Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107052870/bg3060sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107052870/bg3060Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107052870/bg3060IIsup3.hkl |
CCDC references: 672404; 672405
For related literature, see: Allen (2002); Bouziotis et al. (1999); Chelminiak et al. (2005); Femia et al. (2000); Flack (1983); Friebe et al. (2000); Heimbold et al. (2002); Jung et al. (2002); Maresca et al. (2002); Marsh (2005); Nock, Maina, Tisato, Papadopoulos, Raptopoulou, Terzis & Chiotellis (1999); Nock, Maina, Tisato, Raptopoulou, Terzis, Papadopoulos, Refosco & Chiotellis (1999); Noll et al. (2002); Papadopoulos et al. (1999); Tsoukalas et al. (1999).
The synthesis starts with the preparation of the tridentate ligand containing both the sulfur protecting groups and tosyl as leaving group. In the next step, the fluorine is introduced by nucleophilic substitution in acetonitrile with Kryptofix 2.2.2 at 413 K. Subsequently, both sulfur benzyl protecting groups were split off by reductive cleavage in liquid ammonia and metallic sodium. This reaction is accompanied by rearrangement of the ligand molecule, and besides the favoured fluorinated species two by-products are formed (see reaction scheme). Without further purification, the fluorinated tridentate ligand is combined with the monodentate p-methoxybenzenethiol ligand as model compound and Re or Tc in the oxidation state +5 to give a `3 + 1' complex (see reaction scheme). The Re [Tc here?] complexes were separated out by column chromatography on silica gel with dichloromethane as eluent. The fractions were collected and evaporated to dryness. Crystals of the metal complexes were grown from ethanol. Here we describe only the metal complexes of the by-products.
Compound (I) crystallizes in the non-centrosymetric spacegroup P21 and was refined as an inversion twin with a Flack parameter (Flack, 1983) of 0.48 (3). Restraints were used for the thermal vibration parameters of four C atoms (C13–C16).
For compound (II), the low N(obs)/N(tot) ratio is the inescapable result of the poor quality of the crystals available; in various trials no better crystals nor resulting data sets could be obtained. This result was unexpected, since comparable Tc compounds investigated by our group tend to build good quality crystals.
All H atoms in both structures were included using a riding model, with C—H = 0.93–0.97 Å and with Uiso(H) = 1.2–1.5Ueq(C).
For both compounds, data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); 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: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
[Tc(C14H21NS2)(C7H7OS)O] | F(000) = 536 |
Mr = 520.62 | Dx = 1.500 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 775 reflections |
a = 10.885 (7) Å | θ = 3.1–29.6° |
b = 7.247 (4) Å | µ = 0.91 mm−1 |
c = 14.885 (7) Å | T = 273 K |
β = 100.913 (8)° | Plate, brown |
V = 1152.9 (11) Å3 | 0.45 × 0.39 × 0.15 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 4523 independent reflections |
Radiation source: fine-focus sealed tube | 3581 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
ω scans | θmax = 27.5°, θmin = 1.9° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −13→13 |
Tmin = 0.656, Tmax = 0.872 | k = −9→9 |
6818 measured reflections | l = −14→19 |
