Journal of Structural Chemistry. Vol. 54, No. 4, pp. 824-828, 2013
Original Russian Text Copyright © 2013 by Yu. M. Chumakov, V. I. Tsapkov, P. A. Petrenko, S. A. Palomares- Sànchez, A. P. Gulea
CRYSTAL STRUCTURE OF [2-(2-HYDROXYBENZILYDENE)HYDRAZINECARBOXOAMIDATO(1-)][2-(2-HYDROXYBENZILYDENE)HYDRAZINECARBOXOAMIDATO(2-)]CHROMIUM MONOHYDRATE
© Yu. M. Chumakov,1 V. I. Tsapkov,2 P. A. Petrenko,1
S. A. Palomares- Sànchez,3 and A. P. Gulea2
The
crystal
structure
of
UDC 548.736:541.49:546.732:546.742
[2-(2-hydroxybenzilydene)hydrazinecarboxoamidato(1-)][2-(2-hydroxy-
benzilydene)hydrazinecarboxoamidato(2-)]chromium monohydrate [Cr(HL)(L)]⋅H2O (I), where H2L is
salicylaldehyde semicarbazone, is determined. In I the central chromium atom is octahedrally surrounded
by two ligand anions in the mer position and coordinated azomethine nitrogen atoms, phenol and carbamide
oxygen atoms. In both ligands phenol groups are deprotonated; in one of them the imine group is also
deprotonated. In the crystal, complexes of the compound studied are hydrogen bonded into layers along the
[100] direction, with π–π stacking being observed between the phenyl rings inside the layer along with the
X–Н⋯Cg (π ring) interaction.
DOI: 10.1134/S0022476613040276
Keywords: 3d metal complexes, single crystal X-ray diffraction analysis, salycylaldehyde semicarbazone.
Semicarbazide derivatives are known as ligands forming with metal ions coordination compounds different in
composition, structure, and properties [1-3]. They are widely applied in medicine [4], the complexing ability of
semicarbazide derivatives correlating with biological activity [5]. Therefore, it is of scientific and practical interest to find
optimal conditions for the preparation and analysis of the structure of new representatives of complexes containing the
ligands of a series of semicarbazides.
The aim of this work was the synthesis and determination of the structural features of [2-(2-hydroxybenzilydene)hydrazinecarboxoamidato(1-)][2-(2-hydroxybenzilydene)hydrazinecarboxoamidato(2-)]chromium monohydrate
[Cr(HL)(L)]⋅H2O (I), where H2L is salycylaldehyde semicarbazone.
Experimental. Synthesis of compound I: to a Cr(NO3)3⋅9H2O solution (10 mmol) in 20 ml of ethanol an H2L
solution (20 mmol) in 30 ml of ethanol was added under stirring and heating on a water bath (50-55°C). After slow
evaporation (for one day) of the dark green solution formed a fine crystalline precipitate of compound I was obtained. It was
1
Institute of Applied Physics, Academy of Sciences of Moldova, Chisinau. 2Moldova State University, Chisinau;
[email protected]. 3Autonomous University of San Luis Potosi, Mexico. Translated from Zhurnal Strukturnoi Khimii,
Vol. 54, No. 4, pp. 778-782, July-August, 2013. Original article submitted July 10, 2012.
824
0022-4766/13/5404-0824
TABLE 1. Crystallographic Characteristics, Experimental and Refinement Data for the Structure of I
Chemical formula
М
Crystal symmetry, space group, Z
a, b, c, Å; β, deg
V, Å3
dx, g/cm3
Radiation λ, Å
μ, mm–1
Т, K
Sample dimensions, mm
Diffractometer
Scanning type
θmax, deg
h, k, l limits
Number of reflections: meas./indep. (N1),
Rint/I > 2σ(I ) (N2)
Refinement method
Number of parameters
R1/wR2 (N1), R1/wR2 (N2)
S
Δρ(max), Δρ(min), e/Å3
Program
C16H17CrN6O5
425.34
Monoclinic, С2/c, 8
22.474(4), 14.478(3), 13.655(3); 114.27(3)
4050.4(14)
1.392
0.71069
0.603
293(2)
0.3×0.07×0.15
Bruker P4/Smart
θ/2θ
28.01
–29 ≤ h ≤ 27, 0 ≤ k ≤ 19, 0 ≤ l ≤ 18
4455/4304, 0.0719/1678
Least squares technique
259
0.0636/0.1008, 0.1934/0.1357
0.842
0.501, –0. 293
SHELX-97
filtered off, washed with a small amount of ethanol, ether and dried in air. Yield 78%. Found, %: C 45.01, H 3.87, Cr 11.95,
N 19.50; calculated (C16H17СrN6O5), %: C 45.18, H 4.03, Cr 12.22, N 19.76. Compound I is well soluble in
dimethylformamide and dimethyl sulfoxide and soluble in water and alcohols on heating. Single crystals suitable for the Xray diffraction (XRD)analysis were obtained by recrystallization from ethanol.
