metal-organic compounds
Di-μ-sulfato-κ4O:O′-bis{bis[3-(2-pyridyl)pyrazole]cobalt(II)}
aSchool of Chemistry and Life Science, Maoming University, Maoming 525000, People's Republic of China, and bSchool of Chemistry and Life Sciences, Harbin University, Harbin, 150080, People's Republic of China
*Correspondence e-mail: anz_md@163.com
In the centrosymmetric binuclear title molecule, [Co2(SO4)2(C8H7N3)4], the CoII ion is coordinated by two N,N′-bidentate 3-(2-pyridyl)pyrazole ligands and two sulfate ions, generating a distorted cis-CoO2N4 octahedral geometry for the metal atom. The dihedral angles between the pyridine and pyrazole rings in the two ligands are 10.5 (2) and 7.38 (19)°. The bridging sulfate ions generate an eight-membered ring and intramolecular N—H⋯O hydrogen bonds help to establish the molecular conformation.
Related literature
For coordination compounds with pyridyl-pyrazolide ligands, see: Ward et al. (1998, 2001); Zhang et al. (2003).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2004); cell SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; 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.
Supporting information
10.1107/S160053681000797X/hb5349sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053681000797X/hb5349Isup2.hkl
A mixture of cobalt sulfate heptahydrate (1 mmol, 0.25 g), sodium hydroxide (0.04 g, 1 mmol) and 3-(2-pyridyl)pyrazole (1 mmol, 0.15 g) and water (15 ml) was stirred for 30 min in air. The mixture was then transferred to a 25 ml Teflon-lined hydrothermal bomb. The bomb was kept at 433 K for 72 h under autogenous pressure. Upon cooling, red blocks of (I) were obtained from the reaction mixture.
All hydrogen atoms bound to carbon were refined using a riding model with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The H atoms on nitrogen atoms were refined using a riding model with N—H = 0.86 Å and Uiso(H) = 1.2Ueq(C).
Data collection: APEX2 (Bruker, 2004); cell
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).[Co2(SO4)2(C8H7N3)4] | Z = 1 |
Mr = 890.64 | F(000) = 454 |
Triclinic, P1 | Dx = 1.599 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.318 (5) Å | Cell parameters from 3228 reflections |
b = 9.879 (5) Å | θ = 2.1–25.0° |
c = 11.807 (6) Å | µ = 1.08 mm−1 |
α = 100.342 (8)° | T = 294 K |
β = 98.820 (9)° | Block, red |
γ = 99.302 (8)° | 0.12 × 0.10 × 0.08 mm |
V = 925.2 (9) Å3 |
Bruker APEXII CCD diffractometer | 3228 independent reflections |
Radiation source: fine-focus sealed tube | 2990 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.011 |
phi and ω scans | θmax = 25.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −9→9 |
Tmin = 0.882, Tmax = 0.919 | k = −11→11 |