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)] = 0.065 | H-atom parameters constrained |
wR(F2) = 0.144 | w = 1/[σ2(Fo2) + (0.0606P)2 + 3.45P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
4523 reflections | Δρmax = 1.57 e Å−3 |
236 parameters | Δρmin = −0.81 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.49 (3) |
[Tc(C14H21NS2)(C7H7OS)O] | V = 1152.9 (11) Å3 |
Mr = 520.62 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.885 (7) Å | µ = 0.91 mm−1 |
b = 7.247 (4) Å | T = 273 K |
c = 14.885 (7) Å | 0.45 × 0.39 × 0.15 mm |
β = 100.913 (8)° |
Bruker SMART CCD area-detector diffractometer | 4523 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 3581 reflections with I > 2σ(I) |
Tmin = 0.656, Tmax = 0.872 | Rint = 0.045 |
6818 measured reflections |
R[F2 > 2σ(F2)] = 0.065 | H-atom parameters constrained |
wR(F2) = 0.144 | Δρmax = 1.57 e Å−3 |
S = 1.02 | Δρmin = −0.81 e Å−3 |
4523 reflections | Absolute structure: Flack (1983), with how many Friedel pairs? |
236 parameters | Absolute structure parameter: 0.49 (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 | ||
Tc1 | 0.27773 (5) | −0.00001 (10) | 0.07540 (4) | 0.03687 (17) | |
S1 | 0.0771 (2) | 0.1056 (4) | 0.04157 (16) | 0.0558 (6) | |
S2 | 0.3154 (3) | −0.3036 (4) | 0.07132 (16) | 0.0578 (6) | |
S3 | 0.2418 (2) | −0.0742 (4) | 0.21897 (16) | 0.0542 (6) | |
O1 | 0.3972 (6) | 0.1457 (9) | 0.0925 (4) | 0.0532 (16) | |
O2 | −0.0126 (7) | 0.5290 (13) | 0.3822 (5) | 0.077 (2) | |
N1 | 0.2584 (5) | −0.0152 (14) | −0.0751 (4) | 0.0382 (14) | |
C1 | 0.0427 (8) | 0.1003 (15) | −0.0836 (6) | 0.053 (2) | |
H1B | −0.0451 | 0.0727 | −0.1051 | 0.064* | |
H1C | 0.0601 | 0.2200 | −0.1075 | 0.064* | |
C2 | 0.1233 (7) | −0.0470 (13) | −0.1178 (6) | 0.049 (3) | |
H2A | 0.0975 | −0.1686 | −0.1015 | 0.059* | |
H2B | 0.1128 | −0.0406 | −0.1839 | 0.059* | |
C3 | 0.3137 (10) | −0.3489 (12) | −0.0494 (7) | 0.056 (3) | |
H3A | 0.3777 | −0.4390 | −0.0552 | 0.067* | |
H3B | 0.2332 | −0.3999 | −0.0776 | 0.067* | |
C4 | 0.3377 (10) | −0.1700 (16) | −0.0992 (7) | 0.048 (3) | |
H4A | 0.4253 | −0.1365 | −0.0822 | 0.057* | |
H4B | 0.3190 | −0.1903 | −0.1648 | 0.057* | |
C5 | 0.1585 (9) | 0.1125 (14) | 0.2619 (6) | 0.051 (2) | |
C6 | 0.0598 (9) | 0.0655 (14) | 0.3056 (6) | 0.057 (3) | |
H6A | 0.0344 | −0.0569 | 0.3067 | 0.069* | |
C7 | −0.0010 (10) | 0.2015 (17) | 0.3478 (6) | 0.062 (3) | |
H7A | −0.0666 | 0.1711 | 0.3771 | 0.075* | |
C8 | 0.0393 (9) | 0.3838 (14) | 0.3449 (6) | 0.054 (3) | |
C9 | 0.1339 (8) | 0.4258 (14) | 0.2979 (6) | 0.053 (2) | |
H9A | 0.1577 | 0.5482 | 0.2936 | 0.063* | |
C10 | 0.1920 (9) | 0.2946 (14) | 0.2585 (6) | 0.052 (2) | |
H10A | 0.2562 | 0.3273 | 0.2284 | 0.063* | |
C11 | −0.1076 (10) | 0.478 (3) | 0.4361 (7) | 0.090 (4) | |
H11A | −0.1392 | 0.5876 | 0.4601 | 0.135* | |
H11B | −0.0706 | 0.3993 | 0.4858 | 0.135* | |
H11C | −0.1751 | 0.4141 | 0.3977 | 0.135* | |
C12 | 0.3049 (10) | 0.1596 (13) | −0.1091 (7) | 0.042 (2) | |
H12A | 0.3900 | 0.1798 | −0.0768 | 0.050* | |
H12B | 0.2543 | 0.2605 | −0.0934 | 0.050* | |
C13 | 0.3038 (11) | 0.1675 (13) | −0.2140 (6) | 0.0618 (14) | |
H13A | 0.3632 | 0.0786 | −0.2294 | 0.074* | |
H13B | 0.2213 | 0.1345 | −0.2472 | 0.074* | |
C14 | 0.3382 (11) | 0.3619 (14) | −0.2432 (6) | 0.0618 (14) | |
H14A | 0.2720 | 0.4474 | −0.2363 | 0.074* | |
H14B | 0.4144 | 0.4024 | −0.2033 | 0.074* | |
