Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807050714/sj2377sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807050714/sj2377Isup2.hkl |
CCDC reference: 667394
Compound (II) was prepared according to the procedure of Yang et al. (2005). Compound (II) was reacted at room temperature with concentrated HCl to yield a white precipitate. The solvent was removed and the solid residue recrystallized from an ethanol/hexane (4:1, v/v) mixture to yield compound (I) (m.p. 492–494 K).
Hydrogen atoms attached to C, N and O were placed in geometrically idealized positions and refined using a riding model. [C—H = 0.93 Å; Uiso(H) = 1.2Ueq(C) (aromatic CH); C—H = 0.98 Å; Uiso(H) = 1.2Ueq(C) (methine CH) C—H = 0.970 Å; Uiso(H) = 1.2Ueq(C) (methylene CH2) and C—H = 0.960 Å; Uiso(H) = 1.5Ueq(C) (methyl CH3); N—H = 0.90 Å; Uiso(H) = 1.2Ueq(N); O—H =0.82 Å; Uiso(H) = 1.5Ueq(O);]
The search for new chiral ligands to be used in asymmetric catalysis is of great interest in the field of synthetic chemistry. (Cimarelli et al., 2002; Tseng & Yang, 2004). Among them, enantiopure aminoalkyphenols have attracted wide attention as they can be used in asymmetric catalytic reactions (Puigjaner et al., 1999; Guangyou et al., 2003; Li et al., 2004; Watts et al. 2005), an active area of research in organic chemistry (Joshi & Malhotra, 2003). However, most aminoalkylphenols are derived from readily available natural products (Soai & Niwa, 1992). The synthesis of new aminoalkylphenols is therefore of interest because of their potential as asymmetric catalysts.
In this paper, we report the absolute structure of the title compound (I) a hydrochloride derivative of the aminoalkylphenol 2-((R)-1-((S)-1–2-methoxy-5-methylphenyl-2-phenylethylamino)butyl)-4- methylphenol. As well as the known S configuration of C8, the structure reveals an R configuration for the strereogenic centre at C17. The asymmetric unit of the title compound (Fig. 1) consists of a C27H34NO2+ cation and a Cl- anion. The dihedral angles between the benzene rings A (C1—C6), B (C9—C15) and C (C21—C27) are 54.51 ° for A/B, 56.51 ° for A/C and 21.17 ° for B/C respectively.
The conformation of the molecule is influenced by two intramolecular N—H···O hydrogen bonds. In the crystal structure, the Cl- anion forms O—H···Cl and N—H···Cl hydrogen bonds to give a continuous two-dimensional framework structure Table 1, Fig. 2.
For general background, see: Cimarelli et al. (2002); Guangyou et al. (2003); Joshi & Malhotra (2003); Li et al. (2004); Puigjaner et al. (1999); Soai & Niwa (1992); Tseng & Yang (2004); Watts et al. (2005). For related structures, see: Yang et al. (2005).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Bruker, 1997).
C27H34NO2+·Cl− | F(000) = 944 |
