Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100017017/qa0433sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100017017/qa0433Isup2.hkl |
CCDC reference: 156224
The synthesis of (I) and related tripodal amines were first described by Valiyaveettil et al. (1993) starting from tris(aminoethyl)amine and reacting it with the appropriate acid chloride in the presence of triethylamine. An alternate route to the preparation of (I) is described here. To a solution of tris(2-aminoethyl)amine (1.00 g, 6.84 mmol) in chloroform (20 ml) at 273 K was added a solution of benzoic anhydride (4.80 g, 21.2 mmol) in chloroform (20 ml). The reaction was stirred for 3 h and the temperature was allowed to gradually increase to room temperature. The solvent was then removed by rotary evaporation, leaving a yellow coloured oil. This oil was washed with four 20 ml portions of diethyl ether until an off-white solid was obtained, which was then filtered to yield (I) (2.97 g, 6.48 mmol, 95% yield). Crystals suitable for diffraction were obtained from DMF–acetone. 1H NMR (250 MHz, d6-DMSO): 2.73 (t, 6H), 3.48 (q, 6H), 7.36–7.49 (m, 9H), 7.81 (d, 6H), 8.37 (t, 3H) p.p.m. IR (CH2Cl2): 3349 (w), 3325 (m, br), 3056 (w), 2947 (w), 2824 (m), 1650 (s), 1529 (s), 1296 (m), 1165 (w), 1072 (w) cm−1. M.p. 419–421 K.
The H-atom positions were either located directly or calculated based on geometric criterion and allowed to ride on their respective atoms. H-atom U values were assigned as 1.2Ueq of the parent atom.
Data collection: P3-P4/PC (Siemens, 1989); cell refinement: P3-P4/PC; data reduction: XDISK (Siemens, 1989); program(s) used to solve structure: SHELXTL (Sheldrick, 1994); program(s) used to refine structure: SHELXTL; software used to prepare material for publication: SHELXTL.
C27H30N4O3 | Dx = 1.250 Mg m−3 |
Mr = 458.55 | Melting point = 419–421 K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.004 (2) Å | Cell parameters from 40 reflections |
b = 17.151 (4) Å | θ = 5.0–15.0° |
c = 14.472 (3) Å | µ = 0.08 mm−1 |
β = 101.06 (2)° | T = 293 K |
V = 2437.0 (9) Å3 | Block, colourless |
Z = 4 | 0.40 × 0.40 × 0.20 mm |
F(000) = 976 |
Siemens P3 diffractometer | Rint = 0.030 |
Radiation source: normal-focus sealed tube | θmax = 27.6°, θmin = 2.3° |
Graphite monochromator | h = 0→13 |
θ–2θ scans | k = 0→22 |
5938 measured reflections | l = −18→18 |
5625 independent reflections | 3 standard reflections every 300 reflections |
