Buy article online - an online subscription or single-article purchase is required to access this article.
Bis-(3R,4S,8S,9R)-cinchonidinium (2R,3R)-tartrate dihydrate, 2C19H23N2O2+·C4H4O62-·2H2O, is a hydrated salt of cinchonidine, in which the two protonated quinuclidinic nitrogen groups interact with the ionized carboxylate group of the tartrate; the latter has twofold symmetry. The water molecule interacts with the hydroxyl group of the cation and the O atoms of the carboxylate residues to afford a three-dimensional network structure.
Supporting information
CCDC reference: 204698
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.005 Å
- R factor = 0.045
- wR factor = 0.130
- Data-to-parameter ratio = 7.8
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level B:
ABSTM_02 Alert B The ratio of expected to reported Tmax/Tmin(RR') is < 0.75
Tmin and Tmax reported: 0.498 0.876
Tmin' and Tmax expected: 0.964 0.980
RR' = 0.578
Please check that your absorption correction is appropriate.
PLAT_731 Alert B Bond Calc 0.86(5), Rep 0.870(10) .... 5.00 su-Ratio
O1W -H1W1 1.555 1.555
PLAT_735 Alert B D-H Calc 0.86(5), Rep 0.870(10) .... 5.00 su-Ratio
O1W -H1W1 1.555 1.555
Alert Level C:
PLAT_731 Alert C Bond Calc 0.84(4), Rep 0.850(10) .... 4.00 su-Ratio
O4 -H4O 1.555 1.555
PLAT_731 Alert C Bond Calc 0.87(4), Rep 0.860(10) .... 4.00 su-Ratio
O1W -H1W2 1.555 1.555
PLAT_731 Alert C Bond Calc 0.86(3), Rep 0.870(10) .... 3.00 su-Ratio
N1 -H1N 1.555 1.555
PLAT_732 Alert C Angle Calc 106(5), Rep 106(2) .... 2.50 su-Ratio
H1W1 -O1W -H1W2 1.555 1.555 1.555
PLAT_735 Alert C D-H Calc 0.85(3), Rep 0.840(10) .... 3.00 su-Ratio
O1 -H1O 1.555 1.555
PLAT_735 Alert C D-H Calc 0.86(3), Rep 0.870(10) .... 3.00 su-Ratio
N1 -H1N 1.555 1.555
PLAT_735 Alert C D-H Calc 0.84(4), Rep 0.850(10) .... 4.00 su-Ratio
O4 -H4O 1.555 1.555
PLAT_735 Alert C D-H Calc 0.87(4), Rep 0.860(10) .... 4.00 su-Ratio
O1W -H1W2 1.555 1.555
PLAT_736 Alert C H...A Calc 1.84(3), Rep 1.830(10) .... 3.00 su-Ratio
H1N -O2 1.555 1.545
General Notes
ABSTM_02 When printed, the submitted absorption T values will be replaced
by the scaled T values. Since the ratio of scaled T's is
identical to the ratio of reported T values, the scaling does
not imply a change to the absorption corrections used in the
study.
Ratio of Tmax expected/reported 1.118
Tmax scaled 0.980 Tmin scaled 0.557
REFLT_03
From the CIF: _diffrn_reflns_theta_max 26.00
From the CIF: _reflns_number_total 2094
Count of symmetry unique reflns 2104
Completeness (_total/calc) 99.52%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 0
Fraction of Friedel pairs measured 0.000
Are heavy atom types Z>Si present no
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.
0 Alert Level A = Potentially serious problem
3 Alert Level B = Potential problem
9 Alert Level C = Please check
Cinchonidine (2.94 g, 10 mmol) and L-tartaric acid (0.75 g, 5 mmol) were dissolved in a small volume of 50:50 ethanol–water; the solution was kept at about 333 K for 10 h. The dihydrate separated from the solution in 80% yield. Found (calculated) for C42H54N4O10: C 64.8 (65.1), H 7.1 (7.0), N 7.0% (7.2%). IR (KBr pellet): CO2 (asymmetric) 1593, 1509; CO2 (symmetric) 1457, 1419, 1391 cm−1.
