Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112034385/wq3017sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112034385/wq3017Isup2.hkl |
CCDC reference: 826371
4,4'-Bipyridine (0.1 mmol), CoSO4.7H2O (0.1 mmol), propane-1,2-diol (1 ml) and water (4 ml) were mixed and placed in a thick Pyrex tube, which was sealed and heated to 413 K for 96 h. The tube was cooled to ambient temperature spontaneously, whereupon red block-shaped crystals of (I) were obtained. Analysis found: C 22.63 H 3.12 N 5.36%; calculated for C20H38Co3N4O23S3: C 24.62 H 3.90 N 5.74%.
The 4,4'-bipy H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The H atoms of the water molecules were either located in difference Fourier maps or placed in calculated positions so as to form a reasonable hydrogen-bond network, as far as possible. Initially, their positions were refined with tight restraints on the O—H and H···H distances [0.82 (1) and 1.35 (1) Å, respectively] in order to ensure a reasonable geometry. They were then constrained to ride on their parent O atoms, with Uiso(H) = 1.5Ueq(O). The Flack parameter was refined as a full least-squares parameter, with a refined value of 0.40 (2). The twinning has been applied in the refinement with 2531 Friedel pairs.
Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Co(H2O)6][Co(SO4)2(C10H8N2)(H2O)2][Co(SO4)(C10H8N2)(H2O)3] | Z = 1 |
Mr = 975.51 | F(000) = 499 |
Triclinic, P1 | Dx = 1.889 Mg m−3 |
Hall symbol: P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.2860 (15) Å | Cell parameters from 7593 reflections |
b = 11.246 (2) Å | θ = 3.1–27.5° |
c = 11.462 (2) Å | µ = 1.72 mm−1 |
α = 72.21 (3)° | T = 223 K |
β = 73.57 (3)° | Block, pink |
γ = 83.50 (3)° | 0.33 × 0.14 × 0.11 mm |
V = 857.4 (3) Å3 |
Rigaku Graphite Monochromator [MODEL?] diffractometer | 6430 independent reflections |
Radiation source: fine-focus sealed tube | 5533 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω scans | h = −9→9 |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | k = −14→14 |
Tmin = 0.601, Tmax = 0.834 | l = −14→14 |
8553 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.080 | w = 1/[σ2(Fo2) + (0.0229P)2 + 0.8892P] where P = (Fo2 + 2Fc2)/3 |
S = 1.24 | (Δ/σ)max < 0.001 |
6430 reflections | Δρmax = 0.83 e Å−3 |
479 parameters | Δρmin = −0.61 e Å−3 |
3 restraints | Absolute structure: Flack (1983), 2531 Fridel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.402 (14) |
[Co(H2O)6][Co(SO4)2(C10H8N2)(H2O)2][Co(SO4)(C10H8N2)(H2O)3] | γ = 83.50 (3)° |
Mr = 975.51 | V = 857.4 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.2860 (15) Å | Mo Kα radiation |
b = 11.246 (2) Å | µ = 1.72 mm−1 |
c = 11.462 (2) Å | T = 223 K |
α = 72.21 (3)° | 0.33 × 0.14 × 0.11 mm |
β = 73.57 (3)° |
Rigaku Graphite Monochromator [MODEL?] diffractometer | 6430 independent reflections |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | 5533 reflections with I > 2σ(I) |
Tmin = 0.601, Tmax = 0.834 | Rint = 0.023 |
8553 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.080 | Δρmax = 0.83 e Å−3 |
S = 1.24 | Δρmin = −0.61 e Å−3 |
6430 reflections | Absolute structure: Flack (1983), 2531 Fridel pairs |
479 parameters | Absolute structure parameter: 0.402 (14) |
3 restraints |
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 | 0.00000 (9) | 0.50000 (6) | 0.24567 (5) | 0.01934 (15) | |
Co2 | 0.50218 (10) | 0.00192 (7) | 0.71794 (6) | 0.01779 (13) | |
Co3 | 0.50690 (11) | −0.00978 (7) | 0.21887 (7) | 0.02305 (14) | |
S1 | 0.44606 (17) | 0.40461 (11) | 0.20092 (11) | 0.0229 (3) | |
S2 | 0.91175 (17) | −0.00961 (11) | 0.49236 (11) | 0.0210 (3) | |
S3 | 0.09428 (17) | −0.00163 (11) | 0.95204 (10) | 0.0201 (3) | |
O1 | 0.4814 (5) | 0.5366 (3) | 0.1842 (4) | 0.0363 (9) | |
