2,4-Dimethyl-6-[(1R)-1-{[(1R)-2-methyl-1-phenylpropyl]amino}ethyl]phenol, (I), has been synthesized and its absolute configuration has been determined by reference to the crystal structure of the title compound, C20H28NO+·Cl−, (II), the hydrochloride of (I). The new stereogenic centre (the C atom adjacent to the N atom on the phenol side) was unambiguously determined to have an R configuration.
Supporting information
CCDC reference: 605056
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.003 Å
- R factor = 0.044
- wR factor = 0.103
- Data-to-parameter ratio = 17.2
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of . 38.00 A 3
Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 25.49
From the CIF: _reflns_number_total 3687
Count of symmetry unique reflns 2116
Completeness (_total/calc) 174.24%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1571
Fraction of Friedel pairs measured 0.742
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
1 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Bruker, 2001).
N-[(
R)-1-(2-Hydroxy-3,5-dimethylphenyl)ethyl]-
N-[(
R)-2-methyl-1- phenylpropyl]ammonium chloride
top
Crystal data top
C20H28NO+·Cl− | F(000) = 720 |
Mr = 333.88 | Dx = 1.114 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P2ac2ab | Cell parameters from 5813 reflections |
a = 9.0404 (12) Å | θ = 2.5–27.8° |
b = 11.7373 (15) Å | µ = 0.20 mm−1 |
c = 18.768 (2) Å | T = 298 K |
V = 1991.5 (4) Å3 | Block, colourless |
Z = 4 | 0.50 × 0.34 × 0.25 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3558 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.027 |
Graphite monochromator | θmax = 25.5°, θmin = 2.1° |
φ and ω scans | h = −10→6 |
10401 measured reflections | k = −14→14 |
3687 independent reflections | l = −22→21 |
Refinement top
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)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.103 | w = 1/[σ2(Fo2) + (0.0466P)2 + 0.2784P] where P = (Fo2 + 2Fc2)/3 |
S = 1.19 | (Δ/σ)max = 0.001 |
3687 reflections | Δρmax = 0.20 e Å−3 |
214 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.01 (6) |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.7867 (2) | 1.00420 (18) | 0.59293 (11) | 0.0346 (5) | |
C2 | 0.7601 (3) | 1.08093 (19) | 0.53810 (10) | 0.0393 (5) | |
C3 | 0.8773 (3) | 1.1627 (2) | 0.51366 (13) | 0.0581 (7) | |
H3A | 0.9047 | 1.2117 | 0.5524 | 0.087* | |
H3B | 0.8397 | 1.2078 | 0.4750 | 0.087* | |
H3C | 0.9625 | 1.1209 | 0.4979 | 0.087* | |
C4 | 0.6203 (3) | 1.08120 (19) | 0.50680 (11) | 0.0439 (5) | |
H4 | 0.6009 | 1.1334 | 0.4707 | 0.053* | |
