Syntheses, structures, Hirshfeld surface analyses and magnetic properties of a series of homopolynuclear half-salamo-based complexes

Article abstract of DOI:10.1016/j.poly.2018.08.060

Two newly di- and tri-nuclear Cu(II) and Ni(II) complexes constructed from a half-salamo chelating ligand (HL: 2-[O-(1-ethyloxyamide)]oxime-6-methoxyphenol), [Cu₂(L)₂(μ-OAc)₂] (1) and [{Ni₃(μ-OAc)₂(L)₂(OAc)₂]·CHCl₃ (2), and one tetranuclear Co(II) complex [Co₄(L′)₄(MeOH)₄] (3) based on an unexpected ligand H₂L′ derived from the cleavage of HL have been synthesized and characterized by elemental analyses, IR, UV–vis spectra, and single crystal X-ray diffraction analyses. The single crystals of complexes 1, 2 and 3 in the process of synthesis are obtained through different routes. The complex 1 includes two Cu(II) atoms, two completely deprotonated (L)^? units and two μ-acetate ions, which displays a propeller-type motif. The complex 2 contains three Ni(II) atoms, two completely deprotonated (L)^? units, two μ-acetate ions, two chelating acetate ions and one crystallizing chloroform molecule, the crystal structure of complex 2 reveals a butterfly-type motif. The complex 3 is made up of four Co(II) atoms, four completely deprotonated (L′)^2? units (HL′: 2-[O-(1-hydroxyethyl)]oxime-6-methoxyphenol) and four coordinated methanol molecules, which shows a windmill-type motif. Besides, magnetic properties and Hirshfeld surface analyses were discussed.

Full text of DOI:10.1016/j.poly.2018.08.060

Accepted Manuscript
Syntheses, Structures, Hirshfeld Surface Analyses and Magnetic Properties of
a Series of Homopolynuclear Half-Salamo-Based Complexes
Xiao-Yan Li, Chang Liu, Lei Gao, Yin-Xia Sun, Yang Zhang, Wen-Kui Dong
PII:
S0277-5387(18)30528-X
https://doi.org/10.1016/j.poly.2018.08.060
POLY 13383
DOI:
Reference:
Polyhedron
To appear in:
Received Date:
Revised Date:
Accepted Date:
19 July 2018
23 August 2018
27 August 2018
Please cite this article as: X-Y. Li, C. Liu, L. Gao, Y-X. Sun, Y. Zhang, W-K. Dong, Syntheses, Structures, Hirshfeld
Surface Analyses and Magnetic Properties of a Series of Homopolynuclear Half-Salamo-Based Complexes,
Polyhedron (2018), doi: https://doi.org/10.1016/j.poly.2018.08.060
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Syntheses, Structures, Hirshfeld Surface Analyses and
Magnetic Properties of a Series of Homopolynuclear
Half-Salamo-Based Complexes
Xiao-Yan Li, Chang Liu, Lei Gao, Yin-Xia Sun, Yang Zhang and Wen-Kui Dong*
*School of Chemical and Biological Engineering, Lanzhou Jiaotong University,
Lanzhou, Gansu 730070, PR China
Abstract. Two newly di- and tri-nuclear Cu(II) and Ni(II) complexes constructed from
a half-salamo chelating ligand (HL: 2-[O-(1-ethyloxyamide)]oxime-6-methoxyphenol),
[Cu2(L)2(μ-OAc)2] (1) and [{Ni3(μ-OAc)2(L)2(OAc)2]·CHCl3 (2), and one tetranuclear
Co(II) complex [Co4(Lʹ)4(MeOH)4] (3) based on an unexpected ligand H2Lʹ derived
from the cleavage of HL have been synthesized and characterized by elemental analyses,
IR, UV-vis spectra, and single crystal X-ray diffraction analyses. The single crystals of
complexes 1, 2 and 3 in the process of synthesis are obtained through different routes.
The complex 1 includes two Cu(II) atoms, two completely deprotonated (L)- units and
two -acetate ions, which displays a propeller-type motif. The complex 2 contains three
Ni(II) atoms, two completely deprotonated (L)- units, two μ-acetate ions, two chelating
acetate ions and one crystallizing chloroform molecule, the crystal structure of complex
2 reveals a butterfly-type motif. The complex 3 is made up of four Co(II) atoms, four
completely
deprotonated
(Lʹ)2-
units
(HLʹ:
2-[O-(1-hydroxyethyl)]oxime-6-methoxyphenol) and four coordinated methanol
molecules, which shows a windmill-type motif. Besides, magnetic properties and
Hirshfeld surface analyses were discussed.
Keywords: Half-salamo ligand, Multinuclear complex, Synthesis, Crystal structure,
Magnetic property
1. Introduction
*Prof. Dr. Wen-Kui Dong, E-Mail: dongwk@126.com.

Salen-type ligands (R–CH=N–(CH2)2–N=CH–R) and their metal complexes have
been extensively investigated in modern coordination chemistry for several decades
[1–10]. Chemical modifications of substituents or functional groups in the salen ligands
are effective in exchanging the structures or the main functions of complexes, such as
salamo ligand, a salen analogue, (R–CH= N–O–(CH)n–O–N=CH–R) is one of the most
versatile ligand [11–18]. It is reported that salamo-type complexes are at least 104 times
more stable than salen-type complexes [19].
Fig. 1. Construction of complexes 1, 2 and 3 derived from the half-salamo ligand HL.
We have proceeded with the study of coordination behaviors of a series of
multidentate flexible ligands. Half-salamo ligand (R-CH=N-O-(CH)n-O-NH2) as a first
research has been reported in our recent study [20,21]. Flexible ligands may bring new
changes to the structure, and simple synthesis methods will play a catalytic role in the
development of such complexes [22–30]. The diverse coordination modes of acetate
ions play an important role in the construction of complexes [31–38], for example,
acetate ion can bridge two M(II) atoms in monodentate or bidentate mode [31–38].
However, systematic research on its structure and synthesis methods is still insufficient.
In order to supplement and perfect the syntheses and structures of half-salamo
complexes, in this study, we have synthesized three types of metal(II) complexes
[Cu2(L)2(μ-OAc)2] (1), [{Ni3(μ-OAc)2(L)2(OAc)2]·CHCl3 (2), and [Co4(Lʹ)4(MeOH)4]
(3) with a new half-salamo bisoxime ligand (HL), and the unexpected ligand H2Lʹ is
derived from the cleavage of HL in the process of complexation (Fig. 1). It is worth
noting that the di-, tri- and tetra-nuclear complexes are obtained by different synthetic
methods, and the crystal structures of these complexes show propeller-, butterfly- and
windmill-type motifs, respectively.
2. Experimental
2.1. Materials and general methods
3-Methoxysalicylaldehyde (98%) was purchased from Alfa Aesar and used without
further purification. Reagents and solvents were analytical grade reagents purchased
from Tianjin Chemical Reagent Factory. C, H and N elemental analyses were performed
on a GmbH VarioEL V3.00 automatic elemental analysis instrument. Elemental

