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Acta Crystallogr Sect E Struct Rep Online. 2008 November 1; 64(Pt 11): m1467.
Published online 2008 October 31. doi:  10.1107/S1600536808034612
PMCID: PMC2959670

Dichlorido[2,2′-(oxydimethyl­ene)dipyridine]copper(II)

Abstract

In the title complex, [CuCl2(C12H12N2O)], the CuII ion is coordinated in a distorted trigonal-bipyramidal environment. In the crystal structure, there is a weak π–π stacking inter­action between symmetry-related pyridine rings, with a centroid-to-centroid distance of 3.8134 (17) Å. In addition, there is relatively close contact between the pyridine ring π-system and a symmetry-related CuII ion (Cu(...)centroid distance of 3.868 Å).

Related literature

For the isotypic Cd and Zn analogs of the title compound, see: Li (2007 [triangle]) and Li (2008 [triangle]), respectively.

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Object name is e-64-m1467-scheme1.jpg

Experimental

Crystal data

  • [CuCl2(C12H12N2O)]
  • M r = 334.68
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1467-efi1.jpg
  • a = 8.1599 (10) Å
  • b = 12.5534 (15) Å
  • c = 15.3846 (14) Å
  • β = 123.574 (9)°
  • V = 1313.0 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.06 mm−1
  • T = 298 (2) K
  • 0.46 × 0.40 × 0.34 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.451, T max = 0.541 (expected range = 0.414–0.497)
  • 5381 measured reflections
  • 2323 independent reflections
  • 2152 reflections with I > 2σ(I)
  • R int = 0.016

Refinement

  • R[F 2 > 2σ(F 2)] = 0.024
  • wR(F 2) = 0.066
  • S = 1.09
  • 2323 reflections
  • 163 parameters
  • H-atom parameters constrained
  • Δρmax = 0.33 e Å−3
  • Δρmin = −0.27 e Å−3

Data collection: SMART (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808034612/lh2712sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808034612/lh2712Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

2,2'-[oxydi(methylene)]dipyridine is an useful tridentate terminal ligand and the CdII complex with it as ligand has already been published (Li, 2007). Herein the crystal structure of the title complex, (I), is reported.

The molecular structure of (I) is shown in Fig. 1. The atom Cu1 is coordinated in a distorted trigonal-bipyramidal environment (Table 1). In the crystal structure, there is a weak π-π stacking interaction between symmetry related pyridyl rings, with the relevant distances being Cg1···Cg1i = 3.8134 (17) Å and a perpendicular distance of 3.556 Å [symmetry code (i) -x, 2 - y, -z; Cg1 is the centroid of the N1/C2—C6 ring]. In addition, there is close contact between a π-ring system and symmetry related Cu atom, with the relative distances being: Cg2···Cu1ii = 3.868 Å, Cg2perp···Cu1ii = 3.635 Å [symmetry code: (ii) -x, 1 - y, -z; Cg2 is the centroid of the N2/C8—C12 ring; Cg2perp···Cu1ii is the perpendicular distance from Cu1ii to N2/C8—C12 ring]. The title compound is isostructural with the Cadmium analog (Li, 2007) although the Cd analog was solved and refined in the non-standard P21/n setting of space group P21/c.

Experimental

6 ml me thanol solution of 2,2'-[oxydi(methylene)]dipyridine (0.0418 g, 0.209 mmol) was added into 8 ml H2O solution containing CuCl2.2H2O (0.0362 g, 0.212 mmol), and the mixed soulution was stirred for a few minutes. The green single crystals were obtained after the solution had been allowed to stand at room temperature for two weeks.