Mr = 440.00 | Dx = 1.194 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 4734 reflections |
a = 9.8553 (14) Å | θ = 2.3–26.9° |
b = 13.1962 (19) Å | µ = 0.18 mm−1 |
c = 18.825 (3) Å | T = 298 K |
V = 2448.2 (6) Å3 | Block, colourless |
Z = 4 | 0.48 × 0.40 × 0.32 mm |
Bruker SMART CCD area-detecter diffractometer | 4534 independent reflections |
Radiation source: fine-focus sealed tube | 3992 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
φ and ω scans | θmax = 25.5°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997a) | h = −11→11 |
Tmin = 0.919, Tmax = 0.945 | k = −15→15 |
12855 measured reflections | l = −22→15 |
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)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.100 | w = 1/[σ2(Fo2) + (0.0549P)2 + 0.1969P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
4534 reflections | Δρmax = 0.16 e Å−3 |
285 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 1957 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.05 (6) |
C27H34NO2+·Cl− | V = 2448.2 (6) Å3 |
Mr = 440.00 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 9.8553 (14) Å | µ = 0.18 mm−1 |
b = 13.1962 (19) Å | T = 298 K |
c = 18.825 (3) Å | 0.48 × 0.40 × 0.32 mm |
Bruker SMART CCD area-detecter diffractometer | 4534 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997a) | 3992 reflections with I > 2σ(I) |
Tmin = 0.919, Tmax = 0.945 | Rint = 0.026 |
12855 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.100 | Δρmax = 0.16 e Å−3 |
S = 1.03 | Δρmin = −0.15 e Å−3 |
4534 reflections | Absolute structure: Flack (1983), 1957 Friedel pairs |
285 parameters | Absolute structure parameter: −0.05 (6) |
0 restraints |
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 | ||
C1 | 0.5112 (3) | 0.44927 (19) | 0.38399 (13) | 0.0624 (6) | |
H1 | 0.5257 | 0.5105 | 0.3608 | 0.075* | |
C2 | 0.4101 (3) | 0.3849 (2) | 0.36021 (17) | 0.0802 (9) | |
H2 | 0.3591 | 0.4024 | 0.3205 | 0.096* | |
C3 | 0.3847 (3) | 0.2961 (2) | 0.39456 (19) | 0.0798 (9) | |
H3 | 0.3159 | 0.2534 | 0.3790 | 0.096* | |
C4 | 0.4607 (3) | 0.2709 (2) | 0.45149 (17) | 0.0766 (8) | |
H4 | 0.4437 | 0.2103 | 0.4751 | 0.092* | |
C5 | 0.5633 (3) | 0.33371 (18) | 0.47519 (14) | 0.0608 (6) | |
H5 | 0.6147 | 0.3148 | 0.5144 | 0.073* | |
C6 | 0.5905 (2) | 0.42420 (15) | 0.44130 (11) | 0.0465 (5) | |
C7 | 0.6996 (2) | 0.49521 (16) | 0.46668 (12) | 0.0500 (5) | |
H7A | 0.7391 | 0.5302 | 0.4264 | 0.060* | |
H7B | 0.7709 | 0.4568 | 0.4899 | 0.060* | |
C8 | 0.6407 (2) | 0.57302 (14) | 0.51898 (11) | 0.0408 (4) | |
H8 | 0.5527 | 0.5943 | 0.4999 | 0.049* | |
C9 | 0.6151 (2) | 0.53212 (14) | 0.59232 (10) | 0.0388 (4) | |
C10 | 0.4840 (2) | 0.52856 (15) | 0.61839 (12) | 0.0443 (5) | |
H10 | 0.4132 | 0.5502 | 0.5895 | 0.053* | |
C11 | 0.4545 (2) | 0.49376 (16) | 0.68641 (13) | 0.0530 (5) | |