4790 measured reflections | l = −14→10 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H-atom parameters not refined |
S = 1.00 | w = 1/[σ2(Fo2) + (0.078P)2 + 1.7757P] where P = (Fo2 + 2Fc2)/3 |
3228 reflections | (Δ/σ)max = 0.005 |
253 parameters | Δρmax = 0.61 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
[Co2(SO4)2(C8H7N3)4] | γ = 99.302 (8)° |
Mr = 890.64 | V = 925.2 (9) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.318 (5) Å | Mo Kα radiation |
b = 9.879 (5) Å | µ = 1.08 mm−1 |
c = 11.807 (6) Å | T = 294 K |
α = 100.342 (8)° | 0.12 × 0.10 × 0.08 mm |
β = 98.820 (9)° |
Bruker APEXII CCD diffractometer | 3228 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2990 reflections with I > 2σ(I) |
Tmin = 0.882, Tmax = 0.919 | Rint = 0.011 |
4790 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.130 | H-atom parameters not refined |
S = 1.00 | Δρmax = 0.61 e Å−3 |
3228 reflections | Δρmin = −0.54 e Å−3 |
253 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.42221 (5) | 0.79964 (4) | 0.84355 (4) | 0.03040 (18) | |
C1 | −0.0398 (5) | 0.9232 (4) | 0.7050 (3) | 0.0420 (9) | |
H1 | −0.1395 | 0.9531 | 0.7097 | 0.050* | |
C2 | 0.0198 (5) | 0.8857 (4) | 0.6063 (3) | 0.0448 (9) | |
H2 | −0.0302 | 0.8835 | 0.5298 | 0.054* | |
C3 | 0.1714 (4) | 0.8511 (4) | 0.6431 (3) | 0.0318 (7) | |
C4 | 0.2985 (4) | 0.8065 (4) | 0.5790 (3) | 0.0371 (8) | |
C5 | 0.2946 (6) | 0.8116 (6) | 0.4641 (4) | 0.0636 (13) | |
H5 | 0.2092 | 0.8431 | 0.4223 | 0.076* | |
C6 | 0.4197 (7) | 0.7690 (8) | 0.4113 (4) | 0.090 (2) | |
H6 | 0.4207 | 0.7721 | 0.3332 | 0.108* | |
C7 | 0.5414 (7) | 0.7226 (7) | 0.4750 (4) | 0.0846 (19) | |
H7 | 0.6261 | 0.6922 | 0.4406 | 0.102* | |
C8 | 0.5382 (5) | 0.7212 (5) | 0.5893 (4) | 0.0530 (11) | |
H8 | 0.6220 | 0.6890 | 0.6322 | 0.064* | |
C9 | 0.8750 (4) | 0.6412 (4) | 0.9368 (4) | 0.0403 (8) | |
H9 | 0.9883 | 0.6490 | 0.9619 | 0.048* | |
C10 | 0.7598 (4) | 0.5198 (3) | 0.9034 (3) | 0.0368 (8) | |
H10 | 0.7774 | 0.4287 | 0.9004 | 0.044* | |
C11 | 0.6107 (4) | 0.5620 (3) | 0.8748 (3) | 0.0249 (6) | |
C12 | 0.4408 (4) | 0.4824 (3) | 0.8353 (3) | 0.0252 (6) | |
C13 | 0.4011 (4) | 0.3396 (3) | 0.8316 (3) | 0.0342 (7) | |
H13 | 0.4828 | 0.2898 | 0.8524 | 0.041* | |
C14 | 0.2386 (5) | 0.2743 (4) | 0.7967 (4) | 0.0490 (10) | |
H14 | 0.2081 | 0.1786 | 0.7933 | 0.059* | |
C15 | 0.1224 (5) | 0.3493 (4) | 0.7670 (4) | 0.0517 (10) | |
H15 | 0.0114 | 0.3059 | 0.7434 | 0.062* | |
C16 | 0.1705 (4) | 0.4906 (4) | 0.7721 (3) | 0.0425 (8) | |
H16 | 0.0898 | 0.5414 | 0.7512 | 0.051* | |
N1 | 0.0705 (3) | 0.9095 (3) | 0.7943 (2) | 0.0293 (6) | |
H1A | 0.0596 | 0.9270 | 0.8664 | 0.035* | |
N2 | 0.2007 (3) | 0.8649 (3) | 0.7574 (2) | 0.0283 (6) | |
N3 | 0.4193 (4) | 0.7642 (3) | 0.6426 (2) | 0.0355 (6) | |
