Dimethylsulfoxide-induced trinuclear Co(II) and Ni(II) salamo-type complexes: Syntheses, crystal structures and spectral properties

Article abstract of DOI:10.1080/10426507.2018.1452228

Two homotrinuclear Co(II) and Ni(II) complexes, [{CoL(OAc)(DMSO)}₂Co]·2DMSO and [{NiL(OAc)(DMSO)}₂Ni] have been synthesized by the reaction of 4,4′-dichloro-2,2′-[(1,3-propylene)dioxybis(nitrilomethylidyne)]diphenol (H₂L) with cobalt(II) and nickel(II) acetate tetrahydrate in the solution of DMSO, respectively, and characterized by elemental analyses, IR, UV–Vis spectra and X-ray crystallography. In the Co(II) complex, terminal Co2 and Co2^#1 atoms located in the N₂O₂ sites, and are both hexa-coordinated with slightly distorted octahedral geometries. While the central Co1 atom is also hexa-coordinated by six oxygen atoms, four are phenoxy oxygen atoms from two (L)^2? units, and two oxygen atoms from μ₂-acetate ions, which has formed a octahedral geometry. In the Ni(II) complex, coordination environments of the Ni(II) atoms are similar to those of the Co(II) atoms. Infinite 1D supramolecular structure is formed via abundant intermolecular hydrogen bonding interactions in the Co(II) complex.

Full text of DOI:10.1080/10426507.2018.1452228

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
Dimethylsulfoxide-induced Trinuclear Co(II) and
Ni(II) Salamo-type Complexes: Syntheses, Crystal
Structures and Spectral Properties
Xiao-Yan Li, Quan-Peng Kang, Qing Zhao, Jian-Chun Ma & Wen-Kui Dong
To cite this article: Xiao-Yan Li, Quan-Peng Kang, Qing Zhao, Jian-Chun Ma & Wen-Kui Dong
(2018): Dimethylsulfoxide-induced Trinuclear Co(II) and Ni(II) Salamo-type Complexes: Syntheses,
Crystal Structures and Spectral Properties, Phosphorus, Sulfur, and Silicon and the Related
Elements, DOI: 10.1080/10426507.2018.1452228
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Publisher: Taylor & Francis
Journal: Phosphorus, Sulfur, and Silicon and the Related Elements
DOI: https://doi.org/10.1080/10426507.2018.1452228
Dimethylsulfoxide-induced Trinuclear Co(II) and Ni(II)
Salamo-type Complexes: Syntheses, Crystal Structures and
Spectral Properties
Xiao-Yan Li, Quan-Peng Kang, Qing Zhao, Jian-Chun Ma, Wen-Kui Dong*
School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou,
Gansu, 730070, P. R. China
Abstract:
Two
homotrinuclear
Co(II)
and
Ni(II)
complexes,
[{CoL(OAc)(DMSO)}2Co]·2DMSO and [{NiL(OAc)(DMSO)}2Ni] have been synthesized by
the reaction of 4,4ʹ-dichloro-2,2ʹ-[(1,3-propylene)dioxybis(nitrilomethylidyne)]diphenol (H2L)
with cobalt(II) and nickel(II) acetate tetrahydrate in the solution of DMSO, respectively, and
characterized by elemental analyses, IR, UV–Vis spectra and X-ray crystallography. In the
Co(II) complex, terminal Co2 and Co2#1 atoms located in the N2O2 sites, and are both
hexa-coordinated with slightly distorted octahedral geometries. While the central Co1 atom is
also hexa-coordinated by six oxygen atoms, four are phenoxy oxygen atoms from two (L)2-
School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou, Gansu 730070, PR China.
E-mail: dongwk@126.com

units, and two oxygen atoms from µ2-acetate ions, which has formed a octahedral geometry. In
the Ni(II) complex, coordination environments of the Ni(II) atoms are similar to those of the
Co(II) atoms. Infinite 1D supramolecular structure is formed via abundant intermolecular
hydrogen bonding interactions in the Co(II) complex.
Keywords: Salamo-type ligand; Trinuclear complex; DMSO molecule; Synthesis; Crystal
structure
INTRODUCTION
Salen-type1 ligands (R–CH=N–(CH2)n–N=CH–R) and their metal complexes2 have been
extensively investigated in modern coordination chemistry for several decades. Recently, a
novel Salen-type analogue, Salamo3 (R–CH=N–O–(CH2)n–O–N=CH–R), has been developed.
When an O-alkyl oxime unit substitutes the imine moiety, the greater electronegativity of the O
atoms is predicted to improve significantly the electronic behaviors of the Salamo-type

