Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803007311/fl6027sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803007311/fl6027Isup2.hkl |
CCDC reference: 214597
(1R, 2S)-(-)-Ephedrine (2.5 g, 15 mmol) and salicylic aldehyde (1.6 ml, 15 mmol) were heated under reflux in benzene (20 ml) for 1 h. The calculated amount of water was then removed. The excess of benzene was abstracted by rotary evaporator and the residue recrystallized from alcohol to give the oxazolidine, a white needle-shaped crystal. To one molar equivalent of LiAlH4 (0.5 g, 13.2 mmol) in boiling dry dioxane (20 ml), the dioxane (15 ml) solution of one mole of the oxazolidine (1.5 g, 5.54 mmol) was slowly added, and the mixture refluxed overnight. After cooling, ice and an excess of 10% sodium hydroxide solution was added, the resulting product extracted with benzene and the extract was washed with water till neutral, dried and concentrated to obtain the title compound as an oil. Crystals of (I) were obtained by recrystallization from CH2Cl2/hexane.
The positions of all H atoms were fixed geometrically and distances to H atoms were set by the program.
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. The title compound, drawn with 50% probability displacement parameters. | |
Fig. 2. Crystal packing of title compound, viewed down the a axis. |
C17H21NO2 | F(000) = 584 |
Mr = 271.35 | Dx = 1.207 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 3564 reflections |
a = 6.004 (1) Å | θ = 2.6–24.3° |
b = 10.451 (1) Å | µ = 0.08 mm−1 |
c = 23.790 (3) Å | T = 293 K |
V = 1492.8 (3) Å3 | Block, colorless |
Z = 4 | 0.3 × 0.2 × 0.2 mm |
Bruker SMART APEX CCD area-detector diffractometer | 2605 independent reflections |
Radiation source: fine-focus sealed tube | 1908 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.065 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.7° |
Absorption correction: ψ scan (XPREP; Bruker, 2000) | h = −7→7 |
Tmin = 0.98, Tmax = 0.99 | k = −9→12 |
7631 measured reflections | l = −26→28 |
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)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.074 | w = 1/[σ2(Fo2) + (0.003P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
2605 reflections | Δρmax = 0.14 e Å−3 |
186 parameters | Δρmin = −0.18 e Å−3 |
0 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.034 (2) |
C17H21NO2 | V = 1492.8 (3) Å3 |
Mr = 271.35 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.004 (1) Å | µ = 0.08 mm−1 |
b = 10.451 (1) Å | T = 293 K |
c = 23.790 (3) Å | 0.3 × 0.2 × 0.2 mm |
Bruker SMART APEX CCD area-detector diffractometer | 2605 independent reflections |
