Bis{2-[(2-pyrid­yl)imino­meth­yl]phenolato}copper(II)

Miao, J.; Zhao, Z.; Chen, H.; Wang, D.; Nie, Y.

doi:10.1107/S1600536809026051

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page m904

doi:10.1107/S1600536809026051

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Bis{2-[(2-pyridyl)iminomethyl]phenolato}copper(II)

Jinling Miao,^a Zhitong Zhao,^a Hongwei Chen,^a Daqi Wang ^b and Yong Nie ^a ^*

^aSchool of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, People's Republic of China.
^*Correspondence e-mail: chm_niey@ujn.edu.cn

(Received 1 July 2009; accepted 5 July 2009; online 11 July 2009)

In the title compound, [Cu(C₁₂H₉N₂O)₂], the Cu^II atom lies on a crystallographic inversion center and has a nearly square-planar geometry. The Cu^II center coordinates to the phenolic O and azomethine N atoms of the two symmetry-related 2-[(2-pyridyl)iminomethyl]phenolate ligands. The pyridyl N atoms do not coordinate to the Cu^II atom but participate in intramolecular C—H⋯N hydrogen bonding. π–π stacking between the benzene rings and between the pyridyl rings [centroid–centroid distances 3.8142 (5) and 3.8142 (5) Å, respectively] links the molecules into a chain propagating parallel to [100].

Related literature

For the preparation of the title compound by an electrochemical method, see: Castineiras et al. (1989 ), and by a solution method, see: Parashar et al. (1988 ). For the crystal structures of related compounds, see: Castineiras et al. (1989).

Experimental

Crystal data

[Cu(C₁₂H₉N₂O)₂]
M_r = 457.96
Triclinic, $[P \overline 1]$
a = 3.8142 (5) Å
b = 11.217 (1) Å
c = 11.9001 (12) Å
α = 106.884 (2)°
β = 90.374 (1)°
γ = 90.289 (1)°
V = 487.16 (9) Å³
Z = 1
Mo Kα radiation
μ = 1.15 mm⁻¹
T = 298 K
0.41 × 0.17 × 0.15 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.650, T_max = 0.846
2547 measured reflections
1695 independent reflections
1481 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.077
S = 1.07
1695 reflections
142 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N1	0.93	2.29	2.684 (3)	105

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); 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/S1600536809026051/pv2176sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809026051/pv2176Isup2.hkl

checkCIF report

Comment top

The Schiff base, N-salicylidene 2-aminopyridine, has been widely studied as a potential tridentate ligand. The title compound has been prepared using an electrochemical method by Castineiras et al. (1989) starting from N-salicylidene 2-aminopyridine and copper. Parashar et al. (1988) reported that refluxing a mixture of Cu(OAc)₂ (OAc = acetato) and N-salicylidene 2-aminopyridine in a 1:2 molar ratio resulted in a green complex having the same formula but with an octahedral geometry deduced from spectroscopic properties. We have found that a simple method of solution diffusion produces the brown title compound.

As shown in Fig. 1, the copper atom lies on a crystallographic inversion center and has a square planar geometry. The copper center coordinates to the phenolic oxygen and the azomethine nitrogen atoms of the two symmetry related groups. The pyridyl nitrogen atoms do not coordinate to the copper. The Cu—O bond lengths are 1.9212 (17) Å, and the Cu—N bond lengths are 2.0216 (19) Å, respectively, all similar to those reported in the related structures (Castineiras et al., 1989).

The interplane dihedral angles are found to be as follows: 31.60 (7)° between the N₂O₂ plane and the benzene ring, 54.28 (7)° between the N₂O₂ plane and the pyridyl ring, and 22.75 (9)° between the benzene and the pyridyl ring. The intramolecular hydrogen bond C1—H1···N1 (2.684 (3) Å, 105°, Table 1) further stabilizes the whole structure. The π-π stacking between the benzene rings (centroid to centroid, 3.8142 (5) Å) and the pyridyl rings (centroid to centroid, 3.8142 (5) Å) links the molecules into a one-dimensional chain (Fig. 2).

Related literature top

For the preparation of the title compound by an electrochemical method, see: Castineiras et al. (1989), and by a solution method, see: Parashar et al. (1988). For the crystal structures of related compounds, see: Castineiras et al. (1989).

