supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m2455    [ doi:10.1107/S1600536807042328 ]

Tetra-[mu]-acetato-[kappa]8O:O'-bis[(4-vinylpyridine-[kappa]N)copper(II)](Cu-Cu)

F.-Q. Liu, R.-X. Li, S.-X. Li, L.-S. Sun and G.-Y. Liu

Abstract top

The title compound, [Cu2(C2H3O2)4(C7H7N)2], consists of centrosymmetric dinuclear units, in which four acetate groups bridge the two Cu atoms and a 4-vinylpyridine neutral ligand occupies the axial position of each Cu atom, coordinated to it through the pyridine N atom. Each Cu atom has a distorted octahedral coordination. Weak C-H...O interactions contribute to the crystal packing stability.

Comment top

The title compound,(I), (Fig. 1), consists of centrosymmetric dinuclear units, in which four acetate groups bridge the two copper atoms and a 4-vinylpyridine neutral ligand occupies the axis position of each copper atom, coordinated to them through the pyridine nitrogen atom. Each copper atom has a distorted square-planar pyramidal coordination, with four oxygen atoms in a plane. The distances for Cu—O1, O2, O3 and O4 are 1.979 (4), 1.969 (4), 1.971 (4) and 1.977 (5) Å, respectively. The fifth coordination position is occupied by the pyridine nitrogen, N, of a ligand molecule at 2.178 (5) Å. All these values agree well with those observed in [Cu2(υ-OOCCH3)4(PhNHpy)2] (PhNHpy is 2-anilinopyridine) (Seco et al., 2002). The copper atom rises from the basal plane to the apical N atom by 0.217 (1) Å. The Cu···Cu separation is 2.6405 (14) Å. Weak intramolecular C—H···O interactions contribute to the crystal packing stability.

Related literature top

For related literature, see: Seco et al. (2002).

Experimental top

A solution of 4-vinylpyridine (1.05 g, 10 mmol) in alcohol (10 ml) was added to Cu(OAc)2·H2O (2.00 g, 10 mmol) in alcohol (40 ml). The solution was stirred during 2 h and a precipitate was formed. The blue precipitate was filtered off, washed with alcohol and dried in vacuo over CaCO3. Blue crystals were obtained from recrystallization in alcohol after a few days.

