supplementary materials
A new cobalt(II) complex with 5-(4-pyridyl)tetrazole ligands
The synthesis of the L ligand [L =5-(4'-pyridyl)tetrazole] was
according to the previously published literature (Detert et al., 1999).
A solution of CoCl2.(H2O)6 (0.0238 g, 0.1 mmol)
in 10 ml water was added to the
solution of L (0.0310 g, 0.2 mmol) in 5 ml water, the mixture was
heated with stirring. After 3 h,
the mixture was cooled to room temperature and filtered.
The filtrate was allowed to stand in air at
room temperature for several days.
Red crystals suitable for X-ray diffraction were obtained. Calculated for
C12H20CoN10O6: C 31.35, H 4.35, O 15.65, Co 12.83, N 30.48%; found:
C 31.32, H 4.40%.
To obtain a better refinement result,
eight atoms, namely C(1), H(1), C(2), H(2), C(4), H(4),
C(5) and H(5) have been restrained, and all the distance of C—H were fixed
at 0.93 Å, with Uiso(H) = 1.19Ueq(C).
Other hydrogen atoms were positioned geometrically
and refined using a riding model.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
tetraaquabis[5-(4-pyridyl)tetrazolido-
κN
5]cobalt(II) dihydrate
top
Crystal data top
| [Co(C6H4N5)2(H2O)4]·2H2O | Z = 1 |
| Mr = 459.31 | F(000) = 237 |
| Triclinic, P1 | Dx = 1.594 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 7.2087 (16) Å | Cell parameters from 1859 reflections |
| b = 7.8002 (17) Å | θ = 2.7–26.3° |
| c = 8.6702 (18) Å | µ = 0.95 mm−1 |
| α = 91.406 (3)° | T = 294 K |
| β = 90.482 (3)° | Block, red |
| γ = 100.953 (3)° | 0.20 × 0.20 × 0.14 mm |
| V = 478.45 (18) Å3 | |
Data collection top
Bruker SMART CCD area-detector
diffractometer | 1684 independent reflections |
| Radiation source: fine-focus sealed tube | 1562 reflections with I > 2σ(I) |
| graphite | Rint = 0.013 |
| phi and ω scans | θmax = 25.0°, θmin = 2.4° |
Absorption correction: multi-scan
(SADABS; Sheldrick 1996) | h = −5→8 |
| Tmin = 0.763, Tmax = 0.890 | k = −8→9 |
| 2456 measured reflections | l = −10→7 |
Refinement top
| 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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.12 | w = 1/[σ2(Fo2) + (0.035P)2 + 2.1646P]
where P = (Fo2 + 2Fc2)/3 |
| 1684 reflections | (Δ/σ)max < 0.001 |
| 157 parameters | Δρmax = 0.49 e Å−3 |
| 9 restraints | Δρmin = −0.28 e Å−3 |
Crystal data top
| [Co(C6H4N5)2(H2O)4]·2H2O | γ = 100.953 (3)° |
| Mr = 459.31 | V = 478.45 (18) Å3 |
| Triclinic, P1 | Z = 1 |
| a = 7.2087 (16) Å | Mo Kα radiation |
| b = 7.8002 (17) Å | µ = 0.95 mm−1 |
| c = 8.6702 (18) Å | T = 294 K |
| α = 91.406 (3)° | 0.20 × 0.20 × 0.14 mm |
| β = 90.482 (3)° | |
Data collection top
Bruker SMART CCD area-detector
diffractometer | 1684 independent reflections |
Absorption correction: multi-scan
(SADABS; Sheldrick 1996) | 1562 reflections with I > 2σ(I) |
| Tmin = 0.763, Tmax = 0.890 | Rint = 0.013 |
