30 卷 4 期 结 构 化 学（JIEGOU HUAXUE） Vol. 30, No.

4
2011. 4 Chinese J. Struct. Chem. 514~518

Solvothermal Synthesis, Crystal Structure

and Antimicrobial Activity of a Novel Imide
Nickel Complex [Ni(CH3CONCOCH3)2·2(H2O)] ①

CHEN Wen-Bina② ZHOU Hong-Yinga

YAO Yongb MA Wei-Xinga
a
(Department of Chemical Engineering, Huaihai Institute
of Technology, Lianyungang 222005, China)
b
(Jiangsu Chia Tai-Tianqing Pharmaceutical Co., Ltd., Lianyungang 222006, China)

ABSTRACT A novel imide nickel complex [Ni(CH3CONCOCH3)2·2(H2O)] was synthesized by the

solvothermal reaction of nickel acetate tetrahydrate and acetonitrile. What amazed us is that acetonitrile had
changed into acetyl imide in enol form during the formation process of the title complex. The complex was
characterized by elemental analysis, IR spectrum and X-ray single-crystal diffraction analysis. It crystallizes in
the orthorhombic system, space group Pbca with a = 7.4503(7), b = 13.1089(12), c = 14.1303(14) Å, V =
1380.0(2) Å3, Dc = 1.420 g/cm3, Mr = 294.94, Z = 4, F(000) = 616, μ = 1.422 mm-1, the final R = 0.0487 and
wR = 0.1482. The four-coordinated nickel(II) center is surrounded by 4O atoms from two imide ligands and
has a distorted square planar geometry. The complex is connected to form a supramolecule with an infinite
three-dimensional network through intramolecular and intermolecular hydrogen bonds. Antimicrobial activity
was investigated by agar diffusion method, and the result showed that the complex was active against coli
bacillus, staphylococcus aureus and bacillus subtilis. The thermal stability of the title complex was also
studied by TG-DTA method.
Keywords: solvothermal synthesis, crystal structure, imide nickel complex,
thermal stability, antimicrobial activity

1 INTRODUCTION are favorable for crystal growth[5, 6]. Therefore, hy-

The hydro(solvo)thermal technique has been most
[1]
popular, particularly in the last fifteen years . Though the
term hydrothermal is purely of geological origin, hy-
dro(solvo)thermal method has been demonstrated as a
promising technique in various fields such as materials
synthesis, crystal growth, materials processing, etc[1 3]. In
～
contrast to the conventional methods, hydrothermal
technique has several unique advantages, especially its
[4]
capability of producing metastable compounds
enhancing effectively the metal-ligand interactions which
dro(solvo)thermal technique has been employed on a
large scale to prepare piezoelectric, magnetic, optic,
ceramic and a host of other materials both as single
crystals and polycrystalline materials, especially to
generate MOFs with unique structures and special
properties[1, 7]. However, the hydrothermal reactions are
complicated and unpredictable, so both unpredictable
structures and rational designs under hydrothermal
conditions can be achieved, especially some fantastic
and reactions like hydrolysis, substitution, ligand oxidative,
and so on can also occur[7, 8]
.

Received 11 June 2010; accepted 23 February 2011 (CCDC 757096)

