The title compound, (+)-4-[hydroxy(1-methyl-5-vinyl-1-azoniabicyclo[2.2.2]oct-2-yl)methyl]-1-methylquinolinium diiodide, C21H28N2O2+·2I-, is formed from optically active (11S)-(+)-cinchonine and methyl iodide. The N-Me bond lengths are in the range 1.48 (1)-1.49 (1) Å.
Supporting information
CCDC reference: 232132
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.010 Å
- R factor = 0.049
- wR factor = 0.107
- Data-to-parameter ratio = 19.8
checkCIF/PLATON results
No syntax errors found
Alert level C
SHFSU01_ALERT_2_C The absolute value of parameter shift to su ratio > 0.05
Absolute value of the parameter shift to su ratio given 0.081
Additional refinement cycles may be required.
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT080_ALERT_2_C Maximum Shift/Error ............................ 0.08
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.98
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ?
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 10
PLAT368_ALERT_2_C Short C(sp2)-C(sp2) Bond C20 - C21 = 1.23 Ang.
PLAT390_ALERT_3_C Deviating Methyl C10 X-C-H Bond Angle ...... 117.66 Deg.
PLAT391_ALERT_3_C Deviating Methyl C10 H-C-H Bond Angle ...... 100.43 Deg.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1
C21 H28 N2 O
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2
I
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 3
I
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 30.50
From the CIF: _reflns_number_total 5957
Count of symmetry unique reflns 3652
Completeness (_total/calc) 163.12%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 2305
Fraction of Friedel pairs measured 0.631
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
12 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
4 ALERT type 2 Indicator that the structure model may be wrong or deficient
3 ALERT type 3 Indicator that the structure quality may be low
5 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: TEXSAN (Molecular Structure Corporation, 2000); program(s) used to solve structure: SIR92 (Altomare et al., 1992); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.
Crystal data top
C21H28N2O2+·2I− | F(000) = 564 |
Mr = 578.27 | Dx = 1.682 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.7107 Å |
a = 8.8608 (5) Å | Cell parameters from 14933 reflections |
b = 10.9102 (4) Å | θ = 1.7–30.5° |
c = 12.2876 (5) Å | µ = 2.77 mm−1 |
β = 106.018 (2)° | T = 296 K |
V = 1141.76 (9) Å3 | Prism, yellow |
Z = 2 | 0.20 × 0.15 × 0.10 mm |
Data collection top
Rigaku R-AXIS RAPID Imaging Plate diffractometer | 4656 reflections with I > 2σ(I) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.027 |
ω scans | θmax = 30.5°, θmin = 1.7° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −12→12 |