O2 | 0.5603 (6) | 0.3684 (4) | 0.0896 (3) | 0.0379 (9) | |
O3 | 0.4979 (5) | 0.3232 (4) | 0.3148 (3) | 0.0373 (9) | |
O4 | 0.2432 (5) | 0.3919 (4) | 0.2152 (4) | 0.0308 (9) | |
O5 | 0.9806 (6) | −0.0842 (4) | 0.6012 (4) | 0.0389 (11) | |
O6 | 0.9383 (6) | −0.0833 (4) | 0.4029 (4) | 0.0366 (10) | |
O7 | 1.0165 (6) | 0.1052 (4) | 0.4298 (4) | 0.0441 (11) | |
O8 | 0.7035 (5) | 0.0226 (3) | 0.5345 (3) | 0.0239 (8) | |
O9 | 0.0684 (5) | 0.0797 (4) | 1.0351 (4) | 0.0299 (9) | |
O10 | 0.0129 (5) | 0.0626 (4) | 0.8446 (3) | 0.0296 (9) | |
O11 | −0.0041 (6) | −0.1192 (4) | 1.0245 (4) | 0.0352 (10) | |
O12 | 0.3017 (5) | −0.0303 (3) | 0.9057 (3) | 0.0259 (8) | |
N1 | 0.4733 (7) | −0.1847 (4) | 0.7266 (4) | 0.0243 (10) | |
N2 | 0.5282 (6) | 0.1859 (4) | 0.7158 (4) | 0.0244 (10) | |
N3 | 0.0172 (6) | 0.4964 (4) | 0.4323 (3) | 0.0238 (9) | |
N4 | −0.0110 (6) | 0.5045 (4) | 0.0566 (3) | 0.0228 (9) | |
C1 | 0.4927 (9) | −0.2789 (5) | 0.8260 (5) | 0.0298 (13) | |
H1A | 0.4982 | −0.2608 | 0.8989 | 0.036* | |
C2 | 0.5052 (9) | −0.4024 (5) | 0.8266 (5) | 0.0284 (13) | |
H2A | 0.5211 | −0.4650 | 0.8982 | 0.034* | |
C3 | 0.4942 (8) | −0.4330 (5) | 0.7214 (5) | 0.0230 (11) | |
C4 | 0.4620 (9) | −0.3350 (5) | 0.6200 (5) | 0.0304 (13) | |
H4A | 0.4451 | −0.3510 | 0.5487 | 0.036* | |
C5 | 0.4553 (9) | −0.2141 (5) | 0.6261 (5) | 0.0306 (13) | |
H5A | 0.4373 | −0.1495 | 0.5565 | 0.037* | |
C6 | 0.5253 (9) | 0.2163 (5) | 0.8203 (5) | 0.0340 (14) | |
H6A | 0.5307 | 0.1523 | 0.8933 | 0.041* | |
C7 | 0.5148 (10) | 0.3376 (5) | 0.8251 (5) | 0.0330 (13) | |
H7A | 0.5094 | 0.3539 | 0.9008 | 0.040* | |
C8 | 0.5121 (8) | 0.4355 (5) | 0.7174 (5) | 0.0211 (11) | |
C9 | 0.5234 (9) | 0.4040 (5) | 0.6075 (5) | 0.0281 (13) | |
H9A | 0.5278 | 0.4662 | 0.5316 | 0.034* | |
C10 | 0.5280 (8) | 0.2797 (5) | 0.6116 (4) | 0.0269 (12) | |
H10A | 0.5310 | 0.2605 | 0.5377 | 0.032* | |
C11 | 0.0450 (8) | 0.3922 (5) | 0.5203 (5) | 0.0293 (13) | |
H11A | 0.0688 | 0.3178 | 0.4982 | 0.035* | |
C12 | 0.0405 (9) | 0.3886 (5) | 0.6426 (5) | 0.0316 (13) | |
H12A | 0.0600 | 0.3128 | 0.7003 | 0.038* | |
C13 | 0.0069 (7) | 0.4977 (5) | 0.6802 (4) | 0.0163 (10) | |
C14 | −0.0193 (8) | 0.6061 (5) | 0.5870 (5) | 0.0297 (12) | |
H14A | −0.0397 | 0.6824 | 0.6053 | 0.036* | |
C15 | −0.0150 (8) | 0.6011 (5) | 0.4670 (4) | 0.0245 (11) | |
H15A | −0.0359 | 0.6751 | 0.4074 | 0.029* | |
C16 | −0.0361 (8) | 0.6078 (5) | −0.0338 (5) | 0.0300 (12) | |
H16A | −0.0593 | 0.6829 | −0.0131 | 0.036* | |
C17 | −0.0300 (9) | 0.6102 (5) | −0.1547 (5) | 0.0323 (13) | |
H17A | −0.0459 | 0.6856 | −0.2140 | 0.039* | |
C18 | 0.0000 (8) | 0.4996 (5) | −0.1891 (4) | 0.0227 (11) | |
C19 | 0.0241 (9) | 0.3922 (5) | −0.0962 (4) | 0.0290 (13) | |
H19A | 0.0447 | 0.3158 | −0.1143 | 0.035* | |
C20 | 0.0178 (8) | 0.3972 (5) | 0.0234 (5) | 0.0298 (12) | |
H20A | 0.0342 | 0.3231 | 0.0843 | 0.036* | |
O1W | 0.2806 (5) | 0.0689 (4) | 0.6283 (3) | 0.0297 (9) | |
H1WA | 0.1875 | 0.0656 | 0.6889 | 0.045* | |
H1WB | 0.2561 | 0.0450 | 0.5741 | 0.045* | |
O2W | 0.7302 (5) | −0.0594 (3) | 0.8092 (3) | 0.0267 (8) | |
H2WA | 0.8167 | −0.0836 | 0.7575 | 0.040* | |
H2WB | 0.7691 | −0.0072 | 0.8319 | 0.040* | |
O3W | −0.1445 (5) | 0.3340 (3) | 0.3216 (3) | 0.0333 (9) | |
H3WA | −0.0932 | 0.2688 | 0.3552 | 0.050* | |
H3WB | −0.2527 | 0.3208 | 0.3212 | 0.050* | |
O4W | 0.1576 (5) | 0.6711 (3) | 0.1778 (3) | 0.0295 (8) | |
H4WA | 0.1410 | 0.7295 | 0.1177 | 0.044* | |
H4WB | 0.2692 | 0.6452 | 0.1634 | 0.044* | |
O5W | −0.2586 (5) | 0.6059 (4) | 0.2704 (4) | 0.0347 (10) | |
H5WA | −0.2758 | 0.6736 | 0.2855 | 0.052* | |
H5WB | −0.3403 | 0.5949 | 0.2384 | 0.052* | |
O6W | 0.7459 (5) | −0.1278 (3) | 0.2532 (3) | 0.0281 (8) | |
H6WA | 0.7903 | −0.1147 | 0.3063 | 0.042* | |
