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Acta Cryst. (2007). E63, m2630    [ doi:10.1107/S1600536807046764 ]

Bis[[mu]-5-(pyrazin-2-yl)tetrazol-1-ido]bis[azido(2,2'-bipyridine)copper(II)]

Y.-J. Zhang, X. Fang, M.-L. Cao, H.-Y. Yu and J.-D. Wang

Abstract top

The title compound, [Cu2(C5H3N6)2(N3)2(C10H8N2)2], consists of isolated neutral centrosymmetric dinuclear units. Each molecule comprises two Cu atoms, two 2-tzpz- ligands [2-Htzpz = 2-(1H-tetrazol-5-yl)pyrazine], two 2,2'-bipyridine (bpy) ligands and two azide groups. The 2-tzpz- ligand is tridentate, utilizing N atoms from the tetrazole and pyrazine rings to chelate to one Cu2+ ion and a second tetrazole N atom to form a bridge to the second Cu2+ ion. The coordination geometry about each Cu2+ center is slightly distorted octahedral. The crystal packing is stabilized by intermolecular C-H...N hydrogen bonds.

Comment top

Considerable attention has been paid to the tetrazoles complex in recent years not only because of their structural and topological novelty but also because of their potential applications as molecular-based functional materials in fields such as electrical conductivity, molecular magnetism, molecular absorption, catalysis and optical materials (Demko & Sharpless, 2001; Rodriguez-Dieguez et al., 2007).

The structure of the title tetrazole complex consists of isolated neutral dinuclear units (Fig. 1). The dinuclear unit lies about a center of symmetry and is constructed from two Cu atoms, two 5-pztz− ligands, two bpy ligands and two N3− groups. In the compound, two Cu atoms are bridged through 2-N atoms of the tetrazolide, and the 5-pztz− ligand acts as a tridentate ligand by utilizing its two nitrogen atoms from the tetrazole rings and one nitrogen atom from pyrazine rings to chelate with one Cu2+ ion and bridge another Cu2+ ion. The Cu2+ center is bonded to six nitrogen atoms forming a slightly distorted octahedron, with atoms N1, N4i, N3 and N7 occupying equatorial positions and N2 and N9 in the axial positions. In the crystal structure of (I), the crystal packing is stabilized by intermolecular C—H···N bonds, Table 1.

Related literature top

Considerable attention has been paid to tetrazole complexes in recent years, not only because of their structural and topological novelty but also because of their potential applications as molecular-based functional materials in fields such as electrical conductivity, molecular magnetism, molecular absorption, catalysis and optical materials (Demko & Sharpless, 2001; Rodriguez-Dieguez et al., 2007).

Experimental top

A mixture of CuCl2 (0.3 mmol), NaN3 (0.5 mmol), pyrazine-2-carbonitrile (0.3 mmol), 2,2-bipyridine (0.3 mmol) in 3 ml H2O was heated in a 20 ml Teflon-lined reaction vessel at 130°C for two days. After slowly cooling to room temperature over a period of 12 h, blue block-like crystals of (I) were isolated.

