Di-μ-azido-bis­({N′-[1-(2-pyrid­yl-κN)ethyl­idene]acetohydrazidato-κ2N′,O}dicopper(II))

Datta, A.; Das, K.; Jhou, Y.-M.; Huang, J.-H.; Lee, H.M.

doi:10.1107/S1600536810034860

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page m1271

doi:10.1107/S1600536810034860

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Di-μ-azido-bis({N′-[1-(2-pyridyl-κN)ethylidene]acetohydrazidato-κ²N′,O}dicopper(II))

Amitabha Datta,^a Kuheli Das,^a Yan-Ming Jhou,^a Jui-Hsien Huang ^a and Hon Man Lee ^a ^*

^aNational Changhua University of Education, Department of Chemistry, Changhua, Taiwan 50058
^*Correspondence e-mail: leehm@cc.ncue.edu.tw

(Received 24 August 2010; accepted 30 August 2010; online 18 September 2010)

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 ); Sen et al. (2007 ); Patole et al. (2003 ).

Experimental

Crystal data

[Cu₂(C₉H₁₀N₃O)₂(N₃)₂]
M_r = 563.54
Triclinic, $[P \overline 1]$
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 ) 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[F² > 2σ(F²)] = 0.027
wR(F²) = 0.093
S = 1.08
2358 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 2.08 e Å⁻³
Δρ_min = −2.81 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯N3ⁱ	0.98	2.74	3.710 (4)	171
Symmetry code: (i) -x+1, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: DIAMOND (Brandenburg, 2006 ).

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: DIAMOND (Brandenburg, 2006).

Figures top

	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.

Di-µ-azido-bis({N'-[1-(2-pyridyl- κN)ethylidene]acetohydrazidato-κ²N',O}dicopper(II)) top

Crystal data top

[Cu₂(C₉H₁₀N₃O)₂(N₃)₂]	Z = 1
M_r = 563.54	F(000) = 286
Triclinic, P1	D_x = 1.654 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.589 (3) Å	Cell parameters from 3185 reflections
b = 8.955 (3) Å	θ = 2.9–28.5°
c = 9.693 (4) Å	µ = 1.92 mm⁻¹
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 top

Bruker SMART APEXII diffractometer	2358 independent reflections
Radiation source: fine-focus sealed tube	1591 reflections with I > 2σ
Graphite monochromator	R_int = 0.040
ω scans	θ_max = 27.0°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −9→9
T_min = 0.645, T_max = 0.700	k = −11→10
3858 measured reflections	l = −12→12

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.027	Hydrogen site location: difference Fourier map
wR(F²) = 0.093	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0597P)²] where P = (F_o² + 2F_c²)/3
2358 reflections	(Δ/σ)_max = 0.001
156 parameters	Δρ_max = 2.08 e Å⁻³
0 restraints	Δρ_min = −2.81 e Å⁻³

Crystal data top

[Cu₂(C₉H₁₀N₃O)₂(N₃)₂]	γ = 81.468 (16)°
M_r = 563.54	V = 565.8 (4) Å³
Triclinic, P1	Z = 1
a = 7.589 (3) Å	Mo Kα radiation
b = 8.955 (3) Å	µ = 1.92 mm⁻¹
c = 9.693 (4) Å	T = 150 K
α = 66.534 (15)°	0.25 × 0.20 × 0.20 mm
β = 69.461 (13)°

Data collection top

Bruker SMART APEXII diffractometer	2358 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1591 reflections with I > 2σ
T_min = 0.645, T_max = 0.700	R_int = 0.040
3858 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 1.08	Δρ_max = 2.08 e Å⁻³
2358 reflections	Δρ_min = −2.81 e Å⁻³
156 parameters

