Similar environments for the ClO₄^-, HSO₄^- and H₂PO₄^- anions offered by strychnine self-assemblies

In strychninium chlorate(VII) monohydrate, C₂₁H₂₃N₂O·ClO·H₂O, strychninium hydrogensulfate­(VI) dihydrate, C₂₁H₂₃N₂O·HSO·2H₂O, and strychninium di­hydro­gen­phos­phate(V) dihydrate, C₂₁H₂₃N₂O·H₂PO·2H₂O, the strychninium cations form bilayer sheets separated by water-anion sheets. The strychnine bilayer sheets in the three compounds are similar to one another. In all three structures, the surfaces of the cation and water-anion sheets exhibit donor-acceptor matching.

S1. Comment

The recently described racemic resolution of alanine derivatives by the strychnine (and brucine) has revealed that enantiomeric recognition of the N-protected alanine (Gould & Walkinshaw, 1984; Bialonska & Ciunik, 2004) is dependent on the type of alkaloid self-assembly, which is determined by the donor/acceptor properties of the resolved substrate. Cocrystallization of strychnine with the chloric(VII), sulfuric(VI) or phosphoric(V) acid gives an opportunity to control, by the number of the donor/acceptor sites, the molecular recognition.

Views of the molecules of C₂₁H₂₃N₂O₂⁺·ClO₄⁻·H₂O, (I), C₂₁H₂₃N₂O₂⁺·HSO₄⁻·2H₂O, (II), and C₂₁H₂₃N₂O₂⁺·H₂PO₄⁻·2H₂O, (III), with the atom-numbering schemes, are presented in Fig. 1. The strychnine molecules in (I), (II) and (III) form, in a similar way to many other crystals (NO₃⁻, SO₄²⁻, Cl⁻, Br⁻ and I⁻) (Mostad, 1985; Borkhoven et al., 1951; Ghosh et al., 1989; Robertson & Beevers, 1951; Yuan et al., 1994], herring-bone bilayer sheets separated by anions and water molecules (Fig. 2). The carbonyl O atom and arene ring of the strychnine molecule are directed inwards in the bilayer sheet. This configuration, coupled with protonation of the tertiary amine N atom, causes the surfaces of the strychnine bilayer sheets in all of the crystals under investigation to act as donors.

In the crystal structure of (I), the chlorate(VII) anion adopts two arrangements (in a 2:1 ratio) around the Cl1—O3 bond. Atom O3 atom of the anion is directed towards a flat hole at the surface of the strychnine layer (see Fig. 2a). As presented in Fig. 3(a), protonated amine atom N2 of the strychnine molecule acts as a donor in a biffurcated hydrogen bond, where the water molecule O1W, as well as atom O4 or O4A of the disordered anion, act as acceptors. Both the anion and the water molecule are also directly linked by one branch [O1W—H11W···O4 (or O5A)] of the biffurcated hydrogen bond. Atom O6 (or O6A) of the anion at (−x, y + 1/2, −z + 1) is the other acceptor. The O1W—H12W···O5(x, y + 1, z) (or O6A) interaction complete the hydrogen-bonded network, resulting in anion/water tapes along the [010] direction (Table 1).

Contrary to the crystal structure of (I), in the crystal structure of (II) two water molecules and a hydrogensulfate(VI) anion form, through symmetry operations, a hydrogen-bonded sheet. However, the chlorate(VII) anion/water tapes in (I) and the hydrogensulfate(VI) anion/water layers in (II) exhibit largely similar hydrogen-bonding patterns. This similarity results from (i) similar occupancy of the holes at the surface of the strychnine sheet by the anion (see Fig. 2b) and (ii) the similar environment of the protonated tertiary amine atom, N2, of the strychnine molecule, which in (II) is again the donor in a biffurcated hydrogen bond to the anion and water molecule (Fig. 3b). However, whereas two anions and a water molecule are connected by the biffurcated hydrogen bond in (I), the equivalent interaction in (II) also involves the other water molecule (O2W). The layer results from the fact that besides participating in the N2—H22···O4 hydrogen bond, atom O4 of the hydrogensulfate(VI) anion also acts as a donor in a hydrogen bond to the O1W water molecule from the (−x + 1, y − 1/2, −z + 2) position (Table 2).

