metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

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 CuII 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, ππ 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[Zhang, S., Wang, Y.-J., Ma, D.-S., Liu, Y. & Gao, J.-S. (2010a). Acta Cryst. E66, m701.],b[Zhang, S., Wang, Y.-J., Ma, D.-S., Liu, Y. & Gao, J.-S. (2010b). Acta Cryst. E66, m787.]).

[Scheme 1]

Experimental

Crystal data
  • [CuCl2(C18H16N2O2)]

  • Mr = 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[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.739, Tmax = 0.790

  • 7741 measured reflections

  • 2045 independent reflections

  • 1637 reflections with I > 2σ(I)

  • Rint = 0.035

Refinement
  • R[F2 > 2σ(F2)] = 0.034

  • wR(F2) = 0.081

  • S = 1.05

  • 2045 reflections

  • 114 parameters

  • H-atom parameters constrained

  • Δρmax = 0.31 e Å−3

  • Δρmin = −0.23 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002[Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


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 CuII ion forming a discrete strucutre. Two chlorid counter ions also coordinate to the center CuII 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%.

Refinement top

H atoms bound to C atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å (aromatic C), C—H = 0.97 Å (methene C), and with Uiso(H) = 1.2Ueq(C).

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
[Figure 1] 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.
[Figure 2] 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
Mr = 426.77Dx = 1.588 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 6110 reflections
a = 10.624 (2) Åθ = 3.2–27.5°
b = 19.458 (4) ŵ = 1.54 mm1
c = 8.8063 (18) ÅT = 293 K
β = 101.35 (3)°Block, green
V = 1784.8 (6) Å30.21 × 0.19 × 0.16 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer
2045 independent reflections
Radiation source: fine-focus sealed tube1637 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
ω scansθmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 1313
Tmin = 0.739, Tmax = 0.790k = 2525
7741 measured reflectionsl = 119
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0321P)2 + 1.5862P]
where P = (Fo2 + 2Fc2)/3
2045 reflections(Δ/σ)max < 0.001
114 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
[CuCl2(C18H16N2O2)]V = 1784.8 (6) Å3
Mr = 426.77Z = 4
Monoclinic, C2/cMo Kα radiation
a = 10.624 (2) ŵ = 1.54 mm1
b = 19.458 (4) ÅT = 293 K
c = 8.8063 (18) Å0.21 × 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)
Tmin = 0.739, Tmax = 0.790Rint = 0.035
7741 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.081H-atom parameters constrained
S = 1.05Δρmax = 0.31 e Å3
2045 reflectionsΔρmin = 0.23 e Å3
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
xyzUiso*/Ueq
C10.3928 (2)0.42692 (13)0.4854 (3)0.0455 (6)
H10.41040.45970.56350.055*
C20.3430 (2)0.44885 (14)0.3369 (3)0.0474 (6)
H20.32820.49530.31520.057*
C30.3159 (2)0.40034 (14)0.2217 (3)0.0480 (6)
H30.28250.41350.12030.058*
C40.3387 (2)0.33231 (13)0.2581 (2)0.0431 (6)
H40.31950.29880.18170.052*
C50.3910 (2)0.31374 (12)0.4105 (2)0.0363 (5)
C60.4195 (3)0.24013 (13)0.4492 (3)0.0471 (6)
H6A0.34510.21220.40740.057*
H6B0.49040.22490.40310.057*
O10.4510 (2)0.23204 (9)0.60859 (18)0.0680 (6)
C70.4747 (2)0.16783 (12)0.6701 (3)0.0445 (6)
C80.4510 (2)0.10685 (13)0.5912 (3)0.0489 (6)
H80.41860.10670.48510.059*
C90.4759 (3)0.04561 (14)0.6716 (3)0.0555 (7)
H90.46000.00410.61910.067*
Cl10.69527 (6)0.35669 (4)0.68252 (7)0.0570 (2)