analyses for metals 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 (500-4000 cm-1) and CsI (100–500 cm-1) pellets. UV–vis absorption
1
spectra were recorded on a Shimadzu UV-3900 spectrometer. H NMR spectra were
determined by a German Bruker AVANCE DRX-400 spectrometer. X-ray single crystal
structure determinations were carried out on the Bruker APEX-II CCD and a
SuperNova Dual (Cu at zero) diffractometer. Magnetic susceptibility data were
collected on the powdered samples of complexes 1 and 2 at 1000 Oe in the 2–300 K
temperature range using a Quantum Design model MPMS XL7 SQUID magnetometer.
2.2. Synthesis of HL
1,2-Bis(aminooxy)ethane was synthesized following the literature [7]. The major
reaction steps involved in the synthesis of HL are in accordance with the previously
reported procedure (Fig. 1) [4].
An ethanol solution (50 mL) of 3-methoxysalicylaldehyde (152.15 mg, 1.0 mmol)
was added dropwise to 1,2-bis(aminooxy)ethane (138.15 mg, 1.5 mmol) in ethanol
solution (50 mL). The resulting mixed solution was heated to 55 °C under stirring for 2
h. The solution was concentrated in vacuo and the residue was purified by column
chromatography (SiO2, chloroform / ethyl acetate, 15:1) to get a colorless crystalline
solid (HL). Yield: 78.6 % (177.81 mg). m.p. 90~91 °C. Anal. Calc. for C10H14N2O4 (%):
1
C 53.09; H 6.24; N 12.38. Found: C 53.19; H 6.17; N 12.33. H NMR (400 MHz,
CDCl3), δ 9.87 (s, 1H), 8.22 (s, 1H), 6.91 (dd, J = 7.9, 1.5 Hz, 1H), 6.86 (s, 1H), 6.80
(dd, J = 7.7, 1.7 Hz, 1H), 5.52 (s, 2H), 4.40–4.33 (m, 2H), 4.00–3.94 (m, 2H), 3.91 (s,
3H).
2.3. Synthesis of Complex 1
The copper(II) acetate monohydrate (3.98 mg, 0.02 mmol) was dissolved in 2 mL
ethanol solution, 2 mL n-hexane was slowly added, at this point in the liquid phase can
be observed a clear dividing line, then HL (4.52 mg, 0.02 mmol) in ethanol (6 mL) was
injected, with the gradual diffusion of solvent, several dark-green block-shaped single
crystals suitable for X-ray crystallographic analysis were collected at the bottom after

three days at room temperature. Yield: 52.4 % (3.64 mg). Anal. Calcd for
C24H32Cu2N4O12 ([Cu2(L)2(μ-OAc)2] (1)) (%): C, 41.44; H, 4.64; N, 8.05; Cu, 18.27.
Found (%): C, 41.25; H, 4.76; N, 8.22; Cu, 18.16.
2.4. Synthesis of Complex 2
A solution of HL (4.52 mg, 0.02 mmol) in 1 mL of chloroform was added dropwise
to a methanolic solution (1 mL) of nickel(II) acetate tetrahydrate (2.48 mg, 0.01 mmol).
The color of the mixing solution turned to green immediately, and the mixture was kept
stirring for 10 min. Then the mixture was filtered and the filtrate was obtained. The
several green block-shaped single crystals suitable for X-ray crystallographic analysis
were obtained by vapor diffusion of diethyl ether into the filtrate for three days at room
temperature. Yield: 54.3 % (1.78 mg). Anal. Calcd for C29H39Cl3N4Ni3O16
[{Ni3(μ-OAc)2(L)2(OAc)2]·CHCl3 (2)) (%): C, 35.47; H, 4.00; N, 5.70; Ni, 17.93.
Found (%): C, 35.23; H, 4.16; N, 5.87; Ni, 17.71.
2.5. Synthesis of Complex 3
A solution of HL (4.52 mg, 0.02 mmol) in 2 mL of ethyl acetate was added
dropwise to a methanolic solution (2 mL) of cobalt(II) nitrate hexahydrate (5.82 mg,
0.02 mmol). The color of the mixing solution turned to reddish brown immediately, the
mixture solution was filtered and the filtrate was allowed to stand for about one week in
the dark. The solvent was partially evaporated and several reddish brown block-shaped
single crystals suitable for X-ray crystallographic analysis were collected by filtration
and washed with n-hexane. Yield: 48.8 % (2.93 mg). Anal. Calcd for C44H60Co4N4O20
([Co4(Lʹ)4(MeOH)4] (3)) (%): C, 44.01; H, 5.04; N, 4.67; Co, 19.63. Found (%): C,
43.82; H, 5.17; N, 4.77; Co, 19.41.
2.6. X-ray Structure Determinations of Complexes 1, 2 and 3
The crystal diffractometer provides a monochromatic beam of Mo Kα radiation
(0.71073 Å) produced using Graphite monochromator from a sealed Mo X-ray tube was
used for obtaining crystal data of complexes 1, 2 at 296(2) and 3 at 173.00(10) K,
respectively. There are no special reasons for measuring the temperature of these
complexes, mainly due to the different measurement methods used in different
laboratories. The LP factor semi-empirical absorption corrections were applied using

the SADABS program [39]. The structures were solved by the direct methods
(SHELXS-2014), and the H atoms were included at the calculated positions and
constrained to ride on their parent atoms. All non-hydrogen atoms were refined
anisotropically using a full-matrix least-squares procedure on F2 with SHELXL-2014
[40]. The crystal data and experimental parameters relevant to the structure
determinations are listed in Table 1. Supplementary crystallographic data for this paper
have been deposited at Cambridge Crystallographic Data Centre (1579841, 1579840
and 1579842 for complexes 1, 2 and 3) and can be obtained free of charge via
www.ccdc.cam.ac.uk/conts/retrieving.html.
Table 1 Crystallographic data and refinement parameters for complexes 1, 2 and 3.
3. Results and Discussion
3.1. IR Spectra
As shown in Fig. 2, the FT-IR spectra of HL and its complexes 1, 2 and 3 exhibit
various bands in the 500–4000 cm-1 region. Before the measurement of HL and its
complexes 1, 2 and 3, the air scanning was carried out.
Fig. 2. The FT-IR spectra of the ligand HL and its complexes 1, 2 and 3 (cm-1).
A typical C=N stretching band of the free ligand HL appears at 1575 cm-1, while
those of complexes 1, 2 and 3 are observed at 1606, 1605 and 1601 cm-1, respectively
[41]. The C=N stretching frequencies are shifted to high frequencies, indicating that the
metal(II) atoms are coordinated by oxime nitrogen atoms of the ligand units [42].
Meanwhile, the free ligand HL exhibits Ar–O stretching frequency at 1257 cm-1, while
the Ar–O stretching frequencies of complexes 1, 2 and 3 appear at 1246, 1240 and 1221
cm-1, respectively [43]. The Ar–O stretching frequencies of these complexes are shifted
to low frequencies, which could be evidence of formation of the M–O bonds between
metal(II) atoms and oxygen atoms of phenolic groups [44].
The far-infrared spectrum of the complex 1 shows ν(Cu–O) and ν(Cu–N) vibration
absorption frequencies at 432 and 475 cm-1, and the complex 2 for ν(Ni–O) and ν(Ni–N)
at 456, 472 cm-1; the complex 3 for ν(Co–O), ν(Co–N) at 416, 481 cm-1, respectively.
These assignments are consistent with the literature frequency values [14,18] and are

not present in the spectra of the free ligands.
3.2. UV-vis Absorption Spectra
The UV–vis titration experiments of HL in methanol solution (2.5×10−5 M) were
determined with Cu(OAc)2·H2O, Ni(OAc)2·4H2O and Co(NO3)2·6H2O in methanol
solution (1×10−3 M) are shown in Figs. S1–3, respectively.
Upon coordination of the ligand HL, the absorption intensities of complexes 1, 2
and 3 have undergone varying degrees of change, which indicates that the oxime
nitrogen atoms are involved in coordination to the metal(II) atoms [45]. With the
UV–vis titration experiments of complex 1, the absorbance of the solution hardly
changed after Cu2+ was added up to 1 equiv. The spectroscopic titration has clearly
indicated that the ratio of the replacement reaction is 1:1 (Fig. S1). Similar changes have
also appeared in complexes 2 and 3 (Fig. S2 and Fig. S3), the results are corresponding
to the crystal structures of complexes 1, 2 and 3, respectively [46].
The UV-vis spectra of HL and its complexes 1, 2 and 3 (cm-1) are shown in Fig. 3.
Obviously, the absorption spectrum of the free ligand HL consists of two relatively
intense absorption peaks centered at 268 and 317 nm, respectively, the first peak at 268
nm can be assigned to the π-π* transitions of the phenyl rings, the second peak at 317
nm can be assigned to the π-π* transitions of the oxime group [47]. Upon coordination
of the ligand HL, the π-π* transitions of the phenyl rings in complexes 1, 2 and 3 are
bathochromically shifted to 276, 271 and 270 nm, respectively, which indicates the
coordination of the ligand units with Cu(II), Ni(II) and Co(II) atoms, respectively [48].
Compared with the free ligand HL, the absorption peak at 317 nm disappears from the
UV–vis spectra of complexes 1, 2 and 3, which indicates that the oxime nitrogen atoms
are involved in coordination to the Cu(II), Ni(II) and Co(II) atoms [49]. Additionally,
the new absorption peaks are observed at 378, 376 and 363 nm for complexes 1, 2 and 3,
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 [50].
Fig. 3. The UV-vis spectra of HL and its complexes 1, 2 and 3 in methanol (c =
2.5×10−5 M).
3.3. Crystal Structure Descriptions

3.3.1. Complex 1
As depicted in Fig. 4 and Table 2, complex 1 ([Cu2(L)2(μ-OAc)2]) crystallizes in
the monoclinic system, space group P 21 / c, and the crystal structure indicates that
complex 1 is a symmetric homo-dinuclear complex, which consists of two Cu(II) atoms,
#
two completely deprotonated (L)- unit and two μ-acetate ions. The symmetry code is
-x+1, -y+1, -z+2.
Fig. 4. (a) Molecular structure and atom numberings of complex 1 with 30%
probability displacement ellipsoids (hydrogen atoms are omitted for clarity). (b)
Coordination polyhedra for Cu1 and Cu1# atoms of complex 1.
Table 2 Selected bond lengths (Å) and angles (°) for complex 1.
The Cu(II) atom (Cu1) is penta-coordinated by two oxime nitrogen (N1 and N2) and
one phenoxo oxygen (O2) atom from the completely deprotonated (L)- units and two
μ-acetate oxygen (O5 and O5#) atoms (Fig. 4a). The coordination environment around
the Cu1 atom is best described as a slightly distorted tetragonal pyramidal geometry.
The τ value is estimated to be τ = 0.1295 (Fig. 4b) [51–54]. The oxime nitrogen (N1 and
N2) atoms and phenolic oxygen (O2) atom of the (L)- unit, and the μ-acetate oxygen
(O5) atom constitute together the basal plane (Cu1-N1, 1.996(2) Å; Cu1-N2, 1.985(2) Å;
Cu1-O2, 1.906(2) Å and Cu1-O5, 1.988(2) Å), and another μ-acetate oxygen (O5#)
atom occupies the vertex position (Cu1-O5#, 2.413(2) Å). The four coordination (N1,
N2, O2 and O5) atoms on the base plane deviate from the mean plane, with N2 and O2
above average by 0.249(2) and 0.287(2) Å, and N1 and O5 below average by 0.246(2)
and 0.289(2) Å, respectively. Meanwhile, the Cu1 atom is 0.276(2) Å displaced from
the mean plane and the Cu···Cu distance is 3.359(2) Å. Additionally, the dihedral angle
between the coordination planes of O2–Cu1–N1 and O5–Cu1–N2 is 23.59(2). The
dihedral angle between the benzene ring and basal plane (metal N2O plane) is 11.82(2),
which defined as shown in Fig. S4a.
It is worth noting that the μ-acetate ions play an important role in the construction of
propeller-type motif. As shown in Figs. 5 and 6, in the complex 1, the two monodentate
acetate ions bridge two Cu(II) atoms through the oxygen atoms, forming a binuclear
symmetric structure. In the process of forming complex 1, the oxygen (O5 and O5#)