The holes at the surface of the strychnine bilayer sheet in (III) are occupied by the O2W water molecules (Fig. 2c), and atom N2 of the strychnine molecule acts as a donor of a hydrogen bond of which atom O4 of the dihydrogenphosphate(V) anion is the only acceptor (Fig. 3c). The anion/water layer that results from the hydrogen-bond network formed by the dihydrogenphosphate(V) anions and water molecules is quite different from the layers in (II). In (III), each O atom of the anion participates in short hydrogen bonds (Table 3). Atoms O3 and O5 atoms of the anion act as hydrogen-bond donors to water molecule O1W and atom O6 in the adjacent anion at (−x, y + 1/2, −z + 2), respectively. Each of the two remaining O atoms (O4 and O6) acts as an acceptor of three hydrogen bonds; besides the above-mentioned interactions with atom O5 or N2 as donor, water molecules O1W and O2W, as bridges, are the donors of the other two bonds.

In summary, the chlorate(VII), hydrogensulfate(VI) and dihydrogenphosphate(V) anions are recognized by similar strychnine self-assembled bilayers in (I), (I) and (III), respectively. However, the molecular recognition of the anions, resulting from the control of their donor/acceptor sites, shows a great diversity of non-covalent interactions inside the water/anion sheet. The various hydrogen-bonding patterns in the anion/water sheet are determined by the different numbers of water molecules and especially by the different occupancy of the holes at the surface of the strychnine bilayer, by the anion in (I) and (II), and by a water molecule in (III). Furthermore, the formation of bifurcated hydrogen bonds or participation of one acceptor in several intermolecular interactions cause the surfaces of both the water/anion and the strychnine sheets to fit well in accordance with their donor/acceptor properties.

S2. Experimental

Strychnine (POCh, Poland) and a suitable acid were dissolved in water in a molar ratio of 1:1. Crystals of (I), (II) and (III) were grew after slow evaporation of the solvent.

S3. Refinement

Atoms O4A, O5A and O6A in (I) have an occupancy of 0.327 (7) and were refined isotropically. All H atoms were located from difference maps and then treated as riding, with C—H distances of 0.95–1.00 Å, N—H distances of 0.93 Å and O—H distances of 0.84–0.86 Å. The absolute structures of (I)–(III) were determined from the known absolute configuration of strychnine (Robertson & Beevers, 1951) and confirmed by the values of the Flack (1983) parameter.

Computing details

For all compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2001); cell refinement: CrysAlis RED (Oxford Diffraction, 2001); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT (Bruker, 1999). Software used to prepare material for publication: SHELXL97 for (I), (II); SHELXL97 (Sheldrick, 1997) for (III).

Figures

	Fig. 1. The independent components in (a) compound (I), (b) compound (II) and (c) compound (III), with the atom-numbering schemes. Displacement ellipsoids are shown at the 50% probability level. The anion in (I) is disordered over two sets of sites with occupancies of 0.673 (7) and 0.327 (7).
	Fig. 2. The molecular packing of (a) (I), (b) (II) and (c) (III), showing the similarity of the strychnine bilayers and the variety of their water/anion environments. For clarity, H atoms have been omited.
	Fig. 3. The hydrogen bonds of the anion/water tape in the structure of (I) (a) and the anion/water layers in the crystals of (II) (b) and (III) (c). Bonds to the two alternative positions of the anion in (I) are distinguished by solid and open dashed lines.