C5 | 0.5093 (3) | 1.0069 (2) | 0.52732 (12) | 0.0445 (5) | |
C6 | 0.3561 (3) | 1.0118 (3) | 0.49533 (15) | 0.0641 (7) | |
H6A | 0.3160 | 0.9362 | 0.4925 | 0.096* | |
H6B | 0.3614 | 1.0441 | 0.4484 | 0.096* | |
H6C | 0.2935 | 1.0581 | 0.5248 | 0.096* | |
C7 | 0.5420 (2) | 0.9293 (2) | 0.58019 (11) | 0.0406 (5) | |
H7 | 0.4698 | 0.8774 | 0.5940 | 0.049* | |
C8 | 0.6788 (2) | 0.92612 (18) | 0.61338 (10) | 0.0361 (5) | |
C9 | 0.7089 (3) | 0.83649 (18) | 0.66925 (11) | 0.0395 (5) | |
H9 | 0.6157 | 0.7971 | 0.6792 | 0.047* | |
C10 | 0.8211 (3) | 0.7479 (2) | 0.64618 (14) | 0.0597 (7) | |
H10A | 0.9142 | 0.7843 | 0.6368 | 0.090* | |
H10B | 0.7868 | 0.7108 | 0.6037 | 0.090* | |
H10C | 0.8333 | 0.6926 | 0.6834 | 0.090* | |
C11 | 0.6566 (2) | 0.97554 (17) | 0.77096 (11) | 0.0346 (4) | |
H11 | 0.6503 | 1.0414 | 0.7390 | 0.042* | |
C12 | 0.7206 (2) | 1.01646 (19) | 0.84199 (12) | 0.0424 (5) | |
H12 | 0.7225 | 0.9516 | 0.8749 | 0.051* | |
C13 | 0.8779 (3) | 1.0610 (3) | 0.83406 (15) | 0.0633 (7) | |
H13A | 0.8811 | 1.1166 | 0.7966 | 0.095* | |
H13B | 0.9429 | 0.9989 | 0.8226 | 0.095* | |
H13C | 0.9089 | 1.0954 | 0.8780 | 0.095* | |
C14 | 0.6213 (4) | 1.1080 (3) | 0.87370 (17) | 0.0749 (9) | |
H14A | 0.6610 | 1.1324 | 0.9186 | 0.112* | |
H14B | 0.5238 | 1.0776 | 0.8807 | 0.112* | |
H14C | 0.6164 | 1.1718 | 0.8417 | 0.112* | |
C15 | 0.5039 (2) | 0.92488 (19) | 0.77748 (11) | 0.0373 (5) | |
C16 | 0.4803 (3) | 0.8275 (2) | 0.81781 (12) | 0.0433 (5) | |
H16 | 0.5594 | 0.7917 | 0.8402 | 0.052* | |
C17 | 0.3381 (3) | 0.7837 (2) | 0.82465 (13) | 0.0552 (7) | |
H17 | 0.3224 | 0.7184 | 0.8517 | 0.066* | |
C18 | 0.2212 (3) | 0.8359 (3) | 0.79186 (16) | 0.0632 (8) | |
H18 | 0.1263 | 0.8061 | 0.7965 | 0.076* | |
C19 | 0.2444 (3) | 0.9327 (3) | 0.75190 (16) | 0.0619 (7) | |
H19 | 0.1650 | 0.9684 | 0.7297 | 0.074* | |
C20 | 0.3847 (2) | 0.9767 (2) | 0.74479 (13) | 0.0469 (6) | |
H20 | 0.3995 | 1.0421 | 0.7177 | 0.056* | |
N1 | 0.76150 (18) | 0.89025 (15) | 0.73773 (9) | 0.0345 (4) | |
H1A | 0.8482 | 0.9254 | 0.7293 | 0.041* | |
H1B | 0.7787 | 0.8345 | 0.7696 | 0.041* | |
O1 | 0.91879 (17) | 1.00074 (15) | 0.62997 (8) | 0.0470 (4) | |
H1 | 0.9657 | 1.0593 | 0.6223 | 0.071* | |
Cl1 | 0.85722 (7) | 0.70061 (5) | 0.84406 (3) | 0.04755 (16) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0353 (11) | 0.0352 (11) | 0.0333 (10) | −0.0017 (10) | −0.0011 (9) | −0.0024 (8) |
C2 | 0.0504 (13) | 0.0383 (11) | 0.0292 (9) | −0.0031 (11) | 0.0023 (10) | −0.0023 (9) |
C3 | 0.0709 (18) | 0.0581 (15) | 0.0454 (13) | −0.0188 (15) | −0.0022 (12) | 0.0128 (11) |
