Chlorido(pyridine-2-carbaldehyde oximato-κ2N,N′)(pyridine-2-carbaldehyde oxime-κ2N,N′)copper(II)

Wu, G.; Wu, D.

doi:10.1107/S1600536808014748

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page m828

doi:10.1107/S1600536808014748

Open

access

Chlorido(pyridine-2-carbaldehyde oximato-κ²N,N′)(pyridine-2-carbaldehyde oxime-κ²N,N′)copper(II)

Genhua Wu ^a and Dayu Wu ^a ^*

^aSchool of Chemistry and Chemical Engineering, Anqing Teachers College, Anqing 246011, People's Republic of China
^*Correspondence e-mail: wudayu_nju@yahoo.com.cn

(Received 10 April 2008; accepted 15 May 2008; online 21 May 2008)

In the title compound, [Cu(C₆H₅N₂O)Cl(C₆H₆N₂O)], the Cu atom is coordinated by one neutral and one deprotonated pyridine-2-carboxaldehyde oxime (pco) ligand, resulting in the formation of two five-membered CuN₂C₂ rings. Together with the additional coordinating chloride anion, the coordination polyhedron of copper is best described as a distorted square-pyramid, the distortion parameter being 0.288. The two organic ligands are linked by an intramolecular O—H⋯O hydrogen bond.

Related literature

For related literature, see: Addison et al. (1984 ); Afrati et al. (2005 ); Korpi et al. (2005 ); Pearse et al. (1989 ); Stamatatos et al. (2006 ).

Experimental

Crystal data

[Cu(C₆H₅N₂O)Cl(C₆H₆N₂O)]
M_r = 342.24
Monoclinic, C 2/c
a = 16.686 (2) Å
b = 12.064 (2) Å
c = 13.805 (1) Å
β = 109.02 (1)°
V = 2627.3 (5) Å³
Z = 8
Mo Kα radiation
μ = 1.87 mm⁻¹
T = 293 (2) K
0.22 × 0.18 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SHELXTL; Sheldrick, 2008 ) T_min = 0.488, T_max = 0.594 (expected range = 0.620–0.755)
6487 measured reflections
2318 independent reflections
1788 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.110
S = 1.01
2318 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯O2	0.82	1.70	2.488 (5)	162

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808014748/im2064sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808014748/im2064Isup2.hkl

checkCIF report

Comment top

Pyridine-2-carbaldehyde oxime ligands usually bind to metals in a bidentate fashion, either chelating one metal center or bridging two metals. Their complexes find application in diverse areas such as functional supramolecular design, magnetic materials and catalysis (Korpi et al., 2005; Pearse et al., 1989; Afrati et al., 2005; Stamatatos et al., 2006). The title compound is a new copper complex from the reaction of CuCl₂ with pyridine-2-carbaldehyde oxime (pco). The compound consists of two N,N-chelating ligands and one chloride anion. The two pco ligands are coordinated to copper to form two five-membered CuC₂N₂ rings. The copper atom adopts a distorted 4 + 1 square-pyramidal coordination mode with the distortion parameter being 0.288 (Addison et al., 1984) and the angles around copper ion ranging from 79.07 (1)° for N3—Cu1—N4 to 168.37 (1)° for N2—Cu1—N3. From the viewpoint of charge balance, it is presumed there exists one deprotonated and one protonated oxime ligand with a strong intramolecular hydrogen bond between the OH group and the negatively charged oxygen of the other ligand (O1···O2 = 2.488 Å) which would also give an explanation for the rather unusal cis-arrangement of the ligands (Scheme 1, Figure 1. ).

Related literature top

For related literature, see: Addison et al. (1984); Afrati et al. (2005); Korpi et al. (2005); Pearse et al. (1989); Stamatatos et al. (2006).

Experimental top

A methanolic solution (15 ml) containing pco (0.1 mmol, 0.012 g) was added to an methanolic solution (10 ml) containing CuCl₂ × 2 H₂O (0.1 mmol, 0.017 g). After stirring for 2 h, the solution was filtered. Dark green needle-like crystals suitable for single-crystal X-ray diffraction were obtained by evaporating the resulting filtrate in air for several days (yield 65.6% based on the ligand).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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

Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids were drawn at the 50% probability level.