(I) Strychninium chlorate(VII) monohydrate

Crystal data

C21H23N2O2^+·ClO4^−·H2O	F(000) = 476
Mr = 452.88	Dx = 1.525 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2062 reflections
a = 7.8016 (8) Å	θ = 3.5–29.0°
b = 7.6538 (9) Å	µ = 0.24 mm^−1
c = 16.5597 (17) Å	T = 100 K
β = 93.966 (9)°	Plate, colourless
V = 986.44 (18) Å^3	0.10 × 0.10 × 0.05 mm
Z = 2

Data collection

Kuma KM-4 CCD diffractometer	3083 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.084
Graphite monochromator	θmax = 29.0°, θmin = 3.5°
ω scans	h = −10→10
13754 measured reflections	k = −10→8
4042 independent reflections	l = −22→22

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.055	H-atom parameters constrained
wR(F^2) = 0.140	w = 1/[σ^2(Fo^2) + (0.0818P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
4042 reflections	Δρmax = 0.91 e Å^−3
293 parameters	Δρmin = −0.87 e Å^−3
40 restraints	Absolute structure: from known structure (Robertson & Beevers, 1951), Flack (1983), 1225 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.09 (10)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	1.0320 (3)	0.9704 (4)	0.21457 (14)	0.0211 (5)
O2	0.9146 (3)	0.5133 (3)	0.03046 (16)	0.0256 (6)
N1	0.7777 (3)	0.5609 (4)	0.14534 (16)	0.0148 (6)
N2	0.5137 (4)	0.8238 (4)	0.35552 (17)	0.0176 (6)
H22	0.4188	0.8176	0.3864	0.021*
C1	0.5933 (5)	0.3442 (5)	0.0637 (2)	0.0203 (7)
H1	0.6772	0.3173	0.0267	0.024*
C2	0.4300 (5)	0.2668 (5)	0.0573 (2)	0.0219 (7)
H2	0.4031	0.1860	0.0147	0.026*
C3	0.3072 (5)	0.3041 (5)	0.1108 (2)	0.0235 (8)
H3A	0.1972	0.2506	0.1043	0.028*
C4	0.3440 (4)	0.4201 (4)	0.1744 (2)	0.0188 (7)
H4	0.2611	0.4439	0.2124	0.023*
C5	0.5050 (4)	0.5010 (4)	0.18157 (19)	0.0163 (6)
C6	0.6268 (4)	0.4621 (4)	0.12664 (19)	0.0167 (6)
C7	0.5773 (4)	0.6253 (4)	0.2461 (2)	0.0143 (6)
C8	0.7456 (4)	0.6905 (4)	0.2096 (2)	0.0138 (6)
H8	0.8429	0.6889	0.2522	0.017*
C9	0.8976 (4)	0.5985 (4)	0.0919 (2)	0.0183 (7)
C10	1.0118 (4)	0.7532 (4)	0.1146 (2)	0.0197 (7)
H10A	1.0721	0.7878	0.0665	0.024*
H10B	1.1003	0.7149	0.1566	0.024*