atoms of the two μ-acetate ions both occupy the vertex positions of the tetragonal
pyramidal geometries and participate in the construction of the base plane of another
tetragonal pyramidal geometry, which makes the structure of complex 1 exhibiting a
highly distorted symmetry configuration.
Fig. 5. Acetic acid coordinated modes for complexes 1 and 2.
Fig. 6. Perspectives of the core in complexes 1, 2 and 3.
3.3.2. Complex 2
As shown in Fig. 7 and Table 3, X-ray crystallographic analysis of complex 2
([{Ni3(μ-OAc)2(L)2(OAc)2]·CHCl3) reveals an asymmetric trinuclear structure. It
crystallizes in the triclinic system, space group P -1, consists of three Ni(II) atoms, two
completely deprotonated (L)- units, two μ-acetate ions, two chelating acetate ions and
one crystallized chloroform molecule.
Fig. 7. (a) Molecular structure and atom numberings of complex 2 with 30% probability
displacement ellipsoids (hydrogen atoms are omitted for clarity). (b) Coordination
polyhedra for Ni1, Ni2 and Ni3 atoms of complex 2.
Table 3 Selected bond lengths (Å) and angles (º) for complex 2.
As illustrated in Fig. 7a, the coordination model around the terminal Ni(II) (Ni2 and
Ni3) atoms are very similar. Ni2 is hexa-coordinated by two oxime nitrogen (N3 and N4)
atoms and one phenolic oxygen (O6) atom of the completely deprotonated (L)- unit, two
oxygen (O13 and O14) atoms from the chelating acetate ion and one oxygen (O9) atom
from the μ-acetate ion. Ni3 is also hexa-coordinated by two oxime nitrogen (N1 and N2)
atoms and one phenolic oxygen (O2) atom of the completely deprotonated (L)- unit, two
oxygen (O15 and O16) atoms from the chelating acetate ion and one oxygen (O12)
atom from the μ-acetate ion. The coordination geometry around the terminal Ni(II) (Ni2
or Ni3) atom is found to be a slightly distorted octahedron [55–58]. The two Ni···Ni
distances between the terminal (Ni2 or Ni3) and central Ni1 atoms are 3.496(2) and
3.507(2) Å, respectively. Meanwhile, the coordination sphere of the central Ni(II) (Ni1)
atom is completed by two μ-phenoxo oxygen (O2 and O6) atoms and two methoxyl

oxygen (O1 and O5) atoms from two (L)- units and two μ-acetate oxygen (O10 and O11)
atoms, which indicates the central Ni1 atom finally has an O2O2O2 coordination
environment (Fig. 7b) [59–61]. The μ-acetate ions and two chelating acetate ions have
two different coordination modes in the structure of complex 2 (Fig. 5). The two
μ-acetate ions has been bridged with central Ni1 and terminal Ni2 or Ni3 atoms in both
cases via familiar Ni–O–C–O–Ni bridges with the four μ-acetate oxygen (O9, O10, O11
and O12) atoms [62]. The dihedral angles between the benzene rings and basal planes
(N2O planes) are 16.71(2) and 10.74(2), respectively, which defined as shown in Fig.
S4b. Besides, the four oxygen (O13, O14, O15 and O16) atoms of the chelating acetate
ions coordinated with the terminal Ni2 or Ni3 atom, respectively, which satisfies the
coordination number of Ni(II) atoms [63–66]. As shown in Figs. 5 and 6. Different from
complex 1, in the complex 2, two bidentate acetate ions bridge the two terminals Ni(II)
atoms by the two oxygen atoms, in addition, two acetate ions coordinate to the two
terminal Ni(II) atoms in chelating bidentate, forming a trinuclear asymmetric structure.
Different amounts of bridging metal centers of acetate ions may be due to different
coordination numbers of different metal atoms, Cu(II) atoms tend to form a
tetra-coordinated or penta-coordinated structures, and Ni(II) atoms are usually
hexa-coordinated structures. In the asymmetric trinuclear structure, the framework of
the butterfly-type motif is constructed by three Ni(II) atoms, and the deprotonated (L)-
units as the wings of the butterfly.
3.3.3. Complex 3
The crystallographic data reveal that complex 3 ([Co4(Lʹ)4(MeOH)4]) crystallizes
in the triclinic system, space group P -1, consists of four Co(II) atoms, four completely
deprotonated (Lʹ)2- units and four coordinated methanol molecules.
As shown in Fig. 8a and Table 4, the crystal structure indicates that complex 3 is an
asymmetric homo-tetranuclear complex, the coordination environment of Co1 atom is
hexa-coordinated by one oxime nitrogen (N1) atom, one phenolic oxygen (O6) atom
and one hydroxyl oxygen (O2) atom from the completely deprotonated (Lʹ)2- unit, one
oxygen (O9) atom from the coordinated methanol molecule and the other two hydroxyl
oxygen (O1 and O3) atoms from the adjacent half-salamo units. The coordination
environment of other three Co(II) atoms in complex 3 are similar to Co1. All of the
Co(II) atoms in complex 3 have slightly distorted octahedral geometries (Fig. 8b) [67].

