Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680201512X/cf6195sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680201512X/cf6195Isup2.hkl |
CCDC reference: 197481
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.003 Å
- R factor = 0.028
- wR factor = 0.067
- Data-to-parameter ratio = 11.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 25.00 From the CIF: _reflns_number_total 3144 Count of symmetry unique reflns 1906 Completeness (_total/calc) 164.95% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1238 Fraction of Friedel pairs measured 0.650 Are heavy atom types Z>Si present yes 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.
(+)-Escholinine was isolated as a perchlorate salt from the roots of Eschscholtzia californica Cham. (Slavík & Dolejš, 1973) and recrystallized from methanol; m.p. 482–483 K, [α]D25 = +74° (0.3 M in methanol).
Data collection: Xcalibur (Oxford Diffraction Ltd, 2001); cell refinement: Xcalibur; data reduction: Xcalibur; program(s) used to solve structure: SHELXTL (Bruker, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. A perspective view of (+)-escholinine perchlorate with the atom numbering. Ellipsoids are drawn at the 50% probability level. |
C21H26NO4+·ClO4− | F(000) = 480 |
Mr = 455.88 | Dx = 1.451 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.450 (1) Å | Cell parameters from 500 reflections |
b = 17.010 (3) Å | θ = 4.5–27.8° |
c = 9.038 (2) Å | µ = 0.23 mm−1 |
β = 114.32 (3)° | T = 120 K |
V = 1043.7 (3) Å3 | Prism, colourless |
Z = 2 | 0.40 × 0.40 × 0.20 mm |
Kuma KM-4 CCD diffractometer | 3001 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.035 |
Graphite monochromator | θmax = 25.0°, θmin = 3.4° |
Detector resolution: 0.06 mm pixels mm-1 | h = −8→8 |
ω scans | k = −20→19 |
6727 measured reflections | l = −10→9 |
3144 independent reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.028 | w = 1/[σ2(Fo2) + (0.0353P)2 + 0.1452P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.067 | (Δ/σ)max = 0.001 |
S = 1.04 | Δρmax = 0.20 e Å−3 |
3144 reflections | Δρmin = −0.20 e Å−3 |
281 parameters | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0106 (15) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 1276 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.04 (5) |
C21H26NO4+·ClO4− | V = 1043.7 (3) Å3 |
Mr = 455.88 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.450 (1) Å | µ = 0.23 mm−1 |
b = 17.010 (3) Å | T = 120 K |
c = 9.038 (2) Å | 0.40 × 0.40 × 0.20 mm |