Refinement

All H atoms were placed in calculated positions and refined as riding, C—H = 0.93–0.97 Å, with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
View of complex (I), showing the the atom numbering scheme with thermal ellipsoids drawn at the 30% probability level

Crystal data

[CuCl2(C12H12N2O)]F(000) = 676
Mr = 334.68Dx = 1.693 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4907 reflections
a = 8.1599 (10) Åθ = 2.3–28.3°
b = 12.5534 (15) ŵ = 2.06 mm1
c = 15.3846 (14) ÅT = 298 K
β = 123.574 (9)°Block, green
V = 1313.0 (3) Å30.46 × 0.40 × 0.34 mm
Z = 4

Data collection

Bruker SMART APEX CCD diffractometer2323 independent reflections
Radiation source: fine-focus sealed tube2152 reflections with I > 2σ(I)
graphiteRint = 0.016
[var phi] and ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −9→9
Tmin = 0.451, Tmax = 0.541k = −11→14
5381 measured reflectionsl = −18→13

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.024Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066H-atom parameters constrained
S = 1.09w = 1/[σ2(Fo2) + (0.0361P)2 + 0.5176P] where P = (Fo2 + 2Fc2)/3
2323 reflections(Δ/σ)max = 0.001
163 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = −0.27 e Å3

Special details

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)

xyzUiso*/Ueq
C1−0.0360 (3)0.76246 (18)−0.10853 (17)0.0407 (5)
H1A−0.14990.7554−0.17950.049*
H1B0.06870.7967−0.11030.049*
C2−0.0341 (4)0.8555 (2)0.1167 (2)0.0481 (6)
H20.02970.83720.18680.058*
C3−0.1666 (4)0.9378 (2)0.0794 (2)0.0576 (7)
H3−0.19090.97500.12350.069*
C4−0.2628 (4)0.9644 (2)−0.0242 (2)0.0604 (7)
H4−0.35321.0200−0.05160.072*
C5−0.2232 (4)0.9072 (2)−0.0868 (2)0.0507 (6)
H5−0.28820.9231−0.15740.061*
C6−0.0864 (3)0.82611 (17)−0.04415 (17)0.0357 (5)
C70.1210 (3)0.59462 (18)−0.09417 (16)0.0369 (5)
H7A0.20930.6368−0.10390.044*
H7B0.02430.5614−0.16010.044*
C80.2343 (3)0.51119 (17)−0.01249 (15)0.0320 (4)
C90.3812 (3)0.46002 (18)0.15917 (17)0.0368 (5)
H90.40900.47350.22550.044*
C100.4063 (3)0.34591 (18)0.0442 (2)0.0427 (5)
H100.45070.28360.03110.051*
C110.2964 (3)0.41864 (18)−0.03445 (18)0.0405 (5)
H110.26450.4055−0.10160.049*
C120.4491 (3)0.36715 (19)0.14218 (19)0.0420 (5)
H120.52310.31930.19650.050*
Cl10.46540 (8)0.76638 (5)0.12142 (4)0.04202 (15)
Cl20.20944 (9)0.63873 (5)0.25169 (4)0.04202 (15)
Cu10.18810 (4)0.673873 (19)0.102078 (18)0.03121 (10)
N10.0076 (3)0.80023 (14)0.05709 (14)0.0359 (4)
N20.2764 (2)0.53190 (13)0.08332 (13)0.0310 (4)
O10.0261 (2)0.66050 (11)−0.05971 (11)0.0324 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0432 (12)0.0411 (13)0.0352 (11)0.0067 (10)0.0201 (10)0.0108 (10)
C20.0580 (15)0.0417 (13)0.0490 (14)0.0070 (12)0.0323 (12)−0.0021 (11)
C30.0632 (17)0.0426 (14)0.0748 (19)0.0087 (13)0.0430 (16)−0.0074 (13)
C40.0536 (15)0.0377 (14)0.086 (2)0.0142 (12)0.0366 (15)0.0069 (14)
C50.0452 (13)0.0427 (14)0.0552 (15)0.0097 (11)0.0221 (12)0.0123 (12)
C60.0320 (11)0.0316 (11)0.0395 (12)0.0005 (8)0.0173 (10)0.0059 (9)
C70.0425 (12)0.0396 (12)0.0326 (11)−0.0007 (10)0.0232 (10)−0.0024 (9)
C80.0300 (10)0.0321 (11)0.0352 (10)−0.0050 (8)0.0189 (9)−0.0044 (9)
C90.0341 (11)0.0374 (12)0.0345 (11)0.0015 (9)0.0162 (9)0.0023 (9)
C100.0391 (12)0.0308 (11)0.0646 (16)0.0000 (9)0.0327 (12)−0.0045 (11)
C110.0420 (12)0.0394 (13)0.0470 (13)−0.0066 (10)0.0290 (11)−0.0112 (10)
C120.0355 (11)0.0354 (12)0.0523 (14)0.0047 (10)0.0225 (11)0.0072 (10)
Cl10.0417 (3)0.0411 (3)0.0482 (3)−0.0068 (2)0.0279 (3)−0.0045 (2)
Cl20.0550 (3)0.0420 (3)0.0353 (3)−0.0009 (3)0.0289 (3)0.0015 (2)
Cu10.03650 (16)0.02880 (16)0.02902 (15)0.00285 (10)0.01855 (12)0.00079 (9)
N10.0363 (10)0.0307 (9)0.0402 (10)0.0028 (8)0.0209 (8)0.0014 (8)
N20.0314 (8)0.0288 (9)0.0325 (9)−0.0017 (7)0.0175 (7)−0.0023 (7)
O10.0341 (8)0.0336 (8)0.0286 (7)0.0023 (6)0.0168 (6)0.0025 (6)