Tmin = 0.559, Tmax = 0.758 | k = −13→15 |
13000 measured reflections | l = −17→17 |
5957 independent reflections | |
Refinement top
Refinement on F2 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.049 | (Δ/σ)max = 0.081 |
wR(F2) = 0.107 | Δρmax = 1.34 e Å−3 |
S = 1.48 | Δρmin = −0.45 e Å−3 |
4656 reflections | Absolute structure: Flack (1983), 2305 Friedel pairs |
235 parameters | Absolute structure parameter: −0.02 (3) |
H-atom parameters not refined | |
Special details top
Refinement. Refinement using reflections with F2 > -10.0 σ(F2). The
weighted R-factor (wR) and goodness of fit (S) are based
on F2. R-factor (gt) are based on F. The threshold
expression of F2 > 2.0 σ(F2) is used only for calculating
R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
I1 | −0.11325 (4) | −0.69411 (4) | −0.75256 (3) | 0.0662 (1) | |
I2 | −0.64094 (4) | −0.17588 (3) | −0.70539 (3) | 0.0653 (1) | |
O1 | −0.0142 (4) | −0.1589 (4) | −0.8642 (3) | 0.0564 (10) | |
N1 | −0.2313 (6) | −0.0613 (5) | −0.5431 (4) | 0.058 (1) | |
N2 | −0.1862 (6) | −0.3694 (4) | −0.9846 (4) | 0.055 (1) | |
C1 | −0.1577 (8) | −0.3791 (6) | −0.6126 (5) | 0.056 (2) | |
C2 | −0.2018 (9) | −0.4427 (6) | −0.5309 (6) | 0.069 (2) | |
C3 | −0.259 (1) | −0.376 (1) | −0.4513 (7) | 0.077 (3) | |
C4 | −0.2697 (7) | −0.2546 (8) | −0.4555 (5) | 0.065 (2) | |
C5 | −0.2237 (5) | −0.1869 (8) | −0.5397 (3) | 0.051 (1) | |
C6 | −0.1705 (5) | −0.2524 (5) | −0.6223 (4) | 0.045 (1) | |
C7 | −0.1316 (5) | −0.1834 (6) | −0.7095 (3) | 0.0433 (9) | |
C8 | −0.1413 (7) | −0.0575 (6) | −0.7058 (5) | 0.057 (1) | |
C9 | −0.1908 (9) | 0.0017 (6) | −0.6234 (7) | 0.060 (2) | |
C10 | −0.286 (1) | 0.008 (1) | −0.4582 (9) | 0.091 (3) | |
C11 | −0.0794 (6) | −0.2446 (5) | −0.8046 (4) | 0.044 (1) | |
C12 | −0.2222 (6) | −0.3036 (4) | −0.8847 (4) | 0.0426 (10) | |
C13 | −0.3564 (5) | −0.2160 (5) | −0.9340 (4) | 0.047 (1) | |
C14 | −0.4502 (7) | −0.2621 (6) | −1.0490 (5) | 0.056 (1) | |
C15 | −0.470 (1) | −0.4007 (8) | −1.0448 (6) | 0.078 (2) | |
C16 | −0.314 (1) | −0.4636 (6) | −1.0250 (5) | 0.077 (2) | |
C17 | −0.033 (1) | −0.4366 (8) | −0.9520 (7) | 0.087 (3) | |
C18 | −0.1922 (8) | −0.2830 (6) | −1.0814 (4) | 0.064 (2) | |
C19 | −0.3536 (9) | −0.2350 (6) | −1.1338 (5) | 0.060 (2) | |
C20 | −0.354 (1) | −0.1009 (7) | −1.1677 (7) | 0.081 (2) | |
C21 | −0.460 (1) | −0.0441 (10) | −1.2351 (8) | 0.097 (3) | |
H1 | −0.1164 | −0.4236 | −0.6657 | 0.0718* | |
H2 | −0.1865 | −0.5298 | −0.5238 | 0.0846* | |
H3 | −0.2937 | −0.4204 | −0.3979 | 0.0884* | |
H4 | −0.3091 | −0.2160 | −0.3993 | 0.0740* | |
H5 | −0.1104 | −0.0110 | −0.7628 | 0.0687* | |
H6 | −0.1969 | 0.0895 | −0.6239 | 0.0674* | |
H7 | −0.2908 | 0.0930 | −0.4649 | 0.1170* | |
H8 | −0.2276 | −0.0116 | −0.3788 | 0.1170* | |
