supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

Acta Cryst. (2009). E65, m738    [ doi:10.1107/S1600536809020546 ]

[5-Chloro-2-hydroxy-N'-(2-oxidobenzylidene)benzohydrazidato]pyridinecopper(II)

P. Li, D. Li and X. Shi

Abstract top

In the title complex, [Cu(C14H9ClN2O3)(C5H5N)], the CuII ion exhibits a distorted trans-CuN2O2 square-planar geometry arising from the O,O,N-tridentate ligand and a pyridine molecule. An intramolecular O-H...N hydrogen bond occurs. In the crystal structure, weak intermolecular C-H...[pi] interactions generate a chain. The crystal studied was an inversion twin.

Comment top

The chemistry of aroylhydrazones has gained a special attraction due to their coordination abilities to metal ions (Bai et al.,2005). However, researches on the complexes with salicylaldehyde-5-chlorosalicylichydrazone have not reported. So we have synthesized a new complex(Fig.1), which has been characterized by X-ray diffraction and elemental analysis. The structure of the title complex, (I), contains one ligand molecule, one pyridine molecule and one copper(II). The copper(II) coordination environment in the complex exhibits a distorted quadrilateral geometry (Table 1). In the crystal packing, the complex molecules are linked into one-dimensional chain by intermolecular C—H···π interactions (Nishio, 2004) (Table 2, Fig. 2).

Related literature top

For background on the coordination chemistry of salicylaldehyde-type ligands, see: Bai et al. (2005). For information on C—H···π interactions, see: Nishio (2004).

Experimental top

A solution of salicylaldehyde (1.46 g, 12 mmol) in ethanol (10 ml) was added to a solution of 5-chlorosalicylichydrazine (1.87 g, 10 mmol) in ehanol (10 ml). The mixture was refluxed for 3 h, and then the precipitate was collected, washed several times with ethanol and dried in vacuo (yield 75.6%). m.p. > 300 K. A solution of Cu(OAc)2 (0.04 g, 0.2 mmol)in methanol (10 ml) was added to the mixture of salicylaldehyde -5-chlorosalicylichydrazone (0.058 g, 0.2 mmol)and sodium methylate (0.0324 g, 0.6 mmol) in pyridine (10 ml). A green solution was obtained after stirring for 4 h. After being filtrated, dimethyl ether was slowly diffused into the filtrate, then green blocks of (I) were obtained after several weeks (m.p. >400 K) Elemental analysis calculated for C19H14Cl1N3O3Cu1: C, 52.90; H, 3.27; N, 9.74. Found (%): C, 52.95; H, 3.19; N, 9.69