H6WB | 0.8278 | −0.1200 | 0.1857 | 0.042* | |
O7W | 0.2731 (6) | 0.1037 (4) | 0.1880 (4) | 0.0373 (10) | |
H7WA | 0.2068 | 0.1353 | 0.2422 | 0.056* | |
H7WB | 0.2179 | 0.1078 | 0.1336 | 0.056* | |
O8W | 0.4817 (6) | 0.0654 (4) | 0.3679 (3) | 0.0344 (9) | |
H8WA | 0.4329 | 0.1360 | 0.3540 | 0.052* | |
H8WB | 0.5408 | 0.0537 | 0.4218 | 0.052* | |
O9W | 0.6757 (6) | 0.1339 (4) | 0.0936 (4) | 0.0386 (10) | |
H9WA | 0.6366 | 0.1995 | 0.1106 | 0.058* | |
H9WB | 0.7928 | 0.1280 | 0.0789 | 0.058* | |
O10W | 0.5297 (6) | −0.1009 (4) | 0.0751 (3) | 0.0366 (10) | |
H10W | 0.4576 | −0.0831 | 0.0284 | 0.055* | |
HW10 | 0.6420 | −0.0954 | 0.0338 | 0.055* | |
O11W | 0.3219 (6) | −0.1573 (4) | 0.3334 (4) | 0.0430 (11) | |
H11W | 0.2131 | −0.1264 | 0.3443 | 0.064* | |
HW11 | 0.3342 | −0.2084 | 0.2935 | 0.064* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0203 (3) | 0.0211 (3) | 0.0191 (4) | 0.0016 (2) | −0.0088 (3) | −0.0067 (3) |
Co2 | 0.0216 (3) | 0.0148 (3) | 0.0188 (3) | 0.0004 (2) | −0.0057 (2) | −0.0074 (2) |
Co3 | 0.0208 (3) | 0.0284 (4) | 0.0202 (3) | 0.0018 (2) | −0.0058 (2) | −0.0078 (3) |
S1 | 0.0217 (6) | 0.0248 (6) | 0.0247 (6) | 0.0032 (5) | −0.0099 (5) | −0.0085 (5) |
S2 | 0.0194 (6) | 0.0225 (6) | 0.0234 (6) | 0.0009 (5) | −0.0065 (5) | −0.0094 (5) |
S3 | 0.0212 (6) | 0.0203 (6) | 0.0199 (5) | −0.0005 (5) | −0.0055 (5) | −0.0074 (5) |
O1 | 0.032 (2) | 0.029 (2) | 0.055 (2) | −0.0009 (16) | −0.0208 (19) | −0.0141 (18) |
O2 | 0.043 (2) | 0.037 (2) | 0.0293 (19) | 0.0099 (18) | −0.0043 (17) | −0.0113 (17) |
O3 | 0.037 (2) | 0.045 (2) | 0.0300 (19) | −0.0002 (18) | −0.0183 (17) | −0.0019 (18) |
O4 | 0.0172 (19) | 0.031 (2) | 0.054 (2) | 0.0035 (15) | −0.0143 (17) | −0.0234 (18) |
O5 | 0.036 (2) | 0.051 (3) | 0.033 (2) | 0.019 (2) | −0.0167 (19) | −0.0168 (19) |
O6 | 0.034 (2) | 0.049 (3) | 0.038 (2) | 0.007 (2) | −0.0114 (19) | −0.029 (2) |
O7 | 0.026 (2) | 0.033 (2) | 0.069 (3) | −0.0044 (18) | −0.001 (2) | −0.017 (2) |
O8 | 0.0174 (19) | 0.030 (2) | 0.0250 (17) | 0.0042 (15) | −0.0061 (15) | −0.0099 (15) |
O9 | 0.025 (2) | 0.036 (2) | 0.039 (2) | 0.0045 (17) | −0.0101 (17) | −0.0258 (18) |
O10 | 0.024 (2) | 0.039 (2) | 0.0248 (18) | 0.0025 (17) | −0.0092 (16) | −0.0067 (17) |
O11 | 0.042 (3) | 0.021 (2) | 0.034 (2) | −0.0068 (18) | −0.0010 (18) | −0.0024 (17) |
O12 | 0.025 (2) | 0.031 (2) | 0.0220 (17) | 0.0057 (16) | −0.0069 (15) | −0.0094 (15) |
N1 | 0.035 (3) | 0.015 (2) | 0.024 (2) | 0.0023 (19) | −0.0081 (19) | −0.0086 (17) |
N2 | 0.037 (3) | 0.016 (2) | 0.0218 (19) | −0.0016 (19) | −0.0059 (19) | −0.0086 (16) |
N3 | 0.029 (2) | 0.024 (2) | 0.022 (2) | −0.0033 (18) | −0.0087 (19) | −0.0099 (18) |
N4 | 0.030 (2) | 0.025 (2) | 0.0164 (18) | 0.0051 (18) | −0.0111 (17) | −0.0076 (17) |
C1 | 0.048 (4) | 0.021 (3) | 0.024 (2) | −0.002 (2) | −0.011 (2) | −0.011 (2) |
C2 | 0.047 (4) | 0.016 (3) | 0.023 (3) | −0.003 (2) | −0.015 (2) | −0.002 (2) |
C3 | 0.024 (3) | 0.015 (3) | 0.030 (2) | −0.001 (2) | −0.007 (2) | −0.007 (2) |
C4 | 0.046 (4) | 0.023 (3) | 0.028 (3) | −0.002 (2) | −0.017 (3) | −0.010 (2) |
C5 | 0.049 (4) | 0.017 (3) | 0.030 (3) | 0.000 (2) | −0.018 (3) | −0.007 (2) |
C6 | 0.064 (4) | 0.015 (3) | 0.024 (2) | −0.001 (3) | −0.019 (3) | −0.002 (2) |
C7 | 0.057 (4) | 0.021 (3) | 0.028 (3) | 0.001 (3) | −0.018 (3) | −0.013 (2) |
C8 | 0.023 (3) | 0.016 (2) | 0.025 (2) | 0.000 (2) | −0.004 (2) | −0.009 (2) |
C9 | 0.048 (4) | 0.017 (3) | 0.018 (2) | −0.002 (2) | −0.010 (2) | −0.002 (2) |
C10 | 0.044 (4) | 0.023 (3) | 0.019 (2) | −0.006 (2) | −0.010 (2) | −0.010 (2) |
C11 | 0.051 (4) | 0.021 (3) | 0.019 (2) | 0.008 (2) | −0.016 (2) | −0.006 (2) |
C12 | 0.046 (4) | 0.024 (3) | 0.029 (3) | 0.010 (2) | −0.020 (3) | −0.009 (2) |
