Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101018406/bm1475sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101018406/bm1475Isup2.hkl |
CCDC reference: 181990
Reaction of Co(BF4)2·6H2O, P(OMe)2Ph and tetramethylthiuram disulfide (molar ratio of 2:4:1) in MeOH/CH2Cl2 afforded cis-[Co(dtc)2{P(OMe)2Ph}2]BF4 (III). Irradiation by UV-light for 5 h of an MeOH solution of III and NH4PF6 afforded thin brown platey crystals of the trans-isomer, II. Repeated recrystallization of II from CH3CN/Et2O and then from MeOH/CH2Cl2 gave purple prismatic crystals of I whose 1H NMR spectrum was consistent with the dinuclear structure. The 1H NMR data of complex I in CD3CN (303 K, 400 MHz) are: δ 2.852 (s, –NCH3, 3H), 2.903 (s, –NCH3, 3H), 3.235 (s, –NCH3, 3H), 3.273 (s, –NCH3, 3H), 3.825 (d, –OCH3, J = 10.8 Hz, 3H), 3.915 (d, –OCH3, J = 10.4 Hz, 3H), and 7.40–7.71 (m, –C6H5, 5H).
Methyl H atoms attached to the N atoms of the dimethyldithiocarbamate ligands were located from ΔF syntheses and refined as a part of a rigid groups which were allowed to rotate but not tip or distort, and with C—H = 0.96 Å and Uiso(H) = 1.2Ueq(C). Other H atoms were placed geometrically and refined using a riding model with C—H = 0.96 Å (for methyl H) or 0.93 Å (for phenyl H) and Uiso(H) = 1.2Ueq(C).
Data collection: MSC/AFC Diffractometer Control (Rigaku Co. Ltd, 1985); cell refinement: MSC/AFC Diffractometer Control (Rigaku Co. Ltd, 1985); data reduction: TEXSAN ver. 1.11 (Molecular Structure Corporation and Rigaku Co. Ltd, 2000); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Johnson, 1970); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Fig. 1. A perspective view of the complex dication in (I). H atoms have been omitted for clarity and displacement ellipsoids are drawn at the 50% probability level. Symmetry code: (i) -x,y,1/2 - z. |
[Co(C3H6NS2)4(C8H11O2P)2]·2(PF6) | F(000) = 2496 |
Mr = 1228.91 | Dx = 1.697 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
a = 26.454 (3) Å | Cell parameters from 24 reflections |
b = 14.499 (3) Å | θ = 14.7–15.0° |
c = 14.517 (3) Å | µ = 1.26 mm−1 |
β = 120.276 (10)° | T = 296 K |
V = 4808.8 (16) Å3 | Square prism, purple |
Z = 4 | 0.28 × 0.26 × 0.18 mm |
Rigaku AFC5R diffractometer | 3741 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.023 |
Graphite monochromator | θmax = 30.0°, θmin = 2.6° |
ω–2θ scans | h = 0→37 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→20 |
Tmin = 0.744, Tmax = 0.798 | l = −20→17 |
