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Acta Crystallogr Sect E Struct Rep Online. 2010 April 1; 66(Pt 4): m410.
Published online 2010 March 17. doi:  10.1107/S1600536810009050
PMCID: PMC2984065

Bis{N-[5-(4-methoxy­phen­yl)-1,3,4-oxa­diazol-2-yl]ethanimidamidato}copper(II)

Abstract

The title compound, [Cu(C11H11N4O2)2], was prepared by solvothermal synthesis using 2-amino-5-(4-methoxy­phen­yl)-1,3,4-oxadiazole and copper sulfate penta­hydrate in an acetonitrile solution. The CuII atom lies on an inversion center and is four-coordinated in a slightly distorted square-planar geometry by four N atoms of the ligands obtained from the formation of a bond between the amine N atom of the oxadiazole mol­ecule and the nitrile C atom of the solvent. In the crystal structure an inter­molecular N—H(...)N hydrogen bond links inversion-related mol­ecules.

Related literature

For comparative bond lengths in similar coordination compounds, see: Cai, (2009 [triangle]). For applications of complexes formed by Schiff base ligands, see: Lu & Schauss (2002 [triangle]). For chemotherapeutic effects of 2,5-substituted-1,3,4-oxadiazole derivatives, see: Cao et al. (2002 [triangle]); Kadi et al. (2007 [triangle]); Zareef et al. (2006 [triangle], 2007 [triangle], 2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m410-scheme1.jpg

Experimental

Crystal data

  • [Cu(C11H11N4O2)2]
  • M r = 526.02
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m410-efi1.jpg
  • a = 4.9020 (6) Å
  • b = 11.2083 (14) Å
  • c = 11.5739 (14) Å
  • α = 111.501 (5)°
  • β = 99.274 (6)°
  • γ = 91.564 (5)°
  • V = 581.33 (12) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 0.99 mm−1
  • T = 120 K
  • 0.53 × 0.23 × 0.07 mm

Data collection

  • Bruker APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2002 [triangle]) T min = 0.707, T max = 0.933
  • 6654 measured reflections
  • 2633 independent reflections
  • 2417 reflections with I > 2σ(I)
  • R int = 0.035

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.087
  • S = 1.06
  • 2633 reflections
  • 166 parameters
  • H-atom parameters constrained
  • Δρmax = 0.42 e Å−3
  • Δρmin = −0.29 e Å−3

Data collection: SMART (Bruker, 2002 [triangle]); cell refinement: SAINT (Bruker, 2002 [triangle]); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810009050/pk2228sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810009050/pk2228Isup2.hkl

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

Acknowledgments

This work was supported by the Laboratoire de Chimie des Materiaux, Faculté des Sciences, Université Mentouri. We would like to thank J.-Y. Saillard of Rennes 1 University for providing diffraction facilities.

supplementary crystallographic information

Comment

In recent years, there has been a considerable effort towards preparation of new materials containing polyfunctional organic ligands able to bind metallic ions by solvothermal synthesis. For example, with Schiff bases ligands, such complexes could be applied in different areas, including biochemistry, electrochemistry, and catalysis (Lu et al., 2002).

The 2,5-substituted-1,3,4-oxadiazole derivatives are of significant interest due to their chemotherapeutic effects (Kadi et al., 2007; Zareef et al., 2008; Zareef et al., 2007; Zareef et al., 2006; Cao et al., 2002). In this paper, we report the structure of one of these compounds with copper (II).

In the centrosymmetric title complex, the Cu (II) atom is located on an inversion center and is four-coordinated in a square planar geometry by four N atoms of the ligands obtained from the formation of a bond between N-amine of the oxadiazole molecule and C-nitrile of the solvent. All the coordinated bond lengths are typical and comparable with those in similar copper (II) complexes (Cai,2009). In the title compound, there is just one weak hydrogen bond N1-H1···N8 linking different inversion (-x, -y, -Z+1) related molecules.

Experimental

5-(4-Methoxy-phenyl)-2amino-1, 3, 4-oxadiazole (0,2 mmole) and (0,1 mmole) copper sulfate pentahydrate were mixed in 5 ml of acetonitrile. The mixture was placed in a Teflon-lined stainless steel vessel, and heated to 160° C for 16 h. It was then cooled to room temperature over a period of 24 h, and washed using acetonitrile. Brown crystals suitable for X-Ray crystallography were obtained.

Refinement

H atoms were placed at calculated positions (C-H = 0..88-0.98 Å) and were treated as riding on their parent atoms, with Uiso(H) set to 1.2-1.5 times Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound in 30% probability displacement ellipsoids for non-H atoms.

