metal-organic compounds
Hexaaquacobalt(II) 5,5′-(propane-1,3-diyldithio)bis(1H-tetrazole-1-acetate)
aCollege of Chemistry and Chemical Engineering, Guangxi Normal University, Guilin, Guangxi 541004, People's Republic of China
*Correspondence e-mail: gxnuchem312@yahoo.com.cn
The 2O)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 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.
of the title complex, [Co(HRelated literature
For related structures, see: Du et al. (2004); Jiang & Li (2004); Liu et al. (2004).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 1997); cell SAINT (Bruker, 1997); data reduction: SAINT; 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 and PLATON (Spek, 2009).
Supporting information
10.1107/S1600536809028463/hk2740sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809028463/hk2740Isup2.hkl
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.
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).
Data collection: SMART (Bruker, 1997); cell
SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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) and PLATON (Spek, 2009).[Co(H2O)6](C9H10N8O4S2) | F(000) = 1084 |
Mr = 525.42 | Dx = 1.797 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 3230 reflections |
a = 19.420 (2) Å | θ = 2.8–28.0° |
b = 7.9069 (11) Å | µ = 1.17 mm−1 |
c = 13.7356 (17) Å | T = 298 K |
β = 112.957 (2)° | Block, pink |
V = 1942.1 (4) Å3 | 0.38 × 0.35 × 0.20 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 1716 independent reflections |
Radiation source: fine-focus sealed tube | 1518 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −22→22 |
Tmin = 0.665, Tmax = 0.800 | k = −5→9 |
4714 measured reflections | l = −16→16 |
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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.068 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0317P)2 + 3P] where P = (Fo2 + 2Fc2)/3 |
1716 reflections | (Δ/σ)max < 0.001 |
142 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
[Co(H2O)6](C9H10N8O4S2) | V = 1942.1 (4) Å3 |
Mr = 525.42 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 19.420 (2) Å | µ = 1.17 mm−1 |
b = 7.9069 (11) Å | T = 298 K |
c = 13.7356 (17) Å | 0.38 × 0.35 × 0.20 mm |
β = 112.957 (2)° |
Bruker SMART CCD area-detector diffractometer | 1716 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 1518 reflections with I > 2σ(I) |
Tmin = 0.665, Tmax = 0.800 | Rint = 0.024 |
4714 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.068 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.24 e Å−3 |
1716 reflections | Δρmin = −0.36 e Å−3 |
142 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.2500 | 0.2500 | 0.0000 | 0.01988 (13) | |
S1 | 0.43307 (3) | 0.19008 (9) | 0.57138 (5) | 0.03941 (18) | |
O1 | 0.31180 (8) | 0.09876 (18) | 0.31741 (11) | 0.0285 (3) | |
O2 | 0.23139 (9) | 0.23926 (18) | 0.36776 (14) | 0.0344 (4) | |
O3 | 0.30995 (8) | 0.07215 (18) | 0.11553 (11) | 0.0263 (3) | |
H3A | 0.3132 | 0.0970 | 0.1774 | 0.032* | |
H3B | 0.3001 | −0.0328 | 0.1066 | 0.032* | |
O4 | 0.32343 (8) | 0.43840 (19) | 0.09350 (12) | 0.0298 (3) | |
H4A | 0.3105 | 0.5351 | 0.1074 | 0.036* | |
H4B | 0.3708 | 0.4302 | 0.1214 | 0.036* | |
O5 | 0.18294 (8) | 0.30070 (18) | 0.08298 (11) | 0.0262 (3) | |
