Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807053597/rz2170sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807053597/rz2170Isup2.hkl |
CCDC reference: 672586
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.
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).
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).
[Cu(C6H5N5)2] | F(000) = 1432 |
Mr = 355.82 | Dx = 1.774 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 5746 reflections |
a = 8.5905 (9) Å | θ = 2.9–26.3° |
b = 14.8361 (16) Å | µ = 1.66 mm−1 |
c = 20.905 (2) Å | T = 294 K |
V = 2664.3 (5) Å3 | Block, black |
Z = 8 | 0.30 × 0.28 × 0.28 mm |
Bruker SMART CCD area-detector diffractometer | 2348 independent reflections |
Radiation source: fine-focus sealed tube | 1951 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −10→5 |
Tmin = 0.584, Tmax = 0.630 | k = −17→15 |
12543 measured reflections | l = −24→24 |
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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.066 | H-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 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
[Cu(C6H5N5)2] | V = 2664.3 (5) Å3 |
Mr = 355.82 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 8.5905 (9) Å | µ = 1.66 mm−1 |
b = 14.8361 (16) Å | T = 294 K |
c = 20.905 (2) Å | 0.30 × 0.28 × 0.28 mm |
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 = 0.630 | Rint = 0.034 |
12543 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.25 e Å−3 |
2348 reflections | Δρmin = −0.31 e Å−3 |
208 parameters |
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 | 0.14469 (3) | 0.665133 (18) | 0.410674 (12) | 0.02476 (11) | |
N1 | 0.0006 (2) | 0.70131 (12) | 0.48135 (8) | 0.0251 (4) | |
N2 | −0.1087 (2) | 0.76313 (13) | 0.49385 (9) | 0.0283 (5) | |
N3 | −0.1560 (2) | 0.74998 (13) | 0.55297 (9) | 0.0278 (4) | |
N4 | −0.0808 (2) | 0.68002 (13) | 0.58008 (9) | 0.0298 (5) | |
N5 | 0.1939 (2) | 0.56565 (12) | 0.47656 (9) | 0.0255 (4) | |
N6 | 0.2346 (2) | 0.60614 (13) | 0.33463 (9) | 0.0325 (5) | |
N7 | 0.3321 (3) | 0.53800 (15) | 0.31895 (11) | 0.0449 (6) | |
N8 | 0.3451 (3) | 0.53719 (16) | 0.25631 (11) | 0.0465 (6) | |
N9 | 0.2584 (3) | 0.60382 (15) | 0.23010 (9) | 0.0409 (6) | |
N10 | 0.0545 (2) | 0.74744 (13) | 0.34215 (8) | 0.0283 (4) | |
C1 | 0.0149 (3) | 0.65195 (15) | 0.53450 (10) | 0.0238 (5) | |
C2 | 0.1234 (3) | 0.57621 (15) | 0.53389 (11) | 0.0258 (5) | |
C3 | 0.1519 (3) | 0.51949 (16) | 0.58505 (11) | 0.0323 (6) | |
H3A | 0.1013 | 0.5280 | 0.6239 | 0.039* | |
C4 | 0.2575 (3) | 0.44974 (17) | 0.57718 (12) | 0.0381 (6) | |
H4A | 0.2803 | 0.4111 | 0.6109 | 0.046* | |
C5 | 0.3281 (3) | 0.43854 (17) | 0.51872 (13) | 0.0369 (6) | |
H5A | 0.3986 | 0.3918 | 0.5124 | 0.044* | |
C6 | 0.2936 (3) | 0.49731 (16) | 0.46930 (12) | 0.0311 (6) | |
H6A | 0.3413 | 0.4890 | 0.4298 | 0.037* | |
C7 | 0.1927 (3) | 0.64422 (16) | 0.27966 (11) | 0.0301 (6) | |
C8 | 0.0905 (3) | 0.72220 (16) | 0.28170 (10) | 0.0292 (5) | |
C9 | 0.0337 (3) | 0.76779 (18) | 0.22914 (11) | 0.0387 (6) | |
