Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807056814/zl2076sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807056814/zl2076Isup2.hkl |
CCDC reference: 672661
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.009 Å
- R factor = 0.035
- wR factor = 0.078
- Data-to-parameter ratio = 21.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.53 Ratio PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C13 PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 9
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The first intermediate bis(2-benzylthioethyl)amine was prepared by the reaction of benzyl mercaptane and bis(2-chloroethyl)amine hydrochloride (Fluka) as described in (Corbin et al., 1984). Then the hydroxypropyl group was introduced by reaction of bromopropanol with the bis(2-benzylthioethyl)amine. For fluorination of this compound it was necessary to insert a tosyl group at the hydroxypropyl group as leaving group. In the next step the flourine was introduced by nucleophilic substitution using the KF crown ether kryptofix 2.2.2 complex in acetonitrile at 140°C. Subsequent both benzyl protecting groups were split off by reductive cleavage in liquid ammonia and metallic sodium to get the fluorine substituted tridentate NS2 ligand. This reaction is accompanied by a competitive reaction forming the N,N-bis(mercaptoethyl)-N-(propyl)amine by cleavage the flourine. Without further purification the reaction mixture was combined with the monodentate p-methoxy benzene thiol ligand as model compound and Re at the oxidation state +5 to give "3 + 1" complexes. The two Re complexes were separated by column chromatography on silica gel and methylene chloride as eluent. The fractions were collected and evaporated to dryness. The crystals of the metal complex were grown from ethanol. Here we describe the metal complex of the by-product as shown in Fig. 3.
All H atoms were included using a riding model, with C–H: 0.93–0.97 Å, U(H)iso=1.2–1.5× U(host)equiv. The H atoms of the methyl group were treated as being static.
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).
C14H22NO2ReS3 | F(000) = 1008 |
Mr = 518.71 | Dx = 1.918 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1013 reflections |
a = 12.160 (3) Å | θ = 2.7–27.9° |
b = 16.809 (4) Å | µ = 7.12 mm−1 |
c = 9.441 (2) Å | T = 295 K |
β = 111.459 (4)° | Needle, red |
V = 1796.0 (7) Å3 | 0.45 × 0.4 × 0.2 mm |
Z = 4 |
Bruker SMART CCD diffractometer | 4013 independent reflections |
Radiation source: fine-focus sealed tube | 2835 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.060 |
ω–scan | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→15 |
Tmin = 0.058, Tmax = 0.247 | k = −18→21 |
10348 measured reflections | l = −12→11 |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 0.89 | w = 1/[σ2(Fo2) + (0.0372P)2] where P = (Fo2 + 2Fc2)/3 |
4013 reflections | (Δ/σ)max = 0.001 |
190 parameters | Δρmax = 1.68 e Å−3 |
0 restraints | Δρmin = −1.24 e Å−3 |
C14H22NO2ReS3 | V = 1796.0 (7) Å3 |
Mr = 518.71 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.160 (3) Å | µ = 7.12 mm−1 |
b = 16.809 (4) Å | T = 295 K |
c = 9.441 (2) Å | 0.45 × 0.4 × 0.2 mm |
β = 111.459 (4)° |
Bruker SMART CCD diffractometer | 4013 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2835 reflections with I > 2σ(I) |
Tmin = 0.058, Tmax = 0.247 | Rint = 0.060 |
10348 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 0.89 | Δρmax = 1.68 e Å−3 |
4013 reflections | Δρmin = −1.24 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 | ||
Re | 0.700310 (19) | 0.893135 (12) | 0.01570 (2) | 0.04417 (9) | |
S2 | 0.72046 (17) | 1.02603 (9) | 0.06904 (18) | 0.0645 (5) | |
S1 | 0.52443 (14) | 0.82875 (9) | −0.04378 (17) | 0.0609 (4) | |
S3 | 0.63447 (14) | 0.92485 (10) | −0.23912 (16) | 0.0575 (4) | |
N | 0.7014 (4) | 0.8856 (2) | 0.2477 (5) | 0.0473 (11) | |
O1 | 0.8211 (3) | 0.8372 (2) | 0.0448 (4) | 0.0608 (11) | |
O2 | 0.8870 (4) | 1.2026 (3) | −0.3639 (5) | 0.0802 (14) | |
C1 | 0.5151 (6) | 0.8080 (4) | 0.1407 (6) | 0.0689 (18) | |
H1B | 0.4615 | 0.8455 | 0.1597 | 0.083* | |
H1C | 0.4837 | 0.7549 | 0.1402 | 0.083* | |
C2 | 0.6344 (6) | 0.8141 (4) | 0.2648 (7) | 0.0703 (19) | |
H2A | 0.6249 | 0.8166 | 0.3623 | 0.084* | |
H2B | 0.6797 | 0.7667 | 0.2641 | 0.084* | |
C3 | 0.7113 (6) | 1.0310 (3) | 0.2570 (6) | 0.0638 (17) | |
H3A | 0.7902 | 1.0329 | 0.3343 | 0.077* | |
H3B | 0.6696 | 1.0789 | 0.2655 | 0.077* | |
C4 | 0.6471 (5) | 0.9593 (3) | 0.2808 (6) | 0.0544 (15) | |
H4A | 0.6508 | 0.9581 | 0.3852 | 0.065* | |
H4B | 0.5647 | 0.9621 | 0.2143 | 0.065* | |
C5 | 0.7100 (5) | 1.0101 (3) | −0.2697 (6) | 0.0483 (14) | |
C6 | 0.8320 (5) | 1.0194 (4) | −0.2006 (6) | 0.0553 (15) | |
H6A | 0.8766 | 0.9817 | −0.1313 | 0.066* | |
C7 | 0.8863 (6) | 1.0841 (4) | −0.2349 (7) | 0.0605 (16) | |
H7A | 0.9677 | 1.0898 | −0.1882 | 0.073* | |
C8 | 0.8217 (6) | 1.1413 (4) | −0.3381 (7) | 0.0573 (15) | |
C9 | 0.7015 (6) | 1.1325 (4) | −0.4051 (7) | 0.0582 (16) | |
H9A | 0.6569 | 1.1704 | −0.4739 | 0.070* | |
C10 | 0.6463 (5) | 1.0677 (4) | −0.3710 (6) | 0.0570 (15) | |
H10A | 0.5647 | 1.0627 | −0.4169 | 0.068* | |
C11 | 0.8255 (7) | 1.2612 (4) | −0.4715 (9) | 0.101 (3) | |
H11A | 0.8803 | 1.3004 | −0.4794 | 0.151* | |
H11B | 0.7677 | 1.2862 | −0.4391 | 0.151* | |
H11C | 0.7867 | 1.2366 | −0.5689 | 0.151* | |
C12 | 0.8277 (5) | 0.8757 (3) | 0.3550 (6) | 0.0576 (16) | |
H12A | 0.8746 | 0.9178 | 0.3351 | 0.069* | |
H12B | 0.8572 | 0.8256 | 0.3320 | 0.069* | |
C13 | 0.8477 (7) | 0.8768 (4) | 0.5254 (7) | 0.074 (2) | |
H13A | 0.8189 | 0.9267 | 0.5500 | 0.088* | |
H13B | 0.8027 | 0.8341 | 0.5473 | 0.088* | |
C14 | 0.9746 (8) | 0.8674 (6) | 0.6222 (8) | 0.124 (3) | |
H14A | 0.9835 | 0.8685 | 0.7275 | 0.186* | |
H14B | 1.0192 | 0.9100 | 0.6019 | 0.186* | |
H14C | 1.0029 | 0.8175 | 0.5996 | 0.186* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Re | 0.04516 (15) | 0.04144 (14) | 0.04578 (15) | 0.00048 (10) | 0.01648 (10) | −0.00574 (10) |
S2 | 0.1001 (14) | 0.0421 (8) | 0.0571 (9) | −0.0062 (8) | 0.0356 (9) | −0.0031 (7) |
S1 | 0.0518 (9) | 0.0694 (10) | 0.0571 (9) | −0.0097 (8) | 0.0146 (7) | −0.0114 (8) |
S3 | 0.0595 (10) | 0.0647 (9) | 0.0461 (8) | −0.0043 (8) | 0.0166 (7) | −0.0062 (7) |
N | 0.045 (3) | 0.040 (3) | 0.053 (3) | 0.000 (2) | 0.014 (2) | −0.003 (2) |
O1 | 0.062 (3) | 0.056 (3) | 0.064 (2) | 0.004 (2) | 0.023 (2) | −0.008 (2) |
O2 | 0.087 (4) | 0.069 (3) | 0.079 (3) | −0.009 (3) | 0.024 (3) | 0.015 (2) |
C1 | 0.070 (5) | 0.076 (4) | 0.062 (4) | −0.028 (4) | 0.028 (3) | −0.008 (3) |
C2 | 0.079 (5) | 0.065 (4) | 0.062 (4) | −0.021 (4) | 0.019 (3) | 0.002 (3) |
C3 | 0.088 (5) | 0.051 (4) | 0.054 (4) | 0.010 (3) | 0.027 (3) | −0.007 (3) |
C4 | 0.056 (4) | 0.059 (4) | 0.049 (3) | 0.005 (3) | 0.021 (3) | −0.005 (3) |
C5 | 0.052 (4) | 0.061 (4) | 0.033 (3) | 0.005 (3) | 0.016 (2) | −0.004 (3) |
C6 | 0.055 (4) | 0.064 (4) | 0.045 (3) | 0.008 (3) | 0.017 (3) | 0.007 (3) |
C7 | 0.045 (4) | 0.077 (4) | 0.054 (4) | 0.006 (3) | 0.012 (3) | 0.005 (3) |
C8 | 0.065 (4) | 0.058 (4) | 0.053 (4) | 0.004 (3) | 0.026 (3) | 0.002 (3) |
C9 | 0.059 (4) | 0.060 (4) | 0.051 (4) | 0.011 (3) | 0.014 (3) | 0.008 (3) |
C10 | 0.049 (4) | 0.070 (4) | 0.049 (3) | 0.006 (3) | 0.013 (3) | −0.003 (3) |
C11 | 0.124 (7) | 0.067 (5) | 0.104 (6) | −0.001 (4) | 0.034 (5) | 0.028 (4) |
C12 | 0.056 (4) | 0.058 (4) | 0.055 (4) | −0.001 (3) | 0.016 (3) | 0.001 (3) |
C13 | 0.079 (5) | 0.089 (5) | 0.048 (4) | 0.002 (4) | 0.018 (3) | 0.001 (3) |
C14 | 0.088 (6) | 0.193 (9) | 0.062 (5) | 0.030 (7) | −0.007 (4) | −0.010 (6) |
Re—O1 | 1.679 (4) | C5—C10 | 1.382 (7) |
Re—N | 2.189 (5) | C5—C6 | 1.393 (7) |
Re—S1 | 2.2762 (16) | C6—C7 | 1.370 (8) |
Re—S2 | 2.2833 (16) | C6—H6A | 0.9300 |
Re—S3 | 2.3030 (16) | C7—C8 | 1.390 (8) |
S2—C3 | 1.820 (6) | C7—H7A | 0.9300 |
S1—C1 | 1.820 (6) | C8—C9 | 1.372 (8) |
S3—C5 | 1.782 (6) | C9—C10 | 1.377 (8) |
N—C4 | 1.489 (6) | C9—H9A | 0.9300 |
N—C2 | 1.493 (7) | C10—H10A | 0.9300 |
N—C12 | 1.509 (7) | C11—H11A | 0.9600 |
O2—C8 | 1.376 (7) | C11—H11B | 0.9600 |
O2—C11 | 1.416 (7) | C11—H11C | 0.9600 |
C1—C2 | 1.498 (8) | C12—C13 | 1.536 (8) |
C1—H1B | 0.9700 | C12—H12A | 0.9700 |
C1—H1C | 0.9700 | C12—H12B | 0.9700 |
C2—H2A | 0.9700 | C13—C14 | 1.486 (10) |
C2—H2B | 0.9700 | C13—H13A | 0.9700 |
C3—C4 | 1.497 (8) | 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—Re—N | 96.85 (18) | H4A—C4—H4B | 108.2 |
O1—Re—S1 | 117.42 (14) | C10—C5—C6 | 118.4 (5) |
N—Re—S1 | 83.14 (12) | C10—C5—S3 | 118.9 (5) |
O1—Re—S2 | 119.65 (14) | C6—C5—S3 | 122.6 (4) |
N—Re—S2 | 82.81 (11) | C7—C6—C5 | 120.0 (5) |
S1—Re—S2 | 122.34 (6) | C7—C6—H6A | 120.0 |
O1—Re—S3 | 104.45 (14) | C5—C6—H6A | 120.0 |
N—Re—S3 | 158.59 (13) | C6—C7—C8 | 121.2 (6) |
S1—Re—S3 | 85.19 (6) | C6—C7—H7A | 119.4 |
S2—Re—S3 | 88.41 (6) | C8—C7—H7A | 119.4 |
C3—S2—Re | 102.7 (2) | C9—C8—O2 | 125.9 (6) |
C1—S1—Re | 103.7 (2) | C9—C8—C7 | 118.8 (6) |
C5—S3—Re | 110.64 (18) | O2—C8—C7 | 115.3 (6) |
C4—N—C2 | 110.2 (5) | C8—C9—C10 | 120.4 (6) |
C4—N—C12 | 111.8 (4) | C8—C9—H9A | 119.8 |
C2—N—C12 | 107.4 (4) | C10—C9—H9A | 119.8 |
C4—N—Re | 108.7 (3) | C9—C10—C5 | 121.2 (6) |
C2—N—Re | 110.5 (3) | C9—C10—H10A | 119.4 |
C12—N—Re | 108.1 (4) | C5—C10—H10A | 119.4 |
C8—O2—C11 | 117.4 (6) | O2—C11—H11A | 109.5 |
C2—C1—S1 | 110.7 (5) | O2—C11—H11B | 109.5 |
C2—C1—H1B | 109.5 | H11A—C11—H11B | 109.5 |
S1—C1—H1B | 109.5 | O2—C11—H11C | 109.5 |
C2—C1—H1C | 109.5 | H11A—C11—H11C | 109.5 |
S1—C1—H1C | 109.5 | H11B—C11—H11C | 109.5 |
H1B—C1—H1C | 108.1 | N—C12—C13 | 115.7 (5) |
N—C2—C1 | 112.4 (5) | N—C12—H12A | 108.4 |
N—C2—H2A | 109.1 | C13—C12—H12A | 108.4 |
C1—C2—H2A | 109.1 | N—C12—H12B | 108.4 |
N—C2—H2B | 109.1 | C13—C12—H12B | 108.4 |
C1—C2—H2B | 109.1 | H12A—C12—H12B | 107.4 |
H2A—C2—H2B | 107.9 | C14—C13—C12 | 111.9 (6) |
C4—C3—S2 | 109.3 (4) | C14—C13—H13A | 109.2 |
C4—C3—H3A | 109.8 | C12—C13—H13A | 109.2 |
S2—C3—H3A | 109.8 | C14—C13—H13B | 109.2 |
C4—C3—H3B | 109.8 | C12—C13—H13B | 109.2 |
S2—C3—H3B | 109.8 | H13A—C13—H13B | 107.9 |
H3A—C3—H3B | 108.3 | C13—C14—H14A | 109.5 |
N—C4—C3 | 110.0 (5) | C13—C14—H14B | 109.5 |
N—C4—H4A | 109.7 | H14A—C14—H14B | 109.5 |
C3—C4—H4A | 109.7 | C13—C14—H14C | 109.5 |
N—C4—H4B | 109.7 | H14A—C14—H14C | 109.5 |
C3—C4—H4B | 109.7 | H14B—C14—H14C | 109.5 |
Experimental details
Crystal data | |
Chemical formula | C14H22NO2ReS3 |
Mr | 518.71 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 12.160 (3), 16.809 (4), 9.441 (2) |
β (°) | 111.459 (4) |
V (Å3) | 1796.0 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 7.12 |
Crystal size (mm) | 0.45 × 0.4 × 0.2 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.058, 0.247 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10348, 4013, 2835 |
Rint | 0.060 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.078, 0.89 |
No. of reflections | 4013 |
No. of parameters | 190 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.68, −1.24 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).
Recently a new method has been described that allows to use metal complexes as prosthetic groups in fluorine-18 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 rhenium complexes. To better understand the reaction route a non-radioactive fluorine model compound was prepared and all by-products obtained were characterized by X-ray structure analysis, among them the title compound. Similar complexes are currently under study as model compounds with regard to the development of novel technetium-based radiopharmaceuticals for the noninvasive diagnosis of myocardial metabolism (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).
The molecular structure of the title complex reveals a neutral square pyramidal mononuclear complex, depicted in Fig. 1. The Re atom is coordinated by two sulfur atoms and a nitrogen atom from the tridentate ligand; another sulfur atom from the 4-methoxybenzenethiol ligand and an additional oxygen atom complete the square pyramidal coordination sphere with an axial Re—O distance of 1.679 (4) Å, a Re—N distance of 2.189 (5) Å and with Re—S bond lengths ranging from 2.2762 (16) to 2.3030 (16) Å. The Re—S3—C5 angle between the methoxyphenyl moiety and the central Re atom amounts to 110.64 (18)°, the torsion angle S2—Re—S3—C5 to -35.52 (1)°. The values mentioned above are in good agreement with those reported in the CCSD (Version 5.27; Allen, 2002); (dRe—O = 1.663–1.720 Å, av: 1.693 Å; dRe—N = 2.149–2.245 Å, av: 2.213 Å; dRe—S = 2.221–2.320 Å, av. 2.287 Å). The averages are based on 45 structures. A weak intramolecular hydrogen bond can be found in the crystal structure, namely C12—H12B ··· O1 with H ··· A=2.59, D ··· A=2.971 (6) Å and an inclined angle of 103°. It should be noticed, that this hydrogen bond is more likely a result of the compound geometry than of any attractive interaction. The analysis of the crystal packing reveals that no classic hydrogen bonds and π-π interactions are present. The head to tail arrangement of the molecules within the layers leads to a zigzag formation of the Re atoms along the c axis, with a Re—Re distance of 6.7410 (2) Å (Fig. 2.).