supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

lh2807 scheme

Acta Cryst. (2009). E65, m646    [ doi:10.1107/S160053680901719X ]

Tetra-[mu]-acetato-[kappa]8O:O'-bis[(N2,N2-dimethylpyrazin-2-amine-[kappa]N4)copper(II)\]

L. Meng, L. Y. Yang and J. M. Shi

Abstract top

The title binuclear complex, [Cu2(C2H3O2)4(C6H9N3)2], lies on an inversion center with four acetate ligands bridging two CuII ions and two monodentate N,N-dimethylpyrazine-2-amine ligands coordinating each CuII ion via N atoms, forming slightly distorted square-pyramidal environments.

Comment top

Both acetate anions and pyrazine derivatives are useful ligands and a large number of multi-atom complexes have been synthesized with these as bridging ligands (Zhang et al., 2007; Li et al., 2003). We attempted to synthesize a mixed bridged multi-nuclear CuII complex by using acetate and N,N-dimethylpyrazine-2-amine as bridging ligands. The title complex was obtained and here we report its crystal structure, (I), Fig. 1.

The unique CuII ion is in a slightly distorted square-pyramidal coordination geometry with atom N1 lying at the apex. Four acetate ligands coordinate to two symmetry-related CuII atoms, with a Cu1···Cu1i separation of 2.6326 (6) Å and inversion centre lies at the middle of the Cu1···Cu1i vector (symmetry code, (i): -x + 1, -y + 1, -z + 2) resulting in the formation of a binuclear complex. The title complex is similar to a reported binuclear CuII complex (Zhang et al., 2007) except the title complex exhibits a slightly shorter Cu—N bond and a slightly longer Cu—Cu distance.

Related literature top

For related structures, see: Zhang et al. (2007); Li et al. (2003).

Experimental top

N,N-dimethylpyrazine-2-amine (0.0954 g, 0.0696 mmol) was dissolved in 10 ml methanol and it was added into 10 ml water solution containing copper acetate (0.1390 g, 0.696 mmol), and the mixed solution was stirred for a few minutes. The blue single crystals were obtained after the solution had been allowed to stand at room temperature for five months.