7153 measured reflections | 3 standard reflections every 150 reflections |
7017 independent reflections | intensity decay: 1.1% |
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)] = 0.047 | Hydrogen site location: see text |
wR(F2) = 0.164 | See text |
S = 1.04 | w = 1/[σ2(Fo2) + (0.082P)2 + 1.623P] where P = (Fo2 + 2Fc2)/3 |
7017 reflections | (Δ/σ)max = 0.019 |
284 parameters | Δρmax = 0.94 e Å−3 |
0 restraints | Δρmin = −0.63 e Å−3 |
[Co(C3H6NS2)4(C8H11O2P)2]·2(PF6) | V = 4808.8 (16) Å3 |
Mr = 1228.91 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 26.454 (3) Å | µ = 1.26 mm−1 |
b = 14.499 (3) Å | T = 296 K |
c = 14.517 (3) Å | 0.28 × 0.26 × 0.18 mm |
β = 120.276 (10)° |
Rigaku AFC5R diffractometer | 3741 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.023 |
Tmin = 0.744, Tmax = 0.798 | 3 standard reflections every 150 reflections |
7153 measured reflections | intensity decay: 1.1% |
7017 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.164 | See text |
S = 1.04 | Δρmax = 0.94 e Å−3 |
7017 reflections | Δρmin = −0.63 e Å−3 |
284 parameters |
Experimental. none |
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 | ||
Co | 0.06306 (2) | 0.23665 (3) | 0.24314 (4) | 0.03142 (13) | |
S1 | −0.03434 (4) | 0.25486 (6) | 0.12626 (7) | 0.03358 (19) | |
S2 | 0.05701 (4) | 0.38723 (6) | 0.20155 (8) | 0.0384 (2) | |
S3 | 0.15851 (4) | 0.21982 (7) | 0.36901 (8) | 0.0411 (2) | |
S4 | 0.06887 (4) | 0.08504 (6) | 0.28897 (8) | 0.0366 (2) | |
P1 | 0.08938 (4) | 0.20933 (8) | 0.12470 (9) | 0.0417 (2) | |
O1 | 0.13616 (17) | 0.2836 (2) | 0.1339 (4) | 0.0742 (11) | |
O2 | 0.03351 (15) | 0.2163 (3) | 0.0098 (3) | 0.0730 (11) | |
N1 | −0.05476 (14) | 0.4364 (2) | 0.0706 (3) | 0.0423 (7) | |
N2 | 0.18158 (14) | 0.0417 (2) | 0.4250 (3) | 0.0450 (8) | |
C1 | −0.01636 (16) | 0.3719 (3) | 0.1245 (3) | 0.0361 (7) | |
C2 | −0.11718 (19) | 0.4194 (3) | 0.0130 (4) | 0.0563 (12) | |
H2A | −0.1353 | 0.4561 | −0.0507 | 0.068* | |
H2B | −0.1333 | 0.4356 | 0.0571 | 0.068* | |
H2C | −0.1243 | 0.3553 | −0.0056 | 0.068* | |
C3 | −0.0359 (2) | 0.5329 (3) | 0.0771 (4) | 0.0561 (12) | |
H3A | −0.0491 | 0.5684 | 0.1168 | 0.067* | |
H3B | −0.0524 | 0.5579 | 0.0065 | 0.067* | |
H3C | 0.0060 | 0.5355 | 0.1123 | 0.067* | |
C4 | 0.14212 (15) | 0.1055 (3) | 0.3708 (3) | 0.0356 (8) | |
C5 | 0.24357 (18) | 0.0643 (4) | 0.4903 (4) | 0.0673 (14) | |
H5A | 0.2665 | 0.0092 | 0.5039 | 0.084* | |
H5B | 0.2509 | 0.0903 | 0.5567 | 0.084* | |
H5C | 0.2541 | 0.1081 | 0.4533 | 0.084* | |
C6 | 0.1654 (2) | −0.0551 (3) | 0.4163 (4) | 0.0573 (11) | |
H6A | 0.1680 | −0.0750 | 0.4816 | 0.071* | |
H6B | 0.1916 | −0.0912 | 0.4032 | 0.071* | |
H6C | 0.1261 | −0.0631 | 0.3584 | 0.071* | |
C7 | 0.1701 (3) | 0.2912 (5) | 0.0866 (6) | 0.093 (2) | |
H7A | 0.1904 | 0.2341 | 0.0946 | 0.108* | |
H7B | 0.1981 | 0.3399 | 0.1202 | 0.108* | |
H7C | 0.1455 | 0.3048 | 0.0121 | 0.108* | |
C8 | 0.0306 (3) | 0.2033 (5) | −0.0915 (4) | 0.0781 (17) | |
H8A | −0.0093 | 0.1933 | −0.1462 | 0.093* | |
H8B | 0.0537 | 0.1507 | −0.0873 | 0.093* | |
H8C | 0.0455 | 0.2572 | −0.1083 | 0.093* | |
C9 | 0.12132 (18) | 0.0983 (3) | 0.1292 (3) | 0.0430 (9) | |
C10 | 0.1817 (2) | 0.0843 (3) | 0.1883 (4) | 0.0501 (10) | |
H10 | 0.2067 | 0.1338 | 0.2221 | 0.061* | |
C11 | 0.2046 (2) | −0.0037 (4) | 0.1967 (4) | 0.0697 (15) | |
H11 | 0.2448 | −0.0128 | 0.2360 | 0.085* | |
C12 | 0.1685 (3) | −0.0766 (4) | 0.1478 (5) | 0.0803 (18) | |
H12 | 0.1841 | −0.1353 | 0.1544 | 0.093* | |
C13 | 0.1082 (3) | −0.0637 (4) | 0.0882 (5) | 0.0803 (18) | |
H13 | 0.0837 | −0.1136 | 0.0541 | 0.102* | |
C14 | 0.0850 (2) | 0.0223 (4) | 0.0795 (4) | 0.0641 (13) | |
H14 | 0.0447 | 0.0304 | 0.0402 | 0.076* | |
P2 | 0.14661 (6) | 0.65956 (9) | 0.28257 (12) | 0.0594 (3) | |
F1 | 0.1629 (3) | 0.5615 (3) | 0.2593 (5) | 0.153 (2) | |
F2 | 0.1821 (2) | 0.6980 (4) | 0.2325 (5) | 0.162 (2) | |
F3 | 0.2018 (3) | 0.6613 (5) | 0.3924 (4) | 0.191 (3) | |
F4 | 0.0928 (2) | 0.6543 (5) | 0.1689 (4) | 0.172 (3) | |
F5 | 0.1119 (4) | 0.6165 (5) | 0.3277 (7) | 0.235 (4) | |
F6 | 0.1309 (3) | 0.7550 (3) | 0.3068 (5) | 0.166 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co | 0.0275 (2) | 0.0289 (2) | 0.0393 (3) | 0.00133 (17) | 0.0180 (2) | 0.00202 (19) |
S1 | 0.0297 (4) | 0.0335 (4) | 0.0381 (4) | 0.0015 (3) | 0.0175 (4) | −0.0001 (3) |
S2 | 0.0361 (5) | 0.0323 (5) | 0.0496 (5) | −0.0002 (3) | 0.0237 (4) | 0.0040 (4) |
S3 | 0.0289 (4) | 0.0372 (5) | 0.0518 (6) | −0.0021 (3) | 0.0163 (4) | 0.0015 (4) |
S4 | 0.0304 (4) | 0.0319 (4) | 0.0478 (5) | −0.0006 (3) | 0.0199 (4) | 0.0020 (4) |
P1 | 0.0384 (5) | 0.0458 (6) | 0.0488 (6) | 0.0074 (4) | 0.0278 (5) | 0.0058 (4) |
O1 | 0.090 (3) | 0.0493 (19) | 0.131 (3) | 0.0104 (18) | 0.092 (3) | 0.018 (2) |
O2 | 0.055 (2) | 0.123 (3) | 0.0419 (17) | 0.033 (2) | 0.0248 (16) | 0.0108 (19) |
N1 | 0.0393 (17) | 0.0428 (18) | 0.0463 (18) | 0.0092 (14) | 0.0228 (15) | 0.0091 (14) |
N2 | 0.0307 (15) | 0.0468 (19) | 0.053 (2) | 0.0033 (13) | 0.0182 (15) | 0.0110 (15) |
C1 | 0.0375 (18) | 0.0346 (18) | 0.0415 (19) | 0.0032 (14) | 0.0239 (16) | 0.0033 (15) |