C4 | 0.0598 (14) | 0.0405 (12) | 0.0313 (10) | 0.0030 (12) | −0.0062 (10) | −0.0002 (9) |
C5 | 0.0467 (13) | 0.0486 (13) | 0.0381 (11) | 0.0078 (11) | −0.0051 (10) | −0.0089 (10) |
C6 | 0.0543 (15) | 0.0728 (18) | 0.0653 (16) | 0.0049 (16) | −0.0148 (15) | −0.0036 (14) |
C7 | 0.0381 (12) | 0.0416 (12) | 0.0421 (11) | −0.0055 (10) | 0.0015 (10) | −0.0046 (10) |
C8 | 0.0400 (12) | 0.0333 (10) | 0.0348 (10) | −0.0010 (9) | −0.0002 (9) | −0.0015 (8) |
C9 | 0.0399 (11) | 0.0350 (11) | 0.0436 (12) | −0.0051 (10) | 0.0030 (10) | 0.0017 (9) |
C10 | 0.079 (2) | 0.0425 (13) | 0.0581 (14) | 0.0150 (13) | 0.0070 (14) | 0.0004 (11) |
C11 | 0.0340 (11) | 0.0306 (10) | 0.0393 (10) | 0.0022 (9) | 0.0008 (9) | 0.0076 (8) |
C12 | 0.0435 (12) | 0.0403 (11) | 0.0435 (11) | −0.0012 (10) | −0.0007 (11) | 0.0023 (10) |
C13 | 0.0570 (16) | 0.0727 (17) | 0.0604 (16) | −0.0205 (15) | −0.0073 (13) | −0.0024 (14) |
C14 | 0.074 (2) | 0.0728 (19) | 0.0776 (19) | 0.0112 (18) | −0.0037 (16) | −0.0280 (16) |
C15 | 0.0355 (11) | 0.0376 (11) | 0.0388 (10) | 0.0014 (10) | 0.0019 (9) | 0.0007 (9) |
C16 | 0.0403 (12) | 0.0443 (13) | 0.0452 (12) | −0.0001 (11) | 0.0016 (10) | 0.0061 (10) |
C17 | 0.0572 (16) | 0.0511 (13) | 0.0572 (14) | −0.0125 (13) | 0.0174 (12) | 0.0055 (11) |
C18 | 0.0345 (13) | 0.0753 (19) | 0.0798 (19) | −0.0129 (14) | 0.0130 (13) | −0.0100 (16) |
C19 | 0.0348 (13) | 0.0749 (19) | 0.0761 (18) | 0.0104 (13) | −0.0022 (13) | 0.0066 (15) |
C20 | 0.0383 (13) | 0.0484 (13) | 0.0541 (14) | 0.0089 (11) | 0.0025 (11) | 0.0086 (11) |
N1 | 0.0298 (9) | 0.0345 (9) | 0.0392 (9) | −0.0001 (7) | 0.0001 (7) | 0.0068 (7) |
O1 | 0.0403 (9) | 0.0501 (10) | 0.0507 (9) | −0.0103 (8) | −0.0055 (7) | 0.0130 (8) |
Cl1 | 0.0462 (3) | 0.0451 (3) | 0.0514 (3) | 0.0079 (3) | −0.0075 (3) | 0.0077 (2) |
Geometric parameters (Å, º) top
C1—O1 | 1.383 (2) | C11—C12 | 1.531 (3) |
C1—C2 | 1.388 (3) | C11—H11 | 0.9800 |
C1—C8 | 1.392 (3) | C12—C14 | 1.522 (4) |
C2—C4 | 1.394 (3) | C12—C13 | 1.522 (3) |
C2—C3 | 1.501 (3) | C12—H12 | 0.9800 |
C3—H3A | 0.9600 | C13—H13A | 0.9600 |
C3—H3B | 0.9600 | C13—H13B | 0.9600 |
C3—H3C | 0.9600 | C13—H13C | 0.9600 |
C4—C5 | 1.384 (3) | C14—H14A | 0.9600 |
C4—H4 | 0.9300 | C14—H14B | 0.9600 |
C5—C7 | 1.379 (3) | C14—H14C | 0.9600 |
C5—C6 | 1.511 (3) | C15—C20 | 1.381 (3) |
C6—H6A | 0.9600 | C15—C16 | 1.387 (3) |
C6—H6B | 0.9600 | C16—C17 | 1.390 (4) |
C6—H6C | 0.9600 | C16—H16 | 0.9300 |
C7—C8 | 1.385 (3) | C17—C18 | 1.368 (4) |
C7—H7 | 0.9300 | C17—H17 | 0.9300 |
C8—C9 | 1.510 (3) | C18—C19 | 1.377 (4) |
C9—N1 | 1.508 (3) | C18—H18 | 0.9300 |