C11	0.9205 (4)	0.9167 (4)	0.1466 (2)	0.0168 (7)
H11	0.9148	1.0103	0.1044	0.020*
C12	0.9844 (5)	1.1313 (5)	0.2512 (2)	0.0238 (8)
H12A	0.9300	1.2092	0.2092	0.029*
H12B	1.0889	1.1902	0.2752	0.029*
C13	0.8630 (4)	1.1014 (5)	0.3153 (2)	0.0199 (7)
H13	0.8996	1.1264	0.3700	0.024*
C14	0.7045 (4)	1.0407 (4)	0.2984 (2)	0.0188 (7)
C15	0.5841 (4)	1.0065 (4)	0.3624 (2)	0.0198 (7)
H15A	0.4882	1.0914	0.3573	0.024*
H15B	0.6450	1.0225	0.4164	0.024*
C16	0.6416 (4)	0.6876 (4)	0.3873 (2)	0.0192 (7)
H16A	0.6173	0.6511	0.4427	0.023*
H16B	0.7602	0.7339	0.3884	0.023*
C17	0.6191 (4)	0.5352 (4)	0.3289 (2)	0.0182 (7)
H17A	0.5238	0.4583	0.3431	0.022*
H17B	0.7258	0.4654	0.3284	0.022*
C18	0.7374 (4)	0.8668 (4)	0.16764 (19)	0.0140 (6)
H18	0.6710	0.8470	0.1146	0.017*
C19	0.6344 (4)	1.0032 (4)	0.2125 (2)	0.0157 (6)
H19	0.6309	1.1147	0.1810	0.019*
C20	0.4520 (4)	0.9315 (4)	0.2140 (2)	0.0161 (7)
H20A	0.3754	1.0218	0.2346	0.019*
H20B	0.4077	0.8993	0.1585	0.019*
C21	0.4548 (4)	0.7722 (4)	0.2683 (2)	0.0162 (6)
H21	0.3357	0.7237	0.2679	0.019*
Cl1	0.14780 (12)	0.47191 (15)	0.41366 (6)	0.0361 (3)
O3	0.0787 (4)	0.5136 (5)	0.33459 (17)	0.0480 (9)
O4	0.2722 (6)	0.5986 (6)	0.4434 (3)	0.0331 (11)	0.673 (7)
O5	0.2463 (5)	0.3113 (5)	0.4020 (3)	0.0344 (12)	0.673 (7)
O6	0.0206 (8)	0.4325 (12)	0.4667 (4)	0.0734 (19)	0.673 (7)
O4A	0.3173 (8)	0.5295 (16)	0.4352 (7)	0.038 (3)*	0.327 (7)
O5A	0.0523 (17)	0.6000 (16)	0.4575 (8)	0.072 (4)*	0.327 (7)
O6A	0.0732 (13)	0.3358 (12)	0.4598 (6)	0.038 (3)*	0.327 (7)
O1W	0.2410 (4)	0.9535 (5)	0.43438 (19)	0.0451 (8)
H11W	0.1795	0.9016	0.4684	0.068*
H12W	0.2203	1.0640	0.4350	0.068*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0138 (10)	0.0210 (12)	0.0282 (12)	−0.0025 (10)	−0.0002 (9)	−0.0054 (11)
O2	0.0265 (12)	0.0265 (14)	0.0245 (13)	−0.0009 (11)	0.0068 (11)	−0.0037 (11)
N1	0.0164 (13)	0.0112 (12)	0.0168 (14)	−0.0013 (10)	0.0015 (11)	−0.0030 (10)
N2	0.0169 (14)	0.0172 (14)	0.0192 (14)	−0.0029 (11)	0.0042 (12)	−0.0007 (11)
C1	0.0263 (18)	0.0171 (16)	0.0171 (16)	−0.0001 (14)	0.0000 (14)	0.0028 (13)