C2 | 0.043 (2) | 0.062 (3) | 0.057 (3) | 0.015 (2) | 0.020 (2) | 0.008 (2) |
C3 | 0.068 (3) | 0.038 (2) | 0.072 (3) | 0.012 (2) | 0.043 (3) | 0.015 (2) |
C4 | 0.0296 (17) | 0.0382 (18) | 0.043 (2) | 0.0010 (14) | 0.0208 (16) | 0.0048 (15) |
C5 | 0.030 (2) | 0.074 (3) | 0.079 (4) | 0.007 (2) | 0.015 (2) | 0.023 (3) |
C6 | 0.056 (3) | 0.041 (2) | 0.073 (3) | 0.012 (2) | 0.031 (2) | 0.016 (2) |
C7 | 0.086 (4) | 0.083 (4) | 0.140 (6) | 0.017 (3) | 0.080 (5) | 0.038 (4) |
C8 | 0.074 (4) | 0.118 (5) | 0.048 (3) | 0.022 (3) | 0.036 (3) | 0.009 (3) |
C9 | 0.044 (2) | 0.044 (2) | 0.050 (2) | −0.0022 (17) | 0.0305 (19) | −0.0042 (17) |
C10 | 0.048 (2) | 0.044 (2) | 0.068 (3) | 0.0026 (18) | 0.036 (2) | 0.0018 (19) |
C11 | 0.079 (4) | 0.063 (3) | 0.080 (4) | 0.028 (3) | 0.049 (3) | 0.020 (3) |
C12 | 0.128 (6) | 0.047 (3) | 0.098 (5) | 0.017 (3) | 0.081 (5) | 0.006 (3) |
C13 | 0.120 (6) | 0.056 (3) | 0.096 (4) | −0.028 (3) | 0.078 (4) | −0.029 (3) |
C14 | 0.067 (3) | 0.062 (3) | 0.078 (3) | −0.020 (2) | 0.047 (3) | −0.021 (3) |
P2 | 0.0570 (7) | 0.0516 (7) | 0.0704 (8) | −0.0039 (6) | 0.0327 (7) | 0.0018 (6) |
F1 | 0.204 (6) | 0.093 (3) | 0.187 (5) | 0.037 (4) | 0.117 (5) | −0.005 (3) |
F2 | 0.149 (5) | 0.181 (6) | 0.188 (6) | −0.059 (4) | 0.108 (4) | 0.016 (4) |
F3 | 0.150 (5) | 0.238 (8) | 0.095 (3) | 0.029 (5) | −0.006 (3) | −0.020 (4) |
F4 | 0.087 (3) | 0.282 (8) | 0.105 (3) | 0.035 (4) | 0.016 (3) | −0.049 (4) |
F5 | 0.368 (11) | 0.198 (7) | 0.316 (9) | −0.145 (7) | 0.304 (9) | −0.089 (6) |
F6 | 0.181 (6) | 0.080 (3) | 0.213 (6) | 0.032 (3) | 0.082 (5) | −0.035 (3) |
Co—P1 | 2.1921 (11) | C5—H5B | 0.9600 |
Co—S1 | 2.2757 (10) | C5—H5C | 0.9600 |
Co—S2 | 2.2493 (11) | C6—H6A | 0.9600 |
Co—S3 | 2.2633 (11) | C6—H6B | 0.9600 |
Co—S4 | 2.2793 (11) | C6—H6C | 0.9600 |
Co—S1i | 2.3865 (11) | C7—H7A | 0.9600 |
S1—C1 | 1.766 (4) | C7—H7B | 0.9600 |
S2—C1 | 1.696 (4) | C7—H7C | 0.9600 |
S3—C4 | 1.716 (4) | C8—H8A | 0.9600 |
S4—C4 | 1.713 (4) | C8—H8B | 0.9600 |
P1—O1 | 1.594 (4) | C8—H8C | 0.9600 |
P1—O2 | 1.578 (3) | C9—C10 | 1.396 (6) |
P1—C9 | 1.804 (4) | C9—C14 | 1.399 (6) |
O1—C7 | 1.384 (6) | C10—C11 | 1.390 (6) |
O2—C8 | 1.446 (6) | C10—H10 | 0.9300 |
N1—C1 | 1.310 (5) | C11—C12 | 1.360 (8) |
N1—C2 | 1.447 (5) | C11—H11 | 0.9300 |
N1—C3 | 1.473 (5) | C12—C13 | 1.390 (9) |
N2—C4 | 1.318 (5) | C12—H12 | 0.9300 |
N2—C6 | 1.455 (6) | C13—C14 | 1.368 (8) |
N2—C5 | 1.458 (5) | C13—H13 | 0.9300 |
C2—H2A | 0.9600 | C14—H14 | 0.9300 |
C2—H2B | 0.9600 | P2—F1 | 1.571 (5) |
C2—H2C | 0.9600 | P2—F2 | 1.552 (5) |