C12 | 0.5602 (2) | 0.45930 (17) | 0.72691 (13) | 0.0573 (6) | |
H12 | 0.5424 | 0.4340 | 0.7721 | 0.069* | |
C13 | 0.6923 (2) | 0.46093 (17) | 0.70283 (12) | 0.0535 (5) | |
H13 | 0.7621 | 0.4364 | 0.7313 | 0.064* | |
C14 | 0.72006 (19) | 0.49929 (14) | 0.63609 (11) | 0.0444 (5) | |
C15 | 0.3097 (3) | 0.4976 (2) | 0.71320 (18) | 0.0828 (9) | |
H15A | 0.2549 | 0.4512 | 0.6864 | 0.124* | |
H15B | 0.2748 | 0.5651 | 0.7077 | 0.124* | |
H15C | 0.3076 | 0.4790 | 0.7625 | 0.124* | |
C16 | 0.9601 (2) | 0.4959 (2) | 0.65607 (15) | 0.0716 (7) | |
H16A | 0.9458 | 0.5351 | 0.6984 | 0.107* | |
H16B | 1.0424 | 0.5175 | 0.6334 | 0.107* | |
H16C | 0.9671 | 0.4254 | 0.6683 | 0.107* | |
C17 | 0.6689 (2) | 0.75214 (14) | 0.56655 (10) | 0.0426 (5) | |
H17 | 0.5706 | 0.7415 | 0.5681 | 0.051* | |
C18 | 0.6927 (3) | 0.85349 (15) | 0.53024 (12) | 0.0524 (5) | |
H18A | 0.7893 | 0.8674 | 0.5290 | 0.063* | |
H18B | 0.6606 | 0.8497 | 0.4816 | 0.063* | |
C19 | 0.6206 (3) | 0.93971 (18) | 0.56818 (15) | 0.0762 (8) | |
H19A | 0.5263 | 0.9212 | 0.5754 | 0.091* | |
H19B | 0.6614 | 0.9491 | 0.6146 | 0.091* | |
C20 | 0.6263 (4) | 1.0368 (2) | 0.52876 (17) | 0.0946 (10) | |
H20A | 0.7188 | 1.0517 | 0.5166 | 0.142* | |
H20B | 0.5906 | 1.0901 | 0.5579 | 0.142* | |
H20C | 0.5733 | 1.0313 | 0.4861 | 0.142* | |
C21 | 0.71962 (19) | 0.74655 (13) | 0.64187 (10) | 0.0413 (4) | |
C22 | 0.6296 (2) | 0.73690 (15) | 0.69791 (11) | 0.0465 (5) | |
H22 | 0.5371 | 0.7343 | 0.6882 | 0.056* | |
C23 | 0.6720 (3) | 0.73095 (17) | 0.76779 (12) | 0.0554 (6) | |
C24 | 0.5724 (3) | 0.7149 (2) | 0.82768 (14) | 0.0807 (8) | |
H24A | 0.4818 | 0.7261 | 0.8106 | 0.121* | |
H24B | 0.5917 | 0.7617 | 0.8654 | 0.121* | |
H24C | 0.5803 | 0.6468 | 0.8451 | 0.121* | |
C25 | 0.8098 (3) | 0.73871 (18) | 0.78093 (12) | 0.0581 (6) | |
H25 | 0.8408 | 0.7364 | 0.8276 | 0.070* | |
C26 | 0.9023 (2) | 0.74980 (17) | 0.72650 (12) | 0.0542 (5) | |
H26 | 0.9943 | 0.7556 | 0.7367 | 0.065* | |
C27 | 0.85830 (19) | 0.75234 (15) | 0.65706 (10) | 0.0437 (5) | |
N1 | 0.72890 (17) | 0.66615 (12) | 0.52202 (8) | 0.0419 (4) | |
H1A | 0.7427 | 0.6888 | 0.4775 | 0.050* | |
H1B | 0.8102 | 0.6490 | 0.5402 | 0.050* | |
O1 | 0.94600 (13) | 0.75705 (13) | 0.60056 (7) | 0.0544 (4) | |
H1C | 1.0242 | 0.7609 | 0.6152 | 0.082* | |
O2 | 0.84902 (14) | 0.51013 (12) | 0.60891 (8) | 0.0544 (4) | |
Cl1 | 0.24550 (5) | 0.77487 (5) | 0.63820 (3) | 0.05994 (17) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0754 (16) | 0.0561 (13) | 0.0558 (14) | 0.0171 (13) | −0.0103 (13) | −0.0065 (11) |
C2 | 0.0720 (17) | 0.094 (2) | 0.0746 (18) | 0.0262 (16) | −0.0246 (16) | −0.0237 (18) |
C3 | 0.0617 (16) | 0.078 (2) | 0.100 (2) | −0.0006 (14) | 0.0007 (17) | −0.0346 (18) |
