PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): m738.
Published online 2009 June 6. doi:  10.1107/S1600536809020546
PMCID: PMC2969500

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

Abstract

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(...)π inter­actions generate a chain. The crystal studied was an inversion twin.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-65-0m738-scheme1.jpg

Experimental

Crystal data

  • [Cu(C14H9ClN2O3)(C5H5N)]
  • M r = 431.32
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m738-efi1.jpg
  • a = 23.586 (2) Å
  • b = 4.8268 (6) Å
  • c = 17.88540 (18) Å
  • β = 120.809 (2)°
  • V = 1748.8 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.43 mm−1
  • T = 298 K
  • 0.39 × 0.28 × 0.17 mm

Data collection

  • Siemens SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Siemens, 1996 [triangle]) T min = 0.606, T max = 0.793
  • 4087 measured reflections
  • 2273 independent reflections
  • 1849 reflections with I > 2σ(I)
  • R int = 0.021

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.116
  • S = 1.00
  • 2273 reflections
  • 244 parameters
  • 2 restraints
  • H-atom parameters constrained
  • Δρmax = 0.37 e Å−3
  • Δρmin = −0.19 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 725 Friedel pairs
  • Flack parameter: 0.50 (2)

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

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809020546/hb2989sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809020546/hb2989Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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.

supplementary crystallographic information

Comment

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).

Experimental

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

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).

Figures

Fig. 1.
The molecular structure of (I), showing 40% probability displacement ellipsoids. H atoms have been omitted for clarity.
Fig. 2.
View of the chains in (I). Intermolecular C—H···π are shown as dashed lines. Most of H atoms are omitted.

Crystal data

[Cu(C14H9ClN2O3)(C5H5N)]F(000) = 876
Mr = 431.32Dx = 1.638 Mg m3
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 mm1
β = 120.809 (2)°T = 298 K
V = 1748.8 (3) Å3Block, green
Z = 40.39 × 0.28 × 0.17 mm

Data collection

Siemens SMART CCD diffractometer2273 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

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) = 0.116w = 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 Å3
244 parametersΔρmin = −0.19 e Å3
2 restraintsAbsolute structure: Flack (1983), 725 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.50 (2)

Special details

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)

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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2989).

References

  • Bai, Y., Dang, D. B., Duan, C. Y., Song, Y. & Meng, Q. J. (2005). Inorg. Chem.44, 5972–5974. [PubMed]
  • 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. [PubMed]
  • Siemens (1996). SMART, SAINT and SADABS Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography