Open coordination sites-induced structural diversity of a new series of Cu(II) complexes with tridentate aroylhydrazone Schiff base

Article abstract of DOI:10.1016/j.molstruc.2016.05.034

Six Cu(II) complexes containing the NO₂ donor tridentate asymmetrical aroylhydrazone ligand (E)-4-hydroxy-N′-((2-hydroxynaphthalen-1-yl)methylene)benzohydrazide (HL), namely, [Cu(L)Cl]·2H₂O (1), [Cu(L)(CH₃OH)₂]·

Full text of DOI:10.1016/j.molstruc.2016.05.034

Accepted Manuscript
Open coordination sites-induced structural diversity of a new series of Cu(II)
complexes with tridentate aroylhydrazone Schiff base
Guohong Xu, Beibei Tang, Leilei Gu, Pei Zhou, Hui Li
PII:
S0022-2860(16)30480-X
10.1016/j.molstruc.2016.05.034
MOLSTR 22548
DOI:
Reference:
To appear in: Journal of Molecular Structure
Received Date: 11 March 2016
Revised Date: 10 May 2016
Accepted Date: 11 May 2016
Please cite this article as: G. Xu, B. Tang, L. Gu, P. Zhou, H. Li, Open coordination sites-induced
structural diversity of a new series of Cu(II) complexes with tridentate aroylhydrazone Schiff base,
Journal of Molecular Structure (2016), doi: 10.1016/j.molstruc.2016.05.034.
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ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
Open coordination sites-induced structural diversity of a new
series of Cu(II) complexes with tridentate aroylhydrazone Schiff
base
Guohong Xu, Beibei Tang, Leilei Gu, Pei Zhou and Hui Li*
Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry,
Beijing Institute of Technology, Beijing, 100081
Abstract
Six Cu(II) complexes containing the NO2 donor tridentate asymmetrical aroylhydrazone ligand
(E)-4-hydroxy-N'-((2-hydroxynaphthalen-1-yl)methylene)benzohydrazide
[Cu(L)Cl]·2H2O (1), [Cu(L)(CH3OH)2]·NO3 (2), [Cu(L)(NO3)(H2O)]·H2O
[Cu(L)(CH3OH)Cl]·CH3OH (4), [Cu(L)(SCN)(DMF)]·DMF (5)
(HL),
namely,
(3),
and
{[Cu(L)(4,4’-bipy)]ClO4·4DMF}n (6) have been synthesized and analysized by x-ray singal
crystal diffraction. The structures of 1-6 are varied from zero-dimensional (0D) mononuclear
complex to one-dimensional (1D) polymer based on the control of solvents, anions or auxiliary
ligands, which can occupy the open coordination sites of Cu(II). Different hydrogen bonding
interactions can also be observed in these complexes.
Keywords: Aroylhydrazone, Open coordination sites, Cu complex, Self-assembly, Hydrogen
bonding, Supramolecular architecture
1. Introduction
Supramolecular metal-organic complexes have attracted enormous attentions owing to their
interesting structures [1-14] and intriguing properties [15-25] for decades, which can be generated
by coordination bond, hydrogen-bond, aromatic stacking, van der Waals interactions, and so on.
Despite some advancement, the controllable synthesis of supramolecular complexes with
pre-designed structures and desirable properties is a frontier and also a challenging task [26, 27].
Using appropriate organic ligands to design and creat coordinatively opening sites of metal, which
can be occupied by various ancillary moiety has been an effective approach to construct the
diverse structures [28-36] and to tune the functional properties, such as fluorescence [28, 32, 35],
magnetic [29-31], gas adsorptions [33, 36], and so on. Hence, to study the effect of the solvents,
anions and auxiliary ligands on the self-assembly process based on multidentate ligands with

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specific structural features is one of the crucial tasks.
We subsequently employed the aroylhydrazone Schiff base as ligand because of the following
reasons: (ⅰ) this class of diprotic ligands typically act as tridentate, planar chelate ligands
coordinating through the imine-N, carbonyl-O and phenolic-O atom, therefore, they have
advantages in creating the open coordination sites of metal ion in complexes which can be
occupied by auxiliary ligands, anions or solvents [37, 42-43], that is in favor of constructing the
multy-nuclears or high-dimensional structures further. In addition, this kind of ligands with
several oxygen donors and nitrogen donors can act as mono- and dianionic ligands due to their
keto–enol tautomerism [37-42], therefore, which exhibit highly versatile coordination behaviour
towards metal cations; (ⅱ) aroylhydrazones constitute an interesting class of complexes with
versatile structural features and fascinating potential application in advanced materials[44-48] and
potential antimicrobial and antitumor activities [49-51].
Transition metal complexes derived from aroylhydrazone ligands can form diverse
supramolecular networks as reported previously [41, 42, 44, 52]. Recently, one tetranuclear Zn(II)
complex was synthesized by our group, which can be assembled into 3D diamondoid
supramolecular framework through strong hydrogen bonding [44]. Thus, the wise modulation and
tuning of the complementary sites responsible for hydrogen-bond formation have led to its
application in supramolecular electronics [53], host-guest chemistry [54, 55], self-assembly of
molecular capsules [56], and so forth.
In the present work, we have synthesized a NO2 donor aroylhydrazone ligand through the
condensation of 2-hydroxynaphthalene-1-carbaldehyde with 4-hydroxybenzohydrazide, namely,
(E)-4-hydroxy-N'-((2-hydroxynaphthalen-1-yl)methylene)benzohydrazide. To understand the role
of the solvents, anions and auxiliary ligands in the self-assembly process, we studied the crystal
structure and supramolecular assembly of Cu(II) complexes with the asymmetrical aroylhydrazone
ligand HL: [Cu(L)Cl]·1.5H2O (1), [Cu(L)(CH3OH)2]·NO3 (2), [Cu(L)(NO3)(H2O)]·H2O (3),
[Cu(L)(CH3OH)Cl]·CH3OH
(4),
[Cu(L)(SCN)(DMF)]·DMF
(5)
and
{[Cu(L)(4,4’-bipy)]·ClO4·4DMF}n (6). Additionally, the complexes were characterized by means
of FT-IR, UV-vis spectroscopy, elemental analysis and thermogravimetric analysis.
2. Experimental
2.1. Materials and measurements