C4 | 0.0858 (18) | 0.0517 (14) | 0.092 (2) | −0.0097 (14) | 0.0121 (17) | −0.0063 (14) |
C5 | 0.0716 (16) | 0.0556 (14) | 0.0553 (14) | 0.0041 (12) | −0.0036 (13) | 0.0042 (11) |
C6 | 0.0585 (12) | 0.0420 (11) | 0.0389 (11) | 0.0080 (9) | 0.0027 (10) | −0.0065 (9) |
C7 | 0.0540 (12) | 0.0513 (12) | 0.0449 (11) | 0.0008 (10) | 0.0058 (10) | −0.0046 (10) |
C8 | 0.0398 (10) | 0.0410 (10) | 0.0416 (11) | 0.0006 (8) | −0.0037 (9) | −0.0001 (8) |
C9 | 0.0425 (10) | 0.0347 (9) | 0.0392 (11) | 0.0006 (8) | −0.0011 (9) | 0.0001 (8) |
C10 | 0.0395 (10) | 0.0404 (10) | 0.0530 (12) | 0.0027 (8) | −0.0014 (9) | 0.0048 (9) |
C11 | 0.0526 (12) | 0.0468 (12) | 0.0595 (13) | −0.0027 (10) | 0.0099 (11) | 0.0079 (11) |
C12 | 0.0689 (15) | 0.0530 (12) | 0.0501 (13) | −0.0002 (11) | 0.0064 (12) | 0.0147 (11) |
C13 | 0.0575 (13) | 0.0509 (12) | 0.0522 (13) | 0.0078 (10) | −0.0092 (11) | 0.0112 (10) |
C14 | 0.0437 (11) | 0.0409 (10) | 0.0487 (11) | 0.0042 (9) | −0.0026 (9) | −0.0009 (9) |
C15 | 0.0637 (15) | 0.0852 (19) | 0.099 (2) | 0.0069 (15) | 0.0311 (16) | 0.0299 (17) |
C16 | 0.0501 (12) | 0.0897 (18) | 0.0751 (17) | 0.0157 (13) | −0.0160 (13) | −0.0003 (15) |
C17 | 0.0427 (10) | 0.0412 (11) | 0.0438 (11) | 0.0015 (9) | −0.0007 (9) | −0.0031 (9) |
C18 | 0.0666 (14) | 0.0466 (12) | 0.0440 (11) | −0.0007 (10) | −0.0109 (11) | 0.0021 (9) |
C19 | 0.112 (2) | 0.0498 (14) | 0.0672 (17) | 0.0066 (14) | −0.0046 (17) | −0.0053 (12) |
C20 | 0.141 (3) | 0.0593 (15) | 0.084 (2) | 0.0184 (18) | −0.030 (2) | −0.0071 (15) |
C21 | 0.0461 (10) | 0.0360 (9) | 0.0417 (10) | 0.0006 (8) | −0.0008 (9) | −0.0002 (8) |
C22 | 0.0512 (11) | 0.0395 (10) | 0.0489 (12) | 0.0003 (9) | 0.0073 (10) | −0.0019 (9) |
C23 | 0.0738 (15) | 0.0475 (12) | 0.0449 (12) | 0.0054 (11) | 0.0129 (11) | 0.0023 (10) |
C24 | 0.101 (2) | 0.0830 (18) | 0.0579 (16) | 0.0039 (16) | 0.0287 (16) | 0.0080 (14) |
C25 | 0.0784 (16) | 0.0618 (14) | 0.0340 (10) | 0.0073 (13) | −0.0051 (11) | 0.0002 (10) |
C26 | 0.0569 (12) | 0.0582 (13) | 0.0474 (12) | 0.0036 (11) | −0.0074 (10) | 0.0000 (11) |
C27 | 0.0476 (11) | 0.0459 (11) | 0.0376 (10) | −0.0008 (9) | −0.0009 (9) | −0.0011 (9) |
N1 | 0.0431 (9) | 0.0456 (9) | 0.0369 (8) | 0.0009 (7) | −0.0019 (8) | −0.0018 (7) |
O1 | 0.0426 (7) | 0.0778 (11) | 0.0429 (8) | −0.0060 (8) | −0.0001 (7) | 0.0022 (8) |
O2 | 0.0373 (7) | 0.0730 (10) | 0.0529 (9) | 0.0089 (7) | −0.0032 (7) | 0.0043 (8) |
Cl1 | 0.0536 (3) | 0.0789 (4) | 0.0473 (3) | −0.0029 (3) | −0.0117 (3) | 0.0066 (3) |
C1—C6 | 1.372 (3) | C16—H16A | 0.9600 |
C1—C2 | 1.384 (4) | C16—H16B | 0.9600 |
C1—H1 | 0.9300 | C16—H16C | 0.9600 |
C2—C3 | 1.361 (4) | C17—C21 | 1.505 (3) |
C2—H2 | 0.9300 | C17—C18 | 1.520 (3) |
C3—C4 | 1.349 (4) | C17—N1 | 1.530 (2) |
C3—H3 | 0.9300 | C17—H17 | 0.9800 |
C4—C5 | 1.382 (4) | C18—C19 | 1.520 (3) |
