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Acta Crystallogr Sect E Struct Rep Online. 2010 October 1; 66(Pt 10): m1271.
Published online 2010 September 18. doi:  10.1107/S1600536810034860
PMCID: PMC2983124

Di-μ-azido-bis­({N′-[1-(2-pyrid­yl-κN)ethyl­idene]acetohydrazidato-κ2 N′,O}dicopper(II))

Abstract

The dimeric title compound, [Cu2(C9H10N3O)2(N3)2], is located on a crystallographic inversion center. The Cu atom is coordinated by a tridentate anionic hydrazone ligand and two bridging azide ligands in a distorted square-pyramidal coordination geometry. The non-bonding Cu(...)Cu distance is 3.238 (1) Å. Non-classical inter­molecular C—H(...)N hydrogen bonds link the dimers into chains along the c axis.

Related literature

For related dimeric copper(II) complexes with similar tridentate ligands, see: Recio Despaigne et al. (2009 [triangle]); Sen et al. (2007 [triangle]); Patole et al. (2003 [triangle]).

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Object name is e-66-m1271-scheme1.jpg

Experimental

Crystal data

  • [Cu2(C9H10N3O)2(N3)2]
  • M r = 563.54
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1271-efi1.jpg
  • a = 7.589 (3) Å
  • b = 8.955 (3) Å
  • c = 9.693 (4) Å
  • α = 66.534 (15)°
  • β = 69.461 (13)°
  • γ = 81.468 (16)°
  • V = 565.8 (4) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 1.92 mm−1
  • T = 150 K
  • 0.25 × 0.20 × 0.20 mm

Data collection

  • Bruker SMART APEXII diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003 [triangle]) T min = 0.645, T max = 0.700
  • 3858 measured reflections
  • 2358 independent reflections
  • 1591 reflections with I > 2σ
  • R int = 0.040

Refinement

  • R[F 2 > 2σ(F 2)] = 0.027
  • wR(F 2) = 0.093
  • S = 1.08
  • 2358 reflections
  • 156 parameters
  • H-atom parameters constrained
  • Δρmax = 2.08 e Å−3
  • Δρmin = −2.81 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [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: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: DIAMOND (Brandenburg, 2006 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810034860/pv2324sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810034860/pv2324Isup2.hkl

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

Acknowledgments

We are grateful to the National Science Council of Taiwan for financial support of this work.

supplementary crystallographic information

Comment

The title compound is a dimeric copper(II) complex. Each copper atom is coordinated by a tridentate, anionic hydrazone ligand and two bridging azide ligands. The non-bonding Cu···Cu distance is 3.238 (1) Å, which is slightly longer than that in a related dicopper azido complex (Sen et al.., 2007).

The dimer is located on a crystallographic inversion center. The non-classical intermolecular hydrogen bonds of the type C—H···N link the dimeric compounds into one dimensional chains along the c axis.

Dimeric copper(II) complexes with similar tridentate ligands have been reported in the literature (Recio Despaigne et al., 2009; Sen et al. 2007; Patole et al. 2003).

Experimental

The tridentate ligand precursor, 2-benzoylpyridine-methyl hydrazone, was prepared according to the literature procedure (Recio Despaigne et al., 2009). To the tridentate ligand precursor (1.0 mmol), methanolic solution (20 ml) of copper nitrate trihydrate (0.241 g, 1.0 mmol), was added, followed by the addition, with constant stirring of a solution of sodium azide (0.065 g, 1.0 mmol) in minimum volume of water/methanol mixture. The final solution was kept at room temperature yielding brown square-shaped crystals suitable for X-ray diffraction after few days. Crystals were isolated by filtration and were air-dried.

Refinement

All the hydrogen atoms were located in the difference Fourier map, nevertheless, all the H atoms were positioned geometrically and refined as riding atoms, with Caryl—H = 0.95, Cmethyl—H = 0.98 Å while Uiso(H) = 1.2Ueq(Caryl) and 1.5Ueq(Cmethyl) H atoms. Although the residual electron in the final difference map is high, the refinement model appears to be reliable since the largest peak and hole are located near the heavy Cu atom at distances of 0.70 and 0.03 Å, respectively.

Figures

Fig. 1.
The structure of the title compound, showing 50% probability displacement ellipsoids for the non-hydrogen atoms. The unlabelled atoms are related to the labelled ones by symmetry operation: 1 - x, 2 - y, 2 - z.
Fig. 2.
A view of the crystal packing along the b axis. Hydrogen bonds are shown as dashed lines and H-atoms not involved in H-bonds have been excluded for clarity.