β = 114.32 (3)° |
Kuma KM-4 CCD diffractometer | 3001 reflections with I > 2σ(I) |
6727 measured reflections | Rint = 0.035 |
3144 independent reflections |
R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
wR(F2) = 0.067 | Δρmax = 0.20 e Å−3 |
S = 1.04 | Δρmin = −0.20 e Å−3 |
3144 reflections | Absolute structure: Flack (1983), 1276 Friedel pairs |
281 parameters | Absolute structure parameter: −0.04 (5) |
1 restraint |
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 | ||
Cl29 | 0.04206 (8) | 0.06289 (3) | 0.08370 (6) | 0.02160 (14) | |
O28 | −0.0756 (3) | 0.08890 (10) | 0.1642 (2) | 0.0433 (5) | |
O27 | 0.0058 (3) | 0.11044 (11) | −0.05612 (19) | 0.0371 (4) | |
O26 | 0.2430 (2) | 0.07085 (15) | 0.19146 (19) | 0.0560 (6) | |
O25 | −0.0030 (4) | −0.01597 (11) | 0.0364 (2) | 0.0673 (7) | |
C1 | 0.4345 (3) | 0.03234 (12) | 0.5776 (2) | 0.0152 (4) | |
H1A | 0.3487 | 0.0226 | 0.4605 | 0.018* | |
O22 | 0.4412 (2) | −0.24707 (9) | 0.90425 (18) | 0.0277 (4) | |
O21 | 0.4109 (2) | −0.25527 (8) | 0.64040 (18) | 0.0250 (4) | |
O24 | 0.9781 (2) | −0.20592 (9) | 0.39460 (16) | 0.0217 (3) | |
C5 | 0.4450 (3) | −0.10299 (13) | 0.9166 (2) | 0.0209 (5) | |
H5A | 0.4541 | −0.1003 | 1.0244 | 0.025* | |
C7 | 0.4145 (3) | −0.17829 (11) | 0.6841 (2) | 0.0176 (5) | |
C19 | 0.9865 (3) | −0.20774 (14) | 0.8413 (2) | 0.0248 (5) | |
H19A | 1.0528 | −0.2557 | 0.8975 | 0.037* | |
H19B | 0.8494 | −0.2082 | 0.8285 | 0.037* | |
H19C | 1.0541 | −0.1617 | 0.9052 | 0.037* | |
C9 | 0.6428 (3) | 0.04954 (12) | 0.5914 (2) | 0.0176 (5) | |
H9A | 0.6384 | 0.0966 | 0.5256 | 0.021* | |
H9B | 0.7289 | 0.0618 | 0.7060 | 0.021* | |
C14 | 0.8057 (3) | −0.08073 (12) | 0.3299 (2) | 0.0197 (5) | |
H14A | 0.8015 | −0.0805 | 0.2235 | 0.024* | |
O23 | 0.9913 (2) | −0.20434 (9) | 0.68597 (16) | 0.0199 (3) | |
N2 | 0.3486 (3) | 0.10224 (10) | 0.63232 (19) | 0.0172 (4) | |
C12 | 0.9047 (3) | −0.14084 (12) | 0.5923 (2) | 0.0149 (4) | |
C4A | 0.4422 (3) | −0.03480 (13) | 0.8294 (2) | 0.0169 (5) | |
C8A | 0.4248 (3) | −0.03982 (12) | 0.6714 (2) | 0.0145 (4) | |
C6 | 0.4344 (3) | −0.17285 (13) | 0.8421 (2) | 0.0187 (5) | |
C10 | 0.7314 (3) | −0.01735 (12) | 0.5362 (2) | 0.0160 (4) | |
C11 | 0.8279 (3) | −0.07786 (12) | 0.6423 (2) | 0.0173 (5) | |
H11A | 0.8410 | −0.0757 | 0.7513 | 0.021* | |
C18 | 0.3916 (4) | −0.29875 (13) | 0.7679 (3) | 0.0275 (6) | |
H18A | 0.4813 | −0.3446 | 0.7974 | 0.033* | |
H18B | 0.2548 | −0.3180 | 0.7328 | 0.033* | |