Absorption correction: ψ scan (XPREP; Bruker, 2000) | 1908 reflections with I > 2σ(I) |
Tmin = 0.98, Tmax = 0.99 | Rint = 0.065 |
7631 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.14 e Å−3 |
2605 reflections | Δρmin = −0.18 e Å−3 |
186 parameters |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) − 2.5865 (0.0045) x + 8.9177 (0.0049) y + 6.9893 (0.0190) z = 1.6697 (0.0054) * 0.0012 (0.0015) C11 * 0.0035 (0.0015) C12 * −0.0048 (0.0015) C13 * 0.0014 (0.0015) C14 * 0.0033 (0.0015) C15 * −0.0046 (0.0014) C16 Rms deviation of fitted atoms = 0.0034 2.7995 (0.0050) x − 8.3604 (0.0062) y + 8.9853 (0.0201) z = 3.4770 (0.0088) Angle to previous plane (with approximate e.s.d.) = 39.42 (0.07) * −0.0015 (0.0016) C4 * −0.0018 (0.0016) C5 * −0.0001 (0.0017) C6 * 0.0052 (0.0019) C7 * −0.0085 (0.0017) C8 * 0.0067 (0.0016) C9 Rms deviation of fitted atoms = 0.0050 |
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 | ||
N1 | 0.6882 (3) | 0.17953 (16) | 0.16647 (6) | 0.0432 (4) | |
O1 | 0.7091 (3) | −0.03212 (14) | 0.26390 (5) | 0.0605 (5) | |
H1A | 0.7976 | −0.0616 | 0.2867 | 0.091* | |
O2 | 0.9930 (3) | 0.35305 (15) | 0.15982 (5) | 0.0600 (5) | |
H2A | 0.9148 | 0.2967 | 0.1735 | 0.090* | |
C1 | 0.7225 (4) | 0.10431 (19) | 0.26442 (8) | 0.0477 (6) | |
H1 | 0.8749 | 0.1283 | 0.2541 | 0.057* | |
C2 | 0.5650 (3) | 0.1584 (2) | 0.21954 (7) | 0.0475 (6) | |
H2 | 0.5186 | 0.2430 | 0.2328 | 0.057* | |
C3 | 0.3518 (4) | 0.0804 (2) | 0.21174 (9) | 0.0733 (8) | |
H3A | 0.2586 | 0.1213 | 0.1843 | 0.110* | |
H3B | 0.2738 | 0.0752 | 0.2469 | 0.110* | |
H3C | 0.3891 | −0.0041 | 0.1991 | 0.110* | |
C4 | 0.6762 (4) | 0.1575 (2) | 0.32261 (8) | 0.0506 (6) | |
C5 | 0.8298 (4) | 0.2362 (2) | 0.34798 (9) | 0.0610 (7) | |
H5 | 0.9585 | 0.2586 | 0.3286 | 0.073* | |
C6 | 0.7969 (5) | 0.2826 (2) | 0.40162 (11) | 0.0734 (8) | |
H6 | 0.9023 | 0.3359 | 0.4181 | 0.088* | |
C7 | 0.6082 (5) | 0.2497 (3) | 0.43038 (10) | 0.0739 (8) | |
H7 | 0.5865 | 0.2799 | 0.4667 | 0.089* | |
C8 | 0.4503 (5) | 0.1722 (2) | 0.40599 (10) | 0.0689 (8) | |
H8 | 0.3204 | 0.1518 | 0.4253 | 0.083* | |
C9 | 0.4871 (4) | 0.1250 (2) | 0.35228 (9) | 0.0596 (7) | |
H9 | 0.3826 | 0.0707 | 0.3360 | 0.071* | |
C10 | 0.5666 (3) | 0.2637 (2) | 0.12710 (8) | 0.0462 (6) | |
H10A | 0.4851 | 0.3278 | 0.1483 | 0.055* | |
H10B | 0.4597 | 0.2134 | 0.1060 | 0.055* | |
C11 | 0.7237 (4) | 0.3292 (2) | 0.08685 (8) | 0.0443 (6) | |
C12 | 0.9293 (4) | 0.3746 (2) | 0.10531 (8) | 0.0465 (6) | |
C13 | 1.0683 (4) | 0.4414 (2) | 0.07036 (8) | 0.0523 (6) | |
H13A | 1.2057 | 0.4700 | 0.0833 | 0.063* | |
C14 | 1.0029 (4) | 0.4660 (2) | 0.01572 (8) | 0.0548 (6) | |
H14 | 1.0962 | 0.5120 | −0.0080 | 0.066* | |
