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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): m1690.
Published online 2009 November 28. doi:  10.1107/S1600536809050041
PMCID: PMC2972063

Tetra-μ-acetato-κ8 O:O′-bis­{[2-(m-tolyl­amino)pyridine-κN]copper(II)}

Abstract

In the crystal structure of the title compound, [Cu2(C2H3O2)4(C12H12N2)2], the binuclear mol­ecule lies about a center of inversion; the four acetate groups each bridge a pair of CuII atoms. The coordination of the metal atom is distorted square-pyramidal, with the bonding O atoms comprising a square basal plane and the coordinating N atom of the N-heterocycle occupying the apical position. The pyridine ring is twisted with respect to the benzene ring at a dihedral angle of 45.68 (16)°. Intra­molecular N—H(...)O hydrogen bonding is present between the imino and carb­oxy groups.

Related literature

There are many examples of tetra­kisacetatobis[(substituted pyridine)copper] complexes. For examples of 2-amino­pyridyl derivatives, see: Barquín et al. (2004 [triangle]); Seco et al. (2004 [triangle]); Sieroń (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-m1690-scheme1.jpg

Experimental

Crystal data

  • [Cu2(C2H3O2)4(C12H12N2)2]
  • M r = 731.73
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1690-efi1.jpg
  • a = 7.7143 (2) Å
  • b = 10.5625 (3) Å
  • c = 11.2413 (3) Å
  • α = 66.531 (2)°
  • β = 85.740 (2)°
  • γ = 78.568 (2)°
  • V = 823.51 (4) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 1.35 mm−1
  • T = 293 K
  • 0.25 × 0.15 × 0.05 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.730, T max = 0.936
  • 6451 measured reflections
  • 3678 independent reflections
  • 2915 reflections with I > 2σ(I)
  • R int = 0.023

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.098
  • S = 1.07
  • 3678 reflections
  • 211 parameters
  • H-atom parameters constrained
  • Δρmax = 0.49 e Å−3
  • Δρmin = −0.59 e Å−3

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809050041/xu2688sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809050041/xu2688Isup2.hkl

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

Acknowledgments

We thank the University of Malaya (grant No. RG027/09AFR, PS374/09 A) for supporting this study.

supplementary crystallographic information

Experimental

Copper acetate (0.1 g, 0.5 mmol) was dissolved in acetonitrile (5 ml). The solution was mixed with a solution of 3-tolylamino-2-pyridine (0.2 g, 1.1 mmol) dissolved in acetonitrile (15 ml). The green precipitate that formed was recrystallized from acetonitrile.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C–H 0.93–0.96 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2–1.5U(C). The amino H-atom was similarly treated.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of Cu2(C2H3O2)4(C12H12N2)2 at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. Dashed lines indicate the hydrogen bonding.

Crystal data

[Cu2(C2H3O2)4(C12H12N2)2]Z = 1
Mr = 731.73F(000) = 378
Triclinic, P1Dx = 1.475 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.7143 (2) ÅCell parameters from 2561 reflections
b = 10.5625 (3) Åθ = 2.3–27.6°
c = 11.2413 (3) ŵ = 1.35 mm1
α = 66.531 (2)°T = 293 K
β = 85.740 (2)°Prism, green
γ = 78.568 (2)°0.25 × 0.15 × 0.05 mm
V = 823.51 (4) Å3

Data collection

Bruker SMART APEX diffractometer3678 independent reflections
Radiation source: fine-focus sealed tube2915 reflections with I > 2σ(I)
graphiteRint = 0.023
ω scansθmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −10→9
Tmin = 0.730, Tmax = 0.936k = −13→13
6451 measured reflectionsl = −14→14

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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H-atom parameters constrained
S = 1.07w = 1/[σ2(Fo2) + (0.0426P)2 + 0.4239P] where P = (Fo2 + 2Fc2)/3
3678 reflections(Δ/σ)max = 0.001
211 parametersΔρmax = 0.49 e Å3
0 restraintsΔρmin = −0.59 e Å3