Refinement top

All H atoms were placed in calculated positions and refined as riding with C—H = 0.96 Å, Uiso = 1.5Ueq(C)for methyl group and C—H = 0.93 Å, Uiso = 1.2Ueq(C) for pyrazinyl H atoms.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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
[Figure 1] Fig. 1. The molecular structure of title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Primed atoms are related by the symmetry operator (-x + 1, -y + 1, -z + 2).
Tetra-µ-acetato-κ8O:O'-bis[(N2,N2- dimethylpyrazin-2-amine-κN4)copper(II)] top
Crystal data top
[Cu2(C2H3O2)4(C6H9N3)2]Z = 1
Mr = 609.58F000 = 314
Triclinic, P1Dx = 1.572 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 8.1052 (13) ÅCell parameters from 2730 reflections
b = 8.1775 (13) Åθ = 2.7–28.2º
c = 10.6534 (17) ŵ = 1.71 mm−1
α = 67.826 (2)ºT = 298 K
β = 80.013 (2)ºBlock, blue
γ = 87.328 (2)º0.68 × 0.41 × 0.31 mm
V = 643.84 (18) Å3
Data collection top
Bruker SMART APEX CCD
diffractometer		2465 independent reflections
Radiation source: fine-focus sealed tube2317 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.016
T = 298 Kθmax = 26.0º
φ and ω scansθmin = 2.1º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→8
Tmin = 0.390, Tmax = 0.620k = −10→8
3494 measured reflectionsl = −12→13
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)] = 0.032H-atom parameters constrained
wR(F2) = 0.094  w = 1/[σ2(Fo2) + (0.0576P)2 + 0.297P]
where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max = 0.020
2465 reflectionsΔρmax = 0.54 e Å−3
167 parametersΔρmin = −0.44 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu2(C2H3O2)4(C6H9N3)2]γ = 87.328 (2)º
Mr = 609.58V = 643.84 (18) Å3
Triclinic, P1Z = 1
a = 8.1052 (13) ÅMo Kα
b = 8.1775 (13) ŵ = 1.71 mm−1
c = 10.6534 (17) ÅT = 298 K
α = 67.826 (2)º0.68 × 0.41 × 0.31 mm
β = 80.013 (2)º
Data collection top
Bruker SMART APEX CCD
diffractometer		2465 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2317 reflections with I > 2σ(I)
Tmin = 0.390, Tmax = 0.620Rint = 0.016
3494 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.032167 parameters
wR(F2) = 0.094H-atom parameters constrained
S = 1.09Δρmax = 0.54 e Å−3
2465 reflectionsΔρmin = −0.44 e Å−3
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
C10.2373 (3)0.6709 (3)0.9386 (3)0.0309 (5)
C20.0727 (3)0.7590 (4)0.9109 (3)0.0471 (7)
H2A0.09030.85780.82470.071*
H2B0.02730.79950.98320.071*
H2C−0.00430.67590.90720.071*
C30.6075 (3)0.7439 (3)1.0579 (3)0.0362 (6)
C40.6713 (4)0.8898 (4)1.0918 (4)0.0531 (8)
H4A0.72700.97921.00900.080*
H4B0.74870.84271.15480.080*
H4C0.57880.94061.13300.080*
C50.6480 (4)0.8180 (4)0.5613 (3)0.0480 (7)
H50.53510.84370.57680.058*
C60.7422 (4)0.9016 (4)0.4350 (3)0.0577 (9)