| 2456 measured reflections | θmax = 25.0° |
Refinement top
| R[F2 > 2σ(F2)] = 0.031 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.083 | Δρmax = 0.49 e Å−3 |
| S = 1.12 | Δρmin = −0.28 e Å−3 |
| 1684 reflections | Absolute structure: ? |
| 157 parameters | Flack parameter: ? |
| 9 restraints | Rogers parameter: ? |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | |
| Co1 | 0.5000 | 0.5000 | 0.0000 | 0.02432 (16) | |
| O1 | 0.6737 (2) | 0.6584 (2) | 0.16137 (19) | 0.0330 (4) | |
| O2 | 0.7102 (3) | 0.3451 (2) | −0.0278 (2) | 0.0372 (4) | |
| N1 | 0.3835 (3) | 0.3267 (2) | 0.1789 (2) | 0.0285 (4) | |
| N2 | 0.2607 (3) | 0.0110 (3) | 0.6942 (2) | 0.0334 (5) | |
| N3 | 0.2040 (3) | −0.1406 (3) | 0.7653 (2) | 0.0371 (5) | |
| N4 | 0.1459 (3) | −0.2640 (3) | 0.6620 (2) | 0.0376 (5) | |
| N5 | 0.1617 (3) | −0.1980 (3) | 0.5206 (2) | 0.0343 (5) | |
| C1 | 0.3706 (4) | 0.3835 (3) | 0.3237 (3) | 0.0353 (6) | |
| H1 | 0.3975 | 0.5034 | 0.3441 | 0.042* | |
| C2 | 0.3196 (4) | 0.2748 (3) | 0.4445 (3) | 0.0372 (6) | |
| H2 | 0.3120 | 0.3213 | 0.5435 | 0.045* | |
| C3 | 0.2795 (3) | 0.0948 (3) | 0.4185 (3) | 0.0265 (5) | |
| C4 | 0.2848 (5) | 0.0366 (3) | 0.2677 (3) | 0.0443 (7) | |
| H4 | 0.2542 | −0.0823 | 0.2433 | 0.053* | |
| C5 | 0.3357 (5) | 0.1551 (3) | 0.1530 (3) | 0.0445 (7) | |
| H5 | 0.3366 | 0.1127 | 0.0519 | 0.053* | |
| C6 | 0.2333 (3) | −0.0290 (3) | 0.5441 (3) | 0.0271 (5) | |
| O3 | 0.0218 (2) | 0.5988 (2) | 0.25348 (19) | 0.0332 (4) | |
| H1A | 0.670 (4) | 0.7610 (19) | 0.197 (3) | 0.044 (8)* | |
| H1B | 0.782 (3) | 0.629 (4) | 0.170 (4) | 0.073 (12)* | |
| H2A | 0.736 (4) | 0.276 (3) | 0.040 (2) | 0.043 (8)* | |
| H2B | 0.794 (3) | 0.372 (4) | −0.096 (3) | 0.056 (10)* | |
| H3A | 0.066 (4) | 0.662 (3) | 0.332 (2) | 0.040 (8)* | |
| H3B | −0.018 (4) | 0.4918 (15) | 0.272 (3) | 0.052 (9)* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Co1 | 0.0335 (3) | 0.0211 (2) | 0.0174 (2) | 0.00208 (17) | 0.00210 (16) | 0.00325 (16) |
| O1 | 0.0416 (10) | 0.0277 (9) | 0.0283 (9) | 0.0039 (7) | −0.0052 (7) | −0.0036 (7) |
| O2 | 0.0474 (11) | 0.0395 (10) | 0.0289 (10) | 0.0169 (8) | 0.0099 (8) | 0.0130 (8) |
| N1 | 0.0362 (10) | 0.0248 (10) | 0.0229 (10) | 0.0014 (8) | 0.0022 (8) | 0.0034 (8) |
| N2 | 0.0459 (12) | 0.0276 (11) | 0.0247 (11) | 0.0016 (9) | −0.0018 (9) | 0.0068 (8) |
| N3 | 0.0489 (13) | 0.0325 (11) | 0.0279 (11) | 0.0019 (9) | −0.0012 (9) | 0.0104 (9) |
| N4 | 0.0499 (13) | 0.0291 (11) | 0.0313 (12) | −0.0004 (9) | −0.0018 (9) | 0.0121 (9) |
| N5 | 0.0469 (12) | 0.0264 (11) | 0.0267 (11) | −0.0010 (9) | −0.0011 (9) | 0.0078 (8) |
| C1 | 0.0497 (15) | 0.0245 (12) | 0.0282 (13) | −0.0019 (10) | 0.0027 (11) | 0.0028 (10) |
| C2 | 0.0527 (16) | 0.0340 (14) | 0.0217 (12) | −0.0001 (11) | 0.0022 (11) | 0.0016 (10) |
