Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113004484/ov3021sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113004484/ov3021Isup2.hkl |
CCDC reference: 950358
For related literature, see: Datta et al. (2007); Eaton et al. (1968); Forbes & Holm (1968); Jenkins & Brookhart (2004); Jin et al. (2010); Komiya et al. (2011); Mazzeo et al. (2005); Meiners et al. (2007); Meyer et al. (2006); Mori et al. (2005); Muetterties et al. (1966); Naota & Koori (2005); Nishinaga et al. (2010); Pappalardo et al. (2004); Steyl (2005, 2007); Steyl et al. (2010).
2,2'-[Pentane-1,5-diylbis(azanediyl)]ditropone was prepared by condensation of 2-chlorotropone (50 mg, 0.36 mmol) and pentane-1,5-diamine (21 mg, 0.20 mmol) in the presence of triethylamine (36 mg, 0.38 mmol) in boiling ethanol. The title complex, (I), was obtained by reaction of Pd(OAc)2 (27 mg, 0.13 mmol) with the ligand (32 mg, 0.10 mmol) in the presence of N,N,N',N'-tetramethylethylenediamine (39 mg, 0.33 mmol) in boiling toluene. The reaction mixture was subjected to column chromatography (SiO2, eluent EtOAc) to give (I) (15 mg, 35%) as a red solid. Single crystals suitable for X-ray diffraction analysis were obtained by recrystallization from EtOAc–n-hexane [Solvent ratio?]. Spectroscopic analysis: IR (KBr, ν, cm-1): 2958, 2932, 2851, 1594, 1565, 1512, 1447, 1402, 1319, 1215; 1H NMR (CDCl3, 500 MHz, δ, p.p.m.): 1.50–1.64 (m, 4H), 1.86–2.15 (m, 4H), 2.24 (tt, J = 7.5 and 7.5 Hz, 4H), 3.46–3.50 (m, 8H), 6.22 (d, J = 10.5 Hz, 4H, H7), 6.25 (dd, J = 9.0 and 9.0 Hz, 4H, H5), 6.60 (d, J = 11.9 Hz, 4H, H3), 6.61 (ddd, J = 10.5, 9.0 and 1.4 Hz, 4H, H6), 6.87 (ddd, J = 11.9, 9.0 and 1.4 Hz, 4H, H4); MS (ESI) m/z: 830 [M]+.
H atoms were visible in difference maps and were subsequently treated as riding, with C—H = 0.99 (CH2) or 0.95 Å (aromatic), and with Uiso(H) = 1.2Ueq(C).
Data collection: RAPID-AUTO (Rigaku, 1999); cell refinement: RAPID-AUTO (Rigaku, 1999); data reduction: RAPID-AUTO (Rigaku, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010) and ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).
[Pd(C19H20N2O2)2] | F(000) = 1680.00 |
Mr = 829.56 | Dx = 1.643 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 49440 reflections |
a = 16.282 (3) Å | θ = 3.1–27.5° |
b = 17.740 (3) Å | µ = 1.12 mm−1 |
c = 11.608 (2) Å | T = 173 K |
V = 3352.9 (10) Å3 | Block, red |
Z = 4 | 0.40 × 0.20 × 0.20 mm |
Rigaku R-AXIS RAPID diffractometer | 3452 reflections with F2 > 2σ(F2) |
Detector resolution: 10.000 pixels mm-1 | Rint = 0.033 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995) | h = −21→20 |
Tmin = 0.662, Tmax = 0.799 | k = −23→22 |
64124 measured reflections | l = −15→15 |
3829 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.021 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.056 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0272P)2 + 1.7779P] where P = (Fo2 + 2Fc2)/3 |
3829 reflections | (Δ/σ)max = 0.001 |
217 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
Primary atom site location: structure-invariant direct methods |
[Pd(C19H20N2O2)2] | V = 3352.9 (10) Å3 |
Mr = 829.56 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 16.282 (3) Å | µ = 1.12 mm−1 |
b = 17.740 (3) Å | T = 173 K |
c = 11.608 (2) Å | 0.40 × 0.20 × 0.20 mm |
Rigaku R-AXIS RAPID diffractometer | 3829 independent reflections |
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995) | 3452 reflections with F2 > 2σ(F2) |
Tmin = 0.662, Tmax = 0.799 | Rint = 0.033 |
64124 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 0 restraints |
wR(F2) = 0.056 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.38 e Å−3 |