Chlorido(pyridine-2-carbaldehyde oximato-κ²N,N')(pyridine-2- carbaldehyde oxime-κ²N,N')copper(II) top

Crystal data top

[Cu(C₆H₅N₂O)Cl(C₆H₆N₂O)]	F(000) = 1384
M_r = 342.24	D_x = 1.730 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2343 reflections
a = 16.686 (2) Å	θ = 2.4–26.6°
b = 12.064 (2) Å	µ = 1.87 mm⁻¹
c = 13.805 (1) Å	T = 293 K
β = 109.02 (1)°	Block, dark green
V = 2627.3 (5) Å³	0.22 × 0.18 × 0.15 mm
Z = 8

Data collection top

Bruker SMART CCD area-detector diffractometer	2318 independent reflections
Radiation source: fine-focus sealed tube	1788 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SHELXTL; Sheldrick, 2008)	h = −14→19
T_min = 0.488, T_max = 0.594	k = −14→13
6487 measured reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.065P)² + 1.2P] where P = (F_o² + 2F_c²)/3
2318 reflections	(Δ/σ)_max = 0.001
181 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

[Cu(C₆H₅N₂O)Cl(C₆H₆N₂O)]	V = 2627.3 (5) Å³
M_r = 342.24	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 16.686 (2) Å	µ = 1.87 mm⁻¹
b = 12.064 (2) Å	T = 293 K
c = 13.805 (1) Å	0.22 × 0.18 × 0.15 mm
β = 109.02 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2318 independent reflections
Absorption correction: multi-scan (SHELXTL; Sheldrick, 2008)	1788 reflections with I > 2σ(I)
T_min = 0.488, T_max = 0.594	R_int = 0.034
6487 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.01	Δρ_max = 0.40 e Å⁻³
2318 reflections	Δρ_min = −0.39 e Å⁻³
181 parameters

