Diaqua­bis(tetra­zolo[1,5-a]pyridine-8-carboxyl­ato-κ2N1,O)cobalt(II) dihydrate

Xue, M.; Liu, F.-C.

doi:10.1107/S1600536809019187

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page m684

doi:10.1107/S1600536809019187

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Diaquabis(tetrazolo[1,5-a]pyridine-8-carboxylato-κ²N¹,O)cobalt(II) dihydrate

Min Xue ^a and Fu-Chen Liu ^a ^*

^aSchool of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300191, People's Republic of China
^*Correspondence e-mail: fuchenliutj@yahoo.com

(Received 13 May 2009; accepted 20 May 2009; online 23 May 2009)

In the title compound, [Co(C₆H₃N₄O₂)₂(H₂O)₂]·2H₂O, the Co^II 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.

Related literature

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

Crystal data

[Co(C₆H₃N₄O₂)₂(H₂O)₂]·2H₂O
M_r = 457.24
Orthorhombic, P n n a
a = 19.041 (4) Å
b = 11.694 (2) Å
c = 7.5371 (15) Å
V = 1678.3 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.09 mm⁻¹
T = 293 K
0.5 × 0.5 × 0.4 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.530, T_max = 0.667
13120 measured reflections
1482 independent reflections
1203 reflections with I > 2σ(I)
R_int = 0.081

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.090
S = 1.21
1482 reflections
148 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WB⋯O2ⁱ	0.825 (18)	1.950 (19)	2.763 (4)	168 (4)
O1W—H1WA⋯O2Wⁱⁱ	0.842 (19)	1.943 (19)	2.776 (5)	170 (5)
O2W—H2WB⋯O1	0.835 (19)	2.04 (3)	2.845 (4)	163 (4)
O2W—H2WA⋯N2ⁱⁱⁱ	0.842 (19)	2.15 (2)	2.981 (5)	171 (4)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x, y, z+1; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SCXmini Benchtop Crystallography System Software (Rigaku, 2006 ); cell refinement: PROCESS-AUTO (Rigaku, 1998 ); data reduction: PROCESS-AUTO; 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).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809019187/ng2582sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809019187/ng2582Isup2.hkl

checkCIF report

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.

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

	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].
	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]·2H₂O	D_x = 1.810 Mg m⁻³
M_r = 457.24	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnna	Cell parameters from 11987 reflections
a = 19.041 (4) Å	θ = 3.3–27.8°
b = 11.694 (2) Å	µ = 1.09 mm⁻¹
c = 7.5371 (15) Å	T = 293 K
V = 1678.3 (6) Å³	Block, red
Z = 4	0.5 × 0.5 × 0.4 mm
F(000) = 932

Data collection top

Rigaku SCXmini diffractometer	1482 independent reflections
Radiation source: fine-focus sealed tube	1203 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.081
ω scans	θ_max = 25.0°, θ_min = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −22→22
T_min = 0.530, T_max = 0.667	k = −13→13
13120 measured reflections	l = −8→8

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.21	w = 1/[σ²(F_o²) + (0.0256P)² + 2.1174P] where P = (F_o² + 2F_c²)/3
1482 reflections	(Δ/σ)_max < 0.001
148 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.54 e Å⁻³

Crystal data top

[Co(C₆H₃N₄O₂)₂(H₂O)₂]·2H₂O	V = 1678.3 (6) Å³
M_r = 457.24	Z = 4
Orthorhombic, Pnna	Mo Kα radiation
a = 19.041 (4) Å	µ = 1.09 mm⁻¹
b = 11.694 (2) Å	T = 293 K
c = 7.5371 (15) Å	0.5 × 0.5 × 0.4 mm

Data collection top

Rigaku SCXmini diffractometer	1482 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1203 reflections with I > 2σ(I)
T_min = 0.530, T_max = 0.667	R_int = 0.081
13120 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.21	Δρ_max = 0.34 e Å⁻³
1482 reflections	Δρ_min = −0.54 e Å⁻³
148 parameters

