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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): m1006.
Published online 2009 July 29. doi:  10.1107/S1600536809028463
PMCID: PMC2977396

Hexaaqua­cobalt(II) 5,5′-(propane-1,3-diyldithio)bis­(1H-tetra­zole-1-acetate)

Abstract

The asymmetric unit of the title complex, [Co(H2O)6](C9H10N8O4S2), contains one-half of a [Co(H2O)6]2+ cation and one-half of a 5,5′-(propane-1,3-diyldithio)bis­(1H-tetra­zole-1-acetate) (battp2−) anion. The CoII center is coordinated by six H2O mol­ecules in a distorted octa­hedral coordination environment. In the crystal structure, intra- and inter­molecular O—H(...)O and O—H(...)N hydrogen bonds link the cations and anions into a three-dimensional network. π–π contacts between the tetra­zole rings [centroid–centroid distance = 3.346 (1) Å] may further stabilize the structure.

Related literature

For related structures, see: Du et al. (2004 [triangle]); Jiang & Li (2004 [triangle]); Liu et al. (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-m1006-scheme1.jpg

Experimental

Crystal data

  • [Co(H2O)6](C9H10N8O4S2)
  • M r = 525.42
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1006-efi4.jpg
  • a = 19.420 (2) Å
  • b = 7.9069 (11) Å
  • c = 13.7356 (17) Å
  • β = 112.957 (2)°
  • V = 1942.1 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.17 mm−1
  • T = 298 K
  • 0.38 × 0.35 × 0.20 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1997 [triangle]) T min = 0.665, T max = 0.800
  • 4714 measured reflections
  • 1716 independent reflections
  • 1518 reflections with I > 2σ(I)
  • R int = 0.024

Refinement

  • R[F 2 > 2σ(F 2)] = 0.025
  • wR(F 2) = 0.068
  • S = 1.02
  • 1716 reflections
  • 142 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.24 e Å−3
  • Δρmin = −0.36 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809028463/hk2740sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028463/hk2740Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We gratefully acknowledge the Innovation Project of Guangxi Graduate Education (grant No. 2008­106020­703­M242) and the Science Foundation of Guangxi (grant Nos. 0639030, 0731052, 0832098).

supplementary crystallographic information

Comment

Coordination compounds of the type [Co(H2O)6](C10H8O6), [Co(H2O)6](L)2 (L = isonicotinate N-oxide, C6H4NO3) and [Co(H2O)6].2H2O.2L.2ClO4 (L = 1,1'-(propane -1,3-diyl)dipyridinium-4-carboxylate) have been previously prepared and studied by several groups (Liu et al., 2004; Du et al., 2004; Jiang & Li, 2004). We report herein the crystal structure of the new title mononuclear cobalt complex, [Co(H2O)6].(battp) [where battp is 1,3-bis(1-acetic acid-1,2,3,4-tetrazole-5- thioether propane)].

The asymmetric unit of the title complex contains one-half of the [Co(H2O)6]2+ cation and one-half of the [battp]2- anion (Fig. 1). The Co center is coordinated by six H2O molecules in a distorted octahedral coordination environment. The average Co-O bond distance is 2.0973 (14) Å.

In the crystal structure, intra- and intermolecular O-H···O and O-H···N hydrogen bonds (Table 1) link the [Co(H2O)6]2+ cations and [battp]2- anions into a three-dimensional network (Fig. 2), in which they may be effective in the stabilization of the structure. The π–π contact between the tetrazole rings, Cg1—Cg1i [symmetry code: (i) -x, 2 - y, -z, where Cg1 is centroid of the ring A (N1-N4/C1)] may further stabilize the structure, with centroid-centroid distance of 3.346 (1) Å.

Experimental

For the preparation of the title compound, H2battp (0.1440 g, 0.4 mmol) was dissolved in water (5 ml), and the solution of CoClO4.6H2O (0.1832 g, 0.5 mmol) in distilled water (5 ml) was added. The mixture was stirred at 353 K for 3 h, and then cooled and filtered. The filtrate was allowed to slowly evaporate at room temperature. Two weeks later, pink block crystals were obtained.

Refinement

Atom H5 was located in difference Fourier map and refined isotropically. The remaining H atoms were positioned geometrically with O-H = 0.85 Å (for H2O) and C-H = 0.97 Å for methylene H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C,O).

Figures

Fig. 1.
The molecular structure of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level [symmetry codes: (A) 1/2 - x, 1/2 - y, -z; (B) 1 - x, y, 3/2 -z]. Hydrogen atoms have been omitted for clarity. ...
Fig. 2.
A partial packing diagram. Hydrogen bonds are shown as dashed lines.

