metal-organic compounds
Tetra-μ-acetato-κ8O:O′-bis[(pyridine-2-carbonitrile-κN1)copper(II)]
aHefei University of Technology, Hefei, People's Republic of China
*Correspondence e-mail: luomei@pku.edu.cn
The title binuclear compound, [Cu2(CH3COO)4(C6H4N2)2], lies about an inversion center, with the CuII cation bridged by four acetate anions and coordinated by a pyridine N atom in a distorted square-pyramidal geometry. The Cu⋯Cu distance is 2.5997 (15) Å. In the crystal, molecules are linked by weak C—H⋯O and C—H⋯N hydrogen bonds into a three-dimensional supramolecular architecture. The crystal studied was a non-merohedral twin with a minor twin component of 4.1 (1)%.
CCDC reference: 977803
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
CCDC reference: 977803
https://doi.org/10.1107/S1600536813034120/xu5755sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813034120/xu5755Isup2.hkl
2-Cyanopyridine (23.1233 g, 30 mmol) was added to a THF solution (60 ml) of Cu(OAc)2.H2O (1.9972 g, 5 mmol). The reaction mixture was stirred vigorously while refluxing for 48 h. The filtrate was slowly evaporated, the blue single crystals were obtained.
H atoms were placed in calculated position with C—H = 0.93 (aromatic) and 0.96 Å (methyl), and refined in a riding mode with Uiso(H) = 1.2Ueq(C) for aromatic H atoms and 1.5Ueq(C) for methyl H atom.
The Cu–N complexes have occupied an important position in catalytic processes. In connection with on-going studies into the structural characterization of tetrakisacetatobis[(substituted 2-aminopyridyl)copper] complexes (Fairuz et al., 2010; Chang et al. (2011), the title complex, (I), was investigated. The binuclear copper(II) complex, Fig. 1, is situated about a centre of inversion and features two Cu II atoms bridged by four acetate groups. The Cu–O bond distances ranged from 1.941 (4) to 1.980 (4) Å (Table 1). The distorted square-pyramidal coordination environment for the Cu atom is completed by a pyridine-N atom and four carboxyl-O atoms of acetate anions. In the binuclear compound, the Cu ···Cu distance is 2.5997 (15) Å. In the crystal, the molecules are linked by weak C—H···O and C—H···N hydrogen bonds into three dimensional supramolecular architecture.
For related binuclear compounds, see: Fairuz et al. (2010); Chang et al. (2011).
Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. The structure of the title compound with displacement ellipsoids drawn at the 50% probability level. |
[Cu2(C2H3O2)4(C6H4N2)2] | F(000) = 580 |
Mr = 571.48 | Dx = 1.677 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3034 reflections |
a = 7.929 (5) Å | θ = 2.9–30.5° |
b = 19.817 (12) Å | µ = 1.93 mm−1 |
c = 8.222 (5) Å | T = 140 K |
β = 118.83 (2)° | Block, blue |
