Synthesis, characterization, and crystal structure of a dicyanamide-bridged polymeric nickel(II) complex with 4-chloro-2-[(3-dimethylaminopropylimino) methyl]phenol

Article abstract of DOI:10.1080/15533174.2012.761232

A dicyanamide-bridged polymeric nickel(II) complex, [NiL(MeOH) (μ₂-N(CN)₂)]_n, where L is the anionic form of the Schiff base 4-chloro-2-[(3-dimethylaminopropylimino)methyl] phenol, was synthesized and characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. The crystal of the complex crystallizes in the monoclinic space group P2₁/c, with unit cell dimensions a = 9.860(1) A, b = 20.234(2) A, c = 18.601(2) A, β = 103.127(2)°, V = 3614.0(6) A³, Z = 4, R ₁ = 0.0368, wR₂ = 0.0702. The Ni atom of the complex is in an octahedral coordination, with two N atoms of the Schiff base ligand, one methanol O atom, and one teminal N atom of the dicynamide ligand defining the equatorial plane, and with one phenolate O atom of the Schiff base ligand, and one terminal N atom of another dicyanate ligand occupying the two axial positions. Supplemental materials are available for this article. Go to the publisher's online edition of Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry to view the supplemental file. Copyright Taylor & Francis Group, LLC.

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Synthesis, Characterization, and Crystal
Structure of a Dicyanamide-Bridged Polymeric
Nickel(II) Complex With 4-Chloro-2-[(3-
dimethylaminopropylimino)methyl]phenol
Jian-Ying Miao a
a Department of Chemistry and Chemical Engineering , Baoji University of Arts and
Sciences , Baoji , P. R. China
Accepted author version posted online: 23 May 2013.Published online: 25 Aug 2013.
To cite this article: Jian-Ying Miao (2013) Synthesis, Characterization, and Crystal Structure of a Dicyanamide-Bridged
Polymeric Nickel(II) Complex With 4-Chloro-2-[(3-dimethylaminopropylimino)methyl]phenol, Synthesis and Reactivity in
Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:10, 1361-1364, DOI: 10.1080/15533174.2012.761232
To link to this article: http://dx.doi.org/10.1080/15533174.2012.761232
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:1361–1364, 2013
Copyright ꢀ Taylor & Francis Group, LLC
C
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2012.761232
Synthesis, Characterization, and Crystal Structure of a
Dicyanamide-Bridged Polymeric Nickel(II) Complex With
4-Chloro-2-[(3-dimethylaminopropylimino)methyl]phenol
Jian-Ying Miao
Department of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences,
Baoji, P. R. China
have been reported. Dicyanamide, a pseudohalide anion, struc-
turally similar to azide or thiocyanate, has also been widely used
for the construction of polynuclear complexes.[12–15] However,
to the best of my knowledge, no dicyanamide-bridged nickel(II)
complexes with Schiff bases have been reported so far. In
the present study, a polymeric dicyanamide-bridged polymeric
nickel(II) complex, [NiL(MeOH)(μ2-N(CN)2)]n, derived from
the Schiff base 4-chloro-2-[(3-dimethylaminopropylimino)
methyl]phenol (HL), was prepared and characterized.
A
dicyanamide-bridged polymeric nickel(II) complex,
[NiL(MeOH)(μ2-N(CN)2)]n, where L is the anionic form of the
Schiff base 4-chloro-2-[(3-dimethylaminopropylimino)methyl]
phenol, was synthesized and characterized by elemental analysis,
IR spectrum, and single-crystal X-ray diffraction. The crystal
of the complex crystallizes in the monoclinic space group P21/c,
with unit cell dimensions a = 9.860(1) Å, b = 20.234(2) Å, c =
18.601(2) Å, β = 103.127(2)◦, V = 3614.0(6) Å3, Z = 4, R1 = 0.0368,
wR2 = 0.0702. The Ni atom of the complex is in an octahedral
coordination, with two N atoms of the Schiff base ligand, one
methanol O atom, and one teminal N atom of the dicynamide
ligand defining the equatorial plane, and with one phenolate O
atom of the Schiff base ligand, and one terminal N atom of another
dicyanate ligand occupying the two axial positions.
EXPERIMENTAL
Materials and Measurements
5-Chlorosalicylaldehyde and N,N-dimethylpropane-1,3-dia-
mine with AR grade were purchased from Lancaster (Beijing,
China) and used as obtained. C, H, and N elemental analyses
were performed with a Perkin-Elmer 240C elemental analyzer
(Baoji University of Arts and Sciences, Baoji, China). The IR
spectrum was recorded with a Nicolet FT-IR 170-SX spectro-
photometer (Baoji University of Arts and Sciences, Baoji,
China).