Crystal data

[Co(H2O)6](C9H10N8O4S2)F(000) = 1084
Mr = 525.42Dx = 1.797 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3230 reflections
a = 19.420 (2) Åθ = 2.8–28.0°
b = 7.9069 (11) ŵ = 1.17 mm1
c = 13.7356 (17) ÅT = 298 K
β = 112.957 (2)°Block, pink
V = 1942.1 (4) Å30.38 × 0.35 × 0.20 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer1716 independent reflections
Radiation source: fine-focus sealed tube1518 reflections with I > 2σ(I)
graphiteRint = 0.024
[var phi] and ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1997)h = −22→22
Tmin = 0.665, Tmax = 0.800k = −5→9
4714 measured reflectionsl = −16→16

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.068H atoms treated by a mixture of independent and constrained refinement
S = 1.02w = 1/[σ2(Fo2) + (0.0317P)2 + 3P] where P = (Fo2 + 2Fc2)/3
1716 reflections(Δ/σ)max < 0.001
142 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = −0.36 e Å3

Special details

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)

xyzUiso*/Ueq
Co10.25000.25000.00000.01988 (13)
S10.43307 (3)0.19008 (9)0.57138 (5)0.03941 (18)
O10.31180 (8)0.09876 (18)0.31741 (11)0.0285 (3)
O20.23139 (9)0.23926 (18)0.36776 (14)0.0344 (4)
O30.30995 (8)0.07215 (18)0.11553 (11)0.0263 (3)
H3A0.31320.09700.17740.032*
H3B0.3001−0.03280.10660.032*
O40.32343 (8)0.43840 (19)0.09350 (12)0.0298 (3)
H4A0.31050.53510.10740.036*
H4B0.37080.43020.12140.036*
O50.18294 (8)0.30070 (18)0.08298 (11)0.0262 (3)
H5A0.18850.39410.11580.031*
H5B0.13620.28410.05190.031*
N10.41422 (9)0.3568 (2)0.39209 (13)0.0222 (4)
N20.45252 (10)0.4106 (2)0.33400 (14)0.0284 (4)
N30.52125 (10)0.3673 (2)0.38552 (14)0.0314 (4)
N40.52993 (10)0.2844 (2)0.47718 (14)0.0287 (4)
C10.46251 (12)0.2798 (3)0.47931 (16)0.0237 (4)
C20.28859 (12)0.2281 (2)0.34801 (15)0.0225 (4)
C30.33493 (11)0.3904 (3)0.36361 (17)0.0246 (4)
H3C0.31600.45580.29880.030*
H3D0.32900.45780.41880.030*
C40.52031 (11)0.1138 (3)0.67099 (16)0.0282 (5)
H4C0.54670.04390.63870.034*
H4D0.55220.20810.70630.034*
C50.50000.0101 (4)0.75000.0268 (6)
H50.5438 (12)−0.061 (3)0.7883 (18)0.033 (6)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Co10.0184 (2)0.0201 (2)0.0220 (2)0.00018 (14)0.00878 (16)−0.00122 (15)
S10.0235 (3)0.0601 (4)0.0348 (3)0.0030 (3)0.0115 (3)0.0230 (3)
O10.0354 (9)0.0223 (8)0.0279 (8)0.0004 (6)0.0124 (7)0.0000 (6)
O20.0315 (9)0.0284 (9)0.0507 (10)−0.0033 (7)0.0239 (8)0.0010 (7)
O30.0293 (8)0.0234 (7)0.0267 (8)0.0031 (6)0.0115 (6)0.0008 (6)
O40.0196 (7)0.0275 (8)0.0386 (9)−0.0016 (6)0.0073 (6)−0.0095 (7)
O50.0225 (7)0.0268 (8)0.0313 (8)−0.0010 (6)0.0126 (6)−0.0066 (6)
N10.0205 (9)0.0233 (9)0.0236 (9)−0.0013 (7)0.0096 (7)0.0014 (7)
N20.0279 (10)0.0347 (10)0.0260 (9)−0.0019 (8)0.0141 (8)0.0019 (8)
N30.0265 (10)0.0405 (11)0.0302 (10)−0.0008 (8)0.0144 (8)0.0018 (8)
N40.0228 (9)0.0340 (10)0.0300 (10)−0.0008 (8)0.0112 (8)0.0010 (8)
C10.0231 (11)0.0255 (11)0.0225 (10)−0.0012 (8)0.0089 (9)−0.0006 (8)
C20.0243 (11)0.0232 (11)0.0179 (10)0.0008 (8)0.0059 (8)0.0040 (8)
C30.0204 (10)0.0223 (10)0.0304 (11)0.0019 (8)0.0090 (9)0.0018 (9)
C40.0231 (11)0.0357 (12)0.0236 (10)0.0023 (9)0.0066 (9)0.0007 (9)
C50.0282 (17)0.0277 (16)0.0211 (15)0.0000.0061 (13)0.000