Experimental top

To a green solution of salicylaldehyde (23 mg, 0.19 mmol) and Cu(OAc)₂.H₂O (11 mg, 0.05 mmol) in ethanol (7 ml) was added slowly a solution of 2-aminopyridine (21 mg, 0.22 mmol) in ethanol (1 ml). The resulting mixture was allowed to stand still and brown crystalline needles were grown after 1 day. IR (KBr): v = 3435, 1611, 1444, 1326, 1187 cm ^-1.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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, with atom labels and 25% probability thermal ellipsoids.
	Fig. 2. The one-dimensional chain constructed by the π-π stacking.

Bis{2-[(2-pyridyl)iminomethyl]phenolato}copper(II) top

Crystal data top

[Cu(C₁₂H₉N₂O)₂]	Z = 1
M_r = 457.96	F(000) = 235
Triclinic, P1	D_x = 1.561 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 3.8142 (5) Å	Cell parameters from 1475 reflections
b = 11.217 (1) Å	θ = 2.2–27.5°
c = 11.9001 (12) Å	µ = 1.15 mm⁻¹
α = 106.884 (2)°	T = 298 K
β = 90.374 (1)°	Needle, brown
γ = 90.289 (1)°	0.41 × 0.17 × 0.15 mm
V = 487.16 (9) Å³

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	1695 independent reflections
Radiation source: fine-focus sealed tube	1481 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −4→4
T_min = 0.650, T_max = 0.846	k = −13→13
2547 measured reflections	l = −9→14

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0266P)² + 0.355P] where P = (F_o² + 2F_c²)/3
1695 reflections	(Δ/σ)_max < 0.001
142 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

[Cu(C₁₂H₉N₂O)₂]	γ = 90.289 (1)°
M_r = 457.96	V = 487.16 (9) Å³
Triclinic, P1	Z = 1
a = 3.8142 (5) Å	Mo Kα radiation
b = 11.217 (1) Å	µ = 1.15 mm⁻¹
c = 11.9001 (12) Å	T = 298 K
α = 106.884 (2)°	0.41 × 0.17 × 0.15 mm
β = 90.374 (1)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	1695 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1481 reflections with I > 2σ(I)
T_min = 0.650, T_max = 0.846	R_int = 0.015
2547 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.077	H-atom parameters constrained
S = 1.07	Δρ_max = 0.27 e Å⁻³
1695 reflections	Δρ_min = −0.29 e Å⁻³
142 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.5000	0.5000	0.5000	0.03882 (17)
N1	0.2225 (6)	0.15806 (19)	0.55001 (19)	0.0400 (5)
