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Acta Cryst. (2009). E65, m280    [ doi:10.1107/S160053680900470X ]

Diaquabis[5-(2-pyridyl)-1H-tetrazolato-[kappa]2N1,N5]cobalt(II)

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

Abstract top

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 CoII 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.

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 CoII 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 CoII 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%.

Refinement top

All H atoms were placed in calculated positions with C—H = 0.93Å and refined as riding with Uiso(H) = 1.2Ueq(C). The H atoms of the water molecule were located from difference density maps and were refined with distance restraints of d(H–H) = 1.38 (2) Å, d(O–H) = 0.82 (1) Å.

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
[Figure 1] Fig. 1. The molecular structure of (I), around CoII, displacement ellipsoids for the non-hydrogen atoms are drawn at the 50% probability level.
[Figure 2] 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
Mr = 387.25Dx = 1.752 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1346 reflections
a = 7.999 (2) Åθ = 2.6–25.5°
b = 12.870 (3) ŵ = 1.20 mm−1
c = 7.168 (2) ÅT = 296 K
β = 95.99 (1)°Block, red
V = 733.8 (3) Å30.12 × 0.10 × 0.08 mm
Z = 2
Data collection top
Bruker APEXII CCD area-detector
diffractometer		1346 independent reflections
Radiation source: fine-focus sealed tube1270 reflections with I > 2σ(I)
graphiteRint = 0.012
φ and ω scansθmax = 25.5°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −9→7
Tmin = 0.869, Tmax = 0.910k = −15→12
3854 measured reflectionsl = −8→7
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.026H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.073 w = 1/[σ2(Fo2) + (0.036P)2 + 0.7827P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
1346 reflectionsΔρmax = 0.29 e Å−3
122 parametersΔρmin = −0.38 e Å−3
3 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.032 (2)
Crystal data top
[Co(C6H4N5)2(H2O)2]V = 733.8 (3) Å3
Mr = 387.25Z = 2
Monoclinic, P21/cMo Kα radiation
a = 7.999 (2) ŵ = 1.20 mm−1
b = 12.870 (3) ÅT = 296 K
c = 7.168 (2) Å0.12 × 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)
Tmin = 0.869, Tmax = 0.910Rint = 0.012
3854 measured reflectionsθmax = 25.5°
Refinement top
R[F2 > 2σ(F2)] = 0.026H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.073Δρmax = 0.29 e Å−3
S = 1.00Δρmin = −0.38 e Å−3
1346 reflectionsAbsolute structure: ?
122 parametersFlack parameter: ?
3 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Co11.00000.00000.00000.02558 (17)
C10.9245 (2)0.22105 (14)0.0495 (2)0.0238 (4)
C20.7797 (2)0.17179 (15)0.1175 (2)0.0252 (4)
C30.6476 (3)0.22658 (19)0.1749 (3)0.0362 (5)
H30.64480.29880.16900.043*
C40.5198 (3)0.1717 (2)0.2411 (3)0.0459 (6)
H70.42760.20620.28050.055*
C50.5285 (3)0.0653 (2)0.2492 (4)0.0473 (6)
H60.44340.02730.29630.057*
C60.6639 (3)0.01547 (19)0.1872 (3)0.0377 (5)
H50.6690−0.05670.19210.045*
N10.9563 (2)0.32120 (13)0.0376 (2)0.0303 (4)