C15 | 0.8016 (4) | 0.4230 (2) | −0.00363 (8) | 0.0536 (6) | |
H15 | 0.7587 | 0.4401 | −0.0404 | 0.064* | |
C16 | 0.6622 (4) | 0.3543 (2) | 0.03128 (8) | 0.0488 (6) | |
H16 | 0.5264 | 0.3245 | 0.0177 | 0.059* | |
C17 | 0.7625 (4) | 0.0620 (2) | 0.13858 (8) | 0.0602 (7) | |
H17A | 0.8479 | 0.0114 | 0.1645 | 0.090* | |
H17B | 0.8533 | 0.0836 | 0.1067 | 0.090* | |
H17C | 0.6352 | 0.0141 | 0.1263 | 0.090* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0464 (11) | 0.0435 (10) | 0.0397 (9) | 0.0056 (10) | 0.0008 (9) | 0.0033 (8) |
O1 | 0.0741 (12) | 0.0502 (10) | 0.0572 (9) | 0.0075 (10) | −0.0125 (9) | 0.0026 (8) |
O2 | 0.0656 (12) | 0.0664 (12) | 0.0479 (9) | −0.0186 (10) | −0.0132 (8) | 0.0086 (8) |
C1 | 0.0497 (15) | 0.0465 (14) | 0.0468 (12) | 0.0019 (12) | −0.0002 (11) | 0.0057 (11) |
C2 | 0.0470 (14) | 0.0495 (14) | 0.0459 (12) | 0.0048 (12) | 0.0017 (11) | 0.0069 (11) |
C3 | 0.0485 (16) | 0.098 (2) | 0.0738 (15) | −0.0094 (15) | −0.0066 (13) | 0.0268 (15) |
C4 | 0.0590 (17) | 0.0450 (14) | 0.0477 (13) | 0.0027 (14) | 0.0005 (12) | 0.0065 (11) |
C5 | 0.0745 (19) | 0.0522 (15) | 0.0564 (15) | −0.0023 (14) | 0.0010 (14) | 0.0020 (12) |
C6 | 0.095 (2) | 0.0584 (17) | 0.0671 (17) | −0.0022 (17) | −0.0017 (17) | −0.0067 (14) |
C7 | 0.099 (2) | 0.0604 (19) | 0.0620 (17) | 0.0122 (18) | 0.0075 (17) | −0.0050 (15) |
C8 | 0.083 (2) | 0.0606 (18) | 0.0628 (16) | 0.0101 (17) | 0.0138 (16) | 0.0052 (15) |
C9 | 0.0691 (18) | 0.0539 (16) | 0.0557 (14) | 0.0020 (14) | 0.0065 (14) | 0.0044 (12) |
C10 | 0.0489 (14) | 0.0442 (14) | 0.0456 (12) | 0.0022 (11) | −0.0019 (12) | 0.0020 (11) |
C11 | 0.0512 (15) | 0.0404 (13) | 0.0414 (12) | 0.0016 (12) | −0.0009 (11) | 0.0014 (10) |
C12 | 0.0547 (16) | 0.0431 (14) | 0.0417 (12) | −0.0009 (12) | −0.0006 (11) | 0.0022 (11) |
C13 | 0.0579 (17) | 0.0458 (15) | 0.0532 (13) | −0.0014 (13) | 0.0042 (12) | 0.0031 (12) |
C14 | 0.0664 (18) | 0.0481 (14) | 0.0499 (14) | 0.0029 (15) | 0.0122 (13) | 0.0043 (12) |
C15 | 0.0694 (18) | 0.0490 (15) | 0.0424 (12) | 0.0080 (14) | 0.0008 (13) | 0.0034 (11) |
C16 | 0.0585 (16) | 0.0447 (14) | 0.0432 (12) | 0.0048 (13) | −0.0040 (11) | −0.0002 (11) |
C17 | 0.0704 (17) | 0.0536 (15) | 0.0567 (13) | 0.0068 (14) | −0.0017 (13) | −0.0040 (12) |
N1—C17 | 1.466 (2) | C7—C8 | 1.375 (3) |
N1—C10 | 1.478 (2) | C7—H7 | 0.9300 |
N1—C2 | 1.480 (2) | C8—C9 | 1.387 (3) |
O1—C1 | 1.428 (2) | C8—H8 | 0.9300 |
O1—H1A | 0.8200 | C9—H9 | 0.9300 |
O2—C12 | 1.371 (2) | C10—C11 | 1.508 (3) |
O2—H2A | 0.8200 | C10—H10A | 0.9700 |
C1—C4 | 1.517 (3) | C10—H10B | 0.9700 |
C1—C2 | 1.534 (3) | C11—C12 | 1.393 (3) |
C1—H1 | 0.9800 | C11—C16 | 1.397 (3) |