C16 | 0.3633 (4) | 0.17594 (12) | 0.5492 (3) | 0.0240 (5) | |
H16A | 0.3069 | 0.2196 | 0.5867 | 0.036* | |
H16B | 0.2905 | 0.1697 | 0.4316 | 0.036* | |
H16C | 0.5019 | 0.1870 | 0.5746 | 0.036* | |
C15 | 0.7207 (3) | −0.01961 (12) | 0.3804 (2) | 0.0189 (5) | |
H15A | 0.6542 | 0.0212 | 0.3064 | 0.023* | |
C20 | 0.9804 (4) | −0.20572 (15) | 0.2381 (3) | 0.0298 (6) | |
H20A | 1.0419 | −0.2542 | 0.2231 | 0.045* | |
H20B | 1.0558 | −0.1603 | 0.2284 | 0.045* | |
H20C | 0.8450 | −0.2025 | 0.1550 | 0.045* | |
C8 | 0.4067 (3) | −0.11286 (13) | 0.5944 (2) | 0.0172 (4) | |
H8A | 0.3898 | −0.1166 | 0.4845 | 0.021* | |
C4 | 0.4411 (3) | 0.04292 (12) | 0.9072 (2) | 0.0233 (5) | |
H4A | 0.5522 | 0.0440 | 1.0159 | 0.028* | |
H4B | 0.3177 | 0.0472 | 0.9231 | 0.028* | |
C17 | 0.1346 (3) | 0.08731 (13) | 0.5874 (3) | 0.0228 (5) | |
H17A | 0.0779 | 0.1319 | 0.6219 | 0.034* | |
H17B | 0.1196 | 0.0394 | 0.6414 | 0.034* | |
H17C | 0.0662 | 0.0809 | 0.4695 | 0.034* | |
C13 | 0.8959 (3) | −0.14161 (12) | 0.4341 (2) | 0.0171 (4) | |
C3 | 0.4571 (3) | 0.11353 (13) | 0.8127 (2) | 0.0200 (5) | |
H3A | 0.4031 | 0.1601 | 0.8461 | 0.024* | |
H3B | 0.5978 | 0.1239 | 0.8392 | 0.024* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl29 | 0.0223 (3) | 0.0266 (3) | 0.0174 (2) | −0.0004 (2) | 0.0097 (2) | −0.0025 (2) |
O28 | 0.0476 (12) | 0.0484 (12) | 0.0505 (11) | 0.0100 (9) | 0.0371 (10) | 0.0013 (9) |
O27 | 0.0391 (11) | 0.0447 (11) | 0.0251 (9) | 0.0025 (9) | 0.0108 (8) | 0.0109 (8) |
O26 | 0.0223 (9) | 0.1190 (18) | 0.0229 (8) | −0.0034 (12) | 0.0054 (7) | 0.0106 (11) |
O25 | 0.133 (2) | 0.0310 (11) | 0.0516 (13) | −0.0180 (12) | 0.0519 (14) | −0.0163 (10) |
C1 | 0.0184 (11) | 0.0172 (10) | 0.0114 (9) | 0.0017 (9) | 0.0074 (8) | 0.0000 (8) |
O22 | 0.0323 (10) | 0.0226 (9) | 0.0301 (9) | 0.0005 (7) | 0.0149 (8) | 0.0082 (7) |
O21 | 0.0329 (9) | 0.0152 (8) | 0.0325 (9) | 0.0001 (7) | 0.0192 (7) | 0.0003 (7) |
O24 | 0.0278 (9) | 0.0200 (8) | 0.0230 (8) | 0.0023 (7) | 0.0162 (7) | −0.0028 (6) |
C5 | 0.0194 (11) | 0.0283 (13) | 0.0147 (10) | −0.0023 (10) | 0.0068 (9) | 0.0011 (9) |
C7 | 0.0117 (11) | 0.0166 (11) | 0.0255 (11) | 0.0006 (9) | 0.0087 (9) | −0.0029 (9) |
C19 | 0.0278 (13) | 0.0297 (13) | 0.0210 (11) | 0.0034 (11) | 0.0141 (10) | 0.0075 (10) |
C9 | 0.0195 (11) | 0.0179 (12) | 0.0179 (10) | −0.0009 (9) | 0.0102 (9) | 0.0021 (9) |
C14 | 0.0192 (12) | 0.0263 (12) | 0.0143 (10) | −0.0013 (9) | 0.0077 (9) | −0.0011 (9) |
O23 | 0.0223 (8) | 0.0191 (8) | 0.0196 (7) | 0.0027 (7) | 0.0099 (6) | 0.0010 (6) |