N4 | 0.7960 (3) | 0.7468 (3) | 0.9271 (2) | 0.0298 (6) | |
H4 | 0.8437 | 0.8338 | 0.9435 | 0.036* | |
N5 | 0.6333 (3) | 0.7005 (3) | 0.8887 (2) | 0.0249 (5) | |
N6 | 0.3280 (3) | 0.5577 (3) | 0.8057 (2) | 0.0294 (6) | |
O1 | 0.1481 (3) | 0.9642 (2) | 1.03701 (19) | 0.0307 (5) | |
O2 | 0.4260 (3) | 1.0067 (3) | 1.1403 (3) | 0.0592 (9) | |
O3 | 0.2278 (3) | 0.8263 (3) | 1.1747 (2) | 0.0411 (6) | |
O4 | 0.3184 (3) | 0.7973 (3) | 0.9944 (2) | 0.0429 (6) | |
S1 | 0.28057 (8) | 0.89939 (7) | 1.08803 (6) | 0.0206 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0288 (3) | 0.0295 (3) | 0.0343 (3) | 0.00912 (19) | 0.00506 (19) | 0.00780 (19) |
C1 | 0.0307 (18) | 0.055 (2) | 0.044 (2) | 0.0196 (16) | 0.0048 (15) | 0.0114 (17) |
C2 | 0.041 (2) | 0.066 (3) | 0.0311 (18) | 0.0229 (18) | 0.0006 (15) | 0.0126 (17) |
C3 | 0.0290 (17) | 0.0389 (18) | 0.0276 (16) | 0.0088 (14) | 0.0025 (13) | 0.0076 (13) |
C4 | 0.0332 (18) | 0.052 (2) | 0.0267 (17) | 0.0145 (16) | 0.0054 (14) | 0.0047 (15) |
C5 | 0.056 (3) | 0.114 (4) | 0.031 (2) | 0.042 (3) | 0.0086 (18) | 0.018 (2) |
C6 | 0.083 (4) | 0.175 (7) | 0.033 (2) | 0.069 (4) | 0.022 (2) | 0.028 (3) |
C7 | 0.071 (3) | 0.158 (6) | 0.045 (3) | 0.066 (4) | 0.029 (2) | 0.019 (3) |
C8 | 0.042 (2) | 0.084 (3) | 0.040 (2) | 0.031 (2) | 0.0119 (17) | 0.012 (2) |
C9 | 0.0263 (17) | 0.0351 (19) | 0.060 (2) | 0.0111 (14) | 0.0031 (16) | 0.0110 (17) |
C10 | 0.0328 (18) | 0.0241 (16) | 0.055 (2) | 0.0121 (13) | 0.0036 (15) | 0.0092 (15) |
C11 | 0.0291 (16) | 0.0198 (14) | 0.0280 (15) | 0.0069 (12) | 0.0082 (12) | 0.0060 (11) |
C12 | 0.0301 (16) | 0.0218 (15) | 0.0248 (14) | 0.0052 (12) | 0.0095 (12) | 0.0040 (11) |
C13 | 0.043 (2) | 0.0224 (15) | 0.0372 (18) | 0.0033 (14) | 0.0113 (15) | 0.0063 (13) |
C14 | 0.057 (3) | 0.0294 (18) | 0.055 (2) | −0.0076 (17) | 0.0132 (19) | 0.0058 (16) |
C15 | 0.034 (2) | 0.048 (2) | 0.061 (3) | −0.0140 (17) | 0.0075 (18) | 0.0009 (19) |
C16 | 0.0308 (18) | 0.043 (2) | 0.050 (2) | 0.0051 (15) | 0.0048 (16) | 0.0058 (17) |
N1 | 0.0252 (13) | 0.0342 (14) | 0.0300 (14) | 0.0082 (11) | 0.0074 (11) | 0.0068 (11) |
N2 | 0.0234 (13) | 0.0339 (14) | 0.0284 (14) | 0.0061 (11) | 0.0051 (10) | 0.0080 (11) |
N3 | 0.0339 (15) | 0.0463 (17) | 0.0280 (14) | 0.0131 (13) | 0.0062 (12) | 0.0068 (12) |
N4 | 0.0246 (13) | 0.0223 (13) | 0.0421 (15) | 0.0037 (10) | 0.0055 (11) | 0.0075 (11) |
N5 | 0.0231 (13) | 0.0203 (12) | 0.0336 (14) | 0.0067 (10) | 0.0072 (10) | 0.0081 (10) |
N6 | 0.0250 (13) | 0.0277 (13) | 0.0351 (14) | 0.0048 (11) | 0.0064 (11) | 0.0051 (11) |
O1 | 0.0285 (11) | 0.0287 (11) | 0.0361 (12) | 0.0150 (9) | −0.0003 (9) | 0.0068 (9) |
O2 | 0.0386 (15) | 0.0315 (13) | 0.094 (2) | −0.0101 (11) | −0.0226 (15) | 0.0237 (14) |
