Diaqua­bis[5-(2-pyrid­yl)-1H-tetra­zolato-κ2N1,N5]cobalt(II)

Sun, Z.-H.; Meng, L.-B.; Lin, H.

doi:10.1107/S160053680900470X

metal-organic compounds

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Volume 65| Part 3| March 2009| Page m280

doi:10.1107/S160053680900470X

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Diaquabis[5-(2-pyridyl)-1H-tetrazolato-κ²N¹,N⁵]cobalt(II)

Zhen-Hai Sun,^a Ling-Bo Meng ^a ^* and Hua Lin ^a

^aSchool of Chemistry and Life Sciences, Harbin University, Harbin 150080, People's Republic of China
^*Correspondence e-mail: menglb_hu@sina.com

(Received 14 January 2009; accepted 9 February 2009; online 18 February 2009)

In the title compound, [Co(C₆H₄N₅)₂(H₂O)₂], the Co atom is bonded to two water molecules and two bidentate 5-(2-pyridyl)tetrazolate ligands resulting in a slightly distorted octahedral CoN₄O₂ coordination geometry. The Co^II cation is situated on a crystallographic center of inversion. The asymmetric unit therefore comprises one-half of the molecule. The four N atoms belonging to two bidentate 5-(2-pyridyl)tetrazolate ligands lie in the equatorial plane and the two associated water molecules are observed in the axial coordination sites. The crystal structure exhibits a three-dimensional supramolecular network assembled by intermolecular O—H⋯N hydrogen bonds.

Related literature

For general background, see: Caneschi et al. (1989 ); Tsukuda et al. (2002 ); Vostrikova et al. (2000 ); Kuchar et al. (2003 )

Experimental

Crystal data

[Co(C₆H₄N₅)₂(H₂O)₂]
M_r = 387.25
Monoclinic, P 2₁ /c
a = 7.999 (2) Å
b = 12.870 (3) Å
c = 7.168 (2) Å
β = 95.99 (1)°
V = 733.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.20 mm⁻¹
T = 296 K
0.12 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.869, T_max = 0.910
3854 measured reflections
1346 independent reflections
1270 reflections with I > 2σ(I)
R_int = 0.012

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.073
S = 1.00
1346 reflections
122 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H2W⋯N2ⁱ	0.82 (1)	2.00 (1)	2.798 (2)	168 (4)
O1W—H1W⋯N1ⁱⁱ	0.82 (1)	1.92 (1)	2.736 (2)	179 (3)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680900470X/im2097sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680900470X/im2097Isup2.hkl

checkCIF report

Comment top

The design of different kinds of paramagnetic metal coordination architectures with appropriate organic radicals and coligands has been an important subject during the last decade because of its potential usages for molecule-based magnetic materials and optical devices (Caneschi et al., 1989; Tsukuda et al., 2002; Vostrikova et al., 2000; Kuchar et al., 2003). If organic radicals such as the tridentate nitronyl nitroxide radical or the bidentate nitroxide radical are used as an integral part of a ligand system a large number of building blocks with various potentional applications may be achieved. In this paper, we report the structure of the title compound, (I).

The molecular structure of the title compound is shown in Fig. 1. The Co^II atom (site symmetry 1) is bonded to two water molecules and two bidentate 5-(2-pyridyl)tetrazolato ligands resulting in a slightly distorterd octahedral CoN₄O₂ coordination geometry. The Co^II cation is situated on a crystallographic center of inversion. The asymmetric unit therefore comprises one half of the molecule. The four nitrogen atoms belonging to two bidentate 5-(2-pyridyl)tetrazolato ligands lie in the equatorial plane and the two associated water molecules are observed in the axial coordination sites. In the equatorial plane, the Co—N bond lengths are in the range of 2.142 (2)–2.173 (2) Å. The Co—O axial bond length is 2.093 (2) Å. It is also worth noticing that the three-dimensional supramolecular structure is assembled via complicated hydrogen bonds, shown in Fig. 2. The hydrogen bonds are listed in Table 1.

Related literature top

For general background, see: Caneschi et al. (1989); Tsukuda et al. (2002); Vostrikova et al. (2000); Kuchar et al. (2003)

Experimental top

A mixture of cobalt(II) dichloride hexhydrate (1 mmoL), 5-(2-pyridyl)tetrazolate (1 mmoL) in 20 ml mixed solvate(1:1) of methanol and water was refluxed for several hours. After cooling down the solution was filterated and the filtrate was kept in the ice box. One week later, red blocks of (I) were obtained with a yield of ca 56%. Anal. Calc. for C₁₂H₁₂CoN₁₀O₂: C 37.19, H 3.10, N 36.15%; Found: C 37.22, H 3.08, N 36.11%.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), around Co^II, displacement ellipsoids for the non-hydrogen atoms are drawn at the 50% probability level.
	Fig. 2. Packing diagram of (I) showing the hydrogen bond interaction.