The H atoms bonded to the N and O atoms were located and refined subject to N—H = O—H = 0.85±0.01 Å; for the water H atoms, the H···H distance was set to 1.39±0.01 Å. The C-bound H atoms were included in the riding-model approximation. The Uiso values of all H atoms were set at 1.2 times those of their parent atoms. The absolute structure was determined on the basis of the known configuration of L-tartrate.
Data collection: CAD-4 VAX/PC (Enraf-Nonius, 1988); cell refinement: CAD-4 VAX/PC; data reduction: XCAD4 (Harms, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
Crystal data top
2C19H23N2O+·C4H4O62−·2H2O | F(000) = 828 |
Mr = 774.89 | Dx = 1.308 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
a = 19.960 (3) Å | Cell parameters from 25 reflections |
b = 6.625 (2) Å | θ = 15.1–19.2° |
c = 15.530 (2) Å | µ = 0.09 mm−1 |
β = 106.68 (1)° | T = 296 K |
V = 1967.2 (7) Å3 | Block, colorless |
Z = 2 | 0.38 × 0.30 × 0.22 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 1703 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.045 |
Graphite monochromator | θmax = 26.0°, θmin = 1.4° |
ω–2θ scans | h = −24→24 |
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968) | k = −8→0 |
Tmin = 0.498, Tmax = 0.876 | l = −19→19 |
4178 measured reflections | 2 standard reflections every 60 min |
2094 independent reflections | intensity decay: 4% |
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)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.130 | w = 1/[σ2(Fo2) + (0.0693P)2 + 0.1359P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max < 0.001 |
2094 reflections | Δρmax = 0.22 e Å−3 |
268 parameters | Δρmin = −0.17 e Å−3 |
7 restraints | Absolute structure: The calculation of the Flack parameter was suppressed by the use of the
MERG 4 instruction in SHELXL97 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0 |
Crystal data top
2C19H23N2O+·C4H4O62−·2H2O | V = 1967.2 (7) Å3 |
Mr = 774.89 | Z = 2 |
Monoclinic, C2 | Mo Kα radiation |
a = 19.960 (3) Å | µ = 0.09 mm−1 |
b = 6.625 (2) Å | T = 296 K |
c = 15.530 (2) Å | 0.38 × 0.30 × 0.22 mm |
β = 106.68 (1)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 1703 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968) | Rint = 0.045 |
Tmin = 0.498, Tmax = 0.876 | 2 standard reflections every 60 min |
4178 measured reflections | intensity decay: 4% |
2094 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.130 | Δρmax = 0.22 e Å−3 |
S = 1.11 | Δρmin = −0.17 e Å−3 |
2094 reflections | Absolute structure: The calculation of the Flack parameter was suppressed by the use of the
MERG 4 instruction in SHELXL97 |