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

	x	y	z	U_iso*/U_eq
Cu1	0.45583 (2)	0.75857 (3)	0.08754 (3)	0.03490 (18)
Cl1	0.39133 (6)	0.74459 (6)	−0.09737 (7)	0.0452 (3)
N2	0.39301 (17)	0.8985 (2)	0.1014 (2)	0.0365 (6)
N3	0.53622 (18)	0.6345 (2)	0.0978 (2)	0.0432 (7)
N4	0.39418 (17)	0.6311 (2)	0.1352 (2)	0.0386 (7)
O2	0.60997 (16)	0.6484 (2)	0.0801 (2)	0.0594 (7)
C1	0.3107 (2)	0.9115 (3)	0.0892 (3)	0.0445 (9)
H1A	0.2761	0.8491	0.0764	0.053*
N1	0.54953 (17)	0.8713 (2)	0.1156 (2)	0.0431 (7)
C11	0.4316 (2)	0.5328 (3)	0.1314 (3)	0.0427 (9)
C5	0.4419 (2)	0.9892 (3)	0.1166 (3)	0.0433 (8)
O1	0.63020 (15)	0.8491 (3)	0.1224 (2)	0.0666 (8)
H1B	0.6346	0.7834	0.1100	0.100*
C2	0.2750 (3)	1.0126 (4)	0.0946 (3)	0.0585 (11)
H2A	0.2177	1.0187	0.0866	0.070*
C9	0.3236 (3)	0.4362 (4)	0.1762 (3)	0.0647 (12)
H9A	0.3002	0.3707	0.1903	0.078*
C7	0.3232 (2)	0.6295 (3)	0.1599 (3)	0.0457 (9)
H7A	0.2973	0.6968	0.1638	0.055*
C12	0.5115 (2)	0.5390 (3)	0.1109 (3)	0.0463 (9)
H12A	0.5426	0.4760	0.1076	0.056*
C6	0.5299 (2)	0.9703 (3)	0.1257 (3)	0.0483 (9)
H6A	0.5692	1.0276	0.1381	0.058*
C10	0.3975 (3)	0.4349 (3)	0.1509 (3)	0.0579 (11)
H10A	0.4239	0.3680	0.1471	0.069*
C8	0.2865 (3)	0.5352 (4)	0.1798 (3)	0.0593 (11)
H8A	0.2365	0.5388	0.1957	0.071*
C4	0.4094 (3)	1.0927 (3)	0.1215 (3)	0.0636 (12)
H4A	0.4440	1.1550	0.1313	0.076*
C3	0.3253 (3)	1.1034 (3)	0.1118 (4)	0.0718 (13)
H3A	0.3029	1.1729	0.1171	0.086*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0277 (3)	0.0340 (3)	0.0441 (3)	0.00547 (15)	0.0132 (2)	−0.00158 (17)
Cl1	0.0482 (6)	0.0432 (5)	0.0407 (5)	0.0035 (4)	0.0094 (4)	−0.0023 (4)
N2	0.0355 (16)	0.0317 (15)	0.0418 (16)	0.0041 (12)	0.0118 (13)	−0.0026 (12)
N3	0.0398 (17)	0.0480 (19)	0.0432 (17)	0.0156 (14)	0.0152 (14)	0.0003 (14)
N4	0.0385 (16)	0.0366 (16)	0.0392 (16)	0.0031 (12)	0.0107 (13)	0.0023 (12)
O2	0.0440 (16)	0.0712 (19)	0.0731 (19)	0.0207 (14)	0.0327 (14)	0.0047 (15)
C1	0.040 (2)	0.044 (2)	0.049 (2)	0.0096 (16)	0.0142 (17)	0.0009 (16)
N1	0.0286 (16)	0.0516 (19)	0.0505 (18)	−0.0040 (13)	0.0147 (14)	−0.0005 (14)
C11	0.052 (2)	0.0372 (19)	0.032 (2)	0.0057 (16)	0.0044 (17)	−0.0001 (15)
C5	0.052 (2)	0.038 (2)	0.040 (2)	0.0022 (16)	0.0157 (18)	−0.0024 (16)
O1	0.0326 (15)	0.077 (2)	0.092 (2)	−0.0025 (13)	0.0241 (15)	−0.0042 (17)
C2	0.051 (2)	0.066 (3)	0.059 (3)	0.029 (2)	0.019 (2)	0.002 (2)
C9	0.069 (3)	0.058 (3)	0.058 (3)	−0.024 (2)	0.009 (2)	0.009 (2)
C7	0.041 (2)	0.051 (2)	0.047 (2)	−0.0006 (17)	0.0166 (17)	0.0022 (17)
C12	0.052 (2)	0.044 (2)	0.040 (2)	0.0195 (18)	0.0113 (18)	−0.0006 (17)
C6	0.045 (2)	0.045 (2)	0.056 (2)	−0.0115 (17)	0.0177 (18)	−0.0050 (18)
C10	0.071 (3)	0.036 (2)	0.053 (2)	−0.0020 (19)	0.002 (2)	0.0001 (18)
C8	0.052 (3)	0.067 (3)	0.057 (3)	−0.014 (2)	0.016 (2)	0.006 (2)
C4	0.080 (3)	0.031 (2)	0.079 (3)	0.0027 (19)	0.025 (3)	−0.0044 (19)
C3	0.088 (4)	0.044 (3)	0.084 (3)	0.033 (2)	0.029 (3)	−0.004 (2)

Geometric parameters (Å, º) top

Cu1—N3	1.984 (3)	C5—C4	1.371 (5)
Cu1—N1	2.012 (3)	C5—C6	1.451 (5)
Cu1—N2	2.029 (3)	O1—H1B	0.8200
Cu1—N4	2.072 (3)	C2—C3	1.352 (6)
Cu1—Cl1	2.4316 (10)	C2—H2A	0.9300
N2—C1	1.338 (4)	C9—C8	1.354 (6)
N2—C5	1.340 (4)	C9—C10	1.385 (6)
N3—C12	1.256 (5)	C9—H9A	0.9300
N3—O2	1.341 (3)	C7—C8	1.361 (5)
N4—C7	1.335 (4)	C7—H7A	0.9300
N4—C11	1.350 (4)	C12—H12A	0.9300
C1—C2	1.370 (5)	C6—H6A	0.9300
C1—H1A	0.9300	C10—H10A	0.9300
N1—C6	1.258 (4)	C8—H8A	0.9300
N1—O1	1.345 (3)	C4—C3	1.371 (6)
C11—C10	1.375 (5)	C4—H4A	0.9300
C11—C12	1.453 (5)	C3—H3A	0.9300