Refinement top

H atoms were positioned geometrically (C—H = 0.93 Å or 0.96 Å) and allowed to ride on their parent atoms with Uiso(H) = 1.2 or 1.5 times Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001) and local programs.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme, hydrogen atoms were omitted for clarity.
[Figure 2] Fig. 2. The packing of (I), viewed down the b axis.
Tetra-µ-acetato-κ8O:O'-bis[(4-vinylpyridine-κN)copper(II)](Cu—Cu) top
Crystal data top
C22H26Cu2N2O8F000 = 588
Mr = 573.53Dx = 1.520 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3329 reflections
a = 10.696 (2) Åθ = 2.5–25.1º
b = 12.830 (3) ŵ = 1.74 mm−1
c = 9.4820 (19) ÅT = 293 (2) K
β = 105.65 (3)ºBlock, blue
V = 1253.0 (5) Å30.30 × 0.20 × 0.10 mm
Z = 2
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		2358 independent reflections
Radiation source: fine-focus sealed tube1830 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.013
T = 293(2) Kθmax = 26.0º
thin–slice ω scansθmin = 2.0º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −13→12
Tmin = 0.623, Tmax = 0.845k = 0→15
2455 measured reflectionsl = 0→11
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.061H-atom parameters constrained
wR(F2) = 0.182  w = 1/[σ2(Fo2) + (0.1P)2 + 3P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.002
2358 reflectionsΔρmax = 1.47 e Å−3
144 parametersΔρmin = −1.13 e Å−3
1 restraintExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
C22H26Cu2N2O8V = 1253.0 (5) Å3
Mr = 573.53Z = 2
Monoclinic, P21/cMo Kα
a = 10.696 (2) ŵ = 1.74 mm−1
b = 12.830 (3) ÅT = 293 (2) K
c = 9.4820 (19) Å0.30 × 0.20 × 0.10 mm
β = 105.65 (3)º
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		2358 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		1830 reflections with I > 2σ(I)
Tmin = 0.623, Tmax = 0.845Rint = 0.013
2455 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0611 restraint
wR(F2) = 0.182H-atom parameters constrained
S = 1.01Δρmax = 1.47 e Å−3
2358 reflectionsΔρmin = −1.13 e Å−3
144 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
Cu0.40251 (7)0.02266 (5)0.05538 (7)0.0441 (3)
O10.3606 (5)−0.1277 (3)0.0336 (5)0.0612 (11)
O20.4745 (5)0.1639 (3)0.0554 (5)0.0630 (12)
O30.3013 (5)0.0430 (4)−0.1496 (5)0.0641 (12)
O40.5344 (5)−0.0066 (4)0.2417 (5)0.0663 (12)
N0.2542 (5)0.0760 (4)0.1573 (5)0.0508 (11)
C1−0.0518 (10)0.2562 (8)0.4014 (10)0.101
H1A0.02690.29110.43450.121*
H1B−0.12330.27740.43210.121*
C2−0.0617 (10)0.1780 (8)0.3125 (10)0.100
H2A−0.13860.14120.27710.120*
C30.0585 (7)0.1517 (7)0.2715 (8)0.074 (2)
C40.1672 (8)0.2085 (5)0.2806 (8)0.0677 (19)
H4A0.17740.27360.32510.081*
C50.2638 (6)0.1679 (5)0.2221 (7)0.0562 (15)
H5A0.33820.20730.22930.067*
C60.1465 (7)0.0221 (6)0.1532 (8)0.0691 (19)
H6A0.1387−0.04370.11060.083*
C70.0486 (8)0.0551 (8)0.2057 (9)0.083 (2)
H7A−0.02430.01360.19780.099*
C80.6099 (8)0.3033 (6)0.0297 (10)0.082 (2)
H8A0.58590.33360.11110.123*
H8B0.56590.3391−0.05870.123*
H8C0.70200.30930.04480.123*
C90.5718 (6)0.1895 (5)0.0165 (7)0.0501 (14)
C100.7308 (8)−0.0547 (7)0.4061 (7)0.080 (2)
H10A0.8105−0.01620.42460.121*
H10B0.7496−0.12790.41610.121*
H10C0.6842−0.03430.47520.121*
C110.6490 (7)−0.0322 (4)0.2527 (7)0.0563 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu0.0535 (4)0.0386 (4)0.0448 (4)0.0010 (3)0.0212 (3)0.0026 (3)
O10.076 (3)0.044 (2)0.074 (3)−0.012 (2)0.038 (2)0.001 (2)
O20.073 (3)0.042 (2)0.085 (3)−0.007 (2)0.041 (3)0.000 (2)
O30.066 (3)0.073 (3)0.051 (2)0.012 (2)0.011 (2)0.004 (2)
O40.085 (3)0.069 (3)0.045 (2)0.011 (3)0.017 (2)0.004 (2)
N0.054 (3)0.052 (3)0.049 (3)0.000 (2)0.019 (2)−0.001 (2)
C10.1010.1010.1010.0000.0270.000
C20.1000.1000.1000.0000.0270.000
C30.067 (4)0.107 (7)0.058 (4)0.029 (4)0.034 (3)0.028 (4)
C40.099 (5)0.048 (4)0.068 (4)0.020 (4)0.043 (4)0.010 (3)
C50.061 (4)0.053 (4)0.063 (4)0.000 (3)0.030 (3)0.008 (3)
C60.064 (4)0.074 (5)0.077 (5)−0.020 (4)0.033 (4)−0.018 (4)