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

	x	y	z	U_iso*/U_eq
Co1	0.2500	0.0000	0.86713 (10)	0.0185 (3)
O1	0.20211 (15)	0.1011 (2)	0.6721 (4)	0.0258 (7)
O1W	0.20777 (17)	0.1069 (3)	1.0644 (4)	0.0282 (8)
H1WB	0.187 (2)	0.167 (2)	1.037 (5)	0.028 (14)*
H1WA	0.234 (2)	0.120 (4)	1.151 (5)	0.034 (16)*
O2	0.12294 (15)	0.2126 (2)	0.5359 (4)	0.0310 (8)
N1	0.15291 (19)	−0.0903 (3)	0.8639 (4)	0.0220 (8)
N2	0.1335 (2)	−0.1860 (3)	0.9493 (5)	0.0307 (10)
N3	0.0650 (2)	−0.2019 (3)	0.9438 (5)	0.0315 (10)
N4	0.03825 (19)	−0.1111 (3)	0.8530 (5)	0.0236 (9)
C1	0.1390 (2)	0.1307 (3)	0.6326 (5)	0.0220 (10)
C2	0.0793 (2)	0.0595 (3)	0.7064 (6)	0.0199 (9)
C3	0.0093 (2)	0.0832 (4)	0.6782 (6)	0.0251 (11)
H3A	−0.0022	0.1500	0.6180	0.030*
C4	−0.0468 (2)	0.0108 (3)	0.7364 (6)	0.0276 (11)
H4A	−0.0933	0.0318	0.7165	0.033*
C5	−0.0318 (2)	−0.0885 (4)	0.8204 (6)	0.0286 (11)
H5A	−0.0670	−0.1391	0.8547	0.034*
C6	0.0929 (2)	−0.0430 (4)	0.8022 (6)	0.0209 (10)
O2W	0.28936 (19)	0.1261 (3)	0.3682 (4)	0.0363 (9)
H2WB	0.259 (2)	0.108 (4)	0.444 (5)	0.051 (19)*
H2WA	0.312 (2)	0.182 (3)	0.408 (6)	0.042 (16)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0154 (5)	0.0195 (5)	0.0206 (5)	0.0011 (3)	0.000	0.000
O1	0.0205 (17)	0.0295 (17)	0.0274 (18)	−0.0008 (13)	0.0002 (13)	0.0101 (14)
O1W	0.029 (2)	0.0236 (18)	0.032 (2)	0.0111 (14)	−0.0028 (15)	−0.0049 (14)
O2	0.0291 (19)	0.0258 (18)	0.038 (2)	−0.0023 (14)	−0.0044 (15)	0.0131 (15)
N1	0.023 (2)	0.0189 (18)	0.024 (2)	0.0013 (15)	−0.0020 (15)	0.0079 (15)
N2	0.033 (2)	0.023 (2)	0.036 (2)	−0.0045 (17)	−0.0012 (18)	0.0059 (18)
N3	0.033 (2)	0.027 (2)	0.035 (2)	−0.0027 (17)	0.0033 (18)	0.0082 (18)
N4	0.023 (2)	0.0206 (19)	0.027 (2)	−0.0040 (16)	−0.0012 (16)	0.0039 (16)
C1	0.028 (3)	0.019 (2)	0.019 (2)	0.0023 (19)	−0.0032 (19)	−0.0003 (18)
C2	0.022 (2)	0.018 (2)	0.020 (2)	−0.0037 (18)	−0.0049 (18)	0.0002 (18)
C3	0.028 (3)	0.023 (2)	0.024 (3)	0.0014 (19)	−0.0023 (19)	−0.0004 (19)
C4	0.019 (2)	0.034 (3)	0.029 (3)	0.0030 (19)	−0.0016 (19)	−0.003 (2)
C5	0.022 (3)	0.031 (3)	0.033 (3)	−0.008 (2)	0.002 (2)	−0.003 (2)
C6	0.019 (2)	0.022 (2)	0.021 (2)	−0.0030 (18)	−0.0032 (18)	0.0008 (19)
O2W	0.035 (2)	0.042 (2)	0.031 (2)	−0.0088 (17)	0.0054 (16)	−0.0055 (16)

Geometric parameters (Å, º) top

Co1—O1	2.095 (3)	N3—N4	1.362 (5)
Co1—O1ⁱ	2.095 (3)	N4—C6	1.365 (5)
Co1—O1W	2.102 (3)	N4—C5	1.382 (6)
Co1—O1Wⁱ	2.102 (3)	C1—C2	1.516 (6)
Co1—N1	2.129 (4)	C2—C3	1.378 (6)
Co1—N1ⁱ	2.129 (4)	C2—C6	1.424 (6)
O1—C1	1.286 (5)	C3—C4	1.432 (6)
O1W—H1WB	0.825 (18)	C3—H3A	0.9300
O1W—H1WA	0.842 (19)	C4—C5	1.353 (6)
O2—C1	1.242 (5)	C4—H4A	0.9300
N1—N2	1.342 (5)	C5—H5A	0.9300
N1—C6	1.351 (5)	O2W—H2WB	0.835 (19)
N2—N3	1.318 (5)	O2W—H2WA	0.842 (19)