① The project was supported by the Natural Science Foundation of Jiangsu Province (No. BK2005045) and Key Marine Biotechnology Lab. of HHIT
② Corresponding author. Born in 1970, associated professor, majoring in coordination chemistry. Tel: 86-518-85895408, E-mail: chenwenbin111@sohu.com
2011 Vol. 30 结 构 化 学（JIEGOU HUAXUE）Chinese
In order to understand the reaction mechanism under
hydro(solvo)thermal conditions, many approaches or
[1]
models have been proposed , and to obtain a metastable
compound or mediate in any hydro(solvo)thermal reac-
tion is very useful to demonstrate its potential me-
[2]
chanism. As Xu et al. reported, a metastable compound,
protonated acetamide in enolic form, was yielded by the
hydrolysis of acetonitrile with copper chloride under
hydrothermal condition. This intrigues us to study the
hydrolysis of acetonitrile in the presence of transition
metal nickel with solvothermal method. During the
reaction of acetonitrile with nickel acetate, we noted that
acetonitrile had changed into acetyl imide in an enol form
and the latter coordinated to nickel as a bidentate ligand. It
could be proposed that acetic acid is formed through the
hydrolysis of acetonitrile, and then acetic acid and
acetonitrile may exchange their carboxyl and cyano
groups[9]. As the exchange reaction is at an equilibrium
[9]
condition, the reaction intermediate may be imide which
can be better proved by the title complex. Of course, the
proposal needs further more experiments to prove. Herein
we report the solvothermal synthesis, crystal structure,
thermal stability and antimicrobial activity of the novel
title nickel complex [Ni(CH3CONCOCH3)2·2(H2O)].
2 EXPERIMENTAL
2. 1 General
All reagents were of analytical grade without further
purification. Elemental analyses were carried out with a
Perkin-Elmer 2400-II analyzer. IR spectrum was recorded
on a Spectrum One BFT-IR spectrophotometer using KBr
pellets. Thermal analyses were performed on a
e
METTLER TOLEDO TGA/SDTA 851 .
2. 2 Synthesis of the title complex
A mixture of Ni(CH3COO)2·4H2O (248.7 mg, 1 mmol)
and acetonitrile (13 mL) were sealed in a 25 mL
Teflon-lined stainless-steel reactor and placed in an oven
at 180 ℃ for 5 days. After cooling to room temperature,
the solution was filtrated, and on slowly evaporating the
filtrate for 3 day, orange block-shaped crystals suitable for
X-ray analysis were collected. Yield: 37%. Anal. Calcd.
J. Struct. Chem. 515
(%) for C8H16N2NiO6: C, 32.58; H, 5.47; N, 9.50. Found
(%): C, 32.97; H, 5.19; N, 9.36. Main IR bands (KBr,
cm-1): 3500～3000m ν(H2O), 1672wν(C=O); 1592s ν
(C=N); 1378m δ(CH3); 1205m δ(C–O); 1058w ν(C–N).
2. 3 X-ray crystal structure determination
A selected crystal with dimensions of 0.40mm ×
0.38mm × 0.37mm was mounted on a glass fiber. X-ray
diffraction intensity data were collected on a BRUKER
SMART CCD diffractometer equipped with a graphite-
monochromatized MoKα (λ = 0.71073 Å) radiation by
using the ω-2θ scan mode (3.11≤θ≤25.01º) at 296(2) K.
A total of 5251 reflections were collected with 1213
unique ones (Rint = 0.0259). The crystal structure was
solved by direct methods and Fourier synthesis with the
program SHELXS-97[10] and refined by full-matrix
least-squares techniques on F2 using program SHELXL-
97[11]. The non-hydrogen atoms were refined anisotro-
pically and hydrogen atoms were theoretically added. The
final refinement converged at R = 0.0487 and wR =
0.1482 (w = 1/[σ2(Fo2) + (0.0911P)2 + 1.2951P], where P
= (Fo2 + 2Fc2)/3) for 845 observed reflections with I >
2σ(I). S = 1.074, (Δ/σ)max = 0.001, (Δρ)max = 0.561 and
(Δρ)min = –0.489 e/Å3.
2. 4 Antimicrobial activity determination
The title complex was evaluated for antibacterial activity
against coli bacillus, staphylococcus aureus and bacillus
subtilis by the modified agar diffusion method[12, 13]
.
Because the ligand imide without nickel is not obtained in
the experiment, the antibacterial activity of nickel acetate
was tested for comparison. The compounds were dis-
solved in DMF. Nutrient agar thawed by heating in a
water bath was transferred to plates and frozen at 37 ℃.
After the test strains were spread on the solid nutrient agar
surface, stainless steel tubes (7.8mm × 6mm × 10mm)
were spread on the surface. 0.05 mL compound with
certain concentration was injected to the steel tubes
allowed to incubate at 37 ℃ for 24 h. The zones of
inhibition around the disc were calculated as zone
diameter in millimeters. Blank tests showed that DMF in
preparing the test solutions does not affect the test
organisms. All tests were repeated three times and average
data were taken as the final result.
 CHEN W. B. et al.: Solvothermal Synthesis, Crystal Structure and Antimicrobial
516 Activity of a Novel Imide Nickel Complex [Ni(CH3CONCOCH3)2·2(H2O)] No. 4
-1
3 RESULTS AND DISCUSSION that at 1378 cm can be assigned to the methyl group
(ν(C-H)). The above analysis indicates that imide in the
3. 1 IR spectrum characteristics complex is present in an enolic form. The IR spectrum
IR spectrum of the title complex shows one broad band analysis coincides with the X-ray diffraction analysis.
-1
in the 3500 ～3000 cm region, attributable to the 3. 2 Crystal structure of the title complex
-1
vibration of water. The weak band at 1672 cm can be The selected bond lengths and bond angles relevant to
assigned to the carboxyl group of imide (ν(C=O)), and the the Ni(II) coordination sphere are given in Table 1. The
-1
strong band at 1592 cm to imino group of the imide molecular structure of the title complex is shown in Fig. 1,
-1
(ν(C=N)). Bands at 1205 and 1058 cm are the charac- and the packing diagram is viewed along a in Fig. 2.
teristic vibration of δ(C-O) and ν(C-N)[14], respectively, while

