Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803011486/om6145sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803011486/om6145Isup2.hkl |
CCDC reference: 217349
The compound 4,6-dimethylpirimidine-2(1H)-thione (4,6-Me2pymSH) was prepared according to a literature method (Nigam et al., 1983). The title complex was synthesized by the following procedure: 0.42 g (3 mmol) of 4,6-Me2pymSH was dissolved in 20 ml of thf (freshly distilled) in a Schlenk tube kept under N2 atmosphere. To this solution, 0.25 g (1 mmol) of the [Co(O2CCH3)2]·4H2O dissolved in 10 ml of THF was added over 10 min, and the mixture was stirred for about 2 h. Slow evaporation of the solvent in air led to the appearance of a blue microcrystalline solid. Yield: ~96% (0.45 g). Elemental analysis: calculated for C18H23CoN6S3: C 43.71, H 4.68, N 16.99%; found: C 43.69, H 4.64, N 17.1%. FAB MS: m/z 476.0 (14%, M), m/z 337.0 (32%,{Co[4,6-Me2pymS]2}), m/z 198.0 (15%,{Co[4,6-Me2pymS]}).
The intensities of the measured reflections were, in general, weak leading to a slightly high value of Rint. The H atoms of the methyl groups were refined as riding atoms with ideal tetrahedral geometry [d(C—H) = 0.96 Å] allowed to rotate to fit the electron density; the isotropic displacement parameters were fixed to be 50% larger than those of the atoms to which the H atoms were bonded. The aromatic H atoms were constrained to ideal trigonal planar geometry [d(C—H) = 0.93 Å]; their isotropic displacement parameters were set to be 20% larger than the those of the atoms to which the h ATOMS were bonded. H atoms were located in A difference Fourier map and refined freely with isotropic displacement parameters 50% larger than that of the parent O atom. A total of 2326 Friedel pairs were measured.
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Fig. 1. View of molecule with atomic labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 2. The crystal packing diagram of the title compound. |
[Co(C6H7N2S)3]·H2O | F(000) = 1024 |
Mr = 494.56 | Dx = 1.454 Mg m−3 |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2ac | Cell parameters from 3091 reflections |
a = 16.969 (2) Å | θ = 5.5–54.7° |
b = 8.0436 (11) Å | µ = 1.06 mm−1 |
c = 16.552 (2) Å | T = 293 K |
V = 2259.2 (5) Å3 | Block, blue |
Z = 4 | 0.19 × 0.17 × 0.17 mm |
Bruker SMART area-detector diffractometer | 2380 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.103 |
ϕ and ω scans | θmax = 28.1°, θmin = 2.4° |
Absorption correction: multi-scan (DENZO-SMN, Otwinowski & Minor, 1997) | h = −22→22 |
Tmin = 0.824, Tmax = 0.841 | k = −10→5 |
12629 measured reflections | l = −21→21 |
5124 independent 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)] = 0.061 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.139 | w = 1/[σ2(Fo2) + (0.0482P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.85 | (Δ/σ)max = 0.001 |
