Synthesis, characterization, and crystal structure of Di{bis[2-[(2- dimethylaminoethylimino)methyl]-6-methoxyphenolato]thiocyanatozinc(II)} Tetrakis(thiocyanato)zinc(II)

Article abstract of DOI:10.1080/15533174.2010.494276

A new Schiff base zinc(II) complex with the formula 2[Zn(C ₁₂H₁₈N₂O₂)₂(NCS)][Zn(NCS) ₄] was prepared and structurally characterized by elemental analysis, IR spectrum, and single crystal X-

Full text of DOI:10.1080/15533174.2010.494276

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 41:731–735, 2011
Copyright © Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2010.494276
Synthesis, Characterization, and Crystal Structure of
Di{bis[2-[(2-dimethylaminoethylimino)methyl]-6-
methoxyphenolato]thiocyanatozinc(II)}
Tetrakis(thiocyanato)zinc(II)
Chen-Yi Wang
Department of Chemistry, Huzhou University, Huzhou, P. R. China
EXPERIMENTAL
A
new Schiff base zinc(II) complex with the formula
Materials and Measurements
2[Zn(C12H18N2O2)2(NCS)]·[Zn(NCS)4] was prepared and struc-
turally characterized by elemental analysis, IR spectrum, and
single crystal X-ray diffraction. The compound consists of two
mononuclear [Zn(C12H18N2O2)2(NCS)] complex cations, in which
the Zn atom is in a trigonal-bipyramidal geometry, and one
[Zn(NCS)4] complex anion, in which the Zn atom is in a tetra-
hedral geometry.
All chemicals were of reagent grade and used without further
purification. 3-Methoxysalicylaldehyde and N,N-dimethyl-1,2-
diaminoethane were purchased from Lancaster corporation. El-
emental analyses were performed with a Finnigan EA 1112
elemental analyzer. The infrared spectra of KBr pellets were
recorded on an FTS-40 spectrophotometer. The crystal deter-
mination was carried out on a Bruker Smart 1000 CCD area
diffractometer.
Keywords crystal structure, Schiff base, synthesis, thiocyanate, zinc
complex
Synthesis of 2[Zn(C12H18N2O2)2(NCS)]·[Zn(NCS)4]
3-Methoxysalicylaldehyde (0.1 mmol, 15.2 mg) and N,N-
dimethyl-1,2-diaminoethane (0.1 mmol, 8.8 mg) were mixed
in a methanol solution (10 mL). The mixture was stirred for
30 min at room temperature to give a clear yellow solution. To
the solution was slowly added with stirring an aqueous solution
(5 ml) of KSCN (0.2 mmol, 19.5 mg) and a methanol solution
(10 ml) of Zn(CH3COO)2·2H2O (0.1 mmol, 22.0 mg). The final
mixture was stirred for another 30 min to give a clear colorless
solution. The solution was allowed to stand at room temperature
for a week to deposit colorless block-shaped crystals of the com-
plex in 45.0% yield. Anal. calcd. (%) for C54H72N14O8S6Zn3:
C, 45.23; H, 5.01; N, 13.68. Found (%): C, 45.01; H, 5.12; N,
13.80. Selected IR data (cm−1): 3203 (w), 3061 (m), 2936 (m),
2861 (m), 2080 (vs), 1617 (s), 1426 (s), 1220 (s), 754 (m), 655
(w), 470 (w).
INTRODUCTION
In recent years, Schiff base compounds have been widely
used as versatile ligands involved in various metal chelation re-
actions to form transition metal complexes with interesting prop-
erties in material sciences and biological systems.[1–6] These
complexes can be easily synthesized from simple starting ma-
terials, where the metal ions, ligands, and coordination modes
are the important factors for the self-assembly processes. Thio-
cyanate is a versatile ligand, which acts as monodentate or bridg-
ing group with end-on or end-to-end coordination mode to form
complexes with interesting structures.[7–9] In order to investigate
the aggregate of the Schiff base ligand, thiocyanate and zinc ion,
we report in this article the synthesis and crystal structure of the
complex 2[Zn(C12H18N2O2)2(NCS)]·[Zn(NCS)4].
DATA COLLECTION, STRUCTURAL DETERMINATION,
AND REFINEMENT
Received 13 November 2009; accepted 9 May 2010.
This work was financially supported by the Natural Science Foun-
dation of China (No. 31071856), the Natural Science Foundation of
Zhejiang Province (No. Y407318), and the Applied Research Project
on Nonprofit Technology of Zhejiang Province (No. 2010C32060).
Address correspondence to Chen-Yi Wang, Department of
Chemistry, Huzhou University, Huzhou, P. R. China. E-mail:
chenyi wang@163.com
Crystal Structure Determination
A colorless crystal with dimensions of 0.22 mm × 0.20
mm × 0.17 mm for the complex was selected and mounted on a
glass fiber in air. The diffraction data were collected on a Bruker
Smart 1000 CCD area diffractometer equipped with a graphite-
˚
monochromated MoKα radiation (λ = 0.71073 A) in the range
731