C15 | 0.3572 (12) | 0.3658 (14) | −0.3430 (6) | 0.0618 (14) | |
H15A | 0.4310 | 0.2933 | −0.3465 | 0.074* | |
H15B | 0.2864 | 0.3040 | −0.3803 | 0.074* | |
C16 | 0.3715 (11) | 0.5485 (12) | −0.3850 (6) | 0.0618 (14) | |
C17 | 0.4528 (11) | 0.6806 (15) | −0.3383 (7) | 0.065 (3) | |
H17A | 0.4935 | 0.6584 | −0.2785 | 0.078* | |
C18 | 0.4728 (10) | 0.8443 (16) | −0.3809 (8) | 0.067 (3) | |
H18A | 0.5270 | 0.9315 | −0.3493 | 0.081* | |
C19 | 0.4142 (12) | 0.8802 (16) | −0.4688 (8) | 0.074 (3) | |
H19A | 0.4290 | 0.9907 | −0.4967 | 0.088* | |
C20 | 0.3337 (13) | 0.753 (2) | −0.5152 (8) | 0.086 (4) | |
H20A | 0.2932 | 0.7769 | −0.5748 | 0.103* | |
C21 | 0.3121 (11) | 0.5863 (18) | −0.4737 (7) | 0.075 (3) | |
H21A | 0.2574 | 0.5002 | −0.5058 | 0.090* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Tc1 | 0.0352 (3) | 0.0389 (3) | 0.0380 (3) | −0.0005 (4) | 0.0106 (2) | −0.0010 (4) |
S1 | 0.0489 (13) | 0.0742 (16) | 0.0469 (13) | 0.0193 (13) | 0.0157 (10) | −0.0044 (12) |
S2 | 0.0740 (16) | 0.0541 (14) | 0.0492 (14) | −0.0093 (13) | 0.0218 (12) | 0.0071 (11) |
S3 | 0.0599 (14) | 0.0586 (14) | 0.0472 (13) | 0.0035 (12) | 0.0182 (11) | 0.0076 (10) |
O1 | 0.056 (4) | 0.055 (4) | 0.051 (4) | −0.028 (3) | 0.014 (3) | −0.010 (3) |
O2 | 0.070 (4) | 0.081 (7) | 0.079 (5) | 0.020 (5) | 0.011 (4) | −0.032 (5) |
N1 | 0.033 (3) | 0.035 (4) | 0.048 (3) | 0.001 (4) | 0.012 (3) | −0.002 (4) |
C1 | 0.043 (5) | 0.077 (6) | 0.038 (5) | 0.007 (5) | 0.004 (4) | −0.001 (5) |
C2 | 0.039 (4) | 0.066 (8) | 0.044 (4) | −0.006 (4) | 0.011 (4) | −0.007 (4) |
C3 | 0.069 (6) | 0.038 (5) | 0.069 (7) | 0.004 (5) | 0.035 (5) | −0.005 (4) |
C4 | 0.048 (6) | 0.054 (7) | 0.048 (5) | 0.014 (5) | 0.025 (4) | 0.003 (5) |
C5 | 0.059 (6) | 0.058 (6) | 0.038 (5) | 0.002 (5) | 0.015 (4) | −0.005 (4) |
C6 | 0.069 (6) | 0.058 (7) | 0.052 (5) | −0.005 (5) | 0.029 (5) | 0.006 (4) |
C7 | 0.062 (6) | 0.082 (8) | 0.047 (6) | 0.001 (6) | 0.021 (5) | 0.010 (5) |
C8 | 0.051 (6) | 0.060 (7) | 0.047 (5) | 0.014 (5) | −0.001 (4) | −0.004 (4) |
C9 | 0.046 (5) | 0.061 (6) | 0.047 (5) | −0.001 (4) | −0.002 (4) | −0.006 (4) |
C10 | 0.045 (5) | 0.060 (6) | 0.051 (5) | −0.015 (5) | 0.005 (4) | 0.002 (4) |
C11 | 0.085 (7) | 0.126 (12) | 0.064 (6) | 0.033 (10) | 0.028 (5) | −0.008 (9) |
C12 | 0.042 (5) | 0.034 (6) | 0.051 (6) | −0.004 (4) | 0.015 (4) | −0.001 (4) |
C13 | 0.097 (4) | 0.048 (3) | 0.045 (3) | −0.015 (3) | 0.026 (3) | −0.001 (2) |
C14 | 0.097 (4) | 0.048 (3) | 0.045 (3) | −0.015 (3) | 0.026 (3) | −0.001 (2) |
C15 | 0.097 (4) | 0.048 (3) | 0.045 (3) | −0.015 (3) | 0.026 (3) | −0.001 (2) |
C16 | 0.097 (4) | 0.048 (3) | 0.045 (3) | −0.015 (3) | 0.026 (3) | −0.001 (2) |
C17 | 0.084 (8) | 0.058 (6) | 0.051 (6) | −0.012 (6) | 0.009 (5) | 0.002 (5) |
C18 | 0.055 (6) | 0.058 (6) | 0.092 (8) | 0.002 (5) | 0.020 (6) | 0.016 (6) |
C19 | 0.085 (8) | 0.064 (8) | 0.080 (8) | −0.004 (7) | 0.039 (7) | 0.017 (6) |
C20 | 0.105 (10) | 0.096 (10) | 0.057 (7) | 0.020 (9) | 0.017 (7) | 0.033 (7) |
C21 | 0.086 (8) | 0.091 (8) | 0.050 (6) | −0.009 (7) | 0.015 (6) | −0.002 (6) |
Tc1—O1 | 1.657 (6) | C9—C10 | 1.337 (13) |
Tc1—N1 | 2.213 (6) | C9—H9A | 0.9300 |
Tc1—S2 | 2.241 (3) | C10—H10A | 0.9300 |
Tc1—S1 | 2.279 (3) | C11—H11A | 0.9600 |
Tc1—S3 | 2.308 (3) | C11—H11B | 0.9600 |
S1—C1 | 1.830 (9) | C11—H11C | 0.9600 |
S2—C3 | 1.824 (10) | C12—C13 | 1.561 (13) |
S3—C5 | 1.812 (10) | C12—H12A | 0.9700 |