5124 reflections | Δρmax = 0.76 e Å−3 |
269 parameters | Δρmin = −0.33 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.03 (3) |
[Co(C6H7N2S)3]·H2O | V = 2259.2 (5) Å3 |
Mr = 494.56 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 16.969 (2) Å | µ = 1.06 mm−1 |
b = 8.0436 (11) Å | T = 293 K |
c = 16.552 (2) Å | 0.19 × 0.17 × 0.17 mm |
Bruker SMART area-detector diffractometer | 5124 independent reflections |
Absorption correction: multi-scan (DENZO-SMN, Otwinowski & Minor, 1997) | 2380 reflections with I > 2σ(I) |
Tmin = 0.824, Tmax = 0.841 | Rint = 0.103 |
12629 measured reflections |
R[F2 > 2σ(F2)] = 0.061 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.139 | Δρmax = 0.76 e Å−3 |
S = 0.85 | Δρmin = −0.33 e Å−3 |
5124 reflections | Absolute structure: Flack (1983) |
269 parameters | Absolute structure parameter: 0.03 (3) |
1 restraint |
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 | 0.53579 (5) | 0.53650 (11) | 0.01650 (5) | 0.0410 (3) | |
S1 | 0.63209 (13) | 0.4715 (3) | −0.07154 (12) | 0.0565 (6) | |
C11 | 0.6524 (4) | 0.3403 (9) | 0.0069 (5) | 0.0422 (18) | |
N12 | 0.6033 (3) | 0.3685 (7) | 0.0686 (3) | 0.0379 (14) | |
C13 | 0.6098 (4) | 0.2789 (9) | 0.1352 (4) | 0.0397 (18) | |
C131 | 0.5523 (5) | 0.3071 (9) | 0.2026 (4) | 0.059 (2) | |
H13A | 0.4996 | 0.2978 | 0.1821 | 0.088* | |
H13B | 0.5601 | 0.4161 | 0.2247 | 0.088* | |
H13C | 0.5605 | 0.2253 | 0.2440 | 0.088* | |
C14 | 0.6696 (4) | 0.1607 (9) | 0.1408 (5) | 0.048 (2) | |
H14 | 0.6761 | 0.0983 | 0.1876 | 0.058* | |
C15 | 0.7186 (4) | 0.1381 (9) | 0.0756 (5) | 0.053 (2) | |
C151 | 0.7819 (5) | 0.0085 (9) | 0.0770 (5) | 0.071 (2) | |
H15A | 0.8314 | 0.0584 | 0.0631 | 0.106* | |
H15B | 0.7695 | −0.0772 | 0.0387 | 0.106* | |
H15C | 0.7853 | −0.0388 | 0.1302 | 0.106* | |
N16 | 0.7110 (3) | 0.2289 (8) | 0.0068 (4) | 0.0508 (16) | |
S2 | 0.60312 (12) | 0.7456 (3) | 0.07469 (12) | 0.0508 (5) | |
C21 | 0.5206 (4) | 0.7431 (9) | 0.1355 (4) | 0.0417 (18) | |
N22 | 0.4711 (4) | 0.6204 (7) | 0.1075 (3) | 0.0379 (15) | |
C23 | 0.4030 (5) | 0.6024 (9) | 0.1453 (5) | 0.047 (2) | |
C231 | 0.3464 (5) | 0.4733 (10) | 0.1127 (5) | 0.065 (2) | |
H23A | 0.3723 | 0.3673 | 0.1104 | 0.098* | |
H23B | 0.3296 | 0.5049 | 0.0595 | 0.098* | |
H23C | 0.3013 | 0.4658 | 0.1476 | 0.098* | |
C24 | 0.3829 (5) | 0.7049 (10) | 0.2081 (5) | 0.054 (2) | |
H24 | 0.3344 | 0.6945 | 0.2339 | 0.064* | |
C25 | 0.4375 (6) | 0.8259 (10) | 0.2321 (4) | 0.055 (2) | |
C251 | 0.4176 (6) | 0.9406 (11) | 0.2992 (4) | 0.070 (3) | |
H25A | 0.3894 | 1.0346 | 0.2783 | 0.104* | |
H25B | 0.4652 | 0.9780 | 0.3248 | 0.104* | |
H25C | 0.3855 | 0.8836 | 0.3380 | 0.104* | |
N26 | 0.5049 (4) | 0.8462 (8) | 0.1947 (4) | 0.0483 (17) | |
