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Acta Cryst. (2009). E65, m684    [ doi:10.1107/S1600536809019187 ]

Diaquabis(tetrazolo[1,5-a]pyridine-8-carboxylato-[kappa]2N1,O)cobalt(II) dihydrate

M. Xue and F.-C. Liu

Abstract top

In the title compound, [Co(C6H3N4O2)2(H2O)2]·2H2O, the CoII atom is located on an inversion center in a slightly distorted octahedral environment formed by the O atoms of two water molecules, and the N and O atoms of the chelating tetrazolo[1,5-a]pyridine-8-carboxylate anions. Hydrogen bonds of the O-H...O and O-H...N types result in a three-dimensional supramolecular network.

Comment top

Coordination complexes have attracted great attention in recent years. (Liu,et al., 2005). The in-situ reaction which can create new ligand and structure draw much more attention in synthesizing coordination complexes (Li,et al., 2007). Some interesting complexes were ganied by the in-situ reaction. (Chen,et al., 2007).

In the title compound, the cobalt atom the cobalt atom located in the inverse center is six coordinated by two waters and two tetrazolo(1,5-a)pyridine-8-carboxylato, (Fig. 1). Each tetrazolo(1,5-a)pyridine-8-carboxylato chelates to one cobalt atom. One type of water coordinates to the cobalt and the other acts as lattice water. A three dimensional supramolecular net formed by the hydrogen bonds of waters and tetrazolo(1,5-a)pyridine-8-carboxylato ligands intermolecular (Fig. 2).

Related literature top

For background to coordination compounds and their synthesis by in situ reaction, see: Chen & Tong, (2007); Liu et al. (2005); Li et al. (2007).

Experimental top

A mixture of cobalt(II)nitrate and sodium azide (1 mmol), 2-chloronicotinic acid(0.5 mmol), in 10 ml of water was sealed in a Teflon-lined stainless-steel Parr bomb that was heated at 363 K for 48 h. Red crystals of the title complex were collected after the bomb was allowed to cool to room temperature.Yield 20% based on cobalt(II). Caution: Azides may be explosive. Although we have met no problems in this work, only a small amount of them should be prepared and handled with great caution.

Refinement top

Hydrogen atoms were included in calculated positions and treated as riding on their parent C atoms with C—H = 0.93Å and Uiso(H) = 1.2Ueq(C).Hydrogen atom of water were added by difference Fourier maps and refined with restrainated distance of O—H = 0.85Å with a error of 0.02Å, and the restrainated distance of H—H = 1.35Å with a error of 0.01Å of the same water.