C4—H4 | 0.9300 | C18—H18A | 0.9700 |
C5—C6 | 1.380 (3) | C18—H18B | 0.9700 |
C5—H5 | 0.9300 | C19—C20 | 1.481 (4) |
C6—C7 | 1.504 (3) | C19—H19A | 0.9700 |
C7—C8 | 1.536 (3) | C19—H19B | 0.9700 |
C7—H7A | 0.9700 | C20—H20A | 0.9600 |
C7—H7B | 0.9700 | C20—H20B | 0.9600 |
C8—C9 | 1.504 (3) | C20—H20C | 0.9600 |
C8—N1 | 1.506 (2) | C21—C22 | 1.385 (3) |
C8—H8 | 0.9800 | C21—C27 | 1.398 (3) |
C9—C10 | 1.383 (3) | C22—C23 | 1.383 (3) |
C9—C14 | 1.391 (3) | C22—H22 | 0.9300 |
C10—C11 | 1.391 (3) | C23—C25 | 1.384 (3) |
C10—H10 | 0.9300 | C23—C24 | 1.510 (3) |
C11—C12 | 1.368 (3) | C24—H24A | 0.9600 |
C11—C15 | 1.515 (3) | C24—H24B | 0.9600 |
C12—C13 | 1.379 (3) | C24—H24C | 0.9600 |
C12—H12 | 0.9300 | C25—C26 | 1.379 (3) |
C13—C14 | 1.382 (3) | C25—H25 | 0.9300 |
C13—H13 | 0.9300 | C26—C27 | 1.378 (3) |
C14—O2 | 1.378 (2) | C26—H26 | 0.9300 |
C15—H15A | 0.9600 | C27—O1 | 1.372 (2) |
C15—H15B | 0.9600 | N1—H1A | 0.9000 |
C15—H15C | 0.9600 | N1—H1B | 0.9000 |
C16—O2 | 1.422 (3) | O1—H1C | 0.8200 |
C6—C1—C2 | 121.1 (3) | H16A—C16—H16C | 109.5 |
C6—C1—H1 | 119.5 | H16B—C16—H16C | 109.5 |
C2—C1—H1 | 119.5 | C21—C17—C18 | 114.55 (17) |
C3—C2—C1 | 120.5 (3) | C21—C17—N1 | 110.58 (15) |
C3—C2—H2 | 119.8 | C18—C17—N1 | 110.28 (16) |
C1—C2—H2 | 119.8 | C21—C17—H17 | 107.0 |
C4—C3—C2 | 119.2 (3) | C18—C17—H17 | 107.0 |
C4—C3—H3 | 120.4 | N1—C17—H17 | 107.0 |
C2—C3—H3 | 120.4 | C19—C18—C17 | 112.03 (19) |
C3—C4—C5 | 121.0 (3) | C19—C18—H18A | 109.2 |
C3—C4—H4 | 119.5 | C17—C18—H18A | 109.2 |
C5—C4—H4 | 119.5 | C19—C18—H18B | 109.2 |
C6—C5—C4 | 120.8 (3) | C17—C18—H18B | 109.2 |
C6—C5—H5 | 119.6 | H18A—C18—H18B | 107.9 |
C4—C5—H5 | 119.6 | C20—C19—C18 | 113.2 (2) |
C1—C6—C5 | 117.5 (2) | C20—C19—H19A | 108.9 |
C1—C6—C7 | 120.4 (2) | C18—C19—H19A | 108.9 |
C5—C6—C7 | 122.1 (2) | C20—C19—H19B | 108.9 |
C6—C7—C8 | 110.46 (17) | C18—C19—H19B | 108.9 |
C6—C7—H7A | 109.6 | H19A—C19—H19B | 107.8 |
C8—C7—H7A | 109.6 | C19—C20—H20A | 109.5 |
C6—C7—H7B | 109.6 | C19—C20—H20B | 109.5 |
C8—C7—H7B | 109.6 | H20A—C20—H20B | 109.5 |
H7A—C7—H7B | 108.1 | C19—C20—H20C | 109.5 |
C9—C8—N1 | 110.78 (15) | H20A—C20—H20C | 109.5 |
C9—C8—C7 | 114.31 (16) | H20B—C20—H20C | 109.5 |
N1—C8—C7 | 110.58 (16) | C22—C21—C27 | 118.40 (18) |
C9—C8—H8 | 106.9 | C22—C21—C17 | 120.64 (17) |
N1—C8—H8 | 106.9 | C27—C21—C17 | 120.96 (17) |
C7—C8—H8 | 106.9 | C23—C22—C21 | 122.4 (2) |
C10—C9—C14 | 118.27 (18) | C23—C22—H22 | 118.8 |
C10—C9—C8 | 119.65 (18) | C21—C22—H22 | 118.8 |
C14—C9—C8 | 122.07 (18) | C22—C23—C25 | 117.6 (2) |
C9—C10—C11 | 122.22 (19) | C22—C23—C24 | 121.4 (2) |
C9—C10—H10 | 118.9 | C25—C23—C24 | 121.0 (2) |
C11—C10—H10 | 118.9 | C23—C24—H24A | 109.5 |
C12—C11—C10 | 117.6 (2) | C23—C24—H24B | 109.5 |
C12—C11—C15 | 122.9 (2) | H24A—C24—H24B | 109.5 |