N21.1049 (2)0.32543 (13)−0.0308 (2)0.0316 (4)
N31.1587 (2)0.23204 (13)−0.0591 (2)0.0290 (4)
N41.0465 (2)0.16372 (12)−0.0086 (2)0.0246 (4)
N50.7867 (2)0.06737 (13)0.1208 (2)0.0270 (4)
O1W1.13421 (19)−0.00907 (10)0.2663 (2)0.0275 (3)
H1W1.108 (5)−0.0604 (13)0.324 (4)0.080*
H2W1.141 (5)0.0450 (12)0.326 (4)0.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0296 (2)0.0178 (2)0.0309 (2)−0.00067 (13)0.01065 (16)−0.00120 (13)
C10.0315 (10)0.0199 (9)0.0195 (8)0.0036 (7)0.0005 (7)−0.0013 (7)
C20.0291 (10)0.0273 (10)0.0190 (9)0.0042 (8)0.0011 (7)−0.0026 (7)
C30.0361 (12)0.0399 (12)0.0325 (11)0.0140 (9)0.0033 (9)−0.0038 (9)
C40.0289 (11)0.0691 (18)0.0408 (13)0.0128 (11)0.0090 (9)−0.0086 (12)
C50.0300 (12)0.0680 (18)0.0465 (13)−0.0078 (11)0.0160 (10)−0.0051 (12)
C60.0344 (12)0.0375 (12)0.0431 (13)−0.0079 (9)0.0125 (10)−0.0014 (9)
N10.0448 (10)0.0194 (8)0.0263 (9)0.0029 (7)0.0020 (7)0.0005 (7)
N20.0447 (10)0.0207 (8)0.0295 (9)−0.0039 (7)0.0038 (7)0.0018 (7)
N30.0371 (9)0.0218 (8)0.0289 (8)−0.0062 (7)0.0070 (7)0.0005 (7)
N40.0304 (8)0.0177 (8)0.0267 (8)−0.0016 (7)0.0081 (6)−0.0003 (6)
N50.0271 (8)0.0272 (9)0.0278 (8)0.0000 (7)0.0084 (7)−0.0021 (6)
O1W0.0340 (8)0.0203 (7)0.0289 (7)−0.0014 (6)0.0073 (6)−0.0008 (5)
Geometric parameters (Å, °) top
Co1—O1Wi2.0932 (16)C3—H30.9300
Co1—O1W2.0932 (16)C4—C51.372 (4)
Co1—N4i2.1416 (16)C4—H70.9300
Co1—N42.1416 (16)C5—C61.371 (3)
Co1—N5i2.1726 (16)C5—H60.9300
Co1—N52.1726 (16)C6—N51.317 (3)
C1—N11.318 (3)C6—H50.9300
C1—N41.325 (3)N1—N21.333 (3)
C1—C21.448 (3)N2—N31.300 (3)
C2—N51.345 (3)N3—N41.333 (2)
C2—C31.369 (3)O1W—H1W0.817 (10)
C3—C41.368 (4)O1W—H2W0.815 (10)
O1Wi—Co1—O1W180.00 (8)C2—C3—H3121.1
O1Wi—Co1—N4i90.41 (6)C3—C4—C5119.6 (2)
O1W—Co1—N4i89.59 (6)C3—C4—H7120.2
O1Wi—Co1—N489.59 (6)C5—C4—H7120.2
O1W—Co1—N490.41 (6)C6—C5—C4119.4 (2)
N4i—Co1—N4180.000 (15)C6—C5—H6120.3
O1Wi—Co1—N5i90.47 (6)C4—C5—H6120.3
O1W—Co1—N5i89.53 (6)N5—C6—C5121.6 (2)
N4i—Co1—N5i76.39 (6)N5—C6—H5119.2
N4—Co1—N5i103.61 (6)C5—C6—H5119.2
O1Wi—Co1—N589.53 (6)C1—N1—N2104.43 (16)
O1W—Co1—N590.47 (6)N3—N2—N1110.03 (15)
N4i—Co1—N5103.61 (6)N2—N3—N4108.90 (16)
N4—Co1—N576.39 (6)C1—N4—N3104.89 (16)
N5i—Co1—N5180.00 (11)C1—N4—Co1113.77 (13)
N1—C1—N4111.76 (18)N3—N4—Co1141.31 (13)
N1—C1—C2128.05 (18)C6—N5—C2118.81 (18)
N4—C1—C2120.19 (18)C6—N5—Co1126.01 (15)
N5—C2—C3122.8 (2)C2—N5—Co1115.11 (13)
N5—C2—C1114.22 (17)Co1—O1W—H1W112 (2)
C3—C2—C1123.0 (2)Co1—O1W—H2W115 (2)
C4—C3—C2117.8 (2)H1W—O1W—H2W115.5 (19)
C4—C3—H3121.1
Symmetry codes: (i) −x+2, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H2W···N2ii0.82 (1)2.00 (1)2.798 (2)168 (4)
O1W—H1W···N1iii0.82 (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.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H2W···N2i0.82 (1)2.00 (1)2.798 (2)168 (4)
O1W—H1W···N1ii0.82 (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 top

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
References top

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Vostrikova, K. E., Luneau, D., Wernsdorfer, W., Rey, P. & Verdaguer, M. (2000). J. Am. Chem. Soc. 122, 718-719.