| C3 | 0.0282 (11) | 0.0259 (12) | 0.0245 (11) | 0.0026 (9) | 0.0013 (9) | 0.0063 (9) |
| C4 | 0.077 (2) | 0.0223 (13) | 0.0296 (14) | −0.0022 (12) | 0.0049 (13) | 0.0022 (10) |
| C5 | 0.077 (2) | 0.0301 (14) | 0.0217 (12) | −0.0012 (13) | 0.0043 (12) | 0.0026 (10) |
| C6 | 0.0280 (11) | 0.0275 (12) | 0.0254 (11) | 0.0040 (9) | 0.0000 (9) | 0.0057 (9) |
| O3 | 0.0422 (10) | 0.0260 (9) | 0.0292 (9) | 0.0002 (8) | 0.0012 (7) | 0.0040 (7) |
Geometric parameters (Å, °) top
| Co1—O1i | 2.0855 (16) | N3—N4 | 1.304 (3) |
| Co1—O1 | 2.0855 (16) | N4—N5 | 1.339 (3) |
| Co1—O2 | 2.1220 (17) | N5—C6 | 1.331 (3) |
| Co1—O2i | 2.1220 (17) | C1—C2 | 1.372 (3) |
| Co1—N1 | 2.1520 (19) | C1—H1 | 0.9300 |
| Co1—N1i | 2.1521 (19) | C2—C3 | 1.391 (3) |
| O1—H1A | 0.855 (10) | C2—H2 | 0.9300 |
| O1—H1B | 0.857 (10) | C3—C4 | 1.377 (3) |
| O2—H2A | 0.849 (10) | C3—C6 | 1.471 (3) |
| O2—H2B | 0.851 (10) | C4—C5 | 1.378 (4) |
| N1—C5 | 1.331 (3) | C4—H4 | 0.9300 |
| N1—C1 | 1.331 (3) | C5—H5 | 0.9300 |
| N2—C6 | 1.334 (3) | O3—H3A | 0.853 (10) |
| N2—N3 | 1.342 (3) | O3—H3B | 0.849 (10) |
| | | |
| O1i—Co1—O2 | 90.42 (7) | N4—N3—N2 | 109.21 (19) |
| O1—Co1—O2 | 89.58 (7) | N3—N4—N5 | 109.94 (19) |
| O1i—Co1—O2i | 89.58 (7) | C6—N5—N4 | 104.62 (19) |
| O1—Co1—O2i | 90.42 (7) | N1—C1—C2 | 123.5 (2) |
| O1i—Co1—N1 | 89.50 (7) | N1—C1—H1 | 118.2 |
| O1—Co1—N1 | 90.50 (7) | C2—C1—H1 | 118.2 |
| O2—Co1—N1 | 87.51 (7) | C1—C2—C3 | 119.9 (2) |
| O2i—Co1—N1 | 92.49 (7) | C1—C2—H2 | 120.1 |
| O1i—Co1—N1i | 90.50 (7) | C3—C2—H2 | 120.1 |
| O1—Co1—N1i | 89.50 (7) | C4—C3—C2 | 116.5 (2) |
| O2—Co1—N1i | 92.49 (7) | C4—C3—C6 | 121.0 (2) |
| O2i—Co1—N1i | 87.51 (7) | C2—C3—C6 | 122.5 (2) |
| Co1—O1—H1A | 130.6 (18) | C3—C4—C5 | 119.8 (2) |
| Co1—O1—H1B | 112 (2) | C3—C4—H4 | 120.1 |
| H1A—O1—H1B | 114.2 (17) | C5—C4—H4 | 120.1 |
| Co1—O2—H2A | 123.1 (17) | N1—C5—C4 | 123.7 (2) |
| Co1—O2—H2B | 118.7 (18) | N1—C5—H5 | 118.2 |
| H2A—O2—H2B | 115.9 (17) | C4—C5—H5 | 118.2 |
| C5—N1—C1 | 116.5 (2) | N5—C6—N2 | 111.4 (2) |
| C5—N1—Co1 | 121.48 (16) | N5—C6—C3 | 123.4 (2) |
| C1—N1—Co1 | 121.77 (16) | N2—C6—C3 | 125.1 (2) |
| C6—N2—N3 | 104.82 (19) | H3A—O3—H3B | 114.8 (16) |
| Symmetry codes: (i) −x+1, −y+1, −z. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1A···N2ii | 0.86 (1) | 1.97 (1) | 2.795 (3) | 162 (1) |
| O1—H1B···O3iii | 0.86 (1) | 1.93 (1) | 2.753 (3) | 162 (1) |
| O2—H2A···N3iv | 0.85 (1) | 2.10 (1) | 2.939 (3) | 171 (1) |
| O2—H2B···O3i | 0.85 (1) | 1.90 (1) | 2.745 (3) | 172 (1) |
| O3—H3A···N5v | 0.85 (1) | 1.99 (1) | 2.840 (3) | 178 (1) |
| O3—H3B···N4vi | 0.85 (1) | 1.94 (1) | 2.780 (3) | 169 (1) |
| Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z; (iv) −x+1, −y, −z+1; (i) −x+1, −y+1, −z; (v) x, y+1, z; (vi) −x, −y, −z+1. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1A···N2i | 0.86 (1) | 1.97 (1) | 2.795 (3) | 162 (1) |