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All chemicals used for the synthesis were obtained from commercial sources and were used
without further purification. Organic solvents used in this paper were of analytical purity. All
reactions were carried out under atmospheric conditions. FT-IR spectrum is recorded in the
Nicolet-360 FTIR spectrometer as KBr pellets in the 4000–400 cm-1 region, the resolution and the
scan's numbers used to register the FTIR spectra are 4.000 and 32, respectively. Elemental
analyses (C, H, N) were performed on a Flash EA1112 microanalyzer. The UV-vis absorption
spectra were examined on a JASCO UV-1901 spectrophotometer in the wavelength range of
200−800 nm and the solvent used to register the UV-visible spectra is methanol.
Thermo-gravimetric analyses (TGA) were carried out on a SEIKO TG/DTA 6200 thermal
analyzer from room temperature to 800 °C at a ramp rate of 10 °C/min in a flowing 50 mL/min
nitrogen atmosphere. 1HNMR and 13CNMR spectra was recorded on a Bruker ARX400
spectrometer (400 MHz) instrument in DMSO-d6 with Me4Si as the internal standard.
Caution! Perchlorate salts in presence of organic materials are potentially explosive and
should be prepared in small amounts with appropriate precautions.
2.2. Preparation of the ligand HL
The 4-Hydroxybenzhydrazide (10 mmol, 1.522 g) and 2-hydroxy-1-napthaldehyde (10
mmol, 1.720 g) were mixed in 40 mL ethanol in presence of 1 drop of concentrated
hydrochloric acid. Then, the mixture was refluxed for 8 hours (80 °C) with vigorous stirring
and subsequently cooled to room temperature. The resulting yellow precipitate was collected
by vacuum filtration. A yellow powder was obtained after being washed with ethanol and
dried in air (Scheme S1). Yield: 83.4%. Anal. Calcd for C18H14N2O3: C, 70.58; H, 4.61; N,
9.15. Found: C, 70.62; H, 4.68; N, 9.17. Selected IR (KBr pellet, cm-1): ν(O-H) 3433; ν(N-H)
3289, 3167; ν(C=O) 1634; ν(C=N)+ amide 1606-1537. 1HNMR (400 MHz, DMSO-d6): δ (ppm)
12.91 (s, 1H), 12.03 (s, 1H), 10.25 (s, 1H), 9.48 (s, 1H), 8.19 (d, 1H, J = 7.2), 7.90 (m, 4H),
7.62 (s, 1H), 7.42 (s, 1H), 7.24 (d, 1H, J = 8.3), 6.92 (d, 2H, J = 6.9). 13CNMR (100 MHz,
DMSO-d6) δ (ppm) 162.62, 161.50, 158.34, 146.35, 132.94, 132.06, 130.15, 129.46, 128.27,
128.18, 123.97, 123.55, 120.93, 119.42, 115.72, 109.06.
2.3. Preparation of complex [Cu(L)Cl]·1.5H2O (1)

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The water solution (4 mL) of CuCl2·2H2O (9 mg, 0.05 mmol) was placed at the bottom of tube,
and then carefully added the methanol solution (12 mL) of HL (15 mg, 0.05mmol) to allow slow
liquid-to-liquid diffusion. Green needle single crystal suitable for X-ray analysis were produced
by in two days. Yield: 65% .Anal. Calcd for CuC18H16N2O4.5Cl : C, 50.12; H, 3.74; N, 6.49.
Found: C, 50.20; H, 3.53; N, 6.50. Selected IR (KBr pellet, cm-1): ν(O-H)/ν(N-H) 3123;
ν(C=O) 1658 ; ν(C=N)+ amide 1617–1537
.
2.4. Preparation of complex [Cu(L)(CH3OH)2]·NO3 (2)
The solution of Cu(NO3)2·2H2O (12 mg, 0.05 mmol) in 2 mL methanol was added by
methanol / acetonitrile (V : V = 6 : 1) solution (7mL) of HL (15 mg, 0.05mmol) with continuous
stirring for 15 min. The result solution was then filtered and left at room temperature to give a
deep green solution. Green cubic single crystal suitable for X-ray analysis were produced by
slow evaporation of the mother liquor for seven days. Yield: 78% Anal. Calcd for
CuC20H21N3O8: C, 48.53; H, 4.28; N, 8.49. Found: C, 48.51; H, 4.26; N, 8.50. Selected IR
(KBr pellet, cm-1): ν(O-H) 3185; ν(N-H) 3035; ν(C=O) 1600 ; ν(C＝N)+ amide 1576–1511.
2.5. Preparation of complex [Cu(L)(NO3)(H2O)]·H2O (3)
The solution of Cu(NO3)2·2H2O (12 mg, 0.05 mmol) in 2 mL water was added by solution of
HL (15 mg, 0.05mmol) in 6 mL methanol. The reaction solution was filtrated after stirring with
15 minutes. Suitable Green prism single crystals for X-ray diffraction were obtained by slow
evaporation of the mother liquor for three days. Yield: 68%. Anal. Calcd for CuC18H17N3O8: C,
46.30; H, 3.67; N, 9.00; Found: C, 46.28; H, 3.69; N, 8.98. Selected IR (KBr pellet, cm-1): ν(O-H)
3183; ν(N-H) 3020; ν(C=O) 1621 ; ν(C＝N)+ amide 1576–1512.
2.6. Preparation of complex [Cu(L)(CH3OH)Cl]·CH3OH (4)
The methanol solution of HL (26 mg, 0.10mmol) was mixed with the methanol solution of
CuCl (10 mg, 0.10 mmol) with stirring, and then 10d DMSO was added to the mixture solution.
The mixture was stirred with ca. 40 min. at room temperature to give a deep green solution.
Suitable green single crystals for the structure determination were obtained by slow evaporation of
the mother liquor for two days. Yield: 80%. Anal. Calcd for CuC20H21N2O5Cl: C, 51.29; H, 4.52;
N, 5.98. Found: C, 51.25; H, 4.50; N, 5.97. Selected IR (KBr pellet, cm-1): ν(O-H)/ν(N-H) 3157;
ν(C=O) 1654 ; ν(C=N)+ amide 1615–1551.