Fig. 1. Molecular structure of the title complex Fig. 2. Packing diagram of the title complex viewed along a

Table 1. Selected Bond Lengths (Å) and Bond Angles (°)

Bond Dist. Bond Dist. Bond Dist.
Ni(1)–O(1) 1.856(4) Ni(1)–O(1)A 1.856(4) Ni(1)–O(2) 1.867(4)
Ni(1)–O(2)a 1.867(4) N(1)–C(1) 1.342(5) N(1)–C(3) 1.358(5)
O(2)–C(3) 1.294(5) O(1)–C(1) 1.322(5) C(3)–C(4) 1.486(6)
Angle (º) Angle (º) Angle (º)

O(1)a–Ni(1)–O(1) 180.000(1) O(1)A–Ni(1)–O(2) 89.98(12) O(1) –Ni(1)–O(2) 90.02(12)

a A A
O(1) –Ni(1)–O(2) 90.02(12) O(1)–Ni(1)–O(2) 89.98(12) O(2)–Ni(1)–O(2)A 180.000(1)
C(1)–N(1)–C(3) 120.9(3) O(2)–C(3)–N(1) 125.5(4) O(2)–C(3)–C(4) 119.7(4)
N(1)–C(3)–C(4) 114.7(4) O(1)–C(1)–N(1) 126.0(4) O(1)–C(1)–C(2) 117.9(4)
N(1)–C(1)–C(2) 116.0(3) C(1)–O(1)–Ni(1) 128.2(3) C(3)–O(2)–Ni(1) 129.2(3)
Symmetry transformation: A: –x+2, –y+1, –z+1

