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Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): m1181.
Published online 2010 August 28. doi:  10.1107/S1600536810034033
PMCID: PMC3007943

Tetra-μ-acetato-κ8 O:O′-bis­[(N-ethyl­pyrimidin-2-amine)­copper(II)](CuCu)

Abstract

In the centrosymmetric title mol­ecule, [Cu2(CH3COO)4(C6H9N3)2], each of the four acetate groups bridges a pair of CuII atoms [Cu—Cu = 2.6540 (4) Å]. The distorted octa­hedral geometry of the metal atom is completed by an N-donor atom of the N-ethyl­pyrimidin-2-amine ligand: an intra­molecular N—H(...)O hydrogen links its N—H group to an acetate carboxyl­ate O atom. In the crystal, C—H(...)O inter­actions link the mol­ecules into a supra­molecular chain along the b axis.

Related literature

For related examples of tetra­kis­acetato­bis­[(substituted 2-amino­pyrid­yl)copper(II)] complexes, see: Fairuz et al. (2010a [triangle],b [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1181-scheme1.jpg

Experimental

Crystal data

  • [Cu2(C2H3O2)4(C6H9N3)2]
  • M r = 609.58
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1181-efi1.jpg
  • a = 7.8488 (6) Å
  • b = 8.5114 (7) Å
  • c = 10.2999 (8) Å
  • α = 98.404 (1)°
  • β = 92.698 (1)°
  • γ = 105.599 (1)°
  • V = 652.92 (9) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 1.68 mm−1
  • T = 293 K
  • 0.40 × 0.35 × 0.10 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.613, T max = 0.746
  • 6208 measured reflections
  • 2969 independent reflections
  • 2669 reflections with I > 2σ(I)
  • R int = 0.018

Refinement

  • R[F 2 > 2σ(F 2)] = 0.026
  • wR(F 2) = 0.080
  • S = 1.02
  • 2969 reflections
  • 170 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.25 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and DIAMOND (Brandenburg, 2006 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810034033/hb5613sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810034033/hb5613Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

Z. Abdullah thanks the Ministry of Higher Education for a research grant (FS143/2008 C). The authors are also grateful to the University of Malaya for support of the crystallographic facility.

supplementary crystallographic information

Comment

In continuation of on-going structural studies of tetrakisacetatobis[(substituted 2-aminopyridyl)copper] complexes (Fairuz et al., 2010a, 2010b), the title complex, (I), was investigated.

The binuclear copper(II) complex, Fig. 1, is situated about a centre of inversion and features two Cu atoms bridged by four acetate groups. The Cu–O bond distances lie in a narrow range of 1.953 (1) to 1.978 (2) Å, Table 1. The coordination environment for each Cu atom is completed by an N atom derived from the N-ethylpyrimidin-2-amine ligand and the second Cu atom [Cu···Cui = 2.6540 (4) Å for i: 1 - x, 1 - y, 1 - z]. The resulting hexa-coordinated geometry is based on an octahedron. An intramolecular N3–H···O1 interaction contributes to the stability of the dinuclear molecule, Table 2. The N-heterocycle is effectively planar as seen in the C8–N3–C9–C10 torsion angle of -166.6 (2) °. In the crystal packing, the presence of C–H···O interactions connect dinuclear molecules into supramolecular chains along the b axis, Fig. 2 and Table 2.

Experimental

Copper acetate (0.1 g, 0.5 mmol) was dissolved in acetonitrile (15 ml) and mixed with a solution of N-(pyrimidin-2-yl)ethylamine (0.2 g, 1.1 mmol) dissolved in acetonitrile (15 ml). The blue precipitate that formed was recrystallized from acetonitrile to yield blue prisms of (I).

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 to 0.97 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2 to 1.5Uequiv(C). The N-bound H-atom was located in a difference Fourier map and was refined with a distance restraint of N–H 0.86±0.01 Å; the Uiso value was freely refined

Figures

Fig. 1.
The molecular structure of (I) showing displacement ellipsoids at the 35% probability level. Primed atoms are related by the symmetry operation i: 1 - x, 1 - y, 1 - z.
Fig. 2.
Supramolecular chain along the b axis in (I) mediated by C–H···O contacts shown as orange dashed lines.