S3 | 0.46723 (15) | 0.6945 (2) | −0.07179 (13) | 0.0582 (6) | |
C31 | 0.4263 (5) | 0.5012 (9) | −0.0891 (5) | 0.048 (2) | |
N32 | 0.4607 (4) | 0.3891 (7) | −0.0399 (3) | 0.0426 (15) | |
C33 | 0.4395 (5) | 0.2275 (9) | −0.0462 (4) | 0.0432 (19) | |
C331 | 0.4786 (4) | 0.1058 (8) | 0.0058 (5) | 0.052 (2) | |
H33A | 0.4706 | 0.1354 | 0.0614 | 0.078* | |
H33B | 0.5340 | 0.1045 | −0.0058 | 0.078* | |
H33C | 0.4568 | −0.0025 | −0.0040 | 0.078* | |
C34 | 0.3826 (5) | 0.1887 (10) | −0.1014 (4) | 0.049 (2) | |
H34 | 0.3671 | 0.0785 | −0.1072 | 0.059* | |
C35 | 0.3477 (5) | 0.3089 (11) | −0.1490 (5) | 0.053 (2) | |
C351 | 0.2844 (5) | 0.2726 (11) | −0.2079 (5) | 0.077 (3) | |
H35A | 0.2947 | 0.3313 | −0.2573 | 0.115* | |
H35B | 0.2347 | 0.3077 | −0.1862 | 0.115* | |
H35C | 0.2829 | 0.1553 | −0.2184 | 0.115* | |
N36 | 0.3698 (4) | 0.4699 (9) | −0.1418 (4) | 0.0512 (17) | |
O1 | 0.2188 (3) | 0.8035 (7) | 0.3419 (3) | 0.0757 (18) | |
H1A | 0.2407 | 0.8092 | 0.3967 | 0.113* | |
H1B | 0.2009 | 0.7349 | 0.3205 | 0.113* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0494 (6) | 0.0323 (5) | 0.0413 (5) | −0.0056 (5) | 0.0001 (6) | 0.0000 (6) |
S1 | 0.0701 (15) | 0.0526 (13) | 0.0468 (11) | −0.0030 (12) | 0.0136 (11) | 0.0044 (13) |
C11 | 0.037 (4) | 0.045 (4) | 0.045 (5) | −0.007 (4) | 0.014 (4) | −0.007 (4) |
N12 | 0.043 (4) | 0.037 (3) | 0.034 (3) | −0.001 (3) | −0.003 (3) | −0.002 (3) |
C13 | 0.043 (4) | 0.040 (5) | 0.036 (4) | −0.011 (4) | −0.010 (4) | −0.002 (4) |
C131 | 0.089 (7) | 0.048 (5) | 0.039 (4) | −0.006 (5) | −0.007 (5) | 0.005 (4) |
C14 | 0.049 (5) | 0.044 (5) | 0.052 (5) | 0.009 (4) | −0.008 (4) | 0.000 (4) |
C15 | 0.047 (5) | 0.046 (5) | 0.066 (5) | 0.003 (4) | −0.006 (5) | −0.017 (5) |
C151 | 0.051 (5) | 0.068 (6) | 0.093 (6) | 0.009 (4) | −0.002 (5) | −0.005 (6) |
N16 | 0.046 (4) | 0.047 (4) | 0.060 (5) | −0.003 (3) | 0.012 (4) | −0.006 (4) |
S2 | 0.0527 (13) | 0.0428 (11) | 0.0569 (12) | −0.0115 (10) | 0.0027 (11) | −0.0063 (10) |
C21 | 0.051 (5) | 0.031 (4) | 0.043 (4) | 0.006 (4) | −0.006 (4) | 0.005 (3) |
N22 | 0.037 (4) | 0.034 (4) | 0.043 (3) | −0.005 (3) | −0.003 (3) | 0.003 (3) |
C23 | 0.048 (5) | 0.033 (5) | 0.060 (5) | −0.004 (4) | −0.007 (5) | 0.013 (4) |
C231 | 0.052 (5) | 0.050 (5) | 0.094 (6) | −0.021 (5) | 0.022 (5) | −0.011 (5) |
C24 | 0.053 (5) | 0.055 (6) | 0.053 (5) | 0.007 (5) | 0.012 (4) | −0.007 (4) |
C25 | 0.085 (7) | 0.037 (5) | 0.043 (5) | 0.010 (5) | −0.012 (5) | −0.006 (4) |
C251 | 0.081 (7) | 0.068 (6) | 0.060 (6) | 0.009 (6) | −0.005 (5) | −0.013 (5) |
N26 | 0.057 (4) | 0.040 (4) | 0.048 (4) | −0.002 (3) | 0.013 (4) | −0.002 (3) |
S3 | 0.0856 (17) | 0.0330 (12) | 0.0560 (12) | −0.0059 (12) | −0.0200 (14) | 0.0052 (11) |
C31 | 0.067 (6) | 0.036 (5) | 0.040 (4) | 0.003 (4) | 0.008 (4) | −0.005 (4) |