Diaquabis[5-(2-pyridyl)-1Htetrazolato- κ²N¹,N⁵]cobalt(II) top

Crystal data top

[Co(C₆H₄N₅)₂(H₂O)₂]	F(000) = 394
M_r = 387.25	D_x = 1.752 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1346 reflections
a = 7.999 (2) Å	θ = 2.6–25.5°
b = 12.870 (3) Å	µ = 1.20 mm⁻¹
c = 7.168 (2) Å	T = 296 K
β = 95.99 (1)°	Block, red
V = 733.8 (3) Å³	0.12 × 0.10 × 0.08 mm
Z = 2

Data collection top

Bruker APEXII CCD area-detector diffractometer	1346 independent reflections
Radiation source: fine-focus sealed tube	1270 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.012
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→7
T_min = 0.869, T_max = 0.910	k = −15→12
3854 measured reflections	l = −8→7

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.073	w = 1/[σ²(F_o²) + (0.036P)² + 0.7827P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1346 reflections	Δρ_max = 0.29 e Å⁻³
122 parameters	Δρ_min = −0.39 e Å⁻³
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.032 (2)

Crystal data top

[Co(C₆H₄N₅)₂(H₂O)₂]	V = 733.8 (3) Å³
M_r = 387.25	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.999 (2) Å	µ = 1.20 mm⁻¹
b = 12.870 (3) Å	T = 296 K
c = 7.168 (2) Å	0.12 × 0.10 × 0.08 mm
β = 95.99 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1346 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1270 reflections with I > 2σ(I)
T_min = 0.869, T_max = 0.910	R_int = 0.012
3854 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	3 restraints
wR(F²) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.29 e Å⁻³
1346 reflections	Δρ_min = −0.39 e Å⁻³
122 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

	x	y	z	U_iso*/U_eq
Co1	1.0000	0.0000	0.0000	0.02558 (17)
C1	0.9245 (2)	0.22105 (14)	0.0495 (2)	0.0238 (4)
C2	0.7797 (2)	0.17179 (15)	0.1175 (2)	0.0252 (4)
C3	0.6476 (3)	0.22658 (19)	0.1749 (3)	0.0362 (5)
H3	0.6448	0.2988	0.1690	0.043*
C4	0.5198 (3)	0.1717 (2)	0.2411 (3)	0.0459 (6)
H7	0.4276	0.2062	0.2805	0.055*
C5	0.5285 (3)	0.0653 (2)	0.2492 (4)	0.0473 (6)
H6	0.4434	0.0273	0.2963	0.057*
C6	0.6639 (3)	0.01547 (19)	0.1872 (3)	0.0377 (5)
H5	0.6690	−0.0567	0.1921	0.045*
N1	0.9563 (2)	0.32120 (13)	0.0376 (2)	0.0303 (4)
N2	1.1049 (2)	0.32543 (13)	−0.0308 (2)	0.0316 (4)
N3	1.1587 (2)	0.23204 (13)	−0.0591 (2)	0.0290 (4)
N4	1.0465 (2)	0.16372 (12)	−0.0086 (2)	0.0246 (4)
N5	0.7867 (2)	0.06737 (13)	0.1208 (2)	0.0270 (4)
O1W	1.13421 (19)	−0.00907 (10)	0.2663 (2)	0.0275 (3)
H1W	1.108 (5)	−0.0604 (13)	0.324 (4)	0.080*
H2W	1.141 (5)	0.0450 (12)	0.326 (4)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0296 (2)	0.0178 (2)	0.0309 (2)	−0.00067 (13)	0.01065 (16)	−0.00120 (13)
C1	0.0315 (10)	0.0199 (9)	0.0195 (8)	0.0036 (7)	0.0005 (7)	−0.0013 (7)
C2	0.0291 (10)	0.0273 (10)	0.0190 (9)	0.0042 (8)	0.0011 (7)	−0.0026 (7)
C3	0.0361 (12)	0.0399 (12)	0.0325 (11)	0.0140 (9)	0.0033 (9)	−0.0038 (9)
C4	0.0289 (11)	0.0691 (18)	0.0408 (13)	0.0128 (11)	0.0090 (9)	−0.0086 (12)
C5	0.0300 (12)	0.0680 (18)	0.0465 (13)	−0.0078 (11)	0.0160 (10)	−0.0051 (12)
C6	0.0344 (12)	0.0375 (12)	0.0431 (13)	−0.0079 (9)	0.0125 (10)	−0.0014 (9)
N1	0.0448 (10)	0.0194 (8)	0.0263 (9)	0.0029 (7)	0.0020 (7)	0.0005 (7)
N2	0.0447 (10)	0.0207 (8)	0.0295 (9)	−0.0039 (7)	0.0038 (7)	0.0018 (7)
N3	0.0371 (9)	0.0218 (8)	0.0289 (8)	−0.0062 (7)	0.0070 (7)	0.0005 (7)
N4	0.0304 (8)	0.0177 (8)	0.0267 (8)	−0.0016 (7)	0.0081 (6)	−0.0003 (6)
N5	0.0271 (8)	0.0272 (9)	0.0278 (8)	0.0000 (7)	0.0084 (7)	−0.0021 (6)
O1W	0.0340 (8)	0.0203 (7)	0.0289 (7)	−0.0014 (6)	0.0073 (6)	−0.0008 (5)