C13 | 0.016 (2) | 0.018 (2) | 0.016 (2) | −0.0017 (18) | −0.003 (2) | −0.008 (2) |
C14 | 0.040 (3) | 0.028 (3) | 0.027 (3) | 0.007 (2) | −0.015 (2) | −0.013 (2) |
C15 | 0.036 (3) | 0.020 (3) | 0.017 (2) | −0.001 (2) | −0.011 (2) | −0.0015 (19) |
C16 | 0.040 (3) | 0.027 (3) | 0.032 (3) | 0.007 (2) | −0.019 (3) | −0.017 (2) |
C17 | 0.057 (4) | 0.020 (3) | 0.024 (3) | 0.006 (2) | −0.020 (3) | −0.005 (2) |
C18 | 0.024 (3) | 0.029 (3) | 0.015 (2) | 0.003 (2) | −0.006 (2) | −0.007 (2) |
C19 | 0.049 (4) | 0.021 (3) | 0.017 (2) | 0.002 (2) | −0.011 (2) | −0.005 (2) |
C20 | 0.048 (4) | 0.018 (3) | 0.025 (3) | 0.004 (2) | −0.015 (2) | −0.005 (2) |
O1W | 0.028 (2) | 0.040 (2) | 0.0275 (17) | 0.0042 (17) | −0.0116 (16) | −0.0166 (16) |
O2W | 0.026 (2) | 0.029 (2) | 0.0285 (17) | 0.0027 (15) | −0.0101 (15) | −0.0119 (15) |
O3W | 0.030 (2) | 0.027 (2) | 0.041 (2) | −0.0096 (16) | −0.0165 (17) | 0.0037 (17) |
O4W | 0.030 (2) | 0.0234 (19) | 0.0307 (18) | −0.0008 (15) | −0.0066 (16) | −0.0031 (15) |
O5W | 0.030 (2) | 0.034 (2) | 0.053 (2) | 0.0125 (17) | −0.0244 (19) | −0.0243 (19) |
O6W | 0.023 (2) | 0.032 (2) | 0.0308 (18) | 0.0028 (15) | −0.0091 (16) | −0.0104 (16) |
O7W | 0.030 (2) | 0.052 (3) | 0.039 (2) | 0.0178 (19) | −0.0161 (19) | −0.026 (2) |
O8W | 0.044 (2) | 0.040 (2) | 0.0263 (18) | 0.0101 (18) | −0.0183 (17) | −0.0159 (17) |
O9W | 0.031 (2) | 0.028 (2) | 0.046 (2) | 0.0024 (17) | 0.0015 (18) | −0.0061 (18) |
O10W | 0.036 (2) | 0.053 (3) | 0.0264 (19) | 0.0020 (19) | −0.0109 (17) | −0.0178 (19) |
O11W | 0.029 (2) | 0.046 (3) | 0.047 (2) | −0.0028 (18) | 0.0034 (19) | −0.016 (2) |
Co1—O4 | 2.040 (4) | C6—H6A | 0.9300 |
Co1—O3W | 2.070 (4) | C7—C8 | 1.384 (7) |
Co1—O4W | 2.169 (4) | C7—H7A | 0.9300 |
Co1—O5W | 2.108 (4) | C8—C9 | 1.389 (7) |
Co1—N3 | 2.166 (4) | C8—C3ii | 1.483 (5) |
Co1—N4 | 2.177 (4) | C9—C10 | 1.381 (7) |
Co2—O8 | 2.159 (3) | C9—H9A | 0.9300 |
Co2—O12 | 2.182 (3) | C10—H10A | 0.9300 |
Co2—O1W | 2.102 (4) | C11—C12 | 1.381 (7) |
Co2—O2W | 2.147 (4) | C11—H11A | 0.9300 |
Co2—N1 | 2.103 (4) | C12—C13 | 1.396 (7) |
Co2—N2 | 2.091 (4) | C12—H12A | 0.9300 |
Co3—O6W | 2.120 (4) | C13—C14 | 1.389 (7) |
Co3—O7W | 2.056 (4) | C13—C18iii | 1.491 (6) |
Co3—O8W | 2.082 (4) | C14—C15 | 1.385 (7) |
Co3—O9W | 2.054 (4) | C14—H14A | 0.9300 |
Co3—O10W | 2.152 (4) | C15—H15A | 0.9300 |
Co3—O11W | 2.114 (4) | C16—C17 | 1.366 (7) |
S1—O2 | 1.458 (4) | C16—H16A | 0.9300 |
S1—O4 | 1.459 (4) | C17—C18 | 1.393 (7) |
S1—O3 | 1.467 (4) | C17—H17A | 0.9300 |
S1—O1 | 1.481 (4) | C18—C19 | 1.377 (7) |
S2—O7 | 1.453 (4) | C18—C13iv | 1.491 (6) |
S2—O5 | 1.460 (4) | C19—C20 | 1.377 (7) |
S2—O6 | 1.465 (4) | C19—H19A | 0.9300 |
S2—O8 | 1.495 (4) | C20—H20A | 0.9300 |
S3—O11 | 1.469 (4) | O1W—H1WA | 0.8170 |
S3—O10 | 1.470 (4) | O1W—H1WB | 0.8157 |
S3—O9 | 1.474 (3) | O2W—H2WA | 0.8186 |
S3—O12 | 1.487 (4) | O2W—H2WB | 0.8154 |
N1—C1 | 1.327 (7) | O3W—H3WA | 0.8201 |
N1—C5 | 1.335 (7) | O3W—H3WB | 0.8200 |
N2—C10 | 1.330 (7) | O4W—H4WA | 0.8199 |
N2—C6 | 1.337 (6) | O4W—H4WB | 0.8200 |
N3—C15 | 1.330 (6) | O5W—H5WA | 0.8200 |
N3—C11 | 1.331 (6) | O5W—H5WB | 0.8200 |
N4—C16 | 1.334 (7) | O6W—H6WA | 0.8201 |
N4—C20 | 1.349 (6) | O6W—H6WB | 0.8199 |
C1—C2 | 1.379 (7) | O7W—H7WA | 0.8200 |
C1—H1A | 0.9300 | O7W—H7WB | 0.8199 |
C2—C3 | 1.376 (7) | O8W—H8WA | 0.8199 |
C2—H2A | 0.9300 | O8W—H8WB | 0.8200 |
C3—C4 | 1.391 (7) | O9W—H9WA | 0.8200 |
C3—C8i | 1.483 (5) | O9W—H9WB | 0.8200 |
C4—C5 | 1.377 (7) | O10W—H10W | 0.8200 |
C4—H4A | 0.9300 | O10W—HW10 | 0.8200 |
C5—H5A | 0.9300 | O11W—H11W | 0.8200 |
C6—C7 | 1.374 (7) | O11W—HW11 | 0.8200 |
O4—Co1—O3W | 86.12 (16) | C4—C3—C8i | 121.6 (4) |
O4—Co1—O5W | 176.22 (16) | C5—C4—C3 | 119.3 (5) |
O3W—Co1—O5W | 91.71 (16) | C5—C4—H4A | 120.3 |
O4—Co1—O4W | 92.89 (15) | C3—C4—H4A | 120.3 |