Geometric parameters (Å, °)

Co1—O32.1000 (14)O5—H5B0.8500
Co1—O3i2.1000 (14)N1—N21.354 (2)
Co1—O4i2.1150 (14)N1—C11.345 (3)
Co1—O42.1150 (14)N1—C31.458 (3)
Co1—O5i2.0770 (13)N2—N31.290 (2)
Co1—O52.0770 (13)N3—N41.370 (3)
S1—C11.730 (2)N4—C11.321 (3)
S1—C41.816 (2)C2—C31.533 (3)
O1—C21.254 (2)C3—H3C0.9700
O2—C21.245 (3)C3—H3D0.9700
O3—H3A0.8500C4—C51.529 (3)
O3—H3B0.8500C4—H4C0.9700
O4—H4A0.8499C4—H4D0.9700
O4—H4B0.8499C5—C4ii1.529 (3)
O5—H5A0.8500C5—H50.98 (2)
O3—Co1—O3i180.00 (12)H4A—O4—H4B109.2
O3—Co1—O4i91.78 (6)Co1—O5—H5A118.7
O3i—Co1—O4i88.22 (6)Co1—O5—H5B118.1
O3—Co1—O488.22 (6)H5A—O5—H5B106.9
O3i—Co1—O491.78 (6)C1—S1—C4102.11 (10)
O4i—Co1—O4180.00 (14)N4—C1—N1108.69 (18)
O5i—Co1—O390.23 (6)N4—C1—S1129.81 (17)
O5—Co1—O389.77 (6)N1—C1—S1121.49 (16)
O5i—Co1—O3i89.77 (6)O2—C2—O1126.76 (19)
O5—Co1—O3i90.23 (6)O2—C2—C3115.80 (18)
O5i—Co1—O4i87.10 (6)O1—C2—C3117.44 (18)
O5—Co1—O4i92.90 (6)N1—C3—C2112.70 (16)
O5i—Co1—O492.90 (6)N1—C3—H3C109.1
O5—Co1—O487.10 (6)C2—C3—H3C109.1
O5i—Co1—O5180.00 (10)N1—C3—H3D109.1
C1—N1—N2108.35 (16)C2—C3—H3D109.1
C1—N1—C3128.18 (17)H3C—C3—H3D107.8
N2—N1—C3123.36 (16)S1—C4—H4C110.4
N3—N2—N1106.36 (16)S1—C4—H4D110.4
N2—N3—N4111.19 (16)C5—C4—S1106.84 (12)
C1—N4—N3105.41 (17)C5—C4—H4C110.4
Co1—O3—H3A113.8C5—C4—H4D110.4
Co1—O3—H3B121.1H4C—C4—H4D108.6
H3A—O3—H3B107.2C4—C5—C4ii115.2 (3)
Co1—O4—H4A125.6C4—C5—H5106.0 (13)
Co1—O4—H4B125.1C4ii—C5—H5109.5 (13)
C1—N1—N2—N3−0.2 (2)C3—N1—C1—S15.2 (3)
C3—N1—N2—N3176.28 (18)C4—S1—C1—N43.5 (2)
N1—N2—N3—N40.3 (2)C4—S1—C1—N1−178.16 (17)
N2—N3—N4—C1−0.2 (2)C1—N1—C3—C2−63.3 (3)
N3—N4—C1—N10.1 (2)N2—N1—C3—C2120.9 (2)
N3—N4—C1—S1178.55 (17)O2—C2—C3—N1150.83 (18)
N2—N1—C1—N40.1 (2)O1—C2—C3—N1−28.9 (3)
C3—N1—C1—N4−176.20 (19)C1—S1—C4—C5−172.50 (15)
N2—N1—C1—S1−178.54 (15)S1—C4—C5—C4ii−77.35 (11)

Symmetry codes: (i) −x+1/2, −y+1/2, −z; (ii) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3A···O10.851.932.767 (2)166
O4—H4A···O2iii0.851.902.742 (2)172
O4—H4B···N3iv0.852.192.970 (2)152
O5—H5A···O1iii0.851.862.7069 (19)173
O5—H5B···N4v0.851.992.833 (2)173

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2740).

References

  • Bruker (1997). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Du, M., Zhao, X.-J. & Guo, J.-H. (2004). Acta Cryst. E60, m788–m790.
  • Jiang, N.-Y. & Li, S.-L. (2004). Chin. J. Struct. Chem.25, 957–964.
  • Liu, J.-W., Huo, L.-H., Gao, S. & Ng, S. W. (2004). Acta Cryst. E60, m439–m440.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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