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2.7. Preparation of complex [Cu(L)(SCN)(DMF)]·DMF (5)
The MeCN solution (5 ml) of Cu(ClO4)2·6H2O (19mg, 0.05 mmol) was slowly added the
MeCN/DMF (V : V = 5 : 1) solution of the HL (15mg, 0.05 mmol) and KSCN (10mg, 0.1 mmol).
The dark green reaction mixture was stirred for one hour and filtrated. The resulting filtrate was
left at room temperature one day during which green parallelogram single crystals were obtained.
Calcd for CuC25H27N5O5S: C, 52.39; H, 4.75; N, 12.22. Found: C, 52.36; H, 4.765; N, 12.19.
Selected IR (KBr pellet, cm-1): ν(O-H)/ν(N-H) 3037; ν(SCN) 2107; ν(C=O) 1646; ν(C=N)+
amide 1618–1539.
2.8. Preparation of complex {[Cu(L)(4,4’-bipy)]·ClO4·4DMF}n (6)
The ethanolic solution (3 mL) of Cu(ClO4)2·6H2O (37 mg, 0.1 mmol) was slowly added the
ethanolic solution (5 mL) of the HL (30 mg, 0.1 mmol). After ca. 15 min, the ethanolic solution
solution (2 mL) of 4, 4'-bipyridine (20 mg, 0.1 mmol) was added, and then the precipitate
appeared. DMF was added dropwise to the mixture solution until the precipitate dissolved.
Suitable green parallelogram single crystals for X-ray diffraction were obtained by slow
evaporation of the mother liquor for three days. Calcd for CuC34H35N6O9Cl: C, 52.99; H, 4.58; N,
10.90. Found: C, 52.95; H, 4.57; N, 10.91. Selected IR (KBr pellet, cm-1): ν(O-H)/ν(N-H) 3021;
ν(C=O) 1676; ν(C=N)+ amide 1616–1520.
2.9. X-ray crystal structure determinations
Diffraction intensities for six complexes were collected on a Rigaku RAXIS-RAPID CCD
diffractometer equipped with a graphite- monochromatic MoKα radiation (λ =0.71073Å) using an
ω scan mode at 296 ± 2K (complex 2), 153.15 (complex 1, 3-6). Diffraction intensity data were
collected in the θ range of 3.06-29.13° for complex 1, 1.78-24.99° for complex 2, 3.07–27.48° for
complex 3, 2.32-25.00° for complex 4, 3.03- 24.99° for complex 5, and 2.21-29.13° for complex
6. The collected data were reduced using the SAINT program [57], and empirical absorption
corrections were performed using the SADABS program [57]. Six structures were solved by direct
methods [58] and refined using full-matrix least square techniques on F2 [59] with the program
SHELXL-97 [57]. All nonhydrogen atomic positions were located in difference Fourier maps and

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refined anisotropically. Some of hydrogen atoms were placed in their geometrically generated
positions and other hydrogen atoms were located from the different Fourier map and refined
isotropically. Crystallographic data are given in Table 1. Selected bond distances and angles are
given in Table 2.
Table 1 Crystal data and structure refinement for complex 1-6.
1
2
3
4
Formula
CuC18H16N2O4.5Cl
CuC20H21N3O8
CuC18H17N3O8
CuC20H21N2O5Cl
fw
T (K)
Cryst. Syst.
Space group
a (Å)
b (Å)
c (Å)
α (°)
β (°)
431.32
153(2)
monoclinic
P2/n
15.536(3)
6.9299(14)
16.753(3)
90
111.69(3)
90
1675.9(6)
4
494.94
296(2)
466.90
153(2)
468.38
153(2)
triclinic
P-1
7.4373(15)
10.923(2)
12.885(3)
96.54(3)
103.06(3)
104.42(3)
971.4(3)
2
monoclinic
P21/c
9.5931(17)
9.5735(17)
22.945(4)
90
92.029(5)
90
2106.0(6)
4
monoclinic
C2/c
22.441(4)
9.2875(19)
19.111(4)
90
109.28(3)
90
3759.7(13)
8
γ (°)
V (Å3)
Z
ρ calcd. (mg·m-3)
F(000)
θ rang. (°)
ꢀ (mm-1)
λ (Å)
1.705
876
3.06-29.13
1.494
0.71073
0.0395
1.561
1020
1.78-24.99
1.091
0.71073
0.0401
1.650
1912
3.07-27.48
1.216
0.71073
0.0444
1.601
482
2.32-25.00
1.298
0.71073
0.0262
R (int)
FinalR1,wR2[I>2σ(I)]0.0387,0.0840
0.0512, 0.1004
0.0715, 0.1083
0.461, -0.458
6
0.0467, 0.1096
0.1096, 0.1193
0.510, -0.335
0.0382, 0.0813
0.0415, 0.0847
0.820, -0.263
R1, wR2(all data)
0.0500,0.0889
Peak and hole (e Å-3) 0.735,-0.559
5
Formula
CuC25H27N5O5S
CuC34H35N6O9Cl
fw
T (K)
Cryst. Syst.
Space group
a (Å)
b (Å)
c (Å)
α (°)
573.12
153(2)
monoclinic
P21/c
14.275(3)
7.6358(15)
23.608(5)
90
770.67
153(2)
monoclinic
P21/n
10.248(2)
18.178(4)
18.605(4)
90
β (°)
91.66(3)
90
2572.2(9)
4
98.63(3)
90
3426.5(12)
4
γ (°)
V (Å3)
Z
ρ calcd. (mg·m-3)
F(000)
θ rang (°)
ꢀ (mm-1)
λ (Å)
1.480
1188
3.03- 24.99
0.976
0.71073
0.0883
1.494
1596
2.21 -29.13
1.298
0.71073
0.0505
R (int)
FinalR1,wR2[I>2σ(I)]0.0614, 0.1434
R1, wR2(all data) 0.0948, 0.1565
Peak and hole(e Å-3) 1.183, -0.907
0.0557, 0.1058
0.0768, 0.1148
0.389, -0.357

