Bis(cinchonidinium) l-tartrate dihydrate

Zhang, H.; Lin, Z.-Y.; Zhou, Z.-H.; Ng, S.W.

doi:10.1107/S1600536803000850

Bis(cinchonidinium) L-tartrate dihydrate

H. Zhang, Z.-Y. Lin, Z.-H. Zhou and S. W. Ng

Bis-(3R,4S,8S,9R)-cinchonidinium (2R,3R)-tartrate dihydrate, 2C₁₉H₂₃N₂O₂⁺·C₄H₄O₆^2-·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.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803000850/tk6089sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536803000850/tk6089Isup2.hkl Contains datablock I

CCDC reference: 204698

checkCIF report

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

Comment top

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).

Experimental top

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.

Computing details top

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.

Figures top

Fig. 1. ORTEPII (Johnson, 1976) plot of (I), with ellipsoids shown at the 50% probability level. H atoms are drawn as spheres of arbitrary radii.

(I) top

Crystal data top

2C₁₉H₂₃N₂O⁺·C₄H₄O₆²⁻·2H₂O	F(000) = 828
M_r = 774.89	D_x = 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	R_int = 0.045
Graphite monochromator	θ_max = 26.0°, θ_min = 1.4°
ω–2θ scans	h = −24→24
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968)	k = −8→0
T_min = 0.498, T_max = 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(F_o²) + (0.0693P)² + 0.1359P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
2094 reflections	Δρ_max = 0.22 e Å⁻³
268 parameters	Δρ_min = −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
M_r = 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)	R_int = 0.045
T_min = 0.498, T_max = 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	Δρ_max = 0.22 e Å⁻³
S = 1.11	Δρ_min = −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	U_iso*/U_eq
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
M_r	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)
T_min, T_max	0.498, 0.876
No. of measured, independent and observed [I > 2σ(I)] reflections	4178, 2094, 1703
R_int	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
Δρ_max, Δρ_min (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

Computer programs: CAD-4 VAX/PC (Enraf-Nonius, 1988), CAD-4 VAX/PC, XCAD4 (Harms, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.

Selected geometric parameters (Å, º) top

O1—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.

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