3829 reflections | Δρmin = −0.34 e Å−3 |
217 parameters |
Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY |
Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
Pd1 | 0.623341 (8) | 0.760709 (8) | 0.367449 (10) | 0.02564 (5) | |
O1 | 0.58644 (8) | 0.86265 (7) | 0.41360 (11) | 0.0345 (3) | |
O2 | 0.34057 (8) | 0.65744 (7) | 0.17642 (11) | 0.0322 (3) | |
N1 | 0.67320 (8) | 0.82079 (9) | 0.24093 (12) | 0.0285 (3) | |
N2 | 0.42353 (8) | 0.70238 (8) | 0.00220 (12) | 0.0276 (3) | |
C1 | 0.60679 (11) | 0.91671 (11) | 0.34242 (15) | 0.0300 (4) | |
C2 | 0.65593 (10) | 0.89381 (10) | 0.24189 (14) | 0.0282 (4) | |
C3 | 0.68211 (11) | 0.94494 (12) | 0.15400 (16) | 0.0347 (4) | |
C4 | 0.67083 (12) | 1.02111 (12) | 0.14284 (17) | 0.0392 (5) | |
C5 | 0.63270 (12) | 1.07347 (12) | 0.2152 (2) | 0.0436 (5) | |
C6 | 0.59417 (13) | 1.05811 (12) | 0.3171 (2) | 0.0434 (5) | |
C7 | 0.58263 (12) | 0.98905 (12) | 0.37221 (16) | 0.0375 (5) | |
C8 | 0.72596 (11) | 0.78597 (12) | 0.15367 (16) | 0.0338 (4) | |
C9 | 0.68635 (11) | 0.77460 (11) | 0.03450 (16) | 0.0343 (4) | |
C10 | 0.59394 (11) | 0.76029 (10) | 0.03811 (15) | 0.0301 (4) | |
C11 | 0.56234 (11) | 0.73315 (10) | −0.07839 (15) | 0.0302 (4) | |
C12 | 0.46919 (12) | 0.73944 (10) | −0.09013 (15) | 0.0317 (4) | |
C13 | 0.35795 (10) | 0.60526 (11) | 0.10133 (15) | 0.0289 (4) | |
C14 | 0.40696 (10) | 0.62919 (10) | 0.00114 (14) | 0.0278 (4) | |
C15 | 0.43344 (11) | 0.58015 (11) | −0.08863 (16) | 0.0343 (4) | |
C16 | 0.41804 (12) | 0.50485 (12) | −0.10788 (16) | 0.0371 (5) | |
C17 | 0.37316 (12) | 0.45295 (12) | −0.04348 (19) | 0.0398 (5) | |
C18 | 0.33420 (12) | 0.46632 (11) | 0.05929 (18) | 0.0377 (5) | |
C19 | 0.32782 (11) | 0.53300 (11) | 0.12258 (16) | 0.0339 (4) | |
H3A | 0.7124 | 0.9223 | 0.0932 | 0.0416* | |
H4A | 0.6927 | 1.0420 | 0.0740 | 0.0471* | |
H5A | 0.6337 | 1.1247 | 0.1913 | 0.0523* | |
H6A | 0.5721 | 1.1006 | 0.3561 | 0.0521* | |
H7A | 0.5530 | 0.9921 | 0.4425 | 0.0450* | |
H8A | 0.7442 | 0.7362 | 0.1828 | 0.0405* | |
H8B | 0.7755 | 0.8177 | 0.1441 | 0.0405* | |
H9A | 0.6968 | 0.8200 | −0.0129 | 0.0411* | |
H9B | 0.7133 | 0.7314 | −0.0039 | 0.0411* | |
H10A | 0.5652 | 0.8074 | 0.0598 | 0.0361* | |
H10B | 0.5817 | 0.7219 | 0.0975 | 0.0361* | |
H11A | 0.5886 | 0.7632 | −0.1401 | 0.0362* | |
H11B | 0.5787 | 0.6799 | −0.0894 | 0.0362* | |
H12A | 0.4540 | 0.7935 | −0.0917 | 0.0381* | |
H12B | 0.4525 | 0.7171 | −0.1647 | 0.0381* | |
H15A | 0.4676 | 0.6033 | −0.1448 | 0.0412* | |
H16A | 0.4419 | 0.4851 | −0.1762 | 0.0445* | |
H17A | 0.3691 | 0.4033 | −0.0738 | 0.0478* | |
H18A | 0.3076 | 0.4239 | 0.0924 | 0.0452* | |
H19A | 0.2977 | 0.5283 | 0.1923 | 0.0407* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.02373 (8) | 0.03505 (9) | 0.01813 (8) | −0.00128 (5) | 0.00114 (4) | −0.00022 (5) |
O1 | 0.0403 (7) | 0.0364 (7) | 0.0270 (7) | −0.0027 (6) | 0.0088 (6) | −0.0024 (6) |
O2 | 0.0335 (7) | 0.0380 (7) | 0.0250 (6) | −0.0013 (6) | 0.0064 (5) | −0.0010 (6) |
N1 | 0.0236 (7) | 0.0387 (8) | 0.0231 (7) | −0.0014 (6) | 0.0018 (6) | 0.0012 (6) |
N2 | 0.0263 (7) | 0.0384 (8) | 0.0179 (7) | 0.0015 (6) | −0.0000 (6) | 0.0012 (6) |
C1 | 0.0256 (8) | 0.0397 (10) | 0.0246 (9) | −0.0034 (7) | −0.0017 (7) | −0.0021 (8) |
C2 | 0.0217 (8) | 0.0392 (10) | 0.0235 (8) | −0.0039 (7) | −0.0022 (7) | −0.0010 (7) |
C3 | 0.0307 (9) | 0.0436 (11) | 0.0298 (9) | −0.0064 (8) | 0.0017 (8) | 0.0020 (8) |
C4 | 0.0342 (10) | 0.0461 (12) | 0.0374 (11) | −0.0087 (9) | −0.0059 (8) | 0.0124 (9) |
C5 | 0.0377 (11) | 0.0395 (11) | 0.0536 (13) | 0.0008 (9) | −0.0067 (10) | 0.0104 (10) |
C6 | 0.0408 (11) | 0.0375 (11) | 0.0520 (13) | 0.0067 (9) | −0.0036 (10) | −0.0015 (10) |
C7 | 0.0342 (10) | 0.0423 (11) | 0.0361 (11) | 0.0027 (9) | 0.0025 (8) | −0.0028 (9) |
C8 | 0.0260 (9) | 0.0455 (11) | 0.0298 (9) | 0.0021 (8) | 0.0071 (7) | 0.0022 (8) |
C9 | 0.0328 (9) | 0.0429 (11) | 0.0271 (9) | −0.0028 (8) | 0.0097 (7) | −0.0033 (8) |
C10 | 0.0305 (9) | 0.0363 (10) | 0.0235 (9) | 0.0002 (8) | 0.0060 (7) | −0.0019 (7) |
C11 | 0.0357 (10) | 0.0329 (9) | 0.0220 (9) | −0.0008 (8) | 0.0067 (7) | 0.0003 (7) |
C12 | 0.0377 (10) | 0.0391 (10) | 0.0184 (8) | 0.0019 (8) | 0.0019 (7) | 0.0025 (7) |
C13 | 0.0240 (8) | 0.0397 (10) | 0.0228 (8) | 0.0022 (7) | −0.0029 (7) | 0.0005 (7) |
C14 | 0.0231 (8) | 0.0398 (10) | 0.0204 (8) | 0.0017 (7) | −0.0039 (7) | 0.0001 (7) |
C15 | 0.0316 (9) | 0.0469 (11) | 0.0245 (9) | −0.0009 (8) | −0.0003 (7) | −0.0032 (8) |
C16 | 0.0341 (10) | 0.0470 (11) | 0.0302 (9) | 0.0036 (9) | −0.0033 (8) | −0.0106 (9) |
C17 | 0.0378 (11) | 0.0374 (10) | 0.0443 (12) | 0.0042 (8) | −0.0062 (9) | −0.0068 (9) |
C18 | 0.0336 (10) | 0.0348 (10) | 0.0447 (11) | 0.0014 (8) | −0.0017 (9) | 0.0030 (9) |
C19 | 0.0290 (9) | 0.0411 (11) | 0.0315 (10) | 0.0011 (8) | 0.0007 (7) | 0.0025 (8) |
Pd1—O1 | 1.9795 (13) | C15—C16 | 1.377 (3) |
Pd1—O2i | 1.9901 (13) | C16—C17 | 1.393 (3) |
Pd1—N1 | 1.9880 (15) | C17—C18 | 1.372 (3) |
Pd1—N2i | 1.9856 (15) | C18—C19 | 1.396 (3) |
O1—C1 | 1.309 (3) | C3—H3A | 0.950 |
O2—C13 | 1.303 (3) | C4—H4A | 0.950 |
N1—C2 | 1.326 (3) | C5—H5A | 0.950 |
N1—C8 | 1.465 (3) | C6—H6A | 0.950 |
N2—C12 | 1.461 (3) | C7—H7A | 0.950 |
N2—C14 | 1.326 (3) | C8—H8A | 0.990 |
C1—C2 | 1.472 (3) | C8—H8B | 0.990 |
C1—C7 | 1.386 (3) | C9—H9A | 0.990 |
C2—C3 | 1.430 (3) | C9—H9B | 0.990 |
C3—C4 | 1.370 (3) | C10—H10A | 0.990 |
C4—C5 | 1.398 (3) | C10—H10B | 0.990 |
C5—C6 | 1.367 (4) | C11—H11A | 0.990 |
C6—C7 | 1.395 (3) | C11—H11B | 0.990 |
C8—C9 | 1.540 (3) | C12—H12A | 0.990 |
C9—C10 | 1.526 (3) | C12—H12B | 0.990 |
C10—C11 | 1.525 (3) | C15—H15A | 0.950 |
C11—C12 | 1.527 (3) | C16—H16A | 0.950 |
C13—C14 | 1.473 (3) | C17—H17A | 0.950 |
C13—C19 | 1.395 (3) | C18—H18A | 0.950 |
C14—C15 | 1.424 (3) | C19—H19A | 0.950 |
O1···C10i | 3.498 (3) | C9···H6Aii | 3.5569 |
O1···C12i | 3.130 (3) | C9···H17Av | 3.3146 |
O2···C8i | 3.204 (3) | C10···H6Aii | 3.2680 |
N1···C10 | 2.891 (3) | C10···H17Av | 2.9930 |
N2···C10 | 2.988 (3) | C11···H6Aii | 3.0496 |
C1···C4 | 3.144 (3) | C11···H12Bxiv | 3.0059 |
C1···C5 | 3.177 (3) | C11···H17Av | 3.1979 |
C2···C5 | 3.224 (3) | C11···H18Av | 3.5028 |
C2···C6 | 3.205 (3) | C12···H5Axii | 3.1614 |
C2···C9 | 3.242 (3) | C12···H6Aii | 3.3535 |
C2···C10 | 3.496 (3) | C12···H8Bvii | 3.3708 |
C3···C6 | 3.109 (3) | C12···H11Axiv | 3.2976 |
C3···C7 | 3.107 (3) | C12···H12Bxiv | 3.1439 |
C3···C8 | 2.909 (3) | C13···H3Avii | 3.3100 |
C3···C9 | 3.326 (3) | C13···H8Bvii | 3.4335 |
C4···C7 | 3.078 (3) | C13···H9Avii | 3.1133 |
C6···C6i | 3.440 (3) | C13···H16Aviii | 3.3329 |
C11···C14 | 3.264 (3) | C14···H3Avii | 3.4742 |
C11···C15 | 3.433 (3) | C14···H8Bvii | 2.8829 |
C12···C15 | 2.885 (3) | C14···H9Avii | 3.5404 |
C13···C16 | 3.167 (3) | C15···H3Avii | 3.5999 |
C13···C17 | 3.192 (3) | C15···H8Bvii | 3.2109 |
C14···C17 | 3.216 (3) | C15···H15Axiv | 3.5133 |
C14···C18 | 3.195 (3) | C16···H3Avii | 3.5932 |
C15···C18 | 3.104 (3) | C16···H16Axiv | 3.4068 |
C15···C19 | 3.109 (3) | C16···H19Avi | 3.0930 |
C16···C19 | 3.093 (3) | C17···H3Avii | 3.4761 |
C4···C7ii | 3.459 (3) | C17···H4Avii | 2.9610 |
C4···C17iii | 3.521 (3) | C17···H10Bv | 3.2481 |
C4···C18iii | 3.554 (3) | C17···H11Bv | 2.9235 |
C7···C4iv | 3.459 (3) | C17···H15Av | 3.5355 |
