Bis{2-meth­oxy-6-[(3-pyrid­yl)methyl­imino­meth­yl]phenolato}copper(II)

Wang, Y.; Zhu, L.-L.; Sun, B.-W.

doi:10.1107/S1600536809029523

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page m1058

doi:10.1107/S1600536809029523

Open

access

Bis{2-methoxy-6-[(3-pyridyl)methyliminomethyl]phenolato}copper(II)

Yun Wang,^a Li-Li Zhu ^a and Bai-Wang Sun ^b ^*

^aDepartment of Chemistry, Key Laboratory of Medicinal Chemistry for Natural Resources, Ministry of Education, Yunnan University, Kunming 650091, People's Republic of China, and ^bOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: chmsunbw@seu.edu.cn

(Received 12 July 2009; accepted 24 July 2009; online 12 August 2009)

In the mononuclear title complex, [Cu(C₁₄H₁₃N₂O₂)₂], the Cu^II atom lies on an inversion centre and adopts a square-planar coordination geometry. The dihedral angle formed by the pyridine and benzene rings is 74.61 (5)°. Intramolecular C—H⋯O hydrogen bonds are present. The crystal structure is stabilized by weak aromatic π–π stacking interactions involving neighbouring pyridine rings [centroid–centroid distance = 3.853 (2) Å].

Related literature

For a related structure, see: Wang et al. (2008 ). For the synthetic procedure, see: Kannappan et al. (2005 ); Zhao et al. (2008 ).

Experimental

Crystal data

[Cu(C₁₄H₁₃N₂O₂)₂]
M_r = 546.07
Monoclinic, P 2₁ /c
a = 11.455 (2) Å
b = 14.414 (3) Å
c = 7.5491 (15) Å
β = 102.55 (3)°
V = 1216.7 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.94 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.824, T_max = 0.828
11771 measured reflections
2667 independent reflections
2430 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.102
S = 1.41
2667 reflections
169 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9B⋯O2ⁱ	0.97	2.28	2.862 (2)	118
Symmetry code: (i) -x+2, -y+2, -z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809029523/rz2354sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809029523/rz2354Isup2.hkl

Comment top

Schiff base metal complexes have been frequently investigated in the past several years, because of their broad range of properties and applications. We herein report the crystal structure of a new complex formed by reaction of Cu(CH₃COO)₂ and the Schiff base ligand N-(3-pyridylmethyl)-3-methoxy-salicylaldiminato.

As shown in Fig. 1, the mononuclear title complex is centrosymmetric. The copper atom adopts a square planar coordination geometry provided by two trans-arranged phenolate-O and two imine-N atoms from two ligands (Wang et al., 2008). The dihedral angle formed by the pyridine and benzene rings of the same ligand is 74.61 (5)°. An intramolecular C—H···O hydrogen bond (Table 1) stabilizes the molecular conformation. In the crystal structure, weak aromatic π–π stacking interactions involving neighbouring pyridine rings at (x, y, z) and (x, 5/2-y, 1/2+z) are present, with a centroid-to-centroid distance of 3.853 (2) Å.

Related literature top

For a related structure, see: Wang et al. (2008). For the synthetic procedure, see: Kannappan et al. (2005); Zhao et al. (2008).

Experimental top

All chemicals were of reagent grade and were used as received with out further purification. 2-Hydroxy-3-methoxybenzaldehyde (0.152 g, 1 mmol) in ethanol (5 ml) was added to a stirred ethanol solution (5 ml) containing 3-aminomethylpyridine (0.108 g, 1 mmol). The resulting yellow solution was continuously stirred for about 1 h, then Cu(CH₃COO)₂.H₂O (0.100 g, 0.5 mmol) in ethanol (5 ml) was added. The resulting deep green solution was stirred for another 2 h and left to evaporate at room temperature (Kannappan et al.,2005; Zhao et al., 2008). After several days, dark green block crystals suitable for X-ray diffraction analysis were formed.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound with the atom-numbering scheme and all hydrogen atoms. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code A: 2 - x, -y, 1 - z]

Bis{2-methoxy-6-[(3-pyridyl)methyliminomethyl]phenolato}copper(II) top

Crystal data top

[Cu(C₁₄H₁₃N₂O₂)₂]	F(000) = 566
M_r = 546.07	D_x = 1.491 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 10382 reflections
a = 11.455 (2) Å	θ = 3.2–27.5°
b = 14.414 (3) Å	µ = 0.94 mm⁻¹
c = 7.5491 (15) Å	T = 293 K
β = 102.55 (3)°	Block, dark green
V = 1216.7 (4) Å³	0.20 × 0.20 × 0.20 mm
Z = 2