Crystal data

[Cu2(C9H10N3O)2(N3)2]Z = 1
Mr = 563.54F(000) = 286
Triclinic, P1Dx = 1.654 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.589 (3) ÅCell parameters from 3185 reflections
b = 8.955 (3) Åθ = 2.9–28.5°
c = 9.693 (4) ŵ = 1.92 mm1
α = 66.534 (15)°T = 150 K
β = 69.461 (13)°Prism, brown
γ = 81.468 (16)°0.25 × 0.20 × 0.20 mm
V = 565.8 (4) Å3

Data collection

Bruker SMART APEXII diffractometer2358 independent reflections
Radiation source: fine-focus sealed tube1591 reflections with I > 2σ
graphiteRint = 0.040
ω scansθmax = 27.0°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)h = −9→9
Tmin = 0.645, Tmax = 0.700k = −11→10
3858 measured reflectionsl = −12→12

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)] = 0.027Hydrogen site location: difference Fourier map
wR(F2) = 0.093H-atom parameters constrained
S = 1.08w = 1/[σ2(Fo2) + (0.0597P)2] where P = (Fo2 + 2Fc2)/3
2358 reflections(Δ/σ)max = 0.001
156 parametersΔρmax = 2.08 e Å3
0 restraintsΔρmin = −2.81 e Å3

Special details

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)

xyzUiso*/Ueq
Cu10.34274 (3)0.93665 (3)0.95880 (3)0.02989 (14)
N50.2011 (2)0.7390 (2)1.0402 (2)0.0307 (5)
O10.4938 (2)0.8357 (2)0.8052 (2)0.0380 (5)
N10.4648 (3)1.1498 (2)0.8642 (2)0.0329 (5)
N60.2719 (3)0.6294 (3)0.9663 (2)0.0367 (6)
C80.4270 (3)0.6937 (3)0.8443 (3)0.0314 (6)
N20.5605 (3)1.2073 (2)0.7250 (2)0.0358 (6)
N40.1206 (2)0.9791 (2)1.1350 (2)0.0315 (5)
C1−0.0012 (3)0.8504 (3)1.2187 (3)0.0341 (6)
C2−0.1553 (3)0.8504 (4)1.3488 (3)0.0438 (8)
H2−0.24040.76191.40360.053*
C90.5264 (3)0.5944 (3)0.7465 (3)0.0436 (7)
H9A0.49380.63570.64830.065*
H9B0.48810.48060.80670.065*
H9C0.66270.60190.72020.065*
C50.0911 (3)1.1048 (3)1.1831 (3)0.0390 (7)
H50.17581.19351.12540.047*
C60.0467 (3)0.7153 (3)1.1593 (3)0.0351 (7)
C3−0.1850 (3)0.9815 (4)1.3992 (3)0.0470 (9)
H3−0.28880.98251.48910.056*
C4−0.0596 (4)1.1095 (4)1.3148 (3)0.0449 (7)
H4−0.07611.19971.34650.054*
N30.6520 (4)1.2683 (4)0.5959 (3)0.0644 (10)
C7−0.0748 (4)0.5681 (4)1.2321 (4)0.0564 (10)
H7A−0.04110.50991.15940.085*
H7B−0.20730.60221.25160.085*
H7C−0.05560.49621.33280.085*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cu10.03078 (16)0.0297 (2)0.02843 (18)−0.00779 (10)−0.00486 (12)−0.01154 (14)
N50.0319 (7)0.0317 (10)0.0289 (9)−0.0042 (7)−0.0062 (7)−0.0133 (8)
O10.0400 (8)0.0382 (10)0.0350 (9)−0.0100 (6)−0.0044 (7)−0.0163 (8)
N10.0386 (8)0.0306 (10)0.0287 (9)−0.0063 (7)−0.0068 (8)−0.0117 (9)
N60.0383 (9)0.0368 (11)0.0351 (10)−0.0048 (8)−0.0079 (9)−0.0154 (9)
C80.0389 (9)0.0296 (11)0.0318 (10)−0.0017 (8)−0.0140 (9)−0.0148 (9)
N20.0404 (9)0.0327 (10)0.0316 (10)−0.0034 (7)−0.0105 (8)−0.0091 (9)
N40.0303 (7)0.0331 (10)0.0310 (9)−0.0027 (6)−0.0079 (7)−0.0126 (8)
C10.0286 (8)0.0403 (12)0.0295 (11)−0.0040 (7)−0.0073 (8)−0.0098 (10)
C20.0346 (10)0.0535 (16)0.0353 (12)−0.0070 (9)−0.0012 (9)−0.0150 (13)
C90.0495 (12)0.0421 (15)0.0402 (13)−0.0022 (10)−0.0097 (11)−0.0200 (12)
C50.0395 (10)0.0399 (14)0.0386 (12)−0.0032 (9)−0.0109 (10)−0.0162 (12)
C60.0323 (9)0.0352 (12)0.0343 (11)−0.0074 (8)−0.0070 (9)−0.0102 (10)
C30.0388 (10)0.0623 (19)0.0358 (13)0.0030 (10)−0.0028 (10)−0.0234 (14)
C40.0484 (12)0.0489 (16)0.0437 (14)0.0071 (10)−0.0130 (11)−0.0277 (12)
N30.0746 (16)0.0654 (19)0.0323 (12)−0.0125 (13)−0.0042 (12)−0.0045 (14)
C70.0493 (13)0.0495 (18)0.0599 (19)−0.0198 (12)0.0053 (13)−0.0229 (16)