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Table 2 Selected bond distances (Å) and bond angles (°) for complexes 1-6.
1
O(2)-C(7)
N(1)-C(7)
Cu(1)-O(3)
Cu(1)-N(2)
Cu(1)-O(2)
Cu(1)-Cl(1)
1.264(3)
O(3)-Cu(1)-N(2)
O(3)-Cu(1)-O(2)
N(2)-Cu(1)-O(2)
O(3)-Cu(1)-Cl(1)
N(2)-Cu(1)-Cl(1)
O(2)-Cu(1)-Cl(1)
90.26(7)
171.68(7)
81.47(7)
92.59(6)
176.40(6)
95.71(6)
1.341(3)
1.9009(16)
1.9239(19)
1.9601(16)
2.2350(9)
2
O(2)-C(12)
1.268(5)
1.329(5)
2.447(3)
1.875(2)
1.906(3)
1.944(3)
1.950(2)
92.24(12)
91.37(13)
N(1)-Cu(1)-O(4)
O(1)-Cu(1)-O(2)
N(1)-Cu(1)-O(2)
O(4)-Cu(1)-O(2)
O(1)-Cu(1)-O(3)
N(1)-Cu(1)-O(3)
O(4)-Cu(1)-O(3)
O(2)-Cu(1)-O(3)
173.42(13)
172.82(13)
82.25(12)
93.69(12)
93.29(11)
92.69(12)
92.59(14)
91.56(11)
N(2)-C(12)
Cu(1)-O(3)
Cu(1)-O(1)
Cu(1)-N(1)
Cu(1)-O(4)
Cu(1)-O(2)
N(1)-Cu(1)-O(1)
O(1)-Cu(1)-O(4)
3
O(2)-C(12)
1.257(3)
1.355(3)
1.903(2)
1.9190(18)
1.935(2)
1.9923(19)
2.471(2)
90.46(9)
176.08(9)
O(1)-Cu(1)-O(3)
N(1)-Cu(1)-O(2)
O(1)-Cu(1)-O(2)
O(3)-Cu(1)-O(2)
N(1)-Cu(1)-O(5)
O(1)-Cu(1)-O(5)
O(3)-Cu(1)-O(5)
O(2)-Cu(1)-O(5)
92.73(8)
81.96(8)
171.14(8)
95.03(8)
93.59(8)
91.77(8)
84.04(8)
93.27(8)
N(2)-C(12)
Cu(1)-N(1)
Cu(1)-O(1)
Cu(1)-O(3)
Cu(1)-O(2)
Cu(1)-O(5)
N(1)-Cu(1)-O(1)
N(1)-Cu(1)-O(3)
4
O(2)-C(7)
1.269(3)
O(3)-Cu(1)-O(4)
N(2)-Cu(1)-O(4)
O(3)-Cu(1)-O(2)
N(2)-Cu(1)-O(2)
O(4)-Cu(1)-O(2)
Cl(2)-Cu(1)-O(3)
Cl(2)-Cu(1)- N(2)
Cl(2)-Cu(1)-O(4)
Cl(2)-Cu(1)-O(2)
88.81(7)
167.16(8)
168.36(7)
81.76(8)
95.07(7)
96.73(6)
101.55(7)
91.07(6)
94.17(6)
N(1)-C(7)
1.340(3)
Cu(1)-O(3)
Cu(1)-N(2)
Cu(1)-O(4)
Cu(1)-O(2)
Cu(1)-Cl(2)
O(3)-Cu(1)-N(2)
1.8891(18)
1.911(2)
1.9461(18)
1.9752(17)
2.7070(11)
92.04(8)