Computing details top

Data collection: SCXmini Benchtop Crystallography System Software (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the title compound showing the coordination of Co atom with the atom-labelling scheme. Ellipsoids are drawn at the 30% probability level. H atom have been omitted for clarity. [ Symmetry codes: (a)-x+1/2,-y,z].
[Figure 2] Fig. 2. The 3D supramolecular net formed by the hydrogen bonds.
Diaquabis(tetrazolo[1,5-a]pyridine-8-carboxylato- κ2N1,O)cobalt(II) dihydrate top
Crystal data top
[Co(C6H3N4O2)2(H2O)2]·2H2ODx = 1.810 Mg m−3
Mr = 457.24Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PnnaCell parameters from 11987 reflections
a = 19.041 (4) Åθ = 3.3–27.8°
b = 11.694 (2) ŵ = 1.09 mm−1
c = 7.5371 (15) ÅT = 293 K
V = 1678.3 (6) Å3Block, red
Z = 40.5 × 0.5 × 0.4 mm
F(000) = 932
Data collection top
Rigaku SCXmini
diffractometer		1482 independent reflections
Radiation source: fine-focus sealed tube1203 reflections with I > 2σ(I)
graphiteRint = 0.081
ω scansθmax = 25.0°, θmin = 3.2°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −22→22
Tmin = 0.530, Tmax = 0.667k = −13→13
13120 measured reflectionsl = −8→8
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H atoms treated by a mixture of independent and constrained refinement
S = 1.21 w = 1/[σ2(Fo2) + (0.0256P)2 + 2.1174P]
where P = (Fo2 + 2Fc2)/3
1482 reflections(Δ/σ)max < 0.001
148 parametersΔρmax = 0.34 e Å−3
0 restraintsΔρmin = −0.54 e Å−3
Crystal data top
[Co(C6H3N4O2)2(H2O)2]·2H2OV = 1678.3 (6) Å3
Mr = 457.24Z = 4
Orthorhombic, PnnaMo Kα radiation
a = 19.041 (4) ŵ = 1.09 mm−1
b = 11.694 (2) ÅT = 293 K
c = 7.5371 (15) Å0.5 × 0.5 × 0.4 mm
Data collection top
Rigaku SCXmini
diffractometer		1203 reflections with I > 2σ(I)
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		Rint = 0.081
Tmin = 0.530, Tmax = 0.667θmax = 25.0°
13120 measured reflectionsStandard reflections: 0
1482 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.055H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.090Δρmax = 0.34 e Å−3
S = 1.21Δρmin = −0.54 e Å−3
1482 reflectionsAbsolute structure: ?
148 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Co10.25000.00000.86713 (10)0.0185 (3)
O10.20211 (15)0.1011 (2)0.6721 (4)0.0258 (7)
O1W0.20777 (17)0.1069 (3)1.0644 (4)0.0282 (8)
H1WB0.187 (2)0.167 (2)1.037 (5)0.028 (14)*
H1WA0.234 (2)0.120 (4)1.151 (5)0.034 (16)*
O20.12294 (15)0.2126 (2)0.5359 (4)0.0310 (8)
N10.15291 (19)−0.0903 (3)0.8639 (4)0.0220 (8)
N20.1335 (2)−0.1860 (3)0.9493 (5)0.0307 (10)
N30.0650 (2)−0.2019 (3)0.9438 (5)0.0315 (10)
N40.03825 (19)−0.1111 (3)0.8530 (5)0.0236 (9)
C10.1390 (2)0.1307 (3)0.6326 (5)0.0220 (10)
C20.0793 (2)0.0595 (3)0.7064 (6)0.0199 (9)
C30.0093 (2)0.0832 (4)0.6782 (6)0.0251 (11)
H3A−0.00220.15000.61800.030*
C4−0.0468 (2)0.0108 (3)0.7364 (6)0.0276 (11)
H4A−0.09330.03180.71650.033*
C5−0.0318 (2)−0.0885 (4)0.8204 (6)0.0286 (11)
H5A−0.0670−0.13910.85470.034*
C60.0929 (2)−0.0430 (4)0.8022 (6)0.0209 (10)
O2W0.28936 (19)0.1261 (3)0.3682 (4)0.0363 (9)
H2WB0.259 (2)0.108 (4)0.444 (5)0.051 (19)*
H2WA0.312 (2)0.182 (3)0.408 (6)0.042 (16)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0154 (5)0.0195 (5)0.0206 (5)0.0011 (3)0.0000.000
O10.0205 (17)0.0295 (17)0.0274 (18)−0.0008 (13)0.0002 (13)0.0101 (14)
O1W0.029 (2)0.0236 (18)0.032 (2)0.0111 (14)−0.0028 (15)−0.0049 (14)
O20.0291 (19)0.0258 (18)0.038 (2)−0.0023 (14)−0.0044 (15)0.0131 (15)
N10.023 (2)0.0189 (18)0.024 (2)0.0013 (15)−0.0020 (15)0.0079 (15)
N20.033 (2)0.023 (2)0.036 (2)−0.0045 (17)−0.0012 (18)0.0059 (18)
N30.033 (2)0.027 (2)0.035 (2)−0.0027 (17)0.0033 (18)0.0082 (18)
