Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102001579/vj1159sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102001579/vj1159Isup2.hkl |
CCDC reference: 182990
A mixture of CoSO4·7H2O (0.10 g, 0.36 mmol), 4,4'-bipyridine·2H2O (0.05 g, 0.26 mmol) and benzene-1,2,4,5-tetracarboxylic acid anhydride (0.10 g, 0.46 mmol) in H2O (18 ml) was sealed in a 30 ml Teflon-lined stainless steel vessel and heated at 443 K for 6 d under autogeneous pressure. After the reaction, the vessel was slowly cooled to room temperature and red crystals of (I) were produced.
All H atoms were clearly visible in different maps. All H atoms were positioned geometrically and included as riding atoms, with O—H = 0.78–1.03 Å and C—H = 0.93 Å, and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O). Are these the correct restraints? The highest residual peak (0.86 e Å-3) is at (0.2765, 0.1671, 0.1238), which is 1.03 Å from O1; the deepest hole (-0.47 e Å-3) is at (0.2849, 0.0641, 0.0377), which is 0.48 Å from H1A.
Data collection: SMART (Siemens, 1996); cell refinement: SMART and SAINT (Siemens, 1994); data reduction: SMART and SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.
[Co2(C10H8N2)2(H2O)8](C10H2O8)·2H2O | F(000) = 1776 |
Mr = 860.50 | Dx = 1.610 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 20.0909 (4) Å | Cell parameters from 3537 reflections |
b = 11.3466 (1) Å | θ = 2.0–25.0° |
c = 15.6407 (4) Å | µ = 1.02 mm−1 |
β = 95.476 (1)° | T = 293 K |
V = 3549.2 (1) Å3 | Prism, red |
Z = 4 | 0.43 × 0.28 × 0.20 mm |
Siemens SMART CCD area-detector diffractometer | 3129 independent reflections |
Radiation source: fine-focus sealed tube | 2634 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −19→23 |
Tmin = 0.640, Tmax = 0.815 | k = −11→13 |
5567 measured reflections | l = −11→18 |
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)] = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.117 | w = 1/[σ2(Fo2) + (0.0344P)2 + 19.8931P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
3129 reflections | Δρmax = 0.86 e Å−3 |
258 parameters | Δρmin = −0.47 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.000071 (1) |
[Co2(C10H8N2)2(H2O)8](C10H2O8)·2H2O | V = 3549.2 (1) Å3 |
Mr = 860.50 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 20.0909 (4) Å | µ = 1.02 mm−1 |
b = 11.3466 (1) Å | T = 293 K |
c = 15.6407 (4) Å | 0.43 × 0.28 × 0.20 mm |
β = 95.476 (1)° |
Siemens SMART CCD area-detector diffractometer | 3129 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2634 reflections with I > 2σ(I) |
Tmin = 0.640, Tmax = 0.815 | Rint = 0.026 |
5567 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0344P)2 + 19.8931P] where P = (Fo2 + 2Fc2)/3 |
3129 reflections | Δρmax = 0.86 e Å−3 |
258 parameters | Δρmin = −0.47 e Å−3 |
Experimental. Spectroscopic analysis: IR (solid KBr pellet, v, cm-1): 1603 (s), 1581 (s), 1491 (m), 1414 (s), 1367 (s), 1325 (m), 1223 (m), 1140 (m), 1068 (m), 1051 (m), 1012 (m), 1003 (w), 928 (w), 862 (w), 816 (m), 731 (w), 636 (m), 629 (m), 523 (m). |
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 | 0.5000 | 0.00017 (6) | 0.2500 | 0.0243 (2) | |
Co2 | 0.2500 | −0.2500 | 0.5000 | 0.0262 (2) | |
O1 | 0.21289 (15) | −0.3873 (3) | 0.4256 (2) | 0.0467 (8) | |
H1A | 0.1915 | −0.4313 | 0.4543 | 0.070* | |
H1B | 0.2364 | −0.4290 | 0.3889 | 0.070* | |
O2 | 0.39327 (13) | −0.0092 (2) | 0.22512 (17) | 0.0343 (6) | |
H2A | 0.3829 | −0.0064 | 0.1732 | 0.051* | |
H2B | 0.3650 | 0.0104 | 0.2531 | 0.051* | |
O3 | 0.50956 (13) | −0.0050 (2) | 0.11931 (16) | 0.0353 (6) | |
H3B | 0.5318 | 0.0515 | 0.1060 | 0.053* | |
H3A | 0.4752 | −0.0157 | 0.0880 | 0.053* | |
O4 | 0.27910 (16) | −0.1715 (3) | 0.38541 (19) | 0.0495 (8) | |
H4B | 0.2845 | −0.1005 | 0.3929 | 0.074* | |
H4A | 0.2568 | −0.2019 | 0.3343 | 0.074* | |
O5 | 0.08718 (13) | −0.6592 (2) | 0.55844 (19) | 0.0383 (7) | |
O6 | 0.11521 (13) | −0.5317 (2) | 0.45967 (19) | 0.0381 (7) | |
O7 | 0.20436 (15) | −0.5620 (2) | 0.67514 (18) | 0.0389 (7) | |
O8 | 0.22173 (17) | −0.7441 (3) | 0.72660 (18) | 0.0484 (8) | |
O101 | 0.28888 (18) | −0.5089 (3) | 0.3184 (2) | 0.0518 (8) | |
H10A | 0.2634 | −0.4771 | 0.2626 | 0.083 (19)* | |
H10B | 0.2837 | −0.5912 | 0.3098 | 0.09 (2)* | |
C1 | 0.5563 (2) | 0.2506 (4) | 0.2538 (3) | 0.0469 (12) | |
H1C | 0.5965 | 0.2097 | 0.2568 | 0.056* | |
C2 | 0.5498 (2) | −0.2493 (3) | 0.2202 (3) | 0.0422 (11) | |
H2C | 0.5848 | −0.2080 | 0.1991 | 0.051* | |
C3 | 0.0351 (2) | −0.1549 (4) | 0.4961 (3) | 0.0481 (12) | |
H3C | −0.0038 | −0.1988 | 0.4980 | 0.058* | |
C4 | 0.1499 (2) | −0.0396 (4) | 0.4841 (3) | 0.0498 (12) | |
H4C | 0.1891 | 0.0019 | 0.4780 | 0.060* | |
C5 | 0.21783 (19) | −0.6702 (4) | 0.6674 (2) | 0.0323 (9) | |
C6 | 0.0918 (2) | 0.0239 (4) | 0.4892 (4) | 0.0519 (13) | |
H6A | 0.0931 | 0.1058 | 0.4879 | 0.062* | |
C7 | 0.5585 (2) | 0.3720 (4) | 0.2536 (4) | 0.0499 (12) | |
H7A | 0.5994 | 0.4107 | 0.2558 | 0.060* | |
C8 | 0.0955 (2) | −0.2118 (4) | 0.4933 (3) | 0.0481 (12) | |
H8A | 0.0959 | −0.2937 | 0.4955 | 0.058* | |
C9 | 0.5517 (2) | −0.3699 (4) | 0.2194 (3) | 0.0414 (10) | |
H9A | 0.5875 | −0.4088 | 0.1985 | 0.050* | |
C10 | 0.12666 (18) | −0.6200 (3) | 0.5093 (2) | 0.0269 (8) | |
C11 | 0.23237 (18) | −0.7127 (3) | 0.5800 (2) | 0.0246 (8) | |
C12 | 0.19192 (17) | −0.6834 (3) | 0.5059 (2) | 0.0251 (8) | |
C13 | 0.03188 (19) | −0.0328 (4) | 0.4963 (3) | 0.0342 (9) | |
C14 | 0.21005 (18) | −0.7209 (3) | 0.4265 (2) | 0.0270 (8) | |
H14A | 0.1831 | −0.7012 | 0.3769 | 0.032* | |
C15 | 0.5000 | 0.4359 (5) | 0.2500 | 0.0366 (13) | |
C16 | 0.5000 | −0.4342 (5) | 0.2500 | 0.0347 (13) | |
N1 | 0.15326 (16) | −0.1565 (3) | 0.4876 (2) | 0.0345 (8) | |
N2 | 0.5000 | −0.1881 (4) | 0.2500 | 0.0341 (11) | |
N3 | 0.5000 | 0.1886 (4) | 0.2500 | 0.0333 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0276 (4) | 0.0175 (4) | 0.0288 (4) | 0.000 | 0.0078 (3) | 0.000 |
Co2 | 0.0255 (4) | 0.0231 (4) | 0.0303 (4) | 0.0008 (3) | 0.0041 (3) | −0.0009 (3) |
O1 | 0.0427 (17) | 0.0419 (18) | 0.0566 (19) | −0.0034 (14) | 0.0102 (14) | −0.0168 (15) |
O2 | 0.0316 (14) | 0.0398 (16) | 0.0325 (14) | −0.0007 (12) | 0.0078 (11) | −0.0012 (12) |
O3 | 0.0357 (15) | 0.0396 (16) | 0.0314 (14) | −0.0130 (12) | 0.0072 (11) | 0.0017 (12) |
O4 | 0.065 (2) | 0.0431 (18) | 0.0407 (17) | −0.0040 (16) | 0.0067 (15) | 0.0037 (14) |
O5 | 0.0334 (15) | 0.0342 (16) | 0.0498 (17) | 0.0071 (12) | 0.0168 (13) | 0.0059 (13) |
O6 | 0.0293 (14) | 0.0365 (16) | 0.0493 (17) | 0.0117 (12) | 0.0078 (12) | 0.0102 (13) |
O7 | 0.0512 (18) | 0.0283 (15) | 0.0390 (16) | 0.0033 (13) | 0.0130 (13) | −0.0086 (12) |
O8 | 0.069 (2) | 0.0458 (18) | 0.0314 (16) | 0.0172 (16) | 0.0109 (14) | 0.0075 (14) |
O101 | 0.060 (2) | 0.043 (2) | 0.052 (2) | 0.0065 (17) | 0.0061 (16) | 0.0031 (16) |
C1 | 0.035 (2) | 0.023 (2) | 0.084 (4) | 0.0018 (18) | 0.015 (2) | −0.006 (2) |
C2 | 0.048 (3) | 0.023 (2) | 0.060 (3) | 0.0003 (19) | 0.026 (2) | 0.0016 (19) |
C3 | 0.029 (2) | 0.033 (2) | 0.084 (4) | −0.0032 (18) | 0.009 (2) | −0.011 (2) |
C4 | 0.026 (2) | 0.038 (3) | 0.086 (4) | 0.0045 (18) | 0.009 (2) | 0.017 (2) |
C5 | 0.031 (2) | 0.035 (2) | 0.031 (2) | 0.0048 (17) | 0.0054 (16) | 0.0004 (17) |
C6 | 0.034 (2) | 0.024 (2) | 0.098 (4) | 0.0036 (18) | 0.007 (2) | 0.013 (2) |
C7 | 0.040 (3) | 0.022 (2) | 0.090 (4) | −0.0069 (19) | 0.015 (2) | −0.005 (2) |
C8 | 0.034 (2) | 0.030 (2) | 0.081 (3) | 0.0034 (18) | 0.007 (2) | −0.013 (2) |
C9 | 0.042 (2) | 0.025 (2) | 0.061 (3) | 0.0009 (18) | 0.024 (2) | −0.0060 (19) |
C10 | 0.0274 (19) | 0.0209 (18) | 0.033 (2) | 0.0056 (15) | 0.0039 (16) | −0.0044 (15) |
C11 | 0.0279 (19) | 0.0178 (17) | 0.0290 (19) | 0.0025 (14) | 0.0078 (15) | −0.0004 (14) |
C12 | 0.0216 (17) | 0.0201 (18) | 0.0342 (19) | 0.0017 (14) | 0.0058 (15) | 0.0013 (15) |
C13 | 0.027 (2) | 0.033 (2) | 0.043 (2) | 0.0011 (17) | 0.0029 (17) | 0.0002 (17) |
C14 | 0.0276 (19) | 0.0259 (19) | 0.0269 (18) | 0.0056 (15) | −0.0009 (14) | 0.0036 (15) |
C15 | 0.043 (3) | 0.025 (3) | 0.044 (3) | 0.000 | 0.012 (3) | 0.000 |
C16 | 0.040 (3) | 0.026 (3) | 0.041 (3) | 0.000 | 0.012 (3) | 0.000 |
N1 | 0.0282 (17) | 0.0315 (19) | 0.044 (2) | 0.0030 (14) | 0.0030 (14) | −0.0005 (15) |
N2 | 0.044 (3) | 0.021 (2) | 0.040 (3) | 0.000 | 0.016 (2) | 0.000 |
N3 | 0.040 (3) | 0.017 (2) | 0.044 (3) | 0.000 | 0.011 (2) | 0.000 |
Co1—O3i | 2.072 (3) | C2—C9 | 1.369 (6) |
Co1—O3 | 2.072 (3) | C2—H2C | 0.9300 |
Co1—N2 | 2.136 (4) | C3—C8 | 1.379 (6) |
Co1—N3 | 2.138 (4) | C3—C13 | 1.387 (6) |
Co1—O2 | 2.145 (3) | C3—H3C | 0.9300 |
Co1—O2i | 2.145 (3) | C4—N1 | 1.329 (6) |
Co2—O1 | 2.043 (3) | C4—C6 | 1.381 (6) |
Co2—O1ii | 2.043 (3) | C4—H4C | 0.9300 |
Co2—O4ii | 2.133 (3) | C5—C11 | 1.504 (5) |
Co2—O4 | 2.133 (3) | C6—C13 | 1.378 (6) |
Co2—N1 | 2.207 (3) | C6—H6A | 0.9300 |
Co2—N1ii | 2.207 (3) | C7—C15 | 1.377 (5) |
O1—H1A | 0.8200 | C7—H7A | 0.9300 |
O1—H1B | 0.9107 | C8—N1 | 1.329 (5) |
O2—H2A | 0.8200 | C8—H8A | 0.9300 |
O2—H2B | 0.7822 | C9—C16 | 1.391 (5) |
O3—H3B | 0.8200 | C9—H9A | 0.9300 |
O3—H3A | 0.8164 | C10—C12 | 1.501 (5) |
O4—H4B | 0.8200 | C11—C12 | 1.391 (5) |
O4—H4A | 0.9440 | C11—C14iii | 1.392 (5) |
O5—C10 | 1.238 (4) | C12—C14 | 1.394 (5) |
O6—C10 | 1.275 (4) | C13—C13iv | 1.495 (8) |
O7—C5 | 1.265 (5) | C14—C11iii | 1.392 (5) |
O8—C5 | 1.247 (5) | C14—H14A | 0.9300 |
O101—H10A | 1.033 | C15—C7i | 1.377 (5) |
O101—H10B | 0.9482 | C15—C16v | 1.473 (8) |
C1—N3 | 1.328 (5) | C16—C9i | 1.391 (5) |
C1—C7 | 1.379 (6) | C16—C15vi | 1.473 (8) |
C1—H1C | 0.9300 | N2—C2i | 1.338 (5) |
C2—N2 | 1.338 (5) | N3—C1i | 1.328 (5) |
O3—Co1—O3i | 176.8 (2) | C8—C3—H3C | 119.7 |
O3—Co1—N2 | 88.4 (1) | C13—C3—H3C | 119.7 |
O3i—Co1—N2 | 88.4 (1) | N1—C4—C6 | 123.9 (4) |
O3—Co1—N3 | 91.6 (1) | N1—C4—H4C | 118.0 |
O3i—Co1—N3 | 91.6 (1) | C6—C4—H4C | 118.0 |
N2—Co1—N3 | 180.0 (1) | O8—C5—O7 | 125.5 (4) |
O3—Co1—O2 | 90.3 (1) | O8—C5—C11 | 117.1 (3) |
O3i—Co1—O2 | 89.6 (1) | O7—C5—C11 | 117.4 (3) |
N2—Co1—O2 | 87.2 (1) | C13—C6—C4 | 120.7 (4) |
N3—Co1—O2 | 92.8 (1) | C13—C6—H6A | 119.6 |
O3—Co1—O2i | 89.6 (1) | C4—C6—H6A | 119.6 |
O3i—Co1—O2i | 90.3 (1) | C15—C7—C1 | 119.9 (4) |
N2—Co1—O2i | 87.2 (1) | C15—C7—H7A | 120.0 |
N3—Co1—O2i | 92.8 (1) | C1—C7—H7A | 120.0 |
O2—Co1—O2i | 174.3 (1) | N1—C8—C3 | 123.9 (4) |
O1—Co2—O1ii | 180.0 | N1—C8—H8A | 118.1 |
O1—Co2—O4ii | 92.6 (1) | C3—C8—H8A | 118.1 |
O1ii—Co2—O4ii | 87.4 (1) | C2—C9—C16 | 120.0 (4) |
O1—Co2—O4 | 87.4 (1) | C2—C9—H9A | 120.0 |
O1ii—Co2—O4 | 92.6 (1) | C16—C9—H9A | 120.0 |
O4ii—Co2—O4 | 180.0 | O5—C10—O6 | 124.8 (3) |
O1—Co2—N1 | 92.6 (1) | O5—C10—C12 | 117.6 (3) |
O1ii—Co2—N1 | 87.4 (1) | O6—C10—C12 | 117.5 (3) |
O4ii—Co2—N1 | 88.0 (1) | C12—C11—C14iii | 119.5 (3) |
O4—Co2—N1 | 92.0 (1) | C12—C11—C5 | 122.1 (3) |
O1—Co2—N1ii | 87.4 (1) | C14iii—C11—C5 | 118.4 (3) |
O1ii—Co2—N1ii | 92.6 (1) | C11—C12—C14 | 119.2 (3) |
O4ii—Co2—N1ii | 92.0 (1) | C11—C12—C10 | 121.9 (3) |
O4—Co2—N1ii | 88.0 (1) | C14—C12—C10 | 118.8 (3) |
N1—Co2—N1ii | 180.0 | C6—C13—C3 | 115.1 (4) |
Co2—O1—H1A | 109.5 | C6—C13—C13iv | 122.4 (5) |
Co2—O1—H1B | 124.9 | C3—C13—C13iv | 122.5 (5) |
H1A—O1—H1B | 111.1 | C11iii—C14—C12 | 121.3 (3) |
Co1—O2—H2A | 109.5 | C11iii—C14—H14A | 119.3 |
Co1—O2—H2B | 130.7 | C12—C14—H14A | 119.3 |
H2A—O2—H2B | 114.5 | C7i—C15—C7 | 116.5 (5) |
Co1—O3—H3B | 109.5 | C7i—C15—C16v | 121.8 (3) |
Co1—O3—H3A | 116.4 | C7—C15—C16v | 121.8 (3) |
H3B—O3—H3A | 114.4 | C9i—C16—C9 | 116.7 (5) |
Co2—O4—H4B | 109.5 | C9i—C16—C15vi | 121.7 (3) |
Co2—O4—H4A | 114.4 | C9—C16—C15vi | 121.7 (3) |
H4B—O4—H4A | 121.8 | C4—N1—C8 | 115.7 (4) |
H10A—O101—H10B | 100.7 | C4—N1—Co2 | 121.6 (3) |
N3—C1—C7 | 123.8 (4) | C8—N1—Co2 | 122.3 (3) |
N3—C1—H1C | 118.1 | C2i—N2—C2 | 117.5 (5) |
C7—C1—H1C | 118.1 | C2i—N2—Co1 | 121.3 (2) |
N2—C2—C9 | 122.9 (4) | C2—N2—Co1 | 121.3 (2) |
N2—C2—H2C | 118.5 | C1i—N3—C1 | 116.0 (5) |
C9—C2—H2C | 118.5 | C1i—N3—Co1 | 122.0 (2) |
C8—C3—C13 | 120.6 (4) | C1—N3—Co1 | 122.0 (2) |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1/2, −y−1/2, −z+1; (iii) −x+1/2, −y−3/2, −z+1; (iv) −x, −y, −z+1; (v) x, y+1, z; (vi) x, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O6 | 0.82 | 1.92 | 2.650 (4) | 148 |
O1—H1B···O101 | 0.91 | 1.84 | 2.745 (5) | 176 |
O2—H2A···O6vii | 0.82 | 2.10 | 2.890 (4) | 161 |
O2—H2B···O7ii | 0.78 | 1.96 | 2.742 (4) | 179 |
O3—H3B···O5viii | 0.82 | 1.86 | 2.663 (4) | 168 |
O3—H3A···O6vii | 0.82 | 1.91 | 2.704 (4) | 166 |
O4—H4B···O7ii | 0.82 | 2.15 | 2.843 (4) | 142 |
O4—H4A···O8ix | 0.94 | 1.87 | 2.805 (4) | 173 |
O101—H10A···O7ix | 1.03 | 1.78 | 2.797 (5) | 168 |
O101—H10B···O8iii | 0.95 | 1.95 | 2.893 (5) | 170 |
Symmetry codes: (ii) −x+1/2, −y−1/2, −z+1; (iii) −x+1/2, −y−3/2, −z+1; (vii) −x+1/2, y+1/2, −z+1/2; (viii) x+1/2, −y−1/2, z−1/2; (ix) x, −y−1, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Co2(C10H8N2)2(H2O)8](C10H2O8)·2H2O |
Mr | 860.50 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 20.0909 (4), 11.3466 (1), 15.6407 (4) |
β (°) | 95.476 (1) |
V (Å3) | 3549.2 (1) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.02 |
Crystal size (mm) | 0.43 × 0.28 × 0.20 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.640, 0.815 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5567, 3129, 2634 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.117, 1.09 |
No. of reflections | 3129 |
No. of parameters | 258 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
w = 1/[σ2(Fo2) + (0.0344P)2 + 19.8931P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.86, −0.47 |
Computer programs: SMART (Siemens, 1996), SMART and SAINT (Siemens, 1994), SMART and SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.
Co1—O3 | 2.072 (3) | Co2—O1 | 2.043 (3) |
Co1—N2 | 2.136 (4) | Co2—O4 | 2.133 (3) |
Co1—N3 | 2.138 (4) | Co2—N1 | 2.207 (3) |
Co1—O2 | 2.145 (3) | ||
O3—Co1—O3i | 176.8 (2) | O1—Co2—O4ii | 92.6 (1) |
O3—Co1—N2 | 88.4 (1) | O1—Co2—O4 | 87.4 (1) |
O3—Co1—N3 | 91.6 (1) | O4ii—Co2—O4 | 180.0 |
O3—Co1—O2 | 90.3 (1) | O1—Co2—N1 | 92.6 (1) |
N2—Co1—O2 | 87.2 (1) | O4—Co2—N1 | 92.0 (1) |
N3—Co1—O2 | 92.8 (1) | O1—Co2—N1ii | 87.4 (1) |
O3—Co1—O2i | 89.6 (1) | O4—Co2—N1ii | 88.0 (1) |
O2—Co1—O2i | 174.3 (1) | N1—Co2—N1ii | 180.0 |
O1—Co2—O1ii | 180.0 |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1/2, −y−1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O6 | 0.82 | 1.92 | 2.650 (4) | 148 |
O1—H1B···O101 | 0.91 | 1.84 | 2.745 (5) | 176 |
O2—H2A···O6iii | 0.82 | 2.10 | 2.890 (4) | 161 |
O2—H2B···O7ii | 0.78 | 1.96 | 2.742 (4) | 179 |
O3—H3B···O5iv | 0.82 | 1.86 | 2.663 (4) | 168 |
O3—H3A···O6iii | 0.82 | 1.91 | 2.704 (4) | 166 |
O4—H4B···O7ii | 0.82 | 2.15 | 2.843 (4) | 142 |
O4—H4A···O8v | 0.94 | 1.87 | 2.805 (4) | 173 |
O101—H10A···O7v | 1.03 | 1.78 | 2.797 (5) | 168 |
O101—H10B···O8vi | 0.95 | 1.95 | 2.893 (5) | 170 |
Symmetry codes: (ii) −x+1/2, −y−1/2, −z+1; (iii) −x+1/2, y+1/2, −z+1/2; (iv) x+1/2, −y−1/2, z−1/2; (v) x, −y−1, z−1/2; (vi) −x+1/2, −y−3/2, −z+1. |
Polymetallic materials, which are normally constructed by linking transition metal atoms through multidentate bridging ligands, have attracted much attention because of their intriguing topological structures and their potential for interesting applications (Yaghi et al., 1998; Hagrman et al., 1999; Philp & Stoddart, 1996). Complexes with the bridging bis(monodentate) ligand 4,4'-bipyridine (4,4'-bpy) are particularly interesting because of their interesting topological structures, as well as their potential application in areas such as ion exchange, catalysis, separation and magnetism (Kondo et al., 1997; Yaghi & Li, 1995; Fujita et al., 1994; Julve et al., 1987). Various preparative methods have been employed to obtain such materials. As part of our investigations on the hydrothermal synthesis of new polymeric complexes containing 4,4'-bpy and benzene-1,2,4,5-tetracarboxylic acid (H4btc), red single crystals of the title compound, (I), were obtained. \sch
As shown in Fig. 1, the crystal structure of (I) comprises two 4,4'-bpy-bridged crystallographically symmetry-independent CoII centres, water molecules and btc(4-) anions. Bond distances and angles are in good agreement with the values reported for related one-dimensional CoII-4,4'-bpy complexes (Tong et al., 1998; Lu et al., 1998; Dong et al., 2000).
One CoII atom is located at an inversion centre and the other is on a crystallographic twofold axis. Each crystallographically independent CoII centre displays six-coordinate octahedral geometry, coordinated by two N atoms from 4,4'-bpy at the axial positions [Co—N 2.136 (4)–2.207 (3) Å], and four water molecules at the equatorial positions [Co—O 2.043 (3)–2.145 (3) Å], with bond angles involving neighbouring atoms ranging from 87.2 (1) to 92.8 (1)°. These slightly distorted octahedral CoII centres are extended into one-dimensional chains through intervening 4,4'-bpy ligands and are separated by about 11.44 Å.
It is interesting to note that these two one-dimensional polymeric cation arrays, which have a fold of about 60°, are packed into a beautiful three-dimensional architecture through hydrogen bonding (Fig. 2). The btc(4-) anions link the chains through hydrogen bonds involving the non-metalate O atoms of the carboxylate groups and the aqua ligands, with O···O distances in the range 2.650 (4)–2.890 (4) Å.
Finally, it should be noted that the average distance between the O atoms of the solvent water molecules and those of the aqua ligands is about 2.745 (5) Å, while the distances between the solvent O atoms and the O atoms of the carboxylate groups of the btc ligands range from 2.797 (5) to 2.893 (5) Å. Obviously, there is a complex hydrogen-bonding scheme in the packing of (I).