C3—H3A | 0.9600 | P2—F3 | 1.526 (5) |
C3—H3B | 0.9600 | P2—F4 | 1.544 (5) |
C3—H3C | 0.9600 | P2—F5 | 1.505 (5) |
C5—H5A | 0.9600 | P2—F6 | 1.536 (4) |
P1—Co—S2 | 88.43 (4) | H5A—C5—H5B | 109.5 |
P1—Co—S3 | 86.99 (4) | N2—C5—H5C | 109.5 |
S2—Co—S3 | 102.76 (4) | H5A—C5—H5C | 109.5 |
P1—Co—S1 | 97.13 (4) | H5B—C5—H5C | 109.5 |
S2—Co—S1 | 77.68 (4) | N2—C6—H6A | 109.5 |
S3—Co—S1 | 175.88 (4) | N2—C6—H6B | 109.5 |
P1—Co—S4 | 93.06 (4) | H6A—C6—H6B | 109.5 |
S2—Co—S4 | 178.49 (4) | N2—C6—H6C | 109.5 |
S3—Co—S4 | 77.10 (4) | H6A—C6—H6C | 109.5 |
S1—Co—S4 | 102.35 (4) | H6B—C6—H6C | 109.5 |
P1—Co—S1i | 175.94 (4) | O1—C7—H7A | 109.5 |
S2—Co—S1i | 95.61 (4) | O1—C7—H7B | 109.5 |
S3—Co—S1i | 92.47 (4) | H7A—C7—H7B | 109.5 |
S1—Co—S1i | 83.41 (4) | O1—C7—H7C | 109.5 |
S4—Co—S1i | 82.90 (4) | H7A—C7—H7C | 109.5 |
C1—S1—Co | 84.86 (12) | H7B—C7—H7C | 109.5 |
C1—S1—Coi | 108.26 (12) | O2—C8—H8A | 109.5 |
Co—S1—Coi | 95.11 (4) | O2—C8—H8B | 109.5 |
C1—S2—Co | 87.30 (13) | H8A—C8—H8B | 109.5 |
C4—S3—Co | 85.92 (12) | O2—C8—H8C | 109.5 |
C4—S4—Co | 85.49 (13) | H8A—C8—H8C | 109.5 |
O2—P1—O1 | 108.6 (2) | H8B—C8—H8C | 109.5 |
O2—P1—C9 | 105.5 (2) | C10—C9—C14 | 118.5 (4) |
O1—P1—C9 | 105.66 (18) | C10—C9—P1 | 121.5 (3) |
O2—P1—Co | 108.59 (13) | C14—C9—P1 | 119.8 (4) |
O1—P1—Co | 110.63 (15) | C11—C10—C9 | 120.0 (5) |
C9—P1—Co | 117.46 (14) | C11—C10—H10 | 120.0 |
C7—O1—P1 | 133.1 (4) | C9—C10—H10 | 120.0 |
C8—O2—P1 | 127.4 (3) | C12—C11—C10 | 120.5 (5) |
C1—N1—C2 | 122.6 (4) | C12—C11—H11 | 119.7 |
C1—N1—C3 | 120.3 (4) | C10—C11—H11 | 119.7 |
C2—N1—C3 | 116.7 (4) | C11—C12—C13 | 120.2 (5) |
C4—N2—C6 | 121.1 (3) | C11—C12—H12 | 119.9 |
C4—N2—C5 | 121.6 (4) | C13—C12—H12 | 119.9 |
C6—N2—C5 | 117.2 (4) | C14—C13—C12 | 120.0 (5) |
N1—C1—S2 | 125.8 (3) | C14—C13—H13 | 120.0 |
N1—C1—S1 | 124.1 (3) | C12—C13—H13 | 120.0 |
S2—C1—S1 | 110.1 (2) | C13—C14—C9 | 120.7 (5) |
N1—C2—H2A | 109.5 | C13—C14—H14 | 119.6 |
N1—C2—H2B | 109.5 | C9—C14—H14 | 119.6 |
H2A—C2—H2B | 109.5 | F1—P2—F2 | 85.9 (3) |
N1—C2—H2C | 109.5 | F1—P2—F3 | 91.0 (4) |
H2A—C2—H2C | 109.5 | F1—P2—F4 | 86.0 (3) |
H2B—C2—H2C | 109.5 | F1—P2—F5 | 90.7 (4) |
N1—C3—H3A | 109.5 | F1—P2—F6 | 179.3 (4) |
N1—C3—H3B | 109.5 | F2—P2—F3 | 89.8 (4) |
H3A—C3—H3B | 109.5 | F2—P2—F4 | 88.1 (3) |
N1—C3—H3C | 109.5 | F2—P2—F5 | 176.4 (4) |
H3A—C3—H3C | 109.5 | F2—P2—F6 | 94.7 (4) |
H3B—C3—H3C | 109.5 | F3—P2—F4 | 176.5 (4) |
N2—C4—S4 | 124.8 (3) | F3—P2—F5 | 91.4 (5) |
N2—C4—S3 | 123.8 (3) | F3—P2—F6 | 88.5 (3) |
S4—C4—S3 | 111.3 (2) | F4—P2—F5 | 90.5 (5) |