Supplemental materials are available for this article. Go to the
publisher’s online edition of Synthesis and Reactivity in Inorganic,
Metal-Organic, and Nano-Metal Chemistry to view the supplemen-
tal file.
Keywords crystal structure, nickel complex, polymeric complex,
Schiff base, synthesis
Synthesis of the Schiff Base Ligand HL
INTRODUCTION
5-Chlorosalicylaldehyde (1.0 mmol, 157 mg) and N,N-
dimethylpropane-1,3-diamine (1.0 mmol, 102 mg) were mixed
in a methanolic solution (30 mL). The mixture was stirred at
room temperature for 30 min to give a clear yellow solution.
The solvent was removed by distillation to give yellow oily
product of the Schiff base. Anal. Calcd. for C12H17ClN2O: C,
59.87; H, 7.12; N, 11.64. Found: C, 59.72; H, 7.23; N, 11.75%.
In the past few years there has been a burgeoning ef-
fort to study the polynuclear complexes containing bridging
groups, due to their interesting magnetic properties,[1–3] cat-
alytic properties,[4,5] and biological activities.[6, 7] Among the
bridging groups, azide and thiocyanate anions proved to be the
most favorable groups for the construction of polynuclear com-
plexes.[8–11] Schiff bases are a kind of versabile ligands in the
coordination chemistry. To date, a large number of azide or
thiocyanate-bridged polynuclear complexes with Schiff bases
Synthesis of [NiL(MeOH)(␮2-N(CN)2)]n
A 5 ml methanolic solution containing HL (0.1 mmol,
24.0 mg) and sodium dicyanamide (0.1 mmol, 8.9 mg) was
stirred to a 5 mL methanolic solution of Ni(NO3)2·6H2O
(0.1 mmol, 29.1 mg). The mixture was stirred at room tem-
perature for one hour to give a clear green solution. The so-
lution was kept still in air, green block-shaped crystals of the
complex, suitable for X-ray single-crystal determination, were
formed on slow evaporation of the solvents for several days. The
crystals were isolated by filtration and washed with methanol.
Received 29 March 2012; accepted 17 December 2012.
The author acknowledges the Baoji University of Arts and Sciences
for the research grant (project No. zk0615).
Address correspondence to Jian-Ying Miao, Department of Chem-
istry and Chemical Engineering, Baoji University of Arts and Sciences,
Baoji 721007, P. R. China. E-mail: jianying miao@163.com
1361

1362
J.-Y. MIAO
TABLE 1
Crystallographic and experimental data for the complex
TABLE 2
Selected bond lengths (Å) and bond angles (◦) for the complex
Parameter
Value
Bond
d, Å
Bond
d, Å
Formula
Fw
Crystal shape/color
Crystal size, mm
Crystal system
Space group
C30H40Cl2N10Ni2O4
793.0
Block/green
0.27 × 0.23 × 0.22
monoclinic
P21/c
Ni(1)-O(1)
Ni(1)-N(2)
Ni(1)-N(5)
Ni(2)-N(3)
Ni(2)-O(4)
Ni(2)-N(9)
2.007(2)
2.215(3)
2.105(3)
2.022(3)
2.096(2)
2.122(3)
Ni(1)-N(1)
Ni(1)-O(3)
Ni(1)-N(8)
Ni(2)-O(2)
Ni(2)-N(7)
Ni(2)-N(4)
2.026(2)
2.129(2)
2.064(3)
2.025(2)
2.060(3)
2.201(3)
a, Å
b, Å
9.860(1)
20.234(2)
18.601(2)
103.127(2)
3614.0(6)
4
0.71073
298(2)
1.239
Angle
ω, ◦
Angle
ω, ◦
c, Å
O(1)-Ni(1)-N(1)
N(1)-Ni(1)-N(8)
N(1)-Ni(1)-N(5)
O(1)-Ni(1)-O(3)
N(8)-Ni(1)-O(3)
O(1)-Ni(1)-N(2)
N(8)-Ni(1)-N(2)
O(3)-Ni(1)-N(2)
N(3)-Ni(2)-N(7)
88.6(1)
97.0(1)
92.6(1)
82.3(1)
92.3(1)
97.7(1)
87.3(1)
92.0(1)
97.3(1)
O(1)-Ni(1)-N(8) 172.7(1)
O(1)-Ni(1)-N(5)
N(8)-Ni(1)-N(5)
N(1)-Ni(1)-O(3) 170.7(1)
N(5)-Ni(1)-O(3)
N(1)-Ni(1)-N(2)