O3W—Co1—O4W | 176.13 (14) | N1—C5—C4 | 123.5 (5) |
O5W—Co1—O4W | 89.48 (15) | N1—C5—H5A | 118.3 |
O4—Co1—N4 | 86.16 (15) | C4—C5—H5A | 118.3 |
O3W—Co1—N4 | 90.14 (16) | N2—C6—C7 | 123.2 (5) |
O5W—Co1—N4 | 90.76 (15) | N2—C6—H6A | 118.4 |
O4W—Co1—N4 | 93.54 (16) | C7—C6—H6A | 118.4 |
O3W—Co1—N3 | 90.67 (16) | C6—C7—C8 | 120.1 (5) |
O4W—Co1—N3 | 85.64 (15) | C6—C7—H7A | 119.9 |
O5W—Co1—N3 | 90.09 (15) | C8—C7—H7A | 119.9 |
N3—Co1—N4 | 178.8 (2) | C7—C8—C9 | 116.7 (5) |
N3—Co1—O4 | 93.02 (16) | C7—C8—C3ii | 121.0 (4) |
O1W—Co2—N1 | 93.63 (17) | C9—C8—C3ii | 122.3 (4) |
O1W—Co2—N2 | 87.17 (16) | C10—C9—C8 | 119.6 (5) |
O2W—Co2—N2 | 90.68 (16) | C10—C9—H9A | 120.2 |
N1—Co2—N2 | 178.15 (18) | C8—C9—H9A | 120.2 |
O9W—Co3—O7W | 87.62 (18) | N2—C10—C9 | 123.4 (4) |
O7W—Co3—O8W | 85.07 (16) | N2—C10—H10A | 118.3 |
O7W—Co3—O11W | 89.57 (18) | C9—C10—H10A | 118.3 |
O9W—Co3—O6W | 93.01 (16) | N3—C11—C12 | 123.5 (5) |
O7W—Co3—O6W | 179.25 (19) | N3—C11—H11A | 118.2 |
O8W—Co3—O6W | 94.49 (15) | C12—C11—H11A | 118.2 |
O11W—Co3—O6W | 89.84 (16) | C11—C12—C13 | 120.5 (5) |
O7W—Co3—O10W | 97.01 (16) | C11—C12—H12A | 119.8 |
O6W—Co3—O10W | 83.39 (15) | C13—C12—H12A | 119.8 |
O1W—Co2—O2W | 177.85 (17) | C14—C13—C12 | 115.5 (4) |
N1—Co2—O2W | 88.52 (16) | C14—C13—C18iii | 121.6 (4) |
N2—Co2—O8 | 93.74 (15) | C12—C13—C18iii | 122.9 (4) |
O1W—Co2—O8 | 89.64 (14) | C15—C14—C13 | 120.3 (5) |
N1—Co2—O8 | 87.93 (15) | C15—C14—H14A | 119.9 |
O2W—Co2—O8 | 90.39 (14) | C13—C14—H14A | 119.9 |
N2—Co2—O12 | 89.26 (15) | N3—C15—C14 | 123.7 (5) |
O1W—Co2—O12 | 91.66 (14) | N3—C15—H15A | 118.2 |
N1—Co2—O12 | 89.05 (15) | C14—C15—H15A | 118.2 |
O2W—Co2—O12 | 88.42 (14) | N4—C16—C17 | 124.0 (5) |
O8—Co2—O12 | 176.78 (16) | N4—C16—H16A | 118.0 |
O9W—Co3—O8W | 91.15 (17) | C17—C16—H16A | 118.0 |
O9W—Co3—O11W | 174.50 (19) | C16—C17—C18 | 120.0 (5) |
O8W—Co3—O11W | 93.31 (17) | C16—C17—H17A | 120.0 |
O9W—Co3—O10W | 92.63 (17) | C18—C17—H17A | 120.0 |
O8W—Co3—O10W | 175.76 (19) | C19—C18—C17 | 116.4 (4) |
O11W—Co3—O10W | 83.03 (16) | C19—C18—C13iv | 121.8 (4) |
O2—S1—O4 | 109.8 (2) | C17—C18—C13iv | 121.8 (4) |
O2—S1—O3 | 109.6 (2) | C20—C19—C18 | 120.3 (5) |
O4—S1—O3 | 109.0 (2) | C20—C19—H19A | 119.8 |
O2—S1—O1 | 109.2 (2) | C18—C19—H19A | 119.8 |
O4—S1—O1 | 109.0 (2) | N4—C20—C19 | 123.2 (5) |
O3—S1—O1 | 110.3 (2) | N4—C20—H20A | 118.4 |
O7—S2—O5 | 110.7 (3) | C19—C20—H20A | 118.4 |
O7—S2—O6 | 109.6 (3) | Co2—O1W—H1WA | 101.9 |
O5—S2—O6 | 108.6 (2) | Co2—O1W—H1WB | 127.1 |
O7—S2—O8 | 108.9 (2) | H1WA—O1W—H1WB | 111.5 |
O5—S2—O8 | 110.1 (2) | Co2—O2W—H2WA | 105.2 |
O6—S2—O8 | 108.8 (2) | Co2—O2W—H2WB | 115.9 |
O11—S3—O10 | 109.8 (3) | H2WA—O2W—H2WB | 110.2 |
O11—S3—O9 | 109.4 (2) | Co1—O3W—H3WA | 121.3 |
O10—S3—O9 | 109.0 (2) | Co1—O3W—H3WB | 128.5 |
O11—S3—O12 | 108.8 (2) | H3WA—O3W—H3WB | 110.2 |
O10—S3—O12 | 110.4 (2) | Co1—O4W—H4WA | 122.7 |
O9—S3—O12 | 109.5 (2) | Co1—O4W—H4WB | 102.3 |
S1—O4—Co1 | 136.1 (2) | H4WA—O4W—H4WB | 110.5 |
S2—O8—Co2 | 133.7 (2) | Co1—O5W—H5WA | 127.0 |
S3—O12—Co2 | 134.1 (2) | Co1—O5W—H5WB | 118.3 |
C1—N1—C5 | 116.9 (4) | H5WA—O5W—H5WB | 111.0 |
C1—N1—Co2 | 121.8 (3) | Co3—O6W—H6WA | 113.5 |
C5—N1—Co2 | 120.9 (3) | Co3—O6W—H6WB | 108.6 |
C10—N2—C6 | 116.9 (4) | H6WA—O6W—H6WB | 110.7 |
C10—N2—Co2 | 120.4 (3) | Co3—O7W—H7WA | 121.1 |
C6—N2—Co2 | 122.3 (3) | Co3—O7W—H7WB | 125.9 |
C15—N3—C11 | 116.6 (4) | H7WA—O7W—H7WB | 110.9 |
C15—N3—Co1 | 119.7 (3) | Co3—O8W—H8WA | 111.4 |
C11—N3—Co1 | 123.5 (3) | Co3—O8W—H8WB | 133.5 |
C16—N4—C20 | 116.0 (4) | H8WA—O8W—H8WB | 110.7 |
C16—N4—Co1 | 124.7 (3) | Co3—O9W—H9WA | 109.7 |
C20—N4—Co1 | 119.2 (3) | Co3—O9W—H9WB | 121.1 |
N1—C1—C2 | 123.2 (5) | H9WA—O9W—H9WB | 110.3 |
N1—C1—H1A | 118.4 | Co3—O10W—H10W | 122.2 |