As shown in Fig. 1, each ligand imide formed during
solvothermal reaction in the title complex provides two
oxygen atoms as coordination cites, acting as a bidentate
ligand. In the ligand, the C(1)–N(1) (1.342(5) Å) and
C(3)–N(1) (1.358(5) Å) bonds are in the range of C=N
[3]
bond (1.34～1.38 Å) , indicating that the molecule has a
good conjugated system. Furthermore, C(1)–O(1)
(1.322(5) Å) is in the range of the C–O bond (1.30～1.39
[3]
Å) and belongs to a single bond, while C(3)–O(2)
(1.294(5) Å) can be considered as a double bond which
may be elongated during coordination to metal. And
hydrogen atom of hydroxyl group of imide was lost
during the formation of a coordinate bond for the charge
balance. The above-mentioned bond distances further
prove the enolic form of imide ligand in the title complex.
The central Ni(II) is four coordinated by four oxygen
atoms from two ligands, and the five atoms of
Ni(1)O(1)O(2)O(1)AO(2)A are perfectly coplanar. The
bond lengths of Ni(1)–O(1) (1.856(4) Å) and Ni(1)–O(2)
(1.867(4) Å) are somewhat longer than those of other
four-coordinated nickel complexes[12, 13, 15], while the bond
angles of O(1)A–Ni(1)–O(2), O(1)–Ni(1)–O(2), O(1)A–
2011 Vol. 30 结 构 化 学（JIEGOU HUAXUE）Chinese
A A
Ni(1)–O(2) and O(1)–Ni(1)–O(2) are respectively
89.98(12), 90.02(12), 90.02(12) and 89.98(12)º, with their
A
summation to be 360°, and those of O(1) –Ni(1)–O(1)
and O(2)–Ni(1)–O(2)A are 180.00(1)º. These data show
the coordination geometry of Ni(II) center is close to a
perfectly square plane. Through calculation, it can be
known that the two chelating six-membered rings are
almost coplanar (the mean deviation from the plane is
0.0081 Å), thus forming a good conjugated system.
There are two types of hydrogen bonding interactions
between the imide nickel complex and uncoordinated
water in the title complex. As shown in Fig. 3, the oxygen
O(1) atom and nitrogen N(1) of imide are hydrogen-
bonded to oxygen O(3) of the uncoordinated water, for-
ming intramolecular hydrogen bonds O(3)–H(3C)···O(1)
and intermolecular hydrogen bonds O(3)–H(3D)···N(1).
Detailed data for the hydrogen bonds are given in Table 2.
Through these H-bond interactions, the title complex was
J. Struct. Chem. 517
weight loss of the first step is 11.99% in the range of 80～
114 ℃, attributed to the release of uncoordinated water
(calcd. 12.22%). At the same time, an endothermal peak is
observed at 111 ℃, which resulted from the removal of
uncoordinated water. Upon further heating, a weight loss
of 70.29% is observed between 114 and 400 ℃ accom-
panying with a strong endothermal process at 314 ℃,
consistent with the loss of two imide ligands (calcd.
67.89%). At the same time, the residue is nickel, whose
weight percentage of 17.72% is consistent with the
calculated value of 19.9%. When the temperature is up to
900 ℃, the residue content is increased too, which may be
caused by the oxidation of nickel under high temperature.
The final residue may be Ni2O, and the weight percentage
of the experimental value (22.10%) and that of the
calculated value (22.60%) are almost equal to each other.
100

connected to a suparmolecular with an infinite three- 80

TG
DTA

dimensional network, as shown in Fig. 2.

Weight loss /%

60 0

40

-2

20

0 200 400 600 800 1000

o
Temperature / C

Fig. 4. TG-DTA curves of the title complex

3. 4 Antimicrobial activity of the title complex

Fig. 3. Hydrogen bonds in the title complex
3. 3 Thermal stability
The thermal stability of the title complex was studied by
thermal gravimetric (TG) and differential thermal ana-
lyses (DTA) between 50 and 900 ℃. As shown in Fig. 4,
the DTA curve of the title complex reveals two
endothermal peaks during heat decomposition, and the
TG curve corresponds to two weight loss steps. The
It can be seen from Table 3 that the title complex and
Ni(Ac)2·4H2O both exhibited antibacterial activity against
all test organisms. And the activity of these compounds
against the strains enhanced with the increase of con-
centration in the test range. Compared with nickel acetate
tetrahydrate, the antibacterial activity of the title complex
is higher against Staphylococcus aureus, but lower against
the other two strains. The further study is still in progress.

Table 2. Hydrogen Bonding Geometries (Å, º)

D–H···A dD–H dH···A dD···A θDHA
O(3)–H(3C)···O(1) 0.850 2.153 2.987(7) 166.92
O(3)–H(3D)···N(1) a 0.850 2.134 2.968(6) 166.74
Symmetry code: (A) –x+3/2, y+1/2, z
 CHEN W. B. et al.: Solvothermal Synthesis, Crystal Structure and Antimicrobial
518 Activity of a Novel Imide Nickel Complex [Ni(CH3CONCOCH3)2·2(H2O)] No. 4
Table 3. Antibacterial Activity of the Title Complex and Nickel Acetate
Compound Concentration mmol/L Diameter of inhibition zone (mm)
5.0 15.7 11.3 13.5
Ni(Ac)2·4H2O 0.5 13.1 9.0 10.2
0.05 8.3 7.7 8.0
5.0 14.3 12.9 11.8

The title complex 0.5 12.7 10.3 9.7

0.05 7.9 9.3 8.2

DMF 7.82 7.82 7.81

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