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The title compound, C20H25N2O2+·C4H6ClO2-, was crystallized by evaporation of an acetone solution and this is the first published report describing the structure of a crystal phase for this salt. Quinine is commonly used as a resolving agent for classic resolution. The anion was of inter­est because it has several desirable properties for absolute configuration studies, viz. strong acidic pKa for salt formation, a somewhat heavy atom for strong diffraction and a known stereocenter.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805035294/fl6199sup1.cif
Contains datablocks sad1, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805035294/fl6199Isup2.hkl
Contains datablock I

CCDC reference: 293894

Key indicators

  • Single-crystal X-ray study
  • T = 299 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.051
  • wR factor = 0.105
  • Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C2 PLAT850_ALERT_2_C Check Flack Parameter Exact Value 0.00 and su .. 0.11
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 25.46 From the CIF: _reflns_number_total 4091 Count of symmetry unique reflns 2569 Completeness (_total/calc) 159.24% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1522 Fraction of Friedel pairs measured 0.592 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 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 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2003); software used to prepare material for publication: SHELXTL.

6'-methoxy (8α, 9R) Cinchonan-9-ol (2 s)-2-chloro-Butanoate top
Crystal data top
C20H25N2O2+·C4H6ClO2Dx = 1.291 Mg m3
Mr = 446.96Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P43212Cell parameters from 1003 reflections
Hall symbol: P 4nw 2abwθ = 2.0–25.5°
a = 10.5135 (5) ŵ = 0.20 mm1
c = 41.618 (3) ÅT = 299 K
V = 4600.2 (5) Å3Columnar, colorless
Z = 80.38 × 0.38 × 0.33 mm
F(000) = 1904
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
4091 independent reflections
Radiation source: fine-focus sealed tube3651 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
φ and ω scansθmax = 25.5°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
h = 1212
Tmin = 0.835, Tmax = 0.937k = 1212
32606 measured reflectionsl = 4549
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.105 w = 1/[σ2(Fo2) + (0.0337P)2 + 2.0903P]
where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max = 0.009
4091 reflectionsΔρmax = 0.30 e Å3
290 parametersΔρmin = 0.31 e Å3
2 restraintsAbsolute structure: Flack (1983), 1587 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.00 (11)
Special details top

Experimental. Owing to the long c axes, the detector was positioned 10 cm from the crystal in order to differentiate reflections. The data-collection strategy used two different detector positions to achieve acceptable 2θ coverage (Table 2).

