Chlorido[4-chloro-2-(pyridin-2-yl­methyl­imino­meth­yl)phenolato-κ3N,N′,O]copper(II)

Wang, H.; Lang, Y.; Wang, S.

doi:10.1107/S1600536812013359

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page m540

doi:10.1107/S1600536812013359

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Chlorido[4-chloro-2-(pyridin-2-ylmethyliminomethyl)phenolato-κ³N,N′,O]copper(II)

Haixia Wang,^a ^* Yuehe Lang ^a and Shaohong Wang ^a

^aDepartment of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007, People's Republic of China
^*Correspondence e-mail: xxhxwang@126.com

(Received 20 March 2012; accepted 27 March 2012; online 4 April 2012)

In the title complex, [Cu(C₁₃H₁₀ClN₂O)Cl], the Cu^II ion is coordinated by one O atom and two N atoms of the tridentate Schiff base ligand and one chloride ion, forming a slightly distorted square-planar geometry. Weak Cu⋯Cl interactions [2.793 (5) Å] result in the formation of a chain along the a axis.

Related literature

For background to the use of unsymmetrical tridentate Schiff base ligands and their hydrogenated derivatives in coordination chemistry for the assembly of alkoxo-or phenoxo-bridged clusters and polymers, see: Koizumi et al. (2005 ); Boskovic et al. (2003 ); Oshiob et al. (2005 ). For related structures, see: Bluhm et al. (2003 ); Kannappan et al. (2005 ); Sun et al. (2005 ).

Experimental

Crystal data

[Cu(C₁₃H₁₀ClN₂O)Cl]
M_r = 344.67
Orthorhombic, P b c a
a = 7.7975 (11) Å
b = 13.638 (2) Å
c = 24.854 (4) Å
V = 2643.1 (7) Å³
Z = 8
Mo Kα radiation
μ = 2.05 mm⁻¹
T = 293 K
0.15 × 0.12 × 0.09 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ) T_min = 0.749, T_max = 0.837
12098 measured reflections
2325 independent reflections
1580 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.098
S = 1.02
2325 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b ); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812013359/hg5195sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812013359/hg5195Isup2.hkl

checkCIF report

Comment top

Schiff base complexes have all along attracted much attention due to their interesting structures and wide potential applications. Recently, the relative flexible unsymmetrical tridentate Schiff base ligands and their hydrogenerated derivatives have been introduced into the coordination chemistry to assemble alkoxo-or phenoxo-bridged clusters and polymers with beautiful molecular structures and interesting magnetic properties (Koizumi et al., 2005; Boskovic et al., 2003; Oshiob et al., 2005). Herein, we report the structure of a new copper complex based on an unsymmetric tridentate Schiff base ligand.

The molecular structure of title compound is shown in Fig. 1. The Cu ion is four coordinate forming a slightly distorted square planar coordination sphere, in which three positions are occupied by two N atoms and one O atom from the asymmetric tridentate Schiff base ligand, and the other one coming from a coordinated chloride ion. The CuN₂O unit is located in a well plane with the mean deviation of 0.0035 (3) Å, while the chloro ion is obvious out of the above plane with deviation value 0.1249 (5) Å. The bond distances of Cu—O, Cu—N and Cu—Cl are in the normal range compared to the reported complexes containing the analogous unsymmetrical tridentate Schiff base ligands (Bluhm et al., 2003; Kannappan, et al., 2005; Sun et al., 2005). It is worth noting that the asymmetric unit can be linked into one dimensional double chain structure by the weak Cu···Cl intermolecular interactions.

Related literature top

For background to the use of unsymmetrical tridentate Schiff base ligands and their hydrogenerated derivatives in coordination chemistry for the assembly of

alkoxo-or phenoxo-bridged clusters and polymers, see: Koizumi et al. (2005); Boskovic et al. (2003); Oshiob et al. (2005). For related structures, see: Bluhm et al. (2003); Kannappan et al. (2005); Sun et al. (2005).