268 parameters | Absolute structure parameter: 0 |
7 restraints | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.7922 (1) | 0.5001 (4) | 0.2810 (2) | 0.0533 (6) | |
O2 | 0.8693 (1) | 0.9863 (4) | 0.4509 (2) | 0.0513 (6) | |
O3 | 0.8796 (1) | 1.2929 (5) | 0.5111 (2) | 0.0637 (7) | |
O4 | 1.0114 (1) | 1.2489 (5) | 0.6007 (1) | 0.0616 (8) | |
O1W | 0.9137 (2) | 0.6346 (6) | 0.3968 (3) | 0.097 (1) | |
N1 | 0.7418 (1) | 0.1056 (5) | 0.3504 (1) | 0.0399 (6) | |
N2 | 0.8394 (2) | 0.2624 (9) | −0.0033 (2) | 0.077 (1) | |
C1 | 0.8650 (2) | 0.1144 (8) | 0.0583 (2) | 0.061 (1) | |
C2 | 0.9005 (2) | −0.050 (1) | 0.0336 (3) | 0.082 (2) | |
C3 | 0.9278 (2) | −0.202 (1) | 0.0925 (4) | 0.088 (2) | |
C4 | 0.9216 (2) | −0.1971 (9) | 0.1799 (3) | 0.071 (1) | |
C5 | 0.8881 (2) | −0.0391 (6) | 0.2064 (2) | 0.0535 (9) | |
C6 | 0.8584 (2) | 0.1200 (7) | 0.1475 (2) | 0.0478 (8) | |
C7 | 0.8221 (1) | 0.2872 (6) | 0.1703 (2) | 0.0432 (8) | |
C8 | 0.7973 (2) | 0.4341 (7) | 0.1073 (2) | 0.056 (1) | |
C9 | 0.8069 (2) | 0.4119 (9) | 0.0210 (2) | 0.070 (1) | |
C10 | 0.8084 (1) | 0.3008 (5) | 0.2614 (2) | 0.0384 (7) | |
C11 | 0.7469 (1) | 0.1606 (5) | 0.2585 (2) | 0.0367 (7) | |
C12 | 0.6755 (1) | 0.2438 (6) | 0.2035 (2) | 0.0464 (8) | |
C13 | 0.6214 (2) | 0.1976 (6) | 0.2525 (2) | 0.0469 (8) | |
C14 | 0.7135 (2) | 0.2716 (7) | 0.3954 (2) | 0.0524 (9) | |
C15 | 0.6391 (2) | 0.3218 (8) | 0.3399 (2) | 0.065 (1) | |
C16 | 0.6954 (2) | −0.0770 (6) | 0.3405 (2) | 0.0476 (8) | |
C17 | 0.6222 (2) | −0.0257 (6) | 0.2769 (2) | 0.0451 (8) | |
C18 | 0.6014 (2) | −0.1598 (7) | 0.1960 (2) | 0.062 (1) | |
C19 | 0.5421 (3) | −0.249 (1) | 0.1680 (4) | 0.117 (2) | |
C20 | 0.9040 (2) | 1.1285 (6) | 0.4975 (2) | 0.0413 (7) | |
C21 | 0.9827 (1) | 1.0962 (6) | 0.5379 (2) | 0.0392 (7) | |
H1O | 0.830 (1) | 0.561 (6) | 0.308 (2) | 0.064* | |
H4O | 0.982 (2) | 1.341 (5) | 0.599 (3) | 0.074* | |
H1W1 | 0.897 (3) | 0.735 (5) | 0.419 (4) | 0.117* | |
H1W2 | 0.911 (3) | 0.531 (5) | 0.430 (3) | 0.117* | |
H1N | 0.783 (1) | 0.069 (6) | 0.381 (2) | 0.048* | |
H2 | 0.9053 | −0.0546 | −0.0242 | 0.099* | |
H3 | 0.9507 | −0.3094 | 0.0744 | 0.106* | |
H4 | 0.9402 | −0.3009 | 0.2199 | 0.085* | |
H5 | 0.8849 | −0.0365 | 0.2649 | 0.064* | |
H8 | 0.7745 | 0.5468 | 0.1209 | 0.068* | |
H9 | 0.7885 | 0.5116 | −0.0214 | 0.084* | |
H10 | 0.8498 | 0.2544 | 0.3081 | 0.046* | |
H11 | 0.7549 | 0.0351 | 0.2295 | 0.044* | |
H12a | 0.6786 | 0.3885 | 0.1960 | 0.056* | |
H12b | 0.6617 | 0.1819 | 0.1445 | 0.056* | |
H13 | 0.5748 | 0.2349 | 0.2144 | 0.056* | |
H14a | 0.7428 | 0.3904 | 0.4009 | 0.063* | |
H14b | 0.7136 | 0.2295 | 0.4552 | 0.063* | |