2590 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.059 | Hydrogen site location: mixed |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0605P)2 + 0.5052P] where P = (Fo2 + 2Fc2)/3 |
4975 reflections | (Δ/σ)max = −0.001 |
307 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C27H30N4O3 | V = 2437.0 (9) Å3 |
Mr = 458.55 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.004 (2) Å | µ = 0.08 mm−1 |
b = 17.151 (4) Å | T = 293 K |
c = 14.472 (3) Å | 0.40 × 0.40 × 0.20 mm |
β = 101.06 (2)° |
Siemens P3 diffractometer | Rint = 0.030 |
5938 measured reflections | 3 standard reflections every 300 reflections |
5625 independent reflections | intensity decay: none |
2590 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.16 e Å−3 |
4975 reflections | Δρmin = −0.23 e Å−3 |
307 parameters |
Experimental. Crystals suitable for diffraction were grown from DMF-acetone. For the crystallographic experiment, a crystal of approximately 0.40 x 0.40 x 0.30 mm was cut from a much larger chunk and mounted on a glass fiber with epoxy resin. Data were collected using variable speed θ–2θ scans (3.0–30.0°/min), and corrected for decay (min. 0.990, max. 1.023), Lorentz and polarization effects but not for absorption. |
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 on F2 for ALL reflections diffracting out to 0.80 Å resolution (650 reflections were excluded in the 0.75–0.80 Å resolution range due to very weak diffraction–approximately 100 reflections were above the σ(I) threshold). Weighted R-factors wR and all goodnesses 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-factor(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 | ||
O1 | 0.3735 (2) | 0.07346 (12) | 0.53485 (12) | 0.0603 (6) | |
O2 | 0.2793 (2) | 0.13250 (12) | 0.19870 (13) | 0.0549 (5) | |
O3 | 0.6724 (2) | −0.03697 (13) | 0.12240 (13) | 0.0708 (7) | |
N1 | 0.3405 (2) | 0.05056 (13) | 0.37971 (15) | 0.0488 (6) | |
H1 | 0.3522 (2) | 0.06729 (13) | 0.32580 (15) | 0.059* | |
N2 | 0.3029 (2) | 0.06210 (13) | 0.07149 (14) | 0.0461 (6) | |
H2 | 0.3468 (2) | 0.05592 (13) | 0.02642 (14) | 0.055* | |
N3 | 0.6208 (2) | −0.07060 (14) | 0.26062 (15) | 0.0488 (6) | |
H3 | 0.6315 (2) | −0.06003 (14) | 0.31967 (15) | 0.059* | |
N4 | 0.3119 (2) | −0.06074 (12) | 0.22652 (14) | 0.0399 (5) | |
C1 | 0.2081 (3) | −0.0488 (2) | 0.2841 (2) | 0.0470 (7) | |
H1A | 0.1603 (3) | −0.0976 (2) | 0.2877 (2) | 0.056* | |
H1B | 0.1423 (3) | −0.0111 (2) | 0.2530 (2) | 0.056* | |
C2 | 0.2645 (3) | −0.0206 (2) | 0.3832 (2) | 0.0493 (7) | |
H2A | 0.1903 (3) | −0.0114 (2) | 0.4162 (2) | 0.059* | |