Refinement top

All H atoms were located at calculated positions with d(C—H) = 0.93Å and the isotropic displacement parameters refined.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX5 (McArdle, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms. Labelled atoms are related to unlabelled atoms by the symmetry operation (i) = −x,-y + 1, −z
Bis[µ-5-(pyrazin-2-yl)tetrazol-1-ido]bis[azido(2,2'-bipyridine)copper(II)] top
Crystal data top
[Cu2(C5H3N6)2(N3)2(C10H8N2)2]Z = 1
Mr = 817.78F000 = 414
Triclinic, P1Dx = 1.666 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71069 Å
a = 8.189 (2) ÅCell parameters from 4727 reflections
b = 10.252 (2) Åθ = 6.8–55.1º
c = 11.380 (2) ŵ = 1.37 mm−1
α = 107.629 (2)ºT = 298 (2) K
β = 102.061 (2)ºBlock, blue
γ = 108.185 (4)º0.1 × 0.1 × 0.1 mm
V = 815.0 (3) Å3
Data collection top
Rigaku R-AXIS SPIDER CCD
diffractometer		3724 independent reflections
Radiation source: Rotating Anode3001 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.084
T = 173(2) Kθmax = 27.5º
ω oscillation scansθmin = 3.4º
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −10→10
Tmin = 0.792, Tmax = 0.825k = −13→12
7984 measured reflectionsl = −14→14
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.062Only H-atom displacement parameters refined
wR(F2) = 0.174  w = 1/[σ2(Fo2) + (0.0895P)2 + ]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.009
3724 reflectionsΔρmax = 1.44 e Å−3
254 parametersΔρmin = −1.22 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu2(C5H3N6)2(N3)2(C10H8N2)2]γ = 108.185 (4)º
Mr = 817.78V = 815.0 (3) Å3
Triclinic, P1Z = 1
a = 8.189 (2) ÅMo Kα
b = 10.252 (2) ŵ = 1.37 mm−1
c = 11.380 (2) ÅT = 298 (2) K
α = 107.629 (2)º0.1 × 0.1 × 0.1 mm
β = 102.061 (2)º
Data collection top
Rigaku R-AXIS SPIDER CCD
diffractometer		3724 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		3001 reflections with I > 2σ(I)
Tmin = 0.792, Tmax = 0.825Rint = 0.084
7984 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.062254 parameters
wR(F2) = 0.174Only H-atom displacement parameters refined
S = 1.08Δρmax = 1.44 e Å−3
3724 reflectionsΔρmin = −1.22 e Å−3
Special details top