O1—Co1—O1ⁱ	90.89 (16)	N2—N3—N4	106.0 (3)
O1—Co1—O1W	89.66 (13)	N3—N4—C6	108.1 (4)
O1ⁱ—Co1—O1W	176.49 (12)	N3—N4—C5	126.8 (4)
O1—Co1—O1Wⁱ	176.49 (12)	C6—N4—C5	125.1 (4)
O1ⁱ—Co1—O1Wⁱ	89.66 (13)	O2—C1—O1	125.0 (4)
O1W—Co1—O1Wⁱ	89.99 (18)	O2—C1—C2	117.0 (4)
O1—Co1—N1	83.91 (12)	O1—C1—C2	117.9 (4)
O1ⁱ—Co1—N1	95.17 (12)	C3—C2—C6	115.1 (4)
O1W—Co1—N1	88.33 (13)	C3—C2—C1	124.0 (4)
O1Wⁱ—Co1—N1	92.58 (13)	C6—C2—C1	120.8 (4)
O1—Co1—N1ⁱ	95.17 (12)	C2—C3—C4	123.8 (4)
O1ⁱ—Co1—N1ⁱ	83.91 (12)	C2—C3—H3A	118.1
O1W—Co1—N1ⁱ	92.58 (13)	C4—C3—H3A	118.1
O1Wⁱ—Co1—N1ⁱ	88.33 (13)	C5—C4—C3	119.6 (4)
N1—Co1—N1ⁱ	178.70 (19)	C5—C4—H4A	120.2
C1—O1—Co1	136.2 (3)	C3—C4—H4A	120.2
Co1—O1W—H1WB	120 (3)	C4—C5—N4	116.8 (4)
Co1—O1W—H1WA	115 (3)	C4—C5—H5A	121.6
H1WB—O1W—H1WA	109 (2)	N4—C5—H5A	121.6
N2—N1—C6	105.8 (3)	N1—C6—N4	108.0 (4)
N2—N1—Co1	130.3 (3)	N1—C6—C2	132.4 (4)
C6—N1—Co1	122.3 (3)	N4—C6—C2	119.6 (4)
N3—N2—N1	112.1 (3)	H2WB—O2W—H2WA	107 (3)

O1ⁱ—Co1—O1—C1	123.8 (4)	O2—C1—C2—C3	−2.7 (6)
O1W—Co1—O1—C1	−59.7 (4)	O1—C1—C2—C3	178.3 (4)
O1Wⁱ—Co1—O1—C1	25 (2)	O2—C1—C2—C6	173.1 (4)
N1—Co1—O1—C1	28.7 (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—N2	174.9 (4)	C1—C2—C3—C4	174.9 (4)
O1ⁱ—Co1—N1—N2	84.5 (4)	C2—C3—C4—C5	−1.7 (7)
O1W—Co1—N1—N2	−95.3 (4)	C3—C4—C5—N4	3.2 (6)
O1Wⁱ—Co1—N1—N2	−5.3 (4)	N3—N4—C5—C4	176.0 (4)
N1ⁱ—Co1—N1—N2	129.7 (4)	C6—N4—C5—C4	−2.1 (7)
O1—Co1—N1—C6	−21.2 (3)	N2—N1—C6—N4	0.4 (5)
O1ⁱ—Co1—N1—C6	−111.5 (3)	Co1—N1—C6—N4	−166.9 (3)
O1W—Co1—N1—C6	68.6 (3)	N2—N1—C6—C2	178.1 (5)
O1Wⁱ—Co1—N1—C6	158.6 (3)	Co1—N1—C6—C2	10.8 (7)
N1ⁱ—Co1—N1—C6	−66.4 (3)	N3—N4—C6—N1	−1.1 (5)
C6—N1—N2—N3	0.4 (5)	C5—N4—C6—N1	177.4 (4)
Co1—N1—N2—N3	166.3 (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—C6	1.3 (4)	C3—C2—C6—N1	−175.3 (4)
N2—N3—N4—C5	−177.1 (4)	C1—C2—C6—N1	8.6 (7)
Co1—O1—C1—O2	162.2 (3)	C3—C2—C6—N4	2.2 (6)
Co1—O1—C1—C2	−18.9 (6)	C1—C2—C6—N4	−173.9 (4)

Symmetry code: (i) −x+1/2, −y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O2ⁱⁱ	0.83 (2)	1.95 (2)	2.763 (4)	168 (4)
O1W—H1WA···O2Wⁱⁱⁱ	0.84 (2)	1.94 (2)	2.776 (5)	170 (5)
O2W—H2WB···O1	0.84 (2)	2.04 (3)	2.845 (4)	163 (4)
O2W—H2WA···N2^iv	0.84 (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.

Experimental details

Crystal data
Chemical formula	[Co(C₆H₃N₄O₂)₂(H₂O)₂]·2H₂O
M_r	457.24
Crystal system, space group	Orthorhombic, Pnna
Temperature (K)	293
a, b, c (Å)	19.041 (4), 11.694 (2), 7.5371 (15)
V (Å³)	1678.3 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.09
Crystal size (mm)	0.5 × 0.5 × 0.4

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.530, 0.667
No. of measured, independent and observed [I > 2σ(I)] reflections	13120, 1482, 1203
R_int	0.081
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.090, 1.21
No. of reflections	1482
No. of parameters	148
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.54

Computer programs: SCXmini Benchtop Crystallography System Software (Rigaku, 2006), PROCESS-AUTO (Rigaku, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O2ⁱ	0.825 (18)	1.950 (19)	2.763 (4)	168 (4)
O1W—H1WA···O2Wⁱⁱ	0.842 (19)	1.943 (19)	2.776 (5)	170 (5)
O2W—H2WB···O1	0.835 (19)	2.04 (3)	2.845 (4)	163 (4)
O2W—H2WA···N2ⁱⁱⁱ	0.842 (19)	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

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

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