H9 | −0.3972 | −0.0182 | −0.4583 | 0.1170* | |
H10 | −0.0035 | −0.3060 | −0.7732 | 0.0519* | |
H11 | 0.0759 | −0.1213 | −0.8137 | 0.0662* | |
H12 | −0.2616 | −0.3639 | −0.8428 | 0.0501* | |
H13 | −0.4224 | −0.2106 | −0.8854 | 0.0566* | |
H14 | −0.3142 | −0.1373 | −0.9419 | 0.0566* | |
H15 | −0.5498 | −0.2210 | −1.0726 | 0.0681* | |
H16 | −0.5414 | −0.4266 | −1.1116 | 0.0939* | |
H17 | −0.5120 | −0.4174 | −0.9815 | 0.0939* | |
H18 | −0.3051 | −0.4988 | −1.0952 | 0.0938* | |
H19 | −0.3017 | −0.5275 | −0.9709 | 0.0938* | |
H20 | −0.0159 | −0.4776 | −1.0154 | 0.1190* | |
H21 | −0.0295 | −0.4916 | −0.8928 | 0.1190* | |
H22 | 0.0510 | −0.3768 | −0.9261 | 0.1190* | |
H23 | −0.1566 | −0.3257 | −1.1375 | 0.0779* | |
H24 | −0.1229 | −0.2165 | −1.0533 | 0.0779* | |
H25 | −0.3970 | −0.2803 | −1.2007 | 0.0687* | |
H26 | −0.2615 | −0.0568 | −1.1294 | 0.0966* | |
H27 | −0.5548 | −0.0834 | −1.2747 | 0.1134* | |
H28 | −0.4465 | 0.0414 | −1.2486 | 0.1134* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1 | 0.0553 (2) | 0.0589 (2) | 0.0812 (3) | 0.0058 (2) | 0.0134 (2) | 0.0131 (3) |
I2 | 0.0513 (2) | 0.0745 (3) | 0.0657 (2) | 0.0026 (2) | 0.0086 (1) | 0.0020 (2) |
O1 | 0.044 (2) | 0.070 (3) | 0.058 (2) | −0.012 (2) | 0.020 (2) | 0.012 (2) |
N1 | 0.063 (3) | 0.062 (3) | 0.048 (3) | −0.001 (2) | 0.011 (2) | −0.020 (2) |
N2 | 0.076 (3) | 0.044 (2) | 0.046 (2) | 0.007 (2) | 0.019 (2) | 0.002 (2) |
C1 | 0.062 (4) | 0.059 (4) | 0.041 (3) | −0.004 (3) | 0.003 (3) | 0.002 (3) |
C2 | 0.084 (5) | 0.055 (4) | 0.059 (4) | −0.015 (3) | 0.004 (3) | 0.013 (3) |
C3 | 0.082 (6) | 0.103 (7) | 0.043 (4) | −0.028 (4) | 0.009 (3) | 0.018 (4) |
C4 | 0.062 (4) | 0.091 (5) | 0.042 (3) | −0.014 (3) | 0.013 (3) | −0.002 (3) |
C5 | 0.043 (2) | 0.071 (3) | 0.036 (2) | −0.011 (3) | 0.002 (2) | −0.003 (3) |
C6 | 0.037 (2) | 0.054 (3) | 0.040 (2) | −0.009 (2) | 0.002 (2) | 0.004 (2) |
C7 | 0.039 (2) | 0.050 (3) | 0.038 (2) | −0.008 (2) | 0.006 (2) | 0.005 (3) |
C8 | 0.067 (4) | 0.052 (3) | 0.048 (3) | −0.008 (2) | 0.009 (3) | −0.002 (2) |
C9 | 0.071 (4) | 0.044 (3) | 0.057 (4) | −0.003 (3) | 0.007 (3) | −0.007 (3) |
C10 | 0.107 (8) | 0.093 (7) | 0.076 (6) | −0.003 (5) | 0.033 (6) | −0.020 (5) |
C11 | 0.039 (2) | 0.050 (3) | 0.045 (2) | −0.001 (2) | 0.013 (2) | 0.006 (2) |
C12 | 0.053 (3) | 0.039 (2) | 0.040 (2) | −0.003 (2) | 0.020 (2) | 0.004 (2) |
C13 | 0.043 (2) | 0.054 (3) | 0.045 (2) | 0.000 (2) | 0.012 (2) | 0.003 (2) |
C14 | 0.056 (3) | 0.060 (3) | 0.047 (3) | −0.008 (2) | 0.006 (2) | 0.005 (3) |
C15 | 0.096 (5) | 0.072 (5) | 0.056 (3) | −0.040 (4) | 0.002 (3) | 0.000 (3) |
C16 | 0.124 (6) | 0.046 (3) | 0.048 (3) | −0.012 (4) | 0.005 (4) | −0.004 (3) |
C17 | 0.103 (6) | 0.081 (6) | 0.088 (5) | 0.043 (5) | 0.041 (5) | 0.003 (4) |