N2—C5—H5A | 109.5 | F4—P2—F6 | 94.5 (3) |
N2—C5—H5B | 109.5 | F5—P2—F6 | 88.8 (4) |
P1—Co—S1—C1 | −88.81 (13) | O1—P1—O2—C8 | 59.8 (5) |
S2—Co—S1—C1 | −1.99 (12) | C9—P1—O2—C8 | −53.1 (5) |
S4—Co—S1—C1 | 176.46 (12) | Co—P1—O2—C8 | −179.9 (5) |
S1i—Co—S1—C1 | 95.25 (12) | C2—N1—C1—S2 | −175.2 (3) |
P1—Co—S1—Coi | 163.26 (4) | C3—N1—C1—S2 | −2.6 (6) |
S2—Co—S1—Coi | −109.92 (4) | C2—N1—C1—S1 | 5.2 (6) |
S4—Co—S1—Coi | 68.53 (4) | C3—N1—C1—S1 | 177.7 (3) |
S1i—Co—S1—Coi | −12.68 (5) | Co—S2—C1—N1 | 177.6 (3) |
P1—Co—S2—C1 | 99.71 (13) | Co—S2—C1—S1 | −2.77 (17) |
S3—Co—S2—C1 | −173.73 (13) | Co—S1—C1—N1 | −177.6 (3) |
S1—Co—S2—C1 | 2.07 (13) | Coi—S1—C1—N1 | −83.9 (3) |
S1i—Co—S2—C1 | −79.91 (13) | Co—S1—C1—S2 | 2.75 (17) |
P1—Co—S3—C4 | −90.95 (13) | Coi—S1—C1—S2 | 96.44 (18) |
S2—Co—S3—C4 | −178.66 (13) | C6—N2—C4—S4 | 1.9 (6) |
S4—Co—S3—C4 | 2.88 (13) | C5—N2—C4—S4 | 177.9 (4) |
S1i—Co—S3—C4 | 85.02 (13) | C6—N2—C4—S3 | −175.0 (3) |
P1—Co—S4—C4 | 83.31 (13) | C5—N2—C4—S3 | 1.0 (6) |
S3—Co—S4—C4 | −2.89 (13) | Co—S4—C4—N2 | −173.2 (3) |
S1—Co—S4—C4 | −178.70 (13) | Co—S4—C4—S3 | 3.99 (18) |
S1i—Co—S4—C4 | −97.08 (13) | Co—S3—C4—N2 | 173.2 (3) |
S2—Co—P1—O2 | −75.36 (18) | Co—S3—C4—S4 | −4.02 (18) |
S3—Co—P1—O2 | −178.22 (18) | O2—P1—C9—C10 | 147.3 (4) |
S1—Co—P1—O2 | 2.02 (19) | O1—P1—C9—C10 | 32.3 (4) |
S4—Co—P1—O2 | 104.88 (18) | Co—P1—C9—C10 | −91.6 (4) |
S2—Co—P1—O1 | 43.72 (16) | O2—P1—C9—C14 | −37.8 (4) |
S3—Co—P1—O1 | −59.14 (16) | O1—P1—C9—C14 | −152.8 (4) |
S1—Co—P1—O1 | 121.10 (16) | Co—P1—C9—C14 | 83.3 (4) |
S4—Co—P1—O1 | −136.04 (16) | C14—C9—C10—C11 | 0.1 (7) |
S2—Co—P1—C9 | 165.11 (16) | P1—C9—C10—C11 | 175.0 (4) |
S3—Co—P1—C9 | 62.24 (16) | C9—C10—C11—C12 | −0.1 (8) |
S1—Co—P1—C9 | −117.52 (16) | C10—C11—C12—C13 | 0.5 (9) |
S4—Co—P1—C9 | −14.66 (16) | C11—C12—C13—C14 | −0.8 (9) |
O2—P1—O1—C7 | −68.7 (6) | C12—C13—C14—C9 | 0.8 (8) |
C9—P1—O1—C7 | 44.1 (6) | C10—C9—C14—C13 | −0.4 (7) |
Co—P1—O1—C7 | 172.2 (5) | P1—C9—C14—C13 | −175.5 (4) |
Symmetry code: (i) −x, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Co(C3H6NS2)4(C8H11O2P)2]·2(PF6) |
Mr | 1228.91 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 296 |
a, b, c (Å) | 26.454 (3), 14.499 (3), 14.517 (3) |
β (°) | 120.276 (10) |
V (Å3) | 4808.8 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.26 |
Crystal size (mm) | 0.28 × 0.26 × 0.18 |
Data collection | |
Diffractometer | Rigaku AFC5R diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.744, 0.798 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7153, 7017, 3741 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.164, 1.04 |