H15a | 0.6352 | 0.4648 | 0.3259 | 0.078* | |
H15b | 0.6065 | 0.2896 | 0.3737 | 0.078* | |
H16a | 0.6913 | −0.1172 | 0.3988 | 0.057* | |
H16b | 0.7156 | −0.1885 | 0.3160 | 0.057* | |
H17 | 0.5881 | −0.0454 | 0.3107 | 0.054* | |
H18 | 0.6336 | −0.1795 | 0.1638 | 0.075* | |
H19a | 0.5086 | −0.2327 | 0.1986 | 0.140* | |
H19b | 0.5325 | −0.3306 | 0.1171 | 0.140* | |
H21 | 0.9906 | 0.9651 | 0.5683 | 0.047* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.054 (1) | 0.049 (1) | 0.053 (1) | −0.004 (1) | 0.011 (1) | −0.007 (1) |
O2 | 0.034 (1) | 0.056 (1) | 0.054 (1) | −0.004 (1) | −0.002 (1) | 0.006 (1) |
O3 | 0.046 (1) | 0.085 (2) | 0.059 (1) | 0.011 (2) | 0.014 (1) | −0.016 (2) |
O4 | 0.048 (1) | 0.095 (2) | 0.041 (1) | −0.007 (2) | 0.012 (1) | −0.024 (2) |
O1W | 0.098 (2) | 0.055 (2) | 0.110 (3) | −0.002 (2) | −0.016 (2) | −0.010 (2) |
N1 | 0.029 (1) | 0.061 (2) | 0.028 (1) | 0.000 (1) | 0.005 (1) | 0.004 (1) |
N2 | 0.061 (2) | 0.138 (4) | 0.034 (1) | −0.027 (3) | 0.015 (1) | −0.005 (2) |
C1 | 0.044 (2) | 0.097 (3) | 0.041 (2) | −0.024 (2) | 0.013 (1) | −0.018 (2) |
C2 | 0.059 (2) | 0.130 (5) | 0.062 (2) | −0.030 (3) | 0.025 (2) | −0.049 (3) |
C3 | 0.061 (2) | 0.103 (4) | 0.106 (3) | −0.018 (3) | 0.033 (2) | −0.055 (4) |
C4 | 0.046 (2) | 0.079 (3) | 0.087 (3) | −0.005 (2) | 0.019 (2) | −0.018 (3) |
C5 | 0.043 (2) | 0.062 (2) | 0.056 (2) | −0.006 (2) | 0.016 (1) | −0.007 (2) |
C6 | 0.036 (1) | 0.070 (2) | 0.037 (1) | −0.015 (2) | 0.011 (1) | −0.008 (2) |
C7 | 0.034 (1) | 0.059 (2) | 0.033 (1) | −0.014 (2) | 0.005 (1) | 0.001 (2) |
C8 | 0.051 (2) | 0.071 (3) | 0.044 (2) | −0.011 (2) | 0.009 (1) | 0.012 (2) |
C9 | 0.059 (2) | 0.107 (4) | 0.040 (2) | −0.019 (3) | 0.010 (2) | 0.019 (2) |
C10 | 0.035 (1) | 0.044 (2) | 0.032 (1) | −0.002 (1) | 0.004 (1) | 0.001 (1) |
C11 | 0.034 (1) | 0.049 (2) | 0.026 (1) | −0.001 (1) | 0.007 (1) | 0.002 (1) |
C12 | 0.037 (1) | 0.059 (2) | 0.035 (1) | −0.005 (2) | −0.003 (1) | 0.007 (2) |
C13 | 0.031 (1) | 0.067 (2) | 0.038 (1) | 0.006 (2) | 0.002 (1) | −0.005 (2) |
C14 | 0.043 (2) | 0.080 (3) | 0.033 (1) | 0.001 (2) | 0.009 (1) | −0.012 (2) |
C15 | 0.049 (2) | 0.084 (3) | 0.057 (2) | 0.012 (2) | 0.006 (2) | −0.022 (2) |
C16 | 0.038 (2) | 0.065 (2) | 0.041 (1) | −0.005 (2) | 0.012 (1) | 0.011 (2) |
C17 | 0.032 (1) | 0.070 (2) | 0.035 (1) | −0.007 (2) | 0.012 (1) | 0.003 (2) |
C18 | 0.059 (2) | 0.068 (3) | 0.052 (2) | −0.009 (2) | 0.003 (2) | −0.004 (2) |
C19 | 0.078 (3) | 0.115 (5) | 0.137 (4) | −0.029 (4) | −0.002 (3) | −0.052 (5) |
C20 | 0.034 (1) | 0.060 (2) | 0.032 (1) | 0.003 (2) | 0.012 (1) | 0.007 (2) |