Crystal data

[Cu(C11H11N4O2)2]Z = 1
Mr = 526.02F(000) = 271
Triclinic, P1Dx = 1.503 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 4.9020 (6) ÅCell parameters from 2925 reflections
b = 11.2083 (14) Åθ = 3.2–27.4°
c = 11.5739 (14) ŵ = 0.99 mm1
α = 111.501 (5)°T = 120 K
β = 99.274 (6)°Plate, brown
γ = 91.564 (5)°0.53 × 0.23 × 0.07 mm
V = 581.33 (12) Å3

Data collection

Bruker APEXII diffractometer2633 independent reflections
Radiation source: Enraf-Nonius FR5902417 reflections with I > 2σ(I)
graphiteRint = 0.035
CCD rotation images, thin slices scansθmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)h = −6→6
Tmin = 0.707, Tmax = 0.933k = −14→14
6654 measured reflectionsl = −15→15

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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087H-atom parameters constrained
S = 1.06w = 1/[σ2(Fo2) + (0.0355P)2 + 0.2373P] where P = (Fo2 + 2Fc2)/3
2633 reflections(Δ/σ)max < 0.001
166 parametersΔρmax = 0.42 e Å3
0 restraintsΔρmin = −0.29 e Å3

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

xyzUiso*/Ueq
Cu1000.50.02231 (12)
N10.1428 (3)−0.09664 (16)0.34848 (16)0.0245 (4)
H10.0696−0.17690.30980.029*
C20.3294 (4)−0.06281 (19)0.29405 (19)0.0240 (4)
C30.3968 (5)−0.1574 (2)0.1722 (2)0.0314 (5)
H3A0.3138−0.24380.15620.047*
H3B0.5986−0.15810.17940.047*
H3C0.3216−0.13140.10210.047*
N40.4749 (3)0.05335 (16)0.33696 (16)0.0255 (4)
C50.4203 (4)0.14395 (19)0.44061 (19)0.0229 (4)
N60.2379 (3)0.14792 (15)0.51450 (16)0.0230 (4)
O70.5775 (3)0.26005 (13)0.48592 (13)0.0244 (3)
N80.2771 (3)0.26958 (16)0.61315 (17)0.0257 (4)
C90.4788 (4)0.33114 (19)0.59302 (19)0.0234 (4)
C100.6076 (4)0.46056 (19)0.6693 (2)0.0251 (4)
C110.5447 (5)0.5265 (2)0.7888 (2)0.0368 (5)
H110.4170.48650.82020.044*
C120.6665 (5)0.6494 (2)0.8615 (2)0.0385 (6)
H120.62390.69310.94290.046*
C130.8519 (4)0.70962 (19)0.8158 (2)0.0266 (4)
C140.9179 (5)0.6449 (2)0.6975 (2)0.0309 (5)
H141.04550.68490.66610.037*
C150.7950 (5)0.5211 (2)0.6259 (2)0.0321 (5)
H150.84040.47670.54520.038*
O160.9576 (3)0.83100 (14)0.89471 (14)0.0336 (4)
C171.1494 (5)0.8972 (2)0.8518 (2)0.0321 (5)
H17A1.31380.84960.83840.048*
H17B1.2050.98410.91540.048*
H17C1.06010.9030.77220.048*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cu10.02216 (19)0.01886 (19)0.0244 (2)−0.00107 (13)0.00942 (14)0.00450 (14)
N10.0251 (8)0.0203 (8)0.0251 (9)−0.0016 (6)0.0080 (7)0.0039 (7)
C20.0251 (10)0.0244 (10)0.0225 (10)0.0037 (8)0.0058 (8)0.0083 (8)
C30.0365 (12)0.0275 (11)0.0263 (11)−0.0012 (9)0.0110 (9)0.0039 (9)
N40.0290 (9)0.0231 (9)0.0238 (9)−0.0008 (7)0.0106 (7)0.0057 (7)
C50.0225 (9)0.0206 (10)0.0261 (10)−0.0003 (7)0.0048 (8)0.0094 (8)
N60.0233 (8)0.0199 (8)0.0238 (8)0.0002 (6)0.0094 (7)0.0040 (7)
O70.0277 (7)0.0197 (7)0.0247 (7)−0.0024 (5)0.0093 (6)0.0056 (6)
N80.0266 (9)0.0187 (8)0.0279 (9)−0.0001 (7)0.0097 (7)0.0027 (7)
C90.0247 (10)0.0208 (10)0.0243 (10)0.0022 (8)0.0081 (8)0.0064 (8)
C100.0257 (10)0.0203 (10)0.0274 (11)0.0015 (8)0.0068 (8)0.0060 (8)
C110.0446 (13)0.0299 (12)0.0344 (12)−0.0070 (10)0.0200 (11)0.0061 (10)
C120.0540 (15)0.0298 (12)0.0281 (12)−0.0058 (10)0.0201 (11)0.0021 (10)
C130.0294 (10)0.0205 (10)0.0265 (10)−0.0013 (8)0.0053 (9)0.0053 (8)
C140.0354 (12)0.0251 (11)0.0305 (11)−0.0060 (9)0.0127 (9)0.0061 (9)
C150.0397 (12)0.0252 (11)0.0257 (11)−0.0046 (9)0.0157 (9)−0.0004 (9)
O160.0432 (9)0.0231 (8)0.0287 (8)−0.0081 (6)0.0108 (7)0.0021 (6)
C170.0365 (12)0.0225 (11)0.0343 (12)−0.0059 (9)0.0070 (10)0.0075 (9)