Experimental top

The Schiff base was obtained by condensation 2-(aminomethyl)pyridine and 5-chloro-2-hydroxy-benzaldehyde with the ratio 1:1 in methanol. The synthesis of the title complex was carried out by the reaction of CuCl₂.6H₂O and the Schiff-base ligand (1:1, molar ratio) in methanol under the stirring condition at room temperature. The filtrated solution was allowed to partial evaporation and blue single crystals suitable for X-ray diffraction were afforded with the yield about 60% sevral days later.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Figures top

Fig. 1. View of the title compound with the atom-labelling scheme Displacement ellipsoids are drawn at the 30% probability level. All H-atoms are omitted for clarity.

Chlorido[4-chloro-2-(pyridin-2-ylmethyliminomethyl)phenolato- κ³N,N',O]copper(II) top

Crystal data top

[Cu(C₁₃H₁₀ClN₂O)Cl]	F(000) = 1384
M_r = 344.67	D_x = 1.732 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1346 reflections
a = 7.7975 (11) Å	θ = 2.8–26.3°
b = 13.638 (2) Å	µ = 2.05 mm⁻¹
c = 24.854 (4) Å	T = 293 K
V = 2643.1 (7) Å³	Block, blue
Z = 8	0.15 × 0.12 × 0.09 mm

Data collection top

Bruker APEXII diffractometer	2325 independent reflections
Radiation source: fine-focus sealed tube	1580 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −9→9
T_min = 0.749, T_max = 0.837	k = −14→16
12098 measured reflections	l = −27→29

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0418P)² + 1.4463P] where P = (F_o² + 2F_c²)/3
2325 reflections	(Δ/σ)_max = 0.006
172 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

[Cu(C₁₃H₁₀ClN₂O)Cl]	V = 2643.1 (7) Å³
M_r = 344.67	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 7.7975 (11) Å	µ = 2.05 mm⁻¹
b = 13.638 (2) Å	T = 293 K
c = 24.854 (4) Å	0.15 × 0.12 × 0.09 mm