Cu10.50000.34350 (2)0.75000.03802 (14)
N10.41728 (18)0.36093 (10)0.52330 (19)0.0375 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0599 (16)0.0429 (14)0.0324 (12)0.0005 (11)0.0060 (10)0.0007 (10)
C20.0516 (15)0.0499 (15)0.0402 (13)0.0055 (12)0.0078 (10)0.0116 (11)
C30.0450 (14)0.0692 (18)0.0282 (12)0.0031 (12)0.0033 (9)0.0103 (11)
C40.0443 (14)0.0569 (16)0.0265 (10)0.0026 (11)0.0032 (9)0.0041 (10)
C50.0385 (12)0.0432 (13)0.0270 (11)0.0039 (10)0.0059 (8)0.0025 (9)
C60.0662 (16)0.0438 (14)0.0292 (11)0.0031 (12)0.0041 (10)0.0045 (10)
O10.1351 (19)0.0334 (10)0.0290 (9)0.0025 (10)0.0000 (9)0.0006 (7)
C70.0616 (16)0.0345 (13)0.0387 (12)0.0009 (11)0.0133 (11)0.0010 (9)
C80.0631 (16)0.0415 (14)0.0444 (14)0.0022 (12)0.0164 (11)0.0072 (11)
C90.0749 (19)0.0355 (14)0.0625 (15)0.0039 (12)0.0287 (14)0.0074 (11)
Cl10.0554 (4)0.0796 (5)0.0357 (3)0.0167 (3)0.0081 (3)0.0120 (3)
Cu10.0557 (3)0.0337 (2)0.02259 (19)0.0000.00265 (15)0.000
N10.0463 (11)0.0392 (11)0.0254 (9)0.0022 (8)0.0032 (7)0.0012 (7)
Geometric parameters (Å, º) top
C1—N11.339 (3)C6—H6B0.9700
C1—C21.379 (3)O1—C71.365 (3)
C1—H10.9300O1—Cu12.5040 (18)
C2—C31.374 (4)C7—C81.373 (3)
C2—H20.9300C7—C7i1.405 (5)
C3—C41.372 (4)C8—C91.385 (4)
C3—H30.9300C8—H80.9300
C4—C51.395 (3)C9—C9i1.375 (5)
C4—H40.9300C9—H90.9300
C5—N11.341 (3)Cl1—Cu12.2820 (8)
C5—C61.490 (3)Cu1—N1i2.0451 (18)
C6—O11.386 (3)Cu1—N12.0451 (18)
C6—H6A0.9700Cu1—Cl1i2.2820 (8)
N1—C1—C2123.5 (2)C6—O1—Cu1112.98 (14)
N1—C1—H1118.2O1—C7—C8126.1 (2)
C2—C1—H1118.2O1—C7—C7i113.68 (12)
C3—C2—C1118.2 (2)C8—C7—C7i120.18 (15)
C3—C2—H2120.9C7—C8—C9119.2 (2)
C1—C2—H2120.9C7—C8—H8120.4
C4—C3—C2119.3 (2)C9—C8—H8120.4
C4—C3—H3120.4C9i—C9—C8120.63 (15)
C2—C3—H3120.4C9i—C9—H9119.7
C3—C4—C5119.5 (2)C8—C9—H9119.7
C3—C4—H4120.2N1i—Cu1—N1160.91 (11)
C5—C4—H4120.2N1i—Cu1—Cl189.86 (6)
N1—C5—C4121.4 (2)N1—Cu1—Cl188.01 (6)
N1—C5—C6119.02 (19)N1i—Cu1—Cl1i88.01 (6)
C4—C5—C6119.6 (2)N1—Cu1—Cl1i89.86 (6)
O1—C6—C5109.80 (19)Cl1—Cu1—Cl1i167.08 (4)
O1—C6—H6A109.7N1i—Cu1—O1129.53 (7)
C5—C6—H6A109.7N1—Cu1—O169.56 (7)
O1—C6—H6B109.7Cl1—Cu1—O194.51 (6)
C5—C6—H6B109.7Cl1i—Cu1—O196.67 (6)
H6A—C6—H6B108.2C1—N1—C5118.03 (19)
C7—O1—C6119.62 (18)C1—N1—Cu1115.29 (15)
C7—O1—Cu1126.26 (14)C5—N1—Cu1126.61 (16)
Symmetry code: (i) x+1, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6A···Cl1ii0.972.653.541 (3)153
Symmetry code: (ii) x1/2, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formula[CuCl2(C18H16N2O2)]
Mr426.77
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)10.624 (2), 19.458 (4), 8.8063 (18)
β (°) 101.35 (3)
V3)1784.8 (6)
Z4
Radiation typeMo Kα
µ (mm1)1.54
Crystal size (mm)0.21 × 0.19 × 0.16
Data collection
DiffractometerRigaku R-AXIS RAPID
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.739, 0.790
No. of measured, independent and
observed [I > 2σ(I)] reflections
7741, 2045, 1637
Rint0.035
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.081, 1.05
No. of reflections2045
No. of parameters114
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
C6—H6A···Cl1i0.972.653.541 (3)153.2
Symmetry code: (i) x1/2, y+1/2, z1/2.
 

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

First citationHigashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationZhang, 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
First citationZhang, S., Wang, Y.-J., Ma, D.-S., Liu, Y. & Gao, J.-S. (2010b). Acta Cryst. E66, m787.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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ISSN: 2056-9890
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