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5
O(2)-C(15)
N(1)-C(15)
Cu(1)-O(3)
Cu(1)-N(2)
Cu(1)-N(3)
Cu(1)-O(2)
1.261(5)
N(2)-Cu(1)-O(3)
N(3)-Cu(1)-O(3)
N(2)-Cu(1)-N(3)
O(3)-Cu(1)-O(2)
N(2)-Cu(1)-O(2)
N(3)-Cu(1)-O(2)
90.58(14)
93.57(15)
173.61(16)
171.55(12)
81.64(14)
93.92(15)
1.351(5)
1.913(3)
1.923(4)
1.927(4)
2.007(3)
6
O(1)-C(7)
1.269(3)
1.340(3)
1.9057(18)
1.944(2)
1.9822(18)
2.008(2)
2.282(2)
90.27(8)
O(2)-Cu(1)-O(1)
N(2)-Cu(1)-O(1)
N(4)-Cu(1)-O(2)
N(2)-Cu(1)-N(4)
N(4)-Cu(1)-O(1)
N(3)-Cu(1)-O(2)
N(2)-Cu(1)-N(3)
N(3)-Cu(1)-O(1)
N(4)-Cu(1)-N(3)
167.01(7)
80.83(8)
93.27(8)
161.49(8)
92.31(8)
95.63(8)
94.07(8)
94.43(7)
103.63(8)
N(1)-C(7)
Cu(1)-O(2)
Cu(1)-N(2)
Cu(1)-O(1)
Cu(1)-N(4)
Cu(1)-N(3)
N(2)-Cu(1)-O(2)
3. Results and discussion
3.1. Synthesis of the complexes
-
-
With different Cu salts (Cl-, NO3 , ClO4 ) and solvents, four different kinds of mononuclear Cu
complexes 1-4 are obtained. By the employment of the distinct secondary ligands SCN- and
4,4′-bipy, mononuclear Cu complex 5 and 1D coordination complex 6 were constructed.
The phenolic hydroxyl and naphthalene ring introduced in the ligand HL have enhanced the
intermolecular interaction but weaken the bridging role, which prompted the different
mononuclear structure of complexes 1-5, thus addition of the auxiliary ligand (4,4′-bipy) is
advantageous to construct one-dimensional (1D) chain(complex 6). Based upon the synthesis
conditions, the Cu(II) is tetra-coordinated in complex 1 and penta-coordinated in 2-6, it is
noteworthy that the aroylhydrazone ligand in the six complexes are exclusively monoanionic and
in the keto form to coordinate to Cu ion, which can be verified from C=O and C–NH bond lengths
of the amide unit. Amide unit bond lengths for aroylhydrazones are in the ranges of 1.241–1.280
Å (C–O), 1.336–1.386 Å (C–N), and 1.296–1.314 Å (C–O), 1.294–1.310 Å (C–N) in the keto and
enol form, respectively [39-42, 60].

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3.2. Crystal structural description
3.2.1. [Cu(L)Cl]·2H2O (1)
Fig. 1. (a) View of coordination environments of Cu and ligand in 1. Uncoordinated solvent molecule (or anion)
and hydrogen atoms are omitted for clarity. (b) Dimeric unit formed by intermolecular O–H···Cl interaction in 1
(gree dashed line). (c) Packing diagram of 1 showing the zigzag chain formation through N–H···O and O–H···Cl
hydrogen-bonding interactions (pink dashed line). (d) Perspective view of the stacking array of 1 showing the
formation of a 2D layer through C–H···Cl intermolecular interactions (blue dashed line). (e) The 3D structure of 1
by van der Waals ineraction. Hydrogen atoms not involved in hydrogen-bonding interactions are omitted for
clarity.
Single-crystal X-ray analysis on complex 1 shows that it is mononuclear and the copper(II) is
tetra-coordinated. The asymmetric unit of the complex 1 is depicted in Fig. 1a. The
aroylhydrazone ligand is coordinated as a mono-negative tridentate chelating agent via the
imine-N, carbonyl-O and phenoxo-O atom which make one five-membered and one
six-membered chelate rings. The fourth coordination position is occupied by the chloride ligand.
The Cu(1)–O [1.9009(16) Å and 1.9601(16) Å] and Cu(1)–N[1.9239(19)Å] bond distances are
comparable with corresponding values reported in other similar copper(II) complexes [37, 42].
The deviations of the four donor atoms O2, N2, O3, and Cl1 from their least-squares mean plane
through them are 0.026(3), 0.029(6), -0.025(5), and 0.022(2) Å, respectively. The Cu atom
deviates from the mean plane by 0.013(9) Å. The dihedral angle between the mean planes of the
five-membered chelate ring and the six-membered one is 1.5°.
The uncoordinated oxygen atom of terminal -OH group donates a hydrogen bond to the chloride
atom of the adjacent asymmetric unit, resulting in a dimer (Fig. 1b). The crystal packing of
complex 1 shows several intermolecular H-bonds such as O–H···Cl, C–H···Cl and N–H···O as

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shown. The oxygen atom (O5) of the uncoordinated water molecule acts as a single hydrogen
bonding donor to chloride atom (Cl2) of one neighbor (O5–H5B···Cl2A) and a single hydrogen
bonding acceptor from amido group nitrogen atom (N1) of the other neighbor (N1–H1A···O5).
Through these hydrogen bond interactions a 1D chain is generated (Fig. 1c). Apart from these
interactions, C–H···Cl interaction was observed between the chloride atom and the naphthalene
ring. These supramolecular interactions extend 1D chain to a 2D supramolecular layer (Fig. 1d).
The supramolecular layers further stabilize the crystal structure via the van der Waals ineraction
(Fig. 1e).
Table 3 Distances (Å) and angles (°) of hydrogen bonds for 1-6.
D—H…A
d(H…A)
d(D…A)
∠D—H…A
1
2
3
O1–H1···Cl2 #1
O5–H100···Cl2#2
N1–H1A···O5
2.343
2.482
1.891
2.938
3.147
3.225
2.726
3.852
166.91
168.14
163.43
167.7
C11–H11···Cl2
O4–H22···O3#3
O5–H5···O6#4
O3–H23···O6#5
N2–H21···O7#6
1.886
1.966
1.985
2.022
2.686
2.717
2.733
2.873
172.00
151.82
169.26
170.41
N2–H2···O5#7
2.047
1.887
1.784
1.989
1.998
2.788
2.705
2.608
2.833
2.843
143.77
175.93
173.75
171.91
172.14
O4–H4···O1#8
O3–H30 ···O8#9
O8–H8B ···O7#10
O8–H8A ···O4#11
4
N1–H1A···Cl2#12
O1–H1···Cl2#13
O4–H4A ···O5
2.420
2.340
1.856
2.410
3.211
3.138
2.628
3.185
153.27
164.41
150.14
157.82
O5–H5A··· Cl2#14
5
6
N1–H100···O4#15
C25A–H25A···O1
O1–H1···O5#16
2.027
2.468
1.821
2.837
3.402
2.628
156.68
168.5
167.78
C4–H4A···N3
2.713
1.811
3.643
2.629
179.1
O3–H3···O8#17
174.76

