Bis[5-(2-amino-3-pyrid­yl)tetra­zolato]copper(II)

Guo, M.

doi:10.1107/S1600536809034369

metal-organic compounds

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Volume 65| Part 10| October 2009| Page m1160

doi:10.1107/S1600536809034369

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Bis[5-(2-amino-3-pyridyl)tetrazolato]copper(II)

Min Guo ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: guomin625@yahoo.com.cn

(Received 12 May 2009; accepted 27 August 2009; online 5 September 2009)

In the centrosymmetric title complex, [Cu(C₆H₅N₆)₂], the Cu^II ion is coordinated by four N atoms from two symmetry-related bidentate 5-(2-amino-3-pyridyl)tetrazolate ligands in a slightly distorted square-planar environment. There are weak intramolecular N—H⋯N hydrogen bonds between the two ligands. In the crystal structure, there are significant π–π stacking interactions between symmetry-related tetrazole and pyridine rings, with a centroid–centroid distance of 3.6025 (18)°.

Related literature

For the coordination chemistry of tetrazole compounds, see: Butler (1984 ); Zhao et al. (2008 ). For the in situ [2 + 3] cycloaddition synthesis of tetrazole coordination polymers, see: Xiong et al. (2002 ); Ye et al. (2006 ); Fu et al. (2008 ). For coordination polymers synthesized with similar organic ligand derivatives, see: Ye et al. (2005 ); Bhandari et al. (2000 ).

Experimental

Crystal data

[Cu(C₆H₅N₆)₂]
M_r = 385.86
Monoclinic, P 2₁ /c
a = 6.6492 (6) Å
b = 7.9093 (7) Å
c = 13.5581 (12) Å
β = 100.692 (2)°
V = 700.65 (11) Å³
Z = 2
Mo Kα radiation
μ = 1.59 mm⁻¹
T = 294 K
0.15 × 0.13 × 0.09 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.797, T_max = 0.870
3743 measured reflections
1363 independent reflections
1228 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.109
S = 1.07
1363 reflections
115 parameters
H-atom parameters constrained
Δρ_max = 0.69 e Å⁻³
Δρ_min = −0.73 e Å⁻³

Table 1
Selected bond angles (°)

N5ⁱ—Cu1—N5	180
N5—Cu1—N4	89.03 (10)
N5—Cu1—N4ⁱ	90.97 (10)
N4—Cu1—N4ⁱ	180
Symmetry code: (i) -x+1, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯N2ⁱ	0.90	2.50	2.902 (4)	108
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809034369/lh2827sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809034369/lh2827Isup2.hkl

checkCIF report

Comment top

In situ [2+3] cycloaddition synthesis of tetrazole coordination polymers under hydrothermal conditions has proved to be a fast and convenient route to explore novel coordination polymers with rich structural diversities and potential physical properties, such as second harmonic generation (SGH), ferroelectric and dielectric responses (Xiong et al., 2002; Ye et al., 2006; Fu et al. (2008). The crystal structure of the compound formed by our hydrothermal synthesis is reported herein.

The molecular structure of the title compound is shown in Fig. 1. The Cu^II ion lies on an inversion center coordinated by four N atoms from two symmetry related bidentate 3-(2-Amino-pyridyl))tetrazolato ligands in a slightly distorted square-planar environment. In the crystal structure, there are significant π–π stacking interactions between symmetry related tetrazole and pyridine rings with a centroid to centroid distance of 3.6025 (18)°.

Related literature top

For the coordination chemistry of tetrazole compounds, see: Butler (1984); Zhao et al. (2008). For the in situ [2+3] cycloaddition synthesis of tetrazole coordination polymers, see: Xiong et al. (2002); Ye et al. (2006); Fu et al. (2008). For coordination polymers synthesized with similar organic ligand derivatives, see: Ye et al. (2005); Bhandari et al. (2000).

Experimental top

The title compound was prepared by hydrothermal treatment of 2-aminonicotinonitrile (2.3 mmol) and Cu(NO₃)₂ (1.0 mmol) with excess amount of NaN₃ in a sealed Pyrex tuble at 403K for 2–4 days. The resulting green rectangular crystals gave a yield of 75% based on Cu(NO₃)₂.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level. Symmetry code: (a) -x+1, -y+1, -z+1. Hydrogen bonds are shown as dashed lines.