C2	0.0309 (19)	0.0143 (15)	0.0190 (17)	−0.0043 (14)	−0.0074 (15)	0.0004 (13)
C3	0.0250 (18)	0.0155 (17)	0.0293 (19)	−0.0068 (13)	−0.0042 (16)	0.0037 (14)
C4	0.0171 (16)	0.0151 (16)	0.0240 (17)	−0.0015 (12)	−0.0006 (14)	0.0045 (13)
C5	0.0197 (15)	0.0128 (15)	0.0156 (14)	−0.0008 (12)	−0.0042 (12)	0.0053 (12)
C6	0.0195 (14)	0.0107 (14)	0.0194 (14)	−0.0024 (13)	−0.0023 (12)	0.0039 (13)
C7	0.0146 (14)	0.0103 (13)	0.0177 (15)	−0.0007 (11)	−0.0005 (13)	0.0038 (12)
C8	0.0137 (14)	0.0107 (14)	0.0169 (15)	0.0000 (11)	0.0000 (12)	0.0004 (12)
C9	0.0185 (16)	0.0161 (15)	0.0202 (16)	0.0049 (13)	0.0002 (14)	0.0022 (13)
C10	0.0161 (15)	0.0157 (16)	0.0274 (18)	−0.0020 (13)	0.0019 (14)	0.0010 (14)
C11	0.0126 (15)	0.0153 (15)	0.0222 (16)	−0.0019 (11)	0.0000 (13)	0.0010 (13)
C12	0.0168 (16)	0.0206 (17)	0.034 (2)	−0.0048 (14)	0.0040 (15)	−0.0074 (15)
C13	0.0194 (16)	0.0168 (16)	0.0236 (17)	−0.0019 (13)	0.0015 (14)	−0.0040 (14)
C14	0.0188 (16)	0.0137 (15)	0.0238 (17)	0.0013 (13)	−0.0010 (14)	−0.0018 (13)
C15	0.0202 (16)	0.0156 (17)	0.0236 (17)	−0.0043 (12)	0.0011 (14)	−0.0054 (13)
C16	0.0211 (17)	0.0190 (17)	0.0173 (16)	0.0019 (13)	−0.0009 (14)	−0.0006 (13)
C17	0.0234 (16)	0.0128 (14)	0.0183 (16)	0.0000 (12)	0.0013 (14)	0.0038 (12)
C18	0.0130 (14)	0.0128 (15)	0.0160 (15)	−0.0007 (12)	−0.0007 (12)	−0.0018 (12)
C19	0.0140 (13)	0.0110 (15)	0.0215 (15)	0.0006 (11)	−0.0026 (12)	0.0017 (13)
C20	0.0125 (15)	0.0137 (16)	0.0222 (15)	−0.0010 (11)	0.0009 (13)	0.0026 (12)
C21	0.0140 (15)	0.0140 (14)	0.0204 (16)	−0.0021 (12)	0.0000 (13)	−0.0028 (13)
Cl1	0.0313 (5)	0.0430 (6)	0.0326 (5)	−0.0156 (4)	−0.0074 (4)	0.0043 (5)
O3	0.0461 (17)	0.054 (2)	0.0403 (17)	0.0195 (16)	−0.0203 (15)	−0.0117 (16)
O4	0.022 (2)	0.039 (3)	0.037 (2)	0.000 (2)	−0.0042 (19)	−0.008 (2)
O5	0.030 (2)	0.021 (2)	0.050 (3)	−0.0011 (17)	−0.010 (2)	0.0042 (19)
O6	0.058 (3)	0.095 (5)	0.072 (4)	−0.029 (3)	0.041 (3)	−0.035 (3)
O1W	0.0307 (15)	0.053 (2)	0.0543 (19)	−0.0033 (16)	0.0183 (14)	−0.0129 (18)

Geometric parameters (Å, º)

O1—C12	1.433 (4)	C12—C13	1.489 (5)
O1—C11	1.435 (4)	C12—H12A	0.9900
O2—C9	1.223 (4)	C12—H12B	0.9900
N1—C9	1.363 (4)	C13—C14	1.332 (5)
N1—C6	1.415 (4)	C13—H13	0.9500
N1—C8	1.488 (4)	C14—C15	1.488 (5)
N2—C15	1.504 (4)	C14—C19	1.516 (5)
N2—C16	1.512 (4)	C15—H15A	0.9900
N2—C21	1.536 (4)	C15—H15B	0.9900
N2—H22	0.9300	C16—C17	1.518 (5)
C1—C6	1.389 (5)	C16—H16A	0.9900
C1—C2	1.403 (5)	C16—H16B	0.9900
C1—H1	0.9500	C17—H17A	0.9900
C2—C3	1.379 (6)	C17—H17B	0.9900
C2—H2	0.9500	C18—C19	1.540 (4)
C3—C4	1.392 (5)	C18—H18	1.0000
C3—H3A	0.9500	C19—C20	1.527 (4)
C4—C5	1.398 (5)	C19—H19	1.0000
C4—H4	0.9500	C20—C21	1.515 (5)
C5—C6	1.392 (5)	C20—H20A	0.9900
C5—C7	1.511 (4)	C20—H20B	0.9900
C7—C21	1.537 (4)	C21—H21	1.0000
C7—C17	1.548 (5)	Cl1—O6	1.402 (3)
C7—C8	1.565 (4)	Cl1—O4A	1.416 (4)
C8—C18	1.517 (4)	Cl1—O3	1.417 (3)
C8—H8	1.0000	Cl1—O4	1.435 (3)
C9—C10	1.513 (5)	Cl1—O6A	1.438 (4)
C10—C11	1.552 (5)	Cl1—O5A	1.455 (5)
C10—H10A	0.9900	Cl1—O5	1.470 (3)
C10—H10B	0.9900	O1W—H11W	0.86
C11—C18	1.542 (4)	O1W—H12W	0.86
C11—H11	1.0000
C12—O1—C11	114.7 (3)	C14—C13—C12	122.0 (3)
C9—N1—C6	124.7 (3)	C14—C13—H13	119.0
C9—N1—C8	118.7 (3)	C12—C13—H13	119.0
C6—N1—C8	109.5 (2)	C13—C14—C15	122.2 (3)
C15—N2—C16	112.7 (3)	C13—C14—C19	122.2 (3)
C15—N2—C21	113.2 (3)	C15—C14—C19	115.5 (3)
C16—N2—C21	107.3 (2)	C14—C15—N2	110.7 (3)
C15—N2—H22	107.8	C14—C15—H15A	109.5
C16—N2—H22	107.8	N2—C15—H15A	109.5
C21—N2—H22	107.8	C14—C15—H15B	109.5
C6—C1—C2	117.0 (3)	N2—C15—H15B	109.5
C6—C1—H1	121.5	H15A—C15—H15B	108.1
C2—C1—H1	121.5	N2—C16—C17	105.3 (3)
C3—C2—C1	122.1 (3)	N2—C16—H16A	110.7
C3—C2—H2	119.0	C17—C16—H16A	110.7
C1—C2—H2	119.0	N2—C16—H16B	110.7
C2—C3—C4	120.1 (3)	C17—C16—H16B	110.7
C2—C3—H3A	119.9	H16A—C16—H16B	108.8
C4—C3—H3A	119.9	C16—C17—C7	103.3 (3)
C3—C4—C5	118.9 (3)	C16—C17—H17A	111.1
C3—C4—H4	120.5	C7—C17—H17A	111.1
C5—C4—H4	120.5	C16—C17—H17B	111.1
C6—C5—C4	120.0 (3)	C7—C17—H17B	111.1
C6—C5—C7	111.0 (3)	H17A—C17—H17B	109.1
C4—C5—C7	128.9 (3)	C8—C18—C19	112.9 (3)
C1—C6—C5	121.8 (3)	C8—C18—C11	108.3 (3)
C1—C6—N1	128.5 (3)	C19—C18—C11	117.6 (3)
C5—C6—N1	109.7 (3)	C8—C18—H18	105.7