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

	x	y	z	U_iso*/U_eq
Cu1	0.34274 (3)	0.93665 (3)	0.95880 (3)	0.02989 (14)
N5	0.2011 (2)	0.7390 (2)	1.0402 (2)	0.0307 (5)
O1	0.4938 (2)	0.8357 (2)	0.8052 (2)	0.0380 (5)
N1	0.4648 (3)	1.1498 (2)	0.8642 (2)	0.0329 (5)
N6	0.2719 (3)	0.6294 (3)	0.9663 (2)	0.0367 (6)
C8	0.4270 (3)	0.6937 (3)	0.8443 (3)	0.0314 (6)
N2	0.5605 (3)	1.2073 (2)	0.7250 (2)	0.0358 (6)
N4	0.1206 (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	−0.2404	0.7619	1.4036	0.053*
C9	0.5264 (3)	0.5944 (3)	0.7465 (3)	0.0436 (7)
H9A	0.4938	0.6357	0.6483	0.065*
H9B	0.4881	0.4806	0.8067	0.065*
H9C	0.6627	0.6019	0.7202	0.065*
C5	0.0911 (3)	1.1048 (3)	1.1831 (3)	0.0390 (7)
H5	0.1758	1.1935	1.1254	0.047*
C6	0.0467 (3)	0.7153 (3)	1.1593 (3)	0.0351 (7)
C3	−0.1850 (3)	0.9815 (4)	1.3992 (3)	0.0470 (9)
H3	−0.2888	0.9825	1.4891	0.056*
C4	−0.0596 (4)	1.1095 (4)	1.3148 (3)	0.0449 (7)
H4	−0.0761	1.1997	1.3465	0.054*
N3	0.6520 (4)	1.2683 (4)	0.5959 (3)	0.0644 (10)
C7	−0.0748 (4)	0.5681 (4)	1.2321 (4)	0.0564 (10)
H7A	−0.0411	0.5099	1.1594	0.085*
H7B	−0.2073	0.6022	1.2516	0.085*
H7C	−0.0556	0.4962	1.3328	0.085*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.03078 (16)	0.0297 (2)	0.02843 (18)	−0.00779 (10)	−0.00486 (12)	−0.01154 (14)
N5	0.0319 (7)	0.0317 (10)	0.0289 (9)	−0.0042 (7)	−0.0062 (7)	−0.0133 (8)
O1	0.0400 (8)	0.0382 (10)	0.0350 (9)	−0.0100 (6)	−0.0044 (7)	−0.0163 (8)
N1	0.0386 (8)	0.0306 (10)	0.0287 (9)	−0.0063 (7)	−0.0068 (8)	−0.0117 (9)
N6	0.0383 (9)	0.0368 (11)	0.0351 (10)	−0.0048 (8)	−0.0079 (9)	−0.0154 (9)
C8	0.0389 (9)	0.0296 (11)	0.0318 (10)	−0.0017 (8)	−0.0140 (9)	−0.0148 (9)
N2	0.0404 (9)	0.0327 (10)	0.0316 (10)	−0.0034 (7)	−0.0105 (8)	−0.0091 (9)
N4	0.0303 (7)	0.0331 (10)	0.0310 (9)	−0.0027 (6)	−0.0079 (7)	−0.0126 (8)
C1	0.0286 (8)	0.0403 (12)	0.0295 (11)	−0.0040 (7)	−0.0073 (8)	−0.0098 (10)
C2	0.0346 (10)	0.0535 (16)	0.0353 (12)	−0.0070 (9)	−0.0012 (9)	−0.0150 (13)
C9	0.0495 (12)	0.0421 (15)	0.0402 (13)	−0.0022 (10)	−0.0097 (11)	−0.0200 (12)
C5	0.0395 (10)	0.0399 (14)	0.0386 (12)	−0.0032 (9)	−0.0109 (10)	−0.0162 (12)
C6	0.0323 (9)	0.0352 (12)	0.0343 (11)	−0.0074 (8)	−0.0070 (9)	−0.0102 (10)
C3	0.0388 (10)	0.0623 (19)	0.0358 (13)	0.0030 (10)	−0.0028 (10)	−0.0234 (14)
C4	0.0484 (12)	0.0489 (16)	0.0437 (14)	0.0071 (10)	−0.0130 (11)	−0.0277 (12)
N3	0.0746 (16)	0.0654 (19)	0.0323 (12)	−0.0125 (13)	−0.0042 (12)	−0.0045 (14)
C7	0.0493 (13)	0.0495 (18)	0.0599 (19)	−0.0198 (12)	0.0053 (13)	−0.0229 (16)