C15···C17v | 3.551 (3) | C17···H19Avi | 3.3209 |
C16···C19vi | 3.521 (3) | C18···H3Avii | 3.3123 |
C17···C4vii | 3.521 (3) | C18···H4Avii | 2.7791 |
C17···C15v | 3.551 (3) | C18···H11Bv | 2.9767 |
C18···C4vii | 3.554 (3) | C18···H15Av | 3.5959 |
C19···C16viii | 3.521 (3) | C19···H3Avii | 3.2305 |
Pd1···H8A | 2.9422 | C19···H4Avii | 3.4374 |
Pd1···H10Ai | 3.2902 | C19···H16Aviii | 3.0018 |
Pd1···H10B | 3.2794 | H3A···C13iii | 3.3100 |
Pd1···H10Bi | 3.4328 | H3A···C14iii | 3.4742 |
Pd1···H12Ai | 2.9490 | H3A···C15iii | 3.5999 |
O1···H7A | 2.3844 | H3A···C16iii | 3.5932 |
O1···H10Ai | 2.6746 | H3A···C17iii | 3.4761 |
O1···H12Ai | 2.4925 | H3A···C18iii | 3.3123 |
O2···H8Ai | 2.5557 | H3A···C19iii | 3.2305 |
O2···H10Bi | 3.1297 | H3A···H6Aii | 3.6000 |
O2···H19A | 2.4016 | H3A···H7Aii | 3.4783 |
N1···H3A | 2.5672 | H3A···H19Ax | 3.4158 |
N1···H9A | 2.9718 | H4A···O1ii | 3.0531 |
N1···H9B | 3.3201 | H4A···C1ii | 3.1175 |
N1···H10A | 2.7513 | H4A···C7ii | 3.0000 |
N1···H10B | 2.8411 | H4A···C17iii | 2.9610 |
N2···H10A | 3.0396 | H4A···C18iii | 2.7791 |
N2···H10B | 2.8239 | H4A···C19iii | 3.4374 |
N2···H11A | 3.3340 | H4A···H7Aii | 2.8051 |
N2···H11B | 2.7697 | H4A···H17Aiii | 3.0320 |
N2···H15A | 2.5522 | H4A···H18Aiii | 2.7559 |
C1···H3A | 3.3668 | H4A···H19Ax | 3.2161 |
C1···H6A | 3.3148 | H5A···O1ii | 3.3215 |
C1···H10Ai | 3.5906 | H5A···C12xii | 3.1614 |
C2···H4A | 3.3265 | H5A···H8Axi | 2.8074 |
C2···H7A | 3.3581 | H5A···H11Aiv | 2.8855 |
C2···H8A | 3.2170 | H5A···H12Axii | 2.3412 |
C2···H8B | 2.6273 | H5A···H12Bxii | 3.1535 |
C2···H9A | 3.3027 | H5A···H19Ax | 3.4468 |
C2···H10A | 3.0001 | H6A···C9iv | 3.5569 |
C3···H5A | 3.3128 | H6A···C10iv | 3.2680 |
C3···H8B | 2.7244 | H6A···C11iv | 3.0496 |
C3···H9A | 2.9539 | H6A···C12iv | 3.3535 |
C3···H10A | 3.2820 | H6A···H3Aiv | 3.6000 |
C4···H6A | 3.2717 | H6A···H7Axiii | 3.5092 |
C5···H3A | 3.2987 | H6A···H9Aiv | 2.9025 |
C5···H6Ai | 3.4687 | H6A···H10Aiv | 2.8749 |
C5···H7A | 3.2755 | H6A···H11Aiv | 2.4306 |
C6···H4A | 3.2594 | H6A···H12Aiv | 2.7562 |
C6···H6Ai | 3.4553 | H7A···C3iv | 3.4194 |
C7···H5A | 3.3000 | H7A···C4iv | 3.0238 |
C8···H3A | 2.5279 | H7A···C7xiii | 3.1002 |
C8···H10A | 2.8604 | H7A···H3Aiv | 3.4783 |
C8···H10B | 2.6900 | H7A···H4Aiv | 2.8051 |
C9···H3A | 2.7403 | H7A···H6Axiii | 3.5092 |
C9···H11A | 2.5844 | H7A···H7Axiii | 2.1986 |
C9···H11B | 2.8223 | H8A···C5xv | 3.5352 |
C10···H3A | 3.5196 | H8A···H5Axv | 2.8074 |
C10···H8A | 2.9978 | H8A···H11Aix | 3.4119 |
C10···H8B | 3.3605 | H8A···H12Biii | 3.4974 |
C10···H12A | 2.7949 | H8A···H17Av | 3.3371 |
C10···H12B | 3.3812 | H8B···N2iii | 2.9697 |
C11···H9A | 2.7833 | H8B···C12iii | 3.3708 |
C11···H9B | 2.6057 | H8B···C13iii | 3.4335 |
C11···H15A | 2.8776 | H8B···C14iii | 2.8829 |
C12···H10A | 2.6317 | H8B···C15iii | 3.2109 |
C12···H10B | 2.8630 | H8B···H12Aiii | 3.5634 |
C12···H15A | 2.4969 | H8B···H12Biii | 2.9563 |
C13···H15A | 3.3688 | H8B···H15Aiii | 3.4261 |
C13···H18A | 3.3225 | H9A···Pd1xvi | 3.5424 |
C14···H10B | 3.4709 | H9A···O2iii | 3.0395 |
C14···H11B | 3.1193 | H9A···C6ii | 3.3710 |
C14···H12A | 3.1997 | H9A···C13iii | 3.1133 |
C14···H12B | 2.5857 | H9A···C14iii | 3.5404 |
C14···H16A | 3.3310 | H9A···H6Aii | 2.9025 |
C14···H19A | 3.3601 | H9B···Pd1xvi | 3.0532 |
C15···H11B | 2.9533 | H9B···O2iii | 3.4918 |
C15···H12B | 2.6031 | H9B···H17Av | 2.8852 |
C15···H17A | 3.3114 | H9B···H18Av | 2.9584 |
C16···H18A | 3.2714 | H10A···H6Aii | 2.8749 |
C17···H15A | 3.2956 | H10B···C17v | 3.2481 |
C17···H19A | 3.2845 | H10B···H17Av | 2.3769 |
C18···H16A | 3.2647 | H11A···C5ii | 3.4247 |
C19···H17A | 3.3073 | H11A···C6ii | 3.2092 |