Data collection top

Rigaku SCXmini diffractometer	2667 independent reflections
Radiation source: fine-focus sealed tube	2430 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −14→14
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −18→18
T_min = 0.824, T_max = 0.828	l = −9→9
11771 measured reflections

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H-atom parameters constrained
S = 1.41	w = 1/[σ²(F_o²) + (0.0515P)²] where P = (F_o² + 2F_c²)/3
2667 reflections	(Δ/σ)_max = 0.001
169 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.62 e Å⁻³

Crystal data top

[Cu(C₁₄H₁₃N₂O₂)₂]	V = 1216.7 (4) Å³
M_r = 546.07	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.455 (2) Å	µ = 0.94 mm⁻¹
b = 14.414 (3) Å	T = 293 K
c = 7.5491 (15) Å	0.20 × 0.20 × 0.20 mm
β = 102.55 (3)°

Data collection top

Rigaku SCXmini diffractometer	2667 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2430 reflections with I > 2σ(I)
T_min = 0.824, T_max = 0.828	R_int = 0.035
11771 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.41	Δρ_max = 0.25 e Å⁻³
2667 reflections	Δρ_min = −0.62 e Å⁻³
169 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	1.0000	1.0000	0.0000	0.03101 (13)
N1	0.94828 (11)	1.08186 (9)	−0.22373 (17)	0.0269 (3)
C14	1.04327 (16)	1.27619 (11)	−0.3538 (2)	0.0346 (4)
H14A	0.9670	1.2747	−0.4280	0.041*
C9	1.02998 (15)	1.10214 (10)	−0.3470 (2)	0.0307 (4)
H9A	0.9841	1.1069	−0.4708	0.037*
H9B	1.0867	1.0517	−0.3417	0.037*
C11	1.20928 (16)	1.19482 (12)	−0.1813 (2)	0.0359 (4)
H11A	1.2487	1.1403	−0.1375	0.043*
C7	0.74950 (13)	1.11896 (10)	−0.1721 (2)	0.0294 (4)
O1	0.67391 (12)	1.03058 (10)	0.23920 (19)	0.0457 (3)
C8	0.84437 (15)	1.11952 (11)	−0.2697 (2)	0.0308 (4)
H8A	0.8285	1.1511	−0.3798	0.037*
C10	1.09654 (14)	1.19174 (11)	−0.2930 (2)	0.0284 (3)
N2	1.09381 (14)	1.35872 (10)	−0.3131 (2)	0.0413 (4)
C3	0.65892 (13)	1.07713 (11)	0.0778 (2)	0.0315 (4)
C6	0.64554 (16)	1.17021 (12)	−0.2470 (3)	0.0380 (4)
H6A	0.6412	1.2022	−0.3552	0.046*
C4	0.55774 (15)	1.12611 (12)	0.0004 (3)	0.0379 (4)
H4A	0.4931	1.1278	0.0566	0.045*
C13	1.20181 (17)	1.35935 (13)	−0.2044 (3)	0.0416 (4)
H13A	1.2384	1.4164	−0.1730	0.050*
C5	0.55195 (16)	1.17370 (13)	−0.1642 (3)	0.0424 (5)
H5A	0.4839	1.2075	−0.2160	0.051*
C1	0.58255 (19)	1.03860 (17)	0.3375 (3)	0.0501 (5)
H1A	0.6037	1.0030	0.4473	0.075*
H1B	0.5088	1.0157	0.2651	0.075*
H1C	0.5731	1.1026	0.3670	0.075*
C12	1.26288 (17)	1.28035 (13)	−0.1354 (3)	0.0426 (4)
H12A	1.3385	1.2843	−0.0595	0.051*
O2	0.85152 (11)	1.02297 (9)	0.07153 (19)	0.0383 (3)
C2	0.75880 (13)	1.07128 (10)	−0.0065 (2)	0.0287 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.02621 (19)	0.03057 (19)	0.0384 (2)	0.00818 (10)	0.01174 (14)	0.01467 (11)
N1	0.0288 (7)	0.0212 (6)	0.0311 (7)	−0.0008 (5)	0.0075 (6)	0.0041 (5)
C14	0.0332 (9)	0.0296 (8)	0.0420 (9)	0.0005 (7)	0.0106 (7)	0.0065 (7)
C9	0.0374 (8)	0.0259 (8)	0.0310 (8)	0.0015 (7)	0.0123 (7)	0.0027 (6)
C11	0.0352 (9)	0.0339 (9)	0.0398 (10)	0.0047 (7)	0.0110 (8)	0.0057 (7)
C7	0.0267 (8)	0.0229 (7)	0.0368 (9)	0.0024 (6)	0.0028 (7)	0.0022 (6)
O1	0.0404 (8)	0.0547 (8)	0.0475 (8)	0.0114 (7)	0.0217 (7)	0.0147 (7)
C8	0.0350 (9)	0.0236 (8)	0.0326 (8)	−0.0014 (6)	0.0045 (7)	0.0069 (6)
C10	0.0329 (8)	0.0273 (8)	0.0290 (8)	0.0006 (6)	0.0155 (7)	0.0042 (6)
N2	0.0434 (9)	0.0280 (7)	0.0529 (10)	−0.0011 (6)	0.0119 (8)	0.0028 (7)
C3	0.0287 (8)	0.0272 (8)	0.0388 (9)	0.0008 (6)	0.0076 (7)	−0.0020 (7)
C6	0.0384 (9)	0.0342 (9)	0.0377 (9)	0.0084 (7)	0.0001 (8)	0.0054 (7)
C4	0.0291 (9)	0.0381 (9)	0.0466 (10)	0.0035 (7)	0.0085 (8)	−0.0074 (8)
C13	0.0438 (11)	0.0318 (9)	0.0498 (11)	−0.0056 (8)	0.0116 (9)	−0.0027 (8)
C5	0.0311 (9)	0.0437 (10)	0.0480 (11)	0.0134 (8)	−0.0014 (8)	0.0001 (8)
C1	0.0476 (12)	0.0642 (13)	0.0443 (11)	0.0038 (10)	0.0229 (10)	−0.0025 (10)
C12	0.0336 (9)	0.0505 (11)	0.0433 (10)	−0.0040 (8)	0.0074 (8)	−0.0022 (8)
O2	0.0295 (7)	0.0430 (6)	0.0452 (7)	0.0136 (5)	0.0144 (6)	0.0194 (6)
C2	0.0264 (8)	0.0213 (7)	0.0375 (9)	0.0016 (6)	0.0051 (7)	0.0017 (6)