C2—C3 | 1.528 (3) | C12—C13 | 1.369 (3) |
C2—H2 | 0.9800 | C13—C14 | 1.382 (3) |
C3—H3A | 0.9600 | C13—H13A | 0.9300 |
C3—H3B | 0.9600 | C14—C15 | 1.369 (3) |
C3—H3C | 0.9600 | C14—H14 | 0.9300 |
C4—C5 | 1.375 (3) | C15—C16 | 1.381 (3) |
C4—C9 | 1.380 (3) | C15—H15 | 0.9300 |
C5—C6 | 1.379 (3) | C16—H16 | 0.9300 |
C5—H5 | 0.9300 | C17—H17A | 0.9600 |
C6—C7 | 1.368 (4) | C17—H17B | 0.9600 |
C6—H6 | 0.9300 | C17—H17C | 0.9600 |
C17—N1—C10 | 111.25 (15) | C7—C8—H8 | 120.4 |
C17—N1—C2 | 114.41 (16) | C9—C8—H8 | 120.4 |
C10—N1—C2 | 112.48 (16) | C4—C9—C8 | 121.0 (2) |
C1—O1—H1A | 109.5 | C4—C9—H9 | 119.5 |
C12—O2—H2A | 109.5 | C8—C9—H9 | 119.5 |
O1—C1—C4 | 111.29 (16) | N1—C10—C11 | 111.31 (16) |
O1—C1—C2 | 109.07 (18) | N1—C10—H10A | 109.4 |
C4—C1—C2 | 112.79 (18) | C11—C10—H10A | 109.4 |
O1—C1—H1 | 107.8 | N1—C10—H10B | 109.4 |
C4—C1—H1 | 107.8 | C11—C10—H10B | 109.4 |
C2—C1—H1 | 107.8 | H10A—C10—H10B | 108.0 |
N1—C2—C3 | 113.26 (17) | C12—C11—C16 | 117.9 (2) |
N1—C2—C1 | 109.90 (16) | C12—C11—C10 | 120.55 (17) |
C3—C2—C1 | 113.86 (18) | C16—C11—C10 | 121.4 (2) |
N1—C2—H2 | 106.4 | C13—C12—O2 | 119.2 (2) |
C3—C2—H2 | 106.4 | C13—C12—C11 | 121.5 (2) |
C1—C2—H2 | 106.4 | O2—C12—C11 | 119.31 (19) |
C2—C3—H3A | 109.5 | C12—C13—C14 | 119.5 (2) |
C2—C3—H3B | 109.5 | C12—C13—H13A | 120.2 |
H3A—C3—H3B | 109.5 | C14—C13—H13A | 120.2 |
C2—C3—H3C | 109.5 | C15—C14—C13 | 120.4 (2) |
H3A—C3—H3C | 109.5 | C15—C14—H14 | 119.8 |
H3B—C3—H3C | 109.5 | C13—C14—H14 | 119.8 |
C5—C4—C9 | 118.3 (2) | C14—C15—C16 | 120.3 (2) |
C5—C4—C1 | 119.8 (2) | C14—C15—H15 | 119.9 |
C9—C4—C1 | 121.9 (2) | C16—C15—H15 | 119.9 |
C4—C5—C6 | 121.4 (3) | C15—C16—C11 | 120.4 (2) |
C4—C5—H5 | 119.3 | C15—C16—H16 | 119.8 |
C6—C5—H5 | 119.3 | C11—C16—H16 | 119.8 |
C7—C6—C5 | 119.5 (3) | N1—C17—H17A | 109.5 |
C7—C6—H6 | 120.2 | N1—C17—H17B | 109.5 |
C5—C6—H6 | 120.2 | H17A—C17—H17B | 109.5 |
C6—C7—C8 | 120.6 (2) | N1—C17—H17C | 109.5 |
C6—C7—H7 | 119.7 | H17A—C17—H17C | 109.5 |
C8—C7—H7 | 119.7 | H17B—C17—H17C | 109.5 |
C7—C8—C9 | 119.2 (3) | ||
C17—N1—C2—C3 | −60.7 (2) | C1—C4—C9—C8 | 178.5 (2) |
C10—N1—C2—C3 | 67.5 (2) | C7—C8—C9—C4 | −1.8 (3) |
C17—N1—C2—C1 | 67.9 (2) | C17—N1—C10—C11 | −74.7 (2) |
C10—N1—C2—C1 | −163.87 (17) | C2—N1—C10—C11 | 155.47 (17) |
O1—C1—C2—N1 | −93.8 (2) | N1—C10—C11—C12 | −39.5 (3) |
C4—C1—C2—N1 | 142.02 (19) | N1—C10—C11—C16 | 145.10 (19) |
O1—C1—C2—C3 | 34.5 (2) | C16—C11—C12—C13 | −0.2 (3) |
C4—C1—C2—C3 | −89.7 (2) | C10—C11—C12—C13 | −175.83 (19) |
O1—C1—C4—C5 | 124.5 (2) | C16—C11—C12—O2 | 179.13 (19) |
C2—C1—C4—C5 | −112.5 (2) | C10—C11—C12—O2 | 3.5 (3) |
O1—C1—C4—C9 | −52.8 (3) | O2—C12—C13—C14 | −178.6 (2) |