N2	0.4891 (5)	0.31537 (17)	0.48298 (17)	0.0305 (5)
O1	0.8250 (5)	0.46999 (15)	0.37229 (15)	0.0413 (5)
C1	0.5395 (7)	0.2344 (2)	0.3821 (2)	0.0331 (6)
H1	0.4927	0.1517	0.3774	0.040*
C2	0.6590 (7)	0.2583 (2)	0.2773 (2)	0.0325 (6)
C3	0.7979 (7)	0.3757 (2)	0.2770 (2)	0.0326 (6)
C4	0.9196 (7)	0.3865 (3)	0.1691 (2)	0.0389 (6)
H4	1.0121	0.4623	0.1658	0.047*
C5	0.9057 (7)	0.2886 (3)	0.0689 (2)	0.0459 (7)
H5	0.9870	0.2994	−0.0010	0.055*
C6	0.7726 (8)	0.1734 (3)	0.0696 (2)	0.0494 (7)
H6	0.7657	0.1072	0.0011	0.059*
C7	0.6524 (8)	0.1595 (2)	0.1727 (2)	0.0427 (7)
H7	0.5635	0.0825	0.1738	0.051*
C8	0.4001 (6)	0.2651 (2)	0.5769 (2)	0.0316 (6)
C9	0.5106 (7)	0.3277 (3)	0.6892 (2)	0.0412 (6)
H9	0.6317	0.4030	0.7045	0.049*
C10	0.4374 (8)	0.2761 (3)	0.7780 (3)	0.0494 (7)
H10	0.5085	0.3160	0.8547	0.059*
C11	0.2574 (8)	0.1647 (3)	0.7520 (3)	0.0509 (8)
H11	0.2045	0.1278	0.8105	0.061*
C12	0.1583 (8)	0.1094 (3)	0.6381 (3)	0.0491 (8)
H12	0.0394	0.0335	0.6208	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0584 (3)	0.0241 (2)	0.0318 (3)	−0.0022 (2)	0.0154 (2)	0.00443 (18)
N1	0.0457 (14)	0.0298 (11)	0.0452 (13)	−0.0023 (10)	0.0071 (11)	0.0116 (10)
N2	0.0343 (12)	0.0261 (10)	0.0306 (11)	−0.0019 (9)	0.0037 (9)	0.0073 (9)
O1	0.0597 (13)	0.0304 (9)	0.0301 (10)	−0.0079 (9)	0.0143 (9)	0.0029 (8)
C1	0.0363 (15)	0.0233 (12)	0.0375 (14)	0.0001 (10)	0.0005 (11)	0.0054 (11)
C2	0.0341 (14)	0.0286 (13)	0.0312 (13)	0.0052 (11)	0.0027 (11)	0.0030 (10)
C3	0.0335 (14)	0.0330 (13)	0.0290 (13)	0.0046 (11)	0.0036 (11)	0.0051 (11)
C4	0.0384 (16)	0.0444 (15)	0.0339 (14)	−0.0010 (12)	0.0047 (12)	0.0112 (12)
C5	0.0437 (17)	0.065 (2)	0.0258 (14)	0.0025 (14)	0.0037 (12)	0.0081 (13)
C6	0.0526 (19)	0.0517 (18)	0.0318 (15)	0.0027 (14)	0.0007 (13)	−0.0071 (13)
C7	0.0480 (17)	0.0340 (14)	0.0391 (15)	0.0012 (12)	0.0020 (13)	−0.0006 (12)
C8	0.0324 (14)	0.0280 (12)	0.0363 (14)	0.0036 (10)	0.0045 (11)	0.0120 (11)
C9	0.0401 (16)	0.0438 (16)	0.0404 (16)	−0.0012 (12)	−0.0032 (12)	0.0136 (13)
C10	0.0501 (18)	0.064 (2)	0.0370 (16)	0.0118 (15)	0.0021 (13)	0.0186 (14)
C11	0.0545 (19)	0.0555 (19)	0.0544 (19)	0.0185 (15)	0.0182 (15)	0.0336 (16)
C12	0.0541 (19)	0.0367 (15)	0.063 (2)	0.0027 (13)	0.0179 (15)	0.0240 (14)

