Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104030434/hj1033sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104030434/hj1033Isup2.hkl |
CCDC reference: 264793
Cobalt sulfate heptahydrate (0.6 g, 2 mmol) was dissolved in water (10 ml) and the solution was mixed with a dimethylformamide solution (10 ml) of 1,2-tris(4-pyridyl)-ethene (0.4 g, 2 mmol), trimesic acid (0.4 g, 2 mmol) and 2,2'-dithiosalicylic acid (0.6 g, 2 mmol) at 298 K. The reaction mixture was filtered; brown block-shaped crystals separated from the solution after about three months.
The uncoordinated water H atoms were refined subject to the restraint O—H = 0.82 (5) Å. The other H atoms were positioned geometrically and allowed to ride on their parent atoms at distances of 0.82 (O—H), 0.86 (N—H) and 0.93 Å (C—H), with Uiso(H) = 1.2Ueq(parent atom).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
[Co2(C12H11N2)2(C12H10N2)(H2O)8][Co(H2O)6](SO4)4·8H2O | F(000) = 1566 |
Mr = 1506.06 | Dx = 1.610 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -p2ybc | Cell parameters from 5517 reflections |
a = 10.2353 (8) Å | θ = 1.9–25.1° |
b = 12.1885 (9) Å | µ = 1.03 mm−1 |
c = 24.9647 (19) Å | T = 298 K |
β = 93.895 (2)° | Block, brown |
V = 3107.2 (4) Å3 | 0.31 × 0.18 × 0.15 mm |
Z = 2 |
Bruker SMART CCD area detector diffractometer | 5517 independent reflections |
Radiation source: fine-focus sealed tube | 4657 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
600 frames, delta ω = 2 dgr scans | θmax = 25.1°, θmin = 1.9° |
Absorption correction: numerical SADABS (Sheldrick, 1996) | h = −12→12 |
Tmin = 0.81, Tmax = 0.85 | k = −14→14 |
16014 measured reflections | l = −21→29 |
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)] = 0.068 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.144 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.20 | w = 1/[σ2(Fo2) + (0.0549P)2 + 2.9068P] where P = (Fo2 + 2Fc2)/3 |
5517 reflections | (Δ/σ)max = 0.016 |
425 parameters | Δρmax = 0.72 e Å−3 |
8 restraints | Δρmin = −0.47 e Å−3 |
[Co2(C12H11N2)2(C12H10N2)(H2O)8][Co(H2O)6](SO4)4·8H2O | V = 3107.2 (4) Å3 |
Mr = 1506.06 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.2353 (8) Å | µ = 1.03 mm−1 |
b = 12.1885 (9) Å | T = 298 K |
c = 24.9647 (19) Å | 0.31 × 0.18 × 0.15 mm |
β = 93.895 (2)° |
Bruker SMART CCD area detector diffractometer | 5517 independent reflections |
Absorption correction: numerical SADABS (Sheldrick, 1996) | 4657 reflections with I > 2σ(I) |
Tmin = 0.81, Tmax = 0.85 | Rint = 0.057 |
16014 measured reflections |
R[F2 > 2σ(F2)] = 0.068 | 8 restraints |
wR(F2) = 0.144 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.20 | Δρmax = 0.72 e Å−3 |
5517 reflections | Δρmin = −0.47 e Å−3 |
425 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 | 0.16166 (6) | 0.77595 (5) | 0.24691 (2) | 0.01992 (18) | |
Co2 | 0.5000 | 1.0000 | 0.5000 | 0.0275 (2) | |
C1 | 0.0961 (5) | 0.8055 (4) | 0.1258 (2) | 0.0321 (12) | |
H1 | 0.1120 | 0.7304 | 0.1263 | 0.039* | |
C2 | 0.0668 (5) | 0.8539 (4) | 0.0773 (2) | 0.0329 (12) | |
H2 | 0.0626 | 0.8121 | 0.0460 | 0.039* | |
C3 | 0.0431 (4) | 0.9667 (4) | 0.07476 (19) | 0.0283 (11) | |
C4 | 0.0514 (5) | 1.0220 (4) | 0.1230 (2) | 0.0324 (12) | |
H4 | 0.0370 | 1.0973 | 0.1235 | 0.039* | |
C5 | 0.0807 (5) | 0.9668 (4) | 0.1703 (2) | 0.0310 (11) | |
H5 | 0.0849 | 1.0066 | 0.2022 | 0.037* | |
C6 | 0.2395 (5) | 0.7533 (4) | 0.36681 (19) | 0.0362 (13) | |
H6 | 0.2277 | 0.8289 | 0.3651 | 0.043* | |
C7 | 0.2719 (6) | 0.7071 (4) | 0.4162 (2) | 0.0389 (13) | |
H7 | 0.2819 | 0.7508 | 0.4467 | 0.047* | |
C8 | 0.2894 (4) | 0.5937 (4) | 0.41973 (19) | 0.0265 (11) | |
C9 | 0.2726 (5) | 0.5349 (4) | 0.37270 (19) | 0.0298 (11) | |
H9 | 0.2829 | 0.4591 | 0.3732 | 0.036* | |
C10 | 0.2403 (4) | 0.5881 (4) | 0.32457 (18) | 0.0256 (10) | |
H10 | 0.2296 | 0.5465 | 0.2933 | 0.031* | |
C11 | 0.3182 (4) | 0.5379 (4) | 0.47104 (18) | 0.0270 (11) | |
H11 | 0.3097 | 0.4620 | 0.4710 | 0.032* | |
C12 | 0.3552 (5) | 0.5848 (4) | 0.51758 (19) | 0.0307 (11) | |
H12 | 0.3686 | 0.6603 | 0.5175 | 0.037* | |
C13 | 0.3766 (5) | 0.5279 (4) | 0.56884 (19) | 0.0287 (11) | |
C14 | 0.4132 (5) | 0.5855 (4) | 0.61518 (19) | 0.0317 (11) | |
H14 | 0.4279 | 0.6606 | 0.6133 | 0.038* | |
C15 | 0.4283 (5) | 0.5337 (5) | 0.6636 (2) | 0.0381 (13) | |
H15 | 0.4532 | 0.5736 | 0.6944 | 0.046* | |
C17 | 0.3744 (5) | 0.3666 (4) | 0.6233 (2) | 0.0406 (13) | |
H17 | 0.3625 | 0.2913 | 0.6266 | 0.049* | |
C18 | 0.3581 (5) | 0.4144 (4) | 0.5745 (2) | 0.0357 (12) | |
H18 | 0.3344 | 0.3719 | 0.5444 | 0.043* | |
C19 | 0.0118 (5) | 1.0242 (4) | 0.02404 (19) | 0.0314 (11) | |
H19 | 0.0079 | 1.1004 | 0.0252 | 0.038* | |
O1 | 0.0508 (3) | 0.6368 (3) | 0.22274 (13) | 0.0286 (8) | |
H1B | −0.0270 | 0.6490 | 0.2261 | 0.043* | |
H1A | 0.0863 | 0.6052 | 0.1986 | 0.043* | |
O2 | 0.3202 (3) | 0.7055 (3) | 0.20966 (13) | 0.0344 (8) | |
H2B | 0.2932 | 0.6564 | 0.1893 | 0.052* | |
H2A | 0.3890 | 0.7242 | 0.2258 | 0.052* | |
O3 | 0.2776 (3) | 0.9101 (2) | 0.27277 (13) | 0.0315 (8) | |
H3B | 0.3508 | 0.8885 | 0.2831 | 0.047* | |
H3A | 0.2335 | 0.9663 | 0.2702 | 0.047* | |
O4 | −0.0116 (3) | 0.8333 (3) | 0.27725 (14) | 0.0408 (9) | |
H4B | −0.0745 | 0.8131 | 0.2576 | 0.061* | |
H4A | 0.0060 | 0.8677 | 0.3051 | 0.061* | |
O5 | 0.6410 (4) | 0.7879 (3) | 0.64893 (14) | 0.0503 (10) | |
O6 | 0.7881 (3) | 0.8767 (3) | 0.71377 (18) | 0.0494 (11) | |
O7 | 0.7452 (4) | 0.6849 (3) | 0.72121 (16) | 0.0487 (10) | |
O8 | 0.5793 (3) | 0.8159 (3) | 0.73794 (14) | 0.0464 (10) | |
O9 | 0.5717 (3) | 0.8525 (3) | 0.47054 (14) | 0.0372 (9) | |
H9B | 0.6118 | 0.8192 | 0.4950 | 0.056* | |
H9A | 0.6229 | 0.8658 | 0.4475 | 0.056* | |
O10 | 0.5057 (4) | 1.0756 (4) | 0.42341 (15) | 0.0565 (12) | |
H10B | 0.4370 | 1.1088 | 0.4163 | 0.085* | |
H10A | 0.5768 | 1.0637 | 0.4113 | 0.085* | |
O11 | 0.3104 (3) | 0.9471 (3) | 0.48213 (14) | 0.0366 (8) | |
H11B | 0.2782 | 0.9813 | 0.4562 | 0.055* | |
H11A | 0.2682 | 0.9539 | 0.5087 | 0.055* | |
O12 | 0.2940 (4) | −0.0380 (3) | 0.63901 (16) | 0.0537 (11) | |
O13 | 0.0740 (3) | 0.0222 (3) | 0.64645 (14) | 0.0397 (9) | |
