Complexes of acetic acid α-(N-Benzoxazolin-2-one) with Zn(II), Cu(II), and Co(II): Syntheses and crystal structures

Article abstract of DOI:10.1134/S1070328414040010

The results of syntheses and X-ray diffraction analyses of mononuclear complexes [ML₂ (H₂O)₄] (M = Co²⁺(I), Cu²⁺(II), and Zn²⁺(III)) containing water molecules and anions of acetic acid α-(N-benzox -azolin-2-one) (L = C₉H ₆O₄) are presented. The crystals of complexes I-III are isostructural (space group P2₂/n, Z = 2) and are built of discrete neutral complex molecules. The crystallographic data are as follows: for complex I, a = 6.1470(5), b = 5.3310(3), c = 30.5894(17) A, β = 95.056(6)°, V = 998.50(11) A3; for com -plex II, a = 5.9661(6) A, b = 5.1414(4) A, c = 32.672(2) A, β = 92.395(6)°, V = 1001.33(14) A3; and for com -plex III, a = 6.1404(3) A, b = 5.3476(2) A, c = 30.5865(12) A, β = 94.708(4)°, V = 1000.96(7) A₃. The metal atoms (M) of the complexing agents are localized in the crystallographic symmetry centers and have a distorted octahedral environment due to two oxygen atoms of the carboxy groups of two monodentate ligands (L) and four water molecules. The M-O(1w)(H₂O) and M-O(2w)(H₂O) bond lengths for the indi -cated complexes are 2.088(3) and 2.118(3), 2.446(3) and 1.971(3), and 2.113(4) and 2.093(3) A for M = Co²⁺, Cu²⁺, and Zn²⁺, respectively. The crystal structures are formed due to packing of chains built of inter -molecular hydrogen bonds O-H·O.

Full text of DOI:10.1134/S1070328414040010

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2014, Vol. 40, No. 4, pp. 246–250. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © J.M. Ashurov, B.T. Ibragimov, N.S. Mukhamedov, 2014, published in Koordinatsionnaya Khimiya, 2014, Vol. 40, No. 4, pp. 246–250.
Complexes of Acetic Acid
α
ꢀ(NꢀBenzoxazolinꢀ2ꢀone) with Zn(II),
Cu(II), and Co(II): Syntheses and Crystal Structures
a,
a
b
J. M. Ashurov *, B. T. Ibragimov , and N. S. Mukhamedov
a
Sadykov Institute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, Tashkent, Uzbekistan
b
Yunusov Institute of Chemistry of Plant Substances, Academy of Sciences of Uzbekistan, Tashkent, Uzbekistan
*
eꢀmail: atom.uz@mail.ru
Received June 27, 2013
Abstract—The results of syntheses and Xꢀray diffraction analyses of mononuclear complexes [ML (H O)4]
2
2
2
+
2+
2+
(
M = Co (
I
), Cu (II), and Zn (III
)
) containing water molecules and anions of acetic acid
2 /n, Z = 2) and are built of discrete neutral complex molecules. The crystallographic data are as follows:
1
α
ꢀ(Nꢀbenzoxꢀ
azolinꢀ2ꢀone) (L = C H O4) are presented. The crystals of complexes I–III are isostructural (space group
9
6
P
3
for complex
plex II = 5.9661(6)
plex III = 6.1404(3)
metal atoms (M) of the complexing agents are localized in the crystallographic symmetry centers and have
a distorted octahedral environment due to two oxygen atoms of the carboxy groups of two monodentate
ligands (L) and four water molecules. The M–O(1 )(H O) and M–O(2 )(H O) bond lengths for the indiꢀ
cated complexes are 2.088(3) and 2.118(3), 2.446(3) and 1.971(3), and 2.113(4) and 2.093(3) Å for M =
I
,
a
= 6.1470(5),
= 5.1414(4)
= 5.3476(2)
b
= 5.3310(3),
= 32.672(2)
= 30.5865(12)
c
= 30.5894(17)
Å,
β
= 95.056(6)
= 92.395(6) = 1001.33(14) Å ; and for comꢀ
= 94.708(4)°,
°, V = 998.50(11) Å ; for comꢀ
3
,
a
Å,
b
Å
,
c
Å,
β
°, V
3
,
a
Å,
b
Å,
c
Å,
β
V = 1000.96(7) Å . The
w
w
2
2
2+
2+
2+
Co , Cu , and Zn , respectively. The crystal structures are formed due to packing of chains built of interꢀ
…
molecular hydrogen bonds O–H O
.
DOI: 10.1134/S1070328414040010
INTRODUCTION
COOH
N
The study of transition metal complexes with molꢀ
ecules of biologically active compounds is one of
urgent trends in the modern bioinorganic chemistry.
These complexes often have useful biological properꢀ
ties (which are weaker or absent at all in the starting
components) and serve as a basis for new drugs.
O
O
(
HL)
EXPERIMENTAL
It is known that a huge part of biologically active
substances used in diverse areas of national economy
consists of heterocyclic compounds.
Synthesis of ligand HL. A solution of NaOH (0.6 g)
in water (10 mL) was added to benzoxazolinꢀ2ꢀone
(
2 g, 15 mmol), and the mixture was stirred to comꢀ
plete dissolution. A mixture obtained from chloroaceꢀ
tic acid (1.4 g) and NaOH (1.2 g) in water (12 mL) was
added to the obtained solution. After the solutions
were mixed together, the reaction mixture was heated
for 2.5 h and neutralized with hydrochloric acid. Aceꢀ
Increased interest in benzoxazolinꢀ2ꢀone derivaꢀ
tives is caused by their high biological activity and a
wide spectrum of action. Benzoxazolinone and its
methoxy derivatives are natural factors of resistance of
some cereals to diseases and vermin. Benzoxazolinone
and its derivatives possess a growthꢀregulating activity
for plants, which is likely based on the ability of these
compounds to prevent auxin binding with membrane
receptors [1]. In addition, they can be used as febriꢀ
fuges [2].
tic acid
in a yield of 2.44 g (80%).
Synthesis of [Co(L) (H O) ] (I)
α
ꢀ(Nꢀbenzoxazolinꢀ2ꢀone) (HL) was isolated
.
A hot solution of
ꢀbenzoxazolinꢀ2ꢀone) sodium salt
0.46 mmol, 0.1 g) in a water–ethanol (1 : 1 vol/vol)
mixture (4 mL) was added to a solution of CoCl2
0.23 mmol, 0.029 g) in the same mixture (3 mL). The
reaction mixture was stored in an ultrasonic bath
30 kHz) for 10 min. The solution was placed in a nonꢀ
2
2
4
acetic acid
α
ꢀ(N
(
Investigation of the complex formation of new benꢀ
zoxazolinꢀ2ꢀone derivatives with transition metals is
of scientific and practical interest.
(
(
In this work, we synthesized complexes of acetic tightly closed weighing bottle. After 2 days, pink plateꢀ
acid ꢀ( ꢀbenzoxazolinꢀ2ꢀone) (HL) with cations like crystals precipitated. They were filtered off and
), Cu (II), Zn (III
tures by Xꢀray diffraction analysis.
α
N
2
+
2+
2+
Co (
I
)
and studied their strucꢀ recrystallized from ethanol. The yield of
(83%).