No. of reflections | 7017 |
No. of parameters | 284 |
H-atom treatment | See text |
Δρmax, Δρmin (e Å−3) | 0.94, −0.63 |
Computer programs: MSC/AFC Diffractometer Control (Rigaku Co. Ltd, 1985), TEXSAN ver. 1.11 (Molecular Structure Corporation and Rigaku Co. Ltd, 2000), SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP (Johnson, 1970).
Co—P1 | 2.1921 (11) | S2—C1 | 1.696 (4) |
Co—S1 | 2.2757 (10) | S3—C4 | 1.716 (4) |
Co—S2 | 2.2493 (11) | S4—C4 | 1.713 (4) |
Co—S3 | 2.2633 (11) | P1—O1 | 1.594 (4) |
Co—S4 | 2.2793 (11) | P1—O2 | 1.578 (3) |
Co—S1i | 2.3865 (11) | P1—C9 | 1.804 (4) |
S1—C1 | 1.766 (4) | ||
P1—Co—S2 | 88.43 (4) | P1—Co—S1i | 175.94 (4) |
P1—Co—S3 | 86.99 (4) | S1—Co—S1i | 83.41 (4) |
S2—Co—S3 | 102.76 (4) | C1—S1—Co | 84.86 (12) |
P1—Co—S1 | 97.13 (4) | C1—S1—Coi | 108.26 (12) |
S2—Co—S1 | 77.68 (4) | Co—S1—Coi | 95.11 (4) |
P1—Co—S4 | 93.06 (4) | C1—S2—Co | 87.30 (13) |
S3—Co—S4 | 77.10 (4) | C4—S3—Co | 85.92 (12) |
S1—Co—S4 | 102.35 (4) | C4—S4—Co | 85.49 (13) |
Symmetry code: (i) −x, y, −z+1/2. |
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We have undertaken the systematic syntheses and comparison of the structures, chemical and spectroscopic properties of several series of cobalt(III) complexes containing monodentate P-donor ligands, such as [Co(acac)2(P-ligand)2]+ (acac = pentane-2,4-dionate) and [Co(dtc)2(P-ligand)2]+ (dtc = N,N-dimethyldithiocarbamate). It was possible to synthesize a series of dtc complexes with diphenylphosphine (Suzuki, Iwatsuki et al., 2001), phosphites (Matsui et al., 1993), phosphonites and phosphinites (Kashiwabara et al., 2001), as well as tertiary phosphines (Suzuki, Kashiwabara et al., 2001 NOT IN REF LIST), while only tertiary phosphine complexes have been prepared for the series of acac complexes (Suzuki, Kashiwamura et al., 1998; Suzuki, Kaizaki et al., 2000). It was suggested that dtc is the best ligand to stabilize the CoIII–P bond due to its steric compactness and electronic softness (Suzuki, Kashiwamura et al., 2001).
The title compound, [Co2(µ(S)-dtc)2(dtc)2{P(OMe)2Ph}2](PF6)2 (I, Scheme 1) was the unexpected product of the attempted recrystallization of trans-[Co(dtc)2{P(OMe)2Ph}2]PF6, II, in the course of which the mononuclear molecules of II each lost one phosphonite ligand thus permitting the formation of dinuclear complex I in which the Co atoms are bridged by one S of each of two dtc ligands (Fig. 1).