The dihedral angles between the benzene rings and basal planes (NO2 planes) are
14.80(2), 10.45(2), 5.26(2) and 1.52(2) respectively, which defined as shown in Fig.
S4c. The coordinated methanol molecules have satisfied the coordination number of
Co(II) atoms. As shown in Fig. 5, the ligand H2Lʹ is derived from the cleavage of HL in
the complexation of HL and Co(II) salt. The fragility of the ligand is similar to that
reported previously [68–70]. This phenomenon is found in the salamo-type Co(II)
complexes for the first time. The different directions of half-salamo units form the four
sails of the windmill-type motif and the homo-tetranuclear of central position forms the
basic framework. The cubic crystal skeleton is constructed by Co4O4, the four Co(II)
atoms and four oxygen atoms occupy the vertex positions of the cube, respectively, and
each surface is formed by two Co(II) atoms and two oxygen atoms lying on the diagonal,
and the average lengths of the two Co···Co and O···O lengths are in the ranges of
3.132(3)–3.226(2) and 2.680(2)–2.796(3) Å, respectively (Fig. S4c).
Fig. 8. (a) Molecular structure and atom numberings of complex 3 with 30% probability
displacement ellipsoids (hydrogen atoms are omitted for clarity). (b) Coordination
polyhedra for Co1, Co2, Co3 and Co4 atoms of complex 3.
Table 4 Selected bond lengths (Å) and angles (º) for complex 3.
3.4. Intermolecular Interactions
3.4.1. Complex 1
The main interactions in complex 1 are listed in Table S1, two pairs of the
intramolecular N2–H2A···O1, N2–H2A···O2, N2–H2A···O5 and N2–H2B···O6
hydrogen bonds are formed. The protons (-N2H2A and -N2H2B) as donors from the
(L)– units form hydrogen bonds with oxygen (O5) atom of the μ-acetate ion, phenolic
oxygen (O2) and methoxyl oxygen (O1) atoms as acceptors of the (L)– units,
respectively. The proton (-N2H2B) as donor from the (L)– unit forms hydrogen bond
with oxygen (O6) atom as acceptor of the μ-acetate ion (Fig. 9a) [71]. Besides, two of
the intermolecular C-H···π stacking interactions in complex 1 are formed (Fig. 10). The
Cg5 (C2–C7) of phenyl ring as acceptor from the (L)– unit forms two hydrogen bonds
with the protons (-C1H1A and -C8H8) as donors of two adjacent complex 1 molecules,
which adopts a 3D intermolecular structure [72]. The polyhedra of the Cu1 and Cu1#

atoms of complex 1 are shown in Fig. 10. The octahedra around the Cu atoms are
depicted in green colour.
Fig. 9. Intramolecular hydrogen bonds of complexes 1, 2 and 3 (hydrogen atoms, except
those forming hydrogen bonds, are omitted for clarity).
Fig. 10. View of the 3D intermolecular structure of complex 1 showing the C-H···π.
3.4.2. Complex 2
As illustrated in Fig. 9b and Table S2, four of the intramolecular N2–H2B···O10,
N4–H4B···O11, C9–H9A···O15 and C19–H19A···O14 hydrogen bonds in complex 2
are formed. The protons (–N2H2B and –N4H4B) from imine groups of the (L)– units
form hydrogen bonds with oxygen (O10 and O11) atoms of the -acetate ions and the
protons (–C9H9A and –C19H19A) of ethylenedioxime carbon atoms of the (L)– units
form hydrogen bonds with oxygen (O14 and O15) atoms of the chelating acetate ions
[73]. As shown in Fig. 11, the 3D intermolecular structure of complex 2 is composed
of two parts. The first part was linked by intermolecular N2–H2AO15,
N4–H4AO14, C5–H5O16 and C29–H29O16 hydrogen bonds, the protons
(–N2H2A, –N4H4A and –C5H5) of the (L)– units form three hydrogen bonds with the
oxygen (O15, O14 and O16) atoms of three adjacent complex 2 molecules. Meanwhile,
the proton (–C29H29) of the crystallizing chloroform molecule as donor atom forms
hydrogen bond with oxygen (O16) atom of adjacent complex 2 molecule [73]. Another
part was made up of the C-Hπ and C-Cl···π stacking interactions. The Cg6 (C2–C7)
and Cg7 (C12–C17) of phenyl rings as acceptors form two stacking interactions with the
protons (-C29Cl3 and -C11H11A) from the crystallizing chloroform molecules and the
adjacent complex 2 molecules, respectively. The crystallizing chloroform molecules
play an important role in intermolecular construction of complex 2 [74], which are
similar to that in the previously reported complex, the strong intermolecular
interactions were formed by solvent molecule. Finally, the complex formed a 1D
intermolecular structure. The existence of the solvent molecules made the
intermolecular force more abundant, and the structure more stable [75]. In addition,