I was 0.12 g
246

COMPLEXES OF ACETIC ACID
α
ꢀ(N
ꢀBENZOXAZOLINꢀ2ꢀONE) WITH Zn(II)
247
Table 1. Main crystallographic data and refinement results for structures
I
–
III
Value
II
Monoclinic
2 /
Parameter
I
III
Crystal system
Space group
Monoclinic
2 /
Monoclinic
P
n
P
n
P2 /n
1
1
1
a
, Å
, Å
6.1470(5)
5.3310(3)
30.5894(17)
95.056(6)
998.50(11)
2
5.9661(6)
5.1414(4)
32.672(2)
92.395(6)
1001.31(14)
2
6.1404(3),
5.3476(2)
30.5865(12)
94.708(4)
1000.96(7)
2
b
c
, Å
β
, deg
, Å3
V
Z
ρ
μ
, g/cm3
1.714
1.724
1.731
calcd
, mm–1
7.416
2.216
2.381
Crystal sizes, mm
Scan range, deg
Range
0.51
×
0.34
×
0.18
0.52
×
0.38
×
0.2
0.5
×
0.35
×
0.2
θ
5.8–75.7
5.4–66.9
5.8–66.9
h
,
k
,
l
–6
≤
h
k
≤
≤
≤
7,
–7
–6
≤
h
k
≤
≤
≤
7,
6,
–7
–6
–36
≤
h
k
≤
≤
≤
7,
–
6
≤
5,
≤
≤
6,
–
38
≤
l
37
–38
≤
l
38
≤
l
36
Collected reflections
Independent reflections
Rint
6816
2046
0.056
1577
1.06
10216
1776
0.06
3172
1772
0.017
1567
1.05
Reflections with
Goodnessꢀofꢀfit (F 2
R1 wR2 > 2 ))
Δρmax, Δρmin,
/Å3
I
> 2
σ
(
I
)
1437
1.12
)
,
(
I
σ
(I
0.0525, 0.1370
–0.35, 0.35
0.0462, 0.1469
–0.71, 0.39
0.0353, 0.0989
–0.31, 0.64
e
Synthesis of [Cu(L) (H O) ] (II)
.
A hot solution of squares using the SHELXLꢀ97 program [6]. All nonꢀ
ꢀbenzoxazolinꢀ2ꢀone) sodium salt hydrogen atoms were refined anisotropically. Hydroꢀ
0.46 mmol, 0.1 g) in a water–ethanol (1 : 1 vol/vol) gen atoms were localized from the difference synthesis
mixture (4 mL) was added to a solution of and refined isotropically. The molecular drawing was
CuSO4 5H O (0.23 mmol, 0.057 g) in the same mixꢀ plotted using the XP program in the SHELXTLꢀPlus
2
2
4
acetic acid
(
α
ꢀ(N
⋅
2
ture (4 mL). The reaction mixture was stored in an program package [7]. The crystallographic data and
ultrasonic bath (30 kHz) for 15 min. The solution was the results of determination of structures I–III are
placed in a nontightly closed weighing bottle. Blue given in Table 1.
plateꢀlike crystals that precipitated in 2 days were filꢀ
tered off and recrystallized from ethanol. The yield of compounds
II was 0.127 g (81%).
The coordinates of atoms and other parameters for
and II were deposited with the Camꢀ
bridge Crystallographic Data Centre (CCDC nos.
47612 and 947614, respectively; deposit@
I
9
The synthesis of complex [Zn(L) (H O) ] (III) and
2
2
4
ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk).
its Xꢀray diffraction characteristics were described earꢀ
lier [3].
RESULTS AND DISCUSSION
Xꢀray diffraction analyses of I and II. Reflection
sets were obtained at 293 K on an Xcalibur R Oxford
The crystals of complexes I, II, and III are isosꢀ
K radiaꢀ tructural and built of discrete molecules
Diffraction automated diffractometer (Cu
α
tion,
λ
= 1.54184
Å
,
ω
scan mode, graphite monoꢀ
[M(L) (H O)4] (M = Co, Cu, and Zn). The coordinaꢀ
2 2
chromator). Experimental data were collected using tion polyhedra of the M atoms are extended tetragonal
the CrysAlisPro program [4]. An absorption correcꢀ bipyramids arranged in the crystallographic symmetry
tion was applied by the multiꢀscan method in the centers (Fig. 1). The oxygen atoms of four water molꢀ
CrysAlisPro program package. The structures were ecules are localized in the equatorial planes of the tetꢀ
solved by a direct method using the SHELXSꢀ97 proꢀ ragonal bipyramids, and the oxygen atoms of the carꢀ
gram package [5] and refined by fullꢀmatrix least boxy groups of two ligands L occupy the apical posiꢀ
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 40
No. 4
2014

248
ASHUROV et al.