Crystal data

[Cu2(C2H3O2)4(C6H9N3)2]Z = 1
Mr = 609.58F(000) = 314
Triclinic, P1Dx = 1.550 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.8488 (6) ÅCell parameters from 3508 reflections
b = 8.5114 (7) Åθ = 2.5–28.2°
c = 10.2999 (8) ŵ = 1.68 mm1
α = 98.404 (1)°T = 293 K
β = 92.698 (1)°Prism, blue
γ = 105.599 (1)°0.40 × 0.35 × 0.10 mm
V = 652.92 (9) Å3

Data collection

Bruker SMART APEX CCD diffractometer2969 independent reflections
Radiation source: fine-focus sealed tube2669 reflections with I > 2σ(I)
graphiteRint = 0.018
ω scansθmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −10→10
Tmin = 0.613, Tmax = 0.746k = −11→11
6208 measured reflectionsl = −13→13

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080H atoms treated by a mixture of independent and constrained refinement
S = 1.02w = 1/[σ2(Fo2) + (0.051P)2 + 0.1167P] where P = (Fo2 + 2Fc2)/3
2969 reflections(Δ/σ)max = 0.001
170 parametersΔρmax = 0.28 e Å3
1 restraintΔρmin = −0.25 e Å3

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

xyzUiso*/Ueq
Cu0.60458 (3)0.58733 (2)0.42299 (2)0.02818 (9)
O10.3830 (2)0.5272 (2)0.30471 (15)0.0479 (4)
O20.2102 (2)0.3821 (2)0.43330 (16)0.0491 (4)
O30.5310 (2)0.77124 (17)0.51727 (16)0.0474 (4)
O40.3551 (2)0.62484 (18)0.64537 (16)0.0473 (4)
N10.7898 (2)0.7417 (2)0.30101 (17)0.0328 (3)
N20.8689 (3)0.8709 (2)0.11294 (19)0.0473 (4)
N30.5862 (3)0.7135 (2)0.12539 (18)0.0435 (4)
H30.513 (3)0.648 (2)0.165 (2)0.048 (7)*
C10.2361 (3)0.4432 (2)0.3307 (2)0.0364 (4)
C20.0792 (3)0.4133 (4)0.2317 (3)0.0585 (7)
H2A0.09170.50810.18890.088*
H2B−0.02770.39460.27580.088*
H2C0.07360.31800.16720.088*
C30.4244 (3)0.7560 (2)0.6037 (2)0.0361 (4)
C40.3760 (4)0.9086 (3)0.6633 (3)0.0595 (7)
H4A0.39910.98800.60440.089*
H4B0.44570.95520.74590.089*
H4C0.25220.87990.67750.089*
C50.9529 (3)0.8135 (3)0.3561 (2)0.0497 (6)
H50.98360.79260.43890.060*
C61.0798 (3)0.9180 (4)0.2965 (3)0.0650 (8)
H61.19280.97060.33810.078*
C71.0308 (3)0.9397 (3)0.1740 (3)0.0566 (6)
H71.11511.00640.13020.068*
C80.7529 (3)0.7767 (2)0.18107 (19)0.0342 (4)
C90.5238 (4)0.7487 (3)0.0013 (2)0.0564 (6)
H9A0.57160.6922−0.07070.068*
H9B0.56450.86660.00000.068*
C100.3254 (4)0.6923 (4)−0.0163 (3)0.0754 (9)
H10A0.28480.7136−0.09960.113*
H10B0.27850.75130.05340.113*
H10C0.28550.5759−0.01400.113*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cu0.02719 (13)0.02865 (14)0.02816 (14)0.00393 (9)0.00634 (9)0.00911 (9)
O10.0309 (7)0.0684 (10)0.0392 (8)−0.0011 (7)−0.0011 (6)0.0225 (7)
O20.0326 (7)0.0646 (10)0.0454 (9)−0.0021 (7)−0.0016 (6)0.0253 (8)
O30.0602 (10)0.0330 (7)0.0548 (10)0.0145 (7)0.0295 (8)0.0149 (7)
O40.0601 (10)0.0336 (7)0.0526 (9)0.0139 (7)0.0292 (8)0.0122 (7)
N10.0319 (8)0.0309 (8)0.0339 (8)0.0039 (6)0.0071 (6)0.0077 (6)
N20.0493 (11)0.0492 (10)0.0452 (10)0.0069 (8)0.0209 (9)0.0206 (9)
N30.0444 (10)0.0495 (10)0.0344 (9)0.0033 (8)0.0042 (8)0.0178 (8)
C10.0308 (9)0.0396 (10)0.0367 (10)0.0061 (8)−0.0001 (8)0.0081 (8)
C20.0364 (11)0.0801 (18)0.0541 (15)0.0041 (11)−0.0089 (10)0.0223 (13)
C30.0414 (10)0.0314 (9)0.0367 (10)0.0108 (8)0.0080 (8)0.0068 (8)
C40.0823 (18)0.0381 (12)0.0678 (17)0.0253 (12)0.0358 (14)0.0144 (11)
C50.0410 (12)0.0578 (14)0.0434 (12)−0.0030 (10)0.0060 (10)0.0171 (11)
C60.0387 (12)0.0742 (18)0.0664 (18)−0.0164 (12)0.0095 (12)0.0203 (14)
C70.0510 (14)0.0589 (15)0.0581 (15)0.0006 (11)0.0247 (12)0.0254 (12)
C80.0419 (11)0.0298 (9)0.0325 (10)0.0094 (8)0.0137 (8)0.0080 (7)
C90.0632 (16)0.0740 (17)0.0362 (12)0.0191 (13)0.0054 (11)0.0222 (11)
C100.0622 (17)0.116 (3)0.0530 (16)0.0251 (17)−0.0021 (13)0.0323 (17)