compounds,4 which may give rise to novel structures and better properties of the metal(II)
complexes.5 The novel structures of Salamo-type6 complexes are also fascinating, which may
lead to a better in potential application such as biological fields,7 electrochemical,8 catalysis
activity,9 molecular recognition,10 magnetic materials11 and luminescence properties12 etc.
3f
In our previous work, CH3OH,6b,6d,11a CH3CH2OH,13 CH3CH2CH2OH14, CH3COCH3
,
THF3e and H2O6b,12b were involved in the Salamo-type complexes. In order to study the
differences caused by the coordination of different solvents, we first studied the introduction of
DMSO solvent molecules into the salamo-type complexes. Here we report two new
dimethylsulfoxide-induced
complexes,
[{CoL(OAc)(DMSO)}2Co]·2DMSO
and
[{NiL(OAc)(DMSO)}2Ni]. X-ray crystal structures revealed that they have similar molecular
structures. In the Co(II) and Ni(II) complexes, all the Co(II) and Ni(II) atoms are
hexa-coordinated with octahedral geometries.
RESULTS AND DISCUSSION
IR Spectra analyses
As shown in Fig. S 1 (Supplemental Materials), the FT-IR spectra of H2L and its Co(II)
and Ni(II) complexes exhibit various bands in the 4000–400 cm-1 region. A typical C=N
stretching band of the free ligand H2L appears at 1606 cm-1, while those of the Co(II) and Ni(II)
complexes are observed at 1598 and 1602 cm-1, respectively, which indicates that the nitrogen
atoms of C=N group are coordinated to the Co(II) and Ni(II) atoms.15 Meanwhile, the free
ligand H2L exhibits Ar–O stretching frequency at 1263 cm-1, while the Ar–O stretching
frequencies of the Co(II) and Ni(II) complexes appear at 1201 and 1223 cm-1, respectively. The
Ar–O stretching frequencies of these complexes are shifted to low frequencies, which could be
evidence of formation of the Co(II)–O and Ni(II)–O bonds between metal(II) atoms and
oxygen atoms of phenolic groups.16
UV-vis Spectra analyses

The UV-vis spectra of H2L and its Co(II) and Ni(II) complexes are shown in Fig. S 2.
Obviously, the absorption spectrum of the free ligand H2L consists of three relatively intense
absorption peaks centered at 220, 265 and 323 nm; the former two peaks at 220 and 265 nm can
be assigned to the π-π* transitions of the phenyl rings, the latter peak at 323 nm can be assigned
to the π-π* transitions of the oxime group.17 Upon coordination of the ligand H2L, the first peak
of the π-π* transitions of the phenyl rings in the Co(II) and Ni(II) complexes are
bathochromically shifted to 234 and 231 nm, respectively, and the second peak at 265 nm
disappeared, which indicates the coordination of Co(II) or Ni(II) atoms with the ligand units,
respectively.18 Compared with the free ligand H2L, the third absorption peak at 323 nm
disappears from the UV–vis spectra of the Co(II) and Ni(II) complexes, which indicates that the
oxime nitrogen atoms are involved in coordination to the Co(II) and Ni(II) atoms.18
Additionally, the new absorption peaks are observed at 364 and 372 nm for the Co(II) and
Ni(II) complexes, these new absorption peaks can be assigned to L→M charge-transfer
(LMCT) transitions, which are characteristic of the transition metal complexes with N2O2
coordination sphere.19
Description of the crystal structures
The crystal structures of the Co(II) and Ni(II) complexes were determined by
single-crystal X-ray diffraction. The crystal data and experimental parameters relevant to the
structure determinations are listed in Table 1, and their bond lengths and angles are listed in
Table 2.
Table 1 Crystallographic data and refinement parameters for the Co(II) and Ni(II) complexes.
Table 2 Selected bond lengths (Å) and angles (°) of the Co(II) and Ni(II) complexes.

