu1–N2
Cu1–N2–C10
89.28(17)
90.9(2)
128.1(4)
O3–Cu1–N2
N1–Cu1–N2
Cu1–N2–O2
158.00(17)
97.1(2)
117.9(4)
O3–Cu1–N1
Cu1–N1–C3
Cu1–O3–C5
90.4(2)
124.3(4)
127.0(3)
O4–Cu1–N1
Cu1–N1–O1
Cu1–O4–C12 128.2(4)
159.05(18)
126.7(4)
II
II
longer than the Cu–O bond lengths, 1.896(3) and 1.902(4) Å, In the Co complex, the molecule consists of three Co atoms,
2
3–
respectively, which are in agreement with the results of the two (L ) units, one coordinated water, and two coordinated
salamo-type Cu complexes reported earlier.[16,39] The angle and one crystallizing ethanol molecules.
II
[39]
This 2:3 [(L ) :
of O3–Cu1–N1 [90.4(2)°] is nearly equal to that of O4–Cu1– Co ] Co complex is common in the reported salamo-type
2 3–
II
II
II
II
[40,41]
[14,39,40]
N2 [90.9(2)°]. Meanwhile, the Cu atom is displaced Co complexes having the structures of 1:1,
2:3,
42]
II
0
.007(3) Å from the mean plane (O3–N1–N2-O4). The dihe- and 4:8.[ Interestingly, the obtained trinuclear Co complex
II
II
dral angle between the mean plane of Cu1–O4–C12–C11– is totally different from the common reported 2:3 (L:Co ) Co
C10–N2 and its adjacent phenyl ring is 2.55(3)° whereas Cu1– complexes.[
14,39,40]
II
(Figure 5) The terminal Co atom (Co2 or
O3–C5-C4–C3–N1 and its adjacent phenyl ring is 9.43(3)°. Co3) is located in the N O coordination sphere, and coordi-
2
2
However, both the coordination planes (Cu1–O4–C12–C11– nates with one oxygen atom (O14 or O15) of the coordinated
C10–N2 and Cu1–O3–C5-C4–C3–N1) have the dihedral angle ethanol molecule. Meanwhile, the central Co1 atom coordi-
of 35.58(3)°, giving a nonplanar but a ridged configuration. In nates with the four phenol oxygen atoms (O3, O4, O9, and
addition, the ethylenedioxime carbon atoms (C1 and C2) in the O10) and one oxygen atom (O13) of the coordinated water
II
Cu complex are buckled asymmetrically from the Cu1–N1– molecule. It is well known that the coordination number of
II
N2 plane, with the displacement for C1 being 1.428(3) Å to- Co atom is generally four or six and the coordination arrange-
II
[14,40]
ward the plane and for C2 being only 0.599(3) Å in the same ment around the Co atom is tetrahedron or octahedron.
direction.
As a relatively common four-coordinate Cu complex, this amo-type Co complexes.
However, there are a few reports of the five-coordinate sal-
II
II
[39,41]
They have been found to have
mononuclear structure is different from the previously reported distorted square-pyramidal or trigonal-bipyramidal configura-
structures of 1:2,[ 2:2,
21]
[22,24]
2:3, 2:4 (ligand:Cu atom) tions. Herein, we have synthesized a trinuclear Co complex,
[19]
[19]
II
II
II
II
in the salamo-type Cu complexes.
in which the three Co atoms (Co1, Co2, and Co3) are all
five-coordinate with distorted trigonal bipyramids, which were
Description of Crystal Structure of the CoII Complex
deduced by calculating the values of τCo1 = 0.728, τCo2 =
0
.768, and τCo3 = 0.778, respectively.[
43]
II
X-ray crystallographic analysis of the Co complex reveals
formation of a trinuclear structure. The molecular structure of
II
the Co complex is shown in Figure 4. Selected bond lengths Supramolecular Interactions
and angles are given in Table 4.
II
In the crystal structure of the Cu complex, there are three
intermolecular C1–H1B···O5, C2–H2B···O4, and C7–H7···O2
hydrogen bonds, one intermolecular C6–Cl1···Cg4 interaction
and one intermolecular Cg5···Cg5 interaction. (Figures S5 and
S6, Supporting Information, Table 5)
A dimer is built through a pair of intermolecular C7–
H7···O2 hydrogen bonds, which is stabilized through a pair
of C6–Cl1···Cg4 interactions, and one Cg5···Cg5 interaction.
Moreover, one dimer could link another adjacent dimer
through intermolecular C1–H1A···O5 or C2–H2B···O4
hydrogen bonds into an infinite one-dimensional supramolec-
ular structure on the a or b axis, respectively. (Figures S7 and
S8, Supporting Information) Furthermore, one dimer could
link four adjacent dimers into an infinite 2D layer supramolec-
ular structure on the bc crystallographic plane by four pairs of
intermolecular C1–H1B···O5 and C2–H2B···O4 hydrogen
bonds. (Figure S9, Supporting Information)
II
In the crystal structure of the Co complex, there are six
Figure 4. Molecular structure and atom numberings of the CoII com-
plex. Thermal ellipsoids are plotted at 30% probability level.
intramolecular O13–H13B···O11, O13–H13B···O12, O13–
H13C···O5, O14–H14···O10, O15–H15···O4, and O16–
H16···O10 hydrogen bonds, one intermolecular C3–H3···O16
(hydrogen atoms are omitted for clarity).
Z. Anorg. Allg. Chem. 2016, 189–196
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Table 4. Selected bond lengths /Å and angles /° for the CoII complex.