N2 | 0.0177 (10) | 0.0196 (10) | 0.0146 (9) | 0.0034 (7) | 0.0071 (8) | −0.0009 (7) |
C12 | 0.0116 (10) | 0.0166 (11) | 0.0162 (10) | −0.0018 (9) | 0.0054 (8) | 0.0007 (9) |
C4A | 0.0118 (11) | 0.0240 (12) | 0.0152 (10) | −0.0005 (9) | 0.0059 (8) | −0.0002 (8) |
C8A | 0.0110 (11) | 0.0181 (11) | 0.0152 (10) | 0.0015 (9) | 0.0060 (8) | 0.0003 (8) |
C6 | 0.0151 (11) | 0.0206 (12) | 0.0200 (11) | 0.0011 (9) | 0.0069 (9) | 0.0074 (9) |
C10 | 0.0128 (11) | 0.0165 (11) | 0.0195 (10) | −0.0024 (8) | 0.0076 (8) | 0.0000 (8) |
C11 | 0.0167 (11) | 0.0205 (12) | 0.0156 (10) | −0.0029 (9) | 0.0076 (9) | −0.0001 (8) |
C18 | 0.0362 (15) | 0.0170 (12) | 0.0346 (13) | 0.0015 (10) | 0.0201 (12) | 0.0047 (10) |
C16 | 0.0283 (13) | 0.0172 (12) | 0.0287 (12) | 0.0048 (10) | 0.0138 (10) | 0.0036 (10) |
C15 | 0.0201 (12) | 0.0213 (12) | 0.0166 (10) | 0.0012 (9) | 0.0089 (9) | 0.0029 (9) |
C20 | 0.0382 (14) | 0.0315 (13) | 0.0278 (12) | 0.0022 (12) | 0.0217 (11) | −0.0085 (11) |
C8 | 0.0152 (11) | 0.0232 (12) | 0.0159 (10) | −0.0009 (9) | 0.0093 (8) | −0.0014 (9) |
C4 | 0.0287 (13) | 0.0271 (14) | 0.0180 (11) | −0.0016 (10) | 0.0136 (10) | −0.0032 (9) |
C17 | 0.0162 (11) | 0.0274 (13) | 0.0257 (11) | 0.0017 (9) | 0.0096 (9) | −0.0021 (9) |
C13 | 0.0155 (11) | 0.0171 (11) | 0.0199 (11) | −0.0034 (9) | 0.0086 (9) | −0.0036 (9) |
C3 | 0.0192 (12) | 0.0227 (12) | 0.0175 (10) | −0.0007 (10) | 0.0071 (9) | −0.0067 (9) |
Cl29—O25 | 1.406 (2) | N2—C16 | 1.488 (3) |
Cl29—O26 | 1.4164 (18) | N2—C17 | 1.496 (3) |
Cl29—O28 | 1.4211 (17) | N2—C3 | 1.504 (3) |
Cl29—O27 | 1.4292 (17) | C12—C11 | 1.376 (3) |
C1—C8A | 1.510 (3) | C12—C13 | 1.404 (3) |
C1—N2 | 1.526 (2) | C4A—C8A | 1.383 (3) |
C1—C9 | 1.533 (3) | C4A—C4 | 1.499 (3) |
C1—H1A | 1.000 | C8A—C8 | 1.403 (3) |
O22—C6 | 1.374 (2) | C10—C15 | 1.378 (3) |
O22—C18 | 1.433 (3) | C10—C11 | 1.388 (3) |
O21—C7 | 1.365 (2) | C11—H11A | 0.950 |
O21—C18 | 1.425 (3) | C18—H18A | 0.990 |
O24—C13 | 1.371 (2) | C18—H18B | 0.990 |
O24—C20 | 1.421 (3) | C16—H16A | 0.980 |
C5—C6 | 1.352 (3) | C16—H16B | 0.980 |
C5—C4A | 1.397 (3) | C16—H16C | 0.980 |
C5—H5A | 0.950 | C15—H15A | 0.950 |
C7—C8 | 1.364 (3) | C20—H20A | 0.980 |
C7—C6 | 1.377 (3) | C20—H20B | 0.980 |
C19—O23 | 1.420 (2) | C20—H20C | 0.980 |
C19—H19A | 0.980 | C8—H8A | 0.950 |
C19—H19B | 0.980 | C4—C3 | 1.507 (3) |
C19—H19C | 0.980 | C4—H4A | 0.990 |
C9—C10 | 1.500 (3) | C4—H4B | 0.990 |
C9—H9A | 0.990 | C17—H17A | 0.980 |
C9—H9B | 0.990 | C17—H17B | 0.980 |
