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Acta Crystallogr Sect E Struct Rep Online. 2008 November 1; 64(Pt 11): m1478.
Published online 2008 October 31. doi:  10.1107/S1600536808034880
PMCID: PMC2959662

A new cobalt(II) complex with 5-(4-pyrid­yl)tetra­zole ligands

Abstract

A new mononuclear cobalt(II) complex, tetra­aqua­bis[5-(4-pyrid­yl)tetra­zolido-κN 5]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(...)N hydrogen bonds.

Related literature

The corresponding complex with manganese(II) ion as the central metal atom (Lin et al., 2005 [triangle]) has a similar structure to that of the title complex. For related literature, see: Detert & Schollmeier (1999 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-m1478-scheme1.jpg

Experimental

Crystal data

  • [Co(C6H4N5)2(H2O)4]·2H2O
  • M r = 459.31
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1478-efi1.jpg
  • a = 7.2087 (16) Å
  • b = 7.8002 (17) Å
  • c = 8.6702 (18) Å
  • α = 91.406 (3)°
  • β = 90.482 (3)°
  • γ = 100.953 (3)°
  • V = 478.45 (18) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 0.95 mm−1
  • T = 294 (2) K
  • 0.20 × 0.20 × 0.14 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick 1996 [triangle]) T min = 0.763, T max = 0.890
  • 2456 measured reflections
  • 1684 independent reflections
  • 1562 reflections with I > 2σ(I)
  • R int = 0.013

Refinement

  • R[F 2 > 2σ(F 2)] = 0.031
  • wR(F 2) = 0.083
  • S = 1.12
  • 1684 reflections
  • 157 parameters
  • 9 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.49 e Å−3
  • Δρmin = −0.28 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT (Bruker, 1998 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808034880/br2083sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808034880/br2083Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the the Natural Science Foundation of Jiangsu for financial support.

supplementary crystallographic information

Comment

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.

Experimental

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%.

Refinement

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.

Figures

Fig. 1.
An ORTEP view of the title complex with 30% thermal ellipsoids. The H atoms are omitted for clarity.
Fig. 2.
The packing diagram of the title complex.

Crystal data

[Co(C6H4N5)2(H2O)4]·2H2OZ = 1
Mr = 459.31F(000) = 237
Triclinic, P1Dx = 1.594 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.2087 (16) ÅCell parameters from 1859 reflections
b = 7.8002 (17) Åθ = 2.7–26.3°
c = 8.6702 (18) ŵ = 0.95 mm1
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

Bruker SMART CCD area-detector diffractometer1684 independent reflections
Radiation source: fine-focus sealed tube1562 reflections with I > 2σ(I)
graphiteRint = 0.013
phi and ω scansθmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick 1996)h = −5→8
Tmin = 0.763, Tmax = 0.890k = −8→9
2456 measured reflectionsl = −10→7

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H atoms treated by a mixture of independent and constrained refinement
S = 1.12w = 1/[σ2(Fo2) + (0.035P)2 + 2.1646P] where P = (Fo2 + 2Fc2)/3
1684 reflections(Δ/σ)max < 0.001
157 parametersΔρmax = 0.49 e Å3
9 restraintsΔρmin = −0.28 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Co10.50000.50000.00000.02432 (16)
O10.6737 (2)0.6584 (2)0.16137 (19)0.0330 (4)
O20.7102 (3)0.3451 (2)−0.0278 (2)0.0372 (4)
N10.3835 (3)0.3267 (2)0.1789 (2)0.0285 (4)
N20.2607 (3)0.0110 (3)0.6942 (2)0.0334 (5)
N30.2040 (3)−0.1406 (3)0.7653 (2)0.0371 (5)
N40.1459 (3)−0.2640 (3)0.6620 (2)0.0376 (5)
N50.1617 (3)−0.1980 (3)0.5206 (2)0.0343 (5)
C10.3706 (4)0.3835 (3)0.3237 (3)0.0353 (6)
H10.39750.50340.34410.042*
C20.3196 (4)0.2748 (3)0.4445 (3)0.0372 (6)
H20.31200.32130.54350.045*
C30.2795 (3)0.0948 (3)0.4185 (3)0.0265 (5)
C40.2848 (5)0.0366 (3)0.2677 (3)0.0443 (7)
H40.2542−0.08230.24330.053*
C50.3357 (5)0.1551 (3)0.1530 (3)0.0445 (7)
H50.33660.11270.05190.053*
C60.2333 (3)−0.0290 (3)0.5441 (3)0.0271 (5)
O30.0218 (2)0.5988 (2)0.25348 (19)0.0332 (4)
H1A0.670 (4)0.7610 (19)0.197 (3)0.044 (8)*
H1B0.782 (3)0.629 (4)0.170 (4)0.073 (12)*
H2A0.736 (4)0.276 (3)0.040 (2)0.043 (8)*
H2B0.794 (3)0.372 (4)−0.096 (3)0.056 (10)*
H3A0.066 (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)