Crystal structures of the Co(II) and Ni(II) complexes
The crystal structures and atom numberings of the Co(II) and Ni(II) complexes are
in Fig. 1 and Fig. 2, respectively. X-ray crystallographic analysis of the Co(II) complex
a trinuclear structure. It crystallizes in the triclinic system, space group P-1 and consists of
Co(II) atoms, two completely deprotonated (L)2- units, two µ2-acetate ions, two coordinated
DMSO molecules and two crystalling DMSO molecules, which is similar to the previously
reported structure of [{Co(5-ChloroSalamo)(OAc)(THF)}2Co].3e These indicate that the
structures of the Co(II) Salamo-type complexes have no change when the number of carbon
atoms in the alkoxy chain of Salamo-type ligand changed from two to three. In the Co(II)
complex, two terminal Co(II) atoms (Co2 and Co2#1) are located in the N2O2 coordination
spheres of Salamo moieties, one oxygen atom from the coordinated DMSO molecule, the Co2
and Co2#1 atoms are both hexa-coordinated with slightly distorted octahedral geometries.6b
While the central Co(II) atom (Co1) is also hexa-coordinated by six oxygen atoms, four are
phenoxy oxygen atoms from two (L)2- units, and two oxygen atoms from µ2-acetate ions.
Compared with the previously reported complexes3f [{CoL(OAc)(CH3COCH3)}2Co] and
[{CoL(OAc)(MeOH)}2Co]·2MeOH, the DMSO as the solvent molecules involved in the
coordination have been no reported in the Salamo-type complexes until now. Obviously,
complexes informed different intramolecular hydrogen bonds. Because steric hindrance of
these
solvent
molecules
are
different,
the
distances
of
Co2-O7
([{CoL(OAc)(DMSO)}2Co]·2DMSO), Co2-O7 ([{CoL(OAc)(CH3COCH3)}2Co]) and
Co2-O7 ([{CoL(OAc)(MeOH)}2Co]·2MeOH) are 2.152(5), 2.276(2) and 2.136(5) nm,
respectively. The results show that the distances between the metal and the oxygen atoms
the solvent molecules are related to the steric hindrance of these solvent molecules. Structural
similarities may lead to similar properties, so according to our previous reports,3f the Co(II)
complex may have a good antimicrobial activity.

Fig. 1 (a) View of the molecular structure of the Co(II) complex (hydrogen atoms and solvent
molecules are omitted for clarity, and thermal ellipsoids are drawn at the 30% probability
level). (b) Coordination polyhedra for Co(II) atoms of the Co(II) complex.
Fig. 2 (a) View of the molecular structure of the Ni(II) complex (hydrogen atoms and solvent
molecules are omitted for clarity, and thermal ellipsoids are drawn at the 30% probability
level). (b) Coordination polyhedra for Ni(II) atoms of the Ni(II) complex.
The corresponding interactions of the Co(II) and Ni(II) complexes are summarized in
Table S 1. In the Co(II) complex, there are six intramolecular hydrogen bonds, C2H2∙∙∙O5,
C8H8A∙∙∙O3, C8H8A∙∙∙O6, C10H10A∙∙∙O7, C14H14∙∙∙O1 and C21H21A∙∙∙O5. As
shown in Fig. S3. The 1D supramolecular structure20 (Fig. S4) of the Co(II) complex is
formed by intermolecular C20H20A∙∙∙O8, C21H21C∙∙∙O8 and C15H15∙∙∙ O8 hydrogen
bonding interactions.
The Ni(II) complex crystallizes in the monoclinic crystal system, space group P 21/c. The
single-crystal X-ray structure revealed the differences between the Co(II) and Ni(II)
complexes are relatively minor. Contributions to scattering these highly disordered solvent
molecules were removed using the SQUEEZE routine of PLATON. The structure of the
Ni(II) complex was then refined again using the data generated.
The intramolecular hydrogen bonds of CH∙∙∙O (C2H2∙∙∙O6, C8H8A∙∙∙O3,
C8H8A∙∙∙O5, C16H16∙∙∙O1 and C16H16∙∙∙O6) is present in the Ni(II) complex, and the
hydrogen bonds can be seen from Fig. S 5.
EXPERIMENTAL
Materials and general methods