H2B | 0.3235 (3) | −0.0602 (2) | 0.4173 (2) | 0.059* | |
C3 | 0.3932 (3) | 0.0914 (2) | 0.4562 (2) | 0.0429 (7) | |
C4 | 0.4786 (3) | 0.1597 (2) | 0.4417 (2) | 0.0439 (7) | |
C5 | 0.4832 (3) | 0.2234 (2) | 0.5007 (2) | 0.0533 (8) | |
H5 | 0.4329 (3) | 0.2231 (2) | 0.5484 (2) | 0.064* | |
C6 | 0.5611 (3) | 0.2870 (2) | 0.4896 (3) | 0.0700 (10) | |
H6 | 0.5617 (3) | 0.3298 (2) | 0.5290 (3) | 0.084* | |
C7 | 0.6385 (4) | 0.2882 (2) | 0.4210 (3) | 0.0834 (12) | |
H7 | 0.6910 (4) | 0.3316 (2) | 0.4134 (3) | 0.100* | |
C8 | 0.6369 (4) | 0.2238 (3) | 0.3633 (3) | 0.0918 (14) | |
H8 | 0.6907 (4) | 0.2234 (3) | 0.3175 (3) | 0.110* | |
C9 | 0.5566 (3) | 0.1602 (2) | 0.3730 (2) | 0.0686 (10) | |
H9 | 0.5551 (3) | 0.1176 (2) | 0.3331 (2) | 0.082* | |
C10 | 0.2474 (3) | −0.0685 (2) | 0.1270 (2) | 0.0490 (7) | |
H10A | 0.1715 (3) | −0.1044 (2) | 0.1221 (2) | 0.059* | |
H10B | 0.3127 (3) | −0.0911 (2) | 0.0931 (2) | 0.059* | |
C11 | 0.1961 (3) | 0.0075 (2) | 0.0802 (2) | 0.0496 (7) | |
H11A | 0.1440 (3) | −0.0036 (2) | 0.0179 (2) | 0.060* | |
H11B | 0.1351 (3) | 0.0317 (2) | 0.1163 (2) | 0.060* | |
C12 | 0.3362 (3) | 0.1220 (2) | 0.1308 (2) | 0.0440 (7) | |
C13 | 0.4424 (3) | 0.1773 (2) | 0.1111 (2) | 0.0427 (6) | |
C14 | 0.4415 (4) | 0.2520 (2) | 0.1455 (3) | 0.0753 (11) | |
H14 | 0.3752 (4) | 0.2664 (2) | 0.1792 (3) | 0.090* | |
C15 | 0.5377 (4) | 0.3058 (2) | 0.1305 (3) | 0.0827 (12) | |
H15 | 0.5356 (4) | 0.3560 (2) | 0.1543 (3) | 0.099* | |
C16 | 0.6351 (3) | 0.2861 (2) | 0.0815 (2) | 0.0601 (8) | |
H16 | 0.6994 (3) | 0.3225 (2) | 0.0710 (2) | 0.072* | |
C17 | 0.6373 (3) | 0.2118 (2) | 0.0476 (2) | 0.0697 (10) | |
H17 | 0.7044 (3) | 0.1977 (2) | 0.0144 (2) | 0.084* | |
C18 | 0.5416 (3) | 0.1573 (2) | 0.0621 (2) | 0.0613 (9) | |
H18 | 0.5445 (3) | 0.1070 (2) | 0.0384 (2) | 0.074* | |
C19 | 0.3949 (3) | −0.1292 (2) | 0.2579 (2) | 0.0499 (7) | |
H19A | 0.3425 (3) | −0.1755 (2) | 0.2364 (2) | 0.060* | |
H19B | 0.4142 (3) | −0.1301 (2) | 0.3261 (2) | 0.060* | |
C20 | 0.5281 (3) | −0.1325 (2) | 0.2235 (2) | 0.0554 (8) | |
H20A | 0.5715 (3) | −0.1822 (2) | 0.2413 (2) | 0.067* | |
H20B | 0.5095 (3) | −0.1295 (2) | 0.1553 (2) | 0.067* | |
C21 | 0.6907 (3) | −0.0290 (2) | 0.2082 (2) | 0.0455 (7) | |
C22 | 0.7934 (3) | 0.0278 (2) | 0.2572 (2) | 0.0463 (7) | |
C23 | 0.8325 (4) | 0.0326 (2) | 0.3535 (2) | 0.0682 (10) | |
H23 | 0.7916 (4) | 0.0005 (2) | 0.3919 (2) | 0.082* | |
C24 | 0.9322 (4) | 0.0848 (2) | 0.3937 (3) | 0.0882 (12) | |