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.69383 (13)1.07381 (10)0.02488 (2)0.1044 (4)
O30.53144 (19)1.1160 (2)0.10077 (5)0.0563 (5)
O40.7296 (2)1.1820 (2)0.09458 (5)0.0732 (7)
C10.6392 (3)1.1123 (3)0.08781 (6)0.0456 (7)
C20.6598 (3)1.0051 (3)0.06335 (6)0.0459 (7)
H20.58060.95640.06160.055*
C30.7636 (3)0.9159 (4)0.07356 (10)0.0795 (11)
H3A0.74620.88770.09530.095*
H3B0.84330.96230.07400.095*
C40.7800 (4)0.7990 (4)0.05224 (11)0.1083 (16)
H4A0.70010.75550.05030.162*
H4B0.84180.74300.06160.162*
H4C0.80850.82500.03130.162*
O20.30341 (19)0.14784 (18)0.06762 (5)0.0449 (5)
N10.0779 (2)0.33565 (19)0.08616 (5)0.0382 (5)
C50.0938 (2)0.0728 (2)0.11316 (6)0.0399 (6)
O10.0254 (2)0.0165 (2)0.19548 (5)0.0626 (6)
C60.0795 (2)0.1997 (2)0.07447 (6)0.0344 (6)
H60.00290.15830.08280.041*
C70.1920 (3)0.4094 (2)0.07524 (6)0.0432 (6)
H7A0.26810.37600.08540.052*
H7B0.18310.49800.08130.052*
C80.2033 (2)0.3978 (3)0.03854 (6)0.0450 (7)
H8A0.21810.48090.02910.054*
H8B0.27420.34300.03300.054*
C90.0417 (3)0.3986 (3)0.07425 (6)0.0448 (7)
H9A0.05470.47820.08560.054*
H9B0.11420.34400.07840.054*
C100.0639 (2)0.0073 (3)0.14197 (6)0.0431 (6)
H100.08670.07770.14430.052*
N20.0860 (3)0.2748 (2)0.08354 (7)0.0586 (7)
C110.0669 (3)0.2039 (2)0.03739 (6)0.0400 (6)
H11A0.13290.15200.02770.048*
H11B0.01490.16960.03100.048*
C120.0571 (3)0.2027 (3)0.10997 (7)0.0484 (7)
C130.1600 (2)0.0166 (2)0.08693 (6)0.0375 (6)
C140.1948 (2)0.1240 (2)0.08703 (6)0.0365 (6)
H140.21310.15050.10910.044*
C150.0308 (2)0.4241 (2)0.03788 (6)0.0415 (6)
H150.00740.51360.03490.050*
C160.1880 (3)0.0912 (3)0.06103 (7)0.0499 (7)
H160.23290.05740.04380.060*
C170.0016 (3)0.0685 (3)0.16623 (7)0.0506 (7)
C180.1536 (3)0.4011 (3)0.02069 (7)0.0546 (8)
H180.19070.32120.02270.066*
C190.0101 (3)0.2607 (3)0.13533 (8)0.0632 (9)
H190.03610.34480.13340.076*
C200.0225 (3)0.1082 (3)0.20172 (7)0.0592 (8)
H20A0.11190.11070.19710.089*
H20B0.00890.12920.22390.089*
H20C0.02120.16850.18840.089*
C210.1491 (3)0.2187 (3)0.06039 (8)0.0583 (8)
H210.16950.26670.04230.070*
C220.0792 (2)0.3416 (2)0.02558 (6)0.0391 (6)
H220.08040.34300.00200.047*
C230.0372 (3)0.1956 (3)0.16240 (9)0.0636 (9)
H230.08220.23530.17880.076*
C240.2116 (3)0.4845 (4)0.00323 (8)0.0799 (11)
H24A0.17710.56530.00070.096*
H24B0.28790.46370.00680.096*
H99A0.074 (3)0.333 (2)0.1089 (7)0.051 (8)*
H99B0.369 (4)0.121 (4)0.0768 (9)0.102 (15)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.1768 (12)0.0905 (7)0.0458 (5)0.0561 (8)0.0082 (6)0.0032 (5)
O30.0525 (13)0.0727 (15)0.0437 (11)0.0087 (11)0.0019 (10)0.0031 (10)
O40.0710 (15)0.0687 (15)0.0799 (16)0.0203 (13)0.0007 (12)0.0290 (12)
C10.0495 (17)0.0475 (17)0.0397 (15)0.0013 (15)0.0055 (14)0.0026 (13)
C20.0457 (16)0.0479 (17)0.0441 (16)0.0088 (13)0.0000 (12)0.0023 (13)
C30.064 (2)0.076 (2)0.099 (3)0.0089 (19)0.021 (2)0.027 (2)
C40.077 (3)0.100 (3)0.148 (4)0.030 (3)0.021 (3)0.055 (3)
O20.0372 (11)0.0473 (11)0.0503 (11)0.0007 (9)0.0036 (9)0.0098 (9)
N10.0486 (14)0.0329 (12)0.0331 (12)0.0000 (10)0.0021 (10)0.0012 (9)
C50.0384 (14)0.0321 (14)0.0491 (15)0.0043 (12)0.0037 (12)0.0069 (12)
