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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046764/sj2359sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046764/sj2359Isup2.hkl
Contains datablock I

CCDC reference: 658001

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.062
  • wR factor = 0.174
  • Data-to-parameter ratio = 14.7

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 1.06 PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 200 Ang. PLAT220_ALERT_2_C Large Non-Solvent N Ueq(max)/Ueq(min) ... 2.71 Ratio
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 1.057 Tmax scaled 0.872 Tmin scaled 0.838 PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (1) 1.22
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

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.

Structure description 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.

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).

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 = 817.78F(000) = 414
Triclinic, P1Dx = 1.666 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71069 Å
a = 8.189 (2) ÅCell parameters from 4727 reflections
b = 10.252 (2) Åθ = 6.8–55.1°
c = 11.380 (2) ŵ = 1.37 mm1
α = 107.629 (2)°T = 298 K
β = 102.061 (2)°Block, blue
γ = 108.185 (4)°0.1 × 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)
Graphite monochromatorRint = 0.084
ω oscillation scansθmax = 27.5°, θmin = 3.4°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 1010
Tmin = 0.792, Tmax = 0.825k = 1312
7984 measured reflectionsl = 1414
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.062Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.174Only H-atom displacement parameters refined
S = 1.08 w = 1/[σ2(Fo2) + (0.0895P)2 + ]
where P = (Fo2 + 2Fc2)/3
3724 reflections(Δ/σ)max = 0.009
254 parametersΔρmax = 1.44 e Å3
0 restraintsΔρmin = 1.23 e Å3
Crystal data top
[Cu2(C5H3N6)2(N3)2(C10H8N2)2]γ = 108.185 (4)°
Mr = 817.78V = 815.0 (3) Å3
Triclinic, P1Z = 1
a = 8.189 (2) ÅMo Kα radiation
b = 10.252 (2) ŵ = 1.37 mm1
c = 11.380 (2) ÅT = 298 K
α = 107.629 (2)°0.1 × 0.1 × 0.1 mm
β = 102.061 (2)°
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)] = 0.0620 restraints
wR(F2) = 0.174Only H-atom displacement parameters refined
S = 1.08Δρmax = 1.44 e Å3
3724 reflectionsΔρmin = 1.23 e Å3
254 parameters
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)
N10.0628 (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)
N90.1772 (4)0.4647 (3)0.1932 (3)0.0262 (6)
N100.1322 (5)0.5859 (4)0.2741 (3)0.0311 (7)
N110.0945 (7)0.7022 (4)0.3530 (4)0.0528 (11)
C10.1837 (5)0.1860 (4)0.2440 (3)0.0272 (7)
H10.26430.23290.24650.037 (11)*
C20.1948 (6)0.0842 (4)0.3025 (3)0.0313 (8)
H20.28230.06180.34210.038*
C30.0718 (6)0.0168 (4)0.3001 (3)0.0308 (8)
H30.07470.05110.33920.035 (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)
H80.48840.13450.00830.028 (10)*
C90.3925 (5)0.2887 (4)0.0301 (3)0.0284 (8)
H90.46150.32070.07910.034 (11)*
C100.2753 (5)0.3506 (4)0.0035 (3)0.0269 (8)
H100.26630.42610.02320.021 (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, º) 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 code: (i) x, y+1, z.
Hydrogen-bond geometry (Å, º) 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 code: (ii) x, y1, z.

Experimental details

Crystal data
Chemical formula[Cu2(C5H3N6)2(N3)2(C10H8N2)2]
Mr817.78
Crystal system, space groupTriclinic, P1
Temperature (K)298
a, b, c (Å)8.189 (2), 10.252 (2), 11.380 (2)
α, β, γ (°)107.629 (2), 102.061 (2), 108.185 (4)
V3)815.0 (3)
Z1
Radiation typeMo Kα
µ (mm1)1.37
Crystal size (mm)0.1 × 0.1 × 0.1
Data collection
DiffractometerRigaku R-AXIS SPIDER CCD
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.792, 0.825
No. of measured, independent and
observed [I > 2σ(I)] reflections
7984, 3724, 3001
Rint0.084
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.062, 0.174, 1.08
No. of reflections3724
No. of parameters254
H-atom treatmentOnly H-atom displacement parameters refined
Δρmax, Δρmin (e Å3)1.44, 1.23

Computer programs: RAPID-AUTO (Rigaku, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEX5 (McArdle, 1996).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···N11i0.932.543.413 (5)156.8
C7—H7···N5i0.932.523.450 (4)173.9
Symmetry code: (i) x, y1, z.
 

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