H24 | 0.9585 (4) | 0.0870 (2) | 0.4589 (3) | 0.106* | |
C25 | 0.9926 (4) | 0.1331 (2) | 0.3387 (3) | 0.0796 (11) | |
H25 | 1.0580 (4) | 0.1690 (2) | 0.3663 (3) | 0.096* | |
C26 | 0.9567 (4) | 0.1284 (2) | 0.2441 (3) | 0.0758 (10) | |
H26 | 0.9988 (4) | 0.1604 (2) | 0.2063 (3) | 0.091* | |
C27 | 0.8584 (3) | 0.0765 (2) | 0.2033 (2) | 0.0636 (9) | |
H27 | 0.8348 (3) | 0.0740 (2) | 0.1380 (2) | 0.076* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.087 (2) | 0.0652 (14) | 0.0333 (10) | −0.0064 (12) | 0.0224 (10) | −0.0002 (10) |
O2 | 0.0655 (13) | 0.0624 (13) | 0.0431 (11) | −0.0045 (11) | 0.0262 (10) | −0.0023 (9) |
O3 | 0.102 (2) | 0.078 (2) | 0.0374 (11) | −0.0126 (14) | 0.0250 (12) | −0.0080 (11) |
N1 | 0.067 (2) | 0.0511 (15) | 0.0322 (12) | −0.0116 (13) | 0.0191 (11) | −0.0019 (10) |
N2 | 0.0534 (15) | 0.0511 (14) | 0.0357 (12) | −0.0028 (12) | 0.0135 (11) | 0.0016 (11) |
N3 | 0.0507 (14) | 0.060 (2) | 0.0365 (12) | −0.0045 (13) | 0.0107 (11) | −0.0057 (11) |
N4 | 0.0468 (13) | 0.0382 (12) | 0.0364 (11) | −0.0055 (11) | 0.0119 (10) | −0.0033 (10) |
C1 | 0.048 (2) | 0.047 (2) | 0.049 (2) | −0.0098 (14) | 0.0162 (14) | 0.0004 (13) |
C2 | 0.064 (2) | 0.048 (2) | 0.0405 (15) | −0.0049 (15) | 0.0212 (14) | 0.0020 (13) |
C3 | 0.048 (2) | 0.048 (2) | 0.0341 (14) | 0.0077 (13) | 0.0108 (12) | −0.0014 (12) |
C4 | 0.045 (2) | 0.052 (2) | 0.0347 (14) | 0.0014 (14) | 0.0067 (12) | −0.0027 (13) |
C5 | 0.056 (2) | 0.053 (2) | 0.050 (2) | 0.000 (2) | 0.0088 (15) | −0.0042 (14) |
C6 | 0.071 (2) | 0.061 (2) | 0.073 (2) | −0.014 (2) | 0.002 (2) | −0.011 (2) |
C7 | 0.082 (3) | 0.087 (3) | 0.075 (3) | −0.040 (2) | −0.001 (2) | 0.005 (2) |
C8 | 0.085 (3) | 0.126 (4) | 0.072 (2) | −0.048 (3) | 0.033 (2) | −0.015 (2) |
C9 | 0.071 (2) | 0.082 (2) | 0.059 (2) | −0.022 (2) | 0.028 (2) | −0.016 (2) |
C10 | 0.058 (2) | 0.046 (2) | 0.043 (2) | −0.0121 (15) | 0.0091 (13) | −0.0077 (13) |
C11 | 0.050 (2) | 0.061 (2) | 0.0362 (15) | −0.008 (2) | 0.0034 (13) | 0.0005 (14) |
C12 | 0.049 (2) | 0.048 (2) | 0.0362 (14) | 0.0041 (14) | 0.0103 (13) | 0.0054 (13) |
C13 | 0.051 (2) | 0.044 (2) | 0.0347 (14) | 0.0050 (14) | 0.0119 (12) | 0.0038 (12) |
C14 | 0.086 (3) | 0.051 (2) | 0.105 (3) | −0.002 (2) | 0.061 (2) | −0.013 (2) |
C15 | 0.097 (3) | 0.046 (2) | 0.124 (3) | −0.004 (2) | 0.067 (3) | −0.013 (2) |
C16 | 0.063 (2) | 0.052 (2) | 0.071 (2) | −0.008 (2) | 0.027 (2) | −0.001 (2) |
C17 | 0.066 (2) | 0.072 (2) | 0.080 (2) | −0.012 (2) | 0.038 (2) | −0.022 (2) |
C18 | 0.061 (2) | 0.055 (2) | 0.074 (2) | −0.007 (2) | 0.028 (2) | −0.018 (2) |
C19 | 0.058 (2) | 0.039 (2) | 0.054 (2) | −0.0043 (14) | 0.0138 (15) | 0.0012 (14) |
C20 | 0.060 (2) | 0.052 (2) | 0.056 (2) | 0.000 (2) | 0.013 (2) | −0.0073 (15) |
C21 | 0.052 (2) | 0.050 (2) | 0.0368 (15) | 0.0096 (14) | 0.0145 (13) | −0.0028 (13) |
C22 | 0.048 (2) | 0.049 (2) | 0.045 (2) | 0.0080 (14) | 0.0174 (14) | 0.0004 (13) |
C23 | 0.082 (2) | 0.073 (2) | 0.048 (2) | −0.021 (2) | 0.009 (2) | 0.003 (2) |
C24 | 0.101 (3) | 0.094 (3) | 0.063 (2) | −0.033 (3) | −0.002 (2) | −0.004 (2) |
C25 | 0.073 (3) | 0.070 (3) | 0.095 (3) | −0.020 (2) | 0.015 (2) | −0.005 (2) |
C26 | 0.080 (3) | 0.065 (2) | 0.091 (3) | −0.011 (2) | 0.038 (2) | 0.001 (2) |
C27 | 0.072 (2) | 0.070 (2) | 0.056 (2) | 0.000 (2) | 0.030 (2) | 0.001 (2) |
O1—C3 | 1.231 (3) | C7—C8 | 1.383 (5) |
O2—C12 | 1.239 (3) | C8—C9 | 1.378 (5) |
O3—C21 | 1.228 (3) | C10—C11 | 1.513 (4) |
N1—C3 | 1.331 (3) | C12—C13 | 1.492 (4) |
N1—C2 | 1.444 (3) | C13—C18 | 1.370 (4) |
N2—C12 | 1.339 (3) | C13—C14 | 1.374 (4) |
N2—C11 | 1.443 (3) | C14—C15 | 1.380 (4) |
N3—C21 | 1.333 (3) | C15—C16 | 1.353 (4) |
N3—C20 | 1.444 (4) | C16—C17 | 1.367 (4) |
N4—C19 | 1.458 (3) | C17—C18 | 1.383 (4) |
N4—C1 | 1.465 (3) | C19—C20 | 1.510 (4) |
N4—C10 | 1.467 (3) | C21—C22 | 1.492 (4) |
C1—C2 | 1.517 (4) | C22—C23 | 1.376 (4) |
C3—C4 | 1.489 (4) | C22—C27 | 1.388 (4) |
C4—C9 | 1.377 (4) | C23—C24 | 1.382 (5) |
C4—C5 | 1.382 (4) | C24—C25 | 1.368 (5) |
C5—C6 | 1.367 (4) | C25—C26 | 1.350 (5) |
C6—C7 | 1.371 (5) | C26—C27 | 1.373 (5) |
C3—N1—C2 | 122.9 (2) | N2—C12—C13 | 117.6 (2) |
C12—N2—C11 | 122.6 (2) | C18—C13—C14 | 118.5 (3) |
C21—N3—C20 | 123.5 (2) | C18—C13—C12 | 123.5 (3) |
C19—N4—C1 | 111.0 (2) | C14—C13—C12 | 118.0 (3) |
C19—N4—C10 | 110.5 (2) | C13—C14—C15 | 120.9 (3) |
C1—N4—C10 | 110.1 (2) | C16—C15—C14 | 120.6 (3) |
N4—C1—C2 | 114.0 (2) | C15—C16—C17 | 118.9 (3) |
N1—C2—C1 | 109.9 (2) | C16—C17—C18 | 121.1 (3) |
O1—C3—N1 | 122.0 (3) | C13—C18—C17 | 120.0 (3) |
O1—C3—C4 | 121.7 (2) | N4—C19—C20 | 114.4 (2) |
N1—C3—C4 | 116.3 (2) | N3—C20—C19 | 113.2 (2) |
C9—C4—C5 | 119.0 (3) | O3—C21—N3 | 121.5 (3) |
C9—C4—C3 | 121.8 (3) | O3—C21—C22 | 120.6 (3) |
C5—C4—C3 | 119.2 (2) | N3—C21—C22 | 117.9 (2) |
C6—C5—C4 | 120.7 (3) | C23—C22—C27 | 117.4 (3) |
C5—C6—C7 | 120.7 (3) | C23—C22—C21 | 123.8 (3) |
C6—C7—C8 | 118.8 (3) | C27—C22—C21 | 118.7 (3) |
C9—C8—C7 | 120.7 (3) | C22—C23—C24 | 120.5 (3) |
C4—C9—C8 | 120.0 (3) | C25—C24—C23 | 120.8 (4) |
N4—C10—C11 | 114.2 (2) | C26—C25—C24 | 119.5 (4) |