complex 2 molecules form a 3D intermolecular structure by intermolecular hydrogen
bonds, C-Hπ and C-Cl···π stacking interactions. The polyhedra of the Ni1, Ni2 and
Ni3 atoms of complex 2 are shown in Fig. 11. The octahedra around the Ni atoms are
depicted in sky blue colour.
Fig. 11. View of the 3D intermolecular structure of complex 2 showing the C-H···π.
3.4.3. Complex 3
As shown in Fig. 9c and Table S3, there are abundant intramolecular hydrogen
bonds in complex 3. The coordinated methanol hydrogen atoms as donors form
hydrogen bonds with phenolic oxygen (O5, O6, O7 and O8) atoms and methoxyl
oxygen (O11, O13, O14 and O15) atoms. The protons (–C9H9A, –C19H19A and
–C29H29B) from ethylenedioxime carbon atoms form hydrogen bonds with oxime
nitrogen (N1, N3 and N4) atoms [74]. Besides, the protons (–C10H10B, –C20H20B and
–C40H40A) from ethylenedioxime carbon atoms form hydrogen bonds with the
coordinated methanol oxygen (O12,O10 and O9) atoms. Furthermore, complex 3
molecules form a dimer by one pair of intermolecular hydrogen bonds
(C29-H29A···O16) (Fig. 12) [74]. The polyhedra of Co1, Co2, Co3 and Co4 atoms of
complex 3 are depicted in Fig. 12. The octahedra around the Co atoms are depicted in
orange colour.
Fig. 12. View of a dimer formed by complex 3 molecules via the C-H···O hydrogen
bonding interactions.
3.5. Magnetic Properties
The magnetic analyses of the complexes 1 and 2 were tested under the applied
magnetic field of 1000 Oe, and the magnetic susceptibility data of the complexes 1 and
2 in the temperature range of 2–300 K were measured, the measured sample with the
single-crystals of the complexes 1 and 2. The temperature dependence of magnetic
susceptibilities of complexes 1 and 2 are shown in Figs. 13 and 14, respectively.
Because the ligand in the complex 3 is broken, it is not easy to get than the complexes 1

and 2, and the magnetic measurement requires a large number of crystals, so there is no
magnetic study of the complex 3.
The χMT value at 300 K for complex 1 is 0.76 emu K mol-1, which is larger than
the the value of 0.7 emu K mol-1 expected for two Cu(II) (S = 1/2) magnetically isolated
ions. Upon lowering the temperature, the χMT value of complex 1 gradually decreases to
reach a minimum value of 0.65 emu K mol-1 at 50 K, which implies that a weak
antiferromagnetic interaction exists in such a complex [76]. What is more, the magnetic
susceptibilities (1/χM) obey the Curie–Weiss law in the 2–300 K temperature range,
giving a negative Weiss constant θ = –11.56 K and C = 0.81 emu K mol-1 (Fig. 13, inset),
the best-fit for χMT vs. T with a Hamiltonian H = –2J(SCu1·SCu2) leads to the parameters
J = –21.86 cm-1 for complex 1, and confirming the antiferromagnetic interaction
exhibited again [76]. It has similar property to the reported salen-type binuclear Cu(II)
complex [77].
Fig. 13. Plots of χMT vs. T for complex 1 from 2 to 300 K. Inset: Temperature
dependence of χM-1. The red solid lines represent the best fitting results.
The χMT value at 300 K for complex 2 is 4.21 emu K mol-1, which is larger than the
the value of 3 emu K mol-1 expected for three Ni(II) (S = 1) magnetically isolated ions.
Upon lowering the temperature, the χMT value of complex 2 gradually decreases to
reach a maximum value of 5.22 emu K mol-1 at 14 K, the χMT value increased with
decreasing temperature, indicating an intramolecular ferromagnetic interaction between
the three Ni(II) atoms [76]. Then, the χMT value reduced to 1.81 emu K mol-1 when the
temperature reached 2 K. The magnetic susceptibilities (1/χM) obey the Curie–Weiss
law giving a negative Weiss constant θ = 3.32 K and C = 4.22 emu K mol-1 (Fig. 14,
inset), the best-fit for χMT vs. T with a Hamiltonian H = –2J(SNi1·SNi2 + SNi1·SNi3) leads
to the parameters J = 49.76 cm-1 for complex 2, exhibiting the ferromagnetically
interaction in complex 2 [76]. Compared with the similar Ni(II) complex reported
previously [63], it has different properties, probably due to the different coordination
environment and bridging mode of the Ni(II) atoms.
Fig. 14. Plots of χMT vs. T for complex 2 from 80 to 300 K. Inset: Temperature
dependence of χM-1. The red solid lines represent the best fitting results.

3.6. Hirshfeld Surface Analyses
The Hirshfeld surfaces [78] provide a three-dimensional picture of close contacts
in a crystal, and these contacts can be summarized in a fingerprint plot. The Hirshfeld
surfaces of complexes 1, 2 and 3 are depicted in Fig. S5, showing surfaces that have
been mapped over dnorm (a), shape index (b) and curvedness (c). Another important
supplement for Hirshfeld surface is the 2D fingerprint plots [79], allowing quantitative
analysis of the nature and type of intermolecular interactions between molecules. The
O···H/H···O intermolecular interactions are distinct spikes in the 2D fingerprint plot
(Fig. 15). The O···H interactions are represented via a spike in the bottom left (donor)
area of the fingerprint plot (Fig. 15), the H···O interactions are represented via a spike
in the bottom right (acceptor) region of the fingerprint plot. The fingerprint plots can be
decomposed to highlight particular atom pair close contacts. This decomposition
enables separation of contributions from different interaction types, which overlap in the
full fingerprint.
The relative contribution of the different interactions to the Hirshfeld surface was
calculated for complexes 1, 2 and 3 have been given in Fig. 16. The proportion of
O···H/H···O, C···H/H···C and H···H interactions comprises 25.1%, 16.8% and 51.3%
of the total Hirshfeld surfaces for each molecule of the complex 1, respectively. For the
complex 2, the proportion of O···H/H···O, C···H/H···C, Cl···H/H···Cl and H···H
interactions are 20.3%, 6.2%, 21.2%, and 47%, respectively, which can be seen that the
interaction of Cl···H by chloroform molecule is only less than H···H, so the chloroform
molecule makes the structure more stable. For the complex 3, the proportion of
O···H/H···O, C···H/H···C and H···H interactions are 9.1%, 15.9% and 74.4%,
respectively. The main contact in complexes 1, 2 and 3 is H···H interactions. Because
there are more hydrogen atoms in the crystal structures and most of them are
short-range action, the interaction between H...H is the most, which is similar to the
previously reported complexes [80].
Fig. 15. Fingerprint plot of the complexes 1 (a), 2 (b) and 3 (c): full and resolved into