Geometric parameters (Å, °)

C1—O11.428 (3)C7—H7B0.9700
C1—C61.496 (3)C8—N21.341 (3)
C1—H1A0.9700C8—C111.382 (3)
C1—H1B0.9700C9—N21.343 (3)
C2—N11.336 (3)C9—C121.376 (3)
C2—C31.372 (4)C9—H90.9300
C2—H20.9300C10—C121.372 (4)
C3—C41.373 (4)C10—C111.379 (3)
C3—H30.9300C10—H100.9300
C4—C51.375 (4)C11—H110.9300
C4—H40.9300C12—H120.9300
C5—C61.379 (3)Cl1—Cu12.4109 (6)
C5—H50.9300Cl2—Cu12.2538 (6)
C6—N11.341 (3)Cu1—N22.0021 (17)
C7—O11.421 (3)Cu1—N12.0092 (18)
C7—C81.499 (3)Cu1—O12.0813 (14)
C7—H7A0.9700
O1—C1—C6106.14 (17)N2—C9—H9118.9
O1—C1—H1A110.5C12—C9—H9118.9
C6—C1—H1A110.5C12—C10—C11118.8 (2)
O1—C1—H1B110.5C12—C10—H10120.6
C6—C1—H1B110.5C11—C10—H10120.6
H1A—C1—H1B108.7C10—C11—C8119.4 (2)
N1—C2—C3123.0 (2)C10—C11—H11120.3
N1—C2—H2118.5C8—C11—H11120.3
C3—C2—H2118.5C10—C12—C9119.3 (2)
C2—C3—C4118.8 (3)C10—C12—H12120.4
C2—C3—H3120.6C9—C12—H12120.4
C4—C3—H3120.6N2—Cu1—N1155.06 (7)
C3—C4—C5118.8 (2)N2—Cu1—O178.29 (6)
C3—C4—H4120.6N1—Cu1—O177.99 (7)
C5—C4—H4120.6N2—Cu1—Cl298.17 (5)
C4—C5—C6119.6 (2)N1—Cu1—Cl297.71 (6)
C4—C5—H5120.2O1—Cu1—Cl2147.65 (4)
C6—C5—H5120.2N2—Cu1—Cl193.36 (5)
N1—C6—C5121.6 (2)N1—Cu1—Cl196.97 (6)
N1—C6—C1116.70 (18)O1—Cu1—Cl196.81 (4)
C5—C6—C1121.7 (2)Cl2—Cu1—Cl1115.53 (2)
O1—C7—C8107.73 (16)C2—N1—C6118.2 (2)
O1—C7—H7A110.2C2—N1—Cu1126.14 (16)
C8—C7—H7A110.2C6—N1—Cu1115.53 (15)
O1—C7—H7B110.2C8—N2—C9118.52 (18)
C8—C7—H7B110.2C8—N2—Cu1115.92 (14)
H7A—C7—H7B108.5C9—N2—Cu1125.45 (14)
N2—C8—C11121.7 (2)C7—O1—C1115.70 (16)
N2—C8—C7116.77 (18)C7—O1—Cu1112.11 (12)
C11—C8—C7121.47 (19)C1—O1—Cu1111.27 (12)
N2—C9—C12122.3 (2)