C(4)
O(1w)
C(5)
C(6)
M
C(3)
C(2)
O(2w)
O(3)
C(9)
C(7)
O(4)
N(1) C(8)
C(1)
O(1)
O(2)
Fig. 1. Molecular structure and the numeration of atoms in complexes [ML (H O)4] (M = Co2+, Cu2+ and Zn2+).
,
2
2
tions. In complex
equatorial bond lengths are 2.088(3) and 2.118(3) Å, plexes
respectively, and the axial Co–O(4) bond lengths are 126.6(2)°, and 124.19(14)°, respectively). The diheꢀ
.078(3) Å. These distances correspond to those found dral angles between the planes of the carboxy groups
I
, the Co–O(1
w)
and Co–O(2
w)
2.35
°
–2.75°. The MO(4)C(9) bond angles in comꢀ
I,
II, and III are equal in fact (125.5(2)
°,
2
2
+
earlier in the Zn complexes with ligands L. At the and benzoxazole fragment in
same time, the Cu–O(1 ) equatorial bonds 64.09°) somewhat differ from a similar value in comꢀ
2.446(3) Å) in II are noticeably longer than the corꢀ plex II 65.24°).
responding bonds in complexes and III
I (63.55°) and III
w
(
(
(
I
.
The geometric parameters of hydrogen bonds are
In all three structures, the bond angles at the listed in Table 2 and shown in Fig. 2. The presence of
…
M atoms deviate from the ideal octahedral angles by hydrogen bonds О(2w)–H(2wB) O(1w) in II correꢀ
Table 2. Geometric parameters of hydrogen bonds in structures I, II, and III
Distance, Å
Bond
Angle
D–H⋅⋅⋅A, deg
Coordinates
of atom A
D–H⋅⋅⋅
A
D–H
H⋅⋅⋅A
D⋅⋅⋅A
I
O(1
O(1
O(2
O(2
w
w
w
w
)–H(1wA
)
⋅⋅⋅O(2)
0.85(3)
0.86(2)
0.85(3)
0.85(5)
0.97
2.02(4)
1.84(2)
1.98(4)
1.83(5)
2.57
2.792(4)
2.692(4)
2.792(4)
2.643(4)
3.407(5)
151(4)
177(7)
161(6)
160(4)
144
1 +
1 +
, –1 –
1 – , –
x
, 1 +
y
,
z
)–H(1wB
)
⋅⋅⋅O(3)
x
,
y
,
z
)–H(2wA
)
⋅⋅⋅O(4)
1 –
x
y
, –
z
)–H(2wB
)
⋅⋅⋅O(3)
x
y
, –
z
C(8)–H(8
A
)⋅⋅⋅O(3)
x
, –1 +
y, z
II
O(2
O(1
O(2
O(1
w
w
w
w
)–H(2wA
)
⋅⋅⋅O(3)
⋅⋅⋅O(2)
0.85(4)
0.85(4)
0.85(4)
0.86(4)
0.97
1.849(2)
2.08(4)
1.96(4)
1.94(3)
2.47
2.647(5)
2.868(5)
2.772(5)
2.760(5)
3.325(5)
3.484(6)
156.6(4)
154(5)
159(4)
161(5)
147
)–H(1wA
)
3 –
x
, –1 –
y
, 1 – z
)–H(2wB
)–H(1wB
)
⋅⋅⋅O(1w
)
x
, 1 +
, –
, –1 +
–1 +
y
,
z
)
⋅⋅⋅O(3)
3 –
x
y
, 1 –
z
C(8)–H(8
A
)⋅⋅⋅O(3)
x
y
,
,
z
z
C(8)–H(8
B
)⋅⋅⋅O(2)
0.97
2.55
163
x,
y
III
O(1
O(1
O(2
O(2
w
w
w
w
)–H(2wA
)
⋅⋅⋅O(3)
0.85(4)
0.71(4)
0.86(4)
0.86(4)
0.97
1.8542)
2.10(4)
1.96(4)
1.88(4)
2.59
2.702(3)
2.792(3)
2.775(2)
2.645(3)
3.419(3)
174(3)
163(4)
160(3)
146(4)
143
1 – x, –y, –z
)–H(1wB
)
⋅⋅⋅O(2)
1 –
2 –
x
, 1 –
, 1 –
y
, –
z
z
)–H(2wA
)–H(2wB
)⋅⋅⋅O(4)
x
y
, –
)
⋅⋅⋅O(3)
2 –
x, –y, –z
C(8)–H(8
B
)⋅⋅⋅O(3)
x
, 1 + y, z
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 40
No. 4
2014

COMPLEXES OF ACETIC ACID
a)
α
ꢀ(N
ꢀBENZOXAZOLINꢀ2ꢀONE) WITH Zn(II)
249
(
(b)
O(1w)
O(1w)
O(2w)
O(2w)
O(3)
O(3)
O(4)
O(4)
C(8)
C(8)
O(1)
O(1)
O(2)
O(2)
Fig. 2. Chain structures and hydrogen bonds in complexes (a)
Hydrogen atoms are omitted.