Refinement top

The H atoms were positioned with idealized geometry (C—H = 0.93Å, O—H = 0.82Å) and were refined as riding with Uiso(H) = 1.2Ueq(carrier).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 40% probability displacement ellipsoids. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. View of the chains in (I). Intermolecular C—H···π are shown as dashed lines. Most of H atoms are omitted.
[5-Chloro-2-hydroxy-N'-(2- oxidobenzylidene)benzohydrazidato]pyridinecopper(II) top
Crystal data top
[Cu(C14H9ClN2O3)(C5H5N)]F(000) = 876
Mr = 431.32Dx = 1.638 Mg m−3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
a = 23.586 (2) ÅCell parameters from 1781 reflections
b = 4.8268 (6) Åθ = 2.7–23.7°
c = 17.88540 (18) ŵ = 1.43 mm−1
β = 120.809 (2)°T = 298 K
V = 1748.8 (3) Å3Block, green
Z = 40.39 × 0.28 × 0.17 mm
Data collection top
Siemens SMART CCD
diffractometer		2273 independent reflections
Radiation source: fine-focus sealed tube1849 reflections with I > 2σ(I)
graphiteRint = 0.021
ω scansθmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Siemens, 1996)		h = −28→25
Tmin = 0.606, Tmax = 0.793k = −5→5
4087 measured reflectionsl = −17→21
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.116 w = 1/[σ2(Fo2) + (0.0729P)2 + 0.8658P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2273 reflectionsΔρmax = 0.37 e Å−3
244 parametersΔρmin = −0.19 e Å−3
2 restraintsAbsolute structure: Flack (1983), 725 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.50 (2)
Crystal data top
[Cu(C14H9ClN2O3)(C5H5N)]V = 1748.8 (3) Å3
Mr = 431.32Z = 4
Monoclinic, CcMo Kα radiation
a = 23.586 (2) ŵ = 1.43 mm−1
b = 4.8268 (6) ÅT = 298 K
c = 17.88540 (18) Å0.39 × 0.28 × 0.17 mm
β = 120.809 (2)°
Data collection top
Siemens SMART CCD
diffractometer		2273 independent reflections
Absorption correction: multi-scan
(SADABS; Siemens, 1996)		1849 reflections with I > 2σ(I)
Tmin = 0.606, Tmax = 0.793Rint = 0.021
4087 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.116Δρmax = 0.37 e Å−3
S = 1.00Δρmin = −0.19 e Å−3
2273 reflectionsAbsolute structure: Flack (1983), 725 Friedel pairs
244 parametersFlack parameter: 0.50 (2)
2 restraints
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.18179 (4)0.48947 (15)0.25227 (4)0.0455 (2)
Cl10.00840 (11)1.5179 (4)−0.07019 (13)0.0697 (5)
N10.0517 (3)0.6161 (12)0.2113 (3)0.0462 (13)
N20.1052 (3)0.4396 (12)0.2649 (4)0.0452 (14)
N30.2566 (3)0.5850 (12)0.2378 (4)0.0487 (13)
O10.1235 (2)0.7588 (9)0.1676 (3)0.0519 (11)
O2−0.0618 (2)0.8534 (11)0.1447 (4)0.0721 (14)
H2−0.03190.74700.17640.108*
O30.2275 (2)0.1945 (8)0.3304 (3)0.0509 (11)
C10.0675 (3)0.7694 (13)0.1643 (4)0.0468 (15)
C20.0182 (3)0.9709 (11)0.1036 (4)0.0438 (14)
C3−0.0435 (4)1.0041 (13)0.0969 (5)0.0545 (17)
C4−0.0874 (3)1.1994 (15)0.0388 (5)0.064 (2)
H4−0.12821.22360.03430.076*
C5−0.0718 (3)1.3556 (16)−0.0116 (5)0.0611 (19)
H5−0.10201.4840−0.05030.073*
C6−0.0118 (3)1.3239 (12)−0.0053 (4)0.0502 (15)
C70.0333 (3)1.1330 (13)0.0522 (4)0.0478 (15)
H70.07401.11340.05640.057*
C80.0986 (3)0.2719 (14)0.3155 (4)0.0494 (16)
H80.05900.27520.31500.059*
C90.1478 (3)0.0818 (12)0.3722 (4)0.0450 (15)
C100.2086 (3)0.0513 (12)0.3749 (4)0.0460 (15)