N32 | 0.062 (4) | 0.035 (3) | 0.030 (3) | −0.002 (3) | −0.009 (3) | 0.000 (3) |
C33 | 0.056 (5) | 0.032 (5) | 0.042 (4) | 0.004 (4) | 0.008 (4) | −0.004 (4) |
C331 | 0.065 (5) | 0.029 (4) | 0.061 (5) | −0.006 (4) | −0.002 (5) | 0.000 (4) |
C34 | 0.066 (6) | 0.046 (5) | 0.035 (4) | −0.013 (4) | −0.003 (4) | −0.011 (4) |
C35 | 0.055 (6) | 0.059 (6) | 0.044 (5) | −0.014 (5) | −0.011 (4) | −0.005 (5) |
C351 | 0.070 (6) | 0.089 (7) | 0.072 (6) | −0.002 (6) | −0.021 (5) | −0.017 (5) |
N36 | 0.055 (4) | 0.052 (5) | 0.047 (4) | 0.002 (4) | −0.011 (3) | −0.001 (4) |
O1 | 0.076 (4) | 0.085 (4) | 0.066 (4) | −0.007 (3) | −0.017 (3) | 0.008 (3) |
Co1—N12 | 1.970 (6) | C231—H23A | 0.9600 |
Co1—N32 | 1.975 (6) | C231—H23B | 0.9600 |
Co1—N22 | 1.982 (6) | C231—H23C | 0.9600 |
Co1—S2 | 2.250 (2) | C24—C25 | 1.402 (11) |
Co1—S1 | 2.251 (2) | C24—H24 | 0.9300 |
Co1—S3 | 2.259 (2) | C25—N26 | 1.310 (10) |
S1—C11 | 1.708 (8) | C25—C251 | 1.483 (10) |
C11—N12 | 1.338 (8) | C251—H25A | 0.9600 |
C11—N16 | 1.339 (8) | C251—H25B | 0.9600 |
N12—C13 | 1.322 (8) | C251—H25C | 0.9600 |
C13—C14 | 1.393 (9) | S3—C31 | 1.727 (7) |
C13—C131 | 1.498 (10) | C31—N36 | 1.321 (9) |
C131—H13A | 0.9600 | C31—N32 | 1.348 (9) |
C131—H13B | 0.9600 | N32—C33 | 1.353 (8) |
C131—H13C | 0.9600 | C33—C34 | 1.365 (9) |
C14—C15 | 1.374 (10) | C33—C331 | 1.463 (9) |
C14—H14 | 0.9300 | C331—H33A | 0.9600 |
C15—N16 | 1.359 (10) | C331—H33B | 0.9600 |
C15—C151 | 1.497 (9) | C331—H33C | 0.9600 |
C151—H15A | 0.9600 | C34—C35 | 1.380 (10) |
C151—H15B | 0.9600 | C34—H34 | 0.9300 |
C151—H15C | 0.9600 | C35—N36 | 1.354 (9) |
S2—C21 | 1.724 (7) | C35—C351 | 1.479 (10) |
C21—N26 | 1.311 (9) | C351—H35A | 0.9600 |
C21—N22 | 1.377 (8) | C351—H35B | 0.9600 |
N22—C23 | 1.322 (9) | C351—H35C | 0.9600 |
C23—C24 | 1.369 (10) | O1—H1A | 0.9821 |
C23—C231 | 1.515 (10) | O1—H1B | 0.7228 |
N12—Co1—N32 | 99.8 (2) | N22—C23—C231 | 117.4 (7) |
N12—Co1—N22 | 102.8 (2) | C24—C23—C231 | 121.6 (8) |
N32—Co1—N22 | 101.9 (3) | C23—C231—H23A | 109.5 |
N12—Co1—S2 | 91.73 (17) | C23—C231—H23B | 109.5 |
N32—Co1—S2 | 168.17 (19) | H23A—C231—H23B | 109.5 |
N22—Co1—S2 | 72.63 (18) | C23—C231—H23C | 109.5 |
N12—Co1—S1 | 72.69 (18) | H23A—C231—H23C | 109.5 |
N32—Co1—S1 | 91.30 (19) | H23B—C231—H23C | 109.5 |
N22—Co1—S1 | 166.66 (19) | C23—C24—C25 | 117.9 (8) |
S2—Co1—S1 | 94.71 (8) | C23—C24—H24 | 121.1 |
N12—Co1—S3 | 165.56 (18) | C25—C24—H24 | 121.1 |
N32—Co1—S3 | 72.53 (18) | N26—C25—C24 | 122.0 (7) |
N22—Co1—S3 | 90.86 (17) | N26—C25—C251 | 118.4 (8) |
S2—Co1—S3 | 96.77 (8) | C24—C25—C251 | 119.6 (9) |
S1—Co1—S3 | 94.92 (9) | C25—C251—H25A | 109.5 |
C11—S1—Co1 | 78.3 (3) | C25—C251—H25B | 109.5 |
N12—C11—N16 | 125.2 (7) | H25A—C251—H25B | 109.5 |
N12—C11—S1 | 110.5 (5) | C25—C251—H25C | 109.5 |
N16—C11—S1 | 124.2 (6) | H25A—C251—H25C | 109.5 |