H5A | 0.1885 | 0.3941 | 0.1158 | 0.031* | |
H5B | 0.1362 | 0.2841 | 0.0519 | 0.031* | |
N1 | 0.41422 (9) | 0.3568 (2) | 0.39209 (13) | 0.0222 (4) | |
N2 | 0.45252 (10) | 0.4106 (2) | 0.33400 (14) | 0.0284 (4) | |
N3 | 0.52125 (10) | 0.3673 (2) | 0.38552 (14) | 0.0314 (4) | |
N4 | 0.52993 (10) | 0.2844 (2) | 0.47718 (14) | 0.0287 (4) | |
C1 | 0.46251 (12) | 0.2798 (3) | 0.47931 (16) | 0.0237 (4) | |
C2 | 0.28859 (12) | 0.2281 (2) | 0.34801 (15) | 0.0225 (4) | |
C3 | 0.33493 (11) | 0.3904 (3) | 0.36361 (17) | 0.0246 (4) | |
H3C | 0.3160 | 0.4558 | 0.2988 | 0.030* | |
H3D | 0.3290 | 0.4578 | 0.4188 | 0.030* | |
C4 | 0.52031 (11) | 0.1138 (3) | 0.67099 (16) | 0.0282 (5) | |
H4C | 0.5467 | 0.0439 | 0.6387 | 0.034* | |
H4D | 0.5522 | 0.2081 | 0.7063 | 0.034* | |
C5 | 0.5000 | 0.0101 (4) | 0.7500 | 0.0268 (6) | |
H5 | 0.5438 (12) | −0.061 (3) | 0.7883 (18) | 0.033 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0184 (2) | 0.0201 (2) | 0.0220 (2) | 0.00018 (14) | 0.00878 (16) | −0.00122 (15) |
S1 | 0.0235 (3) | 0.0601 (4) | 0.0348 (3) | 0.0030 (3) | 0.0115 (3) | 0.0230 (3) |
O1 | 0.0354 (9) | 0.0223 (8) | 0.0279 (8) | 0.0004 (6) | 0.0124 (7) | 0.0000 (6) |
O2 | 0.0315 (9) | 0.0284 (9) | 0.0507 (10) | −0.0033 (7) | 0.0239 (8) | 0.0010 (7) |
O3 | 0.0293 (8) | 0.0234 (7) | 0.0267 (8) | 0.0031 (6) | 0.0115 (6) | 0.0008 (6) |
O4 | 0.0196 (7) | 0.0275 (8) | 0.0386 (9) | −0.0016 (6) | 0.0073 (6) | −0.0095 (7) |
O5 | 0.0225 (7) | 0.0268 (8) | 0.0313 (8) | −0.0010 (6) | 0.0126 (6) | −0.0066 (6) |
N1 | 0.0205 (9) | 0.0233 (9) | 0.0236 (9) | −0.0013 (7) | 0.0096 (7) | 0.0014 (7) |
N2 | 0.0279 (10) | 0.0347 (10) | 0.0260 (9) | −0.0019 (8) | 0.0141 (8) | 0.0019 (8) |
N3 | 0.0265 (10) | 0.0405 (11) | 0.0302 (10) | −0.0008 (8) | 0.0144 (8) | 0.0018 (8) |
N4 | 0.0228 (9) | 0.0340 (10) | 0.0300 (10) | −0.0008 (8) | 0.0112 (8) | 0.0010 (8) |
C1 | 0.0231 (11) | 0.0255 (11) | 0.0225 (10) | −0.0012 (8) | 0.0089 (9) | −0.0006 (8) |
C2 | 0.0243 (11) | 0.0232 (11) | 0.0179 (10) | 0.0008 (8) | 0.0059 (8) | 0.0040 (8) |
C3 | 0.0204 (10) | 0.0223 (10) | 0.0304 (11) | 0.0019 (8) | 0.0090 (9) | 0.0018 (9) |
C4 | 0.0231 (11) | 0.0357 (12) | 0.0236 (10) | 0.0023 (9) | 0.0066 (9) | 0.0007 (9) |
C5 | 0.0282 (17) | 0.0277 (16) | 0.0211 (15) | 0.000 | 0.0061 (13) | 0.000 |
Co1—O3 | 2.1000 (14) | O5—H5B | 0.8500 |
Co1—O3i | 2.1000 (14) | N1—N2 | 1.354 (2) |
Co1—O4i | 2.1150 (14) | N1—C1 | 1.345 (3) |
Co1—O4 | 2.1150 (14) | N1—C3 | 1.458 (3) |
Co1—O5i | 2.0770 (13) | N2—N3 | 1.290 (2) |
Co1—O5 | 2.0770 (13) | N3—N4 | 1.370 (3) |
S1—C1 | 1.730 (2) | N4—C1 | 1.321 (3) |
S1—C4 | 1.816 (2) | C2—C3 | 1.533 (3) |
O1—C2 | 1.254 (2) | C3—H3C | 0.9700 |
O2—C2 | 1.245 (3) | C3—H3D | 0.9700 |
O3—H3A | 0.8500 | C4—C5 | 1.529 (3) |
O3—H3B | 0.8500 | C4—H4C | 0.9700 |
O4—H4A | 0.8499 | C4—H4D | 0.9700 |
O4—H4B | 0.8499 | C5—C4ii | 1.529 (3) |
O5—H5A | 0.8500 | C5—H5 | 0.98 (2) |
O3—Co1—O3i | 180.00 (12) | H4A—O4—H4B | 109.2 |
O3—Co1—O4i | 91.78 (6) | Co1—O5—H5A | 118.7 |
O3i—Co1—O4i | 88.22 (6) | Co1—O5—H5B | 118.1 |
O3—Co1—O4 | 88.22 (6) | H5A—O5—H5B | 106.9 |
O3i—Co1—O4 | 91.78 (6) | C1—S1—C4 | 102.11 (10) |
O4i—Co1—O4 | 180.00 (14) | N4—C1—N1 | 108.69 (18) |
O5i—Co1—O3 | 90.23 (6) | N4—C1—S1 | 129.81 (17) |
O5—Co1—O3 | 89.77 (6) | N1—C1—S1 | 121.49 (16) |