C21 | 0.033 (1) | 0.052 (2) | 0.030 (1) | −0.002 (2) | 0.006 (1) | 0.002 (1) |
Geometric parameters (Å, º) top
O1—C10 | 1.413 (4) | C21—C21i | 1.526 (5) |
O2—C20 | 1.267 (4) | O1—H1O | 0.84 (1) |
O3—C20 | 1.236 (5) | O4—H4O | 0.85 (1) |
O4—C21 | 1.407 (4) | O1W—H1W1 | 0.87 (1) |
N1—C14 | 1.497 (5) | O1W—H1W2 | 0.86 (1) |
N1—C11 | 1.505 (3) | N1—H1N | 0.87 (1) |
N1—C16 | 1.505 (5) | C2—H2 | 0.9300 |
N2—C9 | 1.298 (7) | C3—H3 | 0.9300 |
N2—C1 | 1.363 (6) | C4—H4 | 0.9300 |
C1—C2 | 1.409 (7) | C5—H5 | 0.9300 |
C1—C6 | 1.429 (4) | C8—H8 | 0.9300 |
C2—C3 | 1.366 (8) | C9—H9 | 0.9300 |
C3—C4 | 1.399 (6) | C10—H10 | 0.9800 |
C4—C5 | 1.366 (6) | C11—H11 | 0.9800 |
C5—C6 | 1.410 (5) | C12—H12a | 0.9700 |
C6—C7 | 1.423 (5) | C12—H12b | 0.9700 |
C7—C8 | 1.369 (5) | C13—H13 | 0.9800 |
C7—C10 | 1.519 (4) | C14—H14a | 0.9700 |
C8—C9 | 1.414 (5) | C14—H14b | 0.9700 |
C10—C11 | 1.528 (4) | C15—H15a | 0.9700 |
C11—C12 | 1.539 (4) | C15—H15b | 0.9700 |
C12—C13 | 1.518 (4) | C16—H16a | 0.9700 |
C13—C17 | 1.527 (6) | C16—H16b | 0.9700 |
C13—C15 | 1.539 (5) | C17—H17 | 0.9800 |
C14—C15 | 1.525 (4) | C18—H18 | 0.9300 |
C16—C17 | 1.548 (4) | C19—H19a | 0.9300 |
C17—C18 | 1.497 (5) | C19—H19b | 0.9300 |
C18—C19 | 1.284 (6) | C21—H21 | 0.9800 |
C20—C21 | 1.530 (4) | | |
| | | |
C14—N1—C11 | 113.7 (3) | C2—C3—H3 | 119.9 |
C14—N1—C16 | 109.6 (2) | C4—C3—H3 | 119.9 |
C11—N1—C16 | 107.8 (2) | C5—C4—H4 | 120.1 |
C9—N2—C1 | 117.6 (3) | C3—C4—H4 | 120.1 |
N2—C1—C2 | 118.8 (4) | C4—C5—H5 | 119.0 |
N2—C1—C6 | 122.7 (4) | C6—C5—H5 | 119.0 |
C2—C1—C6 | 118.5 (4) | C7—C8—H8 | 120.5 |
C3—C2—C1 | 121.6 (4) | C9—C8—H8 | 120.5 |
C2—C3—C4 | 120.1 (5) | N2—C9—H9 | 117.6 |
C5—C4—C3 | 119.8 (5) | C8—C9—H9 | 117.6 |
C4—C5—C6 | 121.9 (3) | O1—C10—H10 | 109.3 |
C5—C6—C7 | 124.7 (3) | C7—C10—H10 | 109.3 |
C5—C6—C1 | 118.0 (4) | C11—C10—H10 | 109.3 |
C7—C6—C1 | 117.2 (4) | N1—C11—H11 | 107.1 |
C8—C7—C6 | 118.7 (3) | C10—C11—H11 | 107.1 |
C8—C7—C10 | 119.9 (3) | C12—C11—H11 | 107.1 |
C6—C7—C10 | 121.3 (3) | C13—C12—H12a | 109.8 |
C7—C8—C9 | 119.0 (4) | C11—C12—H12a | 109.8 |
N2—C9—C8 | 124.7 (4) | C13—C12—H12b | 109.8 |
O1—C10—C7 | 111.7 (3) | C11—C12—H12b | 109.8 |
O1—C10—C11 | 110.0 (2) | H12a—C12—H12b | 108.3 |
C7—C10—C11 | 107.1 (2) | C12—C13—H13 | 109.6 |
N1—C11—C10 | 113.1 (2) | C17—C13—H13 | 109.6 |
N1—C11—C12 | 107.9 (2) | C15—C13—H13 | 109.6 |
C10—C11—C12 | 114.0 (3) | N1—C14—H14a | 109.8 |
C13—C12—C11 | 109.2 (2) | C15—C14—H14a | 109.8 |
C12—C13—C17 | 111.2 (3) | N1—C14—H14b | 109.8 |
C12—C13—C15 | 108.5 (3) | C15—C14—H14b | 109.8 |
C17—C13—C15 | 108.4 (3) | H14a—C14—H14b | 108.2 |
N1—C14—C15 | 109.5 (3) | C14—C15—H15a | 109.9 |