H9A | 0.0582 | 0.7485 | 0.1880 | 0.046* | |
C10 | −0.0593 (3) | 0.84200 (18) | 0.23832 (12) | 0.0410 (6) | |
H10A | −0.0991 | 0.8733 | 0.2034 | 0.049* | |
C11 | −0.0928 (3) | 0.86950 (19) | 0.29970 (12) | 0.0419 (7) | |
H11A | −0.1535 | 0.9204 | 0.3069 | 0.050* | |
C12 | −0.0350 (3) | 0.82024 (17) | 0.35020 (12) | 0.0377 (6) | |
H12A | −0.0592 | 0.8384 | 0.3916 | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.02785 (17) | 0.02881 (17) | 0.01762 (16) | 0.00286 (12) | 0.00096 (12) | −0.00109 (11) |
N1 | 0.0264 (10) | 0.0279 (10) | 0.0210 (9) | 0.0031 (9) | 0.0021 (8) | 0.0001 (8) |
N2 | 0.0309 (11) | 0.0313 (11) | 0.0228 (10) | 0.0050 (9) | 0.0038 (8) | −0.0004 (8) |
N3 | 0.0305 (11) | 0.0311 (10) | 0.0220 (10) | 0.0039 (9) | 0.0024 (8) | −0.0012 (8) |
N4 | 0.0326 (11) | 0.0351 (11) | 0.0217 (10) | 0.0017 (9) | 0.0011 (9) | −0.0008 (8) |
N5 | 0.0254 (10) | 0.0260 (10) | 0.0251 (10) | −0.0008 (8) | −0.0009 (8) | −0.0021 (8) |
N6 | 0.0363 (12) | 0.0352 (11) | 0.0259 (10) | 0.0045 (10) | 0.0019 (9) | −0.0047 (9) |
N7 | 0.0533 (15) | 0.0455 (13) | 0.0359 (13) | 0.0122 (12) | 0.0062 (11) | −0.0072 (10) |
N8 | 0.0541 (15) | 0.0503 (14) | 0.0352 (13) | 0.0064 (12) | 0.0087 (11) | −0.0113 (11) |
N9 | 0.0461 (14) | 0.0500 (14) | 0.0265 (11) | −0.0022 (12) | 0.0059 (10) | −0.0100 (10) |
N10 | 0.0316 (11) | 0.0346 (11) | 0.0187 (9) | −0.0001 (10) | −0.0008 (8) | 0.0002 (8) |
C1 | 0.0230 (12) | 0.0298 (12) | 0.0186 (11) | −0.0030 (10) | −0.0007 (9) | −0.0020 (9) |
C2 | 0.0250 (12) | 0.0279 (12) | 0.0244 (12) | −0.0036 (10) | −0.0029 (10) | −0.0017 (9) |
C3 | 0.0369 (14) | 0.0356 (14) | 0.0246 (12) | −0.0007 (12) | −0.0005 (11) | 0.0019 (10) |
C4 | 0.0440 (16) | 0.0343 (14) | 0.0358 (14) | 0.0007 (12) | −0.0093 (12) | 0.0083 (11) |
C5 | 0.0350 (15) | 0.0292 (13) | 0.0465 (16) | 0.0065 (12) | −0.0070 (12) | 0.0008 (11) |
C6 | 0.0279 (13) | 0.0323 (13) | 0.0330 (13) | 0.0024 (11) | 0.0009 (11) | −0.0032 (10) |
C7 | 0.0309 (13) | 0.0378 (14) | 0.0217 (12) | −0.0077 (11) | 0.0010 (10) | −0.0056 (10) |
C8 | 0.0280 (13) | 0.0389 (14) | 0.0208 (12) | −0.0072 (11) | −0.0009 (10) | −0.0005 (10) |
C9 | 0.0432 (16) | 0.0538 (16) | 0.0191 (12) | −0.0038 (14) | 0.0000 (11) | 0.0016 (11) |
C10 | 0.0463 (16) | 0.0495 (16) | 0.0273 (14) | 0.0014 (14) | −0.0035 (12) | 0.0122 (12) |
C11 | 0.0477 (17) | 0.0437 (15) | 0.0343 (15) | 0.0087 (13) | 0.0033 (12) | 0.0085 (12) |
C12 | 0.0485 (17) | 0.0400 (15) | 0.0245 (13) | 0.0088 (13) | 0.0035 (12) | 0.0008 (11) |
Cu1—N1 | 2.0005 (18) | N10—C8 | 1.354 (3) |
Cu1—N3i | 2.2574 (19) | C1—C2 | 1.460 (3) |
Cu1—N5 | 2.0625 (19) | C2—C3 | 1.383 (3) |
Cu1—N6 | 1.9723 (19) | C3—C4 | 1.386 (4) |
Cu1—N10 | 2.0355 (19) | C3—H3A | 0.9300 |
N1—C1 | 1.336 (3) | C4—C5 | 1.375 (4) |
N1—N2 | 1.339 (3) | C4—H4A | 0.9300 |
N2—N3 | 1.315 (3) | C5—C6 | 1.384 (3) |
N3—N4 | 1.348 (3) | C5—H5A | 0.9300 |
N3—Cu1ii | 2.2574 (19) | C6—H6A | 0.9300 |
N4—C1 | 1.326 (3) | C7—C8 | 1.453 (3) |
N5—C6 | 1.336 (3) | C8—C9 | 1.379 (3) |
N5—C2 | 1.352 (3) | C9—C10 | 1.374 (4) |
N6—C7 | 1.330 (3) | C9—H9A | 0.9300 |