Geometric parameters (Å, º) top

Cu1—O2ⁱ	1.9218 (13)	O1—C3	1.369 (2)
Cu1—O2	1.9218 (13)	O1—C1	1.413 (2)
Cu1—N1	2.0399 (13)	C8—H8A	0.9300
Cu1—N1ⁱ	2.0399 (13)	N2—C13	1.328 (2)
N1—C8	1.285 (2)	C3—C4	1.374 (2)
N1—C9	1.485 (2)	C3—C2	1.427 (2)
C14—N2	1.329 (2)	C6—C5	1.354 (3)
C14—C10	1.394 (2)	C6—H6A	0.9300
C14—H14A	0.9300	C4—C5	1.408 (3)
C9—C10	1.510 (2)	C4—H4A	0.9300
C9—H9A	0.9700	C13—C12	1.378 (3)
C9—H9B	0.9700	C13—H13A	0.9300
C11—C10	1.381 (2)	C5—H5A	0.9300
C11—C12	1.387 (2)	C1—H1A	0.9600
C11—H11A	0.9300	C1—H1B	0.9600
C7—C6	1.411 (2)	C1—H1C	0.9600
C7—C2	1.411 (2)	C12—H12A	0.9300
C7—C8	1.439 (2)	O2—C2	1.2993 (18)

O2ⁱ—Cu1—O2	180.0	C14—C10—C9	119.92 (15)
O2ⁱ—Cu1—N1	89.00 (6)	C13—N2—C14	116.70 (16)
O2—Cu1—N1	91.00 (6)	O1—C3—C4	124.16 (16)
O2ⁱ—Cu1—N1ⁱ	91.00 (6)	O1—C3—C2	114.21 (14)
O2—Cu1—N1ⁱ	89.00 (6)	C4—C3—C2	121.63 (16)
N1—Cu1—N1ⁱ	180.00 (6)	C5—C6—C7	121.24 (17)
C8—N1—C9	114.85 (13)	C5—C6—H6A	119.4
C8—N1—Cu1	123.58 (12)	C7—C6—H6A	119.4
C9—N1—Cu1	121.57 (10)	C3—C4—C5	119.95 (17)
N2—C14—C10	124.60 (17)	C3—C4—H4A	120.0
N2—C14—H14A	117.7	C5—C4—H4A	120.0
C10—C14—H14A	117.7	N2—C13—C12	123.81 (17)
N1—C9—C10	110.44 (12)	N2—C13—H13A	118.1
N1—C9—H9A	109.6	C12—C13—H13A	118.1
C10—C9—H9A	109.6	C6—C5—C4	119.92 (16)
N1—C9—H9B	109.6	C6—C5—H5A	120.0
C10—C9—H9B	109.6	C4—C5—H5A	120.0
H9A—C9—H9B	108.1	O1—C1—H1A	109.5
C10—C11—C12	119.04 (16)	O1—C1—H1B	109.5
C10—C11—H11A	120.5	H1A—C1—H1B	109.5
C12—C11—H11A	120.5	O1—C1—H1C	109.5
C6—C7—C2	120.31 (16)	H1A—C1—H1C	109.5
C6—C7—C8	117.23 (15)	H1B—C1—H1C	109.5
C2—C7—C8	122.44 (14)	C13—C12—C11	118.62 (17)
C3—O1—C1	117.61 (15)	C13—C12—H12A	120.7
N1—C8—C7	128.12 (15)	C11—C12—H12A	120.7
N1—C8—H8A	115.9	C2—O2—Cu1	130.63 (12)
C7—C8—H8A	115.9	O2—C2—C7	124.05 (15)
C11—C10—C14	117.21 (15)	O2—C2—C3	119.02 (15)
C11—C10—C9	122.86 (14)	C7—C2—C3	116.93 (14)