5-Chlorosalicylaldehyde (98%) was purchased from Alfa Aesar and was used without
further purification. 1,3-Dibromoprophane, other reagents and solvents were analytical grade
reagents from Tianjin Chemical Reagent Factory.
Elemental analyses (C, H and N) were performed on a GmbH VarioEL V3.00 automatic
elemental analysis instrument. Elemental analyses for Co(II) or Ni(II) were detected with an
IRIS ER/S-WP–1 ICP atomic emission spectrometer. Melting points were obtained by the use
of a microscopic melting point apparatus made in Beijing Taike Instrument Limited Company
and were uncorrected. IR spectra were recorded on a Vertex70 FT-IR spectrophotometer,
with samples prepared as KBr (4000-500 cm-1). UV–vis absorption spectra were recorded on
a Shimadzu UV-3900 spectrometer. X-ray single crystal structure determinations were carried
out on the Bruker APEX-II CCD and SuperNova, Dual (Cu at zero) Eos four-circle
diffractometers. The Supplemental Materials contains sample characterization data for the
ligand and complexes (Figures S 1 – S 5, Table S 1).
Synthesis of the ligand H2L
The ligand H2L was synthesized according to an analogous method reported earlier.3f,4
(Scheme 1) Yield: 75.8 %. m.p. 164-166 °C. Anal. Calc. for C17H16Cl2N2O4 (%): C 53.02; H
4.11; N 7.45. Found: C 53.28; H 4.21; N 7.31. 1H NMR (400 MHz, CDCl3), δ 2.14 (t, J = 6.0
Hz, 2H, CH2), 4.31 (t, J = 6.0 Hz, 4H, CH2), 6.85 (d, J = 8.0 Hz, 2H, ArH), 7.25 (s, 2H, ArH),
7.33 (d, J = 8.0 Hz, 2H, ArH), 8.09 (s, 2H, CH=N), 9.80 (s, 2H, OH) (Fig. S 6). IR (KBr, cm–
1): 3101 [ν(O-H)], 1606 [ν(C=N)], 1263 [ν(Ar-O)]. UV–Vis (CH3OH), λmax (nm) (εmax): 265
and 323 nm (3.58 × 104, 2.30 × 104 and 1.28 × 104 L·M–1·cm–1).
Scheme 1 Synthetic route to the Salamo-type bisoxime ligand H2L.
Preparation of the Co(II) and Ni(II) complexes

Homotrinuclear Co(II) and Ni(II) complexes were synthesized by the reaction of H2L
with Co(OAc)2 and Ni(OAc)2, respectively (Scheme 2).
Scheme 2 Syntheses of homotrinuclear Co(II) and Ni(II) complexes.
A methanol solution (2 mL) of Co(OAc)2·4H2O (3.74 mg, 0.015 mmol) was slowly
added H2L (3.83 mg, 0.010 mmol) in DMSO (2 mL) and stirred for 0.5 h. The mixed solution
was filtered, and the filtrate was kept undisturbed, several brown blocks single crystals were
obtained after two weeks on slow evaporation of the solution in open atmosphere. Several
brown blocks single crystals suitable for X-ray crystallographic analysis were collected and
then filtration and washed with n-hexane. Yield, 3.43 mg (50.10 %). Anal. Calcd for
C46H58Cl4Co3N4O16S4 (%): C, 40.33; H, 4.27; N, 4.09; Co, 12.91. Found (%): C, 40.64; H,
4.37; N, 3.95; Co, 12.81. IR (KBr, cm–1): 1598 [ν(C=N)], 1303 [ν(Ar-O)]. UV–Vis (CH3OH),
λmax (nm) (εmax): 234 and 364 nm (5.05 × 104 and 1.05 × 104 L·M–1·cm–1).
The Ni(II) complex was prepared by a similar procedure as for the Co(II) complex.
Yield, 3.38 mg (49.30 %). Anal. Calcd for C42H46Cl4Ni3N4O14S4 (%): C, 41.59; H, 3.82; N,
4.62; Ni, 14.52. Found (%): C, 41.75; H, 3.96; N, 4.47; Ni, 14.59. IR (KBr, cm–1): 1602
[ν(C=N)], 1301 [ν(Ar-O)]. UV–Vis (CH3OH), λmax (nm) (εmax): 231 and 372 nm (8.11 × 104
and 1.68 × 104 L·M–1·cm–1).
Further details of the crystal structure investigation may be obtained from the Cambridge
Crystallographic Data Centre, E-mail: deposit@ccdc.cam.ac.uk on quoting the depository
number CCDC–1585966 (The Co(II) complex) and 1585967 (The Ni(II) complex) contain
the supplementary crystallographic data for this article.
CONCLUSIONS

In summary, two homotrinuclear Co(II) and Ni(II) complexes with a Salamo-type
bisoxime ligand H2L have been designed and synthesized. X-ray crystal structures revealed
that they have similar molecular structures. In the Co(II) complex, all the Co atoms are
hexa-coordinated with slightly distorted octahedral geometries. Compared with the reported
complexes, this article compares and discusses the differences in the coordination of different
solvents. The Co(II) complex may have a good antimicrobial activity. Furthermore, the
supramolecular structure of the Co(II) complex is formed via abundant intermolecular
hydrogen bonding interactions leading to a self-assembly infinite 1D chain structure.
ACKNOWLEDGEMENTS
This work was supported by the National Natural Science Foundation of
China (21761018) and the Program for Excellent Team of Scientific Research
in Lanzhou Jiaotong University (201706), which is gratefully acknowledged.