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

xyzUiso*/Ueq
Cu10.58894 (4)0.46743 (4)0.60797 (3)0.03044 (12)
O10.6955 (3)0.6324 (2)0.50147 (18)0.0439 (5)
O20.5505 (3)0.6857 (2)0.31997 (18)0.0419 (5)
O30.7582 (3)0.3494 (2)0.53769 (19)0.0460 (5)
O40.6100 (3)0.4052 (2)0.35536 (19)0.0436 (5)
N10.7506 (3)0.4120 (2)0.7806 (2)0.0304 (5)
N20.5409 (3)0.3175 (3)0.9254 (2)0.0446 (6)
H20.47710.34360.85730.053*
C10.6579 (4)0.7076 (3)0.3856 (3)0.0342 (6)
C20.7467 (5)0.8317 (4)0.3197 (3)0.0570 (9)
H2A0.84480.82370.37170.085*
H2B0.66370.91620.30910.085*
H2C0.78850.83460.23630.085*
C30.7354 (4)0.3375 (3)0.4329 (3)0.0378 (6)
C40.8709 (5)0.2335 (4)0.4000 (3)0.0578 (9)
H4A0.91750.15730.47840.087*
H4B0.96520.27870.35200.087*
H4C0.81690.19790.34850.087*
C50.9143 (4)0.4436 (3)0.7539 (3)0.0389 (7)
H50.94710.48350.66750.047*
C61.0348 (4)0.4198 (3)0.8479 (3)0.0438 (7)
H61.14540.44460.82590.053*
C70.9871 (4)0.3582 (3)0.9752 (3)0.0403 (7)
H71.06620.34001.04110.048*
C80.8228 (4)0.3236 (3)1.0051 (3)0.0395 (7)
H80.78960.28171.09120.047*
C90.7059 (3)0.3518 (3)0.9053 (2)0.0309 (6)
C100.4629 (4)0.2444 (3)1.0447 (2)0.0339 (6)
C110.3760 (4)0.1388 (3)1.0512 (3)0.0365 (6)
H110.37850.11490.97990.044*
C120.2858 (4)0.0682 (3)1.1613 (3)0.0417 (7)
C130.2886 (5)0.1024 (4)1.2678 (3)0.0513 (8)
H130.23270.05391.34400.062*
C140.3736 (5)0.2078 (4)1.2618 (3)0.0522 (8)
H140.37340.23021.33390.063*
C150.4592 (4)0.2808 (3)1.1506 (3)0.0420 (7)
H150.51370.35331.14680.050*
C160.1823 (5)−0.0390 (4)1.1628 (4)0.0658 (10)
H16A0.2210−0.06851.09320.099*
H16B0.05870.00161.15220.099*
H16C0.2012−0.11871.24400.099*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cu10.02917 (19)0.0399 (2)0.02439 (17)−0.01136 (14)0.00032 (12)−0.01252 (14)
O10.0492 (13)0.0523 (13)0.0312 (10)−0.0263 (10)−0.0027 (9)−0.0090 (9)
O20.0452 (12)0.0516 (13)0.0325 (10)−0.0246 (10)−0.0018 (9)−0.0125 (9)
O30.0414 (12)0.0601 (14)0.0384 (11)−0.0004 (10)−0.0021 (9)−0.0250 (10)
O40.0412 (12)0.0558 (13)0.0376 (11)−0.0023 (10)−0.0020 (9)−0.0251 (10)
N10.0282 (12)0.0365 (13)0.0277 (11)−0.0101 (10)−0.0003 (9)−0.0118 (10)
N20.0374 (14)0.0714 (18)0.0249 (11)−0.0241 (13)−0.0002 (10)−0.0123 (12)
C10.0330 (15)0.0411 (16)0.0309 (14)−0.0141 (12)0.0046 (11)−0.0138 (12)
C20.065 (2)0.058 (2)0.0484 (19)−0.0362 (19)−0.0014 (16)−0.0094 (16)
C30.0370 (16)0.0418 (17)0.0353 (15)−0.0110 (13)0.0082 (12)−0.0154 (13)
C40.058 (2)0.062 (2)0.051 (2)0.0063 (18)0.0032 (16)−0.0289 (18)
C50.0349 (16)0.0487 (18)0.0323 (14)−0.0123 (14)0.0022 (12)−0.0133 (13)
C60.0298 (15)0.0532 (19)0.0489 (18)−0.0094 (14)−0.0038 (13)−0.0191 (15)
C70.0344 (16)0.0476 (18)0.0387 (16)−0.0007 (13)−0.0117 (12)−0.0179 (14)
C80.0398 (17)0.0489 (18)0.0277 (14)−0.0074 (14)−0.0039 (12)−0.0125 (13)
C90.0293 (14)0.0353 (15)0.0289 (13)−0.0068 (11)−0.0014 (10)−0.0129 (11)
C100.0299 (14)0.0421 (16)0.0272 (13)−0.0056 (12)0.0013 (10)−0.0117 (12)
C110.0327 (15)0.0406 (16)0.0362 (15)−0.0027 (12)0.0003 (11)−0.0171 (13)
C120.0366 (16)0.0317 (16)0.0494 (18)−0.0040 (13)0.0041 (13)−0.0100 (13)
C130.052 (2)0.055 (2)0.0358 (16)−0.0099 (16)0.0131 (14)−0.0090 (15)
C140.058 (2)0.068 (2)0.0357 (16)−0.0142 (18)0.0102 (14)−0.0261 (16)
C150.0450 (18)0.0476 (18)0.0385 (16)−0.0129 (15)0.0054 (13)−0.0210 (14)
C160.065 (3)0.047 (2)0.080 (3)−0.0220 (19)0.006 (2)−0.0163 (19)