N40.023 (2)0.0206 (19)0.027 (2)−0.0040 (16)−0.0012 (16)0.0039 (16)
C10.028 (3)0.019 (2)0.019 (2)0.0023 (19)−0.0032 (19)−0.0003 (18)
C20.022 (2)0.018 (2)0.020 (2)−0.0037 (18)−0.0049 (18)0.0002 (18)
C30.028 (3)0.023 (2)0.024 (3)0.0014 (19)−0.0023 (19)−0.0004 (19)
C40.019 (2)0.034 (3)0.029 (3)0.0030 (19)−0.0016 (19)−0.003 (2)
C50.022 (3)0.031 (3)0.033 (3)−0.008 (2)0.002 (2)−0.003 (2)
C60.019 (2)0.022 (2)0.021 (2)−0.0030 (18)−0.0032 (18)0.0008 (19)
O2W0.035 (2)0.042 (2)0.031 (2)−0.0088 (17)0.0054 (16)−0.0055 (16)
Geometric parameters (Å, °) top
Co1—O12.095 (3)N3—N41.362 (5)
Co1—O1i2.095 (3)N4—C61.365 (5)
Co1—O1W2.102 (3)N4—C51.382 (6)
Co1—O1Wi2.102 (3)C1—C21.516 (6)
Co1—N12.129 (4)C2—C31.378 (6)
Co1—N1i2.129 (4)C2—C61.424 (6)
O1—C11.286 (5)C3—C41.432 (6)
O1W—H1WB0.825 (18)C3—H3A0.9300
O1W—H1WA0.842 (19)C4—C51.353 (6)
O2—C11.242 (5)C4—H4A0.9300
N1—N21.342 (5)C5—H5A0.9300
N1—C61.351 (5)O2W—H2WB0.835 (19)
N2—N31.318 (5)O2W—H2WA0.842 (19)
O1—Co1—O1i90.89 (16)N2—N3—N4106.0 (3)
O1—Co1—O1W89.66 (13)N3—N4—C6108.1 (4)
O1i—Co1—O1W176.49 (12)N3—N4—C5126.8 (4)
O1—Co1—O1Wi176.49 (12)C6—N4—C5125.1 (4)
O1i—Co1—O1Wi89.66 (13)O2—C1—O1125.0 (4)
O1W—Co1—O1Wi89.99 (18)O2—C1—C2117.0 (4)
O1—Co1—N183.91 (12)O1—C1—C2117.9 (4)
O1i—Co1—N195.17 (12)C3—C2—C6115.1 (4)
O1W—Co1—N188.33 (13)C3—C2—C1124.0 (4)
O1Wi—Co1—N192.58 (13)C6—C2—C1120.8 (4)
O1—Co1—N1i95.17 (12)C2—C3—C4123.8 (4)
O1i—Co1—N1i83.91 (12)C2—C3—H3A118.1
O1W—Co1—N1i92.58 (13)C4—C3—H3A118.1
O1Wi—Co1—N1i88.33 (13)C5—C4—C3119.6 (4)
N1—Co1—N1i178.70 (19)C5—C4—H4A120.2
C1—O1—Co1136.2 (3)C3—C4—H4A120.2
Co1—O1W—H1WB120 (3)C4—C5—N4116.8 (4)
Co1—O1W—H1WA115 (3)C4—C5—H5A121.6
H1WB—O1W—H1WA109 (2)N4—C5—H5A121.6
N2—N1—C6105.8 (3)N1—C6—N4108.0 (4)
N2—N1—Co1130.3 (3)N1—C6—C2132.4 (4)
C6—N1—Co1122.3 (3)N4—C6—C2119.6 (4)
N3—N2—N1112.1 (3)H2WB—O2W—H2WA107 (3)
O1i—Co1—O1—C1123.8 (4)O2—C1—C2—C3−2.7 (6)
O1W—Co1—O1—C1−59.7 (4)O1—C1—C2—C3178.3 (4)
O1Wi—Co1—O1—C125 (2)O2—C1—C2—C6173.1 (4)
N1—Co1—O1—C128.7 (4)O1—C1—C2—C6−5.9 (6)
N1i—Co1—O1—C1−152.2 (4)C6—C2—C3—C4−1.1 (6)
O1—Co1—N1—N2174.9 (4)C1—C2—C3—C4174.9 (4)
O1i—Co1—N1—N284.5 (4)C2—C3—C4—C5−1.7 (7)
O1W—Co1—N1—N2−95.3 (4)C3—C4—C5—N43.2 (6)
O1Wi—Co1—N1—N2−5.3 (4)N3—N4—C5—C4176.0 (4)
N1i—Co1—N1—N2129.7 (4)C6—N4—C5—C4−2.1 (7)
O1—Co1—N1—C6−21.2 (3)N2—N1—C6—N40.4 (5)
O1i—Co1—N1—C6−111.5 (3)Co1—N1—C6—N4−166.9 (3)
O1W—Co1—N1—C668.6 (3)N2—N1—C6—C2178.1 (5)
O1Wi—Co1—N1—C6158.6 (3)Co1—N1—C6—C210.8 (7)
N1i—Co1—N1—C6−66.4 (3)N3—N4—C6—N1−1.1 (5)
C6—N1—N2—N30.4 (5)C5—N4—C6—N1177.4 (4)
Co1—N1—N2—N3166.3 (3)N3—N4—C6—C2−179.1 (4)
N1—N2—N3—N4−1.1 (5)C5—N4—C6—C2−0.7 (6)
N2—N3—N4—C61.3 (4)C3—C2—C6—N1−175.3 (4)
N2—N3—N4—C5−177.1 (4)C1—C2—C6—N18.6 (7)
Co1—O1—C1—O2162.2 (3)C3—C2—C6—N42.2 (6)
Co1—O1—C1—C2−18.9 (6)C1—C2—C6—N4−173.9 (4)
Symmetry codes: (i) −x+1/2, −y, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WB···O2ii0.83 (2)1.95 (2)2.763 (4)168 (4)
O1W—H1WA···O2Wiii0.84 (2)1.94 (2)2.776 (5)170 (5)
O2W—H2WB···O10.84 (2)2.04 (3)2.845 (4)163 (4)
O2W—H2WA···N2iv0.84 (2)2.15 (2)2.981 (5)171 (4)
Symmetry codes: (ii) x, −y+1/2, −z+3/2; (iii) x, y, z+1; (iv) −x+1/2, y+1/2, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WB···O2i0.83 (2)1.95 (2)2.763 (4)168 (4)
O1W—H1WA···O2Wii0.84 (2)1.94 (2)2.776 (5)170 (5)
O2W—H2WB···O10.84 (2)2.04 (3)2.845 (4)163 (4)
O2W—H2WA···N2iii0.84 (2)2.15 (2)2.981 (5)171 (4)
Symmetry codes: (i) x, −y+1/2, −z+3/2; (ii) x, y, z+1; (iii) −x+1/2, y+1/2, −z+3/2.
Acknowledgements top

The authors acknowledge financial support from Tianjin Municipal Education Commission (grant No. 20060503).

references
References top

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