Bis[5-(2-amino-3-pyrid-yl)tetra-zolato]copper(II).

In the centrosymmetric title complex, [Cu(C(6)H(5)N(6))(2)], the Cu(II) ion is coordinated by four N atoms from two symmetry-related bidentate 5-(2-amino-3-pyrid-yl)tetra-zolate ligands in a slightly distorted square-planar environment. There are weak intra-molecular N-H⋯N hydrogen bonds between the two ligands. In the crystal structure, there are significant π-π stacking inter-actions between symmetry-related tetra-zole 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 = 385.86

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.109

S = 1.07

1363 reflections

115 parameters

H-atom parameters constrained

Δρmax = 0.69 e Å−3

Δρmin = −0.73 e Å−3

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 ▶).

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

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

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

[Cu(C6H5N6)2]	F(000) = 390
Mr = 385.86	Dx = 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

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

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(Fo2) + (0.0555P)2 + 1.0273P] where P = (Fo2 + 2Fc2)/3
1363 reflections	(Δ/σ)max < 0.001
115 parameters	Δρmax = 0.69 e Å−3
0 restraints	Δρmin = −0.73 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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

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) .

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) .