C14—C15—C13 | 108.7 (3) | C13—C15—H15a | 109.9 |
N1—C16—C17 | 109.2 (3) | C14—C15—H15b | 109.9 |
C18—C17—C13 | 112.7 (3) | C13—C15—H15b | 109.9 |
C18—C17—C16 | 112.9 (3) | H15a—C15—H15b | 108.3 |
C13—C17—C16 | 108.2 (3) | N1—C16—H16a | 109.8 |
C19—C18—C17 | 124.4 (4) | C17—C16—H16a | 109.8 |
O3—C20—O2 | 125.1 (3) | N1—C16—H16b | 109.8 |
O3—C20—C21 | 117.5 (3) | C17—C16—H16b | 109.8 |
O2—C20—C21 | 117.4 (3) | H16a—C16—H16b | 108.3 |
O4—C21—C21i | 110.5 (2) | C18—C17—H17 | 107.6 |
O4—C21—C20 | 110.4 (3) | C13—C17—H17 | 107.6 |
C21i—C21—C20 | 108.8 (3) | C16—C17—H17 | 107.6 |
C10—O1—H1O | 109 (3) | C19—C18—H18 | 117.8 |
C21—O4—H4O | 110 (3) | C17—C18—H18 | 117.8 |
H1W1—O1W—H1W2 | 106 (2) | C18—C19—H19a | 120.0 |
C14—N1—H1N | 112 (2) | C18—C19—H19b | 120.0 |
C11—N1—H1N | 106 (2) | H19a—C19—H19b | 120.0 |
C16—N1—H1N | 107 (3) | O4—C21—H21 | 109.0 |
C3—C2—H2 | 119.2 | C21i—C21—H21 | 109.0 |
C1—C2—H2 | 119.2 | C20—C21—H21 | 109.0 |
| | | |
C9—N2—C1—C2 | 179.9 (4) | C16—N1—C11—C12 | 70.1 (3) |
C9—N2—C1—C6 | −1.0 (5) | O1—C10—C11—N1 | −77.0 (3) |
N2—C1—C2—C3 | 179.5 (4) | C7—C10—C11—N1 | 161.4 (3) |
C6—C1—C2—C3 | 0.4 (6) | O1—C10—C11—C12 | 46.8 (3) |
C1—C2—C3—C4 | −0.5 (6) | C7—C10—C11—C12 | −74.8 (3) |
C2—C3—C4—C5 | −0.1 (6) | N1—C11—C12—C13 | −12.7 (4) |
C3—C4—C5—C6 | 0.9 (6) | C10—C11—C12—C13 | −139.2 (3) |
C4—C5—C6—C7 | 179.2 (3) | C11—C12—C13—C17 | −51.7 (4) |
C4—C5—C6—C1 | −1.0 (5) | C11—C12—C13—C15 | 67.4 (4) |
N2—C1—C6—C5 | −178.7 (3) | C11—N1—C14—C15 | 62.2 (4) |
C2—C1—C6—C5 | 0.4 (5) | C16—N1—C14—C15 | −58.4 (4) |
N2—C1—C6—C7 | 1.1 (5) | N1—C14—C15—C13 | −5.1 (5) |
C2—C1—C6—C7 | −179.8 (3) | C12—C13—C15—C14 | −56.8 (4) |
C5—C6—C7—C8 | 178.4 (3) | C17—C13—C15—C14 | 64.1 (4) |
C1—C6—C7—C8 | −1.4 (4) | C14—N1—C16—C17 | 64.2 (3) |
C5—C6—C7—C10 | −4.0 (5) | C11—N1—C16—C17 | −60.0 (3) |
C1—C6—C7—C10 | 176.2 (3) | C12—C13—C17—C18 | −64.2 (3) |
C6—C7—C8—C9 | 1.7 (5) | C15—C13—C17—C18 | 176.6 (3) |
C10—C7—C8—C9 | −176.0 (3) | C12—C13—C17—C16 | 61.3 (3) |
C1—N2—C9—C8 | 1.2 (6) | C15—C13—C17—C16 | −57.9 (3) |
C7—C8—C9—N2 | −1.7 (6) | N1—C16—C17—C18 | 121.1 (3) |
C8—C7—C10—O1 | −20.8 (4) | N1—C16—C17—C13 | −4.3 (3) |
C6—C7—C10—O1 | 161.6 (3) | C13—C17—C18—C19 | −105.5 (6) |
C8—C7—C10—C11 | 99.8 (3) | C16—C17—C18—C19 | 131.6 (5) |
C6—C7—C10—C11 | −77.8 (3) | O3—C20—C21—O4 | 12.7 (4) |
C14—N1—C11—C10 | 75.5 (3) | O2—C20—C21—O4 | −169.1 (3) |
C16—N1—C11—C10 | −162.8 (3) | O3—C20—C21—C21i | −108.7 (2) |
C14—N1—C11—C12 | −51.5 (3) | O2—C20—C21—C21i | 69.5 (3) |
Symmetry code: (i) −x+2, y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O1W | 0.84 (1) | 1.91 (2) | 2.722 (4) | 162 (4) |