Bis[5-(2-amino-3-pyridyl)tetrazolato]copper(II) top

Crystal data top

[Cu(C₆H₅N₆)₂]	F(000) = 390
M_r = 385.86	D_x = 1.829 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 723 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 6.6492 (6) Å	Cell parameters from 2942 reflections
b = 7.9093 (7) Å	θ = 3.0–27.5°
c = 13.5581 (12) Å	µ = 1.59 mm⁻¹
β = 100.692 (2)°	T = 294 K
V = 700.65 (11) Å³	Rectangle, green
Z = 2	0.15 × 0.13 × 0.09 mm

Data collection top

Rigaku Mercury2 diffractometer	1363 independent reflections
Radiation source: fine-focus sealed tube	1228 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 13.6612 pixels mm^-1	θ_max = 26.0°, θ_min = 3.0°
ω scans	h = −8→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −8→9
T_min = 0.797, T_max = 0.870	l = −15→16
3743 measured reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0555P)² + 1.0273P] where P = (F_o² + 2F_c²)/3
1363 reflections	(Δ/σ)_max < 0.001
115 parameters	Δρ_max = 0.69 e Å⁻³
0 restraints	Δρ_min = −0.73 e Å⁻³

Crystal data top

[Cu(C₆H₅N₆)₂]	V = 700.65 (11) Å³
M_r = 385.86	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.6492 (6) Å	µ = 1.59 mm⁻¹
b = 7.9093 (7) Å	T = 294 K
c = 13.5581 (12) Å	0.15 × 0.13 × 0.09 mm
β = 100.692 (2)°

Data collection top

Rigaku Mercury2 diffractometer	1363 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1228 reflections with I > 2σ(I)
T_min = 0.797, T_max = 0.870	R_int = 0.020
3743 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.07	Δρ_max = 0.69 e Å⁻³
1363 reflections	Δρ_min = −0.73 e Å⁻³
115 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	0.5000	0.5000	0.5000	0.0265 (2)
N6	1.0060 (4)	0.1967 (3)	0.61317 (18)	0.0302 (6)
C6	0.7920 (5)	0.3986 (4)	0.3685 (2)	0.0260 (6)
C5	0.9283 (4)	0.3088 (4)	0.4476 (2)	0.0263 (6)
N4	0.6177 (4)	0.4748 (3)	0.37835 (19)	0.0294 (6)
C4	0.8741 (5)	0.2899 (4)	0.5446 (2)	0.0258 (6)
N3	0.8245 (4)	0.4167 (4)	0.27476 (19)	0.0345 (6)
C3	1.1079 (5)	0.2369 (4)	0.4307 (2)	0.0322 (7)
H3A	1.1439	0.2497	0.3680	0.039*
N2	0.5399 (4)	0.5422 (4)	0.2875 (2)	0.0365 (6)
C2	1.2364 (5)	0.1461 (4)	0.5041 (3)	0.0364 (7)
H2A	1.3576	0.0997	0.4914	0.044*
C1	1.1816 (5)	0.1263 (4)	0.5947 (2)	0.0349 (7)
H1A	1.2646	0.0642	0.6446	0.042*
N1	0.6643 (5)	0.5072 (4)	0.2266 (2)	0.0385 (7)
N5	0.7116 (4)	0.3534 (3)	0.56979 (17)	0.0291 (6)
H5A	0.7585	0.4076	0.6279	0.035*
H5B	0.6431	0.2629	0.5866	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0241 (3)	0.0352 (3)	0.0227 (3)	0.00433 (19)	0.0104 (2)	0.00138 (19)
N6	0.0281 (14)	0.0330 (14)	0.0300 (13)	0.0006 (10)	0.0068 (11)	0.0029 (10)
C6	0.0267 (15)	0.0296 (14)	0.0243 (13)	−0.0035 (11)	0.0112 (11)	−0.0035 (11)
C5	0.0250 (15)	0.0270 (14)	0.0292 (15)	−0.0012 (11)	0.0108 (12)	−0.0019 (11)
N4	0.0280 (14)	0.0395 (14)	0.0223 (12)	0.0041 (11)	0.0087 (10)	0.0012 (10)
C4	0.0239 (15)	0.0258 (14)	0.0286 (14)	−0.0029 (11)	0.0076 (12)	0.0000 (11)
N3	0.0342 (15)	0.0477 (16)	0.0248 (12)	0.0030 (12)	0.0137 (11)	−0.0019 (11)
C3	0.0325 (17)	0.0347 (16)	0.0328 (16)	0.0011 (13)	0.0151 (13)	−0.0031 (13)
N2	0.0353 (16)	0.0513 (16)	0.0245 (13)	0.0073 (13)	0.0100 (11)	0.0046 (12)
C2	0.0280 (16)	0.0374 (17)	0.0464 (18)	0.0065 (13)	0.0141 (14)	−0.0028 (14)
C1	0.0297 (17)	0.0334 (16)	0.0393 (17)	0.0024 (12)	0.0002 (13)	0.0015 (13)
N1	0.0365 (17)	0.0561 (19)	0.0242 (13)	0.0054 (12)	0.0092 (12)	0.0040 (11)
N5	0.0277 (14)	0.0401 (15)	0.0229 (11)	0.0069 (11)	0.0135 (10)	0.0056 (10)