O2—C8 | 1.361 (12) | C12—H12B | 0.9700 |
O2—C11 | 1.471 (13) | C13—C14 | 1.541 (13) |
N1—C12 | 1.488 (13) | C13—H13A | 0.9700 |
N1—C4 | 1.500 (13) | C13—H13B | 0.9700 |
N1—C2 | 1.505 (10) | C14—C15 | 1.539 (12) |
C1—C2 | 1.529 (12) | C14—H14A | 0.9700 |
C1—H1B | 0.9700 | C14—H14B | 0.9700 |
C1—H1C | 0.9700 | C15—C16 | 1.484 (13) |
C2—H2A | 0.9700 | C15—H15A | 0.9700 |
C2—H2B | 0.9700 | C15—H15B | 0.9700 |
C3—C4 | 1.540 (14) | C16—C21 | 1.383 (14) |
C3—H3A | 0.9700 | C16—C17 | 1.396 (14) |
C3—H3B | 0.9700 | C17—C18 | 1.381 (14) |
C4—H4A | 0.9700 | C17—H17A | 0.9300 |
C4—H4B | 0.9700 | C18—C19 | 1.367 (15) |
C5—C10 | 1.373 (13) | C18—H18A | 0.9300 |
C5—C6 | 1.400 (12) | C19—C20 | 1.368 (16) |
C6—C7 | 1.400 (14) | C19—H19A | 0.9300 |
C6—H6A | 0.9300 | C20—C21 | 1.395 (17) |
C7—C8 | 1.395 (15) | C20—H20A | 0.9300 |
C7—H7A | 0.9300 | C21—H21A | 0.9300 |
C8—C9 | 1.385 (13) | ||
O1—Tc1—N1 | 96.3 (3) | C9—C8—C7 | 119.5 (9) |
O1—Tc1—S2 | 119.2 (3) | C10—C9—C8 | 121.6 (10) |
N1—Tc1—S2 | 84.6 (3) | C10—C9—H9A | 119.2 |
O1—Tc1—S1 | 120.8 (3) | C8—C9—H9A | 119.2 |
N1—Tc1—S1 | 83.65 (16) | C9—C10—C5 | 121.1 (9) |
S2—Tc1—S1 | 119.76 (10) | C9—C10—H10A | 119.4 |
O1—Tc1—S3 | 105.8 (2) | C5—C10—H10A | 119.4 |
N1—Tc1—S3 | 157.8 (2) | O2—C11—H11A | 109.5 |
S2—Tc1—S3 | 81.96 (9) | O2—C11—H11B | 109.5 |
S1—Tc1—S3 | 87.69 (9) | H11A—C11—H11B | 109.5 |
C1—S1—Tc1 | 102.7 (3) | O2—C11—H11C | 109.5 |
C3—S2—Tc1 | 103.6 (3) | H11A—C11—H11C | 109.5 |
C5—S3—Tc1 | 109.6 (3) | H11B—C11—H11C | 109.5 |
C8—O2—C11 | 114.7 (10) | N1—C12—C13 | 115.6 (8) |
C12—N1—C4 | 107.9 (6) | N1—C12—H12A | 108.4 |
C12—N1—C2 | 110.8 (7) | C13—C12—H12A | 108.4 |
C4—N1—C2 | 110.2 (8) | N1—C12—H12B | 108.4 |
C12—N1—Tc1 | 109.2 (6) | C13—C12—H12B | 108.4 |
C4—N1—Tc1 | 109.3 (5) | H12A—C12—H12B | 107.4 |
C2—N1—Tc1 | 109.5 (4) | C14—C13—C12 | 111.1 (7) |
C2—C1—S1 | 109.5 (6) | C14—C13—H13A | 109.4 |
C2—C1—H1B | 109.8 | C12—C13—H13A | 109.4 |
S1—C1—H1B | 109.8 | C14—C13—H13B | 109.4 |
C2—C1—H1C | 109.8 | C12—C13—H13B | 109.4 |
S1—C1—H1C | 109.8 | H13A—C13—H13B | 108.0 |
H1B—C1—H1C | 108.2 | C15—C14—C13 | 111.9 (8) |
N1—C2—C1 | 109.2 (7) | C15—C14—H14A | 109.2 |
N1—C2—H2A | 109.8 | C13—C14—H14A | 109.2 |
C1—C2—H2A | 109.8 | C15—C14—H14B | 109.2 |
N1—C2—H2B | 109.8 | C13—C14—H14B | 109.2 |
C1—C2—H2B | 109.8 | H14A—C14—H14B | 107.9 |
H2A—C2—H2B | 108.3 | C16—C15—C14 | 117.8 (8) |
C4—C3—S2 | 110.6 (7) | C16—C15—H15A | 107.9 |
C4—C3—H3A | 109.5 | C14—C15—H15A | 107.9 |
S2—C3—H3A | 109.5 | C16—C15—H15B | 107.9 |
C4—C3—H3B | 109.5 | C14—C15—H15B | 107.9 |
S2—C3—H3B | 109.5 | H15A—C15—H15B | 107.2 |
H3A—C3—H3B | 108.1 | C21—C16—C17 | 118.5 (9) |
N1—C4—C3 | 110.9 (7) | C21—C16—C15 | 120.7 (9) |
N1—C4—H4A | 109.5 | C17—C16—C15 | 120.6 (9) |
C3—C4—H4A | 109.5 | C18—C17—C16 | 120.0 (10) |
N1—C4—H4B | 109.5 | C18—C17—H17A | 120.0 |
C3—C4—H4B | 109.5 | C16—C17—H17A | 120.0 |
H4A—C4—H4B | 108.0 | C19—C18—C17 | 121.2 (12) |
C10—C5—C6 | 118.9 (9) | C19—C18—H18A | 119.4 |
C10—C5—S3 | 123.4 (8) | C17—C18—H18A | 119.4 |
C6—C5—S3 | 117.5 (8) | C18—C19—C20 | 119.5 (11) |
C5—C6—C7 | 120.5 (10) | C18—C19—H19A | 120.2 |
C5—C6—H6A | 119.8 | C20—C19—H19A | 120.2 |
C7—C6—H6A | 119.8 | C19—C20—C21 | 120.4 (11) |
C8—C7—C6 | 118.3 (9) | C19—C20—H20A | 119.8 |
C8—C7—H7A | 120.8 | C21—C20—H20A | 119.8 |
C6—C7—H7A | 120.8 | C16—C21—C20 | 120.4 (12) |
O2—C8—C9 | 116.3 (10) | C16—C21—H21A | 119.8 |