V = 1131.8 (12) Å3 | 0.32 × 0.12 × 0.06 mm |
Z = 2 |
Bruker APEXII CCD diffractometer | 2077 independent reflections |
Radiation source: fine-focus sealed tube | 1792 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.165 |
φ and ω scans | θmax = 25.3°, θmin = 1.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −9→9 |
Tmin = 0.58, Tmax = 0.89 | k = −23→23 |
7361 measured reflections | l = −9→6 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.159 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0938P)2] where P = (Fo2 + 2Fc2)/3 |
2077 reflections | (Δ/σ)max < 0.001 |
157 parameters | Δρmax = 0.89 e Å−3 |
0 restraints | Δρmin = −1.48 e Å−3 |
[Cu2(C2H3O2)4(C6H4N2)2] | V = 1131.8 (12) Å3 |
Mr = 571.48 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.929 (5) Å | µ = 1.93 mm−1 |
b = 19.817 (12) Å | T = 140 K |
c = 8.222 (5) Å | 0.32 × 0.12 × 0.06 mm |
β = 118.83 (2)° |
Bruker APEXII CCD diffractometer | 2077 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 1792 reflections with I > 2σ(I) |
Tmin = 0.58, Tmax = 0.89 | Rint = 0.165 |
7361 measured reflections |
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.159 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.89 e Å−3 |
2077 reflections | Δρmin = −1.48 e Å−3 |
157 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.40864 (8) | 0.05361 (2) | 0.50591 (7) | 0.0184 (3) | |
N1 | 0.2510 (5) | 0.14273 (19) | 0.5328 (6) | 0.0199 (8) | |
N2 | 0.6530 (7) | 0.2387 (2) | 0.6344 (9) | 0.0436 (14) | |
O1 | 0.4618 (6) | 0.08980 (17) | 0.3114 (5) | 0.0295 (8) | |
O2 | 0.6269 (6) | −0.00139 (17) | 0.3074 (5) | 0.0283 (8) | |
O3 | 0.3373 (5) | −0.08126 (18) | 0.3035 (5) | 0.0318 (8) | |
O4 | 0.1766 (5) | 0.00951 (17) | 0.3166 (5) | 0.0260 (8) | |
C1 | 0.0735 (7) | 0.1301 (2) | 0.5040 (7) | 0.0253 (11) | |
H1 | 0.0229 | 0.0871 | 0.4645 | 0.030* | |
C2 | −0.0387 (7) | 0.1775 (2) | 0.5298 (7) | 0.0270 (11) | |
H2 | −0.1624 | 0.1666 | 0.5070 | 0.032* | |
C3 | 0.0343 (7) | 0.2405 (2) | 0.5895 (7) | 0.0264 (11) | |
H3 | −0.0394 | 0.2731 | 0.6075 | 0.032* | |
C4 | 0.2182 (8) | 0.2557 (2) | 0.6228 (7) | 0.0261 (11) | |
H4 | 0.2711 | 0.2982 | 0.6643 | 0.031* | |
C5 | 0.3216 (7) | 0.2053 (2) | 0.5922 (7) | 0.0201 (10) | |
C6 | 0.5091 (8) | 0.2214 (2) | 0.6174 (8) | 0.0303 (12) | |
C7 | 0.5577 (7) | 0.0559 (2) | 0.2514 (7) | 0.0214 (10) | |
C8 | 0.5910 (9) | 0.0865 (3) | 0.1015 (8) | 0.0320 (12) | |
H8A | 0.6835 | 0.0600 | 0.0860 | 0.048* | |
H8B | 0.6388 | 0.1317 | 0.1362 | 0.048* | |
H8C | 0.4719 | 0.0875 | −0.0131 | 0.048* | |
C9 | 0.1852 (8) | −0.0478 (2) | 0.2547 (7) | 0.0228 (10) | |
C10 | 0.0014 (8) | −0.0787 (3) | 0.1106 (8) | 0.0324 (12) | |
H10A | −0.0097 | −0.0723 | −0.0099 | 0.049* | |
H10B | −0.1056 | −0.0575 | 0.1144 | 0.049* | |