C14—C13 | 1.374 (3) | C17—H17C | 0.980 |
C14—C15 | 1.388 (3) | C3—H3A | 0.990 |
C14—H14A | 0.950 | C3—H3B | 0.990 |
O23—C12 | 1.360 (2) | ||
O25—Cl29—O26 | 110.65 (16) | C5—C6—C7 | 122.32 (19) |
O25—Cl29—O28 | 109.40 (13) | O22—C6—C7 | 109.41 (18) |
O26—Cl29—O28 | 108.54 (12) | C15—C10—C11 | 118.74 (19) |
O25—Cl29—O27 | 109.67 (12) | C15—C10—C9 | 120.87 (18) |
O26—Cl29—O27 | 108.38 (11) | C11—C10—C9 | 120.38 (17) |
O28—Cl29—O27 | 110.17 (11) | C12—C11—C10 | 121.16 (18) |
C8A—C1—N2 | 109.19 (15) | C12—C11—H11A | 119.4 |
C8A—C1—C9 | 112.95 (17) | C10—C11—H11A | 119.4 |
N2—C1—C9 | 111.74 (16) | O21—C18—O22 | 107.50 (17) |
C8A—C1—H1A | 107.6 | O21—C18—H18A | 110.2 |
N2—C1—H1A | 107.6 | O22—C18—H18A | 110.2 |
C9—C1—H1A | 107.6 | O21—C18—H18B | 110.2 |
C6—O22—C18 | 105.02 (15) | O22—C18—H18B | 110.2 |
C7—O21—C18 | 105.11 (16) | H18A—C18—H18B | 108.5 |
C13—O24—C20 | 116.54 (17) | N2—C16—H16A | 109.5 |
C6—C5—C4A | 117.70 (19) | N2—C16—H16B | 109.5 |
C6—C5—H5A | 121.2 | H16A—C16—H16B | 109.5 |
C4A—C5—H5A | 121.2 | N2—C16—H16C | 109.5 |
C8—C7—O21 | 128.32 (18) | H16A—C16—H16C | 109.5 |
C8—C7—C6 | 121.44 (19) | H16B—C16—H16C | 109.5 |
O21—C7—C6 | 110.21 (18) | C10—C15—C14 | 120.94 (19) |
O23—C19—H19A | 109.5 | C10—C15—H15A | 119.5 |
O23—C19—H19B | 109.5 | C14—C15—H15A | 119.5 |
H19A—C19—H19B | 109.5 | O24—C20—H20A | 109.5 |
O23—C19—H19C | 109.5 | O24—C20—H20B | 109.5 |
H19A—C19—H19C | 109.5 | H20A—C20—H20B | 109.5 |
H19B—C19—H19C | 109.5 | O24—C20—H20C | 109.5 |
C10—C9—C1 | 113.42 (17) | H20A—C20—H20C | 109.5 |
C10—C9—H9A | 108.9 | H20B—C20—H20C | 109.5 |
C1—C9—H9A | 108.9 | C7—C8—C8A | 117.13 (18) |
C10—C9—H9B | 108.9 | C7—C8—H8A | 121.4 |
C1—C9—H9B | 108.9 | C8A—C8—H8A | 121.4 |
H9A—C9—H9B | 107.7 | C4A—C4—C3 | 114.85 (17) |
C13—C14—C15 | 120.00 (18) | C4A—C4—H4A | 108.6 |
C13—C14—H14A | 120.0 | C3—C4—H4A | 108.6 |
C15—C14—H14A | 120.0 | C4A—C4—H4B | 108.6 |
C12—O23—C19 | 116.69 (16) | C3—C4—H4B | 108.6 |
C16—N2—C17 | 107.30 (16) | H4A—C4—H4B | 107.5 |
C16—N2—C3 | 108.72 (16) | N2—C17—H17A | 109.5 |
C17—N2—C3 | 110.67 (16) | N2—C17—H17B | 109.5 |
C16—N2—C1 | 111.43 (15) | H17A—C17—H17B | 109.5 |
C17—N2—C1 | 108.78 (16) | N2—C17—H17C | 109.5 |
C3—N2—C1 | 109.92 (16) | H17A—C17—H17C | 109.5 |
O23—C12—C11 | 124.67 (17) | H17B—C17—H17C | 109.5 |
O23—C12—C13 | 115.96 (17) | O24—C13—C14 | 124.60 (18) |
C11—C12—C13 | 119.37 (18) | O24—C13—C12 | 115.73 (17) |
C8A—C4A—C5 | 120.3 (2) | C14—C13—C12 | 119.66 (18) |
C8A—C4A—C4 | 121.51 (19) | N2—C3—C4 | 112.33 (18) |