Bond lengths
Co1–O3
Co1–O13
Co2–N1
Co3–O15
2.089(5)
1.985(6)
2.029(7)
2.031(6)
Co1–O4
Co2–O3
Co2–N2
Co3–N3
1.954(5)
2.018(6)
2.098(7)
2.042(7)
Co1–O9
Co2–O5
Co3–O9
Co3–N4
2.068(5)
1.919(5)
2.026(5)
2.094(7)
Co1–O10
Co2–O14
Co3–O11
1.963(6)
1.998(7)
1.923(6)
Bond angles
O3–Co1–O4
O4–Co1–O9
O9–Co1–O13
O3–Co2–N1
O5–Co2–N2
O9–Co3–O11
O11–Co3–O15
O15–Co3–N4
Co1–O4–C6
Co2–O3–C5
Co2–N1–O1
Co3–O11–C30
Co3–N4–C28
81.8(2)
95.2(2)
91.6(2)
87.3(3)
88.0(3)
96.2(2)
111.9(3)
91.6(2)
112.9(5)
125.9(5)
119.3(5)
132.1(5)
126.5(6)
O3–Co1–O9
O4–Co1–O10
O10–Co1–O13
O3–Co2–N2
O14–Co2–N1
O9–Co3–O15
O11–Co3–N3
N3–Co3–N4
Co1–O9–C23
Co2–O5–C12
Co2–N2–O2
Co3–O15–C39
Co3–N4–O8
175.6(2)
131.9(2)
114.4(3)
176.0(3)
129.9(3)
88.3(2)
O3–Co1–O10
O4–Co1–O13
O3–Co2–O5
O5–Co2–O14
O14–Co2–N2
O9–Co3–N3
O11–Co3–N4
Co1–O3–C5
Co1–O9–Co3
Co2–O14–C37
Co2–N2–C10
Co3–N3–C21
97.1(2)
113.7(3)
95.2(2)
113.3(3)
93.7(3)
86.1(2)
87.8(2)
109.5(5)
119.3(3)
129.8(7)
125.4(6)
126.7(6)
O3–Co1–O13
O9–Co1–O10
O3–Co2–O14
O5–Co2–N1
N1–Co2–N2
O9–Co3–N4
O15–Co3–N3
Co1–O3–Co2
Co1–O10–C24
Co2–N1–C3
Co3–O9–C23
Co3–N3–O7
92.6(2)
82.4(2)
87.2(2)
116.8(3)
89.2(3)
175.7(3)
129.0(3)
118.8(3)
112.3(5)
125.7(6)
125.9(5)
119.2(5)
119.1(3)
90.5(3)
109.7(4)
133.0(5)
123.9(6)
125.7(6)
123.5(5)
Figure 5. The formation of the CoII complex.
Table 5. Putative hydrogen bonds and π···π stacking interactions /Å,° for the CuII complex.
D–H···A
D–H
H···A
DHA
D···A
Symmetry code
C1–H1B···O5
C2–H2B···O4
C7–H7···O2
C6–Cl1···Cg4
Cg5···Cg5
0.97
0.97
0.93
1.7340(52)
–
2.55
2.50
2.45
3.448(3)
–
129
139
154
111.7(2)
–
3.249(8)
3.288(8)
3.308(7)
4.395(6)
3.665(3)
3/2 –x, –1/2 + y, 1 –z
3/2 –x, –1/2 + y, 1 –z
1–x, 1 –y, z
1–x, 1 –y, z
1–x, 1 –y, z
hydrogen bond, four intermolecular C1–H1A···Cg1, C2– tions (Figures S10, S11, and S12, Supporting Information,
H2A···Cg7, C19–H19A···Cg4, and C20–H20A···Cg8 interac- Table 6)
Z. Anorg. Allg. Chem. 2016, 189–196
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ARTICLE
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Table 6. Putative hydrogen bonds /Å,° in the CoII complex.
D–H···A
D–H
H···A
DHA
D···A
Symmetry code
O13–H13B···O11
O13–H13B···O12
O13–H13C···O5
O14–H14···O10
O15–H15···O4
O16–H16···O10
C3–H3···O16
C1–H1A···Cg1
C2–H2A···Cg7
C19–H19A···Cg4
C20–H20A···Cg8
0.85
0.85
0.85
0.82
0.82
0.82
0.93
0.970
0.970
0.970
0.970
1.97
2.57
1.97
1.82
1.78
2.18
2.45
2.91
2.68
2.82
2.99
145
134
144
160
172
168
164
3.714(11)
3.427(11)
3.606(9)
3.471(9)
2.716(8)
3.222(8)
2.704(9)
2.604(9)
2.594(8)
2.990(11)
3.346(12)
140
x, y, z
x, y, z
x, y, z
x, y, z
x, y, z
x, y, z
1–x, 1 –y, –z
1–x, 1 –y, –z
1–x, 1 –y, –z
1/2 –x, 1/2 + y, 1/2 –z
1/2 –x, 1/2 + y, 1/2 –z
134
139
112
[
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1
2
II
II
Two salamo-type ligands H L , H L and their Cu and Co
complexes, [Cu(L )] ·CH Cl and [{Co(L )(EtOH)} Co-
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2
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2
2
2
2
[
[
[
(
H O)]·EtOH, were prepared. In their crystal structures, a di-
2
mer is built through a pair of intermolecular hydrogen bonds.
Each dimer is stabilized through π···π stacking interactions,
and links another adjacent dimer through intermolecular
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[
[
II
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II
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II
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This work was supported by the National Natural Science Foundation
of China (21361015), which is gratefully acknowledged.
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Received: November 2, 2015
Published Online: December 22, 2015
Z. Anorg. Allg. Chem. 2016, 189–196
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