H10C | 0.0014 | −0.1261 | 0.1349 | 0.049* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0166 (4) | 0.0163 (3) | 0.0162 (4) | 0.0018 (2) | 0.0029 (3) | −0.0010 (2) |
N1 | 0.0151 (18) | 0.0218 (18) | 0.018 (2) | 0.0014 (16) | 0.0041 (16) | −0.0018 (16) |
N2 | 0.029 (3) | 0.028 (2) | 0.079 (4) | −0.007 (2) | 0.031 (3) | −0.014 (2) |
O1 | 0.038 (2) | 0.0219 (16) | 0.031 (2) | 0.0029 (16) | 0.0185 (18) | 0.0034 (15) |
O2 | 0.034 (2) | 0.0291 (18) | 0.0237 (19) | 0.0055 (16) | 0.0161 (17) | 0.0009 (15) |
O3 | 0.0231 (18) | 0.0252 (17) | 0.034 (2) | −0.0019 (17) | 0.0034 (17) | −0.0079 (16) |
O4 | 0.0175 (17) | 0.0260 (17) | 0.0216 (19) | 0.0029 (14) | −0.0010 (15) | −0.0027 (14) |
C1 | 0.019 (2) | 0.024 (2) | 0.025 (3) | −0.005 (2) | 0.005 (2) | −0.003 (2) |
C2 | 0.019 (2) | 0.028 (2) | 0.031 (3) | 0.000 (2) | 0.010 (2) | 0.001 (2) |
C3 | 0.023 (3) | 0.024 (2) | 0.029 (3) | 0.006 (2) | 0.010 (2) | 0.001 (2) |
C4 | 0.028 (3) | 0.020 (2) | 0.029 (3) | 0.003 (2) | 0.013 (2) | 0.000 (2) |
C5 | 0.020 (2) | 0.018 (2) | 0.019 (2) | 0.0016 (19) | 0.007 (2) | 0.0021 (18) |
C6 | 0.034 (3) | 0.018 (2) | 0.042 (3) | 0.004 (2) | 0.021 (3) | −0.002 (2) |
C7 | 0.019 (2) | 0.022 (2) | 0.016 (2) | −0.003 (2) | 0.004 (2) | −0.0023 (18) |
C8 | 0.040 (3) | 0.030 (3) | 0.023 (3) | −0.006 (2) | 0.013 (2) | 0.001 (2) |
C9 | 0.022 (3) | 0.022 (2) | 0.014 (2) | −0.003 (2) | 0.001 (2) | 0.0004 (19) |
C10 | 0.024 (3) | 0.029 (3) | 0.026 (3) | −0.005 (2) | −0.003 (2) | 0.001 (2) |
Cu1—O1 | 1.975 (4) | C1—H1 | 0.9300 |
Cu1—O2i | 1.980 (4) | C2—C3 | 1.366 (7) |
Cu1—O3i | 1.941 (4) | C2—H2 | 0.9300 |
Cu1—O4 | 1.952 (4) | C3—C4 | 1.380 (7) |
Cu1—N1 | 2.235 (4) | C3—H3 | 0.9300 |
Cu1—Cu1i | 2.5997 (15) | C4—C5 | 1.389 (7) |
N1—C1 | 1.334 (6) | C4—H4 | 0.9300 |
N1—C5 | 1.352 (6) | C5—C6 | 1.435 (7) |
N2—C6 | 1.133 (7) | C7—C8 | 1.507 (7) |
O1—C7 | 1.279 (6) | C8—H8A | 0.9600 |
O2—C7 | 1.248 (6) | C8—H8B | 0.9600 |
O2—Cu1i | 1.980 (4) | C8—H8C | 0.9600 |
O3—C9 | 1.261 (7) | C9—C10 | 1.496 (7) |
O3—Cu1i | 1.941 (4) | C10—H10A | 0.9600 |
O4—C9 | 1.259 (6) | C10—H10B | 0.9600 |
C1—C2 | 1.379 (7) | C10—H10C | 0.9600 |
O3i—Cu1—O4 | 169.17 (14) | C2—C3—C4 | 119.6 (5) |
O3i—Cu1—O1 | 90.43 (17) | C2—C3—H3 | 120.2 |
O4—Cu1—O1 | 90.23 (16) | C4—C3—H3 | 120.2 |
O3i—Cu1—O2i | 90.11 (17) | C3—C4—C5 | 117.9 (5) |
O4—Cu1—O2i | 87.28 (16) | C3—C4—H4 | 121.1 |
O1—Cu1—O2i | 169.40 (14) | C5—C4—H4 | 121.1 |
O3i—Cu1—N1 | 96.27 (15) | N1—C5—C4 | 123.2 (4) |
O4—Cu1—N1 | 94.34 (15) | N1—C5—C6 | 118.4 (4) |
O1—Cu1—N1 | 98.10 (15) | C4—C5—C6 | 118.4 (4) |
O2i—Cu1—N1 | 92.35 (14) | N2—C6—C5 | 175.1 (6) |
O3i—Cu1—Cu1i | 83.16 (11) | O2—C7—O1 | 125.0 (4) |
O4—Cu1—Cu1i | 86.12 (11) | O2—C7—C8 | 116.7 (4) |
O1—Cu1—Cu1i | 85.76 (11) | O1—C7—C8 | 118.3 (4) |
O2i—Cu1—Cu1i | 83.80 (10) | C7—C8—H8A | 109.5 |