The single crystal XRD analysis of complex I was performed on a Bruker P4/Smart. The structure was solved by a
direct method and refined by the least squares technique in the anisotropic approximation for non-hydrogen atoms using the
SHELX-97 programs [6]. Atoms of solvate water molecules turned out to be disordered and were refined with a site
occupancy multiplicity of 0.17, 0.39, and 0.37. Hydrogen atoms were included in the refinement in geometrically calculated
positions and their thermal factors UH were taken to be 1.2 larger than those of carbon and nitrogen atoms bonded to them,
except the imine nitrogen atom in one of the ligands. Main parameters of the experiment, structure solution and refinement
are given in Table 1; some interatomic distances and bond angles are listed in Tables 2 and 3. Coordinates of basis atoms of
the structures studied have been deposited with the Cambridge Crystal Data Center (CCDC 881217). Geometric calculations
and figures were made using the PLATON program [7]. For the visualization of structure packings we left only hydrogen
atoms involved in hydrogen bonds. For the analysis of the structures obtained we used the Cambridge Crystal Data Center
(version 5.30) [8-10].
Results and discussion. The crystal structure of the compound studied contains complex I (Fig. 1) and a disordered
water molecule. The central Cr(3+) atom is in a distorted octahedral environment. Coordination sites are occupied by
azomethine nitrogen atoms, phenol and carbamide oxygen atoms of two HL− and L2− anionic ligands in the mer position. In
the HL− ligand the phenol group is deprotonated, and in L2− the imine group is also deprotonated: there is no hydrogen at the
N2A atom. Coordination Cr(1)–O(1) and Cr(1)–O(1А) bonds as well as some bond lengths in the ligands themselves (O(1)–
С(3) and O(1А)–С(3А), O(2)–(С8) and O(2А)–С(8А), N(1)–С(1) and N(1А)–С(1А), N(2)–С(8) and N(2А)–С(8А))
somewhat differ from each other, which is due to a different degree of deprotonation (Table 2). In the previously described
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TABLE 2. Selected Interatomic Distances and Bond Angles for Compound I
Bond
Cr(1)–O(1/1А)
Cr(1)–O(2/2А)
Cr(1)–N(1/1А)
O(1/1А)–C(3/3А)
O(2/2А)–C(8/8А)
N(1/1А)–C(1/1А)
N(1/1А)–N(2/2А)
N(2/1А)–C(8/8А)
N(3/3А)–C(8/8А)
C(1/1А)–C(2/2А)
C(2/2А)–C(3/3А)
d, Å
–
2–
HL ligand
L ligand
1.923(4)
2.011(3)
2.016(4)
1.312(6)
1.317(5)
1.310(7)
1.403(6)
1.324(7)
1.303(7)
1.422(8)
1.413(6)
1.943(3)
2.010(4)
2.014(3)
1.346(5)
1.277(5)
1.288(6)
1.388(5)
1.358(6)
1.295(5)
1.453(6)
1.395(6)
ω, deg
HL ligand
L2– ligand
Angle
–
C(3/3А)–O(1/1А)–Cr(1)
C(8/8А)–O(2/2А)–Cr(1)
C(1/1А)–N(1/1А)–N(2/2А)
C(1/1А)–N(1/1А)–Cr(1)
N(2/2А)–N(1/1А)–Cr(1)
C(8/8А)–N(2/2А)–N(1/1А)
N(1/1А)–C(1/1А)–C(2/2А)
C(3/3А)–C(2/2А)–C(1/1А)
O(2/2А)–C(8/8А)–N(2/2А)
127.1(3)
114.2(3)
119.5(4)
126.5(3)
112.9(3)
115.0(4)
123.0(4)
123.2(5)
118.1(5)
128.6(3)
115.8(3)
119.1(4)
128.2(3)
112.4(2)
116.0(4)
123.3(4)
125.2(4)
118.1(5)
TABLE 3. Coordination Angles for the Cr(3+) Atom
Angle
ω, deg
Angle
ω, deg
Angle
ω, deg
O(1)–Cr(1)–O(1A)
O(1)–Cr(1)–N(1A)
O(1A)–Cr(1)–N(1A)
O(1)–Cr(1)–O(2)
O(1A)–Cr(1)–O(2)
90.44(15)
95.16(15)
89.95(13)
166.25(13)
87.61(15)
N(1A)–Cr(1)–O(2)
O(1)–Cr(1)–O(2A)
O(1A)–Cr(1)–O(2A)
N(1A)–Cr(1)–O(2A)
O(2)–Cr(1)–O(2A)
98.44(15)
94.21(14)
167.86(13)
78.47(13)
90.46(13)
O(1)–Cr(1)–N(1)
O(1A)–Cr(1)–N(1)
N(1A)–Cr(1)–N(1)
O(2)–Cr(1)–N(1)
O(2A)–Cr(1)–N(1)
88.70(15)
101.21(14)
168.18(14)
78.35(15)
90.13(13)
Fig. 1. Molecular structure and atom numbering of complex I
(50 % probability thermal ellipsoids).