O5i—Co1—O3i | 89.77 (6) | O2—C2—O1 | 126.76 (19) |
O5—Co1—O3i | 90.23 (6) | O2—C2—C3 | 115.80 (18) |
O5i—Co1—O4i | 87.10 (6) | O1—C2—C3 | 117.44 (18) |
O5—Co1—O4i | 92.90 (6) | N1—C3—C2 | 112.70 (16) |
O5i—Co1—O4 | 92.90 (6) | N1—C3—H3C | 109.1 |
O5—Co1—O4 | 87.10 (6) | C2—C3—H3C | 109.1 |
O5i—Co1—O5 | 180.00 (10) | N1—C3—H3D | 109.1 |
C1—N1—N2 | 108.35 (16) | C2—C3—H3D | 109.1 |
C1—N1—C3 | 128.18 (17) | H3C—C3—H3D | 107.8 |
N2—N1—C3 | 123.36 (16) | S1—C4—H4C | 110.4 |
N3—N2—N1 | 106.36 (16) | S1—C4—H4D | 110.4 |
N2—N3—N4 | 111.19 (16) | C5—C4—S1 | 106.84 (12) |
C1—N4—N3 | 105.41 (17) | C5—C4—H4C | 110.4 |
Co1—O3—H3A | 113.8 | C5—C4—H4D | 110.4 |
Co1—O3—H3B | 121.1 | H4C—C4—H4D | 108.6 |
H3A—O3—H3B | 107.2 | C4—C5—C4ii | 115.2 (3) |
Co1—O4—H4A | 125.6 | C4—C5—H5 | 106.0 (13) |
Co1—O4—H4B | 125.1 | C4ii—C5—H5 | 109.5 (13) |
C1—N1—N2—N3 | −0.2 (2) | C3—N1—C1—S1 | 5.2 (3) |
C3—N1—N2—N3 | 176.28 (18) | C4—S1—C1—N4 | 3.5 (2) |
N1—N2—N3—N4 | 0.3 (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—N1 | 0.1 (2) | N2—N1—C3—C2 | 120.9 (2) |
N3—N4—C1—S1 | 178.55 (17) | O2—C2—C3—N1 | 150.83 (18) |
N2—N1—C1—N4 | 0.1 (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. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O1 | 0.85 | 1.93 | 2.767 (2) | 166 |
O4—H4A···O2iii | 0.85 | 1.90 | 2.742 (2) | 172 |
O4—H4B···N3iv | 0.85 | 2.19 | 2.970 (2) | 152 |
O5—H5A···O1iii | 0.85 | 1.86 | 2.7069 (19) | 173 |
O5—H5B···N4v | 0.85 | 1.99 | 2.833 (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. |
Experimental details
Crystal data | |
Chemical formula | [Co(H2O)6](C9H10N8O4S2) |
Mr | 525.42 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 19.420 (2), 7.9069 (11), 13.7356 (17) |
β (°) | 112.957 (2) |
V (Å3) | 1942.1 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.17 |
Crystal size (mm) | 0.38 × 0.35 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.665, 0.800 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4714, 1716, 1518 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.068, 1.02 |
No. of reflections | 1716 |
No. of parameters | 142 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.36 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O1 | 0.85 | 1.93 | 2.767 (2) | 166.2 |
O4—H4A···O2i | 0.85 | 1.90 | 2.742 (2) | 172.0 |
O4—H4B···N3ii | 0.85 | 2.19 | 2.970 (2) | 151.9 |
O5—H5A···O1i | 0.85 | 1.86 | 2.7069 (19) | 173.0 |
O5—H5B···N4iii | 0.85 | 1.99 | 2.833 (2) | 172.9 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1, y, −z+1/2; (iii) x−1/2, −y+1/2, z−1/2. |
Acknowledgements
We gratefully acknowledge the Innovation Project of Guangxi Graduate Education (grant No. 2008106020703M242) and the Science Foundation of Guangxi (grant Nos. 0639030, 0731052, 0832098).
References
Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Du, M., Zhao, X.-J. & Guo, J.-H. (2004). Acta Cryst. E60, m788–m790. Web of Science CSD CrossRef IUCr Journals Google Scholar
Jiang, N.-Y. & Li, S.-L. (2004). Chin. J. Struct. Chem. 25, 957–964. Google Scholar
Liu, J.-W., Huo, L.-H., Gao, S. & Ng, S. W. (2004). Acta Cryst. E60, m439–m440. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
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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.