N3—Cu1—N1	91.79 (14)	C4—C5—C6	123.0 (4)
N3—Cu1—N2	168.29 (12)	N1—O1—H1B	109.5
N1—Cu1—N2	79.19 (11)	C3—C2—C1	118.4 (4)
N3—Cu1—N4	79.15 (12)	C3—C2—H2A	120.8
N1—Cu1—N4	151.07 (12)	C1—C2—H2A	120.8
N2—Cu1—N4	105.21 (11)	C8—C9—C10	118.3 (4)
N3—Cu1—Cl1	94.60 (9)	C8—C9—H9A	120.9
N1—Cu1—Cl1	107.40 (9)	C10—C9—H9A	120.9
N2—Cu1—Cl1	95.22 (8)	N4—C7—C8	124.0 (4)
N4—Cu1—Cl1	100.71 (8)	N4—C7—H7A	118.0
C1—N2—C5	118.1 (3)	C8—C7—H7A	118.0
C1—N2—Cu1	128.8 (2)	N3—C12—C11	116.1 (3)
C5—N2—Cu1	112.8 (2)	N3—C12—H12A	121.9
C12—N3—O2	120.3 (3)	C11—C12—H12A	121.9
C12—N3—Cu1	117.1 (2)	N1—C6—C5	115.7 (3)
O2—N3—Cu1	122.1 (2)	N1—C6—H6A	122.2
C7—N4—C11	117.2 (3)	C5—C6—H6A	122.2
C7—N4—Cu1	131.7 (2)	C11—C10—C9	119.9 (4)
C11—N4—Cu1	110.9 (2)	C11—C10—H10A	120.0
N2—C1—C2	122.9 (4)	C9—C10—H10A	120.0
N2—C1—H1A	118.5	C9—C8—C7	119.2 (4)
C2—C1—H1A	118.5	C9—C8—H8A	120.4
C6—N1—O1	118.2 (3)	C7—C8—H8A	120.4
C6—N1—Cu1	116.6 (2)	C5—C4—C3	119.3 (4)
O1—N1—Cu1	125.2 (2)	C5—C4—H4A	120.4
N4—C11—C10	121.4 (4)	C3—C4—H4A	120.4
N4—C11—C12	115.3 (3)	C2—C3—C4	119.8 (4)
C10—C11—C12	123.2 (3)	C2—C3—H3A	120.1
N2—C5—C4	121.4 (4)	C4—C3—H3A	120.1
N2—C5—C6	115.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O2	0.82	1.70	2.488 (5)	162

Experimental details

Crystal data
Chemical formula	[Cu(C₆H₅N₂O)Cl(C₆H₆N₂O)]
M_r	342.24
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	16.686 (2), 12.064 (2), 13.805 (1)
β (°)	109.02 (1)
V (Å³)	2627.3 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.87
Crystal size (mm)	0.22 × 0.18 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SHELXTL; Sheldrick, 2008)
T_min, T_max	0.488, 0.594
No. of measured, independent and observed [I > 2σ(I)] reflections	6487, 2318, 1788
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.110, 1.01
No. of reflections	2318
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.39

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O2	0.82	1.70	2.488 (5)	161.5

Acknowledgements

DW thanks Anqing Teachers College for financial support.

References

Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356. CSD CrossRef Web of Science Google Scholar
Afrati, T., Dendrinou-Samara, C., Zaleski, C. M., Kampf, J. W., Pecoraro, V. L. & Kessissoglou, D. P. (2005). Inorg. Chem. Commun. 8, 1173–1176. Web of Science CSD CrossRef CAS Google Scholar
Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Korpi, H., Polamo, M., Leskela, M. & Repo, T. (2005). Inorg. Chem. Commun. 8, 1181–1184. Web of Science CSD CrossRef CAS Google Scholar
Pearse, G. A., Raithby, P. R. & Lewis, J. (1989). Polyhedron, 8, 301–304. CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stamatatos, T. C., Vlahopoulou, J. C., Sanakis, Y., Raptopoulou, C. P., Psycharis, V., Boudalis, A. K. & Perlepes, S. P. (2006). Inorg. Chem. Commun. 9, 814–818. Web of Science CSD CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.