C2—C1—H1A | 118.4 | Co3—O10W—HW10 | 105.5 |
C3—C2—C1 | 120.1 (5) | H10W—O10W—HW10 | 111.1 |
C3—C2—H2A | 120.0 | Co3—O11W—H11W | 106.3 |
C1—C2—H2A | 120.0 | Co3—O11W—HW11 | 107.1 |
C2—C3—C4 | 116.8 (5) | H11W—O11W—HW11 | 110.7 |
C2—C3—C8i | 121.6 (4) | ||
O2—S1—O4—Co1 | −131.7 (3) | O5W—Co1—N4—C16 | 51.3 (5) |
O3—S1—O4—Co1 | 108.3 (4) | O4W—Co1—N4—C16 | −38.2 (4) |
O1—S1—O4—Co1 | −12.2 (4) | O4—Co1—N4—C20 | 45.9 (4) |
O3W—Co1—O4—S1 | −155.3 (4) | O3W—Co1—N4—C20 | −40.2 (4) |
N3—Co1—O4—S1 | −64.9 (4) | O5W—Co1—N4—C20 | −131.9 (4) |
O4W—Co1—O4—S1 | 20.9 (4) | O4W—Co1—N4—C20 | 138.6 (4) |
N4—Co1—O4—S1 | 114.3 (4) | C5—N1—C1—C2 | 3.6 (9) |
O7—S2—O8—Co2 | −112.7 (3) | Co2—N1—C1—C2 | −169.3 (5) |
O5—S2—O8—Co2 | 8.9 (4) | N1—C1—C2—C3 | −1.2 (10) |
O6—S2—O8—Co2 | 127.9 (3) | C1—C2—C3—C4 | −2.8 (9) |
N2—Co2—O8—S2 | 97.6 (3) | C1—C2—C3—C8i | 178.4 (5) |
O1W—Co2—O8—S2 | −175.2 (3) | C2—C3—C4—C5 | 4.1 (9) |
N1—Co2—O8—S2 | −81.6 (3) | C8i—C3—C4—C5 | −177.0 (5) |
O2W—Co2—O8—S2 | 6.9 (3) | C1—N1—C5—C4 | −2.1 (9) |
O11—S3—O12—Co2 | 120.4 (3) | Co2—N1—C5—C4 | 170.9 (5) |
O10—S3—O12—Co2 | −0.2 (4) | C3—C4—C5—N1 | −1.8 (10) |
O9—S3—O12—Co2 | −120.1 (3) | C10—N2—C6—C7 | 2.6 (9) |
N2—Co2—O12—S3 | 80.6 (3) | Co2—N2—C6—C7 | −170.4 (5) |
O1W—Co2—O12—S3 | −6.5 (3) | N2—C6—C7—C8 | −1.9 (10) |
N1—Co2—O12—S3 | −100.1 (3) | C6—C7—C8—C9 | −0.9 (9) |
O2W—Co2—O12—S3 | 171.3 (3) | C6—C7—C8—C3ii | 177.9 (5) |
O1W—Co2—N1—C1 | −142.0 (4) | C7—C8—C9—C10 | 2.8 (9) |
O2W—Co2—N1—C1 | 38.0 (4) | C3ii—C8—C9—C10 | −176.0 (5) |
O8—Co2—N1—C1 | 128.5 (4) | C6—N2—C10—C9 | −0.5 (9) |
O12—Co2—N1—C1 | −50.4 (4) | Co2—N2—C10—C9 | 172.6 (5) |
O1W—Co2—N1—C5 | 45.3 (4) | C8—C9—C10—N2 | −2.2 (10) |
O2W—Co2—N1—C5 | −134.6 (4) | C15—N3—C11—C12 | 0.5 (8) |
O8—Co2—N1—C5 | −44.2 (4) | Co1—N3—C11—C12 | −174.5 (5) |
O12—Co2—N1—C5 | 136.9 (4) | N3—C11—C12—C13 | −0.5 (9) |
O1W—Co2—N2—C10 | −45.1 (4) | C11—C12—C13—C14 | −0.4 (8) |
O2W—Co2—N2—C10 | 134.8 (4) | C11—C12—C13—C18iii | 179.9 (5) |
O8—Co2—N2—C10 | 44.4 (4) | C12—C13—C14—C15 | 1.3 (8) |
O12—Co2—N2—C10 | −136.8 (4) | C18iii—C13—C14—C15 | −179.0 (5) |
O1W—Co2—N2—C6 | 127.7 (5) | C11—N3—C15—C14 | 0.5 (8) |
O2W—Co2—N2—C6 | −52.4 (5) | Co1—N3—C15—C14 | 175.7 (4) |
O8—Co2—N2—C6 | −142.8 (5) | C13—C14—C15—N3 | −1.4 (9) |
O12—Co2—N2—C6 | 36.0 (5) | C20—N4—C16—C17 | −1.5 (9) |
O4—Co1—N3—C15 | 136.2 (4) | Co1—N4—C16—C17 | 175.5 (5) |
O3W—Co1—N3—C15 | −137.7 (4) | N4—C16—C17—C18 | 1.4 (10) |
O5W—Co1—N3—C15 | −46.0 (4) | C16—C17—C18—C19 | −0.6 (9) |
O4W—Co1—N3—C15 | 43.5 (4) | C16—C17—C18—C13iv | 179.7 (5) |
O4—Co1—N3—C11 | −49.0 (5) | C17—C18—C19—C20 | 0.0 (9) |
O3W—Co1—N3—C11 | 37.2 (4) | C13iv—C18—C19—C20 | 179.7 (5) |
O5W—Co1—N3—C11 | 128.9 (4) | C16—N4—C20—C19 | 0.8 (9) |
O4W—Co1—N3—C11 | −141.7 (5) | Co1—N4—C20—C19 | −176.3 (5) |
O4—Co1—N4—C16 | −130.9 (5) | C18—C19—C20—N4 | −0.2 (10) |
O3W—Co1—N4—C16 | 143.0 (4) |
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z; (iii) x, y, z+1; (iv) x, y, z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O10 | 0.82 | 1.87 | 2.674 (5) | 168 |
O1W—H1WB···O5v | 0.82 | 2.50 | 3.066 (6) | 127 |
O2W—H2WA···O5 | 0.82 | 1.85 | 2.631 (5) | 158 |
O2W—H2WB···O10vi | 0.82 | 2.08 | 2.783 (6) | 144 |
O3W—H3WA···O7v | 0.82 | 1.96 | 2.779 (6) | 175 |
O3W—H3WB···O3v | 0.82 | 1.84 | 2.646 (5) | 169 |
O4W—H4WA···O11vii | 0.82 | 2.07 | 2.837 (5) | 156 |
O4W—H4WB···O1 | 0.82 | 1.88 | 2.661 (5) | 158 |
O5W—H5WA···O6Wviii | 0.82 | 2.17 | 2.943 (5) | 158 |
O5W—H5WB···O1v | 0.82 | 1.84 | 2.652 (5) | 168 |
O6W—H6WA···O6 | 0.82 | 1.87 | 2.684 (5) | 169 |
O6W—H6WB···O11ix | 0.82 | 1.90 | 2.717 (5) | 171 |
O7W—H7WA···O7v | 0.82 | 2.15 | 2.875 (6) | 147 |
O7W—H7WB···O9iv | 0.82 | 1.88 | 2.688 (5) | 166 |
O8W—H8WA···O3 | 0.82 | 2.09 | 2.784 (6) | 142 |
O8W—H8WB···O8 | 0.82 | 1.92 | 2.738 (5) | 174 |