full and resolved into O···H, C···H, Cl···H and H···H contacts showing the percentages
of contacts contributed to the total Hirshfeld surface area of molecule.
Fig. 16. Relative contributions of various intermolecular contacts to the Hirshfeld
surface area in complexes 1, 2 and 3.
4. Conclusions
The self-assembling of di-, tri- and tetra-nuclear Cu(II), Ni(II) and Co(II)
complexes based on a half-salamo ligand HL were successfully synthesized and
characterized structerally. The crystal structures of complexes 1, 2 and 3 show
propeller-, butterfly- and windmill-type motifs, respectively. In complexes 1 and 2, the
ideal size, shape as well as strong coordination ability of OAc- as an anion significantly
stabilize the aesthetic structure, while in complex 3, the hydroxyl radical of an
unexpected ligand H2Lʹ, which derived from the cleavage of HL are coordinated with
three Co(II) atoms at the same time. Furthermore, magnetic properties of complexes 1
and 2 were also studied. The magnetic susceptibility measurement of the complex 1
shows that the Cu(II) centers are antiferromagnetically coupled. While, in the complex 2
the Ni(II) ions are ferromagnetically coupled. Quantification of the intermolecular
interactions present in all complexes was realized by Hirshfeld surface analyses and 2D
fingerprint plots. The close contacts of these complexes are dominated by H···H, C···H
and O···H contacts. Meanwhile, the intermolecular interactions presented in the total
crystal structures were discussed by Hirshfeld surface analyses in form of decomposed
fingerprint plots.
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), both of which are gratefully
acknowledged.
Conflicts of Interest: There is no conflict of interest among all authors.

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Table 1 Crystallographic data and refinement parameters for complexes 1, 2 and 3.
Complex
1
2
3
Formula
C24H32Cu2N4O12
695.61
C29H39Cl3N4Ni3O16
982.12
C44H60Co4N4O20
1200.68
173.00(10)
0.71073
Triclinic
P-1
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
Space group
Unit cell dimensions
a (Å)
296 (2)
296(2)
0.71073
Monoclinic
P21/c
0.71073
Triclinic
P-1
10.729(5)
15.964(8)
9.351(5)
90°
116.432(8)°
90°
13.016(4)
13.101(4)
16.083(5)
113.500(7)
95.345(7)
112.054(7)
2233.8(12)
2
14.0570(13)
14.8345(14)
16.9474(16)
70.111(9)
74.191(8)
71.734(8)
3100.9(6)
2
b (Å)
c (Å)
α (°)
β (°)
γ (° )
V (Å3)
1434.1(12)
2
Z
Dc (g cm-3)
μ (mm– 1)
F (000)
1.611
1.551
716
1.460
1.495
1008
1.286
1.117
1240
Crystal size (mm)
θ Range (°)
Index ranges
0.26 × 0.22 × 0.19
2.120–25.004
-12 ≤ h ≤ 12,
-18 ≤ k ≤ 14,
-8 ≤ l ≤ 11
7875
0.28 × 0.26 × 0.22
2.575–25.082
-15 ≤ h ≤ 15,
-15 ≤ k ≤ 14,
-18 ≤ l ≤ 19
7769
0.26 × 0.22 × 0.18
3.350–25.008
-16 ≤ h ≤ 16,
-17 ≤ k ≤ 17,
-17 ≤ l ≤ 20
20058
Reflections collected
Independent reflections
Rint
2522
0.0186
7769
0.0626
10908
0.0487
Completeness
99.8%
98.4%
99.7%
Data/restraints/parameters
GOF
2522/0/192
1.039
7769/0/503
0.980
10908/16/670
1.012
aR1 / bwR2 [I>2σ(I)]
largest differences
peak and hole (e Å– 3)
0.0244/ 0.0657
0.338/–0.197
0.0663/0.1742
1.513/–1.083
0.0495/0.1040
0.645/–0.653
a R1 = Σ‖Fo| − |Fc‖/Σ|Fo|; bwR2 = [Σw(Fo - Fc2)2/Σw(Fo ) ] .
2
2 2 1/2

Table 2 Selected bond lengths (Å) and angles (°) for complex 1.
Bond
Cu1-O2
Cu1-O5
Cu1-O5#
Angles
1.906(2)
1.988(2)
2.413(2)
Cu1-N1
Cu1-N2
Cu1#-O5
2.000(2)
1.985(2)
2.413(2)
O2-Cu1-N2
N2-Cu1-O5
N2-Cu1-N1
O2-Cu1-O5#
O5-Cu1-O5#
Cu1-O5-Cu1#
166.19(7)
86.99(8)
100.62(8)
85.45(6)
80.97(6)
99.03(6)
O2-Cu1-O5
O2-Cu1-N1
O5-Cu1-N1
N2-Cu1-O5#
N1-Cu1-O5#
86.20(8)
90.02(8)
158.42(7)
81.61(6)
119.94(6)
Symmetry transformations used to generate equivalent atoms: # -x+1, -y+1, -z+2