C9—C10 | 1.515 (3) | C19—C20 | 1.376 (4) |
C9—H9 | 0.9800 | C19—H19 | 0.9300 |
C10—H10A | 0.9600 | C20—H20 | 0.9300 |
C10—H10B | 0.9600 | N1—H1A | 0.9000 |
C10—H10C | 0.9600 | N1—H1B | 0.9000 |
C11—C15 | 1.509 (3) | O1—H1 | 0.8200 |
C11—N1 | 1.513 (3) | | |
| | | |
O1—C1—C2 | 122.77 (19) | N1—C11—H11 | 107.9 |
O1—C1—C8 | 116.56 (18) | C12—C11—H11 | 107.9 |
C2—C1—C8 | 120.67 (19) | C14—C12—C13 | 110.3 (2) |
C1—C2—C4 | 118.1 (2) | C14—C12—C11 | 109.8 (2) |
C1—C2—C3 | 121.3 (2) | C13—C12—C11 | 112.1 (2) |
C4—C2—C3 | 120.6 (2) | C14—C12—H12 | 108.2 |
C2—C3—H3A | 109.5 | C13—C12—H12 | 108.2 |
C2—C3—H3B | 109.5 | C11—C12—H12 | 108.2 |
H3A—C3—H3B | 109.5 | C12—C13—H13A | 109.5 |
C2—C3—H3C | 109.5 | C12—C13—H13B | 109.5 |
H3A—C3—H3C | 109.5 | H13A—C13—H13B | 109.5 |
H3B—C3—H3C | 109.5 | C12—C13—H13C | 109.5 |
C5—C4—C2 | 122.6 (2) | H13A—C13—H13C | 109.5 |
C5—C4—H4 | 118.7 | H13B—C13—H13C | 109.5 |
C2—C4—H4 | 118.7 | C12—C14—H14A | 109.5 |
C7—C5—C4 | 117.4 (2) | C12—C14—H14B | 109.5 |
C7—C5—C6 | 120.5 (2) | H14A—C14—H14B | 109.5 |
C4—C5—C6 | 122.0 (2) | C12—C14—H14C | 109.5 |
C5—C6—H6A | 109.5 | H14A—C14—H14C | 109.5 |
C5—C6—H6B | 109.5 | H14B—C14—H14C | 109.5 |
H6A—C6—H6B | 109.5 | C20—C15—C16 | 119.1 (2) |
C5—C6—H6C | 109.5 | C20—C15—C11 | 120.29 (19) |
H6A—C6—H6C | 109.5 | C16—C15—C11 | 120.64 (19) |
H6B—C6—H6C | 109.5 | C15—C16—C17 | 119.8 (2) |
C5—C7—C8 | 122.2 (2) | C15—C16—H16 | 120.1 |
C5—C7—H7 | 118.9 | C17—C16—H16 | 120.1 |
C8—C7—H7 | 118.9 | C18—C17—C16 | 120.5 (2) |
C7—C8—C1 | 118.9 (2) | C18—C17—H17 | 119.8 |
C7—C8—C9 | 119.5 (2) | C16—C17—H17 | 119.8 |
C1—C8—C9 | 121.57 (19) | C17—C18—C19 | 119.8 (2) |
N1—C9—C8 | 110.92 (17) | C17—C18—H18 | 120.1 |
N1—C9—C10 | 108.65 (19) | C19—C18—H18 | 120.1 |
C8—C9—C10 | 113.59 (18) | C20—C19—C18 | 120.2 (2) |
N1—C9—H9 | 107.8 | C20—C19—H19 | 119.9 |
C8—C9—H9 | 107.8 | C18—C19—H19 | 119.9 |
C10—C9—H9 | 107.8 | C19—C20—C15 | 120.7 (2) |
C9—C10—H10A | 109.5 | C19—C20—H20 | 119.7 |
C9—C10—H10B | 109.5 | C15—C20—H20 | 119.7 |
H10A—C10—H10B | 109.5 | C9—N1—C11 | 115.49 (16) |
C9—C10—H10C | 109.5 | C9—N1—H1A | 108.4 |
H10A—C10—H10C | 109.5 | C11—N1—H1A | 108.4 |
H10B—C10—H10C | 109.5 | C9—N1—H1B | 108.4 |
C15—C11—N1 | 110.26 (16) | C11—N1—H1B | 108.4 |
C15—C11—C12 | 113.52 (17) | H1A—N1—H1B | 107.5 |
N1—C11—C12 | 109.25 (16) | C1—O1—H1 | 109.5 |
C15—C11—H11 | 107.9 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.90 | 2.16 | 2.792 (2) | 127 |
N1—H1B···Cl1 | 0.90 | 2.22 | 3.1122 (18) | 171 |
O1—H1···Cl1i | 0.82 | 2.39 | 3.1371 (17) | 152 |
Symmetry code: (i) −x+2, y+1/2, −z+3/2. |