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

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 Cu^II 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.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.037
• wR factor = 0.087
• Data-to-parameter ratio = 15.9

checkCIF/PLATON results

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S1. 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.

Related literature

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

S2. 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.

S3. 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 U_iso(H) set to 1.2-1.5 times U_eq(C).

Computing details

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

Figures

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

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

Crystal data

[Cu(C11H11N4O2)2]	Z = 1
Mr = 526.02	F(000) = 271
Triclinic, P1	Dx = 1.503 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.9020 (6) Å	Cell parameters from 2925 reflections
b = 11.2083 (14) Å	θ = 3.2–27.4°
c = 11.5739 (14) Å	µ = 0.99 mm^−1
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) Å^3

Data collection

Bruker APEXII diffractometer	2633 independent reflections
Radiation source: Enraf-Nonius FR590	2417 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
CCD rotation images, thin slices scans	θmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −6→6
Tmin = 0.707, Tmax = 0.933	k = −14→14
6654 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.087	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0355P)^2 + 0.2373P] where P = (Fo^2 + 2Fc^2)/3
2633 reflections	(Δ/σ)max < 0.001
166 parameters	Δρmax = 0.42 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

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

	x	y	z	Uiso*/Ueq
Cu1	0	0	0.5	0.02231 (12)
N1	0.1428 (3)	−0.09664 (16)	0.34848 (16)	0.0245 (4)
H1	0.0696	−0.1769	0.3098	0.029*
C2	0.3294 (4)	−0.06281 (19)	0.29405 (19)	0.0240 (4)
C3	0.3968 (5)	−0.1574 (2)	0.1722 (2)	0.0314 (5)
H3A	0.3138	−0.2438	0.1562	0.047*
H3B	0.5986	−0.1581	0.1794	0.047*
H3C	0.3216	−0.1314	0.1021	0.047*
N4	0.4749 (3)	0.05335 (16)	0.33696 (16)	0.0255 (4)