N1—C2—C3—C40.7 (4)Cl1—Cu1—N1—C681.62 (15)
C2—C3—C4—C50.2 (4)C11—C8—N2—C9−0.2 (3)
C3—C4—C5—C6−1.0 (4)C7—C8—N2—C9−178.63 (18)
C4—C5—C6—N11.0 (4)C11—C8—N2—Cu1176.38 (15)
C4—C5—C6—C1−179.2 (2)C7—C8—N2—Cu1−2.1 (2)
O1—C1—C6—N127.4 (3)C12—C9—N2—C81.0 (3)
O1—C1—C6—C5−152.4 (2)C12—C9—N2—Cu1−175.19 (16)
O1—C7—C8—N2−20.0 (2)N1—Cu1—N2—C833.8 (2)
O1—C7—C8—C11161.56 (18)O1—Cu1—N2—C815.52 (14)
C12—C10—C11—C80.7 (3)Cl2—Cu1—N2—C8162.86 (13)
N2—C8—C11—C10−0.7 (3)Cl1—Cu1—N2—C8−80.74 (14)
C7—C8—C11—C10177.7 (2)N1—Cu1—N2—C9−149.93 (18)
C11—C10—C12—C90.1 (3)O1—Cu1—N2—C9−168.19 (18)
N2—C9—C12—C10−1.0 (3)Cl2—Cu1—N2—C9−20.85 (17)
C3—C2—N1—C6−0.7 (4)Cl1—Cu1—N2—C995.55 (17)
C3—C2—N1—Cu1−176.6 (2)C8—C7—O1—C1160.80 (17)
C5—C6—N1—C2−0.1 (3)C8—C7—O1—Cu131.76 (19)
C1—C6—N1—C2−180.0 (2)C6—C1—O1—C7−166.95 (17)
C5—C6—N1—Cu1176.21 (18)C6—C1—O1—Cu1−37.49 (19)
C1—C6—N1—Cu1−3.6 (2)N2—Cu1—O1—C7−26.88 (13)
N2—Cu1—N1—C2143.8 (2)N1—Cu1—O1—C7160.88 (14)
O1—Cu1—N1—C2162.1 (2)Cl2—Cu1—O1—C7−113.67 (13)
Cl2—Cu1—N1—C214.7 (2)Cl1—Cu1—O1—C765.17 (13)
Cl1—Cu1—N1—C2−102.4 (2)N2—Cu1—O1—C1−158.20 (14)
N2—Cu1—N1—C6−32.2 (3)N1—Cu1—O1—C129.56 (14)
O1—Cu1—N1—C6−13.90 (15)Cl2—Cu1—O1—C1115.01 (13)
Cl2—Cu1—N1—C6−161.33 (15)Cl1—Cu1—O1—C1−66.16 (13)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH2712).

References

  • Bruker (2007). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Li, J. M. (2007). Acta Cryst. E63, m2241. [PMC free article] [PubMed]
  • Li, J. M. (2008). Acta Cryst. E64, m1468. [PMC free article] [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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