N1—H1N···O2ii | 0.87 (1) | 1.83 (1) | 2.694 (3) | 177 (3) |
O4—H4O···O3 | 0.85 (1) | 2.12 (4) | 2.616 (3) | 117 (4) |
O1W—H1W1···O2 | 0.87 (1) | 1.86 (2) | 2.712 (5) | 167 (5) |
O1W—H1W2···O3ii | 0.86 (1) | 2.23 (2) | 3.071 (5) | 166 (5) |
Symmetry code: (ii) x, y−1, z. |
Experimental details
Crystal data |
Chemical formula | 2C19H23N2O+·C4H4O62−·2H2O |
Mr | 774.89 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 296 |
a, b, c (Å) | 19.960 (3), 6.625 (2), 15.530 (2) |
β (°) | 106.68 (1) |
V (Å3) | 1967.2 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.38 × 0.30 × 0.22 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Empirical (using intensity measurements) via ψ scan (North et al., 1968) |
Tmin, Tmax | 0.498, 0.876 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4178, 2094, 1703 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.130, 1.11 |
No. of reflections | 2094 |
No. of parameters | 268 |
No. of restraints | 7 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.22, −0.17 |
Absolute structure | The calculation of the Flack parameter was suppressed by the use of the
MERG 4 instruction in SHELXL97 |
Absolute structure parameter | 0 |
Selected geometric parameters (Å, º) topO1—C10 | 1.413 (4) | C6—C7 | 1.423 (5) |
O2—C20 | 1.267 (4) | C7—C8 | 1.369 (5) |
O3—C20 | 1.236 (5) | C7—C10 | 1.519 (4) |
O4—C21 | 1.407 (4) | C8—C9 | 1.414 (5) |
N1—C14 | 1.497 (5) | C10—C11 | 1.528 (4) |
N1—C11 | 1.505 (3) | C11—C12 | 1.539 (4) |
N1—C16 | 1.505 (5) | C12—C13 | 1.518 (4) |
N2—C9 | 1.298 (7) | C13—C17 | 1.527 (6) |
N2—C1 | 1.363 (6) | C13—C15 | 1.539 (5) |
C1—C2 | 1.409 (7) | C14—C15 | 1.525 (4) |
C1—C6 | 1.429 (4) | C16—C17 | 1.548 (4) |
C2—C3 | 1.366 (8) | C17—C18 | 1.497 (5) |
C3—C4 | 1.399 (6) | C18—C19 | 1.284 (6) |
C4—C5 | 1.366 (6) | C20—C21 | 1.530 (4) |
C5—C6 | 1.410 (5) | C21—C21i | 1.526 (5) |
| | | |
C14—N1—C11 | 113.7 (3) | C7—C10—C11 | 107.1 (2) |
C14—N1—C16 | 109.6 (2) | N1—C11—C10 | 113.1 (2) |
C11—N1—C16 | 107.8 (2) | N1—C11—C12 | 107.9 (2) |
C9—N2—C1 | 117.6 (3) | C10—C11—C12 | 114.0 (3) |
N2—C1—C2 | 118.8 (4) | C13—C12—C11 | 109.2 (2) |
N2—C1—C6 | 122.7 (4) | C12—C13—C17 | 111.2 (3) |
C2—C1—C6 | 118.5 (4) | C12—C13—C15 | 108.5 (3) |
C3—C2—C1 | 121.6 (4) | C17—C13—C15 | 108.4 (3) |
C2—C3—C4 | 120.1 (5) | N1—C14—C15 | 109.5 (3) |
C5—C4—C3 | 119.8 (5) | C14—C15—C13 | 108.7 (3) |
C4—C5—C6 | 121.9 (3) | N1—C16—C17 | 109.2 (3) |
C5—C6—C7 | 124.7 (3) | C18—C17—C13 | 112.7 (3) |
C5—C6—C1 | 118.0 (4) | C18—C17—C16 | 112.9 (3) |
C7—C6—C1 | 117.2 (4) | C13—C17—C16 | 108.2 (3) |
C8—C7—C6 | 118.7 (3) | C19—C18—C17 | 124.4 (4) |