O10.0683 (14)0.0623 (14)0.0572 (13)0.0088 (12)0.0216 (11)0.0146 (11)
C60.0378 (14)0.0270 (12)0.0383 (13)0.0027 (11)0.0054 (11)0.0023 (10)
C70.0495 (16)0.0320 (14)0.0480 (15)0.0092 (13)0.0048 (13)0.0001 (12)
C80.0404 (15)0.0488 (17)0.0458 (16)0.0032 (13)0.0012 (12)0.0112 (13)
C90.0456 (16)0.0343 (14)0.0544 (17)0.0056 (12)0.0082 (13)0.0000 (12)
C100.0433 (15)0.0366 (15)0.0495 (16)0.0047 (12)0.0058 (13)0.0113 (12)
N20.0712 (18)0.0332 (13)0.0712 (17)0.0023 (13)0.0076 (15)0.0011 (13)
C110.0421 (15)0.0388 (15)0.0390 (14)0.0028 (12)0.0021 (12)0.0059 (12)
C120.0478 (17)0.0327 (15)0.0648 (19)0.0008 (13)0.0069 (15)0.0089 (14)
C130.0384 (14)0.0319 (14)0.0423 (15)0.0044 (11)0.0029 (12)0.0027 (12)
C140.0396 (14)0.0356 (14)0.0343 (13)0.0027 (12)0.0031 (11)0.0008 (11)
C150.0414 (15)0.0335 (14)0.0495 (15)0.0005 (12)0.0003 (12)0.0048 (12)
C160.0569 (18)0.0415 (16)0.0513 (17)0.0051 (13)0.0028 (14)0.0020 (13)
C170.0454 (17)0.0512 (18)0.0553 (18)0.0122 (14)0.0086 (14)0.0156 (15)
C180.0415 (17)0.0551 (19)0.0671 (19)0.0002 (15)0.0024 (15)0.0022 (16)
C190.066 (2)0.0380 (17)0.086 (2)0.0112 (15)0.0030 (19)0.0146 (17)
C200.0496 (18)0.074 (2)0.0539 (18)0.0013 (17)0.0054 (15)0.0001 (16)
C210.075 (2)0.0415 (17)0.0581 (19)0.0096 (16)0.0054 (17)0.0108 (15)
C220.0386 (14)0.0429 (15)0.0359 (13)0.0012 (12)0.0028 (12)0.0031 (12)
C230.062 (2)0.0496 (19)0.079 (2)0.0015 (16)0.0160 (17)0.0237 (18)
C240.055 (2)0.113 (3)0.071 (2)0.002 (2)0.0103 (18)0.030 (2)
Geometric parameters (Å, º) top
Cl1—C21.793 (3)C9—C151.541 (4)
O3—C11.256 (3)C9—H9A0.9700
O4—C11.232 (3)C9—H9B0.9700
C1—C21.534 (4)C10—C171.365 (4)
C2—C31.501 (4)C10—H100.9300
C2—H20.9800N2—C211.310 (4)
C3—C41.525 (5)N2—C121.370 (4)
C3—H3A0.9700C11—C221.534 (4)
C3—H3B0.9700C11—H11A0.9700
C4—H4A0.9600C11—H11B0.9700
C4—H4B0.9600C12—C191.409 (4)
C4—H4C0.9600C13—C161.365 (4)
O2—C141.421 (3)C13—C141.522 (3)
O2—H99B0.84 (4)C14—H140.9800
N1—C71.499 (3)C15—C181.496 (4)
N1—C91.505 (3)C15—C221.534 (4)
N1—C61.510 (3)C15—H150.9800
N1—H99A0.95 (3)C16—C211.402 (4)
C5—C101.418 (4)C16—H160.9300
C5—C131.423 (4)C17—C231.405 (4)
C5—C121.425 (4)C18—C241.292 (4)
O1—C171.364 (3)C18—H180.9300
O1—C201.428 (4)C19—C231.349 (4)
C6—C141.542 (4)C19—H190.9300
C6—C111.550 (3)C20—H20A0.9600
C6—H60.9800C20—H20B0.9600
C7—C81.537 (4)C20—H20C0.9600
C7—H7A0.9700C21—H210.9300
C7—H7B0.9700C22—H220.9800
C8—C221.530 (3)C23—H230.9300
C8—H8A0.9700C24—H24A0.9300
C8—H8B0.9700C24—H24B0.9300
O4—C1—O3125.4 (3)C21—N2—C12117.0 (2)
O4—C1—C2118.7 (3)C22—C11—C6109.8 (2)
O3—C1—C2115.8 (3)C22—C11—H11A109.7
C3—C2—C1112.0 (2)C6—C11—H11A109.7
C3—C2—Cl1111.1 (2)C22—C11—H11B109.7
C1—C2—Cl1108.9 (2)C6—C11—H11B109.7
C3—C2—H2108.2H11A—C11—H11B108.2
C1—C2—H2108.2N2—C12—C19118.3 (3)
Cl1—C2—H2108.2N2—C12—C5123.0 (3)
C2—C3—C4114.9 (3)C19—C12—C5118.7 (3)
C2—C3—H3A108.5C16—C13—C5118.2 (2)
C4—C3—H3A108.5C16—C13—C14120.5 (2)
C2—C3—H3B108.5C5—C13—C14121.2 (2)
C4—C3—H3B108.5O2—C14—C13111.3 (2)
H3A—C3—H3B107.5O2—C14—C6110.4 (2)
C3—C4—H4A109.5C13—C14—C6108.1 (2)
C3—C4—H4B109.5O2—C14—H14109.0
H4A—C4—H4B109.5C13—C14—H14109.0