C5—C4A—C4 | 118.00 (17) | N2—C3—H3A | 109.1 |
C4A—C8A—C8 | 121.06 (19) | C4—C3—H3A | 109.1 |
C4A—C8A—C1 | 121.58 (19) | N2—C3—H3B | 109.1 |
C8—C8A—C1 | 117.30 (17) | C4—C3—H3B | 109.1 |
C5—C6—O22 | 128.27 (18) | H3A—C3—H3B | 107.9 |
C18—O21—C7—C8 | −171.2 (2) | C1—C9—C10—C15 | 95.6 (2) |
C18—O21—C7—C6 | 10.8 (2) | C1—C9—C10—C11 | −85.1 (2) |
C8A—C1—C9—C10 | 57.4 (2) | O23—C12—C11—C10 | −176.16 (19) |
N2—C1—C9—C10 | −179.06 (15) | C13—C12—C11—C10 | 3.9 (3) |
C8A—C1—N2—C16 | 177.27 (16) | C15—C10—C11—C12 | −2.7 (3) |
C9—C1—N2—C16 | 51.6 (2) | C9—C10—C11—C12 | 178.02 (18) |
C8A—C1—N2—C17 | −64.6 (2) | C7—O21—C18—O22 | −16.4 (2) |
C9—C1—N2—C17 | 169.68 (16) | C6—O22—C18—O21 | 15.9 (2) |
C8A—C1—N2—C3 | 56.7 (2) | C11—C10—C15—C14 | −0.5 (3) |
C9—C1—N2—C3 | −69.0 (2) | C9—C10—C15—C14 | 178.80 (19) |
C19—O23—C12—C11 | 5.3 (3) | C13—C14—C15—C10 | 2.4 (3) |
C19—O23—C12—C13 | −174.79 (16) | O21—C7—C8—C8A | −176.3 (2) |
C6—C5—C4A—C8A | 1.3 (3) | C6—C7—C8—C8A | 1.6 (3) |
C6—C5—C4A—C4 | 176.2 (2) | C4A—C8A—C8—C7 | −2.4 (3) |
C5—C4A—C8A—C8 | 1.0 (3) | C1—C8A—C8—C7 | 174.71 (19) |
C4—C4A—C8A—C8 | −173.73 (19) | C8A—C4A—C4—C3 | −10.6 (3) |
C5—C4A—C8A—C1 | −176.0 (2) | C5—C4A—C4—C3 | 174.57 (19) |
C4—C4A—C8A—C1 | 9.3 (3) | C20—O24—C13—C14 | 4.5 (3) |
N2—C1—C8A—C4A | −32.1 (3) | C20—O24—C13—C12 | −176.64 (18) |
C9—C1—C8A—C4A | 92.9 (2) | C15—C14—C13—O24 | 177.65 (19) |
N2—C1—C8A—C8 | 150.79 (17) | C15—C14—C13—C12 | −1.2 (3) |
C9—C1—C8A—C8 | −84.2 (2) | O23—C12—C13—O24 | −0.8 (3) |
C4A—C5—C6—O22 | 177.6 (2) | C11—C12—C13—O24 | 179.15 (18) |
C4A—C5—C6—C7 | −2.2 (3) | O23—C12—C13—C14 | 178.14 (18) |
C18—O22—C6—C5 | 170.8 (2) | C11—C12—C13—C14 | −1.9 (3) |
C18—O22—C6—C7 | −9.4 (2) | C16—N2—C3—C4 | 177.06 (17) |
C8—C7—C6—C5 | 0.8 (3) | C17—N2—C3—C4 | 59.5 (2) |
O21—C7—C6—C5 | 179.0 (2) | C1—N2—C3—C4 | −60.7 (2) |
C8—C7—C6—O22 | −179.08 (19) | C4A—C4—C3—N2 | 36.3 (3) |
O21—C7—C6—O22 | −0.9 (2) |
Experimental details
Crystal data | |
Chemical formula | C21H26NO4+·ClO4− |
Mr | 455.88 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 120 |
a, b, c (Å) | 7.450 (1), 17.010 (3), 9.038 (2) |
β (°) | 114.32 (3) |
V (Å3) | 1043.7 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.23 |
Crystal size (mm) | 0.40 × 0.40 × 0.20 |
Data collection | |
Diffractometer | Kuma KM-4 CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6727, 3144, 3001 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.067, 1.04 |
No. of reflections | 3144 |