O9W—H9WA···O2 | 0.82 | 1.88 | 2.666 (5) | 161 |
O9W—H9WB···O9ix | 0.82 | 1.98 | 2.788 (5) | 168 |
O10W—H10W···O12iv | 0.82 | 1.97 | 2.783 (5) | 175 |
O10W—HW10···O2Wiv | 0.82 | 2.39 | 2.900 (5) | 122 |
O11W—H11W···O6v | 0.82 | 1.98 | 2.786 (6) | 168 |
Symmetry codes: (iv) x, y, z−1; (v) x−1, y, z; (vi) x+1, y, z; (vii) x, y+1, z−1; (viii) x−1, y+1, z; (ix) x+1, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | [Co(H2O)6][Co(SO4)2(C10H8N2)(H2O)2][Co(SO4)(C10H8N2)(H2O)3] |
Mr | 975.51 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 223 |
a, b, c (Å) | 7.2860 (15), 11.246 (2), 11.462 (2) |
α, β, γ (°) | 72.21 (3), 73.57 (3), 83.50 (3) |
V (Å3) | 857.4 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.72 |
Crystal size (mm) | 0.33 × 0.14 × 0.11 |
Data collection | |
Diffractometer | Rigaku Graphite Monochromator [MODEL?] diffractometer |
Absorption correction | Multi-scan (REQAB; Jacobson, 1998) |
Tmin, Tmax | 0.601, 0.834 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8553, 6430, 5533 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.080, 1.24 |
No. of reflections | 6430 |
No. of parameters | 479 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.83, −0.61 |
Absolute structure | Flack (1983), 2531 Fridel pairs |
Absolute structure parameter | 0.402 (14) |
Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Co1—O4 | 2.040 (4) | Co2—O2W | 2.147 (4) |
Co1—O3W | 2.070 (4) | Co2—N1 | 2.103 (4) |
Co1—O4W | 2.169 (4) | Co2—N2 | 2.091 (4) |
Co1—O5W | 2.108 (4) | Co3—O6W | 2.120 (4) |
Co1—N3 | 2.166 (4) | Co3—O7W | 2.056 (4) |
Co1—N4 | 2.177 (4) | Co3—O8W | 2.082 (4) |
Co2—O8 | 2.159 (3) | Co3—O9W | 2.054 (4) |
Co2—O12 | 2.182 (3) | Co3—O10W | 2.152 (4) |
Co2—O1W | 2.102 (4) | Co3—O11W | 2.114 (4) |
O3W—Co1—N3 | 90.67 (16) | O9W—Co3—O7W | 87.62 (18) |
O4W—Co1—N3 | 85.64 (15) | O7W—Co3—O8W | 85.07 (16) |
O5W—Co1—N3 | 90.09 (15) | O7W—Co3—O11W | 89.57 (18) |
N3—Co1—N4 | 178.8 (2) | O9W—Co3—O6W | 93.01 (16) |
N3—Co1—O4 | 93.02 (16) | O7W—Co3—O6W | 179.25 (19) |
O1W—Co2—N1 | 93.63 (17) | O8W—Co3—O6W | 94.49 (15) |
O1W—Co2—N2 | 87.17 (16) | O11W—Co3—O6W | 89.84 (16) |
O2W—Co2—N2 | 90.68 (16) | O7W—Co3—O10W | 97.01 (16) |
N1—Co2—N2 | 178.15 (18) | O6W—Co3—O10W | 83.39 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O10 | 0.82 | 1.87 | 2.674 (5) | 167.6 |
O1W—H1WB···O5i | 0.82 | 2.50 | 3.066 (6) | 127.2 |
O2W—H2WA···O5 | 0.82 | 1.85 | 2.631 (5) | 158.3 |
O2W—H2WB···O10ii | 0.82 | 2.08 | 2.783 (6) | 144.3 |
O3W—H3WA···O7i | 0.82 | 1.96 | 2.779 (6) | 174.9 |
O3W—H3WB···O3i | 0.82 | 1.84 | 2.646 (5) | 169.2 |
O4W—H4WA···O11iii | 0.82 | 2.07 | 2.837 (5) | 156.0 |
O4W—H4WB···O1 | 0.82 | 1.88 | 2.661 (5) | 158.2 |
O5W—H5WA···O6Wiv | 0.82 | 2.17 | 2.943 (5) | 158.4 |
O5W—H5WB···O1i | 0.82 | 1.84 | 2.652 (5) | 168.4 |
O6W—H6WA···O6 | 0.82 | 1.87 | 2.684 (5) | 168.6 |
O6W—H6WB···O11v | 0.82 | 1.90 | 2.717 (5) | 171.3 |
O7W—H7WA···O7i | 0.82 | 2.15 | 2.875 (6) | 147.0 |
O7W—H7WB···O9vi | 0.82 | 1.88 | 2.688 (5) | 166.2 |
O8W—H8WA···O3 | 0.82 | 2.09 | 2.784 (6) | 141.5 |
O8W—H8WB···O8 | 0.82 | 1.92 | 2.738 (5) | 173.7 |
O9W—H9WA···O2 | 0.82 | 1.88 | 2.666 (5) | 160.5 |
O9W—H9WB···O9v | 0.82 | 1.98 | 2.788 (5) | 167.5 |
O10W—H10W···O12vi | 0.82 | 1.97 | 2.783 (5) | 175.0 |
O10W—HW10···O2Wvi | 0.82 | 2.39 | 2.900 (5) | 121.5 |
O11W—H11W···O6i | 0.82 | 1.98 | 2.786 (6) | 167.7 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) x, y+1, z−1; (iv) x−1, y+1, z; (v) x+1, y, z−1; (vi) x, y, z−1. |
