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In the title compound, [Cu(C6H5N5)2]n, the CuII atom is coordinated by five N atoms from three distinct pyridyltetra­zolate anions in a highly distorted square-pyramidal arrangement. The ligands link adjacent CuII atoms to form one-dimensional polymeric chains with a Cu...Cu separation of 6.224 (2) Å. The chains are further linked by π–π stacking inter­actions [centroid–centroid = 3.684 (2) Å and vertical distance = 3.281 (2) Å], forming a three-dimensional supra­molecular framework.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807053597/rz2170sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807053597/rz2170Isup2.hkl
Contains datablock I

CCDC reference: 672586

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.025
  • wR factor = 0.066
  • Data-to-parameter ratio = 11.3

checkCIF/PLATON results

No syntax errors found



Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (1) 1.18
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

The crystal structures of manganese(II), copper(I, II), zinc(II), lanthanum(III) and gadolinium(III) complexes of the 5-(2-pyridyl)tetrazolate ligand have been reported recently (Andrews et al., 2006; Facchetti et al., 2004; Mo et al., 2004; Wang et al., 2003; Zhang et al., 2006). Except for the copper(I, II) complex, which has a two-dimensional structure with Cl- ions co-ligated, all other complexes have a mononuclear structure, in which the pyridyltetrazolate anion adopts a chelating coordination mode using its 1-position N atom of the tetrazolate ring and the pyridine N atom. Herein, we report the title complex, [Cu(C6H5N5)2]n, which has a polymeric one-dimensional structure.

In the title compound, the copper(II) atom is coordinated by five N atoms from three distinct pyridyltetrazolate ligands to form a highly distorted square-pyramidal geometry. The coordination basal plane is provided by two chelating ligands through their 1-position N atoms of the tetrazolate rings and by the pyridine N atoms, while and the apical position is occupied by the third ligand using the 3-position N atoms of its tetrazolate group (Fig. 1). Bond distances and angles around the copper(II) centre are in the range 1.972 (2)–2.257 (2) Å and 79.95 (7)–102.82 (8) °, respectively (Table 1). It is interesting to note that the ligands perform two types of coordination modes: chelating and chelating–bridging. The latter links the metal centres to form polymeric one-dimensional chains running parallel to the a axis with an intrachain Cu···Cu separation of 6.224 (2) Å (Fig. 2). In addition, ππ interactions occurring between the pyridine and tetrazolato rings of adjacent chains extend the structure to form a three-dimensional supramolecular framework as shown in Fig. 3 (Cp1···Cp2i, 3.684 (3) Å; Cp3···Cp4ii, 3.973 (4) Å; Cp1, Cp2, Cp3 and Cp4 are the centroids of the N1–N4/C1, N5/C2–C6, N6–N9/C7 and N10/C8–C12 rings respectively. Symmetry codes: (i) -x, 1 - y, 1 - z; (ii) 1/2 + x, y, 1/2 - z).

Related literature top

For the crystal structures of related compounds, see: Andrews et al. (2006); Facchetti et al. (2004); Mo et al. (2004); Wang et al. (2003); Zhang et al. (2006).

Experimental top

5-(2-Pyridyl)-1H-tetrazole (30 mg, 0.2 mmol) and copper(II) chloride dihydrate (34 mg, 0.2 mmol) were placed in a Teflon-lined stainless-steel Parr bomb along with water (14 ml). The bomb was heated at 431 K for 48 h and then cooled to room temperature over 24 h. Black crystals of the title compound were isolated manually in about 5% yield based on copper(II), with combining light blue crystals which have a mononuclear structure (Mo et al., 2004). Caution: tetrazole derivatives are potentially explosive. Although we have met no problems in this work, only a small amount of them should be prepared and handled with great caution.