C70.066 (4)0.103 (7)0.091 (6)−0.009 (4)0.043 (4)−0.003 (5)
C80.089 (5)0.047 (4)0.120 (7)−0.016 (4)0.047 (5)0.002 (4)
C90.061 (4)0.039 (3)0.056 (3)−0.004 (3)0.024 (3)0.007 (3)
C100.104 (6)0.073 (5)0.051 (4)0.021 (4)−0.002 (4)−0.001 (3)
C110.083 (5)0.034 (3)0.046 (3)0.006 (3)0.006 (3)−0.001 (2)
Geometric parameters (Å, °) top
Cu—O21.969 (4)C3—C71.379 (12)
Cu—O31.971 (4)C4—C51.399 (9)
Cu—O41.977 (5)C4—H4A0.9300
Cu—O11.979 (4)C5—H5A0.9300
Cu—N2.178 (5)C6—C71.343 (10)
Cu—Cui2.6405 (14)C6—H6A0.9300
O1—C9i1.251 (7)C7—H7A0.9300
O2—C91.238 (7)C8—C91.511 (9)
O3—C11i1.240 (8)C8—H8A0.9600
O4—C111.246 (9)C8—H8B0.9600
N—C51.320 (8)C8—H8C0.9600
N—C61.335 (8)C9—O1i1.251 (7)
C1—C21.296 (8)C10—C111.509 (8)
C1—H1A0.9300C10—H10A0.9600
C1—H1B0.9300C10—H10B0.9600
C2—C31.479 (12)C10—H10C0.9600
C2—H2A0.9300C11—O3i1.240 (8)
C3—C41.355 (11)
O2—Cu—O389.4 (2)C3—C4—C5119.2 (7)
O2—Cu—O489.4 (2)C3—C4—H4A120.4
O3—Cu—O4167.5 (2)C5—C4—H4A120.4
O2—Cu—O1167.15 (17)N—C5—C4122.9 (6)
O3—Cu—O188.7 (2)N—C5—H5A118.5
O4—Cu—O189.7 (2)C4—C5—H5A118.5
O2—Cu—N92.43 (19)N—C6—C7125.4 (8)
O3—Cu—N97.14 (19)N—C6—H6A117.3
O4—Cu—N95.30 (19)C7—C6—H6A117.3
O1—Cu—N100.41 (19)C6—C7—C3118.6 (8)
O2—Cu—Cui81.48 (13)C6—C7—H7A120.7
O3—Cu—Cui85.37 (14)C3—C7—H7A120.7
O4—Cu—Cui82.19 (15)C9—C8—H8A109.5
O1—Cu—Cui85.69 (13)C9—C8—H8B109.5
N—Cu—Cui173.42 (15)H8A—C8—H8B109.5
C9i—O1—Cu121.3 (4)C9—C8—H8C109.5
C9—O2—Cu127.2 (4)H8A—C8—H8C109.5
C11i—O3—Cu121.6 (4)H8B—C8—H8C109.5
C11—O4—Cu125.0 (4)O2—C9—O1i124.3 (6)
C5—N—C6115.7 (6)O2—C9—C8117.5 (6)
C5—N—Cu120.8 (4)O1i—C9—C8118.2 (6)
C6—N—Cu123.4 (5)C11—C10—H10A109.5
C2—C1—H1A120.0C11—C10—H10B109.5
C2—C1—H1B120.0H10A—C10—H10B109.5
H1A—C1—H1B120.0C11—C10—H10C109.5
C1—C2—C3115.1 (10)H10A—C10—H10C109.5
C1—C2—H2A122.5H10B—C10—H10C109.5
C3—C2—H2A122.5O3i—C11—O4125.8 (6)
C4—C3—C7118.1 (7)O3i—C11—C10118.6 (7)
C4—C3—C2130.7 (9)O4—C11—C10115.6 (6)
C7—C3—C2111.0 (8)
O2—Cu—O1—C9i4.5 (12)O4—Cu—N—C573.6 (5)
O3—Cu—O1—C9i86.0 (5)O1—Cu—N—C5164.3 (5)
O4—Cu—O1—C9i−81.6 (5)O2—Cu—N—C6160.8 (6)
N—Cu—O1—C9i−177.0 (5)O3—Cu—N—C671.1 (6)
Cui—Cu—O1—C9i0.6 (5)O4—Cu—N—C6−109.6 (6)
O3—Cu—O2—C9−87.1 (6)O1—Cu—N—C6−18.9 (6)
O4—Cu—O2—C980.5 (6)C1—C2—C3—C4−18.3 (14)
O1—Cu—O2—C9−5.7 (12)C1—C2—C3—C7166.1 (9)
N—Cu—O2—C9175.8 (5)C7—C3—C4—C50.6 (11)
Cui—Cu—O2—C9−1.7 (5)C2—C3—C4—C5−174.6 (7)
O2—Cu—O3—C11i80.3 (5)C6—N—C5—C4−1.4 (9)
O4—Cu—O3—C11i−4.3 (13)Cu—N—C5—C4175.7 (5)
O1—Cu—O3—C11i−87.0 (5)C3—C4—C5—N0.2 (10)
N—Cu—O3—C11i172.7 (5)C5—N—C6—C71.8 (12)
Cui—Cu—O3—C11i−1.2 (5)Cu—N—C6—C7−175.2 (7)
O2—Cu—O4—C11−81.0 (5)N—C6—C7—C3−1.0 (14)
O3—Cu—O4—C113.6 (13)C4—C3—C7—C6−0.3 (12)
O1—Cu—O4—C1186.1 (5)C2—C3—C7—C6175.8 (8)
N—Cu—O4—C11−173.4 (5)Cu—O2—C9—O1i1.8 (10)
Cui—Cu—O4—C110.4 (5)Cu—O2—C9—C8−178.7 (5)
O2—Cu—N—C5−16.0 (5)Cu—O4—C11—O3i0.4 (10)
O3—Cu—N—C5−105.7 (5)Cu—O4—C11—C10−177.7 (5)
Symmetry codes: (i) −x+1, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C5—H5A···O20.932.543.083 (8)118
Table 1
Selected geometric parameters (Å, °) top
Cu—O21.969 (4)Cu—O11.979 (4)
Cu—O31.971 (4)Cu—N2.178 (5)
Cu—O41.977 (5)Cu—Cui2.6405 (14)
O2—Cu—O389.4 (2)O1—Cu—N100.41 (19)
O3—Cu—O4167.5 (2)O2—Cu—Cui81.48 (13)
O3—Cu—O188.7 (2)O3—Cu—Cui85.37 (14)
O4—Cu—O189.7 (2)O4—Cu—Cui82.19 (15)
O2—Cu—N92.43 (19)O1—Cu—Cui85.69 (13)
O3—Cu—N97.14 (19)N—Cu—Cui173.42 (15)
O4—Cu—N95.30 (19)
Symmetry codes: (i) −x+1, −y, −z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C5—H5A···O20.932.543.083 (8)118
Acknowledgements top

This work was supported by the National Natural Science Foundation of China (grant No. 20601015) and the Natural Science Foundation of Shandong Province (grant No. Y2006B12).

references
References top

Bruker (2001). SMART (Version 5.628) and SAINT (Version 6.45). Bruker AXS Inc., Madison, Wisconsin, USA.

Seco, J. M., Gonzàlez Garmendia, M. J., Pinilla, E. & Torres, M. R. (2002). Polyhedron, 21, 457–464.

Sheldrick, G. M. (2001). SHELXTL. Version 5.0. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.