O14 | 0.1420 (4) | −0.0409 (4) | 0.56264 (15) | 0.0574 (12) | |
O15 | 0.2246 (4) | 0.1294 (3) | 0.59775 (17) | 0.0527 (11) | |
O16 | 0.1755 (5) | 0.0346 (5) | 0.39738 (19) | 0.0684 (15) | |
O17 | 0.0495 (6) | 0.1771 (4) | 0.4999 (2) | 0.0808 (17) | |
O18 | 0.7246 (5) | 0.7350 (4) | 0.54571 (18) | 0.0501 (11) | |
O19 | 0.5339 (5) | 0.8828 (5) | 0.2999 (3) | 0.0830 (19) | |
N1 | 0.1036 (4) | 0.8586 (3) | 0.17286 (15) | 0.0271 (9) | |
N2 | 0.2240 (4) | 0.6965 (3) | 0.32120 (15) | 0.0266 (9) | |
N3 | 0.4074 (4) | 0.4263 (4) | 0.66699 (17) | 0.0370 (11) | |
H3N | 0.4153 | 0.3947 | 0.6979 | 0.044* | |
S1 | 0.68919 (11) | 0.78988 (9) | 0.70511 (5) | 0.0258 (3) | |
S2 | 0.18357 (11) | 0.01907 (10) | 0.61116 (5) | 0.0278 (3) | |
H16A | 0.105 (4) | 0.022 (5) | 0.387 (2) | 0.042* | |
H16B | 0.202 (6) | 0.059 (5) | 0.3723 (19) | 0.042* | |
H17A | 0.069 (5) | 0.150 (5) | 0.5287 (17) | 0.042* | |
H17B | 0.034 (6) | 0.121 (4) | 0.482 (2) | 0.042* | |
H18A | 0.791 (4) | 0.761 (5) | 0.537 (2) | 0.042* | |
H18B | 0.715 (6) | 0.748 (5) | 0.5755 (16) | 0.042* | |
H19A | 0.561 (6) | 0.934 (4) | 0.284 (3) | 0.042* | |
H19B | 0.560 (5) | 0.927 (4) | 0.322 (2) | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0177 (3) | 0.0241 (3) | 0.0173 (3) | 0.0009 (2) | −0.0035 (2) | 0.0006 (3) |
Co2 | 0.0232 (5) | 0.0319 (5) | 0.0275 (5) | 0.0042 (4) | 0.0019 (4) | −0.0019 (4) |
C1 | 0.038 (3) | 0.030 (3) | 0.027 (3) | −0.004 (2) | −0.004 (2) | 0.000 (2) |
C2 | 0.042 (3) | 0.034 (3) | 0.021 (3) | −0.007 (2) | −0.005 (2) | −0.001 (2) |
C3 | 0.020 (2) | 0.038 (3) | 0.026 (3) | 0.000 (2) | −0.006 (2) | 0.003 (2) |
C4 | 0.031 (3) | 0.031 (3) | 0.034 (3) | 0.005 (2) | −0.004 (2) | 0.002 (2) |
C5 | 0.035 (3) | 0.035 (3) | 0.023 (3) | 0.008 (2) | −0.004 (2) | −0.006 (2) |
C6 | 0.060 (4) | 0.022 (2) | 0.026 (3) | 0.006 (2) | −0.005 (3) | 0.002 (2) |
C7 | 0.058 (4) | 0.030 (3) | 0.027 (3) | 0.005 (3) | −0.008 (3) | −0.004 (2) |
C8 | 0.023 (2) | 0.032 (3) | 0.024 (3) | 0.003 (2) | −0.003 (2) | 0.005 (2) |
C9 | 0.029 (3) | 0.028 (2) | 0.032 (3) | 0.005 (2) | −0.002 (2) | 0.000 (2) |
C10 | 0.030 (3) | 0.027 (2) | 0.019 (2) | 0.002 (2) | −0.004 (2) | −0.003 (2) |
C11 | 0.028 (3) | 0.028 (2) | 0.026 (3) | 0.001 (2) | 0.001 (2) | 0.006 (2) |
C12 | 0.035 (3) | 0.025 (2) | 0.032 (3) | 0.001 (2) | −0.001 (2) | 0.005 (2) |
C13 | 0.024 (3) | 0.036 (3) | 0.026 (3) | 0.005 (2) | 0.001 (2) | 0.004 (2) |
C14 | 0.036 (3) | 0.034 (3) | 0.025 (3) | −0.002 (2) | −0.001 (2) | −0.003 (2) |
C15 | 0.039 (3) | 0.052 (3) | 0.023 (3) | 0.002 (3) | −0.002 (2) | −0.007 (3) |
C17 | 0.050 (3) | 0.036 (3) | 0.036 (3) | 0.004 (3) | −0.001 (3) | 0.005 (3) |
C18 | 0.049 (3) | 0.033 (3) | 0.024 (3) | 0.003 (2) | −0.002 (2) | −0.001 (2) |
C19 | 0.026 (3) | 0.039 (3) | 0.028 (3) | 0.001 (2) | −0.001 (2) | 0.007 (2) |
O1 | 0.0158 (16) | 0.0341 (18) | 0.036 (2) | −0.0008 (14) | 0.0031 (14) | −0.0082 (16) |
O2 | 0.0192 (17) | 0.046 (2) | 0.037 (2) | 0.0022 (15) | −0.0059 (15) | −0.0180 (17) |
O3 | 0.0272 (19) | 0.0264 (17) | 0.039 (2) | −0.0014 (14) | −0.0117 (16) | −0.0024 (17) |
O4 | 0.0239 (18) | 0.062 (3) | 0.036 (2) | 0.0067 (18) | −0.0029 (16) | −0.0216 (19) |
O5 | 0.051 (2) | 0.072 (3) | 0.027 (2) | 0.018 (2) | −0.0020 (18) | 0.004 (2) |
O6 | 0.0187 (18) | 0.0325 (19) | 0.097 (3) | −0.0041 (15) | 0.003 (2) | −0.001 (2) |
O7 | 0.047 (2) | 0.035 (2) | 0.062 (3) | 0.0000 (18) | −0.016 (2) | 0.006 (2) |
O8 | 0.0216 (18) | 0.081 (3) | 0.037 (2) | −0.0092 (19) | 0.0034 (16) | −0.023 (2) |
O9 | 0.039 (2) | 0.037 (2) | 0.036 (2) | 0.0047 (16) | 0.0085 (17) | −0.0009 (17) |
O10 | 0.037 (2) | 0.092 (3) | 0.042 (2) | 0.033 (2) | 0.0118 (19) | 0.026 (2) |
O11 | 0.0257 (18) | 0.050 (2) | 0.034 (2) | 0.0009 (17) | 0.0014 (15) | −0.0061 (19) |
O12 | 0.037 (2) | 0.072 (3) | 0.053 (3) | 0.009 (2) | 0.0061 (19) | 0.025 (2) |
O13 | 0.036 (2) | 0.047 (2) | 0.038 (2) | −0.0005 (17) | 0.0117 (17) | −0.0029 (18) |
O14 | 0.049 (2) | 0.086 (3) | 0.038 (2) | −0.016 (2) | 0.011 (2) | −0.022 (2) |
O15 | 0.062 (3) | 0.038 (2) | 0.061 (3) | −0.0076 (19) | 0.021 (2) | 0.007 (2) |
O16 | 0.042 (3) | 0.106 (4) | 0.054 (3) | −0.027 (3) | −0.019 (2) | 0.031 (3) |
O17 | 0.094 (4) | 0.069 (3) | 0.075 (4) | 0.008 (3) | −0.029 (3) | 0.031 (3) |
O18 | 0.061 (3) | 0.044 (2) | 0.044 (3) | 0.002 (2) | −0.003 (2) | −0.007 (2) |
O19 | 0.048 (3) | 0.093 (4) | 0.103 (5) | 0.007 (3) | −0.024 (3) | −0.052 (4) |
N1 | 0.025 (2) | 0.033 (2) | 0.022 (2) | 0.0023 (17) | −0.0060 (17) | 0.0020 (18) |
N2 | 0.028 (2) | 0.027 (2) | 0.024 (2) | 0.0016 (17) | −0.0039 (17) | 0.0035 (18) |
N3 | 0.035 (2) | 0.049 (3) | 0.027 (2) | 0.007 (2) | 0.0016 (19) | 0.015 (2) |
S1 | 0.0210 (6) | 0.0281 (6) | 0.0278 (6) | −0.0013 (5) | −0.0014 (5) | −0.0002 (5) |
S2 | 0.0245 (6) | 0.0352 (7) | 0.0239 (6) | −0.0004 (5) | 0.0026 (5) | 0.0049 (5) |
Co1—O4 | 2.095 (3) | C14—H14 | 0.9300 |
Co1—O3 | 2.096 (3) | C15—N3 | 1.330 (7) |
Co1—O1 | 2.106 (3) | C15—H15 | 0.9300 |
Co1—O2 | 2.107 (3) | C17—N3 | 1.334 (7) |
Co1—N2 | 2.151 (4) | C17—C18 | 1.352 (7) |
Co1—N1 | 2.153 (4) | C17—H17 | 0.9300 |
Co2—O11i | 2.065 (3) | C18—H18 | 0.9300 |
Co2—O11 | 2.065 (3) | C19—C19ii | 1.345 (9) |
Co2—O9i | 2.094 (3) | C19—H19 | 0.9300 |
Co2—O9 | 2.094 (3) | O1—H1B | 0.8200 |
Co2—O10 | 2.127 (4) | O1—H1A | 0.8202 |
Co2—O10i | 2.127 (4) | O2—H2B | 0.8200 |
C1—N1 | 1.339 (6) | O2—H2A | 0.8201 |
C1—C2 | 1.362 (7) | O3—H3B | 0.8200 |
C1—H1 | 0.9300 | O3—H3A | 0.8200 |
C2—C3 | 1.397 (7) | O4—H4B | 0.8200 |
C2—H2 | 0.9300 | O4—H4A | 0.8200 |
C3—C4 | 1.377 (7) | O5—S1 | 1.455 (4) |
C3—C19 | 1.464 (6) | O6—S1 | 1.471 (3) |
C4—C5 | 1.375 (7) | O7—S1 | 1.448 (4) |
C4—H4 | 0.9300 | O8—S1 | 1.470 (3) |
C5—N1 | 1.341 (6) | O9—H9B | 0.8200 |
C5—H5 | 0.9300 | O9—H9A | 0.8201 |
C6—N2 | 1.333 (6) | O10—H10B | 0.8200 |
C6—C7 | 1.374 (7) | O10—H10A | 0.8200 |
C6—H6 | 0.9300 | O11—H11B | 0.8200 |
C7—C8 | 1.396 (7) | O11—H11A | 0.8200 |
C7—H7 | 0.9300 | O12—S2 | 1.462 (4) |
C8—C9 | 1.376 (7) | O13—S2 | 1.473 (3) |
C8—C11 | 1.462 (6) | O14—S2 | 1.453 (4) |
C9—C10 | 1.385 (6) | O15—S2 | 1.454 (4) |
C9—H9 | 0.9300 | O16—H16A | 0.76 (4) |
C10—N2 | 1.333 (6) | O16—H16B | 0.76 (4) |
