organic compounds
(1S,8R,15S,19R)-17-Benzyl-17-azapentacyclo[6.6.5.02,7.09,14.015,19]nonadeca-2(7),3,5,9(14),10,12-hexaene chloroform monosolvate
aLaboratoire Hétérochimie Fondamentale et Appliquée, UMR CNRS 5069, Université Paul Sabatier, 118 route de Narbonne, 31062 Toulouse Cedex 9, France, and bUniversité de Toulouse, UPS, Institut de Chimie de Toulouse FR2599, 118 route de Narbonne, 31062 Toulouse Cedex 9, France
*Correspondence e-mail: gomez@chimie.ups-tlse.fr
In the title compound, C25H23N·CHCl3, the dihydroanthracene unit is bent with a dihedral angle between the benzene rings of 57.82 (8)°. The N atom of the pyrrolidine heterocycle, which has an with the N atom as the flap, exhibits a pronounced pyramidalization [Σ(C—N—C) = 328.07°], indicating an accentuated N-donor character. In the crystal, this behaviour is evident by the C—H⋯N hydrogen bond involving a solvent molecule and the N atom. The at the C-atom fused positions of the pyrrolidine group were crystallographically confirmed to be S and R.
Related literature
For catalytic applications of 9,10-dihydroanthracene-succinimides and their related pyrrolidine derivatives, see: Sasaoka et al. (2006); Sanhes et al. (2009, 2010). For the synthesis of these ligands, see: Sanhes et al. (2008). For a description of the Cambridge Structural Database, see: Allen (2002).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2006); cell APEX2 and SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).
Supporting information
https://doi.org/10.1107/S1600536812037749/su2490sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812037749/su2490Isup2.hkl
The title compound was prepared by the reduction of the corresponding 9,10-dihydroanthracene-succinimide following the reported procedure (Sanhes et al., 2008). To a solution of the succinimide (920 mg, 2.52 mmol) in 50 ml of THF at 273 K, LiAlH4 (1.43 g, 37.7 mmol) was added in small portions and the mixture was then refluxed for 72 h. The reaction mixture was cooled to 273 K, then diethylether (30 ml) and an aqueous
of Na2SO4 were sequentially added. The precipitate that formed was filtered off and the filtrate washed three times with water. The combined organic layers were dried over anhydrous Na2SO4, filtered and the solvent evaporated under vacuum. Crystals of the title compound were obtained by slow evaporation of a solution in CHCl3. The title compound was characterized by high-resolution (CI, dichloromethane): calc. mass 338.19; found: 338.19 (for C25H23N). Further spectroscopic data for the title compound is available in the archived CIF.All the H atoms were included in calculated positions and treated as riding atoms: C—H = 0.95 Å (aromatic), 0.99 Å (methylene) and 1.00 Å (methine,) with Uiso(H) = 1.2Ueq(C).
9,10-Dihydroanthracene-succinimides are target molecules for pharmaceutical and medical uses (Sanhes et al., 2008), and their related pyrrolidines have also found applications as organocatalysts (Sasaoka et al., 2006; Sanhes et al., 2009; 2010). The synthesis of these compounds is mainly based on thermal-promoted Diels-Alder cycloadditions (for the succinimide derivatives), followed by chemical reduction to give the corresponding heterocyclic
[Sanhes et al., 2008]. From a structural point of view, a large number of 9,10-dihydroanthracene-succinimides have been analyzed by X-ray single-crystal diffraction. A search of the Cambridge Structural Database gave 67 hits (CSD, version 5.33, update No. 4, August 2012; Allen, 2002), however, no crystallographic data is available for the corresponding non-substituted pyrrolidine ligand. Herein, we report on the synthesis and of the title compound.The molecular structure of the title compound is shown in Fig. 1. The 9,10-dihydroanthracenyl is bent with a dihedral angle between the benzene rings of 57.82 (8)°. The pyrrolidine heterocycle has an Σ C—N1—C = 328.07°, which signifies an accentuated N-donor character.
with atom N1 as the flap. It is displaced from the mean plane of the four C-atoms, C15—C18 [maximum deviation = 0.0025 (15) Å] by 0.6313 (14) Å. This mean plane forms a dihedral angle of 50.78 (10)° with the C20—C25 benzyl ring. In contrast to analogous dicarboximide compounds, a pronounced pyramidalization of the atom N1 is observed withIn the crystal, this N-donor behaviour is evident by the C—H···N intermolecular hydrogen bond involving a chloroform solvate molecule (Table 1 and Fig. 2).