Geometric parameters (Å, °)

Cu1—O11.9762 (19)C4—H4C0.9600
Cu1—O2i1.9866 (19)C5—C61.372 (4)
Cu1—O31.967 (2)C5—H50.9300
Cu1—O4i1.966 (2)C6—C71.372 (4)
Cu1—N12.197 (2)C6—H60.9300
Cu1—Cu1i2.6532 (6)C7—C81.370 (4)
O1—C11.246 (3)C7—H70.9300
O2—C11.259 (3)C8—C91.393 (4)
O2—Cu1i1.9866 (19)C8—H80.9300
O3—C31.261 (3)C10—C111.387 (4)
O4—C31.250 (4)C10—C151.385 (4)
O4—Cu1i1.966 (2)C11—C121.384 (4)
N1—C91.339 (3)C11—H110.9300
N1—C51.352 (3)C12—C131.385 (4)
N2—C91.370 (3)C12—C161.503 (4)
N2—C101.413 (3)C13—C141.377 (5)
N2—H20.8600C13—H130.9300
C1—C21.498 (4)C14—C151.380 (4)
C2—H2A0.9600C14—H140.9300
C2—H2B0.9600C15—H150.9300
C2—H2C0.9600C16—H16A0.9600
C3—C41.500 (4)C16—H16B0.9600
C4—H4A0.9600C16—H16C0.9600
C4—H4B0.9600
O4i—Cu1—O3167.64 (8)H4A—C4—H4C109.5
O4i—Cu1—O188.77 (9)H4B—C4—H4C109.5
O3—Cu1—O190.33 (9)N1—C5—C6123.4 (3)
O4i—Cu1—O2i89.16 (9)N1—C5—H5118.3
O3—Cu1—O2i89.01 (9)C6—C5—H5118.3
O1—Cu1—O2i167.27 (8)C5—C6—C7118.1 (3)
O4i—Cu1—N198.40 (8)C5—C6—H6121.0
O3—Cu1—N193.96 (8)C7—C6—H6121.0
O1—Cu1—N194.60 (8)C8—C7—C6119.8 (3)
O2i—Cu1—N198.13 (8)C8—C7—H7120.1
O4i—Cu1—Cu1i84.47 (6)C6—C7—H7120.1
O3—Cu1—Cu1i83.19 (6)C7—C8—C9119.3 (3)
O1—Cu1—Cu1i83.69 (6)C7—C8—H8120.3
O2i—Cu1—Cu1i83.61 (6)C9—C8—H8120.3
N1—Cu1—Cu1i176.65 (6)N1—C9—N2115.0 (2)
C1—O1—Cu1124.57 (18)N1—C9—C8121.4 (2)
C1—O2—Cu1i123.80 (18)N2—C9—C8123.6 (2)
C3—O3—Cu1124.0 (2)C11—C10—C15119.4 (3)
C3—O4—Cu1i122.82 (18)C11—C10—N2117.7 (2)
C9—N1—C5118.0 (2)C15—C10—N2122.7 (3)
C9—N1—Cu1127.85 (17)C10—C11—C12121.6 (3)
C5—N1—Cu1114.18 (17)C10—C11—H11119.2
C9—N2—C10127.9 (2)C12—C11—H11119.2
C9—N2—H2116.1C13—C12—C11118.2 (3)
C10—N2—H2116.1C13—C12—C16121.2 (3)
O1—C1—O2124.3 (2)C11—C12—C16120.6 (3)
O1—C1—C2117.9 (2)C14—C13—C12120.5 (3)
O2—C1—C2117.8 (3)C14—C13—H13119.8
C1—C2—H2A109.5C12—C13—H13119.8
C1—C2—H2B109.5C13—C14—C15121.2 (3)
H2A—C2—H2B109.5C13—C14—H14119.4
C1—C2—H2C109.5C15—C14—H14119.4
H2A—C2—H2C109.5C14—C15—C10119.1 (3)
H2B—C2—H2C109.5C14—C15—H15120.5
O4—C3—O3125.3 (3)C10—C15—H15120.5
O4—C3—C4118.0 (3)C12—C16—H16A109.5