O2—C8—C7 | 124.2 (9) | C20—C21—H21A | 119.8 |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···S1i | 0.97 | 2.78 | 3.650 (9) | 150 |
C4—H4A···O1ii | 0.97 | 2.52 | 3.164 (13) | 124 |
Symmetry codes: (i) −x, y−1/2, −z; (ii) −x+1, y−1/2, −z. |
[Tc(C7H15NS2)(C7H7OS)O] | F(000) = 880 |
Mr = 430.51 | Dx = 1.597 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 907 reflections |
a = 10.610 (7) Å | θ = 3.0–24.4° |
b = 10.356 (7) Å | µ = 1.16 mm−1 |
c = 16.296 (11) Å | T = 273 K |
β = 90.574 (15)° | Plate, brown |
V = 1790 (2) Å3 | 0.15 × 0.09 × 0.02 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 4031 independent reflections |
Radiation source: fine-focus sealed tube | 1809 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.092 |
ω scans | θmax = 27.5°, θmin = 2.3° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −13→11 |
Tmin = 0.879, Tmax = 0.978 | k = −13→13 |
10232 measured reflections | l = −20→17 |
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)] = 0.062 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 0.86 | w = 1/[σ2(Fo2) + (0.0371P)2] where P = (Fo2 + 2Fc2)/3 |
4031 reflections | (Δ/σ)max < 0.001 |
190 parameters | Δρmax = 0.92 e Å−3 |
2 restraints | Δρmin = −0.60 e Å−3 |
[Tc(C7H15NS2)(C7H7OS)O] | V = 1790 (2) Å3 |
Mr = 430.51 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.610 (7) Å | µ = 1.16 mm−1 |
b = 10.356 (7) Å | T = 273 K |
c = 16.296 (11) Å | 0.15 × 0.09 × 0.02 mm |
β = 90.574 (15)° |
Bruker SMART CCD area-detector diffractometer | 4031 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 1809 reflections with I > 2σ(I) |
Tmin = 0.879, Tmax = 0.978 | Rint = 0.092 |
10232 measured reflections |
R[F2 > 2σ(F2)] = 0.062 | 2 restraints |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 0.86 | Δρmax = 0.92 e Å−3 |
4031 reflections | Δρmin = −0.60 e Å−3 |
190 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 | ||
Tc1 | 0.76655 (4) | 0.24888 (5) | 0.15162 (3) | 0.05211 (17) | |
S1 | 0.89303 (16) | 0.08218 (15) | 0.11159 (12) | 0.0775 (5) | |
S2 | 0.60719 (13) | 0.21855 (13) | 0.24244 (10) | 0.0629 (4) | |
S3 | 0.63174 (15) | 0.16995 (16) | 0.05143 (10) | 0.0729 (5) | |
O1 | 0.8032 (3) | 0.3985 (3) | 0.1219 (2) | 0.0648 (10) | |
O2 | 0.1240 (4) | 0.4098 (5) | 0.0654 (3) | 0.0811 (13) | |
N1 | 0.8856 (4) | 0.2457 (4) | 0.2630 (3) | 0.0565 (11) | |
C1 | 0.9964 (5) | 0.0625 (6) | 0.2008 (5) | 0.083 (2) | |
H1B | 1.0166 | −0.0282 | 0.2082 | 0.099* | |
H1C | 1.0744 | 0.1091 | 0.1922 | 0.099* | |
C2 | 0.9322 (5) | 0.1132 (6) | 0.2764 (4) | 0.0718 (18) | |
H2A | 0.8622 | 0.0573 | 0.2901 | 0.086* | |
H2B | 0.9913 | 0.1127 | 0.3222 | 0.086* | |
C3 | 0.6871 (5) | 0.2281 (6) | 0.3424 (3) | 0.0665 (17) | |
H3A | 0.6345 | 0.2753 | 0.3804 | 0.080* | |
H3B | 0.6993 | 0.1417 | 0.3640 | 0.080* | |
C4 | 0.8121 (5) | 0.2941 (6) | 0.3358 (4) | 0.0701 (17) | |
H4A | 0.8607 | 0.2790 | 0.3857 | 0.084* | |
H4B | 0.7991 | 0.3864 | 0.3305 | 0.084* | |
C5 | 0.4808 (5) | 0.2437 (6) | 0.0622 (3) | 0.0604 (14) | |
C6 | 0.4681 (5) | 0.3750 (6) | 0.0706 (4) | 0.0656 (17) | |
H6A | 0.5402 | 0.4257 | 0.0751 | 0.079* | |
C7 | 0.3506 (6) | 0.4341 (6) | 0.0726 (4) | 0.0668 (17) | |
H7A | 0.3445 | 0.5230 | 0.0794 | 0.080* | |
C8 | 0.2429 (5) | 0.3597 (7) | 0.0644 (3) | 0.0586 (15) | |
C9 | 0.2546 (6) | 0.2278 (6) | 0.0560 (4) | 0.0670 (17) | |
H9A | 0.1824 | 0.1774 | 0.0508 | 0.080* | |
C10 | 0.3700 (7) | 0.1698 (6) | 0.0552 (3) | 0.0673 (17) | |
H10A | 0.3755 | 0.0806 | 0.0500 | 0.081* | |
C11 | 0.1083 (5) | 0.5442 (7) | 0.0804 (4) | 0.088 (2) | |
H11A | 0.0201 | 0.5652 | 0.0790 | 0.132* | |
H11B | 0.1511 | 0.5927 | 0.0390 | 0.132* | |
H11C | 0.1429 | 0.5653 | 0.1334 | 0.132* | |
C12 | 0.9946 (5) | 0.3386 (5) | 0.2497 (3) | 0.0617 (16) | |
H12A | 1.0377 | 0.3149 | 0.1997 | 0.074* | |
H12B | 0.9612 | 0.4251 | 0.2423 | 0.074* | |
C13 | 1.0879 (6) | 0.3397 (6) | 0.3194 (4) | 0.096 (2) | |
H13A | 1.0699 | 0.4143 | 0.3534 | 0.115* | |
H13B | 1.0730 | 0.2636 | 0.3526 | 0.115* | |
C14 | 1.2210 (6) | 0.3429 (12) | 0.2996 (5) | 0.181 (5) | |
H14A | 1.2701 | 0.3413 | 0.3494 | 0.271* | |
H14B | 1.2392 | 0.4204 | 0.2697 | 0.271* | |
H14C | 1.2416 | 0.2691 | 0.2667 | 0.271* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Tc1 | 0.0671 (3) | 0.0422 (3) | 0.0469 (3) | 0.0030 (3) | −0.0028 (2) | −0.0003 (3) |
S1 | 0.0841 (11) | 0.0586 (10) | 0.0901 (14) | 0.0114 (9) | 0.0079 (10) | −0.0129 (9) |
S2 | 0.0671 (9) | 0.0645 (11) | 0.0569 (10) | −0.0041 (7) | −0.0024 (8) | −0.0008 (8) |
S3 | 0.0894 (11) | 0.0705 (11) | 0.0586 (11) | 0.0107 (9) | −0.0136 (9) | −0.0207 (9) |
O1 | 0.092 (3) | 0.046 (2) | 0.056 (3) | −0.005 (2) | −0.005 (2) | 0.008 (2) |
O2 | 0.063 (3) | 0.102 (4) | 0.078 (3) | −0.002 (3) | −0.003 (2) | −0.006 (3) |
N1 | 0.066 (3) | 0.050 (3) | 0.053 (3) | −0.004 (3) | −0.003 (2) | 0.008 (3) |
C1 | 0.068 (4) | 0.057 (4) | 0.123 (7) | 0.011 (3) | −0.001 (4) | 0.009 (4) |
C2 | 0.072 (4) | 0.061 (4) | 0.082 (5) | 0.005 (3) | −0.003 (4) | 0.024 (4) |
C3 | 0.074 (4) | 0.077 (5) | 0.049 (4) | −0.005 (3) | −0.002 (3) | 0.011 (3) |
C4 | 0.078 (4) | 0.080 (4) | 0.052 (4) | −0.003 (3) | −0.006 (3) | 0.003 (3) |
C5 | 0.073 (4) | 0.060 (4) | 0.047 (3) | −0.008 (4) | −0.012 (3) | −0.007 (3) |
C6 | 0.062 (4) | 0.063 (4) | 0.071 (5) | −0.007 (3) | −0.017 (3) | −0.005 (3) |
C7 | 0.074 (4) | 0.063 (4) | 0.063 (5) | 0.002 (3) | −0.016 (3) | −0.009 (3) |
C8 | 0.062 (4) | 0.080 (5) | 0.033 (4) | −0.001 (3) | −0.005 (3) | 0.002 (3) |
C9 | 0.073 (4) | 0.070 (5) | 0.057 (4) | −0.022 (4) | −0.005 (3) | −0.005 (3) |
C10 | 0.102 (5) | 0.057 (4) | 0.042 (4) | −0.013 (4) | −0.003 (4) | −0.005 (3) |
C11 | 0.071 (4) | 0.109 (6) | 0.084 (5) | 0.020 (4) | 0.000 (4) | 0.002 (5) |
C12 | 0.073 (4) | 0.058 (4) | 0.054 (4) | −0.010 (3) | −0.008 (3) | 0.007 (3) |
C13 | 0.122 (6) | 0.076 (5) | 0.090 (6) | −0.036 (4) | −0.028 (5) | 0.012 (4) |
C14 | 0.100 (6) | 0.323 (15) | 0.120 (8) | −0.076 (8) | −0.026 (6) | 0.035 (9) |
Tc1—O1 | 1.671 (3) | C5—C6 | 1.373 (7) |
Tc1—N1 | 2.201 (4) | C5—C10 | 1.406 (7) |
Tc1—S2 | 2.2801 (19) | C6—C7 | 1.389 (7) |
Tc1—S1 | 2.2856 (19) | C6—H6A | 0.9300 |
Tc1—S3 | 2.3093 (19) | C7—C8 | 1.383 (7) |
S1—C1 | 1.824 (7) | C7—H7A | 0.9300 |
S2—C3 | 1.831 (6) | C8—C9 | 1.379 (8) |
S3—C5 | 1.785 (6) | C9—C10 | 1.364 (7) |
O2—C8 | 1.364 (6) | C9—H9A | 0.9300 |
O2—C11 | 1.424 (7) | C10—H10A | 0.9300 |
N1—C2 | 1.474 (6) | C11—H11A | 0.9600 |
N1—C4 | 1.512 (7) | C11—H11B | 0.9600 |
N1—C12 | 1.521 (6) | C11—H11C | 0.9600 |
C1—C2 | 1.508 (8) | C12—C13 | 1.499 (6) |
C1—H1B | 0.9700 | C12—H12A | 0.9700 |
C1—H1C | 0.9700 | C12—H12B | 0.9700 |
C2—H2A | 0.9700 | C13—C14 | 1.452 (5) |
C2—H2B | 0.9700 | C13—H13A | 0.9700 |
C3—C4 | 1.497 (7) | C13—H13B | 0.9700 |
C3—H3A | 0.9700 | C14—H14A | 0.9600 |
C3—H3B | 0.9700 | C14—H14B | 0.9600 |
C4—H4A | 0.9700 | C14—H14C | 0.9600 |
C4—H4B | 0.9700 | ||
O1—Tc1—N1 | 96.88 (17) | H4A—C4—H4B | 107.9 |
O1—Tc1—S2 | 119.49 (14) | C6—C5—C10 | 117.6 (5) |
N1—Tc1—S2 | 83.45 (13) | C6—C5—S3 | 121.5 (4) |
O1—Tc1—S1 | 118.61 (15) | C10—C5—S3 | 120.6 (5) |
N1—Tc1—S1 | 83.70 (13) | C5—C6—C7 | 121.8 (5) |
S2—Tc1—S1 | 121.50 (7) | C5—C6—H6A | 119.1 |
O1—Tc1—S3 | 105.52 (14) | C7—C6—H6A | 119.1 |
N1—Tc1—S3 | 157.51 (13) | C8—C7—C6 | 119.6 (6) |
S2—Tc1—S3 | 87.25 (8) | C8—C7—H7A | 120.2 |
S1—Tc1—S3 | 83.81 (7) | C6—C7—H7A | 120.2 |
C1—S1—Tc1 | 102.0 (2) | O2—C8—C9 | 117.5 (6) |
C3—S2—Tc1 | 103.31 (19) | O2—C8—C7 | 123.4 (6) |
C5—S3—Tc1 | 109.2 (2) | C9—C8—C7 | 119.1 (6) |
C8—O2—C11 | 118.9 (5) | C10—C9—C8 | 121.2 (5) |
C2—N1—C4 | 111.5 (5) | C10—C9—H9A | 119.4 |
C2—N1—C12 | 110.8 (4) | C8—C9—H9A | 119.4 |
C4—N1—C12 | 107.5 (4) | C9—C10—C5 | 120.7 (5) |
C2—N1—Tc1 | 109.0 (3) | C9—C10—H10A | 119.7 |
C4—N1—Tc1 | 110.3 (3) | C5—C10—H10A | 119.7 |
C12—N1—Tc1 | 107.7 (3) | O2—C11—H11A | 109.5 |
C2—C1—S1 | 109.8 (4) | O2—C11—H11B | 109.5 |
C2—C1—H1B | 109.7 | H11A—C11—H11B | 109.5 |
S1—C1—H1B | 109.7 | O2—C11—H11C | 109.5 |
C2—C1—H1C | 109.7 | H11A—C11—H11C | 109.5 |
S1—C1—H1C | 109.7 | H11B—C11—H11C | 109.5 |
H1B—C1—H1C | 108.2 | C13—C12—N1 | 113.2 (5) |
N1—C2—C1 | 110.9 (5) | C13—C12—H12A | 108.9 |
N1—C2—H2A | 109.5 | N1—C12—H12A | 108.9 |
C1—C2—H2A | 109.5 | C13—C12—H12B | 108.9 |
N1—C2—H2B | 109.5 | N1—C12—H12B | 108.9 |
C1—C2—H2B | 109.5 | H12A—C12—H12B | 107.7 |
H2A—C2—H2B | 108.1 | C14—C13—C12 | 117.9 (6) |
C4—C3—S2 | 111.3 (4) | C14—C13—H13A | 107.8 |
C4—C3—H3A | 109.4 | C12—C13—H13A | 107.8 |
S2—C3—H3A | 109.4 | C14—C13—H13B | 107.8 |
C4—C3—H3B | 109.4 | C12—C13—H13B | 107.8 |
S2—C3—H3B | 109.4 | H13A—C13—H13B | 107.2 |
H3A—C3—H3B | 108.0 | C13—C14—H14A | 109.5 |
C3—C4—N1 | 111.7 (4) | C13—C14—H14B | 109.5 |
C3—C4—H4A | 109.3 | H14A—C14—H14B | 109.5 |
N1—C4—H4A | 109.3 | C13—C14—H14C | 109.5 |
C3—C4—H4B | 109.3 | H14A—C14—H14C | 109.5 |
N1—C4—H4B | 109.3 | H14B—C14—H14C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3B···O1i | 0.97 | 2.53 | 3.464 (7) | 162 |
C12—H12A···O2ii | 0.97 | 2.58 | 3.396 (7) | 142 |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) x+1, y, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Tc(C14H21NS2)(C7H7OS)O] | [Tc(C7H15NS2)(C7H7OS)O] |
Mr | 520.62 | 430.51 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21/n |
Temperature (K) | 273 | 273 |
a, b, c (Å) | 10.885 (7), 7.247 (4), 14.885 (7) | 10.610 (7), 10.356 (7), 16.296 (11) |
β (°) | 100.913 (8) | 90.574 (15) |
V (Å3) | 1152.9 (11) | 1790 (2) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.91 | 1.16 |
Crystal size (mm) | 0.45 × 0.39 × 0.15 | 0.15 × 0.09 × 0.02 |
Data collection | ||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.656, 0.872 | 0.879, 0.978 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6818, 4523, 3581 | 10232, 4031, 1809 |
Rint | 0.045 | 0.092 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.144, 1.02 | 0.062, 0.095, 0.86 |
No. of reflections | 4523 | 4031 |
No. of parameters | 236 | 190 |
No. of restraints | 1 | 2 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.57, −0.81 | 0.92, −0.60 |
Absolute structure | Flack (1983), with how many Friedel pairs? | ? |
Absolute structure parameter | 0.49 (3) | ? |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).
Tc1—O1 | 1.657 (6) | Tc1—S1 | 2.279 (3) |
Tc1—N1 | 2.213 (6) | Tc1—S3 | 2.308 (3) |
Tc1—S2 | 2.241 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···S1i | 0.97 | 2.78 | 3.650 (9) | 150 |
C4—H4A···O1ii | 0.97 | 2.52 | 3.164 (13) | 124 |
Symmetry codes: (i) −x, y−1/2, −z; (ii) −x+1, y−1/2, −z. |
Tc1—O1 | 1.671 (3) | Tc1—S1 | 2.2856 (19) |
Tc1—N1 | 2.201 (4) | Tc1—S3 | 2.3093 (19) |
Tc1—S2 | 2.2801 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3B···O1i | 0.97 | 2.53 | 3.464 (7) | 162 |
C12—H12A···O2ii | 0.97 | 2.58 | 3.396 (7) | 142 |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) x+1, y, z. |
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Recently a new method has been described that allows the use of metal complexes as a prosthetic group in 18F labelling of biologically relevant molecules (Noll et al., 2002). The principle is based on labelling a tridentate dithiole ligand with 18F and combining it with a monodentate thiole ligand to form mixed-ligand technetium complexes (see scheme). To understand the reaction route, a non-radioactive fluorine model compound was prepared and all by-products obtained were characterized by X-ray crystal structure analysis. Here we describe only the metal complexes of the by-products, the title compounds, (I) and (II).
The molecular structures of (I) and (II) reveal that they are neutral square-pyramidal mononuclear complexes, depicted in Figs. 1 and 2. Similar Re complexes are currently under study for various applications (Bouziotis et al., 1999; Chelminiak et al., 2005; Femia et al., 2000; Friebe et al., 2000; Heimbold et al., 2002; Jung et al., 2002; Maresca et al., 2002; Marsh, 2005; Nock, Maina, Tisato, Papadopoulos et al., 1999; Nock, Maina, Tisato, Raptopoulou et al., 1999; Papadopoulos et al., 1999; Tsoukalas et al., 1999). In the case of the title compounds, the Tc atom is coordinated by two S atoms and an N atom from the tridentate ligand, another S atom provided by the 4-methoxybenzenethiol ligand and an additional O atom to complete the coordination environment. The cation environments in both structures are comparable, with axial Tc—O distances of 1.657 (6) Å in (I) and 1.671 (3) Å in (II), Tc—N distances of 2.213 (6) Å in (I) and 2.201 (4) Å in (II), and Tc—S bond lengths in the range 2.241 (3)–2.308 (3) Å in (I) and 2.2801 (19)–2.3093 (19) Å in (II). The values mentioned above are in good agreement with those reported in the Cambridge Structural Database (Version?; Allen, 2002) (TC—O = 1.654–1.670 Å, mean 1.663 Å; Tc—N = 1.996–2.259 Å, mean 2.194 Å; Tc—S = 2.280–2.359 Å, mean 2.304 Å). The Tc1—S3—C5 angles between the methoxyphenyl moiety and the central Tc atom are nearly similar [109.6 (3)° in (I) and 109.2 (2)° in (II)], whereas the S2—Tc1—S3—C5 torsion angles of -164.02 (35) and 45.49 (21)° in (I) and (II), respectively, indicate the opposite positions of the methoxyphenyl moiety.
The analysis of the crystal packing of the title complexes reveals that the monomeric units are linked via non-classical C—H···O hydrogen bonds in complexes (I) and (II) and C—H···S hydrogen bonds in complex (II) only, to result in a two-dimensional layer structure. Thus, each complex is linked to four others, forming a sheet parallel to (110). The relevant hydrogen-bonding geometries and symmetry codes are listed in Tables 2 and 4.
As illustrated in Figs. 3 and 4, the head-to-tail arrangement of the molecules within the layers leads to a zigzag formation of the Tc atoms, along the a axis in the crystal structure of compound (I) and along the b axis in case of compound (II), with Tc···Tc distances of 6.760 (13) Å and 7.042 (16) Å and 6.102 (4) Å, respectively. [Three values for two compounds - please clarify which applies to which] Due to the larger phenyl propylimine ligand, the distance between adjacent sheets is larger in (I) than in (II); in either case, no π–π interactions are observed.