H60.69110.98560.36750.069*
C70.8757 (3)0.6637 (4)0.6357 (3)0.0367 (6)
H70.92560.58120.70480.044*
C80.9720 (3)0.7479 (4)0.5042 (3)0.0413 (6)
C91.2305 (5)0.8021 (6)0.3383 (4)0.0780 (12)
H9A1.17000.79800.26960.117*
H9B1.33700.74740.32940.117*
H9C1.24780.92290.32610.117*
C101.2205 (4)0.5823 (6)0.5770 (4)0.0647 (9)
H10A1.23740.63120.64300.097*
H10B1.32700.55640.53380.097*
H10C1.15380.47570.62280.097*
Cu10.57009 (3)0.57928 (4)0.87055 (3)0.02811 (13)
N10.7160 (3)0.6997 (3)0.6627 (2)0.0350 (5)
N20.9033 (4)0.8693 (4)0.4033 (3)0.0548 (7)
N31.1350 (3)0.7085 (4)0.4739 (3)0.0577 (7)
O10.4726 (3)0.3816 (3)0.8439 (2)0.0446 (5)
O20.7587 (2)0.4311 (3)0.94000 (19)0.0408 (4)
O30.6383 (2)0.7576 (3)0.9348 (2)0.0411 (4)
O40.3574 (2)0.7044 (2)0.83984 (19)0.0379 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0290 (12)0.0292 (11)0.0330 (13)−0.0015 (9)−0.0048 (10)−0.0099 (10)
C20.0300 (13)0.0478 (16)0.0536 (18)0.0026 (11)−0.0087 (12)−0.0076 (13)
C30.0276 (12)0.0386 (14)0.0479 (16)0.0033 (10)−0.0077 (11)−0.0221 (12)
C40.0561 (18)0.0498 (17)0.063 (2)−0.0056 (14)−0.0098 (15)−0.0309 (15)
C50.0421 (15)0.0538 (17)0.0360 (15)0.0115 (13)0.0022 (12)−0.0083 (13)
C60.064 (2)0.0578 (19)0.0297 (15)0.0184 (16)0.0014 (14)0.0023 (13)
C70.0354 (13)0.0425 (14)0.0271 (12)−0.0005 (11)0.0007 (10)−0.0099 (11)
C80.0405 (14)0.0440 (15)0.0341 (14)−0.0037 (11)0.0065 (11)−0.0139 (12)
C90.061 (2)0.088 (3)0.065 (2)−0.010 (2)0.0353 (19)−0.024 (2)
C100.0394 (17)0.088 (3)0.072 (2)0.0077 (16)−0.0050 (16)−0.039 (2)
Cu10.02545 (18)0.03205 (19)0.02278 (18)−0.00127 (12)0.00141 (12)−0.00789 (13)
N10.0349 (11)0.0380 (11)0.0270 (11)−0.0005 (9)0.0026 (9)−0.0096 (9)
N20.0591 (16)0.0529 (15)0.0328 (13)0.0057 (12)0.0109 (12)−0.0028 (11)
N30.0402 (14)0.0682 (18)0.0511 (16)0.0005 (12)0.0134 (12)−0.0163 (14)
O10.0521 (12)0.0447 (11)0.0411 (11)−0.0074 (9)−0.0005 (9)−0.0228 (9)
O20.0323 (9)0.0473 (11)0.0312 (10)0.0073 (8)0.0004 (7)−0.0048 (8)
O30.0438 (10)0.0409 (10)0.0390 (10)−0.0095 (8)−0.0003 (8)−0.0169 (8)
O40.0307 (9)0.0441 (10)0.0313 (9)0.0039 (7)−0.0032 (7)−0.0070 (8)
Geometric parameters (Å, °) top
C1—O2i1.252 (3)C7—H70.9300
C1—O41.258 (3)C8—N21.342 (4)
C1—C21.507 (3)C8—N31.358 (4)
C2—H2A0.9600C9—N31.451 (4)
C2—H2B0.9600C9—H9A0.9600
C2—H2C0.9600C9—H9B0.9600
C3—O31.255 (3)C9—H9C0.9600
C3—O1i1.259 (3)C10—N31.447 (5)
C3—C41.506 (4)C10—H10A0.9600
C4—H4A0.9600C10—H10B0.9600
C4—H4B0.9600C10—H10C0.9600
C4—H4C0.9600Cu1—O31.9649 (18)
C5—N11.331 (4)Cu1—O11.9654 (19)
C5—C61.363 (4)Cu1—O21.9738 (18)
C5—H50.9300Cu1—O41.9756 (18)
C6—N21.331 (4)Cu1—N12.197 (2)
C6—H60.9300Cu1—Cu1i2.6326 (6)
C7—N11.321 (3)O1—C3i1.259 (3)
C7—C81.411 (4)O2—C1i1.252 (3)
O2i—C1—O4125.7 (2)H9A—C9—H9C109.5
O2i—C1—C2116.0 (2)H9B—C9—H9C109.5
O4—C1—C2118.3 (2)N3—C10—H10A109.5
C1—C2—H2A109.5N3—C10—H10B109.5