O3—C3—C4116.7 (3)C12—C16—H16B109.5
C3—C4—H4A109.5H16A—C16—H16B109.5
C3—C4—H4B109.5C12—C16—H16C109.5
H4A—C4—H4B109.5H16A—C16—H16C109.5
C3—C4—H4C109.5H16B—C16—H16C109.5
O4i—Cu1—O1—C1−84.3 (2)C9—N1—C5—C6−1.4 (4)
O3—Cu1—O1—C183.4 (2)Cu1—N1—C5—C6178.8 (2)
O2i—Cu1—O1—C1−3.6 (6)N1—C5—C6—C71.3 (5)
N1—Cu1—O1—C1177.4 (2)C5—C6—C7—C8−0.5 (5)
Cu1i—Cu1—O1—C10.3 (2)C6—C7—C8—C9−0.1 (5)
O4i—Cu1—O3—C30.2 (6)C5—N1—C9—N2−177.5 (3)
O1—Cu1—O3—C3−85.6 (2)Cu1—N1—C9—N22.2 (4)
O2i—Cu1—O3—C381.7 (2)C5—N1—C9—C80.7 (4)
N1—Cu1—O3—C3179.8 (2)Cu1—N1—C9—C8−179.6 (2)
Cu1i—Cu1—O3—C3−2.0 (2)C10—N2—C9—N1175.0 (3)
O4i—Cu1—N1—C958.8 (2)C10—N2—C9—C8−3.2 (5)
O3—Cu1—N1—C9−121.1 (2)C7—C8—C9—N10.0 (4)
O1—Cu1—N1—C9148.2 (2)C7—C8—C9—N2178.1 (3)
O2i—Cu1—N1—C9−31.6 (2)C9—N2—C10—C11−134.6 (3)
O4i—Cu1—N1—C5−121.5 (2)C9—N2—C10—C1550.2 (5)
O3—Cu1—N1—C558.6 (2)C15—C10—C11—C12−0.2 (4)
O1—Cu1—N1—C5−32.0 (2)N2—C10—C11—C12−175.6 (3)
O2i—Cu1—N1—C5148.2 (2)C10—C11—C12—C13−2.0 (4)
Cu1—O1—C1—O2−2.2 (4)C10—C11—C12—C16175.8 (3)
Cu1—O1—C1—C2178.1 (2)C11—C12—C13—C142.4 (5)
Cu1i—O2—C1—O13.4 (4)C16—C12—C13—C14−175.4 (3)
Cu1i—O2—C1—C2−176.9 (2)C12—C13—C14—C15−0.6 (5)
Cu1i—O4—C3—O3−5.7 (4)C13—C14—C15—C10−1.6 (5)
Cu1i—O4—C3—C4174.4 (2)C11—C10—C15—C142.0 (4)
Cu1—O3—C3—O45.2 (4)N2—C10—C15—C14177.2 (3)
Cu1—O3—C3—C4−175.0 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···O2i0.862.172.913 (3)145

Symmetry codes: (i) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2688).

References

  • Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.
  • Barquín, M., González Garmendia, M. J., Pacheco, S., Pinilla, E., Quintela, S., Seco, J. M. & Torres, M. R. (2004). Inorg. Chim. Acta, 357, 3230–3236.
  • Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Seco, J. M., González Garmendia, M. J., Pinilla, E. & Torres, M. R. (2004). Polyhedron, 21, 457–464.
  • Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Sieroń, L. (2004). Acta Cryst. E60, m577–m578.
  • Westrip, S. P. (2009). publCIF. In preparation.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography