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Acta Cryst. (2009). E65, m1690    [ doi:10.1107/S1600536809050041 ]

Tetra-[mu]-acetato-[kappa]8O:O'-bis{[2-(m-tolylamino)pyridine-[kappa]N]copper(II)}

Z. A. Fairuz, Z. Aiyub, Z. Abdullah and S. W. Ng

Abstract top

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 top

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

Experimental top

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 top

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.

Computing details top

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

Figures top
[Figure 1] 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.
Tetra-µ-acetato-κ8O:O'-bis{[2-(m-tolylamino)pyridine- κN]copper(II)} top
Crystal data top
[Cu2(C2H3O2)4(C12H12N2)2]Z = 1
Mr = 731.73F(000) = 378
Triclinic, P1Dx = 1.475 Mg m−3
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 mm−1
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 top
Bruker SMART APEX
diffractometer		3678 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 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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H-atom parameters constrained
S = 1.07 w = 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 Å−3
0 restraintsΔρmin = −0.59 e Å−3
Crystal data top
[Cu2(C2H3O2)4(C12H12N2)2]γ = 78.568 (2)°
Mr = 731.73V = 823.51 (4) Å3
Triclinic, P1Z = 1
a = 7.7143 (2) ÅMo Kα radiation
b = 10.5625 (3) ŵ = 1.35 mm−1
c = 11.2413 (3) ÅT = 293 K
α = 66.531 (2)°0.25 × 0.15 × 0.05 mm
β = 85.740 (2)°
Data collection top
Bruker SMART APEX
diffractometer		3678 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2915 reflections with I > 2σ(I)
Tmin = 0.730, Tmax = 0.936Rint = 0.023
6451 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.098Δρmax = 0.49 e Å−3
S = 1.07Δρmin = −0.59 e Å−3
3678 reflectionsAbsolute structure: ?
211 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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) top
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, °) top
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, °) top
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.
Table 1
Selected geometric parameters (Å) top
Cu1—O11.9762 (19)Cu1—O4i1.966 (2)
Cu1—O2i1.9866 (19)Cu1—N12.197 (2)
Cu1—O31.967 (2)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
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.
Acknowledgements top

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

references
References top

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Seco, J. M., González Garmendia, M. J., Pinilla, E. & Torres, M. R. (2004). Polyhedron, 21, 457–464.

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Sieroń, L. (2004). Acta Cryst. E60, m577–m578.

Westrip, S. P. (2009). publCIF. In preparation.