732
C.-Y. WANG
of 4.4 < 2θ < 49.0◦ by using an ω scan mode at 298(2) K.
TABLE 1
Crystallographic and experimental data for the complex
The unit cell dimensions were obtained with the least-squares
refinements and the structure was solved by direct methods
with SHELXTL-97 package.[10] The final refinement was per-
formed by full-matrix least-squares techniques with anisotropic
thermal parameters for the non-hydrogen atoms on F2. H(2),
H(4A), H(7A) and H(9) were located on a different Fourier
Formula
FW
C54H72N14O8S6Zn3
1433.73
Crystal shape/colour
Crystal size /mm
Crystal system
Space group
Block/colorless
0.22 × 0.20 × 0.17
Triclinic
P-1
13.907(3)
14.251(3)
19.473(4)
109.50(3)
104.44(3)
93.45(3)
3479.3(13)
2
˚
map, with N–H distances restrained to 0.90(1) A. Other H atoms
were introduced geometrically. Multi-scan absorption correc-
tion was applied by using the SADABS software.[11] The crys-
tallographic data are summarized in Table 1. Crystallographic
data for the complex has been deposited with the Cambridge
Crystallographic Data Centre (CCDC 662890).
˚
a/A
˚
b/A
˚
c/A
α/◦
β/◦
γ /◦
RESULTS AND DISCUSSION
3
˚
V /A
The complex is colorless crystals, stable in air at room tem-
perature, soluble in MeOH, EtOH, MeCN and their mixture
solution, insoluble in water and Et2O.
Z
˚
λ (MoKα) /A
T /K
0.71073
298(2)
1.263
0.7686
µ /mm−1 (Mo-Kα)
Tmin
Synthesis
The synthetic procedure is described as Scheme 1. The Schiff
base ligand was synthesized very easily through the condensa-
tion reaction of 3-methoxysalicylaldehyde with N,N-dimethyl-
1,2-diaminoethane in a methanol solution at room temperature.
The complex was also simply synthesized through the reaction
of the Schiff base ligand and potassium thiocyanate with zinc
acetate in a methanol solution at room temperature.
Tmax
0.8139
14092/790
6027
1488
0.949
Reflections/parameters
Independent reflections
F(000)
Goodness of fit on F2
R1, wR2 [I ≥ 2σ(I)]a
R1, wR2 (all data)a
ꢀ
0.0836, 0.1504
0.1969, 0.1957
ꢀ
ꢀ
aR1
w(Fo2)2]1/2
=
||Fo| − −|Fc||/ |Fo|, wR2 = [ w(Fo2-Fc2)2/
ꢀ
Structure Description of the Complex
.
The structure of the complex is shown in Figure 1. The
molecular packing is shown in Figure 2. The selected bond
lengths and bond angles are listed in Table 2. The distances
CHO
OH
N
MeOH
N
N
H2N
+
OH
OMe
OMe
+
NH
N
N
N
OH
MeOH
NCS
O
2-
Zn(CH COO)
+
KSCN
2
3
2
+
Zn(NCS)4
Zn
OMe
OMe
OMe
O
N
NH
SCH. 1.

SYNTHESIS AND CRYSTAL STRUCTURE OF A ZINC COMPLEX
733
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.
and angles related to the hydrogen bonding are listed in plex cations and one [Zn(NCS)4] complex anion. In each of the
Table 3.
cations, the Zn atom is in a trigonal-bipyramidal coordination
X-ray single crystal analysis revealed that the compound environment, coordinated by two phenolic O atoms from two
consists of two mononuclear [Zn(C12H18N2O2)2(NCS)] com- Schiff bases and one terminal N atom of the thiocyanate group
TABLE 2
◦
˚
Selected bond lengths (A) and bond angles ( ) for the complex
Zn(1)-O(1)
Zn(1)-N(1)
Zn(1)-N(5)
Zn(2)-O(7)
Zn(2)-N(8)
Zn(3)-N(11)
Zn(3)-N(13)
1.996(5)
2.108(6)
2.018(7)
1.976(5)
2.130(6)
1.965(8)
1.937(8)
Zn(1)-O(3)
Zn(1)-N(3)
Zn(2)-O(5)
Zn(2)-N(6)
Zn(2)-N(10)
Zn(3)-N(12)
Zn(3)-N(14)
2.005(5)
2.136(6)
2.000(4)
2.127(6)
2.017(7)
1.952(10)
1.952(8)
O(1)-Zn(1)-O(3)
O(3)-Zn(1)-N(5)
O(3)-Zn(1)-N(1)
O(1)-Zn(1)-N(3)
N5)-Zn(1)-N(3)
O(7)-Zn(2)-O(5)
O(5)-Zn(2)-N(10)
O(5)-Zn(2)-N(6)
O(7)-Zn(2)-N(8)
N(10)-Zn(2)-N(8)
N(13)-Zn(3)-N(14)
N(14)-Zn(3)-N(12)
N(14)-Zn(3)-N(11)
120.7(2)
O(1)-Zn(1)-N(5)
O(1)-Zn(1)-N(1)
N(5)-Zn(1)-N(1)
O(3)-Zn(1)-N(3)
N(1)-Zn(1)-N(3)
O(7)-Zn(2)-N(10)
O(7)-Zn(2)-N(6)
N(10)-Zn(2)-N(6)
O(5)-Zn(2)-N(8)
N(6)-Zn(2)-N(8)
N(13)-Zn(3)-N(12)
N(13)-Zn(3)-N(11)
N(12)-Zn(3)-N(11)
121.1(2)
118.1(2)
91.2(2)
88.7(2)
90.4(3)
116.8(2)
123.0(2)
89.9(2)
88.6(2)
90.2(3)
107.8(3)
111.5(4)
111.0(3)
89.1(2)
92.8(3)
87.9(2)
176.8(2)
120.1(2)
92.7(2)
90.7(3)
88.0(2)
177.8(2)
108.3(4)
113.2(3)
105.1(4)