The self-assembly of coordination polymers and the crystal engineering of metal–organic coordination frameworks have recently attracted great interest, owing to the interesting molecular topologies and potential application as functional materials (Batten & Robson, 1998; Yan & Huang, 2010; Eddaoudi et al., 2001; Dietzel et al., 2005; Chen et al., 2010; Zhang et al., 2010.). 4,4'-Bipyridine (4,4'-bipy) has been widely used as a bridging ligand to construct interesting one-, two- and three-dimensional coordination polymer networks, owing to its rod-like rigidity and length (Lu et al., 1998; Lah & Leban, 2006; Lian et al., 2007; Bo et al., 2008; Li et al., 2009; Zhong et al., 2011). Some interesting coordination polymers assembled with 4,4'-bipy have been reported, showing various structural motifs, such as [Co(SO4)(C10H8N2)(H2O)3].2C2H6O2 (Lu et al., 2006), [Co2(OH)2(4,4'-bipy)8(H2O)2](NO3)2.2(4,4'-bipy).10H2O (Luachan et al., 2007), [Co2(4,4'-bipy)2(SO4)2(H2O)6].4H2O (Prior et al., 2011), [Co(SO4)(4,4'-bipy)(H2O)3].2H2O and [CoCl2(DMSO)2(4,4'-bipy)] (DMSO is dimethyl sulfoxide; Lu et al., 1998). In the present work, we describe the synthesis and structure of a novel complex with 4,4'-bipy coordinated to CoII metal centres, namely {[Co(H2O)6][Co(SO4)2(4,4'-bipy)(H2O)2][Co(SO4)(4,4'-bipy)(H2O)3]}n, (I), which displays a three-dimensional supramolecular network with two kinds of one-dimensional chains and was obtained via a solvothermal reaction.
Part of the structure of (I) is shown in Fig. 1. There are three types of crystallographically independent Co2+ centres, i.e. Co1, Co2 and Co3. Atom Co1 is coordinated by atoms N3 and N4 from bridging 4,4'-bipy ligands occupying the axial positions, atom O4 from a monodentate sulfate ion and water molecules O3W, O4W and O5W occupying the equatorial sites (Fig. 1 and Table 1). Atoms Co1, O4, O3W, O4W and O5W are almost coplanar, the mean deviation from the plane being 0.060 Å. The cis bond angles around each Co1 centre are in the range 85.6 (2)–93.0 (1)° (Fig. 1 and Table 1). The Co2 coordination environment is very similar to that of Co1, with Co2 being octahedrally trans-coordinated in a monodentate mode by sulfate anions and water molecules [Co2—O distances = 2.108 (4) to 2.148 (4) Å]. Atoms N1 and N2 from two symmetry-related 4,4'-bipy ligands occupy the axial positions. The cis bond angles around each Co2 centre lie in the range 87.8 (2)–93.6 (2)° (Table 1 and Fig. 1). The Co3 centre is surrounded by six aqua ligands, having an octahedral geometry. The 4,4'-bipy as bridging ligand links the same CoII centres resulting in two types of one-dimensional linear chain, namely neutral [Co(SO4)(4,4'-bipy)(H2O)3]n chains (bipy–Co1–bipy, chain A) and anionic [Co(SO4)2(4,4'-bipy)(H2O)2]n chains (bipy–Co2–bipy, chain B). The presence of pseudosymmetry in the structure suggests the higher-symmetry space group P1, but attempts to refine the structure in this space group resulted in an unsatisfactory model because of the asymmetry in the coordination environment of the Co2 metal centre. The separation of neighbouring CoII centres in chain A [11.462 (2) Å] is a little longer than that observed in chain B [11.246 (2) Å]. This can be attributed to the coplanarity of the pyridine rings of the bridging 4,4'-bipy ligand in the A chain [dihedral angle between the pyridine rings = 0.9 (2)°], while the pyridine rings of the bridging 4,4'-bipy ligand coordinated to the Co2 atom are puckered in the B chain [corresponding dihedral angle = 8.1 (2)°]. Chains A and B are each arranged in a cross-like fashion, intersecting at the mid-points of the 4,4'-bipy ligands, resulting in rhombic channels (10.504 × 12.208 Å) along the a axis. The [Co(H2O)6]2+ complex cations guest in the structure channels (Fig. 2). Numerous classical O—H···O hydrogen-bonding interactions (Fig. 3 and Table 2) involving the coordinated water molecules and the sulfate ligands result in a three-dimensional supramolecular network.