Geometric parameters (Å, °)

Cu—O11.978 (2)C2—H2A0.9600
Cu—O2i1.963 (2)C2—H2B0.9600
Cu—O31.955 (1)C2—H2C0.9600
Cu—O4i1.953 (1)C3—C41.504 (3)
Cu—N12.246 (2)C4—H4A0.9600
Cu—Cui2.6540 (4)C4—H4B0.9600
O1—C11.247 (2)C4—H4C0.9600
O2—C11.246 (3)C5—C61.378 (3)
O3—C31.247 (2)C5—H50.9300
O4—C31.250 (2)C6—C71.355 (4)
N1—C51.321 (3)C6—H60.9300
N1—C81.349 (3)C7—H70.9300
N2—C71.331 (3)C9—C101.494 (4)
N2—C81.340 (3)C9—H9A0.9700
N3—C81.338 (3)C9—H9B0.9700
N3—C91.448 (3)C10—H10A0.9600
N3—H30.85 (1)C10—H10B0.9600
C1—C21.502 (3)C10—H10C0.9600
O4i—Cu—O3167.23 (6)H2B—C2—H2C109.5
O4i—Cu—O2i88.86 (8)O3—C3—O4125.51 (18)
O3—Cu—O2i89.53 (8)O3—C3—C4117.20 (18)
O4i—Cu—O189.76 (8)O4—C3—C4117.29 (18)
O3—Cu—O188.95 (7)C3—C4—H4A109.5
O2i—Cu—O1166.94 (6)C3—C4—H4B109.5
O4i—Cu—N197.38 (6)H4A—C4—H4B109.5
O3—Cu—N195.36 (6)C3—C4—H4C109.5
O2i—Cu—N193.54 (6)H4A—C4—H4C109.5
O1—Cu—N199.52 (6)H4B—C4—H4C109.5
O4i—Cu—Cui83.74 (4)N1—C5—C6123.0 (2)
O3—Cu—Cui83.49 (4)N1—C5—H5118.5
O2i—Cu—Cui84.07 (5)C6—C5—H5118.5
O1—Cu—Cui82.87 (5)C7—C6—C5116.3 (2)
N1—Cu—Cui177.35 (4)C7—C6—H6121.9
C1—O1—Cu124.63 (14)C5—C6—H6121.9
C1—O2—Cui123.95 (14)N2—C7—C6123.7 (2)
C3—O3—Cu123.73 (13)N2—C7—H7118.2
C3—O4—Cui123.48 (13)C6—C7—H7118.2
C5—N1—C8115.85 (17)N3—C8—N2116.97 (19)
C5—N1—Cu115.99 (14)N3—C8—N1117.50 (17)
C8—N1—Cu128.08 (13)N2—C8—N1125.53 (19)
C7—N2—C8115.5 (2)N3—C9—C10109.8 (2)
C8—N3—C9123.88 (19)N3—C9—H9A109.7
C8—N3—H3118.0 (17)C10—C9—H9A109.7
C9—N3—H3118.1 (17)N3—C9—H9B109.7
O2—C1—O1124.4 (2)C10—C9—H9B109.7
O2—C1—C2117.62 (19)H9A—C9—H9B108.2
O1—C1—C2117.9 (2)C9—C10—H10A109.5
C1—C2—H2A109.5C9—C10—H10B109.5
C1—C2—H2B109.5H10A—C10—H10B109.5
H2A—C2—H2B109.5C9—C10—H10C109.5
C1—C2—H2C109.5H10A—C10—H10C109.5
H2A—C2—H2C109.5H10B—C10—H10C109.5