C13—N12—C11 | 119.5 (6) | H25B—C251—H25C | 109.5 |
C13—N12—Co1 | 142.0 (5) | C25—N26—C21 | 116.9 (7) |
C11—N12—Co1 | 98.3 (4) | C31—S3—Co1 | 78.9 (3) |
N12—C13—C14 | 119.2 (7) | N36—C31—N32 | 125.9 (7) |
N12—C13—C131 | 118.9 (7) | N36—C31—S3 | 125.0 (6) |
C14—C13—C131 | 121.9 (7) | N32—C31—S3 | 109.1 (6) |
C13—C131—H13A | 109.5 | C31—N32—C33 | 118.7 (6) |
C13—C131—H13B | 109.5 | C31—N32—Co1 | 99.4 (5) |
H13A—C131—H13B | 109.5 | C33—N32—Co1 | 141.7 (5) |
C13—C131—H13C | 109.5 | N32—C33—C34 | 117.4 (7) |
H13A—C131—H13C | 109.5 | N32—C33—C331 | 118.5 (7) |
H13B—C131—H13C | 109.5 | C34—C33—C331 | 124.1 (7) |
C15—C14—C13 | 118.7 (7) | C33—C331—H33A | 109.5 |
C15—C14—H14 | 120.7 | C33—C331—H33B | 109.5 |
C13—C14—H14 | 120.7 | H33A—C331—H33B | 109.5 |
N16—C15—C14 | 121.9 (7) | C33—C331—H33C | 109.5 |
N16—C15—C151 | 117.1 (8) | H33A—C331—H33C | 109.5 |
C14—C15—C151 | 120.9 (8) | H33B—C331—H33C | 109.5 |
C15—C151—H15A | 109.5 | C33—C34—C35 | 121.7 (7) |
C15—C151—H15B | 109.5 | C33—C34—H34 | 119.2 |
H15A—C151—H15B | 109.5 | C35—C34—H34 | 119.2 |
C15—C151—H15C | 109.5 | N36—C35—C34 | 120.0 (7) |
H15A—C151—H15C | 109.5 | N36—C35—C351 | 116.6 (8) |
H15B—C151—H15C | 109.5 | C34—C35—C351 | 123.3 (8) |
C11—N16—C15 | 115.5 (7) | C35—C351—H35A | 109.5 |
C21—S2—Co1 | 80.1 (3) | C35—C351—H35B | 109.5 |
N26—C21—N22 | 125.5 (7) | H35A—C351—H35B | 109.5 |
N26—C21—S2 | 126.5 (6) | C35—C351—H35C | 109.5 |
N22—C21—S2 | 107.9 (5) | H35A—C351—H35C | 109.5 |
C23—N22—C21 | 116.9 (6) | H35B—C351—H35C | 109.5 |
C23—N22—Co1 | 143.8 (5) | C31—N36—C35 | 116.2 (7) |
C21—N22—Co1 | 99.3 (5) | H1A—O1—H1B | 130.3 |
N22—C23—C24 | 120.8 (7) | ||
N12—Co1—S1—C11 | 2.6 (3) | N32—Co1—N22—C21 | −169.6 (4) |
N32—Co1—S1—C11 | −97.2 (3) | S2—Co1—N22—C21 | −0.5 (4) |
N22—Co1—S1—C11 | 74.9 (8) | S1—Co1—N22—C21 | 18.5 (10) |
S2—Co1—S1—C11 | 93.0 (2) | S3—Co1—N22—C21 | −97.3 (4) |
S3—Co1—S1—C11 | −169.8 (2) | C21—N22—C23—C24 | 1.5 (10) |
Co1—S1—C11—N12 | −3.9 (4) | Co1—N22—C23—C24 | −176.4 (6) |
Co1—S1—C11—N16 | 178.0 (6) | C21—N22—C23—C231 | 177.2 (7) |
N16—C11—N12—C13 | −1.9 (10) | Co1—N22—C23—C231 | −0.8 (12) |
S1—C11—N12—C13 | −180.0 (5) | N22—C23—C24—C25 | −1.7 (11) |
N16—C11—N12—Co1 | −177.5 (6) | C231—C23—C24—C25 | −177.2 (7) |
S1—C11—N12—Co1 | 4.5 (5) | C23—C24—C25—N26 | 2.4 (12) |
N32—Co1—N12—C13 | −88.8 (8) | C23—C24—C25—C251 | 179.3 (8) |
N22—Co1—N12—C13 | 16.0 (8) | C24—C25—N26—C21 | −2.9 (11) |
S2—Co1—N12—C13 | 88.5 (7) | C251—C25—N26—C21 | −179.8 (7) |
S1—Co1—N12—C13 | −177.1 (8) | N22—C21—N26—C25 | 2.8 (11) |
S3—Co1—N12—C13 | −145.3 (6) | S2—C21—N26—C25 | 178.1 (6) |
N32—Co1—N12—C11 | 85.0 (4) | N12—Co1—S3—C31 | 59.2 (8) |
N22—Co1—N12—C11 | −170.3 (4) | N32—Co1—S3—C31 | −0.3 (3) |
S2—Co1—N12—C11 | −97.7 (4) | N22—Co1—S3—C31 | −102.5 (3) |