N(5)-Ni(1)-N(2) 173.0(1)
N(3)-Ni(2)-O(2) 88.6(1)
O(2)-Ni(2)-N(7) 171.4(1)
β, ◦
89.2(1)
85.8(1)
V, Å3
Z
λ (MoKα), Å
89.4(1)
87.1(1)
T, K
μ, mm−1 (Mo-Kα)
Tmin
0.7309
0.7723
Tmax
Measured reflections
Unique reflections (Rint)
Observed reflections [I ≥ 2σ(I)]
Parameters
16177
5535 (0.0415)
4105
445
2
N(3)-Ni(2)-O(4) 173.2(1)
O(2)-Ni(2)-O(4)
N(3)-Ni(2)-N(9)
N(7)-Ni(2)-N(9)
N(3)-Ni(2)-N(4)
N(7)-Ni(2)-N(4)
84.6(1)
90.1(1)
87.6(1)
87.1(1)
90.5(1)
N(7)-Ni(2)-O(4)
O(2)-Ni(2)-N(9)
O(4)-Ni(2)-N(9)
O(2)-Ni(2)-N(4)
O(4)-Ni(2)-N(4)
89.5(1)
86.0(1)
89.7(1)
96.1(1)
93.4(1)
Restraints
F(000)
1648
1.011
N(9)-Ni(2)-N(4) 176.4(1)
Goodness of fit on F2
R1, wR2 [I ≥ 2σ(I)]a
R1, wR2 (all data)a
Largest diff. peak and hole, e/Å3
0.0368, 0.0702
0.0584, 0.0791
0.361, –0.289
ꢀ
RESULTS AND DISCUSSION
Synthesis
The synthesis of the Schiff base ligand HL is shown in
Scheme 1. The synthesis of the nickel(II) complex is shown
in Scheme 2. The reactions were carried out at room tempera-
ture. It should be pointed out that the complex is the first sample
of the dicynamide-bridged nickel(II) complex with Schiff base
ligand.
ꢀ
ꢀ
ꢀ
aR1 = ||Fo|–|Fc||/ |Fo|, wR2 = [ w(Fo2–Fc2)2/ w(Fo2)2]1/2
.
Yield, 25.0 mg (63%). Anal. Calcd. for C30H40Cl2N10Ni2O4: C,
45.44; H, 5.08; N, 17.66. Found: C, 45.27; H, 5.21; N, 17.60%.
Crystal Structure Determination
The diffraction intensities for the complex were collected on
a Bruker Smart Apex CCD diffractometer (MoKα, λ = 0.71073
Å) at 298(2) K. Absorption corrections were applied using SAD-
ABS.[16] The crystal structure was solved with direct method
and refined with a full-matrix least-squares technique using
SHELXTL.[17] Anisotropic thermal parameters were applied
to all non-hydrogen atoms. The methanolic hydrogen atoms
were located from a difference Fourier map and refined with
isotropic temperature factors, and with O–H distances restrained
to 0.85(1) Å. All other hydrogen atoms on carbon atoms were
generated geometrically (C–H = 0.93–0.97 Å). The crystallo-
graphic data as well as details of data collection and refine-
ment for the complex are summarized in Table 1. Selected bond
lengths and angles are given in Table 2. Drawings were produced
SCH. 1.
SCH. 2.
with SHELXTL[17]
.

DICYANAMIDE-BRIDGED POLYMERIC NICKEL(II) COMPLEX
1363
presence of the dicyanamide ligand. The dicyanamide anion in
NaN(CN)2 showed three sharp and strong characteristic bands
in the frequency region 2290–2170 cm−1, which are attributed
to νas + νs (C≡N) combination modes (2286 cm−1), νas (C≡N)
(2232 cm−1), and νs (C≡N) (2179 cm−1).[18] Upon complex-
ation, these bands shift towards higher frequencies along with
further splitting. In the complex, the doubly splitted νas + νs
(C≡N) bands were located at 2375 and 2311 cm−1. The νas
(C≡N) band appeared at 2245 cm−1 and the bifurcated νs (C≡N)
bands were detected at 2170 and 2166 (s) cm−1. The splitting and
displacement of the bands towards higher frequencies clearly
show the bidentate bridging mode of the dicynamide ligand in
the complex. The weak bands in the region 400–600 cm−1 can
be attributed to the vibration of the Ni-O and Ni-N bonds.
FIG. 1. The structure of the complex, showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 30% probability level. H atoms have
been omitted for clarity.