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Table 1 Crystallographic data and refinement parameters for the Co(II) and Ni(II) complexes.
Complexes
Co(II) complex
Ni(II) complex
Empirical Formula
Formula Weight
Crystal System
Space group
a / Å
C46H58Cl4Co3N4O16S4
1369.79
C42H46Cl4N4Ni3O14S2
1212.88
Triclinic
Monoclinic
P 21/c
P-1
9.184(2)
13.3046(12)
16.1262(16)
15.8073(15)
90
b / Å
11.358(3)
14.494(3)
77.399(18)
82.101(18)
88.077(20)
1461.5(6)
c / Å
a / °
β / °
95.847(9)
90
γ / °
V / Å3
3373.9(5)

Z
1
2
D calc (g/cm3)
1.556
1.194
μ (mm-1)
703
1244
Crystal size (mm)
Temp (K)
0.34 x 0.23 x 0.21
294.76(10)
0.33 x 0.21 x 0.19
295.16(10)
Theta range for collection
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness of fit on F2
Final R indices [I > 2σ(I)]
R indices (all data)
Largest difference peak/hole
3.535 to 26.021
9682
3.328 to 26.020
13894
5728
6611
5728 / 0 / 370
1.026
6611 / 0 / 326
0.906
R1 = 0.0703, wR2 = 0.1095
R1 = 0.1601, wR2 = 0.1606
R1 = 0.0544, wR2 = 0.1132
R1 = 0.0923, wR2 = 0.1312
-3
-3
0.996 / -0.521 e.Å
0.640 / -0.449 e.Å

Table 2 Selected bond lengths (Å) and angles (°) of the Co(II) and Ni(II) complexes.
Co(II) complex
Ni(II) complex
Co2-O1
2.025(4)
2.091(4)
2.043(5)
2.152(5)
2.220(5)
2.143(5)
79.35(16)
98.41(19)
89.83(18)
85.12(17)
163.06(18)
91.35(18)
96.85(17)
164.45(18)
84.56(18)
169.33(18)
90.2(2)
Ni2-O1
2.034(3)
Co2-O4
Ni2-O4
2.017(2)
Co2-O6
Ni2-O5
2.021(3)
Co2-O7
Ni2-O7
2.098(3)
Co2-N3
Ni2-N1
2.151(3)
Co2-N7
Ni2-N2
2.109(3)
O1-Co2-O4
O1-Co2-O6
O1-Co2-O7
O1-Co2-N3
O1-Co2-N7
O4-Co2-O6
O4-Co2-O7
O4-Co2-N3
O4-Co2-N7
O6-Co2-O7
O6-Co2-N3
O6-Co2-N7
O7-Co2-N3
O7-Co2-N7
N3-Co2-N7
O1-Ni2-O4
O1-Ni2-O5
O1-Ni2-O7
O1-Ni2-N1
O1-Ni2-N2
O4-Ni2-O5
O4-Ni2-O7
O4-Ni2-N1
O4-Ni2-N2
O5-Ni2-O7
O5-Ni2-N1
O5-Ni2-N2
O7-Ni2-N1
O7-Ni2-N2
N1-Ni2-N2
80.60(10)
94.26(11)
91.56(10)
83.08(12)
165.00(12)
90.40(11)
97.74(10)
163.61(12)
85.47(12)
170.67(11)
89.36(12)
91.35(12)
84.11(11)
84.81(12)
110.91(14)
87.1(2)
83.74(19)
86.9(2)
111.0(2)

Figure legend
Scheme 1 Synthetic route to the Salamo-type bisoxime ligand H2L.
Scheme 2 Synthesis of homotrinuclear Co(II) and Ni(II) complexes.
Fig. 1 (a) View of the molecular structure of the Co(II) complex (hydrogen atoms and solvent
molecules are omitted for clarity, and thermal ellipsoids are drawn at the 30% probability
level). (b) Coordination polyhedra for Co(II) atoms of the Co(II) complex.

Fig. 2 (a) View of the molecular structure of the Ni(II) complex (hydrogen atoms and solvent
molecules are omitted for clarity, and thermal ellipsoids are drawn at the 30% probability
level). (b) Coordination polyhedra for Ni(II) atoms of the Ni(II) complex.

Scheme 1
Scheme 2

Fig. 1

Fig. 2