Geometric parameters (Å, º) top

Cu1—N5ⁱ	1.930 (2)	N4—N2	1.354 (4)
Cu1—N5	1.930 (2)	C4—N5	1.293 (4)
Cu1—N4	1.963 (2)	N3—N1	1.348 (4)
Cu1—N4ⁱ	1.963 (2)	C3—C2	1.386 (5)
N6—C1	1.358 (4)	C3—H3A	0.9300
N6—C4	1.369 (4)	N2—N1	1.302 (4)
C6—N4	1.335 (4)	C2—C1	1.354 (5)
C6—N3	1.336 (4)	C2—H2A	0.9300
C6—C5	1.455 (4)	C1—H1A	0.9300
C5—C3	1.380 (4)	N5—H5A	0.9000
C5—C4	1.435 (4)	N5—H5B	0.9000

N5ⁱ—Cu1—N5	180	C6—N3—N1	105.3 (2)
N5ⁱ—Cu1—N4	90.97 (10)	C5—C3—C2	122.1 (3)
N5—Cu1—N4	89.03 (10)	C5—C3—H3A	118.9
N5ⁱ—Cu1—N4ⁱ	89.03 (10)	C2—C3—H3A	118.9
N5—Cu1—N4ⁱ	90.97 (10)	N1—N2—N4	108.2 (3)
N4—Cu1—N4ⁱ	180	C1—C2—C3	118.5 (3)
C1—N6—C4	124.1 (3)	C1—C2—H2A	120.7
N4—C6—N3	110.1 (3)	C3—C2—H2A	120.7
N4—C6—C5	125.5 (3)	C2—C1—N6	120.3 (3)
N3—C6—C5	124.4 (3)	C2—C1—H1A	119.8
C3—C5—C4	118.8 (3)	N6—C1—H1A	119.8
C3—C5—C6	121.3 (3)	N2—N1—N3	110.1 (3)
C4—C5—C6	119.9 (3)	C4—N5—Cu1	132.2 (2)
C6—N4—N2	106.2 (2)	C4—N5—H5A	104.2
C6—N4—Cu1	128.3 (2)	Cu1—N5—H5A	104.2
N2—N4—Cu1	125.5 (2)	C4—N5—H5B	104.2
N5—C4—N6	119.4 (3)	Cu1—N5—H5B	104.2
N5—C4—C5	124.5 (3)	H5A—N5—H5B	105.5
N6—C4—C5	116.1 (3)

N4—C6—C5—C3	−178.6 (3)	C6—C5—C4—N6	176.9 (3)
N3—C6—C5—C3	1.2 (5)	N4—C6—N3—N1	0.1 (3)
N4—C6—C5—C4	3.1 (4)	C5—C6—N3—N1	−179.8 (3)
N3—C6—C5—C4	−177.1 (3)	C4—C5—C3—C2	0.5 (5)
N3—C6—N4—N2	0.1 (4)	C6—C5—C3—C2	−177.8 (3)
C5—C6—N4—N2	179.9 (3)	C6—N4—N2—N1	−0.2 (4)
N3—C6—N4—Cu1	−176.5 (2)	Cu1—N4—N2—N1	176.5 (2)
C5—C6—N4—Cu1	3.4 (4)	C5—C3—C2—C1	0.8 (5)
N5—Cu1—N4—C6	−7.2 (3)	C3—C2—C1—N6	−1.1 (5)
N5—Cu1—N4—N2	176.9 (3)	C4—N6—C1—C2	0.1 (5)
C1—N6—C4—N5	−179.3 (3)	N4—N2—N1—N3	0.2 (4)
C1—N6—C4—C5	1.2 (4)	C6—N3—N1—N2	−0.2 (4)
C3—C5—C4—N5	179.0 (3)	N6—C4—N5—Cu1	175.8 (2)
C6—C5—C4—N5	−2.6 (4)	C5—C4—N5—Cu1	−4.7 (5)
C3—C5—C4—N6	−1.4 (4)	N4—Cu1—N5—C4	8.1 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···N2ⁱ	0.90	2.50	2.902 (4)	108

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu(C₆H₅N₆)₂]
M_r	385.86
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	6.6492 (6), 7.9093 (7), 13.5581 (12)
β (°)	100.692 (2)
V (Å³)	700.65 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.59
Crystal size (mm)	0.15 × 0.13 × 0.09

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.797, 0.870
No. of measured, independent and observed [I > 2σ(I)] reflections	3743, 1363, 1228
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.109, 1.07
No. of reflections	1363
No. of parameters	115
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.69, −0.73

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Selected bond angles (º) top

N5ⁱ—Cu1—N5	180	N5—Cu1—N4ⁱ	90.97 (10)
N5—Cu1—N4	89.03 (10)	N4—Cu1—N4ⁱ	180

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···N2ⁱ	0.90	2.50	2.902 (4)	107.5

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

This work was supported by a start-up grant from SEU.

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page m1160

doi:10.1107/S1600536809034369

Open

access