Abstract
C19H16N2OS, triclinic, P1̄ (no. 2), a = 8.1510(3) Å, b = 8.8021(3) Å, c = 11.3953(5) Å, α = 72.546(2)°, β = 84.568(2)°, γ = 80.760(2)°, V = 768.86(5) Å3, Z = 2, Rgt(F) = 0.0491, wRref(F2) = 0.1494, T = 100 K.
The molecular structure is shown in the figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.
Data collection and handling.
| Crystal: | Colourless plate |
| Size: | 0.21 × 0.16 × 0.04 mm |
| Wavelength: | Mo Kα radiation (0.71073 Å) |
| μ: | 0.22 mm−1 |
| Diffractometer, scan mode: | Bruker SMART APEX, φ and ω |
| θmax, completeness: | 28.0°, 99% |
| N(hkl)measured, N(hkl)unique, Rint: | 9366, 3619, 0.040 |
| Criterion for Iobs, N(hkl)gt: | Iobs > 2 σ(Iobs), 2625 |
| N(param)refined: | 220 |
| Programs: | Bruker [1], [2], SHELX [3], [4], Mercury [5], Olex2 [6] |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).
| Atom | x | y | z | Uiso*/Ueq |
|---|---|---|---|---|
| C1 | 0.2649(3) | 0.9263(2) | 0.59895(19) | 0.0194(5) |
| C2 | 0.4020(3) | 0.8573(2) | 0.68386(19) | 0.0170(4) |
| C3 | 0.5422(3) | 0.7529(3) | 0.66942(19) | 0.0214(5) |
| H3 | 0.612709 | 0.721509 | 0.734592 | 0.026* |
| C4 | 0.5961(3) | 0.6864(3) | 0.5733(2) | 0.0262(5) |
| H4 | 0.696426 | 0.617702 | 0.584103 | 0.031* |
| C5 | 0.5225(3) | 0.7078(3) | 0.4652(2) | 0.0254(5) |
| H5 | 0.580316 | 0.654797 | 0.411164 | 0.031* |
| C6 | 0.3712(3) | 0.7996(3) | 0.4269(2) | 0.0232(5) |
| H6 | 0.340482 | 0.797943 | 0.350771 | 0.028* |
| C7 | 0.2605(3) | 0.8920(3) | 0.48436(19) | 0.0223(5) |
| H7 | 0.165653 | 0.941274 | 0.441153 | 0.027* |
| C8 | 0.4611(3) | 0.8454(2) | 0.89677(19) | 0.0173(4) |
| C9 | 0.3829(2) | 0.7484(2) | 1.00027(19) | 0.0172(4) |
| C10 | 0.4672(3) | 0.6839(3) | 1.10903(19) | 0.0205(5) |
| H10 | 0.416279 | 0.618802 | 1.178156 | 0.025* |
| C11 | 0.6259(3) | 0.7165(3) | 1.1144(2) | 0.0210(5) |
| H11 | 0.682462 | 0.671832 | 1.186693 | 0.025* |
| C12 | 0.7015(3) | 0.8159(3) | 1.0120(2) | 0.0218(5) |
| H12 | 0.807463 | 0.839519 | 1.016403 | 0.026* |
| C13 | 0.6186(3) | 0.8802(3) | 0.9025(2) | 0.0198(5) |
| H13 | 0.669291 | 0.946235 | 0.833736 | 0.024* |
| C14 | 0.1056(3) | 0.6179(3) | 1.13132(19) | 0.0193(4) |
| C15 | 0.0507(2) | 0.7064(3) | 1.21541(19) | 0.0184(4) |
| C16 | −0.0269(3) | 0.6290(3) | 1.3276(2) | 0.0219(5) |
| H16 | −0.062511 | 0.684984 | 1.384912 | 0.026* |
| C17 | −0.0509(3) | 0.4700(3) | 1.3539(2) | 0.0247(5) |
| H17 | −0.104983 | 0.421133 | 1.428000 | 0.030* |
| C18 | 0.0044(3) | 0.3819(3) | 1.2714(2) | 0.0263(5) |
| H18 | −0.009798 | 0.274248 | 1.290426 | 0.032* |
| C19 | 0.0811(3) | 0.4578(3) | 1.1605(2) | 0.0229(5) |
| H19 | 0.117034 | 0.400415 | 1.104136 | 0.027* |
| H1 | 0.282(3) | 0.972(3) | 0.788(2) | 0.034(7)* |
| H2A | 0.100(3) | 0.914(3) | 1.109(3) | 0.041(8)* |
| H2B | 0.013(4) | 0.921(3) | 1.240(3) | 0.046(8)* |
| N1 | 0.3736(2) | 0.9092(2) | 0.78604(16) | 0.0194(4) |
| N2 | 0.0760(3) | 0.8639(2) | 1.1906(2) | 0.0247(4) |
| O1 | 0.14534(19) | 1.01392(19) | 0.63363(14) | 0.0271(4) |
| S1 | 0.18083(7) | 0.71275(7) | 0.98081(5) | 0.02337(18) |
Comment
Aminotroponiminates (ATIs) are monoanionic ligands with applications in fields such as hydroamination and polymerization catalysis and the stabilization of low-valent main group species [7], [8], [9], [10], [11], [12]. Their potential to act as redox-active ligands has recently been demonstrated [13], [14], [15]. In the coordination chemistry of ATIs, it has been shown that not only their N,N′-binding pocket, but also their C7-ligand backbone can undergo directed bonding interactions with metal centers [16], [17], [18], [19]. Thus, ATIs can effectively act as ditopic, tridentate ligands. A strategy to further increase the denticity of this class of ligands is to connect two ATI ligands via linkers, generating so-called tropocoronands. These macrocyclic ligands have been employed for the chelation of metal atoms including Co, Ni, Cu, and Rh [20], [21], [22], [23], [24], [25], [26], [27], [28]. We became interested in tropocoronands containing unsaturated linker units. Reaction of 2,2′-thio-dianiline (1) with O-tosyltropone (2) in a 1.0:2.5 stoichiometry gave the title compound 2-((2-((2-aminophenyl)thio)phenyl)amino)-cyclohepta-2,4,6-trien-1-one (3) as the main product, which was isolated and fully characterized. The isolation of compound 3 shows that functionalization of the first N atom in 1 hampers functionalization of the second nitrogen atom in this substrate in the protocol that was employed. The asymmetric unit of the title compounds contains one formula unit of 3 (triclinic, P1̄, Z = 2, see the Figure). The three planar ring systems in 3 are twisted towards each other. The angle between the mean planes of the tropolone and the adjacent phenylene ring amounts to 68.3°. The angle between the mean planes of the two phenylene units is 76.3°. The C—N bond lengths in compound 3 suggest partial double bond character for C2—N1 [1.361(3) Å] and C15—N2 [1.374(3) Å], but not for C8—N1 [1.426(3) Å]. This demonstrates the stronger electron withdrawing character of the tropolon-2-yl unit compared to the phenylene unit in 3. The C—S bond lengths are identical within limits of error and virtually identical to those in the free 2,2′-thiodianiline substituent [1.772(2) Å] [7], [8], [9], [10], [11], [12], [29] In the solid state, the title compound is linked via two N—H⋯O hydrogen bonds, forming dimers with Ci symmetry (see the Figure). In this scenario, O1 acts as a H-bond acceptor, while H2B represents the H-bond donor. Overall, this leads to a so-called R22(22) motif, i.e. a ring strucutre formed by 22 atoms including two hydrogen bond donors and two hydrogen bond acceptors [30]. Using the C7H5ONH fragment, 15 structures of 2-(amino)tropones can be found in the Cambride Structural Database [31]. The majority of these compounds form dimers in the solid state through N—H⋯O hydrogen bonding [32], [33], [34], [35], [36], [37], [38], [39], [40], [41], [42]. In comparison to the title compound, all of these dimers form R22(10) motifs, i.e. the rings generated through hydrogen bonding are significantly smaller. In addition, two examples of hydrogen-bonded coordination polymers and two monomeric species have been reported in the literature [14], [43], [44], [45].
Source of material
Ethanol (30 mL) was added to a mixture of 2,2′-thio-dianiline (1) (157 mg, 0.726 mmol) and O-tosyltropone (2) (500 mg, 1.81 mmol). The reaction mixture was heated under reflux for 3 d. Aqueous sodium hydroxide (2 M, 20 mL) and CH2Cl2 (20 mL) were added, the aqueous phase was separated and extracted with CH2Cl2 (2 × 10 mL). The combined organic phases were dried over Na2CO3 and all volatiles were removed in vacuo. The crude reaction product was purified by column chromatography (Hexan/Ethyl acetate 5:1). The product was obtained as colourless crystals. Yield: 70 mg, 0.220 mmol, 30%.
The atom labeling used for the NMR spectroscopic characterization is the same as the atom labeling in the single crystal X-ray structure analysis.
1H-NMR (500 MHz, CDCl3): δ = 6.72 (td, 1H, 3JHH = 7.50 Hz, 4JHH = 1.29 Hz, 18-H), 6.72 (dd, 1H, 3JHH = 8.10 Hz, 4JHH = 1.35 Hz, 16-H), 6.78 (m, 1H, 5-H), 6.85 (dd, 1H, 3JHH = 10.3 Hz, 4JHH = 0.52 Hz, 3-H), 6.96 (dd, 1H, 3JHH = 7.95 Hz, 4JHH = 1.42 Hz, 10-H), 7.11 (m, 1H, 4-H), 7.14 (m, 1H, 11-H), 7.20 (m, 1H, 17-H), 7.22 (m, 1H, 12-H), 7.32 (m, 3H, 6-H, 7-H, 13-H) 7.36 (dd, 3JHH = 7.7 Hz, 4JHH = 1.5 Hz, 19-H), 8.69 (br. s, 1H, NH) ppm.
13C-NMR (125 MHz, CDCl3): δ = 110.83 (s, 3-C), 113.31 (s, 14-C), 115.66 (s, 16-C), 119.15 (s, 18-C), 124.84 (s, 5-C), 126.33 (s, 13-C), 126.63 (s, 12-C), 127.46 (s, 11-C), 128.19 (s, 10-C), 131.09 (s, 7-C), 131.38 (s, 17-C), 134.45 (s, 9-C), 135.58 (s, 8-C), 136.05 (s, 4-C), 137.42 (s, 19-C), 137.60 (s, 6-C), 149.09 (s, 15-C), 153.96 (s, 2-C), 177.17 (s, 1-C) ppm.
Anal. calc. for C19H16N2OS (320.41 g/mol): C, 71.22; H, 5.03; N, 8.74; found: C, 70.99; H, 4.95; N, 8.61.
m. p.: 175 °C.
Experimental details
The Uiso values of H atoms were set to 1.2 * Ueq of the parent atoms. Coordinates of hydrogen atoms bound to N were refined without any constraints or restraints. All other hydrogen atoms were refined with riding coordinates.
Acknowledgements
The authors thank Prof. Holger Braunschweig for constant support and the Fonds der Chemischen Industrie (Liebig scholarship to C. L.), the DFG, and the University of Würzburg for generous financial support. This publication was supported by the Open Access Publication Fund of the University of Würzburg.
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