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N1–H35···O6#18
N1–H35··· Cl1#18
2.037
2.873
2.859
3.690
159.67
159.39
Symmetry transformations used to generate equivalent atoms: #1: -x+3/2, y, -z+1/2. #2: x+1/2, -y, z+1/2. #3: -x, -y,
-z. #4: x, -y+1/2, z-1/2. #5: x, y, z-1. #6: -x+1, -y+1, -z+1. #7: -x, -y, -z+1. #8: x, -y, z-1/2. #9: -x+1/2, -y+1/2, -z+1.
#10: x, -y, z-1/2. #11: x, y+1, z. #12: -x+1, -y+1, -z+1. #13: x, y-1, z. #14: x-1, y, z. #15: -x, -y+1, -z. #16: x, y, z-1.
#17: x+1, y, z. #18: x+1/2, -y+1/2, z-1/2.
3.2.2. [Cu(L)(CH3OH)2]·NO3 (2), [Cu(L)(NO3)(H2O)]·H2O (3) and [Cu(L)(CH3OH)Cl]·CH3OH
(4)
Under different synthetic conditions, the complexes 2, 3 and 4 which are all mononuclear and
penta-coordinated have been obtained. In them, the obvious difference is that the remaining sites
of Cu(II) in complex 2 are occupied by two solvent atoms to form coordinated cation while in the
others which are occupied by one solvent atom and one anion to form coordination complexes.
The bond lengths in complex 2-4 are within the expected range for Cu(II) complexes with
aroylhydrazone ligands [41, 42].
Fig. 2. (a) View of coordination environments of Cu and ligand in 2. Uncoordinated solvent molecule (or anion)
and hydrogen atoms are omitted for clarity. (b) Dimeric unit formed by intermolecular O–H···O interaction in 2
(green dashed line). (c) Packing diagram of 2 showing the 2D H-bonded network (pink dashed line). Hydrogen
atoms not involved in H-bonding are omitted for clarity. (d)The 3D H-bonding of 2 (blue dashed line) .
Single-crystal X-ray analysis on complex 2 (Fig. 2a) shows that the asymmetric unit contains a
complex cation and a nitrate anion. Therefore, the complex 2 is monocationic and is stabilized by
a nitrate counteranion in the lattice. The ligand is mono-negative and coordinates in a tridentate
mode via the O, N, O-donor atoms. The remaining sites in the penta-coordinate arrangement are
occupied by two methanol oxygen atoms (O3 and O4). The coordination sphere is best described

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as square pyramid by the τ value (0.01) defined by Addison et al. (τ= 0 for an ideal square
pyramid, and 1 for an ideal trigonal bipyramid) [61].
In this description, the methanol-O3 atom occupies an axial position. The long distance of the
Cu1–O3 bond with 2.447(3) Å shows weak bonding of the methanol to the central copper atom
due to the Jahn-Teller effect [62]. The entire aroylhydrazone ligand is nearly planar with a small
twist and the dihedral angle between the benzene and naphthalene rings is 7°. This overall
planarity is consistent with the observation that each of the five- and six-membered chelate rings
is planar having r.m.s. deviations of 0.006(6) and 0.028(5) Å, respectively.
As X-ray study, we conclude significant hydrogen bonding interactions are present in the crystal
structures of 2. The -OH hydrogen atoms of both coordinated methanol molecules of complex 2
are involved in hydrogen bonding (Table 3). The methanol molecule oxygen atom (O4) of one
asymmetric unit act as hydrogen bond donors to the methanol molecule oxygen atom (O3) of an
adjacent unit, forming a dimer via one pair of O4–H22···O3 hydrogen bonds (Fig. 2b). Although
the nitrate anions are not coordinated to the Cu(II) centres in complex 2, they are involved in a
hydrogen bonding. Nitrate anions regard as bridges connecting neighboring Cu(II) dimeric units to
form the 2D net-like open framework structure as shown in Fig. 2c. The nitrate oxygen atom (O6)
acts as a double hydrogen bonding acceptor from methanol oxygen atom (O3) and uncoordinated
phenolic oxygen atom (O5) of the adjacent binuclear entities. (O5–H5···O6 and O3–H23···O6).
Meanwhile, nitrate oxygen atom (O7) acts as a single hydrogen bonding acceptor from
uncoordinated amido nitrogen atom (N2) of another neighboring molecules, resulting in 3D
structure (Fig. 1d and Fig. S4).
Compared with the complex 2, a little different coordination environment is observed in 3. The
key difference is oxygen atom of nitrate anion occupies the axial position in 3 (Fig. 3a). The NO4
coordination donor set defines a square-pyramidal coordination arrangement (τ = 0.08). The five-
and six-membered chelate rings are planar (r.m.s. deviations = 0.004(2) and 0.013(2) Å,
respectively) but a slightly greater twist in the overall aroylhydrazone ligand [dihedral angle
between the benzene rings = 9.7°] is observed in 3 compared with that in 2.