C5	0.4203 (4)	0.14395 (19)	0.44061 (19)	0.0229 (4)
N6	0.2379 (3)	0.14792 (15)	0.51450 (16)	0.0230 (4)
O7	0.5775 (3)	0.26005 (13)	0.48592 (13)	0.0244 (3)
N8	0.2771 (3)	0.26958 (16)	0.61315 (17)	0.0257 (4)
C9	0.4788 (4)	0.33114 (19)	0.59302 (19)	0.0234 (4)
C10	0.6076 (4)	0.46056 (19)	0.6693 (2)	0.0251 (4)
C11	0.5447 (5)	0.5265 (2)	0.7888 (2)	0.0368 (5)
H11	0.417	0.4865	0.8202	0.044*
C12	0.6665 (5)	0.6494 (2)	0.8615 (2)	0.0385 (6)
H12	0.6239	0.6931	0.9429	0.046*
C13	0.8519 (4)	0.70962 (19)	0.8158 (2)	0.0266 (4)
C14	0.9179 (5)	0.6449 (2)	0.6975 (2)	0.0309 (5)
H14	1.0455	0.6849	0.6661	0.037*
C15	0.7950 (5)	0.5211 (2)	0.6259 (2)	0.0321 (5)
H15	0.8404	0.4767	0.5452	0.038*
O16	0.9576 (3)	0.83100 (14)	0.89471 (14)	0.0336 (4)
C17	1.1494 (5)	0.8972 (2)	0.8518 (2)	0.0321 (5)
H17A	1.3138	0.8496	0.8384	0.048*
H17B	1.205	0.9841	0.9154	0.048*
H17C	1.0601	0.903	0.7722	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02216 (19)	0.01886 (19)	0.0244 (2)	−0.00107 (13)	0.00942 (14)	0.00450 (14)
N1	0.0251 (8)	0.0203 (8)	0.0251 (9)	−0.0016 (6)	0.0080 (7)	0.0039 (7)
C2	0.0251 (10)	0.0244 (10)	0.0225 (10)	0.0037 (8)	0.0058 (8)	0.0083 (8)
C3	0.0365 (12)	0.0275 (11)	0.0263 (11)	−0.0012 (9)	0.0110 (9)	0.0039 (9)
N4	0.0290 (9)	0.0231 (9)	0.0238 (9)	−0.0008 (7)	0.0106 (7)	0.0057 (7)
C5	0.0225 (9)	0.0206 (10)	0.0261 (10)	−0.0003 (7)	0.0048 (8)	0.0094 (8)
N6	0.0233 (8)	0.0199 (8)	0.0238 (8)	0.0002 (6)	0.0094 (7)	0.0040 (7)
O7	0.0277 (7)	0.0197 (7)	0.0247 (7)	−0.0024 (5)	0.0093 (6)	0.0056 (6)
N8	0.0266 (9)	0.0187 (8)	0.0279 (9)	−0.0001 (7)	0.0097 (7)	0.0027 (7)
C9	0.0247 (10)	0.0208 (10)	0.0243 (10)	0.0022 (8)	0.0081 (8)	0.0064 (8)
C10	0.0257 (10)	0.0203 (10)	0.0274 (11)	0.0015 (8)	0.0068 (8)	0.0060 (8)
C11	0.0446 (13)	0.0299 (12)	0.0344 (12)	−0.0070 (10)	0.0200 (11)	0.0061 (10)
C12	0.0540 (15)	0.0298 (12)	0.0281 (12)	−0.0058 (10)	0.0201 (11)	0.0021 (10)
C13	0.0294 (10)	0.0205 (10)	0.0265 (10)	−0.0013 (8)	0.0053 (9)	0.0053 (8)
C14	0.0354 (12)	0.0251 (11)	0.0305 (11)	−0.0060 (9)	0.0127 (9)	0.0061 (9)
C15	0.0397 (12)	0.0252 (11)	0.0257 (11)	−0.0046 (9)	0.0157 (9)	−0.0004 (9)
O16	0.0432 (9)	0.0231 (8)	0.0287 (8)	−0.0081 (6)	0.0108 (7)	0.0021 (6)
C17	0.0365 (12)	0.0225 (11)	0.0343 (12)	−0.0059 (9)	0.0070 (10)	0.0075 (9)

