[1,2-Bis(pyridin-2-ylmeth­oxy)benzene-κ4N,O,O′,N′]dichloridocopper(II)

Huang, N.-N.; Zhang, S.; Liu, Y.; Hou, G.-F.; Gao, J.-S.

doi:10.1107/S160053681101333X

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page m596

doi:10.1107/S160053681101333X

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[1,2-Bis(pyridin-2-ylmethoxy)benzene-κ⁴N,O,O′,N′]dichloridocopper(II)

Nan-Nan Huang,^a Shuang Zhang,^b Ying Liu,^c Guang-Feng Hou ^b and Jin-Sheng Gao ^b,^c ^*

^aPharmaceutical College, Heilongjiang University of Traditional Chinese Medicine, Harbin 150040, People's Republic of China, ^bEngineering Research Center of Pesticides of Heilongjiang Province, Heilongjiang University, Harbin 150080, People's Republic of China, and ^cCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China
^*Correspondence e-mail: hgf1000@163.com

(Received 4 April 2011; accepted 8 April 2011; online 16 April 2011)

In the title compound, [CuCl₂(C₁₈H₁₆N₂O₂)], the Cu^II atom lies on a twofold axis and is six-coordinated in a distorted octahedral environment defined by two N and two O atoms from the ligand and by two Cl atoms. In the crystal, π–π interactions [centroid–centroid distance = 3.838 (1) Å] and C—H⋯Cl hydrogen bonds link adjacent molecules into a chain structure along [101].

Related literature

For related structures, see: Zhang et al. (2010a ,b ).

Experimental

Crystal data

[CuCl₂(C₁₈H₁₆N₂O₂)]
M_r = 426.77
Monoclinic, C 2/c
a = 10.624 (2) Å
b = 19.458 (4) Å
c = 8.8063 (18) Å
β = 101.35 (3)°
V = 1784.8 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.54 mm⁻¹
T = 293 K
0.21 × 0.19 × 0.16 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.739, T_max = 0.790
7741 measured reflections
2045 independent reflections
1637 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.081
S = 1.05
2045 reflections
114 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6A⋯Cl1ⁱ	0.97	2.65	3.541 (3)	153
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681101333X/ng5145sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681101333X/ng5145Isup2.hkl

checkCIF report

Comment top

N-heterocyclic ligands coordinated with transition metal ions can form a variety of topology structures, including macrocycles, polyhedra and linear and helical polymers. Our group has report three kinds of flexible pyridyl-based ligands in the previous report. As a part of our continuing work for bipyridyl aromatic ligands, we report the crystal structure of the title compound here.

1,2-Bis(pyridin-2-ylmethoxy)benzene molecule act as a chelating ligand to coordinate with Cu^II ion forming a discrete strucutre. Two chlorid counter ions also coordinate to the center Cu^II ion, resulting a sxi-coordinated distorted octahedral geometry environment (Figure 1).

In the crystal, the πi—πi interactions with distance about 3.838 (1) Å, and the C—H···Cl hydrogen bonds link these isolated molecules to form a chain structure along [101] direction (Figure 2, Table 1).

Related literature top

For related structures, see: Zhang et al. (2010a,b).

Experimental top

The 1,2-Bis(pyridin-2-ylmethoxy)benzene was synthesized by the reaction of ο-dihydroxybenzene and 2-chloromethylpyridine hydrochloride under nitrogen atmosphere and alkaline condition (Zhang et al., 2010a). Title ligand (0.58 g, 0.02 mol) and CuCl₂ (0.27 g, 0.02 mol) were dissolved in 15 mL e thanol, and then the mixture keep stirring for 30 minute. The resulting solution was filtered, and the filtrate was allowed to stand in a desiccator at room temperature for several days. Bule needle crystals were obtained with yield 57%.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level for non-H atoms. Symmetry code I: 1 - x, y, 1.5 - z.
	Fig. 2. A partial packing view, showing the chain structure. Dashed lines indicate the hydrogen bonds (green) and πi—πi interactions (blue), no involving H atoms have been omitted for clarity.