Data collection top

Bruker APEXII diffractometer	2325 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	1580 reflections with I > 2σ(I)
T_min = 0.749, T_max = 0.837	R_int = 0.053
12098 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.02	Δρ_max = 0.29 e Å⁻³
2325 reflections	Δρ_min = −0.33 e Å⁻³
172 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	0.10863 (6)	0.97468 (3)	0.248134 (18)	0.03844 (17)
Cl1	0.43484 (19)	0.64978 (10)	0.45552 (5)	0.0755 (4)
Cl2	−0.09768 (12)	1.09117 (7)	0.25915 (4)	0.0441 (3)
O1	0.1221 (4)	0.9585 (2)	0.32421 (11)	0.0504 (8)
N1	0.2305 (4)	0.8517 (2)	0.23433 (11)	0.0349 (7)
N2	0.1071 (4)	0.9820 (2)	0.16720 (13)	0.0407 (8)
C1	0.2746 (5)	0.8043 (3)	0.32695 (15)	0.0358 (9)
C2	0.1939 (5)	0.8871 (3)	0.35062 (16)	0.0399 (10)
C3	0.1894 (6)	0.8900 (3)	0.40777 (17)	0.0524 (12)
H3	0.1355	0.9426	0.4246	0.063*
C4	0.2610 (6)	0.8186 (3)	0.43873 (17)	0.0564 (12)
H4	0.2573	0.8231	0.4760	0.068*
C5	0.3394 (5)	0.7391 (3)	0.41436 (17)	0.0472 (11)
C6	0.3446 (5)	0.7312 (3)	0.36013 (16)	0.0414 (10)
H6	0.3953	0.6764	0.3446	0.050*
C7	0.2900 (5)	0.7931 (3)	0.27008 (15)	0.0343 (9)
H7	0.3488	0.7381	0.2578	0.041*
C8	0.1920 (5)	0.9084 (3)	0.14267 (15)	0.0392 (10)
C9	0.2162 (6)	0.9091 (3)	0.08752 (17)	0.0544 (12)
H9	0.2736	0.8576	0.0709	0.065*
C10	0.1555 (6)	0.9855 (4)	0.05748 (19)	0.0655 (14)
H10	0.1727	0.9868	0.0205	0.079*
C11	0.0687 (6)	1.0606 (4)	0.08264 (19)	0.0646 (13)
H11	0.0268	1.1134	0.0630	0.077*
C12	0.0453 (6)	1.0559 (3)	0.13728 (17)	0.0535 (12)
H12	−0.0157	1.1057	0.1542	0.064*
C13	0.2559 (5)	0.8271 (3)	0.17772 (14)	0.0407 (10)
H13A	0.1948	0.7671	0.1693	0.049*
H13B	0.3770	0.8163	0.1709	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0423 (3)	0.0278 (3)	0.0452 (3)	0.0030 (2)	0.0022 (3)	−0.0004 (2)
Cl1	0.1064 (11)	0.0612 (8)	0.0589 (7)	0.0109 (8)	−0.0199 (7)	0.0129 (6)
Cl2	0.0358 (5)	0.0300 (5)	0.0665 (7)	0.0016 (4)	0.0006 (5)	−0.0014 (5)
O1	0.065 (2)	0.0367 (17)	0.0496 (17)	0.0140 (15)	0.0072 (15)	0.0007 (14)
N1	0.0397 (19)	0.0258 (17)	0.0392 (18)	−0.0030 (15)	0.0042 (15)	−0.0022 (14)
N2	0.040 (2)	0.0336 (19)	0.0484 (19)	−0.0033 (17)	−0.0025 (16)	0.0041 (16)
C1	0.034 (2)	0.028 (2)	0.045 (2)	−0.0045 (17)	0.0006 (18)	−0.0028 (18)
C2	0.041 (2)	0.032 (2)	0.047 (2)	−0.0053 (19)	0.004 (2)	−0.0024 (19)
C3	0.065 (3)	0.044 (3)	0.048 (3)	0.007 (2)	0.006 (2)	−0.007 (2)
C4	0.070 (3)	0.058 (3)	0.042 (2)	−0.005 (3)	0.002 (2)	−0.003 (2)
C5	0.052 (3)	0.041 (3)	0.048 (3)	−0.003 (2)	−0.004 (2)	0.003 (2)
C6	0.044 (3)	0.030 (2)	0.050 (3)	−0.0025 (18)	−0.0013 (19)	−0.003 (2)
C7	0.031 (2)	0.024 (2)	0.048 (2)	−0.0001 (17)	0.0022 (18)	−0.0048 (18)
C8	0.038 (2)	0.035 (2)	0.044 (2)	−0.0071 (19)	−0.0029 (19)	0.000 (2)
C9	0.063 (3)	0.051 (3)	0.049 (3)	0.000 (2)	0.000 (2)	−0.002 (2)
C10	0.078 (4)	0.074 (4)	0.045 (3)	−0.004 (3)	−0.005 (2)	0.009 (3)
C11	0.074 (4)	0.060 (3)	0.059 (3)	0.002 (3)	−0.008 (3)	0.016 (3)
C12	0.057 (3)	0.045 (3)	0.058 (3)	0.001 (2)	−0.001 (2)	0.004 (2)
C13	0.044 (3)	0.036 (2)	0.042 (2)	0.0012 (19)	0.001 (2)	−0.0045 (18)