Geometric parameters (Å, º)

Cu1—N6^i	1.9403 (16)	C9—C10	1.454 (3)
Cu1—N6	1.9403 (16)	C10—C15	1.386 (3)
Cu1—N1^i	1.9451 (17)	C10—C11	1.398 (3)
Cu1—N1	1.9451 (17)	C11—C12	1.380 (3)
N1—C2	1.311 (3)	C11—H11	0.95
N1—H1	0.88	C12—C13	1.394 (3)
C2—N4	1.346 (3)	C12—H12	0.95
C2—C3	1.515 (3)	C13—O16	1.361 (2)
C3—H3A	0.98	C13—C14	1.390 (3)
C3—H3B	0.98	C14—C15	1.388 (3)
C3—H3C	0.98	C14—H14	0.95
N4—C5	1.329 (3)	C15—H15	0.95
C5—N6	1.324 (3)	O16—C17	1.436 (3)
C5—O7	1.370 (2)	C17—H17A	0.98
N6—N8	1.405 (2)	C17—H17B	0.98
O7—C9	1.377 (2)	C17—H17C	0.98
N8—C9	1.289 (2)
N6^i—Cu1—N6	180.00 (6)	N8—C9—C10	127.92 (19)
N6^i—Cu1—N1^i	87.39 (7)	O7—C9—C10	119.18 (17)
N6—Cu1—N1^i	92.61 (7)	C15—C10—C11	118.54 (19)
N6^i—Cu1—N1	92.61 (7)	C15—C10—C9	121.09 (19)
N6—Cu1—N1	87.39 (7)	C11—C10—C9	120.36 (19)
N1^i—Cu1—N1	180	C12—C11—C10	120.5 (2)
C2—N1—Cu1	131.13 (14)	C12—C11—H11	119.7
C2—N1—H1	114.4	C10—C11—H11	119.7
Cu1—N1—H1	114.4	C11—C12—C13	120.2 (2)
N1—C2—N4	125.48 (18)	C11—C12—H12	119.9
N1—C2—C3	120.38 (18)	C13—C12—H12	119.9
N4—C2—C3	114.13 (17)	O16—C13—C14	124.78 (19)
C2—C3—H3A	109.5	O16—C13—C12	115.32 (19)
C2—C3—H3B	109.5	C14—C13—C12	119.90 (19)
H3A—C3—H3B	109.5	C15—C14—C13	119.2 (2)
C2—C3—H3C	109.5	C15—C14—H14	120.4
H3A—C3—H3C	109.5	C13—C14—H14	120.4
H3B—C3—H3C	109.5	C10—C15—C14	121.6 (2)
C5—N4—C2	118.09 (17)	C10—C15—H15	119.2
N6—C5—N4	133.31 (18)	C14—C15—H15	119.2
N6—C5—O7	109.26 (17)	C13—O16—C17	117.41 (17)
N4—C5—O7	117.43 (17)	O16—C17—H17A	109.5
C5—N6—N8	108.50 (16)	O16—C17—H17B	109.5
C5—N6—Cu1	124.23 (14)	H17A—C17—H17B	109.5
N8—N6—Cu1	126.65 (13)	O16—C17—H17C	109.5
C5—O7—C9	104.03 (14)	H17A—C17—H17C	109.5
C9—N8—N6	105.28 (16)	H17B—C17—H17C	109.5
N8—C9—O7	112.90 (17)
N6^i—Cu1—N1—C2	−177.96 (19)	N6—N8—C9—O7	0.9 (2)
N6—Cu1—N1—C2	2.04 (19)	N6—N8—C9—C10	−178.20 (19)
Cu1—N1—C2—N4	1.8 (3)	C5—O7—C9—N8	−1.4 (2)
Cu1—N1—C2—C3	−178.05 (14)	C5—O7—C9—C10	177.76 (17)
N1—C2—N4—C5	−2.6 (3)	N8—C9—C10—C15	−170.3 (2)
C3—C2—N4—C5	177.23 (17)	O7—C9—C10—C15	10.7 (3)
C2—N4—C5—N6	−2.5 (3)	N8—C9—C10—C11	9.8 (3)
C2—N4—C5—O7	177.53 (17)	O7—C9—C10—C11	−169.16 (19)
N4—C5—N6—N8	179.1 (2)	C15—C10—C11—C12	0.2 (4)
O7—C5—N6—N8	−0.9 (2)	C9—C10—C11—C12	180.0 (2)
N4—C5—N6—Cu1	7.6 (3)	C10—C11—C12—C13	0.7 (4)
O7—C5—N6—Cu1	−172.39 (12)	C11—C12—C13—O16	179.4 (2)
N1^i—Cu1—N6—C5	174.14 (16)	C11—C12—C13—C14	−1.1 (4)
N1—Cu1—N6—C5	−5.86 (16)	O16—C13—C14—C15	−179.9 (2)
N1^i—Cu1—N6—N8	4.22 (16)	C12—C13—C14—C15	0.6 (3)
N1—Cu1—N6—N8	−175.78 (16)	C11—C10—C15—C14	−0.6 (3)
N6—C5—O7—C9	1.4 (2)	C9—C10—C15—C14	179.6 (2)
N4—C5—O7—C9	−178.66 (17)	C13—C14—C15—C10	0.2 (4)
C5—N6—N8—C9	0.0 (2)	C14—C13—O16—C17	0.6 (3)
Cu1—N6—N8—C9	171.26 (14)	C12—C13—O16—C17	−179.9 (2)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N8^i	0.88	2.42	2.983 (2)	123

Symmetry code: (i) −x, −y, −z+1.