Experimental. collimator diameter: 0.800000 mm

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
xyzUiso*/Ueq
Cu10.00291 (5)0.39768 (4)0.13246 (3)0.02186 (19)
N1−0.0628 (4)0.2191 (3)0.1846 (3)0.0228 (6)
N20.1729 (4)0.3079 (3)0.0730 (2)0.0205 (6)
N30.1679 (4)0.6080 (3)0.1614 (2)0.0195 (6)
N40.1678 (4)0.6840 (3)0.0839 (3)0.0213 (6)
N50.2890 (4)0.8210 (3)0.1493 (3)0.0249 (6)
N60.3733 (4)0.8393 (3)0.2721 (3)0.0266 (6)
N70.2331 (4)0.5307 (4)0.3744 (3)0.0275 (7)
N80.5066 (5)0.7371 (4)0.6118 (3)0.0321 (7)
N9−0.1772 (4)0.4647 (3)0.1932 (3)0.0262 (6)
N10−0.1322 (5)0.5859 (4)0.2741 (3)0.0311 (7)
N11−0.0945 (7)0.7022 (4)0.3530 (4)0.0528 (11)
C1−0.1837 (5)0.1860 (4)0.2440 (3)0.0272 (7)
H1−0.26430.23290.24650.037 (11)*
C2−0.1948 (6)0.0842 (4)0.3025 (3)0.0313 (8)
H2−0.28230.06180.34210.038*
C3−0.0718 (6)0.0168 (4)0.3001 (3)0.0308 (8)
H3−0.0747−0.05110.33920.035 (11)*
C40.0549 (5)0.0516 (4)0.2391 (3)0.0251 (7)
H40.13880.00800.23710.027 (10)*
C50.0553 (5)0.1530 (4)0.1807 (3)0.0222 (7)
C60.1808 (5)0.1949 (4)0.1098 (3)0.0208 (7)
C70.2976 (5)0.1272 (4)0.0789 (3)0.0248 (7)
H70.30230.04980.10410.029 (10)*
C80.4063 (5)0.1762 (4)0.0106 (3)0.0263 (7)
H80.48840.1345−0.00830.028 (10)*
C90.3925 (5)0.2887 (4)−0.0301 (3)0.0284 (8)
H90.46150.3207−0.07910.034 (11)*
C100.2753 (5)0.3506 (4)0.0035 (3)0.0269 (8)
H100.26630.4261−0.02320.021 (9)*
C110.2686 (5)0.4979 (4)0.4791 (3)0.0278 (8)
H110.20020.40320.47310.018 (9)*
C120.4035 (5)0.5997 (4)0.5964 (3)0.0301 (8)
H120.42280.57140.66670.032 (11)*
C130.4728 (6)0.7708 (4)0.5076 (3)0.0322 (8)
H130.54220.86530.51390.034 (11)*
C140.3375 (5)0.6694 (4)0.3902 (3)0.0235 (7)
C150.2952 (5)0.7063 (4)0.2756 (3)0.0213 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0287 (3)0.0187 (3)0.0221 (3)0.0138 (2)0.0091 (2)0.0085 (2)
N10.0297 (16)0.0177 (14)0.0205 (12)0.0119 (12)0.0073 (11)0.0052 (11)
N20.0255 (15)0.0211 (14)0.0162 (11)0.0132 (12)0.0057 (11)0.0059 (11)
N30.0286 (15)0.0178 (13)0.0167 (11)0.0133 (12)0.0089 (11)0.0078 (11)
N40.0314 (16)0.0177 (14)0.0186 (12)0.0155 (12)0.0090 (11)0.0060 (11)
N50.0333 (17)0.0208 (15)0.0224 (13)0.0147 (13)0.0081 (12)0.0076 (12)
N60.0337 (17)0.0212 (15)0.0224 (13)0.0119 (13)0.0059 (12)0.0069 (12)
N70.0336 (18)0.0262 (16)0.0230 (13)0.0136 (13)0.0074 (12)0.0097 (13)
N80.0399 (19)0.0312 (17)0.0197 (13)0.0133 (15)0.0046 (13)0.0078 (13)
N90.0315 (17)0.0242 (16)0.0275 (14)0.0147 (13)0.0134 (12)0.0101 (13)
N100.050 (2)0.0293 (18)0.0293 (15)0.0242 (15)0.0215 (14)0.0172 (15)
N110.094 (4)0.037 (2)0.0405 (18)0.036 (2)0.035 (2)0.0137 (18)
C10.032 (2)0.0245 (18)0.0263 (15)0.0150 (15)0.0102 (14)0.0079 (14)
C20.041 (2)0.032 (2)0.0262 (16)0.0176 (17)0.0165 (15)0.0112 (16)
C30.043 (2)0.0269 (19)0.0274 (16)0.0185 (17)0.0107 (15)0.0141 (15)
C40.0315 (19)0.0214 (17)0.0240 (15)0.0146 (15)0.0067 (14)0.0086 (14)
C50.0292 (18)0.0173 (16)0.0170 (13)0.0121 (14)0.0051 (12)0.0018 (13)
C60.0289 (18)0.0179 (15)0.0141 (12)0.0128 (13)0.0044 (12)0.0030 (12)
C70.0321 (19)0.0208 (17)0.0188 (14)0.0141 (14)0.0031 (13)0.0048 (13)
C80.0300 (19)0.0259 (18)0.0250 (15)0.0163 (15)0.0098 (14)0.0070 (14)
C90.036 (2)0.0289 (19)0.0239 (15)0.0154 (16)0.0124 (14)0.0117 (15)
C100.038 (2)0.0248 (17)0.0258 (15)0.0186 (16)0.0109 (14)0.0133 (15)