N2—C11—C10 | 113.9 (2) | C25—C26—C27 | 120.2 (3) |
O2—C12—N2 | 121.6 (3) | C26—C27—C22 | 121.6 (3) |
O2—C12—C13 | 120.7 (3) | ||
C19—N4—C1—C2 | 71.6 (3) | N2—C12—C13—C14 | 155.3 (3) |
C10—N4—C1—C2 | −165.7 (2) | C18—C13—C14—C15 | 0.4 (5) |
C3—N1—C2—C1 | 175.0 (2) | C12—C13—C14—C15 | 179.4 (3) |
N4—C1—C2—N1 | 56.4 (3) | C13—C14—C15—C16 | 0.1 (6) |
C2—N1—C3—O1 | −4.4 (4) | C14—C15—C16—C17 | −0.5 (6) |
C2—N1—C3—C4 | 175.0 (2) | C15—C16—C17—C18 | 0.6 (5) |
O1—C3—C4—C9 | 146.9 (3) | C14—C13—C18—C17 | −0.3 (5) |
N1—C3—C4—C9 | −32.5 (4) | C12—C13—C18—C17 | −179.3 (3) |
O1—C3—C4—C5 | −31.0 (4) | C16—C17—C18—C13 | −0.1 (5) |
N1—C3—C4—C5 | 149.6 (3) | C1—N4—C19—C20 | −162.6 (2) |
C9—C4—C5—C6 | 1.8 (5) | C10—N4—C19—C20 | 75.0 (3) |
C3—C4—C5—C6 | 179.7 (3) | C21—N3—C20—C19 | −135.0 (3) |
C4—C5—C6—C7 | −1.4 (5) | N4—C19—C20—N3 | 65.1 (3) |
C5—C6—C7—C8 | −0.3 (6) | C20—N3—C21—O3 | 5.7 (4) |
C6—C7—C8—C9 | 1.6 (6) | C20—N3—C21—C22 | −174.0 (2) |
C5—C4—C9—C8 | −0.5 (5) | O3—C21—C22—C23 | −171.0 (3) |
C3—C4—C9—C8 | −178.4 (3) | N3—C21—C22—C23 | 8.7 (4) |
C7—C8—C9—C4 | −1.2 (6) | O3—C21—C22—C27 | 6.0 (4) |
C19—N4—C10—C11 | −162.1 (2) | N3—C21—C22—C27 | −174.3 (3) |
C1—N4—C10—C11 | 74.9 (3) | C27—C22—C23—C24 | 0.4 (5) |
C12—N2—C11—C10 | −100.0 (3) | C21—C22—C23—C24 | 177.5 (3) |
N4—C10—C11—N2 | 66.5 (3) | C22—C23—C24—C25 | 0.8 (6) |
C11—N2—C12—O2 | 2.2 (4) | C23—C24—C25—C26 | −1.6 (6) |
C11—N2—C12—C13 | −176.3 (2) | C24—C25—C26—C27 | 1.3 (6) |
O2—C12—C13—C18 | 155.8 (3) | C25—C26—C27—C22 | 0.0 (6) |
N2—C12—C13—C18 | −25.7 (4) | C23—C22—C27—C26 | −0.8 (5) |
O2—C12—C13—C14 | −23.2 (4) | C21—C22—C27—C26 | −178.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.86 | 2.16 | 2.932 (3) | 150 |
N2—H2···O3i | 0.86 | 2.15 | 2.896 (3) | 145 |
N3—H3···O1ii | 0.86 | 2.13 | 2.950 (3) | 160 |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C27H30N4O3 |
Mr | 458.55 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 10.004 (2), 17.151 (4), 14.472 (3) |
β (°) | 101.06 (2) |
V (Å3) | 2437.0 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.40 × 0.40 × 0.20 |
Data collection | |
Diffractometer | Siemens P3 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5938, 5625, 2590 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.165, 1.00 |
No. of reflections | 4975 |
No. of parameters | 307 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.23 |
Computer programs: P3-P4/PC (Siemens, 1989), P3-P4/PC, XDISK (Siemens, 1989), SHELXTL (Sheldrick, 1994), SHELXTL.