O3 | 0.0504 (15) | 0.0437 (14) | 0.0438 (14) | 0.0197 (12) | 0.0231 (12) | 0.0255 (11) |
O4 | 0.0641 (17) | 0.0460 (14) | 0.0352 (13) | 0.0374 (13) | 0.0234 (12) | 0.0156 (11) |
S1 | 0.0194 (4) | 0.0186 (4) | 0.0260 (4) | 0.0064 (3) | 0.0043 (3) | 0.0078 (3) |
Co1—O2i | 2.074 (3) | C9—H9 | 0.9300 |
Co1—O4 | 2.097 (3) | C10—C11 | 1.384 (5) |
Co1—N5 | 2.187 (3) | C10—H10 | 0.9300 |
Co1—N2 | 2.212 (3) | C11—N5 | 1.327 (4) |
Co1—N6 | 2.331 (3) | C11—C12 | 1.463 (4) |
Co1—N3 | 2.331 (3) | C12—N6 | 1.332 (4) |
C1—N1 | 1.329 (4) | C12—C13 | 1.387 (4) |
C1—C2 | 1.351 (5) | C13—C14 | 1.366 (5) |
C1—H1 | 0.9300 | C13—H13 | 0.9300 |
C2—C3 | 1.386 (5) | C14—C15 | 1.351 (6) |
C2—H2 | 0.9300 | C14—H14 | 0.9300 |
C3—N2 | 1.312 (4) | C15—C16 | 1.376 (6) |
C3—C4 | 1.469 (5) | C15—H15 | 0.9300 |
C4—N3 | 1.328 (4) | C16—N6 | 1.334 (4) |
C4—C5 | 1.362 (5) | C16—H16 | 0.9300 |
C5—C6 | 1.376 (6) | N1—N2 | 1.337 (4) |
C5—H5 | 0.9300 | N1—H1A | 0.8600 |
C6—C7 | 1.357 (7) | N4—N5 | 1.336 (4) |
C6—H6 | 0.9300 | N4—H4 | 0.8600 |
C7—C8 | 1.357 (6) | O1—S1 | 1.466 (2) |
C7—H7 | 0.9300 | O2—S1 | 1.446 (3) |
C8—N3 | 1.336 (5) | O2—Co1i | 2.074 (3) |
C8—H8 | 0.9300 | O3—S1 | 1.436 (2) |
C9—N4 | 1.332 (4) | O4—S1 | 1.466 (2) |
C9—C10 | 1.363 (5) | ||
O2i—Co1—O4 | 109.51 (13) | N5—C11—C10 | 110.9 (3) |
O2i—Co1—N5 | 92.56 (11) | N5—C11—C12 | 117.4 (3) |
O4—Co1—N5 | 99.64 (10) | C10—C11—C12 | 131.7 (3) |
O2i—Co1—N2 | 93.38 (11) | N6—C12—C13 | 122.9 (3) |
O4—Co1—N2 | 89.94 (10) | N6—C12—C11 | 115.1 (3) |
N5—Co1—N2 | 166.34 (10) | C13—C12—C11 | 122.0 (3) |
O2i—Co1—N6 | 161.04 (12) | C14—C13—C12 | 118.1 (3) |
O4—Co1—N6 | 83.92 (10) | C14—C13—H13 | 121.0 |
N5—Co1—N6 | 71.51 (10) | C12—C13—H13 | 121.0 |
N2—Co1—N6 | 100.13 (10) | C15—C14—C13 | 119.7 (3) |
O2i—Co1—N3 | 87.49 (13) | C15—C14—H14 | 120.1 |
O4—Co1—N3 | 155.57 (11) | C13—C14—H14 | 120.1 |
N5—Co1—N3 | 96.88 (10) | C14—C15—C16 | 119.2 (4) |
N2—Co1—N3 | 71.12 (10) | C14—C15—H15 | 120.4 |
N6—Co1—N3 | 84.40 (10) | C16—C15—H15 | 120.4 |
N1—C1—C2 | 107.2 (3) | N6—C16—C15 | 122.7 (4) |
N1—C1—H1 | 126.4 | N6—C16—H16 | 118.7 |
C2—C1—H1 | 126.4 | C15—C16—H16 | 118.7 |
C1—C2—C3 | 105.4 (3) | C1—N1—N2 | 111.2 (3) |
C1—C2—H2 | 127.3 | C1—N1—H1A | 124.4 |
C3—C2—H2 | 127.3 | N2—N1—H1A | 124.4 |
N2—C3—C2 | 110.2 (3) | C3—N2—N1 | 106.0 (3) |
N2—C3—C4 | 117.7 (3) | C3—N2—Co1 | 119.5 (2) |
C2—C3—C4 | 132.1 (3) | N1—N2—Co1 | 134.3 (2) |
N3—C4—C5 | 122.7 (3) | C4—N3—C8 | 117.8 (3) |
N3—C4—C3 | 114.8 (3) | C4—N3—Co1 | 116.2 (2) |
C5—C4—C3 | 122.5 (3) | C8—N3—Co1 | 125.5 (2) |
C4—C5—C6 | 118.6 (4) | C9—N4—N5 | 111.4 (3) |
C4—C5—H5 | 120.7 | C9—N4—H4 | 124.3 |
C6—C5—H5 | 120.7 | N5—N4—H4 | 124.3 |
C7—C6—C5 | 119.0 (4) | C11—N5—N4 | 105.3 (2) |
C7—C6—H6 | 120.5 | C11—N5—Co1 | 119.8 (2) |
C5—C6—H6 | 120.5 | N4—N5—Co1 | 134.78 (19) |