O2ⁱ—Cu1—N1—C8	175.74 (14)	C8—C7—C6—C5	−179.88 (16)
O2—Cu1—N1—C8	−4.26 (14)	O1—C3—C4—C5	178.43 (17)
O2ⁱ—Cu1—N1—C9	−4.15 (11)	C2—C3—C4—C5	−1.4 (3)
O2—Cu1—N1—C9	175.85 (11)	C14—N2—C13—C12	0.8 (3)
C8—N1—C9—C10	86.53 (17)	C7—C6—C5—C4	0.4 (3)
Cu1—N1—C9—C10	−93.57 (13)	C3—C4—C5—C6	0.8 (3)
C9—N1—C8—C7	−174.86 (15)	N2—C13—C12—C11	0.0 (3)
Cu1—N1—C8—C7	5.3 (2)	C10—C11—C12—C13	−0.5 (3)
C6—C7—C8—N1	176.48 (16)	N1—Cu1—O2—C2	1.65 (16)
C2—C7—C8—N1	−2.3 (3)	N1ⁱ—Cu1—O2—C2	−178.35 (16)
C12—C11—C10—C14	0.2 (3)	Cu1—O2—C2—C7	0.5 (3)
C12—C11—C10—C9	−178.60 (16)	Cu1—O2—C2—C3	−179.78 (12)
N2—C14—C10—C11	0.7 (3)	C6—C7—C2—O2	−179.72 (16)
N2—C14—C10—C9	179.51 (16)	C8—C7—C2—O2	−1.0 (3)
N1—C9—C10—C11	94.88 (18)	C6—C7—C2—C3	0.5 (2)
N1—C9—C10—C14	−83.88 (18)	C8—C7—C2—C3	179.25 (14)
C10—C14—N2—C13	−1.1 (3)	O1—C3—C2—O2	1.1 (2)
C1—O1—C3—C4	−4.3 (3)	C4—C3—C2—O2	−179.07 (16)
C1—O1—C3—C2	175.52 (16)	O1—C3—C2—C7	−179.13 (14)
C2—C7—C6—C5	−1.1 (3)	C4—C3—C2—C7	0.7 (2)

Symmetry code: (i) −x+2, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···O2ⁱ	0.97	2.28	2.862 (2)	118

Symmetry code: (i) −x+2, −y+2, −z.

Experimental details

Crystal data
Chemical formula	[Cu(C₁₄H₁₃N₂O₂)₂]
M_r	546.07
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.455 (2), 14.414 (3), 7.5491 (15)
β (°)	102.55 (3)
V (Å³)	1216.7 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.94
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.824, 0.828
No. of measured, independent and observed [I > 2σ(I)] reflections	11771, 2667, 2430
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.102, 1.41
No. of reflections	2667
No. of parameters	169
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.62

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···O2ⁱ	0.97	2.28	2.862 (2)	118

Symmetry code: (i) −x+2, −y+2, −z.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (project Nos. 20671019, 20361004) and the Doctoral Fund of the Ministry of Education of China (project No. 20060673015).

References

Kannappan, R., Tanase, S., Mutikainen, I., Turpeinen, U. & Reedijk, J. (2005). Inorg. Chim. Acta, 358, 383–388. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, X.-J., Jian, H.-X., Liu, Z.-P., Ni, Q.-L., Gui, L.-C. & Tang, L.-H. (2008). Polyhedron, 27, 2634–2642. Web of Science CSD CrossRef CAS Google Scholar
Zhao, Q.-H., Zhang, L., Du, L. & Fang, R.-B. (2008). Acta Cryst. E64, m142. Web of Science CSD CrossRef IUCr Journals 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.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page m1058

doi:10.1107/S1600536809029523

Open

access