O1—C3 | 1.231 (3) | N4—C1 | 1.465 (3) |
O2—C12 | 1.239 (3) | N4—C10 | 1.467 (3) |
O3—C21 | 1.228 (3) | C1—C2 | 1.517 (4) |
N1—C3 | 1.331 (3) | C3—C4 | 1.489 (4) |
N1—C2 | 1.444 (3) | C4—C9 | 1.377 (4) |
N2—C12 | 1.339 (3) | C10—C11 | 1.513 (4) |
N2—C11 | 1.443 (3) | C12—C13 | 1.492 (4) |
N3—C21 | 1.333 (3) | C19—C20 | 1.510 (4) |
N3—C20 | 1.444 (4) | C21—C22 | 1.492 (4) |
N4—C19 | 1.458 (3) | ||
C3—N1—C2 | 122.9 (2) | N4—C10—C11 | 114.2 (2) |
C12—N2—C11 | 122.6 (2) | N2—C11—C10 | 113.9 (2) |
C21—N3—C20 | 123.5 (2) | O2—C12—N2 | 121.6 (3) |
C19—N4—C1 | 111.0 (2) | O2—C12—C13 | 120.7 (3) |
C19—N4—C10 | 110.5 (2) | N2—C12—C13 | 117.6 (2) |
C1—N4—C10 | 110.1 (2) | N4—C19—C20 | 114.4 (2) |
N4—C1—C2 | 114.0 (2) | N3—C20—C19 | 113.2 (2) |
N1—C2—C1 | 109.9 (2) | O3—C21—N3 | 121.5 (3) |
O1—C3—N1 | 122.0 (3) | O3—C21—C22 | 120.6 (3) |
O1—C3—C4 | 121.7 (2) | N3—C21—C22 | 117.9 (2) |
N1—C3—C4 | 116.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.86 | 2.16 | 2.932 (3) | 150 |
N2—H2···O3i | 0.86 | 2.15 | 2.896 (3) | 145 |
N3—H3···O1ii | 0.86 | 2.13 | 2.950 (3) | 160 |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1, −y, −z+1. |
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Compounds with amidate donor groups are useful for the stabilization of high valent metals. Additionally, tripodal type ligand structures are useful for enforcing trigonal pyramidal (or similar) geometry in metal complexes. Tris[2-(benzoylamino)ethyl]amine, (I), was synthesized as a tris-amidate tripodal amine-type ligand for the stabilization of high valent metal complexes with trigonal–pyramidal geometry. \scheme
The molecular structure of (I) is similar to the tripodal amine compounds, tris(3-aza-4-oxo-5-hydroxy-5-phenylpent-1-yl)amine, (II) (Byrne et al., 1998), and tris[(4-diphenylphosphinobenzamido)ethyl]amine, (III) (Lang et al., 1995). Compound (I) exhibits a folded structure due to the presence of an intramolecular N1···O2 hydrogen bond. When (I) is viewed down the molecule towards N4, one observes a symmetrical cavity with a average depth of 7.3 Å (distance from N4 to p-phenyl carbons) with closest N···N contact distances between the three arms of 4.1–4.4 Å. This may lead to a restriction in reactivity or solvent accessibility within the cavity since upon metallation of the ligand it is presumed that the three donor arms fold down into the expected tripod motif thereby encapsulating the metal within the cavity.
The folded structure is also observed in (II) and (III), exhibiting one or two intramolecular hydrogen bonds. A symmetrical cavity is observed for (III) (N···P distances of approximately 8.8 Å and closest N···N contact distances between the arms ranging 4.2–4.6 Å). On the other hand, an asymmetrical cavity is observed for (II) due to the presence of the two intramolecular hydrogen bonds `pulling back' the arms which would possibly allow for greater accessibility into the cavity.
In contrast, an extended structure is observed for [N-(1-propan-2-one oxime)]bis[N-2-(N',N''-trimethylacetyl)aminoethyl]amine, (IV) (Goldcamp et al., 2000), and tris[N-(S)-(-)-(α)-methylbenzylcarbamoylmethyl]amine, (IV) (Hammes et al., 1998), which is attributed to the lack of intramolecular hydrogen bonding. This extended structure allows for easy access for metal and solvent interactions.
In addition to the intramolecular hydrogen bond, (I) participates in two intermolecular N—H···O hydrogen bonds (N2···O3 and N3···O1) forming linear chains along the c axis.