S1—Co1—N12—C11 | −3.3 (4) | S2—Co1—S3—C31 | −175.1 (3) |
S3—Co1—N12—C11 | 28.4 (10) | S1—Co1—S3—C31 | 89.5 (3) |
C11—N12—C13—C14 | 2.2 (9) | Co1—S3—C31—N36 | 179.8 (7) |
Co1—N12—C13—C14 | 175.1 (6) | Co1—S3—C31—N32 | 0.4 (5) |
C11—N12—C13—C131 | −177.6 (6) | N36—C31—N32—C33 | 3.4 (11) |
Co1—N12—C13—C131 | −4.7 (11) | S3—C31—N32—C33 | −177.2 (5) |
N12—C13—C14—C15 | −1.7 (10) | N36—C31—N32—Co1 | −179.9 (7) |
C131—C13—C14—C15 | 178.0 (6) | S3—C31—N32—Co1 | −0.5 (5) |
C13—C14—C15—N16 | 0.8 (11) | N12—Co1—N32—C31 | −167.0 (4) |
C13—C14—C15—C151 | −177.7 (6) | N22—Co1—N32—C31 | 87.5 (4) |
N12—C11—N16—C15 | 0.9 (10) | S2—Co1—N32—C31 | 26.2 (11) |
S1—C11—N16—C15 | 178.8 (5) | S1—Co1—N32—C31 | −94.4 (4) |
C14—C15—N16—C11 | −0.4 (10) | S3—Co1—N32—C31 | 0.4 (4) |
C151—C15—N16—C11 | 178.2 (6) | N12—Co1—N32—C33 | 8.3 (9) |
N12—Co1—S2—C21 | −102.5 (3) | N22—Co1—N32—C33 | −97.2 (8) |
N32—Co1—S2—C21 | 64.4 (9) | S2—Co1—N32—C33 | −158.4 (7) |
N22—Co1—S2—C21 | 0.4 (3) | S1—Co1—N32—C33 | 81.0 (8) |
S1—Co1—S2—C21 | −175.3 (2) | S3—Co1—N32—C33 | 175.7 (8) |
S3—Co1—S2—C21 | 89.2 (2) | C31—N32—C33—C34 | −1.4 (10) |
Co1—S2—C21—N26 | −176.5 (7) | Co1—N32—C33—C34 | −176.1 (6) |
Co1—S2—C21—N22 | −0.6 (4) | C31—N32—C33—C331 | 178.4 (6) |
N26—C21—N22—C23 | −2.1 (10) | Co1—N32—C33—C331 | 3.6 (12) |
S2—C21—N22—C23 | −178.1 (5) | N32—C33—C34—C35 | −0.3 (10) |
N26—C21—N22—Co1 | 176.7 (6) | C331—C33—C34—C35 | 180.0 (7) |
S2—C21—N22—Co1 | 0.6 (5) | C33—C34—C35—N36 | 0.3 (12) |
N12—Co1—N22—C23 | −94.6 (8) | C33—C34—C35—C351 | −178.3 (7) |
N32—Co1—N22—C23 | 8.5 (9) | N32—C31—N36—C35 | −3.3 (11) |
S2—Co1—N22—C23 | 177.7 (9) | S3—C31—N36—C35 | 177.4 (6) |
S1—Co1—N22—C23 | −163.4 (6) | C34—C35—N36—C31 | 1.4 (11) |
S3—Co1—N22—C23 | 80.8 (8) | C351—C35—N36—C31 | −179.9 (7) |
N12—Co1—N22—C21 | 87.3 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N16i | 0.98 | 2.02 | 2.990 (8) | 168 |
O1—H1A···S1i | 0.98 | 3.17 | 3.654 (6) | 112 |
O1—H1B···N36ii | 0.72 | 2.52 | 3.088 (8) | 137 |
Symmetry codes: (i) −x+1, −y+1, z+1/2; (ii) −x+1/2, y, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Co(C6H7N2S)3]·H2O |
Mr | 494.56 |
Crystal system, space group | Orthorhombic, Pca21 |
Temperature (K) | 293 |
a, b, c (Å) | 16.969 (2), 8.0436 (11), 16.552 (2) |
V (Å3) | 2259.2 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.06 |
Crystal size (mm) | 0.19 × 0.17 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART area-detector diffractometer |
Absorption correction | Multi-scan (DENZO-SMN, Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.824, 0.841 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12629, 5124, 2380 |
Rint | 0.103 |
(sin θ/λ)max (Å−1) | 0.662 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.061, 0.139, 0.85 |
No. of reflections | 5124 |