Structure Description of the Complex
The molecular structure of the complex is shown in
Figure 1. The complex is a dicynamide-bridged polymeric
nickel(II) complex. The smallest repeat unit of the complex
is [NiL(MeOH)(N(CN)2)]. Each Ni atom of the complex is in
IR Spectra
The IR spectrum of the complex was analyzed and compared an octahedral coordination, with two N atoms of the Schiff base
with that of the free ligand HL in the region 4000–400 cm−1
.
ligand, one methanol O atom, and one teminal N atom of the
The weak and broad bands at 3513 cm−1 for HL and 3427 cm−1 dicynamide ligand defining the equatorial plane, and with one
for the complex are assigned to the O–H stretching vibrations. A phenolate O atom of the Schiff base ligand, and one terminal N
strong sharp absorption band around 1637 cm−1 in the spectrum atom of another dicyanate ligand occupying the two axial po-
of the Schiff base ligand can be assigned to the C N stretch- sitions. The Ni(1) and Ni(2) atoms displaced out of the planes
ing. Upon complexation with the metal, this band is shifted to defined by the four equatorial donor atoms by 0.027(2) and
1615 cm−1 in the complex as a result of the coordination of 0.057(2) Å, respectively. The distance between Ni(1) and Ni(2)
the imine nitrogen to the Ni atom. The typical phenolic C–O is 8.011(2) Å. The chelate rings formed by the atoms Ni(1),
absorption band at 1212 cm−1 observed in the spectrum of HL N(1), C(8)-C(10), N(2) (Ring 1), and by the atoms Ni(2), N(3),
is shifted to lower frequencies (1178 cm−1 in the complex), sup- C(20)-C(22), N4 (Ring 2) have chair conformations. In Ring
porting the deprotonation and the coordination of the phenolic 1, the diagonally positioned atoms, Ni(1) and C(9), are shifted
oxygen atom to the Ni atom. The complex showed sharp absorp- from the least-squares plane defined by the atoms N(1), N(2),
tion bands in the region 2150–2390 cm−1, which indicate the C(8), and C(10) by 1.036(2) and 0.693(3) Å, respectively. In
FIG. 2. The 1D packing diagram of the complex, viewed along the x axis. Hydrogen bonds are shown as dashed lines. H atoms not related to the hydrogen
bonding have been omitted for clarity.

1364
J.-Y. MIAO
Ring 2, the distances of the two diagonally positioned atoms,
Ni(2) and C(21), from the least-squares plane defined by the
atoms N(3), N(4), C(20), and C(22) are 1.078(2) and 0.690(3) Å,
respectively.
In the crystal structure of the complex, the [NiL(MeOH)]
moieties are bridged by dicynamide ligands, as well as in-
termolecular O(3)–H(3)···O(2) and O(4)–H(4)···O(1) hydrogen
bonds, to form 1D chains running along the c axis, as shown in
Figure 2.
7. Mondal, K.C.; Mukherjee, P.S. An antiferromagnetic Mn(II)-azido chain:
synthesis and characterization. Synth. React. Inorg. Met.-Org. Nano-Met.
Chem. 2007, 37, 735.
8. Li, H.-B. Synthesis, characterization, and crystal structure of an
azido-bridged dinuclear nickel(II) complex derived from 4-nitro-2-[(2-
isopropylaminoethylimino)methyl]phenol. Synth. React. Inorg. Met.-Org.
Nano-Met. Chem. 2009, 39, 516.
9. Qian, H.-Y.; You, Z.-L. Synthesis and crystal structures of a pair of azido-
bridged polynuclear Schiff base zinc(II) complexes. Synth. React. Inorg.
Met.-Org. Nano-Met. Chem. 2009, 39, 193.
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SUPPLEMENTARY MATERIALS
Crystallographic data for the complex have been deposited
with the Cambridge Crystallographic Data Centre (CCDC 11. Cornelissen, J.P.; De Graaff, R.A. G.; Haasnoot, J.G.; Prins, R.; Reedijk,
J.; Biagini-Cingi, M.; Manotti-Lanfredi, A.M.; Tiripicchio, A. Struc-
tures and properties of bis(thiocyanato-N)bis(6-methyl[1,2,4]triazolo[1,
871991).
a]pyrimidine-N3)copper(II),
a distorted tetrahedral copper(II) thio-
cyanate compound, and bis(thiocyanato-N)bis(5-methyl[1,2,4]triazolo[1,5-
a]pyrimidine-N3)copper(II), a polynuclear pseudo-layered systemOriginal.
Polyhedron 1989, 8, 2313.
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