[1,2-Bis(pyridin-2-ylmethoxy)benzene- κ⁴N,O,O',N']dichloridocopper(II) top

Crystal data top

[CuCl₂(C₁₈H₁₆N₂O₂)]	F(000) = 868
M_r = 426.77	D_x = 1.588 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6110 reflections
a = 10.624 (2) Å	θ = 3.2–27.5°
b = 19.458 (4) Å	µ = 1.54 mm⁻¹
c = 8.8063 (18) Å	T = 293 K
β = 101.35 (3)°	Block, green
V = 1784.8 (6) Å³	0.21 × 0.19 × 0.16 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	2045 independent reflections
Radiation source: fine-focus sealed tube	1637 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −13→13
T_min = 0.739, T_max = 0.790	k = −25→25
7741 measured reflections	l = −11→9

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0321P)² + 1.5862P] where P = (F_o² + 2F_c²)/3
2045 reflections	(Δ/σ)_max < 0.001
114 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

[CuCl₂(C₁₈H₁₆N₂O₂)]	V = 1784.8 (6) Å³
M_r = 426.77	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 10.624 (2) Å	µ = 1.54 mm⁻¹
b = 19.458 (4) Å	T = 293 K
c = 8.8063 (18) Å	0.21 × 0.19 × 0.16 mm
β = 101.35 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2045 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1637 reflections with I > 2σ(I)
T_min = 0.739, T_max = 0.790	R_int = 0.035
7741 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.081	H-atom parameters constrained
S = 1.05	Δρ_max = 0.31 e Å⁻³
2045 reflections	Δρ_min = −0.23 e Å⁻³
114 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
C1	0.3928 (2)	0.42692 (13)	0.4854 (3)	0.0455 (6)
H1	0.4104	0.4597	0.5635	0.055*
C2	0.3430 (2)	0.44885 (14)	0.3369 (3)	0.0474 (6)
H2	0.3282	0.4953	0.3152	0.057*
C3	0.3159 (2)	0.40034 (14)	0.2217 (3)	0.0480 (6)
H3	0.2825	0.4135	0.1203	0.058*
C4	0.3387 (2)	0.33231 (13)	0.2581 (2)	0.0431 (6)
H4	0.3195	0.2988	0.1817	0.052*
C5	0.3910 (2)	0.31374 (12)	0.4105 (2)	0.0363 (5)
C6	0.4195 (3)	0.24013 (13)	0.4492 (3)	0.0471 (6)
H6A	0.3451	0.2122	0.4074	0.057*
H6B	0.4904	0.2249	0.4031	0.057*
O1	0.4510 (2)	0.23204 (9)	0.60859 (18)	0.0680 (6)
C7	0.4747 (2)	0.16783 (12)	0.6701 (3)	0.0445 (6)
C8	0.4510 (2)	0.10685 (13)	0.5912 (3)	0.0489 (6)
H8	0.4186	0.1067	0.4851	0.059*
C9	0.4759 (3)	0.04561 (14)	0.6716 (3)	0.0555 (7)
H9	0.4600	0.0041	0.6191	0.067*
Cl1	0.69527 (6)	0.35669 (4)	0.68252 (7)	0.0570 (2)
Cu1	0.5000	0.34350 (2)	0.7500	0.03802 (14)
N1	0.41728 (18)	0.36093 (10)	0.52330 (19)	0.0375 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0599 (16)	0.0429 (14)	0.0324 (12)	−0.0005 (11)	0.0060 (10)	0.0007 (10)
C2	0.0516 (15)	0.0499 (15)	0.0402 (13)	0.0055 (12)	0.0078 (10)	0.0116 (11)
C3	0.0450 (14)	0.0692 (18)	0.0282 (12)	0.0031 (12)	0.0033 (9)	0.0103 (11)
C4	0.0443 (14)	0.0569 (16)	0.0265 (10)	−0.0026 (11)	0.0032 (9)	−0.0041 (10)
C5	0.0385 (12)	0.0432 (13)	0.0270 (11)	−0.0039 (10)	0.0059 (8)	−0.0025 (9)
C6	0.0662 (16)	0.0438 (14)	0.0292 (11)	−0.0031 (12)	0.0041 (10)	−0.0045 (10)
O1	0.1351 (19)	0.0334 (10)	0.0290 (9)	0.0025 (10)	0.0000 (9)	−0.0006 (7)
C7	0.0616 (16)	0.0345 (13)	0.0387 (12)	−0.0009 (11)	0.0133 (11)	−0.0010 (9)
C8	0.0631 (16)	0.0415 (14)	0.0444 (14)	−0.0022 (12)	0.0164 (11)	−0.0072 (11)
C9	0.0749 (19)	0.0355 (14)	0.0625 (15)	−0.0039 (12)	0.0287 (14)	−0.0074 (11)
Cl1	0.0554 (4)	0.0796 (5)	0.0357 (3)	0.0167 (3)	0.0081 (3)	0.0120 (3)
Cu1	0.0557 (3)	0.0337 (2)	0.02259 (19)	0.000	0.00265 (15)	0.000
N1	0.0463 (11)	0.0392 (11)	0.0254 (9)	−0.0022 (8)	0.0032 (7)	0.0012 (7)