Geometric parameters (Å, º) top

Cu1—O1	1.9212 (17)	C4—H4	0.9300
Cu1—O1ⁱ	1.9212 (17)	C5—C6	1.388 (4)
Cu1—N2ⁱ	2.0216 (19)	C5—H5	0.9300
Cu1—N2	2.0216 (19)	C6—C7	1.363 (4)
N1—C8	1.330 (3)	C6—H6	0.9300
N1—C12	1.339 (3)	C7—H7	0.9300
N2—C1	1.294 (3)	C8—C9	1.379 (4)
N2—C8	1.433 (3)	C9—C10	1.373 (4)
O1—C3	1.310 (3)	C9—H9	0.9300
C1—C2	1.426 (3)	C10—C11	1.376 (4)
C1—H1	0.9300	C10—H10	0.9300
C2—C7	1.406 (3)	C11—C12	1.366 (4)
C2—C3	1.419 (3)	C11—H11	0.9300
C3—C4	1.406 (3)	C12—H12	0.9300
C4—C5	1.366 (4)

O1—Cu1—O1ⁱ	180.000 (1)	C4—C5—H5	119.4
O1—Cu1—N2ⁱ	90.50 (8)	C6—C5—H5	119.4
O1ⁱ—Cu1—N2ⁱ	89.50 (7)	C7—C6—C5	118.6 (3)
O1—Cu1—N2	89.50 (7)	C7—C6—H6	120.7
O1ⁱ—Cu1—N2	90.50 (8)	C5—C6—H6	120.7
N2ⁱ—Cu1—N2	180.000 (1)	C6—C7—C2	121.8 (3)
C8—N1—C12	116.8 (2)	C6—C7—H7	119.1
C1—N2—C8	115.7 (2)	C2—C7—H7	119.1
C1—N2—Cu1	120.87 (16)	N1—C8—C9	123.6 (2)
C8—N2—Cu1	123.30 (15)	N1—C8—N2	117.7 (2)
C3—O1—Cu1	123.48 (16)	C9—C8—N2	118.7 (2)
N2—C1—C2	127.1 (2)	C10—C9—C8	118.3 (3)
N2—C1—H1	116.4	C10—C9—H9	120.9
C2—C1—H1	116.4	C8—C9—H9	120.9
C7—C2—C3	119.6 (2)	C9—C10—C11	119.2 (3)
C7—C2—C1	118.2 (2)	C9—C10—H10	120.4
C3—C2—C1	122.1 (2)	C11—C10—H10	120.4
O1—C3—C4	120.4 (2)	C12—C11—C10	118.4 (3)
O1—C3—C2	122.7 (2)	C12—C11—H11	120.8
C4—C3—C2	116.9 (2)	C10—C11—H11	120.8
C5—C4—C3	121.8 (3)	N1—C12—C11	123.8 (3)
C5—C4—H4	119.1	N1—C12—H12	118.1
C3—C4—H4	119.1	C11—C12—H12	118.1
C4—C5—C6	121.3 (3)

O1—Cu1—N2—C1	−29.5 (2)	C3—C4—C5—C6	−0.5 (4)
O1ⁱ—Cu1—N2—C1	150.5 (2)	C4—C5—C6—C7	0.5 (4)
O1—Cu1—N2—C8	155.47 (19)	C5—C6—C7—C2	0.2 (4)
O1ⁱ—Cu1—N2—C8	−24.53 (19)	C3—C2—C7—C6	−0.8 (4)
N2ⁱ—Cu1—O1—C3	−138.9 (2)	C1—C2—C7—C6	−177.8 (3)
N2—Cu1—O1—C3	41.1 (2)	C12—N1—C8—C9	−1.5 (4)
C8—N2—C1—C2	−174.2 (2)	C12—N1—C8—N2	176.5 (2)
Cu1—N2—C1—C2	10.4 (4)	C1—N2—C8—N1	−30.6 (3)
N2—C1—C2—C7	−171.7 (3)	Cu1—N2—C8—N1	144.60 (19)
N2—C1—C2—C3	11.3 (4)	C1—N2—C8—C9	147.5 (2)
Cu1—O1—C3—C4	149.6 (2)	Cu1—N2—C8—C9	−37.2 (3)
Cu1—O1—C3—C2	−32.7 (3)	N1—C8—C9—C10	0.8 (4)
C7—C2—C3—O1	−177.1 (2)	N2—C8—C9—C10	−177.2 (2)
C1—C2—C3—O1	−0.2 (4)	C8—C9—C10—C11	−0.1 (4)
C7—C2—C3—C4	0.7 (4)	C9—C10—C11—C12	0.0 (4)
C1—C2—C3—C4	177.6 (2)	C8—N1—C12—C11	1.5 (4)
O1—C3—C4—C5	177.8 (2)	C10—C11—C12—N1	−0.8 (5)
C2—C3—C4—C5	−0.1 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N1	0.93	2.29	2.684 (3)	105

Experimental details

Crystal data
Chemical formula	[Cu(C₁₂H₉N₂O)₂]
M_r	457.96
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	3.8142 (5), 11.217 (1), 11.9001 (12)
α, β, γ (°)	106.884 (2), 90.374 (1), 90.289 (1)
V (Å³)	487.16 (9)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.15
Crystal size (mm)	0.41 × 0.17 × 0.15

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.650, 0.846
No. of measured, independent and observed [I > 2σ(I)] reflections	2547, 1695, 1481
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.077, 1.07
No. of reflections	1695
No. of parameters	142
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.29

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), 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
C1—H1···N1	0.930	2.29	2.684 (3)	105

Acknowledgements

The authors thank the University of Jinan (B0605) for support of this work.

References

Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Castineiras, A., Castro, J. A., Duran, M. L., Garcia-Vazquez, J. A., Macias, A., Romero, J. & Sousa, A. (1989). Polyhedron, 8, 2543–2549. CSD CrossRef CAS Web of Science Google Scholar
Parashar, R. K., Sharma, R. C., Kumar, A. & Mohan, G. (1988). Inorg. Chim. Acta, 151, 201–208. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar