Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801010479/tk6029sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801010479/tk6029Isup2.hkl |
CCDC reference: 170751
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.006 Å
- R factor = 0.037
- wR factor = 0.103
- Data-to-parameter ratio = 14.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_213 Alert C Atom C2 has ADP max/min Ratio ........... 3.60
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
A solution of melamine (0.04 g, 0.33 mmol) and salicylahdehyde (0.12 g, 1 mmol) in methanol solution (20 ml) was heated to 333 K for 3 h with vigorous stirring. After cooling, NaOH (0.04 g, 1 mmol) in methanol (5 ml) was added to the colorless solution. Co(NO3)2·6H2O (0.15 g, 0.5 mmol) was then added and the reaction mixture was stirred for 1 h to give a red solution which was filtered. Deep-red and pale-red crystalline complexes were obtained by keeping the resultant solution open to the air for a week. A deep-red single-crystal was selected for X-ray diffraction.
H-atom positions were generated geometrically and allowed to ride on their respective parent carbon atoms. The O—H atoms were refined with isotropic displacement parameters but fixed in the final cycles of least-squares refinement.
Data collection: SMART (Siemens, 1994); cell refinement: SMART; data reduction: SMART; 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.
Fig. 1. The structure of [Co4(OMe)4L4(MeOH)4]. Displacement ellipsoids are plotted at the 50% probability level (Sheldrick, 1997) |
[Co4(CH3O)4(C7H5O2)4(CH4O)4] | F(000) = 2000 |
Mr = 972.46 | Dx = 1.518 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 14.6546 (5) Å | Cell parameters from 154 reflections |
b = 14.7082 (5) Å | θ = 3.1–20.7° |
c = 20.3235 (7) Å | µ = 1.60 mm−1 |
β = 103.789 (1)° | T = 293 K |
V = 4254.3 (3) Å3 | Block, dark-red |
Z = 4 | 0.50 × 0.45 × 0.45 mm |
Siemens SMART CCD diffractometer | 7411 independent reflections |
Radiation source: fine-focus sealed tube | 5377 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
ω scans | θmax = 24.9°, θmin = 1.6° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −17→17 |
Tmin = 0.454, Tmax = 0.487 | k = −12→17 |
15156 measured reflections | l = −10→24 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0537P)2 + 0.6296P] where P = (Fo2 + 2Fc2)/3 |
7411 reflections | (Δ/σ)max = 0.001 |
521 parameters | Δρmax = 0.58 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
[Co4(CH3O)4(C7H5O2)4(CH4O)4] | V = 4254.3 (3) Å3 |
Mr = 972.46 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.6546 (5) Å | µ = 1.60 mm−1 |
b = 14.7082 (5) Å | T = 293 K |
c = 20.3235 (7) Å | 0.50 × 0.45 × 0.45 mm |
β = 103.789 (1)° |
Siemens SMART CCD diffractometer | 7411 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 5377 reflections with I > 2σ(I) |
Tmin = 0.454, Tmax = 0.487 | Rint = 0.039 |
15156 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.58 e Å−3 |
7411 reflections | Δρmin = −0.37 e Å−3 |
521 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 | 0.61010 (3) | 0.26149 (3) | 0.03310 (2) | 0.03916 (14) | |
Co2 | 0.70158 (3) | 0.24802 (3) | −0.08950 (2) | 0.03774 (13) | |
Co3 | 0.82178 (3) | 0.30894 (3) | 0.05690 (2) | 0.03873 (13) | |
Co4 | 0.75875 (3) | 0.10739 (3) | 0.02696 (2) | 0.03858 (13) | |
O1 | 0.6129 (2) | 0.36420 (19) | 0.10860 (13) | 0.0554 (7) | |
H0A | 0.664 (3) | 0.381 (2) | 0.1210 (18) | 0.046 (12)* | |
O2 | 0.56573 (19) | 0.2969 (2) | −0.14293 (13) | 0.0632 (8) | |
H0B | 0.536 (3) | 0.310 (3) | −0.112 (2) | 0.095 (18)* | |
O3 | 0.94220 (17) | 0.2422 (2) | 0.12119 (13) | 0.0546 (8) | |
H0C | 0.937 (3) | 0.191 (2) | 0.1168 (18) | 0.034 (12)* | |
O4 | 0.7689 (2) | 0.0147 (2) | −0.05559 (15) | 0.0576 (7) | |
H0D | 0.754 (3) | 0.041 (3) | −0.086 (2) | 0.081 (18)* | |
O5 | 0.69698 (14) | 0.34157 (15) | −0.01468 (10) | 0.0379 (5) | |
O6 | 0.63723 (14) | 0.15938 (15) | −0.03310 (10) | 0.0381 (5) | |
O7 | 0.73533 (13) | 0.21335 (15) | 0.09075 (9) | 0.0366 (5) | |
O8 | 0.82575 (14) | 0.21275 (15) | −0.01710 (10) | 0.0370 (5) | |
O11 | 0.52403 (16) | 0.18250 (18) | 0.07986 (12) | 0.0557 (7) | |
O12 | 0.49213 (15) | 0.30573 (17) | −0.03334 (11) | 0.0499 (6) | |
O21 | 0.76493 (17) | 0.33054 (16) | −0.15137 (11) | 0.0509 (6) | |
O22 | 0.71430 (17) | 0.14363 (15) | −0.15242 (10) | 0.0481 (6) | |
O31 | 0.91173 (17) | 0.40862 (18) | 0.03044 (11) | 0.0546 (7) | |
O32 | 0.80070 (16) | 0.39746 (17) | 0.12793 (11) | 0.0514 (6) | |
O41 | 0.68988 (17) | 0.00369 (18) | 0.06603 (12) | 0.0536 (6) | |
O42 | 0.88034 (15) | 0.06955 (17) | 0.09166 (11) | 0.0503 (6) | |
C1 | 0.5456 (3) | 0.4347 (3) | 0.1060 (2) | 0.0766 (13) | |
H1A | 0.5636 | 0.4718 | 0.1458 | 0.115* | |
H1B | 0.4850 | 0.4084 | 0.1039 | 0.115* | |
H1C | 0.5427 | 0.4714 | 0.0665 | 0.115* | |
C2 | 0.5078 (5) | 0.2866 (7) | −0.2050 (3) | 0.208 (5) | |
H2A | 0.4513 | 0.3208 | −0.2076 | 0.311* | |
H2B | 0.4925 | 0.2234 | −0.2128 | 0.311* | |
H2C | 0.5386 | 0.3081 | −0.2388 | 0.311* | |
C3 | 1.0405 (2) | 0.2581 (3) | 0.1278 (2) | 0.0695 (12) | |
H3A | 1.0764 | 0.2164 | 0.1601 | 0.104* | |
H3B | 1.0556 | 0.3193 | 0.1429 | 0.104* | |
H3C | 1.0553 | 0.2494 | 0.0847 | 0.104* | |
C4 | 0.8537 (3) | −0.0334 (3) | −0.0574 (3) | 0.0854 (15) | |
H4A | 0.8434 | −0.0695 | −0.0978 | 0.128* | |
H4B | 0.8712 | −0.0721 | −0.0184 | 0.128* | |
H4C | 0.9032 | 0.0095 | −0.0571 | 0.128* | |
C5 | 0.6783 (3) | 0.4354 (3) | −0.03076 (18) | 0.0556 (10) | |
H5A | 0.6789 | 0.4687 | 0.0100 | 0.083* | |
H5B | 0.6179 | 0.4413 | −0.0616 | 0.083* | |
H5C | 0.7258 | 0.4592 | −0.0514 | 0.083* | |
C6 | 0.5617 (2) | 0.0999 (3) | −0.06551 (18) | 0.0520 (9) | |
H6A | 0.5107 | 0.1355 | −0.0914 | 0.078* | |
H6B | 0.5405 | 0.0660 | −0.0317 | 0.078* | |
H6C | 0.5837 | 0.0588 | −0.0950 | 0.078* | |
C7 | 0.7481 (2) | 0.1963 (3) | 0.16190 (15) | 0.0523 (10) | |
H7A | 0.8106 | 0.1742 | 0.1802 | 0.078* | |
H7B | 0.7034 | 0.1516 | 0.1686 | 0.078* | |
H7C | 0.7387 | 0.2517 | 0.1844 | 0.078* | |
C8 | 0.9097 (2) | 0.2004 (3) | −0.03997 (18) | 0.0501 (9) | |
H8A | 0.9000 | 0.1537 | −0.0740 | 0.075* | |
H8B | 0.9600 | 0.1829 | −0.0025 | 0.075* | |
H8C | 0.9258 | 0.2563 | −0.0589 | 0.075* | |
C11 | 0.4378 (3) | 0.1822 (3) | 0.06512 (18) | 0.0577 (10) | |
H11A | 0.4098 | 0.1433 | 0.0905 | 0.069* | |
C12 | 0.3741 (2) | 0.2341 (3) | 0.01376 (17) | 0.0483 (9) | |
C13 | 0.2762 (3) | 0.2229 (3) | 0.0092 (2) | 0.0679 (12) | |
H13A | 0.2571 | 0.1846 | 0.0397 | 0.082* | |
C14 | 0.2099 (3) | 0.2665 (4) | −0.0386 (3) | 0.0818 (15) | |
H14A | 0.1465 | 0.2601 | −0.0396 | 0.098* | |
C15 | 0.2385 (3) | 0.3206 (3) | −0.0856 (3) | 0.0763 (13) | |
H15A | 0.1933 | 0.3492 | −0.1191 | 0.092* | |
C16 | 0.3320 (3) | 0.3331 (3) | −0.0841 (2) | 0.0635 (11) | |
H16A | 0.3486 | 0.3694 | −0.1168 | 0.076* | |
C17 | 0.4035 (2) | 0.2917 (3) | −0.03349 (17) | 0.0477 (9) | |
C21 | 0.7779 (2) | 0.3085 (2) | −0.20756 (16) | 0.0452 (9) | |
H21A | 0.8017 | 0.3541 | −0.2304 | 0.054* | |
C22 | 0.7615 (2) | 0.2234 (2) | −0.24203 (15) | 0.0369 (7) | |
C23 | 0.7787 (2) | 0.2180 (3) | −0.30763 (16) | 0.0448 (8) | |
H23A | 0.7999 | 0.2693 | −0.3262 | 0.054* | |
C24 | 0.7651 (3) | 0.1397 (3) | −0.34414 (17) | 0.0532 (10) | |
H24A | 0.7773 | 0.1373 | −0.3870 | 0.064* | |
C25 | 0.7326 (3) | 0.0633 (3) | −0.31676 (18) | 0.0580 (10) | |
H25A | 0.7220 | 0.0098 | −0.3418 | 0.070* | |
C26 | 0.7161 (3) | 0.0658 (3) | −0.25292 (18) | 0.0556 (10) | |
H26A | 0.6950 | 0.0133 | −0.2356 | 0.067* | |
C27 | 0.7299 (2) | 0.1449 (2) | −0.21295 (15) | 0.0388 (8) | |
C31 | 0.9500 (3) | 0.4691 (3) | 0.06939 (18) | 0.0576 (10) | |
H31A | 0.9949 | 0.5033 | 0.0549 | 0.069* | |
C32 | 0.9343 (2) | 0.4940 (2) | 0.13429 (17) | 0.0465 (9) | |
C33 | 0.9944 (3) | 0.5610 (3) | 0.1717 (2) | 0.0659 (11) | |
H33A | 1.0406 | 0.5869 | 0.1533 | 0.079* | |
C34 | 0.9861 (3) | 0.5885 (3) | 0.2341 (2) | 0.0794 (14) | |
H34A | 1.0260 | 0.6327 | 0.2580 | 0.095* | |
C35 | 0.9168 (3) | 0.5493 (3) | 0.2618 (2) | 0.0766 (14) | |
H35A | 0.9121 | 0.5660 | 0.3050 | 0.092* | |
C36 | 0.8556 (3) | 0.4865 (3) | 0.22591 (18) | 0.0621 (11) | |
H36A | 0.8086 | 0.4629 | 0.2448 | 0.075* | |
C37 | 0.8617 (2) | 0.4564 (2) | 0.16106 (16) | 0.0450 (9) | |
C41 | 0.7273 (3) | −0.0537 (3) | 0.10748 (17) | 0.0525 (9) | |
H41A | 0.6877 | −0.0984 | 0.1173 | 0.063* | |
C42 | 0.8247 (3) | −0.0612 (2) | 0.14293 (16) | 0.0493 (9) | |
C43 | 0.8490 (4) | −0.1332 (3) | 0.1902 (2) | 0.0726 (12) | |
H43A | 0.8024 | −0.1733 | 0.1960 | 0.087* | |
C44 | 0.9383 (4) | −0.1454 (4) | 0.2273 (2) | 0.0900 (16) | |
H44A | 0.9528 | −0.1936 | 0.2576 | 0.108* | |
C45 | 1.0071 (3) | −0.0855 (4) | 0.2197 (2) | 0.0864 (16) | |
H45A | 1.0682 | −0.0937 | 0.2453 | 0.104* | |
C46 | 0.9876 (3) | −0.0133 (3) | 0.1748 (2) | 0.0679 (12) | |
H46A | 1.0356 | 0.0262 | 0.1711 | 0.082* | |
C47 | 0.8957 (2) | 0.0012 (3) | 0.13453 (16) | 0.0487 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0316 (2) | 0.0468 (3) | 0.0380 (2) | 0.0009 (2) | 0.00628 (18) | 0.0036 (2) |
Co2 | 0.0417 (2) | 0.0391 (3) | 0.0308 (2) | −0.0032 (2) | 0.00539 (18) | 0.00050 (19) |
Co3 | 0.0354 (2) | 0.0461 (3) | 0.0342 (2) | −0.0082 (2) | 0.00738 (17) | −0.0046 (2) |
Co4 | 0.0350 (2) | 0.0402 (3) | 0.0392 (2) | 0.0000 (2) | 0.00617 (18) | 0.0055 (2) |
O1 | 0.0461 (16) | 0.060 (2) | 0.0610 (16) | 0.0014 (15) | 0.0154 (13) | −0.0109 (13) |
O2 | 0.0547 (16) | 0.088 (2) | 0.0403 (14) | 0.0088 (15) | −0.0009 (12) | 0.0099 (14) |
O3 | 0.0336 (13) | 0.067 (2) | 0.0573 (16) | −0.0087 (14) | −0.0011 (11) | −0.0007 (15) |
O4 | 0.0767 (19) | 0.0441 (19) | 0.0573 (17) | 0.0048 (14) | 0.0263 (14) | 0.0057 (14) |
O5 | 0.0379 (12) | 0.0376 (15) | 0.0373 (11) | 0.0009 (10) | 0.0070 (9) | 0.0023 (10) |
O6 | 0.0336 (11) | 0.0402 (14) | 0.0368 (11) | −0.0065 (10) | 0.0008 (9) | 0.0009 (10) |
O7 | 0.0327 (11) | 0.0467 (15) | 0.0291 (10) | −0.0026 (10) | 0.0046 (8) | 0.0050 (10) |
O8 | 0.0330 (11) | 0.0428 (14) | 0.0363 (11) | −0.0039 (10) | 0.0103 (9) | −0.0005 (10) |
O11 | 0.0420 (14) | 0.070 (2) | 0.0548 (14) | −0.0020 (13) | 0.0117 (11) | 0.0152 (13) |
O12 | 0.0355 (12) | 0.0565 (17) | 0.0551 (14) | 0.0012 (11) | 0.0058 (10) | 0.0138 (12) |
O21 | 0.0682 (16) | 0.0409 (16) | 0.0444 (13) | −0.0107 (12) | 0.0153 (12) | −0.0029 (11) |
O22 | 0.0712 (16) | 0.0379 (15) | 0.0368 (12) | −0.0098 (12) | 0.0163 (11) | −0.0015 (10) |
O31 | 0.0608 (15) | 0.0595 (18) | 0.0469 (13) | −0.0230 (14) | 0.0194 (12) | −0.0107 (13) |
O32 | 0.0485 (14) | 0.0604 (18) | 0.0484 (13) | −0.0159 (13) | 0.0177 (11) | −0.0145 (12) |
O41 | 0.0499 (14) | 0.0536 (18) | 0.0556 (14) | −0.0053 (12) | 0.0090 (12) | 0.0142 (13) |
O42 | 0.0389 (12) | 0.0564 (17) | 0.0535 (14) | 0.0053 (12) | 0.0068 (10) | 0.0179 (12) |
C1 | 0.075 (3) | 0.065 (3) | 0.097 (3) | 0.016 (3) | 0.033 (3) | −0.004 (3) |
C2 | 0.103 (5) | 0.455 (15) | 0.048 (3) | 0.084 (7) | −0.014 (3) | 0.001 (5) |
C3 | 0.0338 (19) | 0.089 (4) | 0.079 (3) | −0.007 (2) | 0.0002 (18) | −0.001 (2) |
C4 | 0.087 (3) | 0.062 (3) | 0.126 (4) | 0.008 (3) | 0.064 (3) | 0.000 (3) |
C5 | 0.069 (3) | 0.041 (3) | 0.056 (2) | 0.0014 (19) | 0.0143 (19) | 0.0072 (18) |
C6 | 0.0427 (19) | 0.050 (3) | 0.058 (2) | −0.0135 (17) | 0.0009 (16) | −0.0071 (18) |
C7 | 0.049 (2) | 0.072 (3) | 0.0354 (17) | −0.0032 (19) | 0.0101 (15) | 0.0055 (17) |
C8 | 0.0404 (18) | 0.060 (3) | 0.053 (2) | −0.0049 (17) | 0.0169 (16) | −0.0072 (18) |
C11 | 0.057 (2) | 0.069 (3) | 0.052 (2) | −0.013 (2) | 0.0216 (18) | 0.0003 (19) |
C12 | 0.0410 (18) | 0.053 (3) | 0.052 (2) | −0.0042 (17) | 0.0126 (16) | −0.0146 (18) |
C13 | 0.045 (2) | 0.090 (3) | 0.071 (3) | −0.017 (2) | 0.020 (2) | −0.023 (2) |
C14 | 0.040 (2) | 0.103 (4) | 0.098 (4) | −0.001 (2) | 0.008 (2) | −0.029 (3) |
C15 | 0.044 (2) | 0.070 (3) | 0.101 (3) | 0.011 (2) | −0.011 (2) | −0.008 (3) |
C16 | 0.045 (2) | 0.052 (3) | 0.085 (3) | 0.0052 (19) | 0.000 (2) | 0.003 (2) |
C17 | 0.0387 (18) | 0.045 (2) | 0.055 (2) | 0.0020 (16) | 0.0034 (16) | −0.0079 (17) |
C21 | 0.0468 (19) | 0.045 (2) | 0.0436 (19) | −0.0080 (17) | 0.0099 (15) | 0.0063 (17) |
C22 | 0.0350 (16) | 0.038 (2) | 0.0355 (16) | −0.0006 (15) | 0.0042 (13) | 0.0006 (15) |
C23 | 0.0444 (19) | 0.052 (2) | 0.0394 (18) | −0.0002 (17) | 0.0123 (14) | 0.0068 (17) |
C24 | 0.062 (2) | 0.063 (3) | 0.0366 (18) | 0.008 (2) | 0.0150 (16) | −0.0010 (19) |
C25 | 0.078 (3) | 0.046 (3) | 0.051 (2) | 0.000 (2) | 0.0172 (19) | −0.0135 (19) |
C26 | 0.076 (3) | 0.041 (2) | 0.052 (2) | −0.007 (2) | 0.0191 (19) | −0.0023 (18) |
C27 | 0.0411 (18) | 0.038 (2) | 0.0350 (16) | −0.0004 (15) | 0.0051 (13) | −0.0018 (15) |
C31 | 0.054 (2) | 0.061 (3) | 0.059 (2) | −0.018 (2) | 0.0149 (18) | −0.003 (2) |
C32 | 0.0423 (19) | 0.044 (2) | 0.052 (2) | −0.0034 (17) | 0.0075 (16) | −0.0124 (17) |
C33 | 0.046 (2) | 0.064 (3) | 0.084 (3) | −0.012 (2) | 0.008 (2) | −0.023 (2) |
C34 | 0.055 (3) | 0.084 (4) | 0.091 (3) | −0.004 (2) | 0.002 (2) | −0.051 (3) |
C35 | 0.068 (3) | 0.094 (4) | 0.062 (3) | 0.006 (3) | 0.004 (2) | −0.039 (3) |
C36 | 0.063 (2) | 0.073 (3) | 0.053 (2) | −0.001 (2) | 0.0173 (19) | −0.020 (2) |
C37 | 0.0421 (19) | 0.045 (2) | 0.0447 (18) | 0.0018 (17) | 0.0039 (15) | −0.0072 (17) |
C41 | 0.063 (2) | 0.047 (3) | 0.049 (2) | −0.010 (2) | 0.0171 (18) | 0.0034 (19) |
C42 | 0.070 (2) | 0.041 (2) | 0.0380 (17) | 0.0015 (19) | 0.0141 (17) | 0.0036 (16) |
C43 | 0.103 (4) | 0.055 (3) | 0.057 (2) | 0.006 (3) | 0.013 (2) | 0.013 (2) |
C44 | 0.111 (4) | 0.082 (4) | 0.071 (3) | 0.031 (3) | 0.009 (3) | 0.028 (3) |
C45 | 0.069 (3) | 0.112 (5) | 0.073 (3) | 0.042 (3) | 0.007 (2) | 0.029 (3) |
C46 | 0.049 (2) | 0.089 (4) | 0.064 (2) | 0.019 (2) | 0.0107 (19) | 0.019 (2) |
C47 | 0.053 (2) | 0.056 (3) | 0.0379 (18) | 0.0177 (19) | 0.0122 (15) | 0.0065 (17) |
Co1—O1 | 2.147 (3) | C5—H5C | 0.9600 |
Co1—O5 | 2.131 (2) | C6—H6A | 0.9600 |
Co1—O6 | 2.116 (2) | C6—H6B | 0.9600 |
Co1—O7 | 2.054 (2) | C6—H6C | 0.9600 |
Co1—O11 | 2.101 (2) | C7—H7A | 0.9600 |
Co1—O12 | 2.030 (2) | C7—H7B | 0.9600 |
Co2—O2 | 2.152 (3) | C7—H7C | 0.9600 |
Co2—O5 | 2.064 (2) | C8—H8A | 0.9600 |
Co2—O6 | 2.102 (2) | C8—H8B | 0.9600 |
Co2—O8 | 2.114 (2) | C8—H8C | 0.9600 |
Co2—O21 | 2.115 (2) | C11—C12 | 1.442 (5) |
Co2—O22 | 2.035 (2) | C11—H11A | 0.9300 |
Co3—O3 | 2.165 (3) | C12—C17 | 1.422 (5) |
Co3—O5 | 2.103 (2) | C12—C13 | 1.425 (5) |
Co3—O7 | 2.114 (2) | C13—C14 | 1.359 (6) |
Co3—O8 | 2.076 (2) | C13—H13A | 0.9300 |
Co3—O31 | 2.125 (2) | C14—C15 | 1.382 (6) |
Co3—O32 | 2.022 (2) | C14—H14A | 0.9300 |
Co4—O4 | 2.194 (3) | C15—C16 | 1.376 (6) |
Co4—O6 | 2.052 (2) | C15—H15A | 0.9300 |
Co4—O7 | 2.107 (2) | C16—C17 | 1.419 (5) |
Co4—O8 | 2.141 (2) | C16—H16A | 0.9300 |
Co4—O41 | 2.088 (2) | C21—C22 | 1.426 (5) |
Co4—O42 | 2.024 (2) | C21—H21A | 0.9300 |
O1—C1 | 1.423 (5) | C22—C23 | 1.417 (4) |
O1—H0A | 0.77 (4) | C22—C27 | 1.424 (4) |
O2—C2 | 1.351 (6) | C23—C24 | 1.359 (5) |
O2—H0B | 0.86 (5) | C23—H23A | 0.9300 |
O3—C3 | 1.434 (4) | C24—C25 | 1.387 (5) |
O3—H0C | 0.75 (3) | C24—H24A | 0.9300 |
O4—C4 | 1.438 (5) | C25—C26 | 1.376 (5) |
O4—H0D | 0.72 (4) | C25—H25A | 0.9300 |
O5—C5 | 1.430 (4) | C26—C27 | 1.406 (5) |
O6—C6 | 1.440 (4) | C26—H26A | 0.9300 |
O7—C7 | 1.435 (3) | C31—C32 | 1.439 (5) |
O8—C8 | 1.427 (4) | C31—H31A | 0.9300 |
O11—C11 | 1.227 (4) | C32—C37 | 1.417 (5) |
O12—C17 | 1.314 (4) | C32—C33 | 1.417 (5) |
O21—C21 | 1.244 (4) | C33—C34 | 1.364 (6) |
O22—C27 | 1.304 (3) | C33—H33A | 0.9300 |
O31—C31 | 1.233 (4) | C34—C35 | 1.397 (6) |
O32—C37 | 1.310 (4) | C34—H34A | 0.9300 |
O41—C41 | 1.226 (4) | C35—C36 | 1.370 (6) |
O42—C47 | 1.315 (4) | C35—H35A | 0.9300 |
C1—H1A | 0.9600 | C36—C37 | 1.413 (5) |
C1—H1B | 0.9600 | C36—H36A | 0.9300 |
C1—H1C | 0.9600 | C41—C42 | 1.441 (5) |
C2—H2A | 0.9600 | C41—H41A | 0.9300 |
C2—H2B | 0.9600 | C42—C43 | 1.417 (5) |
C2—H2C | 0.9600 | C42—C47 | 1.428 (5) |
C3—H3A | 0.9600 | C43—C44 | 1.358 (7) |
C3—H3B | 0.9600 | C43—H43A | 0.9300 |
C3—H3C | 0.9600 | C44—C45 | 1.375 (7) |
C4—H4A | 0.9600 | C44—H44A | 0.9300 |
C4—H4B | 0.9600 | C45—C46 | 1.384 (6) |
C4—H4C | 0.9600 | C45—H45A | 0.9300 |
C5—H5A | 0.9600 | C46—C47 | 1.416 (5) |
C5—H5B | 0.9600 | C46—H46A | 0.9300 |
O12—Co1—O5 | 91.51 (8) | H3A—C3—H3B | 109.5 |
O12—Co1—O6 | 93.66 (9) | O3—C3—H3C | 109.5 |
O12—Co1—O7 | 173.41 (9) | H3A—C3—H3C | 109.5 |
O12—Co1—O11 | 88.30 (9) | H3B—C3—H3C | 109.5 |
O5—Co1—O1 | 91.44 (10) | O4—C4—H4A | 109.5 |
O6—Co1—O1 | 168.34 (9) | O4—C4—H4B | 109.5 |
O6—Co1—O5 | 83.07 (8) | H4A—C4—H4B | 109.5 |
O7—Co1—O1 | 88.44 (10) | O4—C4—H4C | 109.5 |
O7—Co1—O5 | 84.30 (8) | H4A—C4—H4C | 109.5 |
O7—Co1—O6 | 80.81 (8) | H4B—C4—H4C | 109.5 |
O7—Co1—O11 | 95.88 (9) | O5—C5—H5A | 109.5 |
O11—Co1—O1 | 88.68 (10) | O5—C5—H5B | 109.5 |
O11—Co1—O5 | 179.78 (9) | H5A—C5—H5B | 109.5 |
O11—Co1—O6 | 96.84 (9) | O5—C5—H5C | 109.5 |
O12—Co1—O1 | 96.77 (10) | H5A—C5—H5C | 109.5 |
O5—Co2—O2 | 87.72 (10) | H5B—C5—H5C | 109.5 |
O5—Co2—O6 | 85.07 (8) | O6—C6—H6A | 109.5 |
O5—Co2—O8 | 79.89 (8) | O6—C6—H6B | 109.5 |
O5—Co2—O21 | 98.71 (9) | H6A—C6—H6B | 109.5 |
O6—Co2—O2 | 90.07 (10) | O6—C6—H6C | 109.5 |
O6—Co2—O8 | 83.79 (8) | H6A—C6—H6C | 109.5 |
O6—Co2—O21 | 176.18 (8) | H6B—C6—H6C | 109.5 |
O8—Co2—O2 | 166.58 (10) | O7—C7—H7A | 109.5 |
O8—Co2—O21 | 97.34 (9) | O7—C7—H7B | 109.5 |
O21—Co2—O2 | 89.57 (10) | H7A—C7—H7B | 109.5 |
O22—Co2—O2 | 98.48 (11) | O7—C7—H7C | 109.5 |
O22—Co2—O5 | 171.91 (9) | H7A—C7—H7C | 109.5 |
O22—Co2—O6 | 89.70 (9) | H7B—C7—H7C | 109.5 |
O22—Co2—O8 | 93.42 (9) | O8—C8—H8A | 109.5 |
O22—Co2—O21 | 86.59 (9) | O8—C8—H8B | 109.5 |
O5—Co3—O3 | 166.01 (11) | H8A—C8—H8B | 109.5 |
O5—Co3—O7 | 83.52 (8) | O8—C8—H8C | 109.5 |
O5—Co3—O31 | 99.04 (9) | H8A—C8—H8C | 109.5 |
O7—Co3—O3 | 88.13 (10) | H8B—C8—H8C | 109.5 |
O7—Co3—O31 | 175.72 (8) | O11—C11—C12 | 128.8 (3) |
O8—Co3—O3 | 88.19 (10) | O11—C11—H11A | 115.6 |
O8—Co3—O5 | 79.88 (8) | C12—C11—H11A | 115.6 |
O8—Co3—O7 | 84.54 (8) | C17—C12—C13 | 119.2 (4) |
O8—Co3—O31 | 99.25 (9) | C17—C12—C11 | 123.7 (3) |
O31—Co3—O3 | 90.01 (11) | C13—C12—C11 | 117.1 (4) |
O32—Co3—O3 | 95.88 (11) | C14—C13—C12 | 121.9 (4) |
O32—Co3—O5 | 95.24 (9) | C14—C13—H13A | 119.0 |
O32—Co3—O7 | 89.46 (9) | C12—C13—H13A | 119.0 |
O32—Co3—O8 | 172.64 (9) | C13—C14—C15 | 118.8 (4) |
O32—Co3—O31 | 86.90 (9) | C13—C14—H14A | 120.6 |
O6—Co4—O4 | 89.08 (10) | C15—C14—H14A | 120.6 |
O6—Co4—O7 | 81.07 (8) | C16—C15—C14 | 121.7 (4) |
O6—Co4—O8 | 84.32 (8) | C16—C15—H15A | 119.1 |
O6—Co4—O41 | 93.95 (9) | C14—C15—H15A | 119.1 |
O7—Co4—O4 | 168.73 (10) | C15—C16—C17 | 121.2 (4) |
O7—Co4—O8 | 83.12 (8) | C15—C16—H16A | 119.4 |
O8—Co4—O4 | 90.50 (9) | C17—C16—H16A | 119.4 |
O41—Co4—O4 | 87.92 (10) | O12—C17—C16 | 119.5 (3) |
O41—Co4—O7 | 98.16 (9) | O12—C17—C12 | 123.4 (3) |
O41—Co4—O8 | 177.67 (9) | C16—C17—C12 | 117.0 (3) |
O42—Co4—O4 | 96.68 (11) | O21—C21—C22 | 129.4 (3) |
O42—Co4—O6 | 173.63 (10) | O21—C21—H21A | 115.3 |
O42—Co4—O7 | 92.92 (9) | C22—C21—H21A | 115.3 |
O42—Co4—O8 | 92.88 (8) | C23—C22—C27 | 119.5 (3) |
O42—Co4—O41 | 89.00 (9) | C23—C22—C21 | 117.7 (3) |
C1—O1—Co1 | 126.2 (3) | C27—C22—C21 | 122.7 (3) |
C1—O1—H0A | 113 (3) | C24—C23—C22 | 121.7 (3) |
Co1—O1—H0A | 108 (3) | C24—C23—H23A | 119.1 |
C2—O2—Co2 | 137.1 (4) | C22—C23—H23A | 119.1 |
C2—O2—H0B | 113 (3) | C23—C24—C25 | 119.2 (3) |
Co2—O2—H0B | 106 (3) | C23—C24—H24A | 120.4 |
C3—O3—Co3 | 129.7 (3) | C25—C24—H24A | 120.4 |
C3—O3—H0C | 104 (3) | C26—C25—C24 | 120.8 (4) |
Co3—O3—H0C | 109 (3) | C26—C25—H25A | 119.6 |
C4—O4—Co4 | 122.8 (3) | C24—C25—H25A | 119.6 |
C4—O4—H0D | 110 (4) | C25—C26—C27 | 122.2 (4) |
Co4—O4—H0D | 105 (4) | C25—C26—H26A | 118.9 |
C5—O5—Co2 | 120.88 (19) | C27—C26—H26A | 118.9 |
C5—O5—Co3 | 117.8 (2) | O22—C27—C26 | 120.0 (3) |
Co2—O5—Co3 | 100.48 (9) | O22—C27—C22 | 123.4 (3) |
C5—O5—Co1 | 122.4 (2) | C26—C27—C22 | 116.6 (3) |
Co2—O5—Co1 | 95.47 (9) | O31—C31—C32 | 128.6 (3) |
Co3—O5—Co1 | 94.26 (8) | O31—C31—H31A | 115.7 |
C6—O6—Co4 | 120.6 (2) | C32—C31—H31A | 115.7 |
C6—O6—Co2 | 121.51 (19) | C37—C32—C33 | 119.5 (3) |
Co4—O6—Co2 | 96.72 (8) | C37—C32—C31 | 123.5 (3) |
C6—O6—Co1 | 118.77 (19) | C33—C32—C31 | 117.0 (3) |
Co4—O6—Co1 | 98.87 (8) | C34—C33—C32 | 121.6 (4) |
Co2—O6—Co1 | 94.77 (9) | C34—C33—H33A | 119.2 |
C7—O7—Co1 | 121.26 (19) | C32—C33—H33A | 119.2 |
C7—O7—Co4 | 119.3 (2) | C33—C34—C35 | 119.1 (4) |
Co1—O7—Co4 | 99.12 (8) | C33—C34—H34A | 120.4 |
C7—O7—Co3 | 120.00 (19) | C35—C34—H34A | 120.4 |
Co1—O7—Co3 | 96.22 (8) | C36—C35—C34 | 120.7 (4) |
Co4—O7—Co3 | 95.37 (8) | C36—C35—H35A | 119.7 |
C8—O8—Co3 | 119.87 (19) | C34—C35—H35A | 119.7 |
C8—O8—Co2 | 118.07 (18) | C35—C36—C37 | 121.9 (4) |
Co3—O8—Co2 | 99.73 (9) | C35—C36—H36A | 119.1 |
C8—O8—Co4 | 124.1 (2) | C37—C36—H36A | 119.1 |
Co3—O8—Co4 | 95.48 (8) | O32—C37—C36 | 119.9 (3) |
Co2—O8—Co4 | 93.69 (8) | O32—C37—C32 | 122.9 (3) |
C11—O11—Co1 | 125.8 (2) | C36—C37—C32 | 117.2 (3) |
C17—O12—Co1 | 129.4 (2) | O41—C41—C42 | 128.6 (3) |
C21—O21—Co2 | 125.5 (2) | O41—C41—H41A | 115.7 |
C27—O22—Co2 | 130.2 (2) | C42—C41—H41A | 115.7 |
C31—O31—Co3 | 123.3 (2) | C43—C42—C47 | 119.2 (4) |
C37—O32—Co3 | 126.3 (2) | C43—C42—C41 | 117.1 (4) |
C41—O41—Co4 | 125.9 (2) | C47—C42—C41 | 123.7 (3) |
C47—O42—Co4 | 128.8 (2) | C44—C43—C42 | 121.9 (5) |
O1—C1—H1A | 109.5 | C44—C43—H43A | 119.1 |
O1—C1—H1B | 109.5 | C42—C43—H43A | 119.1 |
H1A—C1—H1B | 109.5 | C43—C44—C45 | 119.3 (4) |
O1—C1—H1C | 109.5 | C43—C44—H44A | 120.4 |
H1A—C1—H1C | 109.5 | C45—C44—H44A | 120.4 |
H1B—C1—H1C | 109.5 | C44—C45—C46 | 121.6 (4) |
O2—C2—H2A | 109.5 | C44—C45—H45A | 119.2 |
O2—C2—H2B | 109.5 | C46—C45—H45A | 119.2 |
H2A—C2—H2B | 109.5 | C45—C46—C47 | 121.0 (4) |
O2—C2—H2C | 109.5 | C45—C46—H46A | 119.5 |
H2A—C2—H2C | 109.5 | C47—C46—H46A | 119.5 |
H2B—C2—H2C | 109.5 | O42—C47—C46 | 119.2 (4) |
O3—C3—H3A | 109.5 | O42—C47—C42 | 123.8 (3) |
O3—C3—H3B | 109.5 | C46—C47—C42 | 117.0 (3) |
Experimental details
Crystal data | |
Chemical formula | [Co4(CH3O)4(C7H5O2)4(CH4O)4] |
Mr | 972.46 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 14.6546 (5), 14.7082 (5), 20.3235 (7) |
β (°) | 103.789 (1) |
V (Å3) | 4254.3 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.60 |
Crystal size (mm) | 0.50 × 0.45 × 0.45 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.454, 0.487 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15156, 7411, 5377 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.592 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.103, 1.01 |
No. of reflections | 7411 |
No. of parameters | 521 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.58, −0.37 |
Computer programs: SMART (Siemens, 1994), SMART, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.
Co1—O1 | 2.147 (3) | Co3—O3 | 2.165 (3) |
Co1—O5 | 2.131 (2) | Co3—O5 | 2.103 (2) |
Co1—O6 | 2.116 (2) | Co3—O7 | 2.114 (2) |
Co1—O7 | 2.054 (2) | Co3—O8 | 2.076 (2) |
Co1—O11 | 2.101 (2) | Co3—O31 | 2.125 (2) |
Co1—O12 | 2.030 (2) | Co3—O32 | 2.022 (2) |
Co2—O2 | 2.152 (3) | Co4—O4 | 2.194 (3) |
Co2—O5 | 2.064 (2) | Co4—O6 | 2.052 (2) |
Co2—O6 | 2.102 (2) | Co4—O7 | 2.107 (2) |
Co2—O8 | 2.114 (2) | Co4—O8 | 2.141 (2) |
Co2—O21 | 2.115 (2) | Co4—O41 | 2.088 (2) |
Co2—O22 | 2.035 (2) | Co4—O42 | 2.024 (2) |
O12—Co1—O5 | 91.51 (8) | O5—Co3—O3 | 166.01 (11) |
O12—Co1—O6 | 93.66 (9) | O5—Co3—O7 | 83.52 (8) |
O12—Co1—O7 | 173.41 (9) | O5—Co3—O31 | 99.04 (9) |
O12—Co1—O11 | 88.30 (9) | O7—Co3—O3 | 88.13 (10) |
O5—Co1—O1 | 91.44 (10) | O7—Co3—O31 | 175.72 (8) |
O6—Co1—O1 | 168.34 (9) | O8—Co3—O3 | 88.19 (10) |
O6—Co1—O5 | 83.07 (8) | O8—Co3—O5 | 79.88 (8) |
O7—Co1—O1 | 88.44 (10) | O8—Co3—O7 | 84.54 (8) |
O7—Co1—O5 | 84.30 (8) | O8—Co3—O31 | 99.25 (9) |
O7—Co1—O6 | 80.81 (8) | O31—Co3—O3 | 90.01 (11) |
O7—Co1—O11 | 95.88 (9) | O32—Co3—O3 | 95.88 (11) |
O11—Co1—O1 | 88.68 (10) | O32—Co3—O5 | 95.24 (9) |
O11—Co1—O5 | 179.78 (9) | O32—Co3—O7 | 89.46 (9) |
O11—Co1—O6 | 96.84 (9) | O32—Co3—O8 | 172.64 (9) |
O12—Co1—O1 | 96.77 (10) | O32—Co3—O31 | 86.90 (9) |
O5—Co2—O2 | 87.72 (10) | O6—Co4—O4 | 89.08 (10) |
O5—Co2—O6 | 85.07 (8) | O6—Co4—O7 | 81.07 (8) |
O5—Co2—O8 | 79.89 (8) | O6—Co4—O8 | 84.32 (8) |
O5—Co2—O21 | 98.71 (9) | O6—Co4—O41 | 93.95 (9) |
O6—Co2—O2 | 90.07 (10) | O7—Co4—O4 | 168.73 (10) |
O6—Co2—O8 | 83.79 (8) | O7—Co4—O8 | 83.12 (8) |
O6—Co2—O21 | 176.18 (8) | O8—Co4—O4 | 90.50 (9) |
O8—Co2—O2 | 166.58 (10) | O41—Co4—O4 | 87.92 (10) |
O8—Co2—O21 | 97.34 (9) | O41—Co4—O7 | 98.16 (9) |
O21—Co2—O2 | 89.57 (10) | O41—Co4—O8 | 177.67 (9) |
O22—Co2—O2 | 98.48 (11) | O42—Co4—O4 | 96.68 (11) |
O22—Co2—O5 | 171.91 (9) | O42—Co4—O6 | 173.63 (10) |
O22—Co2—O6 | 89.70 (9) | O42—Co4—O7 | 92.92 (9) |
O22—Co2—O8 | 93.42 (9) | O42—Co4—O8 | 92.88 (8) |
O22—Co2—O21 | 86.59 (9) | O42—Co4—O41 | 89.00 (9) |
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In the past two decades, cubane-type polynuclear complexes have received much attention owing to their magnetic and optical properties, as well their biological relevance. Complexes of the type Mn4O4 and their derivatives have been extensively studied for they are thought to have relevance to the Water Oxidation Center (WOC) in the photosynthetic apparatus of green plants and cyanobacteria (Christou, 1989; Brudrig et al., 1991; Dimitrou et al., 1993; Taft et al., 1993; Wieghardt, 1989). Recently, several cubane-type complexes of cobalt and other transition metals, such as nickel, zinc and cadmium, have been reported. For example, Christou and others have reported biologically relevant cubane complexes, e.g. [Co4O4(OAc)2bpy4(ClO4)2], containing the [Co4O4]+4 core, which is structurally analogous to, but more stable than, that of MnIIIMnIV or MnIV4 species (Dimitrou et al., 1993). Two mixed-valence clusters, [Co8O4(O2CPh)12solv4] (solv = DMF, MeCN, H2O) containing the [CoIII4O4]+4 core, [Co8O4(OH)4(OAc)6L2](ClO4)2 [L = 1,2-bis(2,2'-bipyridyl-6-yl)ethane] containing a [Co8µ4-O4(µ3-OH)4]+8 core with an unusual face-sharing triple-cubane architecture, as well as [Co4(2,2-PyC(O)(OH)4(OAc)3(H2O)](ClO4), containing the [CoII4O4]+4 cubane unit, have been also reported (Dimitrou et al., 1995; Grillo et al., 1996; Tong et al., 1999). In an attempt to prepare Schiff base complexes, the unexpected complex, [Co4(OMe)4L4(MeOH)4] (LH = 2-hydroxylbenzaldehyde), was isolated and characterized crystallographically.
As shown in Fig. 1, four Co atoms and four O atoms, each from MeO-, occupy alternate corners of the cubane unit where each Co atom is surrounded by three bridging O atoms derived from MeO-, one from MeOH and two O atoms from chelating 2-formylphenolate so as to form a distorted octahedral geometry. Each of the bridging O atoms has a remarkably distorted tetrahedral geometry. The Co—O(MeOH) bond lengths are longer than those for Co—O(MeO-).