C10—H10 | 0.9300 | O17—H17A | 0.80 (4) |
C11—C12 | 1.327 (6) | O17—H17B | 0.82 (4) |
C11—H11 | 0.9300 | O18—H18A | 0.79 (4) |
C12—C13 | 1.459 (6) | O18—H18B | 0.77 (4) |
C12—H12 | 0.9300 | O19—H19A | 0.81 (4) |
C13—C14 | 1.383 (7) | O19—H19B | 0.80 (4) |
C13—C18 | 1.405 (7) | N3—H3N | 0.8600 |
C14—C15 | 1.363 (7) | ||
O4—Co1—O3 | 95.94 (13) | C13—C12—H12 | 117.3 |
O4—Co1—O1 | 85.40 (13) | C14—C13—C18 | 116.5 (5) |
O3—Co1—O1 | 177.59 (13) | C14—C13—C12 | 120.6 (4) |
O4—Co1—O2 | 172.56 (13) | C18—C13—C12 | 122.9 (5) |
O3—Co1—O2 | 91.00 (13) | C15—C14—C13 | 121.0 (5) |
O1—Co1—O2 | 87.77 (12) | C15—C14—H14 | 119.5 |
O4—Co1—N2 | 92.72 (14) | C13—C14—H14 | 119.5 |
O3—Co1—N2 | 87.54 (14) | N3—C15—C14 | 120.2 (5) |
O1—Co1—N2 | 90.39 (14) | N3—C15—H15 | 119.9 |
O2—Co1—N2 | 90.27 (14) | C14—C15—H15 | 119.9 |
O4—Co1—N1 | 87.90 (14) | N3—C17—C18 | 120.7 (5) |
O3—Co1—N1 | 90.98 (14) | N3—C17—H17 | 119.6 |
O1—Co1—N1 | 91.08 (14) | C18—C17—H17 | 119.6 |
O2—Co1—N1 | 89.29 (14) | C17—C18—C13 | 120.4 (5) |
N2—Co1—N1 | 178.45 (15) | C17—C18—H18 | 119.8 |
O11i—Co2—O11 | 180.0 | C13—C18—H18 | 119.8 |
O11i—Co2—O9i | 90.17 (13) | C19ii—C19—C3 | 125.2 (6) |
O11—Co2—O9i | 89.83 (13) | C19ii—C19—H19 | 117.4 |
O11i—Co2—O9 | 89.83 (13) | C3—C19—H19 | 117.4 |
O11—Co2—O9 | 90.17 (13) | Co1—O1—H1B | 109.5 |
O9i—Co2—O9 | 180.00 (18) | Co1—O1—H1A | 109.4 |
O11i—Co2—O10 | 88.64 (15) | H1B—O1—H1A | 129.9 |
O11—Co2—O10 | 91.36 (15) | Co1—O2—H2B | 109.5 |
O9i—Co2—O10 | 88.60 (15) | Co1—O2—H2A | 109.4 |
O9—Co2—O10 | 91.40 (15) | H2B—O2—H2A | 138.5 |
O11i—Co2—O10i | 91.36 (15) | Co1—O3—H3B | 109.5 |
O11—Co2—O10i | 88.64 (15) | Co1—O3—H3A | 109.3 |
O9i—Co2—O10i | 91.40 (15) | H3B—O3—H3A | 141.2 |
O9—Co2—O10i | 88.60 (15) | Co1—O4—H4B | 109.5 |
O10—Co2—O10i | 180.000 (1) | Co1—O4—H4A | 109.5 |
N1—C1—C2 | 124.6 (5) | H4B—O4—H4A | 141.0 |
N1—C1—H1 | 117.7 | Co2—O9—H9B | 109.5 |
C2—C1—H1 | 117.7 | Co2—O9—H9A | 109.4 |
C1—C2—C3 | 119.5 (5) | H9B—O9—H9A | 108.1 |
C1—C2—H2 | 120.2 | Co2—O10—H10B | 109.5 |
C3—C2—H2 | 120.2 | Co2—O10—H10A | 109.5 |
C4—C3—C2 | 116.2 (5) | H10B—O10—H10A | 140.9 |
C4—C3—C19 | 121.2 (4) | Co2—O11—H11B | 109.5 |
C2—C3—C19 | 122.5 (5) | Co2—O11—H11A | 109.4 |
C5—C4—C3 | 120.6 (5) | H11B—O11—H11A | 112.5 |
C5—C4—H4 | 119.7 | H16A—O16—H16B | 100 (6) |
C3—C4—H4 | 119.7 | H17A—O17—H17B | 100 (6) |
N1—C5—C4 | 123.3 (5) | H18A—O18—H18B | 111 (7) |
N1—C5—H5 | 118.4 | H19A—O19—H19B | 73 (5) |
C4—C5—H5 | 118.4 | C1—N1—C5 | 115.8 (4) |
N2—C6—C7 | 124.1 (4) | C1—N1—Co1 | 121.6 (3) |
N2—C6—H6 | 117.9 | C5—N1—Co1 | 122.5 (3) |
C7—C6—H6 | 117.9 | C6—N2—C10 | 117.0 (4) |
C6—C7—C8 | 119.0 (5) | C6—N2—Co1 | 120.9 (3) |
C6—C7—H7 | 120.5 | C10—N2—Co1 | 121.9 (3) |
C8—C7—H7 | 120.5 | C15—N3—C17 | 121.1 (5) |
C9—C8—C7 | 116.9 (4) | C15—N3—H3N | 119.4 |
C9—C8—C11 | 120.7 (4) | C17—N3—H3N | 119.4 |
C7—C8—C11 | 122.3 (5) | O7—S1—O5 | 110.8 (2) |
C8—C9—C10 | 120.3 (4) | O7—S1—O8 | 109.8 (2) |
C8—C9—H9 | 119.8 | O5—S1—O8 | 108.6 (2) |
C10—C9—H9 | 119.8 | O7—S1—O6 | 109.9 (2) |
N2—C10—C9 | 122.7 (4) | O5—S1—O6 | 109.8 (3) |
N2—C10—H10 | 118.7 | O8—S1—O6 | 107.9 (2) |