Geometric parameters (Å, º) top

Cu1—N5	1.941 (2)	C1—C6	1.484 (4)
Cu1—N1	1.969 (2)	C2—C3	1.403 (5)
Cu1—O1	1.979 (2)	C2—H2	0.9500
Cu1—N4	2.051 (2)	C9—H9A	0.9800
Cu1—N1ⁱ	2.4574 (18)	C9—H9B	0.9800
N5—C6	1.297 (3)	C9—H9C	0.9800
N5—N6	1.377 (4)	C5—C4	1.394 (4)
O1—C8	1.300 (3)	C5—H5	0.9500
N1—N2	1.218 (3)	C6—C7	1.500 (3)
N1—Cu1ⁱ	2.4574 (18)	C3—C4	1.386 (4)
N6—C8	1.341 (3)	C3—H3	0.9500
C8—C9	1.493 (5)	C4—H4	0.9500
N2—N3	1.142 (3)	C7—H7A	0.9800
N4—C5	1.343 (4)	C7—H7B	0.9800
N4—C1	1.374 (3)	C7—H7C	0.9800
C1—C2	1.387 (4)

N5—Cu1—N1	173.44 (6)	C1—C2—C3	119.8 (2)
N5—Cu1—O1	79.78 (9)	C1—C2—H2	120.1
N1—Cu1—O1	101.14 (9)	C3—C2—H2	120.1
N5—Cu1—N4	80.27 (9)	C8—C9—H9A	109.5
N1—Cu1—N4	98.12 (10)	C8—C9—H9B	109.5
O1—Cu1—N4	159.42 (8)	H9A—C9—H9B	109.5
N5—Cu1—N1ⁱ	99.67 (7)	C8—C9—H9C	109.5
N1—Cu1—N1ⁱ	86.64 (6)	H9A—C9—H9C	109.5
O1—Cu1—N1ⁱ	98.75 (8)	H9B—C9—H9C	109.5
N4—Cu1—N1ⁱ	89.51 (8)	N4—C5—C4	122.3 (2)
C6—N5—N6	123.0 (2)	N4—C5—H5	118.9
C6—N5—Cu1	119.7 (2)	C4—C5—H5	118.9
N6—N5—Cu1	117.28 (14)	N5—C6—C1	113.21 (19)
C8—O1—Cu1	110.27 (16)	N5—C6—C7	124.6 (3)
N2—N1—Cu1	122.4 (2)	C1—C6—C7	122.2 (3)
N2—N1—Cu1ⁱ	111.79 (13)	C4—C3—C2	118.5 (3)
Cu1—N1—Cu1ⁱ	93.36 (6)	C4—C3—H3	120.7
C8—N6—N5	107.9 (2)	C2—C3—H3	120.7
O1—C8—N6	124.6 (3)	C3—C4—C5	119.4 (3)
O1—C8—C9	118.6 (2)	C3—C4—H4	120.3
N6—C8—C9	116.8 (2)	C5—C4—H4	120.3
N3—N2—N1	176.3 (3)	C6—C7—H7A	109.5
C5—N4—C1	119.0 (2)	C6—C7—H7B	109.5
C5—N4—Cu1	128.98 (15)	H7A—C7—H7B	109.5
C1—N4—Cu1	111.8 (2)	C6—C7—H7C	109.5
N4—C1—C2	121.1 (3)	H7A—C7—H7C	109.5
N4—C1—C6	114.9 (2)	H7B—C7—H7C	109.5
C2—C1—C6	124.0 (2)

Symmetry code: (i) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···N3ⁱⁱ	0.98	2.74	3.710 (4)	171

Symmetry code: (ii) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₉H₁₀N₃O)₂(N₃)₂]
M_r	563.54
Crystal system, space group	Triclinic, P1
Temperature (K)	150
a, b, c (Å)	7.589 (3), 8.955 (3), 9.693 (4)
α, β, γ (°)	66.534 (15), 69.461 (13), 81.468 (16)
V (Å³)	565.8 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.92
Crystal size (mm)	0.25 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.645, 0.700
No. of measured, independent and observed (I > 2σ) reflections	3858, 2358, 1591
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.093, 1.08
No. of reflections	2358
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.08, −2.81

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···N3ⁱ	0.98	2.74	3.710 (4)	171

Symmetry code: (i) −x+1, −y+2, −z+1.

Acknowledgements

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

References

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