C110.037 (2)0.0272 (19)0.0251 (16)0.0166 (16)0.0117 (15)0.0139 (15)
C120.036 (2)0.036 (2)0.0228 (15)0.0215 (17)0.0102 (14)0.0115 (16)
C130.037 (2)0.030 (2)0.0225 (16)0.0113 (16)0.0033 (15)0.0085 (15)
C140.0305 (19)0.0244 (17)0.0162 (13)0.0157 (15)0.0066 (13)0.0048 (13)
C150.0272 (18)0.0179 (16)0.0199 (14)0.0121 (14)0.0070 (13)0.0065 (13)
Geometric parameters (Å, °) top
Cu1—N91.974 (3)C1—H10.9300
Cu1—N22.014 (3)C2—C31.388 (5)
Cu1—N32.037 (3)C2—H20.9300
Cu1—N12.043 (3)C3—C41.380 (5)
Cu1—N4i2.302 (3)C3—H30.9300
N1—C11.327 (5)C4—C51.392 (5)
N1—C51.344 (4)C4—H40.9300
N2—C101.333 (5)C5—C61.474 (5)
N2—C61.360 (4)C6—C71.389 (5)
N3—C151.333 (4)C7—C81.378 (5)
N3—N41.343 (4)C7—H70.9300
N4—N51.304 (4)C8—C91.393 (5)
N4—Cu1i2.302 (3)C8—H80.9300
N5—N61.350 (4)C9—C101.363 (5)
N6—C151.329 (5)C9—H90.9300
N7—C111.333 (4)C10—H100.9300
N7—C141.344 (5)C11—C121.383 (5)
N8—C131.331 (4)C11—H110.9300
N8—C121.333 (5)C12—H120.9300
N9—N101.186 (4)C13—C141.384 (5)
N10—N111.153 (5)C13—H130.9300
C1—C21.388 (5)C14—C151.468 (4)
N9—Cu1—N2173.54 (12)C3—C4—C5119.0 (3)
N9—Cu1—N392.79 (12)C3—C4—H4120.5
N2—Cu1—N393.43 (12)C5—C4—H4120.5
N9—Cu1—N193.71 (12)N1—C5—C4121.3 (3)
N2—Cu1—N179.96 (12)N1—C5—C6115.0 (3)
N3—Cu1—N1152.23 (11)C4—C5—C6123.6 (3)
N9—Cu1—N4i92.15 (11)N2—C6—C7120.7 (3)
N2—Cu1—N4i88.60 (10)N2—C6—C5114.3 (3)
N3—Cu1—N4i98.96 (10)C7—C6—C5125.0 (3)
N1—Cu1—N4i107.74 (10)C8—C7—C6119.1 (3)
C1—N1—C5119.4 (3)C8—C7—H7120.5
C1—N1—Cu1125.3 (2)C6—C7—H7120.5
C5—N1—Cu1113.7 (2)C7—C8—C9119.5 (3)
C10—N2—C6119.2 (3)C7—C8—H8120.2
C10—N2—Cu1125.7 (2)C9—C8—H8120.2
C6—N2—Cu1115.1 (2)C10—C9—C8118.4 (3)
C15—N3—N4104.9 (3)C10—C9—H9120.8
C15—N3—Cu1123.4 (2)C8—C9—H9120.8
N4—N3—Cu1131.4 (2)N2—C10—C9123.0 (3)
N5—N4—N3109.3 (2)N2—C10—H10118.5
N5—N4—Cu1i121.3 (2)C9—C10—H10118.5
N3—N4—Cu1i129.3 (2)N7—C11—C12122.3 (4)
N4—N5—N6109.7 (3)N7—C11—H11118.8
C15—N6—N5104.4 (3)C12—C11—H11118.8
C11—N7—C14115.6 (3)N8—C12—C11122.0 (3)
C13—N8—C12116.2 (3)N8—C12—H12119.0
N10—N9—Cu1121.3 (3)C11—C12—H12119.0
N11—N10—N9177.6 (5)N8—C13—C14122.0 (4)
N1—C1—C2122.7 (3)N8—C13—H13119.0
N1—C1—H1118.7C14—C13—H13119.0
C2—C1—H1118.7N7—C14—C13121.9 (3)
C1—C2—C3118.2 (4)N7—C14—C15115.4 (3)
C1—C2—H2120.9C13—C14—C15122.6 (3)
C3—C2—H2120.9N6—C15—N3111.7 (3)
C4—C3—C2119.4 (3)N6—C15—C14125.5 (3)
C4—C3—H3120.3N3—C15—C14122.8 (3)
C2—C3—H3120.3
Symmetry codes: (i) −x, −y+1, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···N11ii0.932.543.413 (5)157
C7—H7···N5ii0.932.523.450 (4)174
Symmetry codes: (ii) x, y−1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···N11i0.932.543.413 (5)157
C7—H7···N5i0.932.523.450 (4)174
Symmetry codes: (i) x, y−1, z.
Acknowledgements top

This work was supported by the Foundations of Fujian Province (No. 2006 F5058) and Fuzhou University (No. XRC0527).

references
References top

Demko, Z. P. & Sharpless, B. K. (2001). J. Org. Chem. 66, 7945–7950.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

McArdle, P. (1996). ORTEX5. UCG Crystallography Centre, University College Galway, Ireland.

Rigaku (2004). RAPID-AUTO. Version 3.0. Rigaku Corporation, Tokyo, Japan.

Rodriguez-Dieguez, A., Cano, J., Kivekas, R., Debdoubi, A. & Colacio, E. (2007). Inorg. Chem. 46, 2503–2510.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.