No. of parameters | 281 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.20 |
Absolute structure | Flack (1983), 1276 Friedel pairs |
Absolute structure parameter | −0.04 (5) |
Computer programs: Xcalibur (Oxford Diffraction Ltd, 2001), Xcalibur, SHELXTL (Bruker, 1998), SHELXTL.
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(+)-Escholinine, an N-methyl derivative of (+)-romneine, is a quaternary benzyltetrahydroisoquinoline alkaloid isolated (as the perchlorate of its protonated form) from Eschscholtzia californica Cham. (Papaveraceae) (Slavík & Dolejš, 1973). It is a minor component of the highly polar fraction of alkaloids from this source. Recently, it has been isolated from Romneya coulteri Harv. (Valpuesta et al., 1999). The corresponding tertiary base (+)-romneine also occurs in the same plant species (Stermitz et al., 1966).
(+)-Escholinine perchlorate, (I), possesses a tetrahydroisoquinoline skeleton with a substituted benzyl group attached to C1 (Fig. 1). All bond lengths and angles are within normal ranges. The bond lengths involving tetravalent nitrogen (N2—C1, N2—C3, N2—C16 and N2—C17) are 1.524 (2), 1.509 (3), 1.488 (3) and 1.496 (3) Å, respectively. These are somewhat longer than the corresponding N—C distances in the tertiary tetrahydroisoquinoline alkaloids egenine and armepavine (Dokurno et al., 1993; Marek et al., 1997). The mean of the bond angles around N2 is 109.47°, appropriate for sp3 hybridization. The two methoxy groups at C12 and C13 lie in the plane of their parent benzene ring. The partially saturated nitrogen heterocycle has an almost regular half-chair conformation, with atom N2 lying 0.666 (3) Å out of the least-squares plane C1/C8a/C4a/C4/C3. The dihedral angle between the aromatic rings of the isoquinoline moiety and the benzyl group is 31.44 (7)°.
The molecule of (I) contains one chiral centre, atom C1. From previous steric correlations, it is known that dextrorotatory benzyltetrahydroisoquinoline alkaloids have the S configuration (Šantavý, 1979; Bentley, 1998). In accordance with previous investigations, and with the refinement of the Flack (1983) parameter, the molecule of escholinine in Fig. 1 is depicted as the S enantiomer.
The perchlorate anion is a regular tetrahedron. The mean Cl—O bond length is 1.418 Å. There are no hydrogen bonds and the ions are held together by Coulombic and van der Waals interactions. The isoquinoline rings are stacked in columns parallel to the crystallographic a axis.