H3A···H4A | 2.1585 | H11A···C12xiv | 3.2976 |
H3A···H8A | 3.4989 | H11A···H5Aii | 2.8855 |
H3A···H8B | 2.2024 | H11A···H6Aii | 2.4306 |
H3A···H9A | 2.2081 | H11A···H8Axvi | 3.4119 |
H3A···H9B | 3.5698 | H11A···H12Axiv | 3.2351 |
H3A···H10A | 3.1695 | H11A···H12Bxiv | 2.5013 |
H4A···H5A | 2.2203 | H11B···C17v | 2.9235 |
H5A···H6A | 2.2022 | H11B···C18v | 2.9767 |
H5A···H6Ai | 3.4212 | H11B···H12Bxiv | 2.9737 |
H6A···H6Ai | 3.4022 | H11B···H15Axiv | 3.4542 |
H6A···H7A | 2.1924 | H11B···H17Av | 2.5473 |
H8A···H9A | 2.8214 | H11B···H18Av | 2.6110 |
H8A···H9B | 2.2267 | H12A···C5xii | 3.1016 |
H8A···H10A | 3.4819 | H12A···H5Axii | 2.3412 |
H8A···H10B | 2.8365 | H12A···H6Aii | 2.7562 |
H8B···H9A | 2.2286 | H12A···H8Bvii | 3.5634 |
H8B···H9B | 2.5152 | H12A···H11Axiv | 3.2351 |
H8B···H10A | 3.5662 | H12A···H12Bxiv | 3.4864 |
H9A···H10A | 2.3140 | H12B···C11xiv | 3.0059 |
H9A···H10B | 2.8615 | H12B···C12xiv | 3.1439 |
H9A···H11A | 2.5095 | H12B···H5Axii | 3.1535 |
H9A···H11B | 3.2660 | H12B···H8Avii | 3.4974 |
H9B···H10A | 2.8600 | H12B···H8Bvii | 2.9563 |
H9B···H10B | 2.4511 | H12B···H11Axiv | 2.5013 |
H9B···H11A | 2.6342 | H12B···H11Bxiv | 2.9737 |
H9B···H11B | 2.5736 | H12B···H12Axiv | 3.4864 |
H10A···H11A | 2.4777 | H12B···H12Bxiv | 2.5132 |
H10A···H11B | 2.8573 | H12B···H15Axiv | 3.2647 |
H10A···H12A | 2.5366 | H15A···C15xiv | 3.5133 |
H10A···H12B | 3.5671 | H15A···C17v | 3.5355 |
H10B···H11A | 2.8560 | H15A···C18v | 3.5959 |
H10B···H11B | 2.2945 | H15A···H8Bvii | 3.4261 |
H10B···H12A | 3.2806 | H15A···H11Bxiv | 3.4542 |
H11A···H12A | 2.3257 | H15A···H12Bxiv | 3.2647 |
H11A···H12B | 2.3796 | H15A···H15Axiv | 2.6612 |
H11A···H15A | 3.4548 | H15A···H16Axiv | 3.3001 |
H11B···H12A | 2.8609 | H16A···O2vi | 3.4703 |
H11B···H12B | 2.3280 | H16A···C13vi | 3.3329 |
H11B···H15A | 2.3520 | H16A···C16xiv | 3.4068 |
H12A···H15A | 3.4361 | H16A···C19vi | 3.0018 |
H12B···H15A | 2.0459 | H16A···H15Axiv | 3.3001 |
H15A···H16A | 2.1693 | H16A···H16Axiv | 2.5526 |
H16A···H17A | 2.2185 | H16A···H19Avi | 2.8108 |
H17A···H18A | 2.2035 | H17A···O2vi | 3.1286 |
H18A···H19A | 2.1921 | H17A···C4vii | 3.5865 |
Pd1···H9Aix | 3.5424 | H17A···C9v | 3.3146 |
Pd1···H9Bix | 3.0532 | H17A···C10v | 2.9930 |
O1···H4Aiv | 3.0531 | H17A···C11v | 3.1979 |
O1···H5Aiv | 3.3215 | H17A···H4Avii | 3.0320 |
O2···H9Avii | 3.0395 | H17A···H8Av | 3.3371 |
O2···H9Bvii | 3.4918 | H17A···H9Bv | 2.8852 |
O2···H16Aviii | 3.4703 | H17A···H10Bv | 2.3769 |
O2···H17Aviii | 3.1286 | H17A···H11Bv | 2.5473 |
N1···H18Ax | 3.4461 | H17A···H19Avi | 3.1934 |
N2···H8Bvii | 2.9697 | H18A···N1xvii | 3.4461 |
C1···H4Aiv | 3.1175 | H18A···C1xvii | 3.3581 |
C1···H18Ax | 3.3581 | H18A···C2xvii | 3.1753 |
C2···H18Ax | 3.1753 | H18A···C11v | 3.5028 |
C2···H19Ax | 3.4067 | H18A···H4Avii | 2.7559 |
C3···H7Aii | 3.4194 | H18A···H9Bv | 2.9584 |
C3···H19Ax | 2.9856 | H18A···H11Bv | 2.6110 |
C4···H7Aii | 3.0238 | H19A···C2xvii | 3.4067 |
C4···H17Aiii | 3.5865 | H19A···C3xvii | 2.9856 |
C4···H19Ax | 2.8189 | H19A···C4xvii | 2.8189 |
C5···H8Axi | 3.5352 | H19A···C5xvii | 3.0018 |
C5···H11Aiv | 3.4247 | H19A···C6xvii | 3.3575 |
C5···H12Axii | 3.1016 | H19A···C16viii | 3.0930 |
C5···H19Ax | 3.0018 | H19A···C17viii | 3.3209 |
C6···H9Aiv | 3.3710 | H19A···H3Axvii | 3.4158 |
C6···H11Aiv | 3.2092 | H19A···H4Axvii | 3.2161 |
C6···H19Ax | 3.3575 | H19A···H5Axvii | 3.4468 |
C7···H4Aiv | 3.0000 | H19A···H16Aviii | 2.8108 |
C7···H7Axiii | 3.1002 | H19A···H17Aviii | 3.1934 |
O1—Pd1—O2i | 178.95 (6) | C3—C4—H4A | 114.430 |
O1—Pd1—N1 | 80.45 (6) | C5—C4—H4A | 114.418 |
O1—Pd1—N2i | 98.81 (6) | C4—C5—H5A | 116.859 |