Geometric parameters (Å, º) top

Cu1—O1	1.907 (3)	C4—C5	1.384 (6)
Cu1—N1	1.958 (3)	C4—H4	0.9300
Cu1—N2	2.014 (3)	C5—C6	1.353 (5)
Cu1—Cl2	2.2775 (11)	C6—H6	0.9300
Cl1—C5	1.756 (4)	C7—H7	0.9300
O1—C2	1.300 (4)	C8—C9	1.383 (5)
N1—C7	1.282 (4)	C8—C13	1.495 (5)
N1—C13	1.460 (4)	C9—C10	1.367 (6)
N2—C12	1.342 (5)	C9—H9	0.9300
N2—C8	1.348 (5)	C10—C11	1.377 (6)
C1—C6	1.404 (5)	C10—H10	0.9300
C1—C2	1.421 (5)	C11—C12	1.372 (6)
C1—C7	1.427 (5)	C11—H11	0.9300
C2—C3	1.422 (5)	C12—H12	0.9300
C3—C4	1.362 (6)	C13—H13A	0.9700
C3—H3	0.9300	C13—H13B	0.9700

O1—Cu1—N1	92.74 (12)	C5—C6—C1	121.1 (4)
O1—Cu1—N2	175.25 (13)	C5—C6—H6	119.4
N1—Cu1—N2	82.55 (13)	C1—C6—H6	119.4
O1—Cu1—Cl2	90.03 (9)	N1—C7—C1	126.1 (4)
N1—Cu1—Cl2	164.03 (10)	N1—C7—H7	117.0
N2—Cu1—Cl2	94.67 (10)	C1—C7—H7	117.0
C2—O1—Cu1	127.7 (3)	N2—C8—C9	120.6 (4)
C7—N1—C13	118.4 (3)	N2—C8—C13	116.9 (3)
C7—N1—Cu1	126.0 (3)	C9—C8—C13	122.5 (4)
C13—N1—Cu1	115.6 (2)	C10—C9—C8	120.0 (4)
C12—N2—C8	119.0 (4)	C10—C9—H9	120.0
C12—N2—Cu1	126.4 (3)	C8—C9—H9	120.0
C8—N2—Cu1	114.3 (3)	C9—C10—C11	119.3 (5)
C6—C1—C2	119.6 (4)	C9—C10—H10	120.4
C6—C1—C7	118.2 (4)	C11—C10—H10	120.4
C2—C1—C7	122.2 (3)	C12—C11—C10	118.7 (5)
O1—C2—C1	125.2 (4)	C12—C11—H11	120.7
O1—C2—C3	118.2 (4)	C10—C11—H11	120.7
C1—C2—C3	116.5 (4)	N2—C12—C11	122.4 (4)
C4—C3—C2	122.3 (4)	N2—C12—H12	118.8
C4—C3—H3	118.8	C11—C12—H12	118.8
C2—C3—H3	118.8	N1—C13—C8	110.2 (3)
C3—C4—C5	119.6 (4)	N1—C13—H13A	109.6
C3—C4—H4	120.2	C8—C13—H13A	109.6
C5—C4—H4	120.2	N1—C13—H13B	109.6
C6—C5—C4	120.8 (4)	C8—C13—H13B	109.6
C6—C5—Cl1	120.8 (3)	H13A—C13—H13B	108.1
C4—C5—Cl1	118.4 (3)

Experimental details

Crystal data
Chemical formula	[Cu(C₁₃H₁₀ClN₂O)Cl]
M_r	344.67
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	7.7975 (11), 13.638 (2), 24.854 (4)
V (Å³)	2643.1 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.05
Crystal size (mm)	0.15 × 0.12 × 0.09

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008a)
T_min, T_max	0.749, 0.837
No. of measured, independent and observed [I > 2σ(I)] reflections	12098, 2325, 1580
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.098, 1.02
No. of reflections	2325
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.33

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008b), SHELXL97 (Sheldrick, 2008b), SHELXTL (Sheldrick, 2008b).

Acknowledgements

This work was supported by the Basic and Frontier Research Programs of Henan Province (No. 092300410194)

References

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