C3—C4—H4C109.5C6—C14—H14109.0
H4A—C4—H4C109.5C18—C15—C22113.5 (2)
H4B—C4—H4C109.5C18—C15—C9112.2 (2)
C14—O2—H99B110 (3)C22—C15—C9106.6 (2)
C7—N1—C9109.97 (19)C18—C15—H15108.1
C7—N1—C6112.5 (2)C22—C15—H15108.1
C9—N1—C6108.65 (19)C9—C15—H15108.1
C7—N1—H99A110.4 (17)C13—C16—C21120.1 (3)
C9—N1—H99A107.8 (17)C13—C16—H16119.9
C6—N1—H99A107.4 (16)C21—C16—H16119.9
C10—C5—C13123.7 (2)O1—C17—C10124.8 (3)
C10—C5—C12119.0 (2)O1—C17—C23114.9 (3)
C13—C5—C12117.3 (2)C10—C17—C23120.2 (3)
C17—O1—C20117.2 (2)C24—C18—C15124.5 (3)
N1—C6—C14112.9 (2)C24—C18—H18117.7
N1—C6—C11107.0 (2)C15—C18—H18117.7
C14—C6—C11114.8 (2)C23—C19—C12120.8 (3)
N1—C6—H6107.3C23—C19—H19119.6
C14—C6—H6107.3C12—C19—H19119.6
C11—C6—H6107.3O1—C20—H20A109.5
N1—C7—C8108.8 (2)O1—C20—H20B109.5
N1—C7—H7A109.9H20A—C20—H20B109.5
C8—C7—H7A109.9O1—C20—H20C109.5
N1—C7—H7B109.9H20A—C20—H20C109.5
C8—C7—H7B109.9H20B—C20—H20C109.5
H7A—C7—H7B108.3N2—C21—C16124.4 (3)
C22—C8—C7108.4 (2)N2—C21—H21117.8
C22—C8—H8A110.0C16—C21—H21117.8
C7—C8—H8A110.0C8—C22—C15107.9 (2)
C22—C8—H8B110.0C8—C22—C11108.8 (2)
C7—C8—H8B110.0C15—C22—C11111.3 (2)
H8A—C8—H8B108.4C8—C22—H22109.6
N1—C9—C15109.7 (2)C15—C22—H22109.6
N1—C9—H9A109.7C11—C22—H22109.6
C15—C9—H9A109.7C19—C23—C17121.0 (3)
N1—C9—H9B109.7C19—C23—H23119.5
C15—C9—H9B109.7C17—C23—H23119.5
H9A—C9—H9B108.2C18—C24—H24A120.0
C17—C10—C5120.2 (3)C18—C24—H24B120.0
C17—C10—H10119.9H24A—C24—H24B120.0
C5—C10—H10119.9
O4—C1—C2—C357.8 (4)C16—C13—C14—C692.8 (3)
O3—C1—C2—C3118.0 (3)C5—C13—C14—C684.9 (3)
O4—C1—C2—Cl165.4 (3)N1—C6—C14—O282.7 (3)
O3—C1—C2—Cl1118.8 (2)C11—C6—C14—O240.4 (3)
C1—C2—C3—C4173.8 (3)N1—C6—C14—C13155.4 (2)
Cl1—C2—C3—C464.2 (4)C11—C6—C14—C1381.6 (3)
C7—N1—C6—C1461.3 (3)N1—C9—C15—C18141.3 (2)
C9—N1—C6—C14176.7 (2)N1—C9—C15—C2216.4 (3)
C7—N1—C6—C1165.9 (3)C5—C13—C16—C211.5 (4)
C9—N1—C6—C1156.1 (3)C14—C13—C16—C21176.3 (3)
C9—N1—C7—C867.7 (3)C20—O1—C17—C104.2 (4)
C6—N1—C7—C853.6 (3)C20—O1—C17—C23174.3 (3)
N1—C7—C8—C2212.7 (3)C5—C10—C17—O1176.2 (2)
C7—N1—C9—C1550.5 (3)C5—C10—C17—C232.2 (4)
C6—N1—C9—C1573.0 (3)C22—C15—C18—C24115.6 (3)
C13—C5—C10—C17179.1 (2)C9—C15—C18—C24123.5 (3)
C12—C5—C10—C170.4 (4)N2—C12—C19—C23177.7 (3)
N1—C6—C11—C229.1 (3)C5—C12—C19—C231.3 (5)
C14—C6—C11—C22117.0 (2)C12—N2—C21—C160.2 (5)
C21—N2—C12—C19179.6 (3)C13—C16—C21—N20.2 (5)
C21—N2—C12—C50.7 (4)C7—C8—C22—C1554.0 (3)
C10—C5—C12—N2177.6 (3)C7—C8—C22—C1166.9 (3)
C13—C5—C12—N22.0 (4)C18—C15—C22—C8165.4 (2)
C10—C5—C12—C191.3 (4)C9—C15—C22—C870.6 (2)
C13—C5—C12—C19179.2 (3)C18—C15—C22—C1175.3 (3)
C10—C5—C13—C16177.2 (2)C9—C15—C22—C1148.7 (3)
C12—C5—C13—C162.3 (4)C6—C11—C22—C854.1 (3)
C10—C5—C13—C144.9 (4)C6—C11—C22—C1564.6 (3)
C12—C5—C13—C14175.6 (2)C12—C19—C23—C170.5 (5)
C16—C13—C14—O228.5 (3)O1—C17—C23—C19176.3 (3)
C5—C13—C14—O2153.7 (2)C10—C17—C23—C192.3 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H99B···O3i0.84 (4)1.98 (4)2.786 (3)162 (4)
N1—H99A···O4ii0.95 (3)2.54 (3)3.299 (3)137 (2)
N1—H99A···O3ii0.95 (3)1.82 (3)2.718 (3)158 (2)
Symmetry codes: (i) x, y1, z; (ii) x1/2, y+3/2, z+1/4.
 

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