O4i—Cu—O1—C184.62 (19)Cui—O2—C1—C2−177.97 (16)
O3—Cu—O1—C1−82.68 (19)Cu—O1—C1—O2−2.0 (3)
O2i—Cu—O1—C10.7 (4)Cu—O1—C1—C2178.01 (16)
N1—Cu—O1—C1−177.93 (18)Cu—O3—C3—O42.6 (3)
Cui—Cu—O1—C10.90 (18)Cu—O3—C3—C4−177.68 (17)
O4i—Cu—O3—C3−2.8 (4)Cui—O4—C3—O3−2.2 (3)
O2i—Cu—O3—C3−85.53 (19)Cui—O4—C3—C4178.11 (17)
O1—Cu—O3—C381.49 (18)C8—N1—C5—C6−0.1 (3)
N1—Cu—O3—C3−179.05 (18)Cu—N1—C5—C6−177.0 (2)
Cui—Cu—O3—C3−1.45 (17)N1—C5—C6—C7−2.4 (4)
O4i—Cu—N1—C5−93.37 (16)C8—N2—C7—C60.3 (4)
O3—Cu—N1—C585.80 (16)C5—C6—C7—N22.3 (4)
O2i—Cu—N1—C5−4.07 (16)C9—N3—C8—N2−3.6 (3)
O1—Cu—N1—C5175.63 (16)C9—N3—C8—N1175.8 (2)
Cui—Cu—N1—C521.6 (10)C7—N2—C8—N3176.3 (2)
O4i—Cu—N1—C890.11 (16)C7—N2—C8—N1−3.1 (3)
O3—Cu—N1—C8−90.72 (16)C5—N1—C8—N3−176.44 (19)
O2i—Cu—N1—C8179.42 (16)Cu—N1—C8—N30.1 (3)
O1—Cu—N1—C8−0.89 (17)C5—N1—C8—N23.0 (3)
Cui—Cu—N1—C8−154.9 (8)Cu—N1—C8—N2179.51 (15)
Cui—O2—C1—O12.0 (3)C8—N3—C9—C10−166.6 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H3···O10.85 (1)2.04 (1)2.871 (2)164 (2)
C4—H4a···O3ii0.962.513.458 (3)171

Symmetry codes: (ii) −x+1, −y+2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5613).

References

  • Brandenburg, K. (2006). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Bruker (2009). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Fairuz, Z. A., Aiyub, Z., Abdullah, Z., Ng, S. W. & Tiekink, E. R. T. (2010a). Acta Cryst. E66, m1049–m1050. [PMC free article] [PubMed]
  • Fairuz, Z. A., Aiyub, Z., Abdullah, Z., Ng, S. W. & Tiekink, E. R. T. (2010b). Acta Cryst. E66, m1077–m1078. [PMC free article] [PubMed]
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2010). J. Appl. Cryst.43, 920–925.

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