Geometric parameters (Å, º) top

Co1—O1Wⁱ	2.0932 (16)	C3—H3	0.9300
Co1—O1W	2.0932 (16)	C4—C5	1.372 (4)
Co1—N4ⁱ	2.1416 (16)	C4—H7	0.9300
Co1—N4	2.1416 (16)	C5—C6	1.371 (3)
Co1—N5ⁱ	2.1726 (16)	C5—H6	0.9300
Co1—N5	2.1726 (16)	C6—N5	1.317 (3)
C1—N1	1.318 (3)	C6—H5	0.9300
C1—N4	1.325 (3)	N1—N2	1.333 (3)
C1—C2	1.448 (3)	N2—N3	1.300 (3)
C2—N5	1.345 (3)	N3—N4	1.333 (2)
C2—C3	1.369 (3)	O1W—H1W	0.817 (10)
C3—C4	1.368 (4)	O1W—H2W	0.815 (10)

O1Wⁱ—Co1—O1W	180.00 (8)	C2—C3—H3	121.1
O1Wⁱ—Co1—N4ⁱ	90.41 (6)	C3—C4—C5	119.6 (2)
O1W—Co1—N4ⁱ	89.59 (6)	C3—C4—H7	120.2
O1Wⁱ—Co1—N4	89.59 (6)	C5—C4—H7	120.2
O1W—Co1—N4	90.41 (6)	C6—C5—C4	119.4 (2)
N4ⁱ—Co1—N4	180.000 (15)	C6—C5—H6	120.3
O1Wⁱ—Co1—N5ⁱ	90.47 (6)	C4—C5—H6	120.3
O1W—Co1—N5ⁱ	89.53 (6)	N5—C6—C5	121.6 (2)
N4ⁱ—Co1—N5ⁱ	76.39 (6)	N5—C6—H5	119.2
N4—Co1—N5ⁱ	103.61 (6)	C5—C6—H5	119.2
O1Wⁱ—Co1—N5	89.53 (6)	C1—N1—N2	104.43 (16)
O1W—Co1—N5	90.47 (6)	N3—N2—N1	110.03 (15)
N4ⁱ—Co1—N5	103.61 (6)	N2—N3—N4	108.90 (16)
N4—Co1—N5	76.39 (6)	C1—N4—N3	104.89 (16)
N5ⁱ—Co1—N5	180.00 (11)	C1—N4—Co1	113.77 (13)
N1—C1—N4	111.76 (18)	N3—N4—Co1	141.31 (13)
N1—C1—C2	128.05 (18)	C6—N5—C2	118.81 (18)
N4—C1—C2	120.19 (18)	C6—N5—Co1	126.01 (15)
N5—C2—C3	122.8 (2)	C2—N5—Co1	115.11 (13)
N5—C2—C1	114.22 (17)	Co1—O1W—H1W	112 (2)
C3—C2—C1	123.0 (2)	Co1—O1W—H2W	115 (2)
C4—C3—C2	117.8 (2)	H1W—O1W—H2W	115.5 (19)
C4—C3—H3	121.1

Symmetry code: (i) −x+2, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W···N2ⁱⁱ	0.82 (1)	2.00 (1)	2.798 (2)	168 (4)
O1W—H1W···N1ⁱⁱⁱ	0.82 (1)	1.92 (1)	2.736 (2)	179 (3)

Symmetry codes: (ii) x, −y+1/2, z+1/2; (iii) −x+2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Co(C₆H₄N₅)₂(H₂O)₂]
M_r	387.25
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	7.999 (2), 12.870 (3), 7.168 (2)
β (°)	95.99 (1)
V (Å³)	733.8 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.20
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.869, 0.910
No. of measured, independent and observed [I > 2σ(I)] reflections	3854, 1346, 1270
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.073, 1.00
No. of reflections	1346
No. of parameters	122
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.39

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W···N2ⁱ	0.82 (1)	2.00 (1)	2.798 (2)	168 (4)
O1W—H1W···N1ⁱⁱ	0.82 (1)	1.92 (1)	2.736 (2)	179 (3)

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+2, y−1/2, −z+1/2.

Acknowledgements

The authors are grateful for financial support from the Young Scholar Science Funds of the Science and Technology Bureau of Harbin City (grant No. 2003AFQXJ018).

References

Bruker (2001). SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Caneschi, A., Gatteschi, D., Renard, J. P., Rey, P. & Sessoli, R. (1989). J. Am. Chem. Soc. 111, 785–786. CrossRef CAS Web of Science Google Scholar
Kuchar, J., Cernak, J., Zak, Z. & Massa, W. (2003). Monogr. Ser. Int. Conf. Coord. Chem. 6, 127–132. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tsukuda, T., Suzuki, T. & Kaizaki, S. (2002). J. Chem. Soc. Dalton Trans. pp. 1721–1726. Web of Science CSD CrossRef Google Scholar
Vostrikova, K. E., Luneau, D., Wernsdorfer, W., Rey, P. & Verdaguer, M. (2000). J. Am. Chem. Soc. 122, 718-719. Web of Science CSD CrossRef CAS Google Scholar