C8—C7—C6 | 119.3 (4) | C16—N6—C12 | 117.4 (3) |
C8—C7—H7 | 120.3 | C16—N6—Co1 | 126.2 (2) |
C6—C7—H7 | 120.3 | C12—N6—Co1 | 115.8 (2) |
N3—C8—C7 | 122.5 (4) | S1—O2—Co1i | 153.33 (18) |
N3—C8—H8 | 118.7 | S1—O4—Co1 | 137.65 (16) |
C7—C8—H8 | 118.7 | O3—S1—O2 | 110.08 (18) |
N4—C9—C10 | 107.6 (3) | O3—S1—O4 | 108.22 (15) |
N4—C9—H9 | 126.2 | O2—S1—O4 | 110.2 (2) |
C10—C9—H9 | 126.2 | O3—S1—O1 | 110.61 (15) |
C9—C10—C11 | 104.7 (3) | O2—S1—O1 | 109.36 (15) |
C9—C10—H10 | 127.7 | O4—S1—O1 | 108.40 (14) |
C11—C10—H10 | 127.7 |
Symmetry code: (i) −x+1, −y+2, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.86 | 1.98 | 2.772 (4) | 152 |
N4—H4···O1i | 0.86 | 1.96 | 2.761 (4) | 155 |
Symmetry code: (i) −x+1, −y+2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Co2(SO4)2(C8H7N3)4] |
Mr | 890.64 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 294 |
a, b, c (Å) | 8.318 (5), 9.879 (5), 11.807 (6) |
α, β, γ (°) | 100.342 (8), 98.820 (9), 99.302 (8) |
V (Å3) | 925.2 (9) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.08 |
Crystal size (mm) | 0.12 × 0.10 × 0.08 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.882, 0.919 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4790, 3228, 2990 |
Rint | 0.011 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.130, 1.00 |
No. of reflections | 3228 |
No. of parameters | 253 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.61, −0.54 |
Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Co1—O2i | 2.074 (3) | Co1—N2 | 2.212 (3) |
Co1—O4 | 2.097 (3) | Co1—N6 | 2.331 (3) |
Co1—N5 | 2.187 (3) | Co1—N3 | 2.331 (3) |
N5—Co1—N6 | 71.51 (10) | N2—Co1—N3 | 71.12 (10) |
Symmetry code: (i) −x+1, −y+2, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.86 | 1.98 | 2.772 (4) | 152 |
N4—H4···O1i | 0.86 | 1.96 | 2.761 (4) | 155 |
Symmetry code: (i) −x+1, −y+2, −z+2. |
Acknowledgements
The authors acknowledge financial support from the program for talent introduction in Guangdong Higher Education Institutions and the scientific research start-up funds of talent introduction in Maoming University.
References
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The tridentate ligand 3-(2-pyridyl)pyrazole and its derivatives have been used widely in the construction of supramolecular architectures by way of metal-organic coordination (Ward et al. 1998; 2001; Zhang et al. 2003).
As a continuation of these studies, we now report the crystal structure of the title complex, (I). As shown in Figure 1, two Co(II) cations chelated by two 3-(2-Pyridyl)pyrazole) are linked by two sulfate ions to form one circle in which the cobalt ion is hexacoordinated by two 3-(2-Pyridyl)pyrazole) ligands and two O from two sulfate ions (Table 1).