O2i—Pd1—N1 | 100.60 (6) | C6—C5—H5A | 116.854 |
O2i—Pd1—N2i | 80.14 (6) | C5—C6—H6A | 115.331 |
N1—Pd1—N2i | 177.90 (6) | C7—C6—H6A | 115.336 |
Pd1—O1—C1 | 114.95 (12) | C1—C7—H7A | 114.322 |
Pd1i—O2—C13 | 114.76 (12) | C6—C7—H7A | 114.319 |
Pd1—N1—C2 | 115.54 (11) | N1—C8—H8A | 108.399 |
Pd1—N1—C8 | 121.62 (13) | N1—C8—H8B | 108.401 |
C2—N1—C8 | 122.84 (15) | C9—C8—H8A | 108.392 |
Pd1i—N2—C12 | 121.35 (11) | C9—C8—H8B | 108.392 |
Pd1i—N2—C14 | 116.04 (11) | H8A—C8—H8B | 107.453 |
C12—N2—C14 | 122.51 (14) | C8—C9—H9A | 108.701 |
O1—C1—C2 | 115.85 (17) | C8—C9—H9B | 108.711 |
O1—C1—C7 | 116.69 (16) | C10—C9—H9A | 108.705 |
C2—C1—C7 | 127.41 (17) | C10—C9—H9B | 108.701 |
N1—C2—C1 | 113.06 (15) | H9A—C9—H9B | 107.624 |
N1—C2—C3 | 123.40 (16) | C9—C10—H10A | 109.398 |
C1—C2—C3 | 123.54 (17) | C9—C10—H10B | 109.405 |
C2—C3—C4 | 130.78 (18) | C11—C10—H10A | 109.412 |
C3—C4—C5 | 131.2 (2) | C11—C10—H10B | 109.410 |
C4—C5—C6 | 126.3 (2) | H10A—C10—H10B | 108.013 |
C5—C6—C7 | 129.3 (2) | C10—C11—H11A | 108.982 |
C1—C7—C6 | 131.36 (19) | C10—C11—H11B | 108.977 |
N1—C8—C9 | 115.53 (15) | C12—C11—H11A | 108.969 |
C8—C9—C10 | 114.21 (15) | C12—C11—H11B | 108.976 |
C9—C10—C11 | 111.14 (15) | H11A—C11—H11B | 107.774 |
C10—C11—C12 | 113.03 (15) | N2—C12—H12A | 108.749 |
N2—C12—C11 | 114.03 (15) | N2—C12—H12B | 108.747 |
O2—C13—C14 | 116.19 (17) | C11—C12—H12A | 108.742 |
O2—C13—C19 | 117.29 (16) | C11—C12—H12B | 108.747 |
C14—C13—C19 | 126.52 (17) | H12A—C12—H12B | 107.645 |
N2—C14—C13 | 112.65 (15) | C14—C15—H15A | 114.511 |
N2—C14—C15 | 122.90 (16) | C16—C15—H15A | 114.498 |
C13—C14—C15 | 124.45 (17) | C15—C16—H16A | 114.757 |
C14—C15—C16 | 130.99 (18) | C17—C16—H16A | 114.747 |
C15—C16—C17 | 130.50 (19) | C16—C17—H17A | 116.750 |
C16—C17—C18 | 126.5 (2) | C18—C17—H17A | 116.738 |
C17—C18—C19 | 129.68 (19) | C17—C18—H18A | 115.169 |
C13—C19—C18 | 131.26 (18) | C19—C18—H18A | 115.156 |
C2—C3—H3A | 114.617 | C13—C19—H19A | 114.372 |
C4—C3—H3A | 114.605 | C18—C19—H19A | 114.370 |
O1—Pd1—N1—C2 | −3.76 (9) | O1—C1—C2—N1 | −1.2 (2) |
O1—Pd1—N1—C8 | 175.74 (10) | O1—C1—C2—C3 | 178.58 (14) |
N1—Pd1—O1—C1 | 3.04 (9) | O1—C1—C7—C6 | 179.78 (17) |
O1—Pd1—N2i—C12i | −0.33 (10) | C2—C1—C7—C6 | 2.6 (4) |
O1—Pd1—N2i—C14i | −176.74 (9) | C7—C1—C2—N1 | 176.06 (17) |
N2i—Pd1—O1—C1 | −178.96 (9) | C7—C1—C2—C3 | −4.2 (3) |
O2i—Pd1—N1—C2 | 176.26 (9) | N1—C2—C3—C4 | −178.88 (16) |
O2i—Pd1—N1—C8 | −4.24 (10) | C1—C2—C3—C4 | 1.4 (3) |
N1—Pd1—O2i—C13i | 173.62 (9) | C2—C3—C4—C5 | 2.4 (4) |
O2i—Pd1—N2i—C12i | 179.69 (10) | C3—C4—C5—C6 | −2.2 (4) |
O2i—Pd1—N2i—C14i | 3.27 (9) | C4—C5—C6—C7 | −0.8 (4) |
N2i—Pd1—O2i—C13i | −4.38 (9) | C5—C6—C7—C1 | 0.9 (4) |
Pd1—O1—C1—C2 | −1.94 (18) | N1—C8—C9—C10 | −31.2 (3) |
Pd1—O1—C1—C7 | −179.49 (10) | C8—C9—C10—C11 | −167.86 (14) |
Pd1i—O2—C13—C14 | 4.77 (18) | C9—C10—C11—C12 | −163.59 (13) |
Pd1i—O2—C13—C19 | −174.48 (9) | C10—C11—C12—N2 | −53.82 (19) |
Pd1—N1—C2—C1 | 3.73 (17) | O2—C13—C14—N2 | −2.0 (2) |
Pd1—N1—C2—C3 | −176.04 (10) | O2—C13—C14—C15 | 178.65 (14) |
Pd1—N1—C8—C9 | 104.82 (15) | O2—C13—C19—C18 | 178.75 (16) |
C2—N1—C8—C9 | −75.7 (2) | C14—C13—C19—C18 | −0.4 (3) |
C8—N1—C2—C1 | −175.76 (13) | C19—C13—C14—N2 | 177.13 (16) |
C8—N1—C2—C3 | 4.5 (3) | C19—C13—C14—C15 | −2.2 (3) |
Pd1i—N2—C12—C11 | 100.34 (13) | N2—C14—C15—C16 | −175.43 (16) |
Pd1i—N2—C14—C13 | −1.72 (17) | C13—C14—C15—C16 | 3.8 (3) |
Pd1i—N2—C14—C15 | 177.60 (10) | C14—C15—C16—C17 | −1.7 (4) |
C12—N2—C14—C13 | −178.09 (13) | C15—C16—C17—C18 | −1.5 (4) |
C12—N2—C14—C15 | 1.2 (3) | C16—C17—C18—C19 | 1.6 (4) |