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Fig. 3. (a) View of coordination environments of Cu and ligand in 3. Uncoordinated solvent molecule (or anion)
and hydrogen atoms are omitted for clarity. (b) Dimeric unit formed by intermolecular N–H···O interaction in 3
(green dashed line). (c) Packing diagram of 3 showing the zigzag chain formation through O–H···
O
hydrogen-bonding interactions (pink dashed line). (d) Perspective view of the stacking array of 3 showing the
formation of a 2D layer through O–H···O intermolecular interactions(red dashed line). Hydrogen atoms not
involved in hydrogen-bonding interactions are omitted for clarity.
The hydrogen atom H2 of the amido (–NH–) group forms a strong hydrogen bond with the
oxygen atom O5 of the coordinated nitrate anion of a centrosymmetrically related unit to form a
hydrogen bonded dimeric entity (Fig. 3b). Additionally, each molecule of 3 interacts with two
neighbors to form 1D zigzag chain by intermolecular hydrogen-bonding interactions between the
uncoordinated oxygen atoms of terminal -OH groups in ligand and coordinated -OH groups (Fig.
3c). The 1D chains are further connected via O8–H8B···O7 and O8–H8A··O4 interactions from
two adjacent chains to form a 2D layer-like structure (Fig. 3d). In addition, the presence of
interlayer hydrogen bonds (O3–H30···O8) leads to the formation of a 3D supramolecular network
(Fig. S5 and Fig. S6), which contributes to the additional stability of the structure.
In the process of synthesizing complex 2 and 3, only the solvent is different. Distinct structural
differences between 2 and 3 indicated that the solvent remarkably affect the structure of the
resulting complexes. Although the structures of 2 and 3 apparently look very similar, a
comparison of the structures and dimensions in Table 1, clearly show that the arrangement of the
donor atoms around the metal is very different.

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By changing the metal salt and solvents, obtained the mononuclear complex 4. The copper(II)
in 4 is NO3Cl penta-coordinated and chloride atom occupies the axial position (Fig. 4a). The
coordination polyhedron around the Cu(II) ion could be best described as square pyramidal, which
is reflected by the τ value(0.02). The basal plane is built by two oxygen atom sand one nitrogen
atom from the aroylhydrazone ligand and one methanol molecular. The base is nearly coplanar,
with the largest deviation from the mean plane is 0.019(3) Å for N2. As is commonly observed in
square pyramidal complexes, the Cu (II) ion is displaced by 0.194(7) Å from the basal plane
towards the apical chloride. In addition, there is an appreciable Jahn-Teller effect highlighted by
an axial Cu1–Cl2 distance (2.7070(11) Å) significantly longer than that observed for equatorial
Cu1–Cl1 distance in 1 (2.2350(9) Å) and shorter than that in dichlorido-bridged Cu(II) complex
[43].
Fig. 4. (a) View of coordination environments of Cu and ligand in 4. Uncoordinated solvent molecule (or anion)
and hydrogen atoms are omitted for clarity. (b) Dimeric unit formed by intermolecular N–H···Cl interaction in 4
(green dashed line). (c) Packing diagram of 4 showing the 1D chain formation through O–H···Cl and O–H···O
hydrogen-bonding interactions (pink dashed line). (d) Perspective view of the stacking array of 4 showing the
formation of a 2D layer through O–H···Cl intermolecular interactions (red dashed line). Hydrogen atoms not
involved in hydrogen-bonding interactions are omitted for clarity.
In 4, the amido group nitrogen atom (N1) of one asymmetric unit act as hydrogen bond donors to
chloride atom (Cl2) of an adjacent unit, forming a dimer, and the two aroylhydrazone ligands in
the dimer are nearly parallel (Fig. 4b). There exist intermolecular hydrogen bonds between the

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uncoordinated oxygen atom of terminal -OH group and the chloride atom, O1–H1···Cl2, through
which a 1D supramolecular chain is generated (Fig. 4c). The oxygen atom (O5) of the
uncoordinated methanol molecular acts as a single hydrogen bonding donor to chloride atom (Cl2)
of one neighbor and a single hydrogen bonding acceptor from coordinated methanol molecular
oxygen atom (O4) of another neighbor, resulting in a 2D layer structure(Fig. 4d). The adjacent
layers are extended to a 3D supramolecular architecture by van der Waals ineraction (Fig. S7).
3.2.3. [Cu(L)(SCN)(DMF)]·DMF (5) and {[Cu(L)(4,4’-bipy)]·ClO4·4DMF}n (6)
As mentioned above, the aroylhydrazone ligand HL has advantages in generating the open
coordination sites of copper ion in complexes which can be occupied by anions, solvents or
auxiliary ligands to construct new structure entities which can be self-assembled into higher order
architectures. To study this academic point of view, besides tuning the anions and solvents in the
complexes 1-4, we further employed the thiocyanate and 4,4'-bipyridine as auxiliary ligand in the
complex 5 and 6, respectively.
By adding potassium thiocyanate as the auxiliary ligand, obtained the new complex 5.
Single-crystal X-ray studies revealed that the copmplex 5 crystallises in the monoclinic space
group P21/c. A view of the molecular structure of 5 is presented in Fig. 5. The complex 5
consistings of one mono-negative Schiff base L-, one N-terminal SCN- anions and two solvent
DMF molecules. The Cu(II) ion displays square-pyramid coordination(τ=0.03) with three ligating
atoms O2, O3, and N2 from the same ligand , one N3 atom from one terminal SCN – anion and
one O4 atom from DMF molecule. The thiocyanate group acts as a monodentate ligand and is
linear within the experimental error [N3-C17-S2 = 178.1(5)°]. The Cu1–N3–C17 angle of
170.9(4)° is usual for terminally coordinated N-bonded thiocyanate [63]. The deviations of the
four donor atoms O2, O3, N2, and N3 from their least-squares mean plane through them are
–0.008(9), -0.008 (6), 0.009(4), and 0.008 (1) Å. The Cu atom deviates from the mean plane by
0.070(5) Å. The dihedral angles between the two planes [N2–Cu1–O3 and O2–Cu1–N3] is 6.1°.
The two diagonal O3–Cu1–O2 and N2–Cu1–N3 angles of the complex [171.55(12) and
173.61(16)] are less than 180°.