734
C.-Y. WANG
TABLE 3
◦
˚
Distances (A) and angles ( ) involving hydrogen bonding of the complex
D–H· · ·A
d(D–H)
d(H· · ·A)
d(D· · ·A)
Angle(D–H· · ·A)
N(2)–H(2)· · ·O(3)
N(2)–H(2)· · ·O(4)
N(9)–H(9)· · ·O(5)
N(9)–H(9)· · ·O(6)
N(7)–H(7A)· · ·O(7)
N(7)–H(7A)· · ·O(8)
N(4)–H(4A)· · ·O(1)
N(4)–H(4A)· · ·O(2)
0.900(10)
0.900(10)
0.903(10)
0.903(10)
0.900(10)
0.900(10)
0.900(10)
0.900(10)
1.828(19)
2.64(7)
1.81(3)
2.40(7)
1.84(3)
2.41(7)
1.92(5)
2.32(6)
2.718(8)
3.187(8)
2.686(7)
2.975(8)
2.717(8)
2.990(9)
2.713(8)
3.014(8)
170(8)
120(6)
162(7)
122(6)
163(8)
122(6)
145(7)
134(6)
TABLE 4
Parameters between the planes
Distance between ring
Dihedral
angle (◦)
Perpendicular distance
of Cg(I) on Cg(J) (A)
Perpendicular distance
of Cg(J) on Cg(I) (A)
˚
˚
˚
Cg
centroids (A)
Cg(2)· · ·Cg(3)i
Cg(2)· · ·Cg(4)i
Cg(2)· · ·Cg(4)ii
Cg(3)· · ·Cg(2)iii
Cg(3)· · ·Cg(5)
Cg(3)· · ·Cg(5)iv
Cg(4)· · ·Cg(2)iii
Cg(4)· · ·Cg(2)ii
Cg(4)· · ·Cg(5)iv
Cg(5)· · ·Cg(1)v
Cg(5)· · ·Cg(5)iv
4.9920
4.7697
5.3297
4.9920
5.3521
5.0636
4.7697
5.3297
5.2133
5.7757
3.6996
44.39
43.99
43.99
44.39
86.21
86.21
43.99
43.99
88.54
77.59
0.00
4.522
4.585
2.811
3.118
2.363
1.079
2.430
4.271
1.426
1.329
3.442
3.118
2.430
4.271
4.522
3.849
4.782
4.585
2.811
4.749
4.817
3.442
Symmetry codes: (i) –1 +x, y, z; (ii) 1 – x, 2 – y, 1 – z; (iii) 1 +x, y, z; (iv) 2 – x, 2 – y, – z; (v) 1 – x, 1 – y, – z. Cg(1), Cg(2), Cg(3), Cg(4), and
Cg(5) are the centroids of the rings C(1)-C(2)-C(3)-C(4)-C(5)-C(6), C(13)-C(14)-C(15)-C(16)-C(17)-C(18), Zn(2)-O(5)-C(27)-C(26)-C(32)-
N(6), C(26)-C(27)-C(28)-C(29)-C(30)-C(31), and C(38)-C(39)-C(40)-C(41)-C(42)-C(43), respectively.
at the basal plane, and by two imine N atoms from two Schiff
bases at the apical positions. In the anion, the Zn atom is coor-
dinated by four N atoms from four thiocyanate ligands (Zn–N
˚
= 1.937(8) – 1.965(8) A); the bond angles subtended at the Zn3
atom are range from 105.1(4) to 113.2(3)◦, showing a distorted
tetrahedral coordination environment. In either the cations or
the anion, the thiocyanate groups are nearly linear with the N–
C–S bond angles in the range 176.0(11) to 179.6(10)◦. All the
coordinate bond values are within normal ranges and compara-
ble to those observed in the similar zinc(II) complexes reported
previously.[12–15]
In the crystal structure, relatively shorter centroid distances
(Table 4) between the adjacent rings are observed, implying the
existence of π-π stacking interactions in the complex.[16]
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