Refinement top

All H atoms were included in calculated positions and treated in the subsequent refinement as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2 Ueq(C, N).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with displacement ellipsoid drawn at the 40% probability level. Symmetry codes: (A) 1/2 + x, 3/2 - y, 1 - z; (B) x - 1/2, 3/2 - y, 1 - z.
[Figure 2] Fig. 2. The polymeric one-dimensional chain structure of the title compound running parallel to the a axis. Displacement ellipsoid are drawn at the 40% probability level.
[Figure 3] Fig. 3. Packing diagram of the title compound viewed along the a axis. Displacement ellipsoid are drawn at the 40% probability level. Hydrogen atoms are omitted for clarity.
catena-Poly[[[5-(2-pyridyl)tetrazolato-κ2N1,N5]copper(II)]-µ- 5-(2-pyridyl)tetrazolato-κ2N1,N5:N3] top
Crystal data top
[Cu(C6H5N5)2]F(000) = 1432
Mr = 355.82Dx = 1.774 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 5746 reflections
a = 8.5905 (9) Åθ = 2.9–26.3°
b = 14.8361 (16) ŵ = 1.66 mm1
c = 20.905 (2) ÅT = 294 K
V = 2664.3 (5) Å3Block, black
Z = 80.30 × 0.28 × 0.28 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2348 independent reflections
Radiation source: fine-focus sealed tube1951 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
ϕ and ω scansθmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
h = 105
Tmin = 0.584, Tmax = 0.630k = 1715
12543 measured reflectionsl = 2424
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)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0285P)2 + 2.1688P]
where P = (Fo2 + 2Fc2)/3
2348 reflections(Δ/σ)max = 0.001
208 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.31 e Å3
Crystal data top
[Cu(C6H5N5)2]V = 2664.3 (5) Å3
Mr = 355.82Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 8.5905 (9) ŵ = 1.66 mm1
b = 14.8361 (16) ÅT = 294 K
c = 20.905 (2) Å0.30 × 0.28 × 0.28 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2348 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
1951 reflections with I > 2σ(I)
Tmin = 0.584, Tmax = 0.630Rint = 0.034
12543 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0250 restraints
wR(F2) = 0.066H-atom parameters constrained
S = 1.05Δρmax = 0.25 e Å3
2348 reflectionsΔρmin = 0.31 e Å3
208 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
xyzUiso*/Ueq
Cu10.14469 (3)0.665133 (18)0.410674 (12)0.02476 (11)
N10.0006 (2)0.70131 (12)0.48135 (8)0.0251 (4)
N20.1087 (2)0.76313 (13)0.49385 (9)0.0283 (5)
N30.1560 (2)0.74998 (13)0.55297 (9)0.0278 (4)
N40.0808 (2)0.68002 (13)0.58008 (9)0.0298 (5)
N50.1939 (2)0.56565 (12)0.47656 (9)0.0255 (4)
N60.2346 (2)0.60614 (13)0.33463 (9)0.0325 (5)
N70.3321 (3)0.53800 (15)0.31895 (11)0.0449 (6)
N80.3451 (3)0.53719 (16)0.25631 (11)0.0465 (6)
N90.2584 (3)0.60382 (15)0.23010 (9)0.0409 (6)
N100.0545 (2)0.74744 (13)0.34215 (8)0.0283 (4)
C10.0149 (3)0.65195 (15)0.53450 (10)0.0238 (5)
C20.1234 (3)0.57621 (15)0.53389 (11)0.0258 (5)
C30.1519 (3)0.51949 (16)0.58505 (11)0.0323 (6)
H3A0.10130.52800.62390.039*
C40.2575 (3)0.44974 (17)0.57718 (12)0.0381 (6)
H4A0.28030.41110.61090.046*
C50.3281 (3)0.43854 (17)0.51872 (13)0.0369 (6)
H5A0.39860.39180.51240.044*
C60.2936 (3)0.49731 (16)0.46930 (12)0.0311 (6)
H6A0.34130.48900.42980.037*
C70.1927 (3)0.64422 (16)0.27966 (11)0.0301 (6)
C80.0905 (3)0.72220 (16)0.28170 (10)0.0292 (5)
C90.0337 (3)0.76779 (18)0.22914 (11)0.0387 (6)
H9A0.05820.74850.18800.046*
C100.0593 (3)0.84200 (18)0.23832 (12)0.0410 (6)
H10A0.09910.87330.20340.049*
C110.0928 (3)0.86950 (19)0.29970 (12)0.0419 (7)
H11A0.15350.92040.30690.050*