The coordination mode for dithiocarbamates (R2dtc: R2NCS2-) bridging two metal centers by one of the S atoms, µ2(S)—R2dtc-κ3S,S,S', has often been observed: the April 2001 release of the Cambridge Structural Database (Allen & Kennard, 1993) contains more than 60 reports of compounds with such an R2dtc coordination mode. Typical examples involving bis(µ2(S)—R2dtc-κ3S,S,S') ligands are the dinuclear complexes composed of two edge-sharing square-pyramidal polyhedra, each of which consists of the square-planar MII(dtc)2 (M = Mo, Fe, Cu, Zn, Cd or Hg) moiety and an apical bridging S atom (types A1 and A2 in Scheme 2, in which bold lines represent R2dtc chelates). [Co2(Et2dtc)5]BF4 (Hendrickson et al., 1975) is the only example within CoIII complexes, and the structure of the cation is illustrated in Scheme 2, type B; it consists of two edge-sharing octahedra, of [Co(Et2dtc)3] and cis-[Co(Et2dtc)2]+. This type of dinuclear species was also found for [Rh2(dtc)5]BF4 (Hendrickson et al., 1976) and [Ru2(iPr2dtc)5]+ (Raston & White, 1975a). The structure of the complex cation in (I) can be categorized as type C1 in Scheme 2: two P(OMe)2Ph ligands are sited at the transoid positions of two edge-sharing octahedra. The complex cation has C2 symmetry, so it can be considered as a type A1 species with two monodentate ligands added. This kind of structure has already been found in [Ru2(Et2dtc)4(CO)2] (Raston & White, 1975b) and [Re2(Et2dtc)4{NB(C6F5)3}2] (Abram, 1999). Interestingly, all three examples of the [M2(µ-dtc)2(dtc)2L2] structure are of type C1. There are four other possible isomers for the [M2(µ-dtc)2(dtc)2L2]-type of dinuclear complex (i.e., types C2, C3, C4 and C5), but no complex having these structures has been reported to date. Furthermore, for the related [M2(µ-dtc)2L6]-type dinuclear complexes, [Pt2(µ-dtc)2(CH3)6] (Heard et al., 2000), [Ru2(µ-dtc)2([9]aneS3)2]2+ (Landgrafe & Sheldrick, 1994) and [Mo2(µ-Et2dtc)2(CO)4(NO)2] (Shiu et al., 1995), all the reported structures are of type D1 rather than type D2 (Scheme 2).
The two bridging Co–S bond lengths in complex I are 2.276 (1) and 2.387 (1) Å. The latter (Co–S1i bond) is appreciably longer than those than those [2.298 (8) and 2.333 (8) Å] in [Co2(Et2dtc)5]BF4 (Hendrickson et al., 1975), suggesting that the bridge which forms the dinuclear structure is not as strong in complex I as in [Co2(Et2dtc)5]BF4. The structure of the Co(dtc)2{P(OMe)2Ph} moiety is similar to that of the Co(dtc)2(PMe2Ph)+ cation in trans-[Co(dtc)2(PMe2Ph)2]BF4 (Suzuki, Kashiwamura et al., 2001), the phenyl ring being located directly above one of the S atoms, S4 in complex I, with a stacking interaction to the dtc plane. The dihedral angle between the phenyl ring and the dtc mean plane is 19.6 (2)°. The S–Co–S bite angles, 77.68 (4) and 77.10 (4)°, of dtc in complex I are comparable to those in trans-[Co(dtc)2(PMe3-nPhn)2]BF4 (Suzuki, Kashiwamura et al., 2001) and also in [Co(dtc)3] (Iwasaki & Kobayashi, 1980).
The Co—P bond lengths in complex I are 2.192 (1) Å. There are only a few reports of structural analyses of CoIII complexes containing P(OMe)2Ph. Except for four organometallic CoIII complexes, complex I is only the third example of such non-organometallic CoIII—P(OMe)2Ph complexes, the other two being trans-[Co(Hdmg)2Cl{P(OMe)2Ph}] (Hdmg = dimethylglyoximate monoanion; Bresciani-Pahor et al., 1982) and cis-[Co(dtc)2{P(OMe)2Ph}2]PF6 (Kashiwabara et al., 2001), where the Co—P bond lengths are reported as 2.213 (2) and average 2.218 (3) Å, respectively.