C9—C10—H10 | 118.7 | O14—S2—O15 | 110.2 (3) |
C12—C11—C8 | 126.5 (4) | O14—S2—O12 | 109.3 (3) |
C12—C11—H11 | 116.7 | O15—S2—O12 | 108.9 (3) |
C8—C11—H11 | 116.7 | O14—S2—O13 | 108.7 (2) |
C11—C12—C13 | 125.5 (4) | O15—S2—O13 | 110.9 (2) |
C11—C12—H12 | 117.3 | O12—S2—O13 | 108.8 (2) |
N1—C1—C2—C3 | 0.4 (8) | C4—C5—N1—Co1 | 175.9 (4) |
C1—C2—C3—C4 | 0.0 (7) | O4—Co1—N1—C1 | −125.8 (4) |
C1—C2—C3—C19 | 179.7 (4) | O3—Co1—N1—C1 | 138.3 (4) |
C2—C3—C4—C5 | −0.4 (7) | O1—Co1—N1—C1 | −40.5 (4) |
C19—C3—C4—C5 | 179.9 (4) | O2—Co1—N1—C1 | 47.3 (4) |
C3—C4—C5—N1 | 0.5 (8) | N2—Co1—N1—C1 | 121 (5) |
N2—C6—C7—C8 | −0.3 (9) | O4—Co1—N1—C5 | 58.4 (4) |
C6—C7—C8—C9 | −0.1 (8) | O3—Co1—N1—C5 | −37.5 (4) |
C6—C7—C8—C11 | −177.2 (5) | O1—Co1—N1—C5 | 143.8 (4) |
C7—C8—C9—C10 | 0.3 (7) | O2—Co1—N1—C5 | −128.5 (4) |
C11—C8—C9—C10 | 177.5 (4) | N2—Co1—N1—C5 | −55 (6) |
C8—C9—C10—N2 | −0.1 (7) | C7—C6—N2—C10 | 0.5 (8) |
C9—C8—C11—C12 | 169.4 (5) | C7—C6—N2—Co1 | 176.2 (4) |
C7—C8—C11—C12 | −13.6 (8) | C9—C10—N2—C6 | −0.3 (7) |
C8—C11—C12—C13 | 176.5 (4) | C9—C10—N2—Co1 | −175.9 (3) |
C11—C12—C13—C14 | −179.0 (5) | O4—Co1—N2—C6 | −58.2 (4) |
C11—C12—C13—C18 | −0.9 (8) | O3—Co1—N2—C6 | 37.7 (4) |
C18—C13—C14—C15 | −0.9 (7) | O1—Co1—N2—C6 | −143.6 (4) |
C12—C13—C14—C15 | 177.3 (5) | O2—Co1—N2—C6 | 128.7 (4) |
C13—C14—C15—N3 | −0.2 (8) | N1—Co1—N2—C6 | 55 (6) |
N3—C17—C18—C13 | 0.5 (8) | O4—Co1—N2—C10 | 117.3 (4) |
C14—C13—C18—C17 | 0.8 (7) | O3—Co1—N2—C10 | −146.9 (4) |
C12—C13—C18—C17 | −177.4 (5) | O1—Co1—N2—C10 | 31.9 (4) |
C4—C3—C19—C19ii | −172.6 (6) | O2—Co1—N2—C10 | −55.9 (4) |
C2—C3—C19—C19ii | 7.7 (9) | N1—Co1—N2—C10 | −129 (5) |
C2—C1—N1—C5 | −0.4 (7) | C14—C15—N3—C17 | 1.5 (8) |
C2—C1—N1—Co1 | −176.4 (4) | C18—C17—N3—C15 | −1.7 (8) |
C4—C5—N1—C1 | −0.1 (7) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x, −y+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1B···O6iii | 0.82 | 1.92 | 2.688 (4) | 155 |
O1—H1A···O13iv | 0.82 | 2.02 | 2.738 (5) | 145 |
O2—H2B···O12iv | 0.82 | 1.91 | 2.699 (5) | 160 |
O2—H2A···O8v | 0.82 | 2.01 | 2.711 (4) | 143 |
O3—H3B···O19 | 0.82 | 1.89 | 2.686 (6) | 162 |
O3—H3A···O6i | 0.82 | 1.97 | 2.711 (5) | 150 |
O4—H4B···O7iii | 0.82 | 2.00 | 2.781 (5) | 159 |
O4—H4A···O13vi | 0.82 | 2.02 | 2.703 (5) | 141 |
O9—H9B···O18 | 0.82 | 1.95 | 2.761 (6) | 172 |
O10—H10B···O5i | 0.82 | 2.17 | 2.813 (5) | 136 |
O10—H10A···O12vii | 0.82 | 1.91 | 2.698 (5) | 161 |
O11—H11B···O16viii | 0.82 | 1.86 | 2.669 (6) | 167 |
O11—H11A···O14viii | 0.82 | 1.93 | 2.739 (5) | 169 |
N3—H3N···O8ix | 0.86 | 1.87 | 2.723 (5) | 174 |
O16—H16A···O13x | 0.76 (4) | 2.04 (4) | 2.797 (6) | 174 (6) |
O16—H16B···O6vii | 0.76 (4) | 2.30 (4) | 3.024 (6) | 161 (6) |
O17—H17A···O15 | 0.80 (4) | 2.28 (5) | 2.987 (7) | 147 (5) |
O17—H17B···O14x | 0.82 (4) | 2.28 (5) | 2.936 (7) | 138 (6) |
O18—H18A···O17vii | 0.79 (4) | 2.07 (4) | 2.855 (8) | 170 (6) |
O18—H18B···O5 | 0.77 (4) | 2.09 (4) | 2.844 (6) | 166 (6) |