C18 | 0.085 (4) | 0.069 (4) | 0.046 (3) | 0.006 (3) | 0.030 (3) | 0.011 (3) |
C19 | 0.077 (4) | 0.063 (4) | 0.034 (3) | −0.013 (3) | 0.005 (3) | 0.001 (2) |
C20 | 0.101 (6) | 0.071 (5) | 0.062 (4) | 0.006 (4) | 0.007 (4) | 0.018 (3) |
C21 | 0.086 (6) | 0.102 (6) | 0.107 (6) | 0.012 (5) | 0.036 (5) | 0.027 (5) |
Geometric parameters (Å, º) top
O1—C11 | 1.406 (7) | C11—C12 | 1.516 (6) |
O1—H11 | 0.958 | C11—H10 | 0.952 |
N1—C5 | 1.37 (1) | C12—C13 | 1.515 (6) |
N1—C9 | 1.331 (10) | C12—H12 | 0.959 |
N1—C10 | 1.48 (1) | C13—C14 | 1.513 (7) |
N2—C12 | 1.529 (7) | C13—H13 | 0.946 |
N2—C16 | 1.507 (9) | C13—H14 | 0.953 |
N2—C17 | 1.49 (1) | C14—C15 | 1.52 (1) |
N2—C18 | 1.507 (8) | C14—C19 | 1.548 (10) |
C1—C2 | 1.36 (1) | C14—H15 | 0.961 |
C1—C6 | 1.389 (8) | C15—C16 | 1.50 (1) |
C1—H1 | 0.963 | C15—H16 | 0.932 |
C2—C3 | 1.42 (1) | C15—H17 | 0.970 |
C2—H2 | 0.961 | C16—H18 | 0.966 |
C3—C4 | 1.33 (1) | C16—H19 | 0.950 |
C3—H3 | 0.933 | C17—H20 | 0.947 |
C4—C5 | 1.420 (9) | C17—H21 | 0.937 |
C4—H4 | 0.954 | C17—H22 | 0.976 |
C5—C6 | 1.424 (8) | C18—C19 | 1.492 (9) |
C6—C7 | 1.427 (7) | C18—H23 | 0.954 |
C7—C8 | 1.378 (9) | C18—H24 | 0.952 |
C7—C11 | 1.525 (8) | C19—C20 | 1.52 (1) |
C8—C9 | 1.37 (1) | C19—H25 | 0.945 |
C8—H5 | 0.964 | C20—C21 | 1.23 (1) |
C9—H6 | 0.959 | C20—H26 | 0.957 |
C10—H7 | 0.928 | C21—H27 | 0.946 |
C10—H8 | 0.994 | C21—H28 | 0.961 |
C10—H9 | 1.024 | | |
| | | |
I2···O1i | 3.350 (3) | C2···C9iii | 3.53 (1) |
O1···C17ii | 3.42 (1) | C10···C21iv | 3.54 (2) |
| | | |
C11—O1—H11 | 109.6 | C11—C12—C13 | 114.5 (4) |
C5—N1—C9 | 121.1 (5) | C11—C12—H12 | 107.7 |
C5—N1—C10 | 121.0 (6) | C13—C12—H12 | 106.6 |
C9—N1—C10 | 117.9 (7) | C12—C13—C14 | 109.4 (4) |
C12—N2—C16 | 106.3 (5) | C12—C13—H13 | 109.9 |
C12—N2—C17 | 112.9 (5) | C12—C13—H14 | 108.8 |
C12—N2—C18 | 111.7 (4) | C14—C13—H13 | 109.5 |
C16—N2—C17 | 107.3 (5) | C14—C13—H14 | 109.6 |
C16—N2—C18 | 107.8 (4) | H13—C13—H14 | 109.6 |
C17—N2—C18 | 110.5 (6) | C13—C14—C15 | 109.7 (5) |
C2—C1—C6 | 122.4 (7) | C13—C14—C19 | 107.6 (5) |
C2—C1—H1 | 118.8 | C13—C14—H15 | 110.4 |
C6—C1—H1 | 118.7 | C15—C14—C19 | 107.5 (6) |
C1—C2—C3 | 118.4 (7) | C15—C14—H15 | 111.7 |
C1—C2—H2 | 120.6 | C19—C14—H15 | 109.9 |
C3—C2—H2 | 120.9 | C14—C15—C16 | 110.5 (7) |
C2—C3—C4 | 121.3 (8) | C14—C15—H16 | 109.1 |
C2—C3—H3 | 117.7 | C14—C15—H17 | 106.6 |
C4—C3—H3 | 121.0 | C16—C15—H16 | 112.2 |
C3—C4—C5 | 121.1 (7) | C16—C15—H17 | 109.0 |
C3—C4—H4 | 116.6 | H16—C15—H17 | 109.2 |
C5—C4—H4 | 122.3 | N2—C16—C15 | 108.4 (5) |
N1—C5—C4 | 121.3 (6) | N2—C16—H18 | 109.1 |
N1—C5—C6 | 120.2 (5) | N2—C16—H19 | 109.9 |
C4—C5—C6 | 118.4 (7) | C15—C16—H18 | 109.5 |
C1—C6—C5 | 118.3 (6) | C15—C16—H19 | 111.8 |
C1—C6—C7 | 123.9 (5) | H18—C16—H19 | 108.1 |
C5—C6—C7 | 117.8 (5) | N2—C17—H20 | 110.6 |
C6—C7—C8 | 118.1 (5) | N2—C17—H21 | 111.0 |