No. of parameters | 269 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.76, −0.33 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.03 (3) |
Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
Co1—N12 | 1.970 (6) | Co1—S2 | 2.250 (2) |
Co1—N32 | 1.975 (6) | Co1—S1 | 2.251 (2) |
Co1—N22 | 1.982 (6) | Co1—S3 | 2.259 (2) |
N12—Co1—N32 | 99.8 (2) | N32—Co1—S1 | 91.30 (19) |
N12—Co1—N22 | 102.8 (2) | S2—Co1—S1 | 94.71 (8) |
N32—Co1—N22 | 101.9 (3) | N32—Co1—S3 | 72.53 (18) |
N12—Co1—S2 | 91.73 (17) | N22—Co1—S3 | 90.86 (17) |
N22—Co1—S2 | 72.63 (18) | S2—Co1—S3 | 96.77 (8) |
N12—Co1—S1 | 72.69 (18) | S1—Co1—S3 | 94.92 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N16i | 0.98 | 2.02 | 2.990 (8) | 168 |
O1—H1A···S1i | 0.98 | 3.17 | 3.654 (6) | 112 |
O1—H1B···N36ii | 0.72 | 2.52 | 3.088 (8) | 137 |
Symmetry codes: (i) −x+1, −y+1, z+1/2; (ii) −x+1/2, y, z+1/2. |
As part of our systematic work on the coordination mode of the potential ambidentate ligand 4,6-dimethylpirimidine-2(1H)-thione (4,6-Me2pymSH) (Lang et al., 2002; Fernandes et al., 2002; Oliveira et al., 2002), we studied the reaction of the ligand with the cobalt(II) acetate tetrahydrate. Aerial oxidization with slow evaporation of tetrahydrofuran produced the crystals of the blue CoIII title compound, (I), in the acentric orthorhombic space group Pca21 (Fig. 1). The selected crystal showed only the Δ optical isomer with no racemic twinning. Seth (1994) reported the first polymorph of the title compound in the acentric monoclinic space group P21; racemic twinning was not reported.
The Co(4,6-Me2pymS)3 molecule of (I) shows almost the same strongly distorted fac-octahedral geometry, due to the small bite angle of the three bidentate 4,6-Me2pymS ligands, as that reported in the earlier polymorph. The planes formed by each of the three ligands are mutually perpendicular, with angles of 85.82 (12), 87.35 (12) and 86.19 (13)° between them. The Co atom is situated 0.1322 Å from the point defined by the intersection of the three planes. The bond distances and angles within the ligands are close to those reported for similar compounds.
The difference between the two polymorphs lies in the packing and the position of the water solvate molecule. The packing diagram of the title compound is shown in Fig. 2. In the unit cell of the first polymorph, the water molecule forms a hydrogen bond to only one imidizolium N atom with a O···N distance of 2.969 (7) Å. In the new polymorph, the water molecule bridges between two neighbouring Co(4,6-Me2pymS)3 molecules, forming hydrogen bonding to two different N atoms, as shown in Table 4. Comparing the volume of the asymmetric units, the first polymorph occupies a slightly larger volume, 572.6 (1) Å−3, than the new polymorph, 564.8 (1) Å−3, implying a greater packing efficiency in the latter.