O19—H19B···O12vii | 0.80 (4) | 2.20 (5) | 2.939 (7) | 155 (6) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (iii) x−1, −y+3/2, z−1/2; (iv) x, −y+1/2, z−1/2; (v) x, −y+3/2, z−1/2; (vi) −x, −y+1, −z+1; (vii) −x+1, −y+1, −z+1; (viii) x, y+1, z; (ix) −x+1, y−1/2, −z+3/2; (x) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Co2(C12H11N2)2(C12H10N2)(H2O)8][Co(H2O)6](SO4)4·8H2O |
Mr | 1506.06 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 10.2353 (8), 12.1885 (9), 24.9647 (19) |
β (°) | 93.895 (2) |
V (Å3) | 3107.2 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.03 |
Crystal size (mm) | 0.31 × 0.18 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART CCD area detector diffractometer |
Absorption correction | Numerical SADABS (Sheldrick, 1996) |
Tmin, Tmax | 0.81, 0.85 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16014, 5517, 4657 |
Rint | 0.057 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.068, 0.144, 1.20 |
No. of reflections | 5517 |
No. of parameters | 425 |
No. of restraints | 8 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.72, −0.47 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
Co1—O4 | 2.095 (3) | Co1—N1 | 2.153 (4) |
Co1—O3 | 2.096 (3) | Co2—O11 | 2.065 (3) |
Co1—O1 | 2.106 (3) | Co2—O9 | 2.094 (3) |
Co1—O2 | 2.107 (3) | Co2—O10 | 2.127 (4) |
Co1—N2 | 2.151 (4) | ||
O4—Co1—O3 | 95.94 (13) | O1—Co1—N1 | 91.08 (14) |
O4—Co1—O1 | 85.40 (13) | O2—Co1—N1 | 89.29 (14) |
O3—Co1—O1 | 177.59 (13) | N2—Co1—N1 | 178.45 (15) |
O4—Co1—O2 | 172.56 (13) | O11i—Co2—O11 | 180.0 |
O3—Co1—O2 | 91.00 (13) | O11i—Co2—O9 | 89.83 (13) |
O1—Co1—O2 | 87.77 (12) | O11—Co2—O9 | 90.17 (13) |
O4—Co1—N2 | 92.72 (14) | O9i—Co2—O9 | 180.00 (18) |
O3—Co1—N2 | 87.54 (14) | O11i—Co2—O10 | 88.64 (15) |
O1—Co1—N2 | 90.39 (14) | O11—Co2—O10 | 91.36 (15) |
O2—Co1—N2 | 90.27 (14) | O9i—Co2—O10 | 88.60 (15) |
O4—Co1—N1 | 87.90 (14) | O9—Co2—O10 | 91.40 (15) |
O3—Co1—N1 | 90.98 (14) | O10—Co2—O10i | 180.000 (1) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1B···O6ii | 0.82 | 1.92 | 2.688 (4) | 155 |
O1—H1A···O13iii | 0.82 | 2.02 | 2.738 (5) | 145 |
O2—H2B···O12iii | 0.82 | 1.91 | 2.699 (5) | 160 |
O2—H2A···O8iv | 0.82 | 2.01 | 2.711 (4) | 143 |
O3—H3B···O19 | 0.82 | 1.89 | 2.686 (6) | 162 |
O3—H3A···O6i | 0.82 | 1.97 | 2.711 (5) | 150 |
O4—H4B···O7ii | 0.82 | 2.00 | 2.781 (5) | 159 |
O4—H4A···O13v | 0.82 | 2.02 | 2.703 (5) | 141 |
O9—H9B···O18 | 0.82 | 1.95 | 2.761 (6) | 172 |
O10—H10B···O5i | 0.82 | 2.17 | 2.813 (5) | 136 |
O10—H10A···O12vi | 0.82 | 1.91 | 2.698 (5) | 161 |
O11—H11B···O16vii | 0.82 | 1.86 | 2.669 (6) | 167 |
O11—H11A···O14vii | 0.82 | 1.93 | 2.739 (5) | 169 |
N3—H3N···O8viii | 0.86 | 1.87 | 2.723 (5) | 174 |
O16—H16A···O13ix | 0.76 (4) | 2.04 (4) | 2.797 (6) | 174 (6) |
O16—H16B···O6vi | 0.76 (4) | 2.30 (4) | 3.024 (6) | 161 (6) |
O17—H17A···O15 | 0.80 (4) | 2.28 (5) | 2.987 (7) | 147 (5) |
O17—H17B···O14ix | 0.82 (4) | 2.28 (5) | 2.936 (7) | 138 (6) |
O18—H18A···O17vi | 0.79 (4) | 2.07 (4) | 2.855 (8) | 170 (6) |
O18—H18B···O5 | 0.77 (4) | 2.09 (4) | 2.844 (6) | 166 (6) |