C110.2519 (3)−0.1564 (13)0.4325 (5)0.0539 (16)
H110.2920−0.18600.43570.065*
C120.2365 (3)−0.3133 (13)0.4832 (4)0.0576 (17)
H120.2661−0.44720.51970.069*
C130.1771 (4)−0.2753 (13)0.4808 (4)0.0579 (19)
H130.1671−0.37970.51620.069*
C140.1341 (4)−0.0825 (14)0.4255 (5)0.0540 (16)
H140.0940−0.05870.42300.065*
C150.2503 (4)0.7717 (17)0.1806 (5)0.069 (2)
H150.20910.85200.14520.083*
C160.3020 (4)0.8541 (18)0.1705 (6)0.076 (2)
H160.29580.99050.13020.092*
C170.3626 (3)0.7324 (16)0.2205 (5)0.0635 (18)
H170.39810.78030.21430.076*
C180.3687 (4)0.5405 (17)0.2790 (6)0.080 (3)
H180.40900.45350.31430.095*
C190.3141 (4)0.4733 (15)0.2863 (6)0.068 (2)
H190.31930.34310.32770.082*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0378 (3)0.0493 (4)0.0461 (4)0.0027 (3)0.0192 (3)−0.0002 (4)
Cl10.0771 (12)0.0676 (12)0.0674 (12)0.0189 (9)0.0392 (10)0.0148 (9)
N10.039 (3)0.044 (3)0.046 (3)0.012 (3)0.015 (3)0.000 (3)
N20.036 (3)0.052 (3)0.038 (3)0.000 (3)0.012 (3)−0.010 (3)
N30.045 (3)0.051 (3)0.053 (4)0.002 (3)0.027 (3)0.002 (3)
O10.041 (2)0.061 (3)0.053 (3)0.007 (2)0.024 (2)0.008 (2)
O20.060 (3)0.079 (3)0.090 (4)0.019 (3)0.048 (3)0.013 (3)
O30.045 (2)0.046 (2)0.060 (3)0.007 (2)0.026 (2)0.005 (2)
C10.041 (3)0.045 (3)0.044 (4)0.002 (3)0.013 (3)−0.010 (3)
C20.040 (3)0.044 (3)0.044 (3)0.004 (3)0.019 (3)−0.011 (3)
C30.047 (4)0.057 (4)0.061 (4)0.005 (3)0.028 (3)−0.004 (3)
C40.046 (3)0.068 (5)0.072 (5)0.013 (3)0.027 (4)−0.006 (4)
C50.049 (4)0.062 (4)0.057 (5)0.020 (4)0.016 (3)−0.003 (4)
C60.054 (4)0.045 (4)0.043 (4)0.006 (3)0.019 (3)−0.006 (3)
C70.041 (3)0.049 (4)0.049 (4)0.005 (3)0.019 (3)−0.012 (3)
C80.045 (3)0.054 (4)0.054 (4)−0.004 (3)0.030 (3)−0.009 (3)
C90.053 (3)0.035 (3)0.048 (4)−0.003 (3)0.026 (3)−0.010 (3)
C100.048 (3)0.038 (3)0.048 (4)−0.006 (3)0.021 (3)−0.010 (3)
C110.054 (4)0.040 (3)0.065 (4)−0.005 (3)0.028 (3)−0.006 (3)
C120.060 (4)0.043 (4)0.057 (4)0.003 (3)0.021 (3)−0.001 (3)
C130.069 (4)0.053 (4)0.050 (5)−0.013 (4)0.028 (4)−0.005 (3)
C140.060 (4)0.051 (4)0.053 (4)−0.003 (3)0.031 (3)−0.003 (3)
C150.050 (4)0.083 (5)0.067 (5)0.015 (4)0.024 (4)0.017 (4)
C160.078 (5)0.083 (5)0.084 (6)0.018 (5)0.053 (5)0.031 (5)
C170.052 (4)0.081 (5)0.062 (4)−0.001 (4)0.031 (3)0.000 (4)
C180.047 (4)0.095 (6)0.092 (6)0.009 (4)0.033 (4)0.033 (5)
C190.049 (4)0.074 (6)0.072 (6)0.002 (3)0.024 (4)0.023 (4)
Geometric parameters (Å, °) top
Cu1—O31.897 (4)C7—H70.9300
Cu1—O11.934 (4)C8—C91.419 (9)
Cu1—N21.945 (6)C8—H80.9300
Cu1—N31.965 (6)C9—C141.401 (10)
Cl1—C61.737 (7)C9—C101.416 (9)
N1—C11.310 (9)C10—C111.426 (10)
N1—N21.413 (8)C11—C121.364 (10)
N2—C81.282 (9)C11—H110.9300
N3—C191.296 (10)C12—C131.393 (10)
N3—C151.313 (9)C12—H120.9300
O1—C11.292 (7)C13—C141.359 (9)
O2—C31.351 (9)C13—H130.9300
O2—H20.8200C14—H140.9300
O3—C101.293 (8)C15—C161.380 (11)
C1—C21.478 (8)C15—H150.9300
C2—C71.386 (10)C16—C171.370 (10)
C2—C31.405 (10)C16—H160.9300
C3—C41.393 (10)C17—C181.349 (11)
C4—C51.362 (11)C17—H170.9300
C4—H40.9300C18—C191.396 (12)
C5—C61.370 (10)C18—H180.9300
C5—H50.9300C19—H190.9300
C6—C71.385 (9)
O3—Cu1—O1171.5 (2)N2—C8—C9124.1 (6)
O3—Cu1—N291.9 (2)N2—C8—H8117.9
O1—Cu1—N281.0 (2)C9—C8—H8117.9
O3—Cu1—N393.6 (2)C14—C9—C10120.1 (6)
O1—Cu1—N393.7 (2)C14—C9—C8117.5 (6)