| O1—H1B···O3ii | 0.86 (1) | 1.93 (1) | 2.753 (3) | 162 (1) |
| O2—H2A···N3iii | 0.85 (1) | 2.10 (1) | 2.939 (3) | 171 (1) |
| O2—H2B···O3iv | 0.85 (1) | 1.90 (1) | 2.745 (3) | 172 (1) |
| O3—H3A···N5v | 0.85 (1) | 1.99 (1) | 2.840 (3) | 178 (1) |
| O3—H3B···N4vi | 0.85 (1) | 1.94 (1) | 2.780 (3) | 169 (1) |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z; (iii) −x+1, −y, −z+1; (iv) −x+1, −y+1, −z; (v) x, y+1, z; (vi) −x, −y, −z+1. |
The authors thank the the Natural Science Foundation of Jiangsu for financial
support.
Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Detert, H. & Schollmeier, D. (1999). Synthesis, pp. 999–1004.
Lin, P., Clegg, W., Harrington, R. W. & Henderson, R. A. (2005). Dalton. Trans. pp. 2388-2394.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
![[kappa]](/logos/entities/kappa_rmgif.gif)
N5]cobalt(II) dihydrate, [Co(C6H4N5)2(H2O)4]·2H2O, has been synthesized and structurally characterized. The CoII atom is coordinated by two N atoms from 5-(4-pyridyl)tetrazole ligands (L), as well as four O atoms from coordinated water molecules. The molecule is centrosymmetric, with pairs of equivalent ligands lying trans to each other in a slightly distorted octahedral coordination geometry. A prominent feature of the complex is the formation of a three-dimensional supramolecular network via O-H
O and O-H![[Figure 1]](./br2083fig1thm.gif)
![[Figure 2]](./br2083fig2thm.gif)
A wide range of applications of tetrazoles have found in areas as diverse as coordination chemistry, medicinal chemistry and materials science. The study of complexes containing substituted tetrazole ligands is of interest to describe the ways in which tetrazoles bind to metal centres. However, in the title complex reported here, the substituted tetrazole ligands bind to metal centres by the N atoms from pyridyls. In this contribution, we chose 5-(4'-pyridyl)tetrazole (L) as organic ligands and synthesized a new mononuclear complex, namely (CoL2(H2O)4).H2O.
Single crystal X-ray diffraction analysis reveals that the vicinity of the cobalt(II) ion is constituted by two nitrogen atoms from the L ligands and four oxygen atoms from coordinated water moleculars. The molecule is centrosymmetric, so pairs of equivalent ligands lie trans to each other in a slightly distorted octahedral coordination geometry. Four oxygen atoms from coordinated water moleculars occupy the four equatorial positions while two nitrogen atoms, N(1) and N(1 A) from the L ligands are in the axial sites. A diagram of the molecule is shown in Fig. 1. The complex is further connected into a three dimensional supramolecular structure via O—H···O and O—H···N hydrogen bonds, which is shown in Fig. 2.