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

Zhu, W.-F.; Zhou, X.-F.

doi:10.1107/S1600536808034880

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page m1478

doi:10.1107/S1600536808034880

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

Wei-Feng Zhu ^a ^* and Xing-Fen Zhou ^b

^aDepartment of Chemistry, Nanjing Institute of Railway Technology, Suzhou 215137, People's Republic of China, and ^bSuzhou Institute of Trade & Commerce, Suzhou 215009, People's Republic of China
^*Correspondence e-mail: szhzhuweifeng@yahoo.cn

(Received 28 September 2008; accepted 27 October 2008; online 31 October 2008)

A new mononuclear cobalt(II) complex, tetraaquabis[5-(4-pyridyl)tetrazolido-κN⁵]cobalt(II) dihydrate, [Co(C₆H₄N₅)₂(H₂O)₄]·2H₂O, has been synthesized and structurally characterized. The Co^II 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 ) has a similar structure to that of the title complex. For related literature, see: Detert & Schollmeier (1999 ).

Experimental

Crystal data

[Co(C₆H₄N₅)₂(H₂O)₄]·2H₂O
M_r = 459.31
Triclinic, $[P \overline 1]$
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 ) 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[F² > 2σ(F²)] = 0.031
wR(F²) = 0.083
S = 1.12
1684 reflections
157 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N2ⁱ	0.855 (10)	1.968 (10)	2.795 (3)	161.84 (3)
O1—H1B⋯O3ⁱⁱ	0.857 (10)	1.93 (1)	2.753 (3)	161.83 (3)
O2—H2A⋯N3ⁱⁱⁱ	0.849 (10)	2.10 (1)	2.939 (3)	170.66 (3)
O2—H2B⋯O3^iv	0.851 (3)	1.90 (1)	2.745 (3)	172.44 (3)
O3—H3A⋯N5^v	0.853 (10)	1.99 (1)	2.840 (3)	177.52 (3)
O3—H3B⋯N4^vi	0.849 (10)	1.942 (10)	2.780 (3)	168.93 (3)
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.

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

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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%.

Computing details top

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).

Figures top

	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.

tetraaquabis[5-(4-pyridyl)tetrazolido-κN⁵]cobalt(II) dihydrate top

Crystal data top

[Co(C₆H₄N₅)₂(H₂O)₄]·2H₂O	Z = 1
M_r = 459.31	F(000) = 237
Triclinic, P1	D_x = 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 monochromator	R_int = 0.013
phi and ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick 1996)	h = −5→8
T_min = 0.763, T_max = 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(F_o²) + (0.035P)² + 2.1646P] where P = (F_o² + 2F_c²)/3
1684 reflections	(Δ/σ)_max < 0.001
157 parameters	Δρ_max = 0.49 e Å⁻³
9 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[Co(C₆H₄N₅)₂(H₂O)₄]·2H₂O	γ = 100.953 (3)°
M_r = 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)
T_min = 0.763, T_max = 0.890	R_int = 0.013
2456 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	9 restraints
wR(F²) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.49 e Å⁻³
1684 reflections	Δρ_min = −0.28 e Å⁻³
157 parameters

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

	x	y	z	U_iso*/U_eq
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, º) 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 code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) 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···N3^iv	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···N5^v	0.85 (1)	1.99 (1)	2.840 (3)	178 (1)
O3—H3B···N4^vi	0.85 (1)	1.94 (1)	2.780 (3)	169 (1)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z; (iv) −x+1, −y, −z+1; (v) x, y+1, z; (vi) −x, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[Co(C₆H₄N₅)₂(H₂O)₄]·2H₂O
M_r	459.31
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	7.2087 (16), 7.8002 (17), 8.6702 (18)
α, β, γ (°)	91.406 (3), 90.482 (3), 100.953 (3)
V (Å³)	478.45 (18)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.95
Crystal size (mm)	0.20 × 0.20 × 0.14

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick 1996)
T_min, T_max	0.763, 0.890
No. of measured, independent and observed [I > 2σ(I)] reflections	2456, 1684, 1562
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.083, 1.12
No. of reflections	1684
No. of parameters	157
No. of restraints	9
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.28

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N2ⁱ	0.855 (10)	1.968 (10)	2.795 (3)	161.84 (3)
O1—H1B···O3ⁱⁱ	0.857 (10)	1.93 (1)	2.753 (3)	161.83 (3)
O2—H2A···N3ⁱⁱⁱ	0.849 (10)	2.10 (1)	2.939 (3)	170.66 (3)
O2—H2B···O3^iv	0.851 (3)	1.90 (1)	2.745 (3)	172.44 (3)
O3—H3A···N5^v	0.853 (10)	1.99 (1)	2.840 (3)	177.52 (3)
O3—H3B···N4^vi	0.849 (10)	1.942 (10)	2.780 (3)	168.93 (3)

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.

Acknowledgements

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

References

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