N1—Cu1—Cu1i | 176.10 (10) | C7—C8—H8B | 109.5 |
C1—N1—C5 | 117.0 (4) | H8A—C8—H8B | 109.5 |
C1—N1—Cu1 | 115.2 (3) | C7—C8—H8C | 109.5 |
C5—N1—Cu1 | 127.4 (3) | H8A—C8—H8C | 109.5 |
C7—O1—Cu1 | 121.3 (3) | H8B—C8—H8C | 109.5 |
C7—O2—Cu1i | 124.0 (3) | O4—C9—O3 | 125.1 (5) |
C9—O3—Cu1i | 124.7 (3) | O4—C9—C10 | 117.9 (5) |
C9—O4—Cu1 | 120.8 (3) | O3—C9—C10 | 117.0 (4) |
N1—C1—C2 | 123.3 (5) | C9—C10—H10A | 109.5 |
N1—C1—H1 | 118.4 | C9—C10—H10B | 109.5 |
C2—C1—H1 | 118.4 | H10A—C10—H10B | 109.5 |
C3—C2—C1 | 119.1 (4) | C9—C10—H10C | 109.5 |
C3—C2—H2 | 120.5 | H10A—C10—H10C | 109.5 |
C1—C2—H2 | 120.5 | H10B—C10—H10C | 109.5 |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···N2ii | 0.93 | 2.60 | 3.196 (9) | 122 |
C8—H8B···N2iii | 0.96 | 2.57 | 3.491 (8) | 160 |
C10—H10A···O4iv | 0.96 | 2.54 | 3.381 (7) | 147 |
Symmetry codes: (ii) x−1, y, z; (iii) x, −y+1/2, z−1/2; (iv) −x, −y, −z. |
Cu1—O1 | 1.975 (4) | Cu1—O4 | 1.952 (4) |
Cu1—O2i | 1.980 (4) | Cu1—N1 | 2.235 (4) |
Cu1—O3i | 1.941 (4) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···N2ii | 0.93 | 2.60 | 3.196 (9) | 122 |
C8—H8B···N2iii | 0.96 | 2.57 | 3.491 (8) | 160 |
C10—H10A···O4iv | 0.96 | 2.54 | 3.381 (7) | 147 |
Symmetry codes: (ii) x−1, y, z; (iii) x, −y+1/2, z−1/2; (iv) −x, −y, −z. |
Acknowledgements
This work was supported by Hefei University of Technology, China. The data were collected at the University of Science and Technology of China.
References
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chang, H.-C., Cole, J. M., Lin, T.-C. & Waddell, P. G. (2011). Acta Cryst. E67, m691. Web of Science CSD CrossRef IUCr Journals Google Scholar
Fairuz, Z. A., Aiyub, Z., Abdullah, Z., Ng, S. W. & Tiekink, E. R. T. (2010). Acta Cryst. E66, m1077–m1078. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
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The Cu–N complexes have occupied an important position in catalytic processes. In connection with on-going studies into the structural characterization of tetrakisacetatobis[(substituted 2-aminopyridyl)copper] complexes (Fairuz et al., 2010; Chang et al. (2011), the title complex, (I), was investigated. The binuclear copper(II) complex, Fig. 1, is situated about a centre of inversion and features two Cu II atoms bridged by four acetate groups. The Cu–O bond distances ranged from 1.941 (4) to 1.980 (4) Å (Table 1). The distorted square-pyramidal coordination environment for the Cu atom is completed by a pyridine-N atom and four carboxyl-O atoms of acetate anions. In the binuclear compound, the Cu ···Cu distance is 2.5997 (15) Å. In the crystal, the molecules are linked by weak C—H···O and C—H···N hydrogen bonds into three dimensional supramolecular architecture.