N6—N7 | 1.353 (3) | C10—C11 | 1.377 (4) |
N7—N8 | 1.314 (3) | C10—H10A | 0.9300 |
N8—N9 | 1.354 (3) | C11—C12 | 1.377 (4) |
N9—C7 | 1.323 (3) | C11—H11A | 0.9300 |
N10—C12 | 1.337 (3) | C12—H12A | 0.9300 |
N1—Cu1—N3i | 94.06 (7) | N5—C2—C3 | 122.4 (2) |
N1—Cu1—N5 | 79.95 (7) | N5—C2—C1 | 112.50 (19) |
N1—Cu1—N10 | 97.09 (8) | C3—C2—C1 | 125.1 (2) |
N5—Cu1—N3i | 91.09 (7) | C2—C3—C4 | 118.6 (2) |
N6—Cu1—N1 | 163.06 (8) | C2—C3—H3A | 120.7 |
N6—Cu1—N3i | 102.82 (8) | C4—C3—H3A | 120.7 |
N6—Cu1—N5 | 98.08 (8) | C5—C4—C3 | 119.0 (2) |
N6—Cu1—N10 | 81.26 (8) | C5—C4—H4A | 120.5 |
N10—Cu1—N3i | 101.01 (7) | C3—C4—H4A | 120.5 |
N10—Cu1—N5 | 167.75 (8) | C4—C5—C6 | 119.5 (2) |
C1—N1—N2 | 106.11 (18) | C4—C5—H5A | 120.2 |
C1—N1—Cu1 | 114.22 (15) | C6—C5—H5A | 120.2 |
N2—N1—Cu1 | 139.65 (14) | N5—C6—C5 | 122.1 (2) |
N3—N2—N1 | 107.36 (17) | N5—C6—H6A | 119.0 |
N2—N3—N4 | 111.19 (17) | C5—C6—H6A | 119.0 |
N2—N3—Cu1ii | 117.88 (14) | N9—C7—N6 | 111.6 (2) |
N4—N3—Cu1ii | 130.67 (14) | N9—C7—C8 | 129.9 (2) |
C1—N4—N3 | 103.71 (18) | N6—C7—C8 | 118.5 (2) |
C6—N5—C2 | 118.4 (2) | N10—C8—C9 | 121.8 (2) |
C6—N5—Cu1 | 126.76 (16) | N10—C8—C7 | 112.7 (2) |
C2—N5—Cu1 | 114.68 (15) | C9—C8—C7 | 125.5 (2) |
C7—N6—N7 | 106.01 (19) | C10—C9—C8 | 119.2 (2) |
C7—N6—Cu1 | 113.68 (16) | C10—C9—H9A | 120.4 |
N7—N6—Cu1 | 140.28 (16) | C8—C9—H9A | 120.4 |
N8—N7—N6 | 107.5 (2) | C9—C10—C11 | 119.3 (2) |
N7—N8—N9 | 110.5 (2) | C9—C10—H10A | 120.3 |
C7—N9—N8 | 104.4 (2) | C11—C10—H10A | 120.3 |
C12—N10—C8 | 118.2 (2) | C12—C11—C10 | 118.8 (3) |
C12—N10—Cu1 | 127.96 (15) | C12—C11—H11A | 120.6 |
C8—N10—Cu1 | 113.84 (16) | C10—C11—H11A | 120.6 |
N4—C1—N1 | 111.6 (2) | N10—C12—C11 | 122.7 (2) |
N4—C1—C2 | 130.1 (2) | N10—C12—H12A | 118.7 |
N1—C1—C2 | 118.24 (19) | C11—C12—H12A | 118.7 |
Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) x−1/2, −y+3/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C6H5N5)2] |
Mr | 355.82 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 294 |
a, b, c (Å) | 8.5905 (9), 14.8361 (16), 20.905 (2) |
V (Å3) | 2664.3 (5) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.66 |
Crystal size (mm) | 0.30 × 0.28 × 0.28 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.584, 0.630 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12543, 2348, 1951 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.066, 1.05 |
No. of reflections | 2348 |
No. of parameters | 208 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.31 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998).
Cu1—N1 | 2.0005 (18) | Cu1—N6 | 1.9723 (19) |
Cu1—N3i | 2.2574 (19) | Cu1—N10 | 2.0355 (19) |
Cu1—N5 | 2.0625 (19) | ||
N1—Cu1—N3i | 94.06 (7) | N6—Cu1—N3i | 102.82 (8) |
N1—Cu1—N5 | 79.95 (7) | N6—Cu1—N5 | 98.08 (8) |
N1—Cu1—N10 | 97.09 (8) | N6—Cu1—N10 | 81.26 (8) |
N5—Cu1—N3i | 91.09 (7) | N10—Cu1—N3i | 101.01 (7) |
N6—Cu1—N1 | 163.06 (8) | N10—Cu1—N5 | 167.75 (8) |
Symmetry code: (i) x+1/2, −y+3/2, −z+1. |
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, π–π 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).