C6—C7—C11 | 122.1 (5) | N2—C17—H22 | 108.3 |
C8—C7—C11 | 119.8 (5) | H20—C17—H21 | 110.9 |
C7—C8—C9 | 122.0 (6) | H20—C17—H22 | 107.5 |
C7—C8—H5 | 117.9 | H21—C17—H22 | 108.4 |
C9—C8—H5 | 120.1 | N2—C18—C19 | 112.4 (6) |
N1—C9—C8 | 120.7 (6) | N2—C18—H23 | 108.6 |
N1—C9—H6 | 119.7 | N2—C18—H24 | 108.1 |
C8—C9—H6 | 119.6 | C19—C18—H23 | 109.2 |
N1—C10—H7 | 117.6 | C19—C18—H24 | 109.5 |
N1—C10—H8 | 113.3 | H23—C18—H24 | 108.9 |
N1—C10—H9 | 111.0 | C14—C19—C18 | 106.5 (5) |
H7—C10—H8 | 107.6 | C14—C19—C20 | 114.0 (6) |
H7—C10—H9 | 105.2 | C14—C19—H25 | 108.5 |
H8—C10—H9 | 100.5 | C18—C19—C20 | 112.8 (6) |
O1—C11—C7 | 111.3 (4) | C18—C19—H25 | 107.6 |
O1—C11—C12 | 109.5 (4) | C20—C19—H25 | 107.1 |
O1—C11—H10 | 109.5 | C19—C20—C21 | 127.7 (8) |
C7—C11—C12 | 107.9 (4) | C19—C20—H26 | 114.2 |
C7—C11—H10 | 109.1 | C21—C20—H26 | 118.0 |
C12—C11—H10 | 109.6 | C20—C21—H27 | 121.2 |
N2—C12—C11 | 113.5 (4) | C20—C21—H28 | 119.5 |
N2—C12—C13 | 106.9 (4) | H27—C21—H28 | 119.2 |
N2—C12—H12 | 107.3 | | |
| | | |
O1—C11—C7—C6 | −166.6 (4) | C6—C7—C8—C9 | −1.8 (7) |
O1—C11—C7—C8 | 13.0 (5) | C6—C7—C11—C12 | 73.3 (5) |
O1—C11—C12—N2 | 59.1 (5) | C7—C11—C12—C13 | 57.3 (6) |
O1—C11—C12—C13 | −64.0 (6) | C8—C7—C11—C12 | −107.1 (5) |
N1—C5—C4—C3 | −178.6 (6) | C8—C9—N1—C10 | −178.9 (7) |
N1—C5—C6—C1 | 177.0 (4) | C9—C8—C7—C11 | 178.6 (5) |
N1—C5—C6—C7 | −2.1 (6) | C11—C12—N2—C16 | 156.6 (4) |
N1—C9—C8—C7 | 0.2 (9) | C11—C12—N2—C17 | 39.2 (7) |
N2—C12—C11—C7 | −179.7 (4) | C11—C12—N2—C18 | −86.1 (5) |
N2—C12—C13—C14 | 24.9 (6) | C11—C12—C13—C14 | 151.5 (5) |
N2—C16—C15—C14 | 15.2 (8) | C12—N2—C16—C15 | 52.1 (6) |
N2—C18—C19—C14 | 15.6 (6) | C12—N2—C18—C19 | −66.1 (6) |
N2—C18—C19—C20 | 141.5 (6) | C12—C13—C14—C15 | 41.4 (7) |
C1—C2—C3—C4 | 0 (1) | C12—C13—C14—C19 | −75.2 (6) |
C1—C6—C5—C4 | −3.6 (6) | C13—C12—N2—C16 | −76.2 (5) |
C1—C6—C7—C8 | −176.4 (5) | C13—C12—N2—C17 | 166.4 (5) |
C1—C6—C7—C11 | 3.2 (7) | C13—C12—N2—C18 | 41.1 (6) |
C2—C1—C6—C5 | 3.5 (8) | C13—C14—C15—C16 | −65.8 (7) |
C2—C1—C6—C7 | −177.3 (5) | C13—C14—C19—C18 | 50.2 (6) |
C2—C3—C4—C5 | 0 (1) | C13—C14—C19—C20 | −74.9 (6) |
C3—C2—C1—C6 | −1.6 (10) | C14—C19—C20—C21 | −77 (1) |
C3—C4—C5—C6 | 2.0 (8) | C15—C14—C19—C18 | −67.9 (6) |
C4—C5—N1—C9 | −178.8 (5) | C15—C14—C19—C20 | 167.0 (5) |
C4—C5—N1—C10 | 0.6 (8) | C15—C16—N2—C17 | 173.2 (6) |
C4—C5—C6—C7 | 177.2 (4) | C15—C16—N2—C18 | −67.8 (7) |
C5—N1—C9—C8 | 0.5 (9) | C16—N2—C18—C19 | 50.3 (7) |
C5—C6—C7—C8 | 2.7 (6) | C16—C15—C14—C19 | 50.9 (7) |
C5—C6—C7—C11 | −177.7 (4) | C17—N2—C18—C19 | 167.2 (5) |
C6—C5—N1—C9 | 0.6 (7) | C18—C19—C20—C21 | 161.2 (10) |
C6—C5—N1—C10 | 179.9 (6) | C18—C19—C20—C21 | 161.2 (10) |
Symmetry codes: (i) x−1, y, z; (ii) −x, y+1/2, −z−2; (iii) −x, y−1/2, −z−1; (iv) x, y, z+1. |