C2—C1—C4—C9 | 70.2 (3) | C11—C12—C13—C14 | 0.8 (3) |
C9—C4—C5—C6 | −0.3 (3) | C12—C13—C14—C15 | −0.6 (3) |
C1—C4—C5—C6 | −177.7 (2) | C13—C14—C15—C16 | −0.2 (3) |
C4—C5—C6—C7 | 0.2 (4) | C14—C15—C16—C11 | 0.8 (3) |
C5—C6—C7—C8 | −0.8 (4) | C12—C11—C16—C15 | −0.5 (3) |
C6—C7—C8—C9 | 1.6 (4) | C10—C11—C16—C15 | 175.00 (19) |
C5—C4—C9—C8 | 1.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O2i | 0.82 | 2.00 | 2.8165 (19) | 176 |
O2—H2A···N1 | 0.82 | 1.84 | 2.581 (2) | 150 |
C17—H17A···O1 | 0.96 | 2.55 | 3.156 (2) | 121 |
Symmetry code: (i) −x+2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C17H21NO2 |
Mr | 271.35 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 6.004 (1), 10.451 (1), 23.790 (3) |
V (Å3) | 1492.8 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.3 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | ψ scan (XPREP; Bruker, 2000) |
Tmin, Tmax | 0.98, 0.99 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7631, 2605, 1908 |
Rint | 0.065 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.074, 1.08 |
No. of reflections | 2605 |
No. of parameters | 186 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.14, −0.18 |
Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O2i | 0.82 | 2.00 | 2.8165 (19) | 176 |
O2—H2A···N1 | 0.82 | 1.84 | 2.581 (2) | 150 |
C17—H17A···O1 | 0.96 | 2.55 | 3.156 (2) | 121 |
Symmetry code: (i) −x+2, y−1/2, −z+1/2. |
Ephedrine and its derivatives have been studied for a long time and the preparation of N-substituted ephedrines is common (Neelakantan, 1971). They are inexpensive and readily available in enantiomerically pure form. Therefore, with the development of stereochemistry and organometallic chemistry, they have become more and more important as a chiral ligands (Kuznetsov et al., 1999). Recently, the focus of our group has been on the organogallium complexes with chiral ligands, such as ephedrine and its derivatives. We report here the structure and relative stereochemistry of the title compound, (I), which resulted from the condensation of (-)-ephedrine with salicylic aldehyde.
The molecule looks like a camber, with the two aromatic rings located at opposite ends of the C1—C2—N1—C10 camber chain. The dihedral angle between the best planes through the aromatic rings is 39.42 (7)°. There are two chiral carbons (C1 and C2) in the molecule which are of opposite hands (1S, 2R or 1R, 2S). Two intramolecular hydrogen bonds (O2—H2a···N1 and C17—H17A···O1) and one intermolecular hydrogen bond (O1—H1a···O2 at −x + 2, y − 1/2, −z + 1/2) were found. The intermolecular hydrogen bond links the molecules into a one-dimensional helical chain (see Fig. 2).