N2—Cu1—N3173.5 (3)C10—C9—C8122.4 (6)
C1—N1—N2109.1 (5)O3—C10—C9125.8 (6)
C8—N2—N1118.0 (6)O3—C10—C11118.4 (6)
C8—N2—Cu1128.0 (5)C9—C10—C11115.8 (6)
N1—N2—Cu1114.0 (4)C12—C11—C10122.4 (7)
C19—N3—C15118.0 (7)C12—C11—H11118.8
C19—N3—Cu1121.1 (6)C10—C11—H11118.8
C15—N3—Cu1120.8 (5)C11—C12—C13120.8 (6)
C1—O1—Cu1111.3 (4)C11—C12—H12119.6
C3—O2—H2109.5C13—C12—H12119.6
C10—O3—Cu1127.5 (4)C14—C13—C12118.5 (6)
O1—C1—N1124.6 (5)C14—C13—H13120.7
O1—C1—C2117.5 (6)C12—C13—H13120.7
N1—C1—C2117.9 (5)C13—C14—C9122.4 (7)
C7—C2—C3119.1 (6)C13—C14—H14118.8
C7—C2—C1119.0 (6)C9—C14—H14118.8
C3—C2—C1121.9 (6)N3—C15—C16123.0 (7)
O2—C3—C4118.6 (7)N3—C15—H15118.5
O2—C3—C2122.5 (6)C16—C15—H15118.5
C4—C3—C2118.9 (7)C17—C16—C15119.1 (7)
C5—C4—C3121.2 (7)C17—C16—H16120.4
C5—C4—H4119.4C15—C16—H16120.4
C3—C4—H4119.4C18—C17—C16117.6 (7)
C4—C5—C6120.1 (6)C18—C17—H17121.2
C4—C5—H5120.0C16—C17—H17121.2
C6—C5—H5120.0C17—C18—C19119.6 (7)
C5—C6—C7120.3 (7)C17—C18—H18120.2
C5—C6—Cl1120.7 (5)C19—C18—H18120.2
C7—C6—Cl1119.0 (5)N3—C19—C18122.7 (8)
C6—C7—C2120.5 (6)N3—C19—H19118.7
C6—C7—H7119.8C18—C19—H19118.7
C2—C7—H7119.8
C1—N1—N2—C8−179.6 (6)O1—C1—C2—C3−178.1 (6)
C1—N1—N2—Cu11.2 (6)N1—C1—C2—C31.3 (9)
O3—Cu1—N2—C84.3 (6)C7—C2—C3—O2179.9 (6)
O1—Cu1—N2—C8179.6 (6)C7—C2—C3—C4−0.1 (9)
N3—Cu1—N2—C8−143 (2)C1—C2—C3—C4179.5 (6)
O3—Cu1—N2—N1−176.6 (4)O2—C3—C4—C5−179.4 (7)
O1—Cu1—N2—N1−1.2 (4)C4—C5—C6—Cl1179.1 (6)
N3—Cu1—N2—N136 (3)C5—C6—C7—C20.4 (9)
O3—Cu1—N3—C19−9.1 (7)Cl1—C6—C7—C2−178.7 (5)
O1—Cu1—N3—C19175.1 (7)C3—C2—C7—C6−0.4 (9)
N2—Cu1—N3—C19139 (2)C1—C2—C7—C6−180.0 (5)
O3—Cu1—N3—C15173.4 (6)N1—N2—C8—C9179.5 (5)
O1—Cu1—N3—C15−2.5 (6)N2—C8—C9—C14178.1 (6)
N2—Cu1—N3—C15−39 (3)Cu1—O3—C10—C91.9 (9)
O3—Cu1—O1—C134.5 (18)Cu1—O3—C10—C11−177.8 (4)
N2—Cu1—O1—C11.0 (4)C14—C9—C10—O3−178.4 (6)
N3—Cu1—O1—C1−175.1 (4)C8—C9—C10—O32.9 (9)
O1—Cu1—O3—C10−37.5 (19)C14—C9—C10—C111.3 (8)
N2—Cu1—O3—C10−4.5 (5)C8—C9—C10—C11−177.4 (6)
N3—Cu1—O3—C10172.0 (5)O3—C10—C11—C12178.6 (6)
Cu1—O1—C1—N1−0.6 (7)C9—C10—C11—C12−1.0 (9)
Cu1—O1—C1—C2178.7 (4)C8—C9—C14—C13178.5 (6)
N2—N1—C1—O1−0.4 (8)Cu1—N3—C15—C16177.2 (7)
N2—N1—C1—C2−179.7 (5)N3—C15—C16—C171.7 (14)
O1—C1—C2—C71.4 (8)Cu1—N3—C19—C18−178.7 (7)
N1—C1—C2—C7−179.2 (6)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2···N10.821.852.575 (9)147
C16—H16···Cg1i0.932.813.48 (3)130
Symmetry codes: (i) x, −y+1, z−1/2.
Table 1
Selected geometric parameters (Å) top
Cu1—O31.897 (4)Cu1—N21.945 (6)
Cu1—O11.934 (4)Cu1—N31.965 (6)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2···N10.821.852.575 (9)147
C16—H16···Cg1i0.932.813.48 (3)130
Symmetry codes: (i) x, −y+1, z−1/2.
Acknowledgements top

We acknowledge the National Natural Science Foundation of China (grant No. 20771053) and the Natural Science Foundation of Shandong Province (grant No. 2005ZX09) for financial support.

references
References top

Bai, Y., Dang, D. B., Duan, C. Y., Song, Y. & Meng, Q. J. (2005). Inorg. Chem. 44, 5972–5974.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Nishio, M. (2004). CrystEngComm, 6, 130–158.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Siemens (1996). SMART, SAINT and SADABS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.