Geometric parameters (Å, º) top

C1—N1	1.339 (3)	C6—H6B	0.9700
C1—C2	1.379 (3)	O1—C7	1.365 (3)
C1—H1	0.9300	O1—Cu1	2.5040 (18)
C2—C3	1.374 (4)	C7—C8	1.373 (3)
C2—H2	0.9300	C7—C7ⁱ	1.405 (5)
C3—C4	1.372 (4)	C8—C9	1.385 (4)
C3—H3	0.9300	C8—H8	0.9300
C4—C5	1.395 (3)	C9—C9ⁱ	1.375 (5)
C4—H4	0.9300	C9—H9	0.9300
C5—N1	1.341 (3)	Cl1—Cu1	2.2820 (8)
C5—C6	1.490 (3)	Cu1—N1ⁱ	2.0451 (18)
C6—O1	1.386 (3)	Cu1—N1	2.0451 (18)
C6—H6A	0.9700	Cu1—Cl1ⁱ	2.2820 (8)

N1—C1—C2	123.5 (2)	C6—O1—Cu1	112.98 (14)
N1—C1—H1	118.2	O1—C7—C8	126.1 (2)
C2—C1—H1	118.2	O1—C7—C7ⁱ	113.68 (12)
C3—C2—C1	118.2 (2)	C8—C7—C7ⁱ	120.18 (15)
C3—C2—H2	120.9	C7—C8—C9	119.2 (2)
C1—C2—H2	120.9	C7—C8—H8	120.4
C4—C3—C2	119.3 (2)	C9—C8—H8	120.4
C4—C3—H3	120.4	C9ⁱ—C9—C8	120.63 (15)
C2—C3—H3	120.4	C9ⁱ—C9—H9	119.7
C3—C4—C5	119.5 (2)	C8—C9—H9	119.7
C3—C4—H4	120.2	N1ⁱ—Cu1—N1	160.91 (11)
C5—C4—H4	120.2	N1ⁱ—Cu1—Cl1	89.86 (6)
N1—C5—C4	121.4 (2)	N1—Cu1—Cl1	88.01 (6)
N1—C5—C6	119.02 (19)	N1ⁱ—Cu1—Cl1ⁱ	88.01 (6)
C4—C5—C6	119.6 (2)	N1—Cu1—Cl1ⁱ	89.86 (6)
O1—C6—C5	109.80 (19)	Cl1—Cu1—Cl1ⁱ	167.08 (4)
O1—C6—H6A	109.7	N1ⁱ—Cu1—O1	129.53 (7)
C5—C6—H6A	109.7	N1—Cu1—O1	69.56 (7)
O1—C6—H6B	109.7	Cl1—Cu1—O1	94.51 (6)
C5—C6—H6B	109.7	Cl1ⁱ—Cu1—O1	96.67 (6)
H6A—C6—H6B	108.2	C1—N1—C5	118.03 (19)
C7—O1—C6	119.62 (18)	C1—N1—Cu1	115.29 (15)
C7—O1—Cu1	126.26 (14)	C5—N1—Cu1	126.61 (16)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···Cl1ⁱⁱ	0.97	2.65	3.541 (3)	153

Symmetry code: (ii) x−1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[CuCl₂(C₁₈H₁₆N₂O₂)]
M_r	426.77
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	10.624 (2), 19.458 (4), 8.8063 (18)
β (°)	101.35 (3)
V (Å³)	1784.8 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.54
Crystal size (mm)	0.21 × 0.19 × 0.16

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.739, 0.790
No. of measured, independent and observed [I > 2σ(I)] reflections	7741, 2045, 1637
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.081, 1.05
No. of reflections	2045
No. of parameters	114
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.23

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), 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
C6—H6A···Cl1ⁱ	0.97	2.65	3.541 (3)	153.2

Symmetry code: (i) x−1/2, −y+1/2, z−1/2.

Acknowledgements

The authors thank the Special Funds for the Research of Scientific and Technological Innovative Talents of Harbin Municipal Science and Technology Bureau (2009RFXXG027), the Science and Technology Planning Project of Heilongjiang Province (GZ08A401) and Heilongjiang University for supporting this study.

References

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, S., Wang, Y.-J., Ma, D.-S., Liu, Y. & Gao, J.-S. (2010a). Acta Cryst. E66, m701. Web of Science CSD CrossRef IUCr Journals Google Scholar
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