U11U22U33U12U13U23
Co10.0335 (3)0.0211 (2)0.0174 (2)0.00208 (17)0.00210 (16)0.00325 (16)
O10.0416 (10)0.0277 (9)0.0283 (9)0.0039 (7)−0.0052 (7)−0.0036 (7)
O20.0474 (11)0.0395 (10)0.0289 (10)0.0169 (8)0.0099 (8)0.0130 (8)
N10.0362 (10)0.0248 (10)0.0229 (10)0.0014 (8)0.0022 (8)0.0034 (8)
N20.0459 (12)0.0276 (11)0.0247 (11)0.0016 (9)−0.0018 (9)0.0068 (8)
N30.0489 (13)0.0325 (11)0.0279 (11)0.0019 (9)−0.0012 (9)0.0104 (9)
N40.0499 (13)0.0291 (11)0.0313 (12)−0.0004 (9)−0.0018 (9)0.0121 (9)
N50.0469 (12)0.0264 (11)0.0267 (11)−0.0010 (9)−0.0011 (9)0.0078 (8)
C10.0497 (15)0.0245 (12)0.0282 (13)−0.0019 (10)0.0027 (11)0.0028 (10)
C20.0527 (16)0.0340 (14)0.0217 (12)−0.0001 (11)0.0022 (11)0.0016 (10)
C30.0282 (11)0.0259 (12)0.0245 (11)0.0026 (9)0.0013 (9)0.0063 (9)
C40.077 (2)0.0223 (13)0.0296 (14)−0.0022 (12)0.0049 (13)0.0022 (10)
C50.077 (2)0.0301 (14)0.0217 (12)−0.0012 (13)0.0043 (12)0.0026 (10)
C60.0280 (11)0.0275 (12)0.0254 (11)0.0040 (9)0.0000 (9)0.0057 (9)
O30.0422 (10)0.0260 (9)0.0292 (9)0.0002 (8)0.0012 (7)0.0040 (7)

Geometric parameters (Å, °)

Co1—O1i2.0855 (16)N3—N41.304 (3)
Co1—O12.0855 (16)N4—N51.339 (3)
Co1—O22.1220 (17)N5—C61.331 (3)
Co1—O2i2.1220 (17)C1—C21.372 (3)
Co1—N12.1520 (19)C1—H10.9300
Co1—N1i2.1521 (19)C2—C31.391 (3)
O1—H1A0.855 (10)C2—H20.9300
O1—H1B0.857 (10)C3—C41.377 (3)
O2—H2A0.849 (10)C3—C61.471 (3)
O2—H2B0.851 (10)C4—C51.378 (4)
N1—C51.331 (3)C4—H40.9300
N1—C11.331 (3)C5—H50.9300
N2—C61.334 (3)O3—H3A0.853 (10)
N2—N31.342 (3)O3—H3B0.849 (10)
O1i—Co1—O290.42 (7)N4—N3—N2109.21 (19)
O1—Co1—O289.58 (7)N3—N4—N5109.94 (19)
O1i—Co1—O2i89.58 (7)C6—N5—N4104.62 (19)
O1—Co1—O2i90.42 (7)N1—C1—C2123.5 (2)
O1i—Co1—N189.50 (7)N1—C1—H1118.2
O1—Co1—N190.50 (7)C2—C1—H1118.2
O2—Co1—N187.51 (7)C1—C2—C3119.9 (2)
O2i—Co1—N192.49 (7)C1—C2—H2120.1
O1i—Co1—N1i90.50 (7)C3—C2—H2120.1
O1—Co1—N1i89.50 (7)C4—C3—C2116.5 (2)
O2—Co1—N1i92.49 (7)C4—C3—C6121.0 (2)
O2i—Co1—N1i87.51 (7)C2—C3—C6122.5 (2)
Co1—O1—H1A130.6 (18)C3—C4—C5119.8 (2)
Co1—O1—H1B112 (2)C3—C4—H4120.1
H1A—O1—H1B114.2 (17)C5—C4—H4120.1
Co1—O2—H2A123.1 (17)N1—C5—C4123.7 (2)
Co1—O2—H2B118.7 (18)N1—C5—H5118.2
H2A—O2—H2B115.9 (17)C4—C5—H5118.2
C5—N1—C1116.5 (2)N5—C6—N2111.4 (2)
C5—N1—Co1121.48 (16)N5—C6—C3123.4 (2)
C1—N1—Co1121.77 (16)N2—C6—C3125.1 (2)
C6—N2—N3104.82 (19)H3A—O3—H3B114.8 (16)

Symmetry codes: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1A···N2ii0.86 (1)1.97 (1)2.795 (3)162 (1)
O1—H1B···O3iii0.86 (1)1.93 (1)2.753 (3)162 (1)
O2—H2A···N3iv0.85 (1)2.10 (1)2.939 (3)171 (1)
O2—H2B···O3i0.85 (1)1.90 (1)2.745 (3)172 (1)
O3—H3A···N5v0.85 (1)1.99 (1)2.840 (3)178 (1)
O3—H3B···N4vi0.85 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BR2083).

References

  • 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. [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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