C14—N2—C12—C11 | −83.48 (18) | C17—C18—C19—C13 | 0.4 (4) |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) x, −y+2, z−1/2; (iii) x+1/2, −y+3/2, −z; (iv) x, −y+2, z+1/2; (v) −x+1, −y+1, −z; (vi) x, −y+1, z−1/2; (vii) x−1/2, −y+3/2, −z; (viii) x, −y+1, z+1/2; (ix) −x+3/2, −y+3/2, z+1/2; (x) x+1/2, y+1/2, −z+1/2; (xi) −x+3/2, y+1/2, z; (xii) −x+1, −y+2, −z; (xiii) −x+1, −y+2, −z+1; (xiv) −x+1, y, −z−1/2; (xv) −x+3/2, y−1/2, z; (xvi) −x+3/2, −y+3/2, z−1/2; (xvii) x−1/2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Pd(C19H20N2O2)2] |
Mr | 829.56 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 173 |
a, b, c (Å) | 16.282 (3), 17.740 (3), 11.608 (2) |
V (Å3) | 3352.9 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.12 |
Crystal size (mm) | 0.40 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Rigaku, 1995) |
Tmin, Tmax | 0.662, 0.799 |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 64124, 3829, 3452 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.056, 1.09 |
No. of reflections | 3829 |
No. of parameters | 217 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.34 |
Computer programs: RAPID-AUTO (Rigaku, 1999), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), CrystalStructure (Rigaku, 2010) and ORTEPIII (Burnett & Johnson, 1996), CrystalStructure (Rigaku, 2010).
Pd1—O1 | 1.9795 (13) | C4—C5 | 1.398 (3) |
Pd1—O2i | 1.9901 (13) | C5—C6 | 1.367 (4) |
Pd1—N1 | 1.9880 (15) | C6—C7 | 1.395 (3) |
Pd1—N2i | 1.9856 (15) | C8—C9 | 1.540 (3) |
O1—C1 | 1.309 (3) | C9—C10 | 1.526 (3) |
O2—C13 | 1.303 (3) | C10—C11 | 1.525 (3) |
N1—C2 | 1.326 (3) | C11—C12 | 1.527 (3) |
N1—C8 | 1.465 (3) | C13—C14 | 1.473 (3) |
N2—C12 | 1.461 (3) | C13—C19 | 1.395 (3) |
N2—C14 | 1.326 (3) | C14—C15 | 1.424 (3) |
C1—C2 | 1.472 (3) | C15—C16 | 1.377 (3) |
C1—C7 | 1.386 (3) | C16—C17 | 1.393 (3) |
C2—C3 | 1.430 (3) | C17—C18 | 1.372 (3) |
C3—C4 | 1.370 (3) | C18—C19 | 1.396 (3) |
O1—Pd1—O2i | 178.95 (6) | C3—C4—C5 | 131.2 (2) |
O1—Pd1—N1 | 80.45 (6) | C4—C5—C6 | 126.3 (2) |
O1—Pd1—N2i | 98.81 (6) | C5—C6—C7 | 129.3 (2) |
O2i—Pd1—N1 | 100.60 (6) | C1—C7—C6 | 131.36 (19) |
O2i—Pd1—N2i | 80.14 (6) | N1—C8—C9 | 115.53 (15) |
N1—Pd1—N2i | 177.90 (6) | C8—C9—C10 | 114.21 (15) |
Pd1—O1—C1 | 114.95 (12) | C9—C10—C11 | 111.14 (15) |
Pd1i—O2—C13 | 114.76 (12) | C10—C11—C12 | 113.03 (15) |
Pd1—N1—C2 | 115.54 (11) | N2—C12—C11 | 114.03 (15) |
Pd1—N1—C8 | 121.62 (13) | O2—C13—C14 | 116.19 (17) |
C2—N1—C8 | 122.84 (15) | O2—C13—C19 | 117.29 (16) |
Pd1i—N2—C12 | 121.35 (11) | C14—C13—C19 | 126.52 (17) |
Pd1i—N2—C14 | 116.04 (11) | N2—C14—C13 | 112.65 (15) |
C12—N2—C14 | 122.51 (14) | N2—C14—C15 | 122.90 (16) |
O1—C1—C2 | 115.85 (17) | C13—C14—C15 | 124.45 (17) |
O1—C1—C7 | 116.69 (16) | C14—C15—C16 | 130.99 (18) |
C2—C1—C7 | 127.41 (17) | C15—C16—C17 | 130.50 (19) |
N1—C2—C1 | 113.06 (15) | C16—C17—C18 | 126.5 (2) |
N1—C2—C3 | 123.40 (16) | C17—C18—C19 | 129.68 (19) |
C1—C2—C3 | 123.54 (17) | C13—C19—C18 | 131.26 (18) |
C2—C3—C4 | 130.78 (18) |
Symmetry code: (i) −x+1, y, −z+1/2. |
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A variety of 2-aminotroponate complexes, ML2 and MLX (L is 2-aminotroponate), with metal centres such as NiII (Jenkins & Brookhart, 2004), CaII (Datta et al., 2007), TiIV (Mazzeo et al., 2005), AlIII (Pappalardo et al., 2004), ZnII (Meyer et al., 2006; Jin et al., 2010), AuI (Meiners et al., 2007), RhI (Steyl, 2007) and CuII (Mori et al., 2005; Nishinaga et al., 2010; Steyl et al., 2010), have been extensively studied for the development of functional materials that exhibit catalytic activity for molecular transformation, luminescence, magnetic properties and liquid-crystalline behaviour.
As part of our programme towards the development of transition metal-based functional materials with three-dimensional superstructures [Pd (Naota & Koori, 2005) and Pt (Komiya et al., 2011)], we have synthesized a clothes-peg shaped binuclear trans-bis(2-aminotroponato)palladium(II) complex bearing flexible pentamethylene spacers, namely rac-bis{µ-trans-2,2'-[pentane-1,5-diylbis(azanediyl)]ditroponato}dipalladium(II), (I). This is the first example of an (aminotroponato-κ2N,O)palladium(II) complex [see (II) in the scheme]. Reported troponatopalladium complexes are limited to (tropolonato-κ2O,O')palladium(II), (III) (Muetterties et al., 1966; Steyl, 2005), (aminotroponiminato-κ2N,N')palladium(II), (IV) (Eaton et al., 1968), and (dithiotropolonato-κ2S,S')palladium(II), (V) (Forbes & Holm, 1968), the last two of which have not yet been fully characterized with respect to their molecular structures.
Single-crystal X-ray diffraction analysis of (I) shows that the two highly planar trans-bis(2-aminotroponato)palladium coordination sites are doubly linked by pentamethylene spacers in an anti conformation. Each molecular unit undergoes intermolecular offset π-stacking of the tropone rings to afford heterochiral interpenetrating dimers. Such an interpenetrating stacking interaction of clothes-peg shaped binuclear transition metal complexes has been extensively studied as a new motif for stimuli-responsive molecular aggregations (Naota & Koori, 2005; Komiya et al., 2011). In this paper, we describe the synthesis, crystal structure and molecular arrangement of (I) with respect to the characteristic cofacial interpenetrating packing motif of the clothes-peg shaped unit.
Binuclear complex (I) was prepared by reaction of Pd(OAc)2 and 2,2'-[pentane-1,5-diylbis(azanediyl)]ditropone in boiling ethanol. The trans and anti conformation of (I) was established unequivocally by X-ray diffraction analysis of a racemate crystal obtained from a solution in EtOAc–n-hexane [Solvent ratio?] (Fig. 1). The C1—O1 [1.309 (3) Å] and C13—O2 [1.303 (3) Å] bonds are similar to those in (2-aminotroponato)copper(II) [C—O = 1.2970 (18) and 1.2958 (18) Å; C—N = 1.3210 (19) and 1.3196 (19) Å; Steyl et al., 2010]. The two cofacial coordination blades are highly planar, as indicated by the torsion angles along the four coordination sites [N-coordination: C1—C2—N1—Pd1 = 3.73 (17)° and C13i—C14i—N2i—Pd1 = 1.72 (17)°; O-coordination: C2—C1—O1—Pd1 = 1.94 (18)° and C14i—C13i—O2i—Pd1 = 4.77 (18)°; symmetry code: (i) -x + 1, y, -z + 1/2] and by the macroscopic angles of C5—Pd1—C17i = 176° and C5i—Pd1—C17 = 176°.
The packing motif of (I) in the crystalline state is shown in Fig. 2. Each molecular unit undergoes an intermolecular offset π-stacking interaction between cofacial tropone rings to afford heterochiral interpenetrating dimers [C15(R)—C17ii(S) = 3.551 (2) Å; C17(R)—C15ii(S) = 3.551 (2) Å; symmetry code: (ii) -x + 1, -y + 1, -z] (Fig. 2). It is noteworthy that the dimer unit is bound with inward stacking, although double outward stacking is another motif for interpenetrative association of H-shaped units. This can be interpreted as a result of compensation to obtain broad-range crystal stability from the intra- and intermolecular interactions, rather than locally strong stabilization from double outward intermolecular stacking.
Fig. 3 shows the packing structure of (I), where the heterochiral dimers are aligned in a layer-by-layer structure with the unit-height direction along the crystallographic a axis (Fig. 3a). The layer in the ac plane consists of a herring-bone packing structure supported by a homochiral C—H···π interaction between the tropone rings, with C4(R)—H19iii(R)/C4ii(S)—H19iv(S) = 2.83 Å [symmetry codes: (iii) x + 1/2, -y + 3/2, -z; (iv) -x + 1/2, y - 1/2, z] (Fig. 3b). Thus, the present clothes-peg shaped molecule is packed mainly by heterochiral π–π and C—H···π interactions.