C8—C7—C10 | 119.9 (3) | O3—C20—O2 | 125.1 (3) |
C6—C7—C10 | 121.3 (3) | O3—C20—C21 | 117.5 (3) |
C7—C8—C9 | 119.0 (4) | O2—C20—C21 | 117.4 (3) |
N2—C9—C8 | 124.7 (4) | O4—C21—C21i | 110.5 (2) |
O1—C10—C7 | 111.7 (3) | O4—C21—C20 | 110.4 (3) |
O1—C10—C11 | 110.0 (2) | C21i—C21—C20 | 108.8 (3) |
Symmetry code: (i) −x+2, y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O1W | 0.84 (1) | 1.91 (2) | 2.722 (4) | 162 (4) |
N1—H1N···O2ii | 0.87 (1) | 1.83 (1) | 2.694 (3) | 177 (3) |
O4—H4O···O3 | 0.85 (1) | 2.12 (4) | 2.616 (3) | 117 (4) |
O1W—H1W1···O2 | 0.87 (1) | 1.86 (2) | 2.712 (5) | 167 (5) |
O1W—H1W2···O3ii | 0.86 (1) | 2.23 (2) | 3.071 (5) | 166 (5) |
Symmetry code: (ii) x, y−1, z. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
Chincona alkaloids are widely used for the resolution of racemic acids and tartaric acid is commonly employed for the separation of optically active bases (Eliel, 1996; Collet, 1999). Amongst these alkaloids, (3R,4S,8R,9S)-cinchonan-9-ol owes its physiological activity to the stereochemistry of the chiral atoms C8 and C9 and also to the amino group (on the C8 atom) and the hydroxyl group (on the C9 atom) to form hydrogen bonds with receptors. This alkaloid when treated with one molar equivalent of L-tartaric acid affords cinchoninium L-bitartrate tetrahydrate (Puliti et al., 2001); the bitartrate anions are linked by a carboxyl–hydroxyl hydrogen bond into a chain running along the b axis of the monoclinic unit cell. When the stereochemistry of the alkaloid is altered to 8S,9R, as in (3R,4S,8S,9R)-cinchonan-9-ol, the synthesis furnishes the title diammonium tartrate, (I), as a dihydrate (see Scheme, Fig. 1 and Table 1). The asymmetric unit comprises the cinchonidinium cation, a lattice water molecule and half the tartrate dianion, that lies on a twofold axis.
The carboxylic acid group of the tartrate anion shows almost equivalent bond lengths consistent with deprotonation. The carboxyl O2 atom is strongly hydrogen bonded to the aliphatic ammonium group [N···O = 2.694 (3) Å] and the O4 atom is linked to the hydroxyl group within the same anion [O···O = 2.616 (3) Å]. The lattice water molecule interacts with the hydroxyl group of the cation and two O atoms of carboxylate groups derived from two different anions to afford a three-dimensional network motif. Hydrogen-bonding contacts are summarized in Table 2. The crystal packing is somewhat less compact than that of cinchoninium L-bitartrate tetrahydrate, as noted from the densities of the two salts, which are 1.308 and 1.332 Mg m−3 for di- and tetrahydrates, respectively (Puliti et al., 2001).