I
and III and (b) II. Hydrogen bonds are shown by dashed lines.
y
0
z
x
Fig. 3. Structure of the layer in complexes I, II, and III. Hydrogen atoms are omitted.
…
late with the elongation of the Cu O(1
w
)
equatorial cules into chains along the
x
direction (Fig. 3). The
and axes involving
the hydrogen atoms of the benzene ring form a threeꢀ
atom towards the square polyhedron compared to dimensional lattice of weak hydrogen bonds C(5)–
bond and, most likely, is the main reason for the disꢀ molecules arranged along the
x
y
tortion of the coordination polyhedron of the Cu2
+
…
. In all three structures, the intramolecular
structures and III
I
.
H(5)
π
…
hydrogen bond O(2wB)–H(2wB) O(3) is formed and
stabilizes the complex in solution.
Other hydrogen bonds in the studied crystal strucꢀ
…
tures are similar. The O(2
w
)–H(2wA) O(4) and
)–H(1wB) O(2) hydrogen bonds crossꢀlink the
…
O(1w
Thus, the Xꢀray diffraction analyses of the strucꢀ
molecules bound by the inversion centers into chains tures of the complexes of acetic acid
α
ꢀ(
)– linꢀ2ꢀone) with the Co , Cu , and Zn cations
H(1wA) O(3) hydrogen bonds crossꢀlink the moleꢀ showed that the synthesized complexes were isostrucꢀ
Nꢀbenzoxazoꢀ
2+
2+
2+
extended along the
y direction, and the O(1w
…
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 40
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2014

250
ASHUROV et al.
tural. The threeꢀdimensional lattice of hydrogen
bonds is formed in all three crystal structures. The
hydrogen bonds in complex II are somewhat different
2. Bonte, J.P., Lesieur, D., Lespagnol, Ch., et al., Eur. J.
Med. Chem., 1974, vol. 9, no. 5, p. 491.
3. Ashurov, J., Karimova, G., Mukhamedov, N., et al.,
compared to those in complexes
I
and III
.
Acta Crystallogr., Sect. E: Structure Reports Online
011, vol. 67, p. m432.
,
2
4.
CrysAlisPro. Version 1.171.33.40, UK: Oxford Diffracꢀ
tion, 2007.
ACKNOWLEDGMENTS
This work was supported by the Foundation for
Basic Research (project no. F7ꢀT048) of the Academy
of Sciences of Uzbekistan.
5. Sheldrick, G.M., Acta Crystallogr., Sect. A: Found.
Crystallogr., 1990, vol. 46, p. 467.
6. Sheldrick, G.M., SHELXLꢀ97. Program for the Solution
and Refinement of Crystal Structures, Göttingen (Gerꢀ
many): Univ. of Göttingen, 1997.
REFERENCES
7. Siemens, XP. Molecular Graphics Program. Version 5.03,
Madison (WI, USA): Siemens Analytical Xꢀray Instruꢀ
ments Inc., 1994.
1.
Pestitsidy. Khimiya, tekhnologiya i primenenie (Pestiꢀ
cides. Chemistry, Engineering, and Applications),
Mel’nikov, N.N., Ed., Moscow: Khimiya, 1987.
Translated by E. Yablonskaya
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 40
No. 4
2014