C10—C11—C15 | 119.5 (2) | C23—C24—H24C | 109.5 |
C11—C12—C13 | 122.0 (2) | H24A—C24—H24C | 109.5 |
C11—C12—H12 | 119.0 | H24B—C24—H24C | 109.5 |
C13—C12—H12 | 119.0 | C26—C25—C23 | 121.6 (2) |
C12—C13—C14 | 119.4 (2) | C26—C25—H25 | 119.2 |
C12—C13—H13 | 120.3 | C23—C25—H25 | 119.2 |
C14—C13—H13 | 120.3 | C27—C26—C25 | 120.0 (2) |
O2—C14—C13 | 123.95 (19) | C27—C26—H26 | 120.0 |
O2—C14—C9 | 115.68 (18) | C25—C26—H26 | 120.0 |
C13—C14—C9 | 120.36 (19) | O1—C27—C26 | 122.58 (18) |
C11—C15—H15A | 109.5 | O1—C27—C21 | 117.36 (17) |
C11—C15—H15B | 109.5 | C26—C27—C21 | 120.02 (19) |
H15A—C15—H15B | 109.5 | C8—N1—C17 | 113.77 (14) |
C11—C15—H15C | 109.5 | C8—N1—H1A | 108.8 |
H15A—C15—H15C | 109.5 | C17—N1—H1A | 108.8 |
H15B—C15—H15C | 109.5 | C8—N1—H1B | 108.8 |
O2—C16—H16A | 109.5 | C17—N1—H1B | 108.8 |
O2—C16—H16B | 109.5 | H1A—N1—H1B | 107.7 |
H16A—C16—H16B | 109.5 | C27—O1—H1C | 109.5 |
O2—C16—H16C | 109.5 | C14—O2—C16 | 117.69 (17) |
C6—C1—C2—C3 | 1.8 (4) | C8—C9—C14—C13 | −179.15 (19) |
C1—C2—C3—C4 | −1.0 (4) | C21—C17—C18—C19 | −61.2 (3) |
C2—C3—C4—C5 | 0.0 (4) | N1—C17—C18—C19 | 173.31 (19) |
C3—C4—C5—C6 | 0.2 (4) | C17—C18—C19—C20 | −172.2 (2) |
C2—C1—C6—C5 | −1.5 (3) | C18—C17—C21—C22 | 113.4 (2) |
C2—C1—C6—C7 | −179.8 (2) | N1—C17—C21—C22 | −121.26 (19) |
C4—C5—C6—C1 | 0.5 (3) | C18—C17—C21—C27 | −65.7 (2) |
C4—C5—C6—C7 | 178.7 (2) | N1—C17—C21—C27 | 59.6 (2) |
C1—C6—C7—C8 | 86.5 (2) | C27—C21—C22—C23 | −1.2 (3) |
C5—C6—C7—C8 | −91.7 (2) | C17—C21—C22—C23 | 179.64 (19) |
C6—C7—C8—C9 | 76.7 (2) | C21—C22—C23—C25 | 2.3 (3) |
C6—C7—C8—N1 | −157.42 (17) | C21—C22—C23—C24 | −176.7 (2) |
N1—C8—C9—C10 | 117.71 (19) | C22—C23—C25—C26 | −1.4 (4) |
C7—C8—C9—C10 | −116.6 (2) | C24—C23—C25—C26 | 177.7 (2) |
N1—C8—C9—C14 | −60.9 (2) | C23—C25—C26—C27 | −0.7 (4) |
C7—C8—C9—C14 | 64.9 (2) | C25—C26—C27—O1 | −176.0 (2) |
C14—C9—C10—C11 | 0.2 (3) | C25—C26—C27—C21 | 1.8 (3) |
C8—C9—C10—C11 | −178.45 (19) | C22—C21—C27—O1 | 177.00 (17) |
C9—C10—C11—C12 | −2.1 (3) | C17—C21—C27—O1 | −3.9 (3) |
C9—C10—C11—C15 | 176.4 (2) | C22—C21—C27—C26 | −0.9 (3) |
C10—C11—C12—C13 | 1.7 (4) | C17—C21—C27—C26 | 178.25 (18) |
C15—C11—C12—C13 | −176.8 (2) | C9—C8—N1—C17 | −58.7 (2) |
C11—C12—C13—C14 | 0.6 (4) | C7—C8—N1—C17 | 173.50 (16) |
C12—C13—C14—O2 | 175.8 (2) | C21—C17—N1—C8 | 93.05 (18) |
C12—C13—C14—C9 | −2.7 (3) | C18—C17—N1—C8 | −139.22 (17) |
C10—C9—C14—O2 | −176.33 (17) | C13—C14—O2—C16 | −10.1 (3) |
C8—C9—C14—O2 | 2.3 (3) | C9—C14—O2—C16 | 168.4 (2) |
C10—C9—C14—C13 | 2.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1C···Cl1i | 0.82 | 2.23 | 3.0446 (15) | 171 |
N1—H1A···Cl1ii | 0.90 | 2.23 | 3.1193 (18) | 169 |
N1—H1B···O2 | 0.90 | 2.28 | 2.884 (2) | 125 |
N1—H1B···O1 | 0.90 | 2.26 | 2.864 (2) | 124 |