Table 3 Selected bond lengths (Å) and angles (º) for complex 2.
Bond
Ni1-O6
Ni1-O10
Ni1-O2
Ni1-O11
Ni1-O5
Ni1-O1
Ni3-O2
Ni3-O12
Ni3-O16
Angles
2.007(5)
2.010(5)
2.021(5)
2.022(4)
2.132(4)
2.178(5)
1.996(4)
2.100(4)
2.127(5)
Ni2-O6
Ni2-O9
Ni2-O13
Ni2-O14
Ni2-N3
Ni2-N4
Ni3-O15
Ni3-N1
Ni3-N2
2.021(5)
2.071(4)
2.117(5)
2.160(5)
2.109(5)
2.053(5)
2.139(4)
2.107(6)
2.048(6)
O6-Ni1-O10
O6-Ni1-O2
O10-Ni1-O2
O6-Ni1-O11
O10-Ni1-O11
O2-Ni1-O11
O6-Ni1-O5
O10-Ni1-O5
O2-Ni1-O5
O11-Ni1-O5
O6-Ni1-O1
O10-Ni1-O1
O2-Ni1-O1
O11-Ni1-O1
O5-Ni1-O1
O2-Ni3-N2
O2-Ni3-O12
O12-Ni3-O15
N2-Ni3-O12
O2-Ni3-N1
N2-Ni3-N1
N2-Ni3-O16
N1-Ni3-O16
Ni3-O2-Ni1
94.61(19)
163.18(18)
96.93(18)
97.67(18)
92.78(18)
93.96(18)
78.68(17)
91.70(18)
88.76(18)
174.44(17)
90.41(19)
174.02(19)
77.49(19)
89.77(18)
86.09(18)
93.9(2)
O6-Ni2-N4
O6-Ni2-O9
N4-Ni2-O9
O6-Ni2-N3
N4-Ni2-N3
O9-Ni2-N3
O6-Ni2-O13
N4-Ni2-O13
O9-Ni2-O13
N3-Ni2-O13
O6-Ni2-O14
N4-Ni2-O14
O9-Ni2-O14
N3-Ni2-O14
O13-Ni2-O14
O2-Ni3-O15
N2-Ni3-O15
O12-Ni3-N1
N1-Ni3-O15
O16-Ni3-O15
O2-Ni3-O16
O12-Ni3-O16
Ni1-O6-Ni2
93.2(2)
94.98(18)
88.90(19)
84.5(2)
91.4(2)
179.4(2)
97.80(19)
168.9(2)
88.42(19)
91.4(2)
159.62(17)
107.2(2)
86.72(19)
93.7(2)
61.90(18)
159.28(19)
106.8(2)
177.95(19)
96.1(2)
93.23(18)
85.96(17)
89.4(2)
84.8(2)
62.41(17)
96.87(18)
86.85(19)
120.3(2)
90.0(2)
168.8(2)
94.1(2)
121.8(2)

Table 4 Selected bond lengths (Å) and angles (º) for complex 3.
Bond
Co1-O1
Co1-O2
Co1-O3
Co1-O6
Co1-O9
Co1-N1
Co3-O1
Co3-O2
Co3-O4
Co3-O7
Co3-O18
Co3-N3
Angles
2.192(2)
2.020(2)
2.114(3)
1.991(2)
2.159(3)
2.105(3)
2.010(2)
2.174(2)
2.103(3)
1.987(2)
2.171(3)
2.110(3)
Co2-O2
Co2-O3
Co2-O4
Co2-O5
Co2-O10
Co2-N2
Co4-O1
Co4-O3
Co4-O4
Co4-O8
Co4-O12
Co4-N4
2.108(3)
2.198(2)
2.010(2)
1.981(2)
2.199(3)
2.102(3)
2.118(3)
2.020(2)
2.184(2)
2.001(2)
2.146(2)
2.114(4)
O2-Co1-O1
O2-Co1-O3
O2-Co1-O9
O2-Co1-N1
O3-Co1-O1
O3-Co1-O9
O6-Co1-O1
O6-Co1-O2
O6-Co1-O3
O6-Co1-O9
O6-Co1-N1
O9-Co1-O1
N1-Co1-O1
N1-Co1-O3
N1-Co1-O9
O1-Co3-O2
O1-Co3-O4
O1-Co3-O18
O1-Co3-N3
O4-Co3-O2
O4-Co3-O18
O4-Co3-N3
O7-Co3-O1
O7-Co3-O2
O7-Co3-O4
O7-Co3-O18
O7-Co3-N3
O18-Co3-O2
79.24(9)
85.06(9)
O2-Co2-O3
O2-Co2-O10
O3-Co2-O10
O4-Co2-O2
O4-Co2-O3
O4-Co2-O10
O4-Co2-N2
O5-Co2-O2
O5-Co2-O3
O5-Co2-O4
O5-Co2-O10
O5-Co2-N2
N2-Co2-O2
N2-Co2-O3
N2-Co2-O10
O1-Co4-O4
O1-Co4-O12
O3-Co4-O1
O3-Co4-O4
O3-Co4-O12
O3-Co4-N4
O8-Co4-O1
O8-Co4-O3
O8-Co4-O4
O8-Co4-O12
O8-Co4-N4
O12-Co4-O4
N4-Co4-O1
80.94(9)
85.41(10)
164.34(10)
84.28(10)
78.97(9)
93.63(9)
92.25(11)
80.72(9)
85.69(10)
87.83(9)
92.11(10)
93.38(11)
95.50(10)
88.77(9)
166.56(10)
96.55(10)
99.79(10)
88.10(11)
165.11(10)
107.40(11)
170.86(10)
85.77(11)
79.90(9)
167.63(9)
100.21(10)
88.70(11)
170.75(11)
107.44(11)
85.73(12)
79.96(9)
84.45(10)
90.44(10)
93.02(11)
80.50(9)
84.88(10)
84.72(10)
79.09(9)
93.59(10)
92.12(12)
97.93(11)
166.00(9)
87.80(9)
86.24(11)
170.01(10)
170.16(10)
90.45(9)
95.97(10)
99.41(11)
88.18(11)
164.24(11)
100.33(10)
87.38(13)
163.67(10)
170.18(11)

N3-Co3-O2
N3-Co3-O18
Co3-O1-Co1
Co4-O1-Co1
Co1-O2-Co3
Co1-O3-Co2
Co4-O3-Co2
Co2-O4-Co4
108.62(11)
84.12(12)
100.18(9)
93.64(10)
100.50(9)
93.22(10)
100.48(10)
101.25(10)
N4-Co4-O4
N4-Co4-O12
Co3-O1-Co4
Co1-O2-Co2
Co2-O2-Co3
Co4-O3-Co1
Co2-O4-Co3
Co3-O4-Co4
108.62(11)
86.04(12)
99.24(10)
98.77(11)
94.02(9)
99.01(11)
99.17(10)
94.40(9)

Fig. 1. Construction of complexes 1, 2 and 3 derived from the half-salamo ligand HL.

Fig. 2. The FT-IR spectra of the ligand HL and its complexes 1, 2 and 3 (cm-1).

Fig. 3. The UV-vis spectra of HL and its complexes 1, 2 and 3 in methanol (c = 2.5×10−5
M).

Fig. 4. (a) Molecular structure and atom numberings of complex 1 with 30%
probability displacement ellipsoids (hydrogen atoms are omitted for clarity). (b)
Coordination polyhedra for Cu1 and Cu1# atoms of complex 1.