C120.0350 (3)0.82024 (17)0.35020 (12)0.0377 (6)
H12A0.05920.83840.39160.045*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02785 (17)0.02881 (17)0.01762 (16)0.00286 (12)0.00096 (12)0.00109 (11)
N10.0264 (10)0.0279 (10)0.0210 (9)0.0031 (9)0.0021 (8)0.0001 (8)
N20.0309 (11)0.0313 (11)0.0228 (10)0.0050 (9)0.0038 (8)0.0004 (8)
N30.0305 (11)0.0311 (10)0.0220 (10)0.0039 (9)0.0024 (8)0.0012 (8)
N40.0326 (11)0.0351 (11)0.0217 (10)0.0017 (9)0.0011 (9)0.0008 (8)
N50.0254 (10)0.0260 (10)0.0251 (10)0.0008 (8)0.0009 (8)0.0021 (8)
N60.0363 (12)0.0352 (11)0.0259 (10)0.0045 (10)0.0019 (9)0.0047 (9)
N70.0533 (15)0.0455 (13)0.0359 (13)0.0122 (12)0.0062 (11)0.0072 (10)
N80.0541 (15)0.0503 (14)0.0352 (13)0.0064 (12)0.0087 (11)0.0113 (11)
N90.0461 (14)0.0500 (14)0.0265 (11)0.0022 (12)0.0059 (10)0.0100 (10)
N100.0316 (11)0.0346 (11)0.0187 (9)0.0001 (10)0.0008 (8)0.0002 (8)
C10.0230 (12)0.0298 (12)0.0186 (11)0.0030 (10)0.0007 (9)0.0020 (9)
C20.0250 (12)0.0279 (12)0.0244 (12)0.0036 (10)0.0029 (10)0.0017 (9)
C30.0369 (14)0.0356 (14)0.0246 (12)0.0007 (12)0.0005 (11)0.0019 (10)
C40.0440 (16)0.0343 (14)0.0358 (14)0.0007 (12)0.0093 (12)0.0083 (11)
C50.0350 (15)0.0292 (13)0.0465 (16)0.0065 (12)0.0070 (12)0.0008 (11)
C60.0279 (13)0.0323 (13)0.0330 (13)0.0024 (11)0.0009 (11)0.0032 (10)
C70.0309 (13)0.0378 (14)0.0217 (12)0.0077 (11)0.0010 (10)0.0056 (10)
C80.0280 (13)0.0389 (14)0.0208 (12)0.0072 (11)0.0009 (10)0.0005 (10)
C90.0432 (16)0.0538 (16)0.0191 (12)0.0038 (14)0.0000 (11)0.0016 (11)
C100.0463 (16)0.0495 (16)0.0273 (14)0.0014 (14)0.0035 (12)0.0122 (12)
C110.0477 (17)0.0437 (15)0.0343 (15)0.0087 (13)0.0033 (12)0.0085 (12)
C120.0485 (17)0.0400 (15)0.0245 (13)0.0088 (13)0.0035 (12)0.0008 (11)
Geometric parameters (Å, º) top
Cu1—N12.0005 (18)N10—C81.354 (3)
Cu1—N3i2.2574 (19)C1—C21.460 (3)
Cu1—N52.0625 (19)C2—C31.383 (3)
Cu1—N61.9723 (19)C3—C41.386 (4)
Cu1—N102.0355 (19)C3—H3A0.9300
N1—C11.336 (3)C4—C51.375 (4)
N1—N21.339 (3)C4—H4A0.9300
N2—N31.315 (3)C5—C61.384 (3)
N3—N41.348 (3)C5—H5A0.9300
N3—Cu1ii2.2574 (19)C6—H6A0.9300
N4—C11.326 (3)C7—C81.453 (3)
N5—C61.336 (3)C8—C91.379 (3)
N5—C21.352 (3)C9—C101.374 (4)
N6—C71.330 (3)C9—H9A0.9300
N6—N71.353 (3)C10—C111.377 (4)
N7—N81.314 (3)C10—H10A0.9300
N8—N91.354 (3)C11—C121.377 (4)
N9—C71.323 (3)C11—H11A0.9300
N10—C121.337 (3)C12—H12A0.9300
N1—Cu1—N3i94.06 (7)N5—C2—C3122.4 (2)
N1—Cu1—N579.95 (7)N5—C2—C1112.50 (19)
N1—Cu1—N1097.09 (8)C3—C2—C1125.1 (2)
N5—Cu1—N3i91.09 (7)C2—C3—C4118.6 (2)
N6—Cu1—N1163.06 (8)C2—C3—H3A120.7
N6—Cu1—N3i102.82 (8)C4—C3—H3A120.7
N6—Cu1—N598.08 (8)C5—C4—C3119.0 (2)
N6—Cu1—N1081.26 (8)C5—C4—H4A120.5
N10—Cu1—N3i101.01 (7)C3—C4—H4A120.5
N10—Cu1—N5167.75 (8)C4—C5—C6119.5 (2)
C1—N1—N2106.11 (18)C4—C5—H5A120.2
C1—N1—Cu1114.22 (15)C6—C5—H5A120.2
N2—N1—Cu1139.65 (14)N5—C6—C5122.1 (2)
N3—N2—N1107.36 (17)N5—C6—H6A119.0
N2—N3—N4111.19 (17)C5—C6—H6A119.0
N2—N3—Cu1ii117.88 (14)N9—C7—N6111.6 (2)
N4—N3—Cu1ii130.67 (14)N9—C7—C8129.9 (2)
C1—N4—N3103.71 (18)N6—C7—C8118.5 (2)
C6—N5—C2118.4 (2)N10—C8—C9121.8 (2)
C6—N5—Cu1126.76 (16)N10—C8—C7112.7 (2)
C2—N5—Cu1114.68 (15)C9—C8—C7125.5 (2)
C7—N6—N7106.01 (19)C10—C9—C8119.2 (2)
C7—N6—Cu1113.68 (16)C10—C9—H9A120.4
N7—N6—Cu1140.28 (16)C8—C9—H9A120.4
N8—N7—N6107.5 (2)C9—C10—C11119.3 (2)
N7—N8—N9110.5 (2)C9—C10—H10A120.3
C7—N9—N8104.4 (2)C11—C10—H10A120.3
C12—N10—C8118.2 (2)C12—C11—C10118.8 (3)
C12—N10—Cu1127.96 (15)C12—C11—H11A120.6
C8—N10—Cu1113.84 (16)C10—C11—H11A120.6
N4—C1—N1111.6 (2)N10—C12—C11122.7 (2)
N4—C1—C2130.1 (2)N10—C12—H12A118.7
N1—C1—C2118.24 (19)C11—C12—H12A118.7
Symmetry codes: (i) x+1/2, y+3/2, z+1; (ii) x1/2, y+3/2, z+1.