O19—H19B···O12vi | 0.80 (4) | 2.20 (5) | 2.939 (7) | 155 (6) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1, −y+3/2, z−1/2; (iii) x, −y+1/2, z−1/2; (iv) x, −y+3/2, z−1/2; (v) −x, −y+1, −z+1; (vi) −x+1, −y+1, −z+1; (vii) x, y+1, z; (viii) −x+1, y−1/2, −z+3/2; (ix) −x, −y, −z+1. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
Much interest at present is focused on the deliberate construction of coordination polymers (Carlucci et al., 1994; Munakata et al., 1999; Hirsch et al., 1997; Hoskins & Robson, 1990), and a large amount of this interest has involved linear pyridyl-donor ligands. These include pyrazine (Carlucci et al., 1995), 4,4'-bipyridine (bipy; Yaghi & Li, 1996) and longer bridges (Soma & Iwamoto, 1997). Bipy has been used extensively before (Huang & Xiong, 1997); however few coordination polymers are known for the other ligands (Batten et al., 1999). Against this background, we report here the structure of the title compound to outline further studies on coordination polymers constructed through the interaction of metal ions with pyridyl-donor ligands with two-connecting geometry.
The title compound, (I), consists of [C36H48Co2N6O8]6+ cations, hexaaquacobalt cations, sulfate anions and water solvent molecules (Fig. 1). In the C36H48Co2N6O8]6+ cation, the Co2+ ion coordinates to four O atoms from four water molecules and two N atoms from a protonated 1,2-tris(4-pyridyl)-ethene and a 1,2-tris(4-pyridyl)-ethene ligand, and the geometry around the Co2+ ion is that of a distorted octahedron. The 1,2-tris(4-pyridyl)-ethene ligand bridges two Co2+ ions, forming a centrosymmetric dimer. In this dimeric cation, two 1,2-tris(4-pyridyl)-ethene ligands are protonated at one end, and the two bridging ligands act in a monodentate mode. This coordination mode is quite different from that reported by Batten et al. (1999) for [Cu{1,2-tris(4-pyridyl)-ethene}2] .(BF4).CH3CN, in which the 1,2-tris(4-pyridyl)-ethene ligand coordinates in a bridging fashion. It is interesting to note that there is a six coordinated hexaaquacobalt cation to the balance charge, and there are complex hydrogen bonds in this compound (Table 2).
The C36H48Co2N6O8]6+ cations are arranged in a parallel fashion, but only the terminal protonated 1,2-tris(4-pyridyl)-ethene ligands of each [C36H48Co2N6O8]6+ cation are overlapped. The sulfate anions, water molecules and hexaaquacobalt cations are distributed regularly between the overlap area (Fig. 2). There are two kinds of parallel arrangement directions of [C36H48Co2N6O8]6+ cations, which cross one another. The angle between the crossing molecules is 57.75 (3) °, and there are also significant face-to-face π–π interactions of the pyridyl rings between the molecules; the average distance is about 3.329 Å. The crossing [C36H48Co2N6O8]6+ cations form a regular grid structure, and interact with π–π interactions, forming alternate layers. There are channels between the layer grids, and the sulfate anions, hexaaquacobalt cations, and water molecules reside in channels through the structure, interacting via numerous hydrogen bonds (Table 2 and Fig. 3).