Tetra-μ-acetato-κ8O:O′-bis­[(pyridine-2-carbo­nitrile-κN1)copper(II)]

Luo, M.; Wang, L.; Zhang, J.-C.

doi:10.1107/S1600536813034120

metal-organic compounds

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Volume 70| Part 1| January 2014| Page m27

https://doi.org/10.1107/S1600536813034120

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Tetra-μ-acetato-κ⁸O:O′-bis[(pyridine-2-carbonitrile-κN¹)copper(II)]

Mei Luo,^a ^* Lei Wang ^a and Jing-Cheng Zhang ^a

^aHefei University of Technology, Hefei, People's Republic of China
^*Correspondence e-mail: luomei@pku.edu.cn

(Received 25 November 2013; accepted 18 December 2013; online 24 December 2013)

The title binuclear compound, [Cu₂(CH₃COO)₄(C₆H₄N₂)₂], lies about an inversion center, with the Cu^II 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

Related literature

For related binuclear compounds, see: Fairuz et al. (2010 ); Chang et al. (2011 ).

Experimental

Crystal data

[Cu₂(C₂H₃O₂)₄(C₆H₄N₂)₂]
M_r = 571.48
Monoclinic, P 2₁ /c
a = 7.929 (5) Å
b = 19.817 (12) Å
c = 8.222 (5) Å
β = 118.83 (2)°
V = 1131.8 (12) Å³
Z = 2
Mo Kα radiation
μ = 1.93 mm⁻¹
T = 140 K
0.32 × 0.12 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.58, T_max = 0.89
7361 measured reflections
2077 independent reflections
1792 reflections with I > 2σ(I)
R_int = 0.165

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.159
S = 1.07
2077 reflections
157 parameters
H-atom parameters constrained
Δρ_max = 0.89 e Å⁻³
Δρ_min = −1.48 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O1	1.975 (4)
Cu1—O2ⁱ	1.980 (4)
Cu1—O3ⁱ	1.941 (4)
Cu1—O4	1.952 (4)
Cu1—N1	2.235 (4)
Symmetry code: (i) -x+1, -y, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

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⋯O4^iv	0.96	2.54	3.381 (7)	147
Symmetry codes: (ii) x-1, y, z; (iii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) -x, -y, -z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813034120/xu5755sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813034120/xu5755Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

For related binuclear compounds, see: Fairuz et al. (2010); Chang et al. (2011).

Experimental top

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.

Structure description top

For related binuclear compounds, see: Fairuz et al. (2010); Chang et al. (2011).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: 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).

Figures top

Fig. 1. The structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

Tetra-µ-acetato-κ⁸O:O'-bis[(pyridine-2-carbonitrile-κN¹)copper(II)] top

Crystal data top

[Cu₂(C₂H₃O₂)₄(C₆H₄N₂)₂]	F(000) = 580
M_r = 571.48	D_x = 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

Data collection top

Bruker APEXII CCD diffractometer	2077 independent reflections
Radiation source: fine-focus sealed tube	1792 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.165
φ and ω scans	θ_max = 25.3°, θ_min = 1.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→9
T_min = 0.58, T_max = 0.89	k = −23→23
7361 measured reflections	l = −9→6

Refinement top

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(F_o²) + (0.0938P)²] where P = (F_o² + 2F_c²)/3
2077 reflections	(Δ/σ)_max < 0.001
157 parameters	Δρ_max = 0.89 e Å⁻³
0 restraints	Δρ_min = −1.48 e Å⁻³

Crystal data top

[Cu₂(C₂H₃O₂)₄(C₆H₄N₂)₂]	V = 1131.8 (12) Å³
M_r = 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)°

Data collection top

Bruker APEXII CCD diffractometer	2077 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1792 reflections with I > 2σ(I)
T_min = 0.58, T_max = 0.89	R_int = 0.165
7361 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.159	H-atom parameters constrained
S = 1.07	Δρ_max = 0.89 e Å⁻³
2077 reflections	Δρ_min = −1.48 e Å⁻³
157 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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···O4^iv	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.

Selected bond lengths (Å) top

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.

Hydrogen-bond geometry (Å, º) top

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···O4^iv	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

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