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Fig. 5. (a) View of coordination environments of Cu and ligand in 5. Uncoordinated solvent molecule and
hydrogen atoms are omitted for clarity. (b) Dimeric unit formed by intermolecular N–H···O interaction in 5 (green
dashed line). (c) Packing diagram of 5 showing the 1D chain formation through C–H···O hydrogen-bonding
interactions indicated (pink dashed line). (d) Perspective view of the stacking array of 5 showing the formation of a
2D layer through O–H···O intermolecular interactions (red dashed line). Hydrogen atoms not involved in
hydrogen-bonding interactions are omitted for clarity.
Firstly, the amido group nitrogen atom (N3) of one asymmetric unit act as hydrogen bond
donors to the DMF molecule oxygen atom (O4) of an adjacent unit, forming a dimer via one pair
of N1–H100···O4 hydrogen bonds (Fig. 5b). Secondly, the dimmers form a 1D supramolecular
chain by non-conventional hydrogen bonds among benzene group and uncoordinated -OH group
(C25A–H25A···O1) (Fig. 5c). The uncoordinated DMF molecular is involved in constructing
hydrogen bonding. The hydrogen bond O–H···O joins neighbouring 1D chains together to form a
2D supramolecular layer (Fig. 5d). The DMF molecular oxygen atom (O5) acts as a hydrogen
bonding acceptor from uncoordinated phenolic oxygen atom (O1) of the adjacent chains. Finally,
the van der Waals force connects adjacent 2D supramolecular layers and results in the formation
of the 3D supramolecular network (Fig. S8).

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Fig. 6. (a) Crystal structure of 6 with atom numbering scheme. (b) The infinite 1D zigzag chain structure of 6. (c)
The 2D structure of 6. Hydrogen atoms not involved in hydrogen-bonding interactions are omitted for clarity.
By adding 4,4'-bipyridine as the auxiliary ligand, with its bridging role, a 1-D zigzag chain
structure of Cu complex 6 was build. X-ray crystallographic analysis revealed that the complex 6
crystallizes in the monoclinic space group of P21/n and the asymmetric unit contains one Cu(II)
-
center, one ligand anion L-, one 4,4’-bipyridine, one ClO4 anion and four free DMF molecules.
The coordination environment around the Cu (II) center in 6 is presented in Fig. 6 with atom
numbering scheme. Each Cu (II) atom is penta-coordinated by O1, O2 and N2 atoms from one
tridentate ligand and two N atoms (N3 and N4) from two 4, 4’-bipyridine molecules to form a
CuN3O2 coordination environment. The Cu (II) atom adopts an approximately square pyramidal
geometry, which is reflected by the τ value (0.092) defined by Addison et al.
The basal plane of the square pyramid is defined by O1, O2, N2 and N4 atoms, with the bond
distances ranging from 1.9057(18) to 2.008(2) Å and bond angles ranging from 80.83(8) to
167.01(7) °. The Cu(II) atom lies approximately in the equatorial position with a deviation (0.2432
Å) from the basal plane. The axial coordination site is occupied by N3 atom from another 4,
4’-bipyridine molecule with Cu-N3 of 2.282(2) Å. Thus, the coordination geometry of the Cu (II)
atom in 6 can be regarded as a distorted square pyramid. On the other hand, the ligand L- anion,

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also employed as a tridentate chelating agent, coordinated to the Cu (II) atom with its ONO donor
atoms in meridional fashion. And the bridging 4,4’-bipyridine molecules also link the Cu(L) units
to form a 1D zigzag chain structure (Fig. 6b). In this zigzag chain, the chain length d =17.178(4)
Å, and the bending angle θ = 106.040(4)°. The two pyridyl rings of 4,4’-bipyridine are twisted at
an angle of 17.280° with respect to one another, and the corresponding Cu…Cu intermetallic
distance separated by 4,4’-bipyridine is 11.3777 Å.
The adjacent 1D chains were further assembled by hydrogen bonds to produce an infinite 2D
network. The resulting 2D supramolecular structure is held together via non-conventional
H-bonding C–H···N (Fig. 6c). The C4 atom of benzene ring and N3 atom of amido group are
involved in the formation of C-H···N hydrogen bonds. Moreover, the uncoordinated N atom of
amido group and perchlorate are interlinked through N-H···O and N-H···Cl hydrogen bonds,
ultimately leading to a 3D supramolecular framework (Fig. S9 and Fig. S10). Therefore, 1D chain
entities are self-assembled through the H-bonding into a 3D noninterpenetrated diamond-like
network.
4. Conclusion
In conclusion, we have synthesized six Cu(II) complexes with diverse structures by using a
asymmetrical aroylhydrazone ligand. The coordinated modes of them altered by simply changing
the reaction conditions, leading to the variation from 0D mononuclear to 1D polymer. It is clear
that the auxiliary ligands, anions and solvents which can occupied the open coordination sites of
Cu(II) and play a crucial role in the molecular structure and supramolecular assembly.
Furthermore, the systematic investigation of the influence of reaction conditions on the
self-assembly process based on the open coordination sites simultaneously provides a valuable
approach for the construction of novel metal-organic complexes with different structures and
functional properties.
Acknowledgment
We thank the National Science Council of the People’s Republic of China for supporting this
research (Nos. 21071018, 21271026).
Appendix A. Supplementary material
Crystallographic data for the structural analysis have been deposited at the Cambridge
Crystallographic Data Centre, CCDC No 1052939-1052942, 1052944 and 1052945. These data

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can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK: fax: (+44) 01223-336-033; e-mail:
deposit@ccdc.cam.ac.
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1
2
3
Six Cu(II) complexes containing asymmetrical aroylhydrazone ligand were synthesized
and analysized by x-ray singal crystal diffraction.
By controlling the synthetic conditions and guest species, an effective way to create the
open coordination sites in coordination complexes was offered.
Hydrogen bonds exist in all six complexes to construct supramolecular architecture.