Geometric parameters (Å, °)

Cu1—N6i1.9403 (16)C9—C101.454 (3)
Cu1—N61.9403 (16)C10—C151.386 (3)
Cu1—N1i1.9451 (17)C10—C111.398 (3)
Cu1—N11.9451 (17)C11—C121.380 (3)
N1—C21.311 (3)C11—H110.95
N1—H10.88C12—C131.394 (3)
C2—N41.346 (3)C12—H120.95
C2—C31.515 (3)C13—O161.361 (2)
C3—H3A0.98C13—C141.390 (3)
C3—H3B0.98C14—C151.388 (3)
C3—H3C0.98C14—H140.95
N4—C51.329 (3)C15—H150.95
C5—N61.324 (3)O16—C171.436 (3)
C5—O71.370 (2)C17—H17A0.98
N6—N81.405 (2)C17—H17B0.98
O7—C91.377 (2)C17—H17C0.98
N8—C91.289 (2)
N6i—Cu1—N6180.00 (6)N8—C9—C10127.92 (19)
N6i—Cu1—N1i87.39 (7)O7—C9—C10119.18 (17)
N6—Cu1—N1i92.61 (7)C15—C10—C11118.54 (19)
N6i—Cu1—N192.61 (7)C15—C10—C9121.09 (19)
N6—Cu1—N187.39 (7)C11—C10—C9120.36 (19)
N1i—Cu1—N1180C12—C11—C10120.5 (2)
C2—N1—Cu1131.13 (14)C12—C11—H11119.7
C2—N1—H1114.4C10—C11—H11119.7
Cu1—N1—H1114.4C11—C12—C13120.2 (2)
N1—C2—N4125.48 (18)C11—C12—H12119.9
N1—C2—C3120.38 (18)C13—C12—H12119.9
N4—C2—C3114.13 (17)O16—C13—C14124.78 (19)
C2—C3—H3A109.5O16—C13—C12115.32 (19)
C2—C3—H3B109.5C14—C13—C12119.90 (19)
H3A—C3—H3B109.5C15—C14—C13119.2 (2)
C2—C3—H3C109.5C15—C14—H14120.4
H3A—C3—H3C109.5C13—C14—H14120.4
H3B—C3—H3C109.5C10—C15—C14121.6 (2)
C5—N4—C2118.09 (17)C10—C15—H15119.2
N6—C5—N4133.31 (18)C14—C15—H15119.2
N6—C5—O7109.26 (17)C13—O16—C17117.41 (17)
N4—C5—O7117.43 (17)O16—C17—H17A109.5
C5—N6—N8108.50 (16)O16—C17—H17B109.5
C5—N6—Cu1124.23 (14)H17A—C17—H17B109.5
N8—N6—Cu1126.65 (13)O16—C17—H17C109.5
C5—O7—C9104.03 (14)H17A—C17—H17C109.5
C9—N8—N6105.28 (16)H17B—C17—H17C109.5
N8—C9—O7112.90 (17)
N6i—Cu1—N1—C2−177.96 (19)N6—N8—C9—O70.9 (2)
N6—Cu1—N1—C22.04 (19)N6—N8—C9—C10−178.20 (19)
Cu1—N1—C2—N41.8 (3)C5—O7—C9—N8−1.4 (2)
Cu1—N1—C2—C3−178.05 (14)C5—O7—C9—C10177.76 (17)
N1—C2—N4—C5−2.6 (3)N8—C9—C10—C15−170.3 (2)
C3—C2—N4—C5177.23 (17)O7—C9—C10—C1510.7 (3)
C2—N4—C5—N6−2.5 (3)N8—C9—C10—C119.8 (3)
C2—N4—C5—O7177.53 (17)O7—C9—C10—C11−169.16 (19)
N4—C5—N6—N8179.1 (2)C15—C10—C11—C120.2 (4)
O7—C5—N6—N8−0.9 (2)C9—C10—C11—C12180.0 (2)
N4—C5—N6—Cu17.6 (3)C10—C11—C12—C130.7 (4)
O7—C5—N6—Cu1−172.39 (12)C11—C12—C13—O16179.4 (2)
N1i—Cu1—N6—C5174.14 (16)C11—C12—C13—C14−1.1 (4)
N1—Cu1—N6—C5−5.86 (16)O16—C13—C14—C15−179.9 (2)
N1i—Cu1—N6—N84.22 (16)C12—C13—C14—C150.6 (3)
N1—Cu1—N6—N8−175.78 (16)C11—C10—C15—C14−0.6 (3)
N6—C5—O7—C91.4 (2)C9—C10—C15—C14179.6 (2)
N4—C5—O7—C9−178.66 (17)C13—C14—C15—C100.2 (4)
C5—N6—N8—C90.0 (2)C14—C13—O16—C170.6 (3)
Cu1—N6—N8—C9171.26 (14)C12—C13—O16—C17−179.9 (2)

Symmetry codes: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···N8i0.882.422.983 (2)123

Symmetry codes: (i) −x, −y, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PK2228).

References

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