[Cr(HL)2]Cl⋅H2O complex [11], where in HL− only the phenol group is deprotonated, the coordination bonds of the metal
atom with the corresponding ligand atoms and the distances between the similar atoms in the ligands are consistent with each
other within 3σ. An exception is only Cr(1)–O(1/1А) (1.947(2)/1.905(2) Å) and Cr(1)–O(2/А) (2.003(2)/2.023(2) Å) bonds.
In complex I HL− and L2− conformations are somewhat different: the angle between the А(Cr(1)O(1)N(1)C(1)C(2)C(3)) and
В(Cr(1)O(2)N(1)N(2)C(8)) rings in HL− is 12.5°, while the angles between the phenol ring and А and В rings is 7.0° and
826
Fig. 2. Formation of layers along the [100] direction (a), packing
fragment in compound I (b).
TABLE 4. Geometric Parameters of Hydrogen Bonds for Compound I
D–H⋯A bond
N3A–H3A...O1
N2–H2…O1А
С1–H1…O2А
С7–H7…O2А
D–H
Distance, Å
H⋯A
D⋯A
0.86
0.86
0.93
0.93
2.24
2.24(7)
2.58
2.55
3.039(6)
2.803(5)
3.396(6)
3.386(8)
DHA angle, deg
Coordinates of
the A atom
154
139(7)
146
148
x, –y, 1/2+z
–x, y, 1/2–z
–x, –y, 1–z
–x, –y, 1–z
19.3°. In L2− the corresponding values are 4.9°, 7.5°, and 11.5°. The angle between the planes defined by donor ligand atoms
is 89.07°. The volume of the coordination octahedron of the chromium atom is 10.238 Å3. In the crystal the molecules of
complex I are hydrogen bonded into layers by N–H…O and С–H…O bonds along the [100] direction (Table 4, Fig. 2).
according to the criterion proposed in [7] (CgI⋯CgJ < 6.0 Å, β < 60.0°, where β is the angle between the CgICgJ vector and
the normal to the Cg1 aromatic ring). In the crystal the π–π stacking interaction is observed between the phenol rings inside
the layer. The CgI⋯Cg1(–x, y, 1/2–z) distance between the centroids of these fragments is 3.664 Å, and β takes a value of
20.9°. Along with the mentioned π–π stacking interaction, in complex I inside the layers there is also the X–Н⋯Cg
interaction (π ring) (Н⋯Cg < 3.0 Å, γ < 30.0°, where γ is the angle between the НCg vector and the normal to the aromatic
ring). Thus, for the С4A–Н4A⋯Cg interaction (C(2)C(3)C(4)C(5)C(6)C(7)) the (x, –y, –1/2+z) distance between the Н4A
hydrogen atom and the phenol ring centroid is 2.99 Å, and the γ value is 17.4°.
Thus, the study performed shows that the reaction of chromium nitrate with salycylaldehyde semicarbazone in hot
ethanol is not finished by the formation of nitrate of the respective complex cation, but continues to the secondary
deprotonation of one of the ligands and is completed by the formation of [2-(2-hydroxybenzilydene)-hydrazinecarboxoamidato(1−)][2-(2-hydroxybenzilydene)hydrazinecarboxoamidato(2-)]chromium monohydrate [Cr(HL)(L)]⋅H2O.
827
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