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+3/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C27H34NO2+·Cl− |
Mr | 440.00 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 298 |
a, b, c (Å) | 9.8553 (14), 13.1962 (19), 18.825 (3) |
V (Å3) | 2448.2 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.18 |
Crystal size (mm) | 0.48 × 0.40 × 0.32 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detecter |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1997a) |
Tmin, Tmax | 0.919, 0.945 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12855, 4534, 3992 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.100, 1.03 |
No. of reflections | 4534 |
No. of parameters | 285 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.15 |
Absolute structure | Flack (1983), 1957 Friedel pairs |
Absolute structure parameter | −0.05 (6) |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997b), SHELXL97 (Sheldrick, 1997b), PLATON (Spek, 2003), SHELXTL (Bruker, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1C···Cl1i | 0.82 | 2.23 | 3.0446 (15) | 171.4 |
N1—H1A···Cl1ii | 0.90 | 2.23 | 3.1193 (18) | 169.3 |
N1—H1B···O2 | 0.90 | 2.28 | 2.884 (2) | 124.7 |
N1—H1B···O1 | 0.90 | 2.26 | 2.864 (2) | 124.0 |
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+3/2, −z+1. |
The search for new chiral ligands to be used in asymmetric catalysis is of great interest in the field of synthetic chemistry. (Cimarelli et al., 2002; Tseng & Yang, 2004). Among them, enantiopure aminoalkyphenols have attracted wide attention as they can be used in asymmetric catalytic reactions (Puigjaner et al., 1999; Guangyou et al., 2003; Li et al., 2004; Watts et al. 2005), an active area of research in organic chemistry (Joshi & Malhotra, 2003). However, most aminoalkylphenols are derived from readily available natural products (Soai & Niwa, 1992). The synthesis of new aminoalkylphenols is therefore of interest because of their potential as asymmetric catalysts.
In this paper, we report the absolute structure of the title compound (I) a hydrochloride derivative of the aminoalkylphenol 2-((R)-1-((S)-1–2-methoxy-5-methylphenyl-2-phenylethylamino)butyl)-4- methylphenol. As well as the known S configuration of C8, the structure reveals an R configuration for the strereogenic centre at C17. The asymmetric unit of the title compound (Fig. 1) consists of a C27H34NO2+ cation and a Cl- anion. The dihedral angles between the benzene rings A (C1—C6), B (C9—C15) and C (C21—C27) are 54.51 ° for A/B, 56.51 ° for A/C and 21.17 ° for B/C respectively.
The conformation of the molecule is influenced by two intramolecular N—H···O hydrogen bonds. In the crystal structure, the Cl- anion forms O—H···Cl and N—H···Cl hydrogen bonds to give a continuous two-dimensional framework structure Table 1, Fig. 2.