Geometric parameters (Å, °)

Cu1—N51.941 (2)C1—C61.484 (4)
Cu1—N11.969 (2)C2—C31.403 (5)
Cu1—O11.979 (2)C2—H20.9500
Cu1—N42.051 (2)C9—H9A0.9800
Cu1—N1i2.4574 (18)C9—H9B0.9800
N5—C61.297 (3)C9—H9C0.9800
N5—N61.377 (4)C5—C41.394 (4)
O1—C81.300 (3)C5—H50.9500
N1—N21.218 (3)C6—C71.500 (3)
N1—Cu1i2.4574 (18)C3—C41.386 (4)
N6—C81.341 (3)C3—H30.9500
C8—C91.493 (5)C4—H40.9500
N2—N31.142 (3)C7—H7A0.9800
N4—C51.343 (4)C7—H7B0.9800
N4—C11.374 (3)C7—H7C0.9800
C1—C21.387 (4)
N5—Cu1—N1173.44 (6)C1—C2—C3119.8 (2)
N5—Cu1—O179.78 (9)C1—C2—H2120.1
N1—Cu1—O1101.14 (9)C3—C2—H2120.1
N5—Cu1—N480.27 (9)C8—C9—H9A109.5
N1—Cu1—N498.12 (10)C8—C9—H9B109.5
O1—Cu1—N4159.42 (8)H9A—C9—H9B109.5
N5—Cu1—N1i99.67 (7)C8—C9—H9C109.5
N1—Cu1—N1i86.64 (6)H9A—C9—H9C109.5
O1—Cu1—N1i98.75 (8)H9B—C9—H9C109.5
N4—Cu1—N1i89.51 (8)N4—C5—C4122.3 (2)
C6—N5—N6123.0 (2)N4—C5—H5118.9
C6—N5—Cu1119.7 (2)C4—C5—H5118.9
N6—N5—Cu1117.28 (14)N5—C6—C1113.21 (19)
C8—O1—Cu1110.27 (16)N5—C6—C7124.6 (3)
N2—N1—Cu1122.4 (2)C1—C6—C7122.2 (3)
N2—N1—Cu1i111.79 (13)C4—C3—C2118.5 (3)
Cu1—N1—Cu1i93.36 (6)C4—C3—H3120.7
C8—N6—N5107.9 (2)C2—C3—H3120.7
O1—C8—N6124.6 (3)C3—C4—C5119.4 (3)
O1—C8—C9118.6 (2)C3—C4—H4120.3
N6—C8—C9116.8 (2)C5—C4—H4120.3
N3—N2—N1176.3 (3)C6—C7—H7A109.5
C5—N4—C1119.0 (2)C6—C7—H7B109.5
C5—N4—Cu1128.98 (15)H7A—C7—H7B109.5
C1—N4—Cu1111.8 (2)C6—C7—H7C109.5
N4—C1—C2121.1 (3)H7A—C7—H7C109.5
N4—C1—C6114.9 (2)H7B—C7—H7C109.5
C2—C1—C6124.0 (2)

Symmetry codes: (i) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C9—H9A···N3ii0.982.743.710 (4)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: PV2324).

References

  • Brandenburg, K. (2006). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Patole, J., Sandbhor, U., Padhye, S., Deobagkar, D. N., Anson, C. E. & Powell, A. (2003). Bioorg. Med. Chem. Lett.13, 51–55. [PubMed]
  • Recio Despaigne, A. A., Da Silva, J. G., Do Carmo, A. C. M., Piro, O. E., Castellano, E. E. & Beraldo, H. (2009). J. Mol. Struct.920, 97–102.
  • Sen, S., Mitra, S., Hughes, D. L., Rosair, G. & Desplanches, C. (2007). Polyhedron, 26, 1740–1744.
  • Sheldrick, G. M. (2003). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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