The
of atoms C15 and C16 was crystallographically confirmed to be S and R, respectively (Fig. 1).For catalytic applications of 9,10-dihydroanthracene-succinimides and their related pyrrolidine derivatives, see: Sasaoka et al. (2006); Sanhes et al. (2009, 2010). For the synthesis of these ligands, see: Sanhes et al. (2008). For a description of the Cambridge Structural Database, see: Allen (2002).
Data collection: APEX2 (Bruker, 2006); cell
APEX2 and SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).C25H23N·CHCl3 | F(000) = 476 |
Mr = 456.81 | Dx = 1.343 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 9897 reflections |
a = 8.6455 (2) Å | θ = 2.4–34.7° |
b = 10.7338 (3) Å | µ = 0.42 mm−1 |
c = 12.3310 (3) Å | T = 193 K |
β = 99.055 (1)° | Block, colourless |
V = 1130.04 (5) Å3 | 0.80 × 0.70 × 0.40 mm |
Z = 2 |
Bruker SMART APEXII diffractometer | 6678 independent reflections |
Radiation source: fine-focus sealed tube | 6147 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
phi and ω scans | θmax = 30.5°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | h = −12→12 |
Tmin = 0.730, Tmax = 0.850 | k = −15→15 |
19688 measured reflections | l = −17→17 |
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)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.119 | w = 1/[σ2(Fo2) + (0.0672P)2 + 0.2655P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
6678 reflections | Δρmax = 0.59 e Å−3 |
271 parameters | Δρmin = −0.54 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 3057 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.01 (5) |
C25H23N·CHCl3 | V = 1130.04 (5) Å3 |
Mr = 456.81 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.6455 (2) Å | µ = 0.42 mm−1 |
b = 10.7338 (3) Å | T = 193 K |
c = 12.3310 (3) Å | 0.80 × 0.70 × 0.40 mm |
β = 99.055 (1)° |
Bruker SMART APEXII diffractometer | 6678 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | 6147 reflections with I > 2σ(I) |
Tmin = 0.730, Tmax = 0.850 | Rint = 0.021 |
19688 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.119 | Δρmax = 0.59 e Å−3 |
S = 1.04 | Δρmin = −0.54 e Å−3 |
6678 reflections | Absolute structure: Flack (1983), 3057 Friedel pairs |
271 parameters | Absolute structure parameter: −0.01 (5) |
1 restraint |
Experimental. Spectroscopic data for the title compound: 1H NMR (300 MHz in CDCl3): 7.31 – 7.34 (m, 7H, Harom), 7.24 – 7.27 (m, 2H, Harom), 7.14 – 7.19 (m, 4H, Harom), 4.20 (s, 2H, H9,10), 3.31 (s, 2H, H19), 2.87 (m, 2H, H17 or H18), 2.78 (m, 2H, H15,16), 1.90 (m, 2H, H17 or H18) 13C NMR (75 MHz in CDCl3): 143.9, 141.8 (C11,12,13,14), 128.8, 128.1, 125.8, 125.7, 125.6, 123.6 (CH arom), 60.0 (C19), 57.0 (C17,18), 47.3 (C9,10), 44.3 (C15,16). |
x | y | z | Uiso*/Ueq | ||
N1 | 0.39289 (16) | 0.52587 (12) | 0.43293 (11) | 0.0266 (2) | |
C1 | 0.1444 (2) | 0.50798 (18) | −0.04276 (14) | 0.0345 (3) | |
H1 | 0.1492 | 0.5921 | −0.0659 | 0.041* | |
C2 | 0.0421 (2) | 0.4244 (2) | −0.10382 (15) | 0.0429 (4) | |
H2 | −0.0227 | 0.4516 | −0.1689 | 0.051* | |
C3 | 0.0345 (2) | 0.3016 (2) | −0.06997 (17) | 0.0435 (4) | |
H3 | −0.0364 | 0.2456 | −0.1117 | 0.052* | |
C4 | 0.1298 (2) | 0.25967 (18) | 0.02461 (15) | 0.0352 (3) | |
H4 | 0.1250 | 0.1754 | 0.0473 | 0.042* | |
C5 | 0.6395 (2) | 0.28010 (16) | 0.18645 (14) | 0.0326 (3) | |
H5 | 0.6355 | 0.1963 | 0.2107 | 0.039* | |
C6 | 0.7800 (2) | 0.33116 (18) | 0.16495 (15) | 0.0376 (4) | |
H6 | 0.8722 | 0.2816 | 0.1747 | 0.045* | |
C7 | 0.7867 (2) | 0.45386 (19) | 0.12935 (15) | 0.0365 (4) | |
H7 | 0.8829 | 0.4871 | 0.1143 | 0.044* | |
C8 | 0.65237 (19) | 0.52818 (16) | 0.11575 (13) | 0.0309 (3) | |
H8 | 0.6569 | 0.6122 | 0.0922 | 0.037* | |
C9 | 0.35679 (17) | 0.54536 (13) | 0.12701 (12) | 0.0255 (3) | |
H9 | 0.3634 | 0.6325 | 0.0995 | 0.031* | |
C10 | 0.34340 (18) | 0.31443 (14) | 0.19041 (13) | 0.0265 (3) | |
H10 | 0.3398 | 0.2246 | 0.2114 | 0.032* | |
C11 | 0.23268 (18) | 0.34320 (14) | 0.08567 (13) | 0.0280 (3) | |
C12 | 0.50511 (18) | 0.35394 (14) | 0.17174 (12) | 0.0260 (3) | |
C13 | 0.51215 (17) | 0.47792 (14) | 0.13708 (12) | 0.0253 (3) | |
C14 | 0.23907 (18) | 0.46747 (14) | 0.05191 (12) | 0.0268 (3) | |
C15 | 0.30194 (18) | 0.54093 (13) | 0.24191 (12) | 0.0250 (3) | |
H15 | 0.1958 | 0.5797 | 0.2359 | 0.030* | |
C16 | 0.29201 (17) | 0.40197 (13) | 0.27884 (12) | 0.0253 (3) | |
H16 | 0.1816 | 0.3822 | 0.2875 | 0.030* | |
C17 | 0.39598 (19) | 0.39743 (14) | 0.39155 (13) | 0.0285 (3) | |
H17A | 0.3534 | 0.3384 | 0.4410 | 0.034* | |
H17B | 0.5041 | 0.3720 | 0.3846 | 0.034* | |
C18 | 0.4115 (2) | 0.60275 (14) | 0.33636 (12) | 0.0293 (3) | |
H18A | 0.5213 | 0.6014 | 0.3226 | 0.035* | |
H18B | 0.3801 | 0.6901 | 0.3467 | 0.035* | |
C19 | 0.5165 (2) | 0.55150 (17) | 0.52496 (13) | 0.0337 (3) | |
H19A | 0.5195 | 0.6423 | 0.5391 | 0.040* | |
H19B | 0.6182 | 0.5276 | 0.5038 | 0.040* | |
C20 | 0.49863 (19) | 0.48467 (14) | 0.63052 (12) | 0.0272 (3) | |
C21 | 0.3573 (2) | 0.43277 (17) | 0.64887 (14) | 0.0325 (3) | |
H21 | 0.2688 | 0.4345 | 0.5925 | 0.039* | |
C22 | 0.3457 (2) | 0.37825 (18) | 0.75005 (16) | 0.0387 (4) | |
H22 | 0.2495 | 0.3418 | 0.7616 | 0.046* | |
C23 | 0.4726 (3) | 0.37670 (18) | 0.83363 (14) | 0.0390 (4) | |
H23 | 0.4630 | 0.3412 | 0.9028 | 0.047* | |
C24 | 0.6135 (2) | 0.42704 (18) | 0.81587 (14) | 0.0385 (4) | |
H24 | 0.7013 | 0.4259 | 0.8729 | 0.046* | |
C25 | 0.6271 (2) | 0.47953 (16) | 0.71431 (14) | 0.0325 (3) | |
H25 | 0.7250 | 0.5122 | 0.7021 | 0.039* | |
C26 | 0.0596 (2) | 0.65871 (19) | 0.47279 (19) | 0.0438 (4) | |
H26 | 0.1596 | 0.6107 | 0.4782 | 0.053* | |
Cl1 | −0.07721 (8) | 0.59279 (8) | 0.36846 (6) | 0.06723 (19) | |
Cl2 | 0.09629 (12) | 0.81306 (8) | 0.44019 (12) | 0.1005 (3) | |
Cl3 | −0.00976 (9) | 0.64798 (9) | 0.59955 (6) | 0.0731 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0317 (6) | 0.0213 (5) | 0.0280 (6) | −0.0020 (4) | 0.0080 (5) | 0.0010 (4) |
C1 | 0.0287 (7) | 0.0446 (9) | 0.0315 (7) | 0.0070 (6) | 0.0083 (6) | 0.0030 (6) |
C2 | 0.0287 (8) | 0.0663 (13) | 0.0335 (8) | 0.0056 (8) | 0.0043 (6) | −0.0026 (8) |
C3 | 0.0276 (8) | 0.0604 (12) | 0.0430 (9) | −0.0087 (8) | 0.0075 (7) | −0.0170 (9) |
C4 | 0.0303 (7) | 0.0368 (8) | 0.0410 (8) | −0.0070 (6) | 0.0141 (6) | −0.0106 (7) |
C5 | 0.0333 (8) | 0.0304 (7) | 0.0349 (8) | 0.0073 (6) | 0.0079 (6) | −0.0003 (6) |
C6 | 0.0291 (7) | 0.0446 (10) | 0.0398 (8) | 0.0083 (7) | 0.0077 (6) | −0.0056 (7) |
C7 | 0.0257 (7) | 0.0491 (10) | 0.0363 (8) | −0.0037 (7) | 0.0101 (6) | −0.0060 (7) |
C8 | 0.0308 (7) | 0.0327 (7) | 0.0310 (7) | −0.0064 (6) | 0.0108 (6) | −0.0013 (6) |
C9 | 0.0279 (6) | 0.0207 (6) | 0.0290 (6) | −0.0007 (5) | 0.0079 (5) | 0.0030 (5) |
C10 | 0.0295 (7) | 0.0187 (5) | 0.0331 (7) | −0.0007 (5) | 0.0103 (5) | −0.0002 (5) |
C11 | 0.0252 (6) | 0.0293 (7) | 0.0312 (7) | −0.0017 (5) | 0.0096 (5) | −0.0039 (5) |
C12 | 0.0279 (6) | 0.0237 (6) | 0.0276 (6) | 0.0000 (5) | 0.0083 (5) | −0.0017 (5) |
C13 | 0.0251 (6) | 0.0253 (6) | 0.0262 (6) | −0.0002 (5) | 0.0066 (5) | 0.0003 (5) |
C14 | 0.0246 (6) | 0.0277 (6) | 0.0297 (7) | 0.0023 (5) | 0.0088 (5) | −0.0001 (5) |
C15 | 0.0291 (6) | 0.0192 (5) | 0.0280 (6) | 0.0014 (5) | 0.0091 (5) | 0.0030 (5) |
C16 | 0.0282 (6) | 0.0202 (6) | 0.0292 (6) | −0.0012 (5) | 0.0096 (5) | 0.0020 (5) |
C17 | 0.0352 (7) | 0.0224 (6) | 0.0295 (7) | 0.0027 (5) | 0.0095 (6) | 0.0034 (5) |
C18 | 0.0388 (8) | 0.0210 (6) | 0.0292 (6) | −0.0031 (6) | 0.0095 (6) | 0.0013 (5) |
C19 | 0.0354 (8) | 0.0343 (8) | 0.0316 (7) | −0.0085 (6) | 0.0057 (6) | 0.0019 (6) |
C20 | 0.0295 (7) | 0.0255 (6) | 0.0271 (6) | 0.0002 (5) | 0.0063 (5) | −0.0032 (5) |
C21 | 0.0289 (7) | 0.0366 (8) | 0.0330 (7) | 0.0001 (6) | 0.0084 (6) | 0.0002 (6) |
C22 | 0.0403 (9) | 0.0402 (9) | 0.0401 (9) | −0.0023 (7) | 0.0201 (7) | −0.0001 (7) |
C23 | 0.0529 (10) | 0.0375 (9) | 0.0296 (8) | 0.0037 (7) | 0.0155 (7) | −0.0003 (6) |
C24 | 0.0427 (9) | 0.0405 (9) | 0.0310 (8) | 0.0037 (7) | 0.0014 (7) | −0.0054 (7) |
C25 | 0.0309 (7) | 0.0332 (7) | 0.0332 (7) | −0.0026 (6) | 0.0043 (6) | −0.0054 (6) |
C26 | 0.0380 (9) | 0.0372 (9) | 0.0568 (11) | 0.0008 (7) | 0.0096 (8) | −0.0027 (8) |
Cl1 | 0.0523 (3) | 0.0910 (5) | 0.0566 (3) | −0.0100 (3) | 0.0033 (2) | −0.0085 (3) |
Cl2 | 0.0901 (6) | 0.0433 (3) | 0.1741 (10) | −0.0087 (4) | 0.0397 (6) | 0.0149 (5) |
Cl3 | 0.0745 (4) | 0.0909 (5) | 0.0582 (3) | −0.0120 (4) | 0.0239 (3) | −0.0231 (3) |
N1—C19 | 1.457 (2) | C11—C14 | 1.401 (2) |
N1—C17 | 1.4718 (19) | C12—C13 | 1.402 (2) |
N1—C18 | 1.4782 (19) | C15—C18 | 1.532 (2) |
C1—C14 | 1.386 (2) | C15—C16 | 1.5659 (19) |
C1—C2 | 1.395 (3) | C15—H15 | 1.0000 |
C1—H1 | 0.9500 | C16—C17 | 1.533 (2) |
C2—C3 | 1.386 (3) | C16—H16 | 1.0000 |
C2—H2 | 0.9500 | C17—H17A | 0.9900 |
C3—C4 | 1.393 (3) | C17—H17B | 0.9900 |
C3—H3 | 0.9500 | C18—H18A | 0.9900 |
C4—C11 | 1.397 (2) | C18—H18B | 0.9900 |
C4—H4 | 0.9500 | C19—C20 | 1.515 (2) |
C5—C12 | 1.394 (2) | C19—H19A | 0.9900 |
C5—C6 | 1.396 (3) | C19—H19B | 0.9900 |
C5—H5 | 0.9500 | C20—C21 | 1.393 (2) |
C6—C7 | 1.392 (3) | C20—C25 | 1.394 (2) |
C6—H6 | 0.9500 | C21—C22 | 1.396 (2) |
C7—C8 | 1.397 (3) | C21—H21 | 0.9500 |
C7—H7 | 0.9500 | C22—C23 | 1.382 (3) |
C8—C13 | 1.389 (2) | C22—H22 | 0.9500 |
C8—H8 | 0.9500 | C23—C24 | 1.382 (3) |
C9—C13 | 1.514 (2) | C23—H23 | 0.9500 |
C9—C14 | 1.515 (2) | C24—C25 | 1.395 (3) |
C9—C15 | 1.564 (2) | C24—H24 | 0.9500 |
C9—H9 | 1.0000 | C25—H25 | 0.9500 |
C10—C12 | 1.513 (2) | C26—Cl2 | 1.746 (2) |
C10—C11 | 1.513 (2) | C26—Cl1 | 1.754 (2) |
C10—C16 | 1.556 (2) | C26—Cl3 | 1.764 (2) |
C10—H10 | 1.0000 | C26—H26 | 1.0000 |
C19—N1—C17 | 113.31 (13) | C9—C15—C16 | 109.31 (11) |
C19—N1—C18 | 111.26 (12) | C18—C15—H15 | 109.0 |
C17—N1—C18 | 103.50 (11) | C9—C15—H15 | 109.0 |
C14—C1—C2 | 119.54 (18) | C16—C15—H15 | 109.0 |
C14—C1—H1 | 120.2 | C17—C16—C10 | 115.14 (12) |
C2—C1—H1 | 120.2 | C17—C16—C15 | 104.06 (12) |
C3—C2—C1 | 120.33 (17) | C10—C16—C15 | 109.67 (11) |
C3—C2—H2 | 119.8 | C17—C16—H16 | 109.3 |
C1—C2—H2 | 119.8 | C10—C16—H16 | 109.3 |
C2—C3—C4 | 120.64 (17) | C15—C16—H16 | 109.3 |
C2—C3—H3 | 119.7 | N1—C17—C16 | 104.15 (12) |
C4—C3—H3 | 119.7 | N1—C17—H17A | 110.9 |
C3—C4—C11 | 119.10 (18) | C16—C17—H17A | 110.9 |
C3—C4—H4 | 120.4 | N1—C17—H17B | 110.9 |
C11—C4—H4 | 120.4 | C16—C17—H17B | 110.9 |
C12—C5—C6 | 118.98 (15) | H17A—C17—H17B | 108.9 |
C12—C5—H5 | 120.5 | N1—C18—C15 | 103.77 (12) |
C6—C5—H5 | 120.5 | N1—C18—H18A | 111.0 |
C7—C6—C5 | 120.79 (16) | C15—C18—H18A | 111.0 |
C7—C6—H6 | 119.6 | N1—C18—H18B | 111.0 |
C5—C6—H6 | 119.6 | C15—C18—H18B | 111.0 |
C6—C7—C8 | 120.20 (16) | H18A—C18—H18B | 109.0 |
C6—C7—H7 | 119.9 | N1—C19—C20 | 114.73 (13) |
C8—C7—H7 | 119.9 | N1—C19—H19A | 108.6 |
C13—C8—C7 | 119.28 (16) | C20—C19—H19A | 108.6 |
C13—C8—H8 | 120.4 | N1—C19—H19B | 108.6 |
C7—C8—H8 | 120.4 | C20—C19—H19B | 108.6 |
C13—C9—C14 | 106.76 (12) | H19A—C19—H19B | 107.6 |
C13—C9—C15 | 107.63 (12) | C21—C20—C25 | 118.72 (15) |
C14—C9—C15 | 105.46 (12) | C21—C20—C19 | 122.63 (14) |
C13—C9—H9 | 112.2 | C25—C20—C19 | 118.59 (14) |
C14—C9—H9 | 112.2 | C20—C21—C22 | 120.06 (16) |
C15—C9—H9 | 112.2 | C20—C21—H21 | 120.0 |
C12—C10—C11 | 106.76 (12) | C22—C21—H21 | 120.0 |
C12—C10—C16 | 108.06 (12) | C23—C22—C21 | 120.75 (17) |
C11—C10—C16 | 105.24 (12) | C23—C22—H22 | 119.6 |
C12—C10—H10 | 112.1 | C21—C22—H22 | 119.6 |
C11—C10—H10 | 112.1 | C24—C23—C22 | 119.57 (16) |
C16—C10—H10 | 112.1 | C24—C23—H23 | 120.2 |
C4—C11—C14 | 120.17 (15) | C22—C23—H23 | 120.2 |
C4—C11—C10 | 126.34 (15) | C23—C24—C25 | 120.07 (16) |
C14—C11—C10 | 113.49 (13) | C23—C24—H24 | 120.0 |
C5—C12—C13 | 120.26 (14) | C25—C24—H24 | 120.0 |
C5—C12—C10 | 126.29 (14) | C20—C25—C24 | 120.78 (16) |
C13—C12—C10 | 113.45 (13) | C20—C25—H25 | 119.6 |
C8—C13—C12 | 120.49 (14) | C24—C25—H25 | 119.6 |
C8—C13—C9 | 126.03 (14) | Cl2—C26—Cl1 | 109.88 (13) |
C12—C13—C9 | 113.48 (13) | Cl2—C26—Cl3 | 111.44 (12) |
C1—C14—C11 | 120.22 (15) | Cl1—C26—Cl3 | 109.86 (12) |
C1—C14—C9 | 126.33 (15) | Cl2—C26—H26 | 108.5 |
C11—C14—C9 | 113.45 (13) | Cl1—C26—H26 | 108.5 |
C18—C15—C9 | 115.86 (12) | Cl3—C26—H26 | 108.5 |
C18—C15—C16 | 104.31 (12) |
Experimental details
Crystal data | |
Chemical formula | C25H23N·CHCl3 |
Mr | 456.81 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 193 |
a, b, c (Å) | 8.6455 (2), 10.7338 (3), 12.3310 (3) |
β (°) | 99.055 (1) |
V (Å3) | 1130.04 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.42 |
Crystal size (mm) | 0.80 × 0.70 × 0.40 |
Data collection | |
Diffractometer | Bruker SMART APEXII |
Absorption correction | Multi-scan (SADABS; Bruker, 2006) |
Tmin, Tmax | 0.730, 0.850 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19688, 6678, 6147 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.714 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.119, 1.04 |
No. of reflections | 6678 |
No. of parameters | 271 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.59, −0.54 |
Absolute structure | Flack (1983), 3057 Friedel pairs |
Absolute structure parameter | −0.01 (5) |
Computer programs: APEX2 (Bruker, 2006), APEX2 and SAINT (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).
Acknowledgements
This work was financially supported by the Centre National de la Recherche Scientifique (CNRS) and by Université Paul Sabatier. IB is grateful to the Ministère de l'Enseignement Supérieur et de la Recherche for a PhD grant.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
9,10-Dihydroanthracene-succinimides are target molecules for pharmaceutical and medical uses (Sanhes et al., 2008), and their related pyrrolidines have also found applications as organocatalysts (Sasaoka et al., 2006; Sanhes et al., 2009; 2010). The synthesis of these compounds is mainly based on thermal-promoted Diels-Alder cycloadditions (for the succinimide derivatives), followed by chemical reduction to give the corresponding heterocyclic amines [Sanhes et al., 2008]. From a structural point of view, a large number of 9,10-dihydroanthracene-succinimides have been analyzed by X-ray single-crystal diffraction. A search of the Cambridge Structural Database gave 67 hits (CSD, version 5.33, update No. 4, August 2012; Allen, 2002), however, no crystallographic data is available for the corresponding non-substituted pyrrolidine ligand. Herein, we report on the synthesis and crystal structure of the title compound.
The molecular structure of the title compound is shown in Fig. 1. The 9,10-dihydroanthracenyl is bent with a dihedral angle between the benzene rings of 57.82 (8)°. The pyrrolidine heterocycle has an envelope conformation with atom N1 as the flap. It is displaced from the mean plane of the four C-atoms, C15—C18 [maximum deviation = 0.0025 (15) Å] by 0.6313 (14) Å. This mean plane forms a dihedral angle of 50.78 (10)° with the C20—C25 benzyl ring. In contrast to analogous dicarboximide compounds, a pronounced pyramidalization of the atom N1 is observed with Σ C—N1—C = 328.07°, which signifies an accentuated N-donor character.
In the crystal, this N-donor behaviour is evident by the C—H···N intermolecular hydrogen bond involving a chloroform solvate molecule (Table 1 and Fig. 2).
The absolute configuration of atoms C15 and C16 was crystallographically confirmed to be S and R, respectively (Fig. 1).