C1—C2—H2B109.5H10A—C10—H10B109.5
H2A—C2—H2B109.5N3—C10—H10C109.5
C1—C2—H2C109.5H10A—C10—H10C109.5
H2A—C2—H2C109.5H10B—C10—H10C109.5
H2B—C2—H2C109.5O3—Cu1—O1168.16 (8)
O3—C3—O1i125.6 (2)O3—Cu1—O289.93 (9)
O3—C3—C4117.4 (3)O1—Cu1—O290.44 (9)
O1i—C3—C4117.0 (2)O3—Cu1—O488.93 (8)
C3—C4—H4A109.5O1—Cu1—O488.32 (9)
C3—C4—H4B109.5O2—Cu1—O4168.35 (7)
H4A—C4—H4B109.5O3—Cu1—N194.74 (8)
C3—C4—H4C109.5O1—Cu1—N197.07 (8)
H4A—C4—H4C109.5O2—Cu1—N192.23 (8)
H4B—C4—H4C109.5O4—Cu1—N199.42 (8)
N1—C5—C6120.7 (3)O3—Cu1—Cu1i83.66 (6)
N1—C5—H5119.7O1—Cu1—Cu1i84.71 (6)
C6—C5—H5119.7O2—Cu1—Cu1i81.05 (6)
N2—C6—C5123.5 (3)O4—Cu1—Cu1i87.31 (5)
N2—C6—H6118.3N1—Cu1—Cu1i173.08 (6)
C5—C6—H6118.3C7—N1—C5117.8 (2)
N1—C7—C8121.3 (3)C7—N1—Cu1121.20 (18)
N1—C7—H7119.3C5—N1—Cu1120.88 (18)
C8—C7—H7119.3C6—N2—C8116.2 (2)
N2—C8—N3117.6 (3)C8—N3—C10121.5 (3)
N2—C8—C7120.4 (3)C8—N3—C9120.0 (3)
N3—C8—C7122.0 (3)C10—N3—C9118.4 (3)
N3—C9—H9A109.5C3i—O1—Cu1122.29 (17)
N3—C9—H9B109.5C1i—O2—Cu1126.74 (17)
H9A—C9—H9B109.5C3—O3—Cu1123.65 (17)
N3—C9—H9C109.5C1—O4—Cu1119.15 (16)
N1—C5—C6—N21.7 (6)O3—Cu1—O1—C3i−13.5 (5)
N1—C7—C8—N20.9 (4)O2—Cu1—O1—C3i78.2 (2)
N1—C7—C8—N3−178.1 (3)O4—Cu1—O1—C3i−90.2 (2)
C8—C7—N1—C50.3 (4)N1—Cu1—O1—C3i170.5 (2)
C8—C7—N1—Cu1−176.6 (2)Cu1i—Cu1—O1—C3i−2.7 (2)
C6—C5—N1—C7−1.5 (5)O3—Cu1—O2—C1i81.6 (2)
C6—C5—N1—Cu1175.3 (3)O1—Cu1—O2—C1i−86.6 (2)
O3—Cu1—N1—C785.5 (2)O4—Cu1—O2—C1i−2.8 (5)
O1—Cu1—N1—C7−95.3 (2)N1—Cu1—O2—C1i176.3 (2)
O2—Cu1—N1—C7−4.6 (2)Cu1i—Cu1—O2—C1i−2.0 (2)
O4—Cu1—N1—C7175.2 (2)O1i—C3—O3—Cu1−1.4 (4)
Cu1i—Cu1—N1—C79.2 (6)C4—C3—O3—Cu1178.70 (18)
O3—Cu1—N1—C5−91.3 (2)O1—Cu1—O3—C313.4 (5)
O1—Cu1—N1—C587.9 (2)O2—Cu1—O3—C3−78.4 (2)
O2—Cu1—N1—C5178.6 (2)O4—Cu1—O3—C390.0 (2)
O4—Cu1—N1—C5−1.6 (2)N1—Cu1—O3—C3−170.7 (2)
Cu1i—Cu1—N1—C5−167.6 (4)Cu1i—Cu1—O3—C32.6 (2)
C5—C6—N2—C8−0.4 (5)O2i—C1—O4—Cu13.5 (4)
N3—C8—N2—C6178.2 (3)C2—C1—O4—Cu1−176.12 (18)
C7—C8—N2—C6−0.8 (5)O3—Cu1—O4—C1−85.17 (19)
N2—C8—N3—C10178.6 (3)O1—Cu1—O4—C183.31 (19)
C7—C8—N3—C10−2.4 (5)O2—Cu1—O4—C1−0.7 (5)
N2—C8—N3—C92.7 (5)N1—Cu1—O4—C1−179.80 (18)
C7—C8—N3—C9−178.2 (3)Cu1i—Cu1—O4—C1−1.47 (18)
Symmetry codes: (i) −x+1, −y+1, −z+2.
Table 1
Selected geometric parameters (Å, °) top
Cu1—O31.9649 (18)Cu1—O41.9756 (18)
Cu1—O11.9654 (19)Cu1—N12.197 (2)
Cu1—O21.9738 (18)
O3—Cu1—O1168.16 (8)O2—Cu1—O4168.35 (7)
O3—Cu1—O289.93 (9)O3—Cu1—N194.74 (8)
O1—Cu1—O290.44 (9)O1—Cu1—N197.07 (8)
O3—Cu1—O488.93 (8)O2—Cu1—N192.23 (8)
O1—Cu1—O488.32 (9)O4—Cu1—N199.42 (8)
references
References top

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Li, J. M., Shi, J. M., Wu, C. J. & Xu, W. (2003). J. Coord. Chem. 56, 869–875.

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

Zhang, S.-G., Liu, Q.-S. & Shi, J.-M. (2007). Acta Cryst. E63, m2082.