Experimental details

Crystal data
Chemical formula[Cu(C6H5N5)2]
Mr355.82
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)294
a, b, c (Å)8.5905 (9), 14.8361 (16), 20.905 (2)
V3)2664.3 (5)
Z8
Radiation typeMo Kα
µ (mm1)1.66
Crystal size (mm)0.30 × 0.28 × 0.28
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1998)
Tmin, Tmax0.584, 0.630
No. of measured, independent and
observed [I > 2σ(I)] reflections
12543, 2348, 1951
Rint0.034
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.066, 1.05
No. of reflections2348
No. of parameters208
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.31

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998).

Selected geometric parameters (Å, º) top
Cu1—N12.0005 (18)Cu1—N61.9723 (19)
Cu1—N3i2.2574 (19)Cu1—N102.0355 (19)
Cu1—N52.0625 (19)
N1—Cu1—N3i94.06 (7)N6—Cu1—N3i102.82 (8)
N1—Cu1—N579.95 (7)N6—Cu1—N598.08 (8)
N1—Cu1—N1097.09 (8)N6—Cu1—N1081.26 (8)
N5—Cu1—N3i91.09 (7)N10—Cu1—N3i101.01 (7)
N6—Cu1—N1163.06 (8)N10—Cu1—N5167.75 (8)
Symmetry code: (i) x+1/2, y+3/2, z+1.
 

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