C5—C7—C21	115.0 (3)	C19—C18—H18	105.7
C5—C7—C17	113.0 (3)	C11—C18—H18	105.7
C21—C7—C17	102.2 (3)	C14—C19—C20	109.2 (3)
C5—C7—C8	102.1 (3)	C14—C19—C18	114.5 (3)
C21—C7—C8	114.3 (3)	C20—C19—C18	106.4 (3)
C17—C7—C8	110.7 (3)	C14—C19—H19	108.9
N1—C8—C18	105.6 (2)	C20—C19—H19	108.9
N1—C8—C7	104.6 (2)	C18—C19—H19	108.9
C18—C8—C7	116.8 (3)	C21—C20—C19	108.9 (3)
N1—C8—H8	109.9	C21—C20—H20A	109.9
C18—C8—H8	109.9	C19—C20—H20A	109.9
C7—C8—H8	109.9	C21—C20—H20B	109.9
O2—C9—N1	123.1 (3)	C19—C20—H20B	109.9
O2—C9—C10	121.9 (3)	H20A—C20—H20B	108.3
N1—C9—C10	115.0 (3)	C20—C21—N2	110.1 (3)
C9—C10—C11	116.1 (3)	C20—C21—C7	115.5 (3)
C9—C10—H10A	108.3	N2—C21—C7	105.2 (3)
C11—C10—H10A	108.3	C20—C21—H21	108.6
C9—C10—H10B	108.3	N2—C21—H21	108.6
C11—C10—H10B	108.3	C7—C21—H21	108.6
H10A—C10—H10B	107.4	O6—Cl1—O3	112.7 (4)
O1—C11—C18	114.5 (3)	O4A—Cl1—O3	116.8 (5)
O1—C11—C10	103.3 (3)	O6—Cl1—O4	114.9 (3)
C18—C11—C10	109.4 (3)	O3—Cl1—O4	111.7 (3)
O1—C11—H11	109.8	O4A—Cl1—O6A	119.8 (6)
C18—C11—H11	109.8	O3—Cl1—O6A	120.8 (5)
C10—C11—H11	109.8	O4A—Cl1—O5A	99.5 (8)
O1—C12—C13	111.5 (3)	O3—Cl1—O5A	97.7 (6)
O1—C12—H12A	109.3	O6A—Cl1—O5A	89.0 (7)
C13—C12—H12A	109.3	O6—Cl1—O5	107.5 (4)
O1—C12—H12B	109.3	O3—Cl1—O5	103.7 (2)
C13—C12—H12B	109.3	O4—Cl1—O5	105.3 (3)
H12A—C12—H12B	108.0	H11W—O1W—H12W	109.4
C6—C1—C2—C3	−0.3 (5)	C12—C13—C14—C15	178.5 (3)
C1—C2—C3—C4	−0.9 (5)	C12—C13—C14—C19	−2.0 (5)
C2—C3—C4—C5	1.8 (5)	C13—C14—C15—N2	−127.3 (3)
C3—C4—C5—C6	−1.4 (5)	C19—C14—C15—N2	53.1 (4)
C3—C4—C5—C7	−177.6 (3)	C16—N2—C15—C14	76.5 (4)
C2—C1—C6—C5	0.6 (5)	C21—N2—C15—C14	−45.6 (4)
C2—C1—C6—N1	−178.2 (3)	C15—N2—C16—C17	−140.5 (3)
C4—C5—C6—C1	0.2 (5)	C21—N2—C16—C17	−15.2 (3)
C7—C5—C6—C1	177.0 (3)	N2—C16—C17—C7	34.9 (3)
C4—C5—C6—N1	179.2 (3)	C5—C7—C17—C16	−165.2 (3)
C7—C5—C6—N1	−4.0 (4)	C21—C7—C17—C16	−41.1 (3)
C9—N1—C6—C1	21.0 (5)	C8—C7—C17—C16	81.0 (3)
C8—N1—C6—C1	170.9 (3)	N1—C8—C18—C19	156.1 (2)
C9—N1—C6—C5	−158.0 (3)	C7—C8—C18—C19	40.5 (4)
C8—N1—C6—C5	−8.0 (4)	N1—C8—C18—C11	−71.8 (3)
C6—C5—C7—C21	137.6 (3)	C7—C8—C18—C11	172.5 (3)
C4—C5—C7—C21	−45.9 (4)	O1—C11—C18—C8	−73.9 (3)
C6—C5—C7—C17	−105.6 (3)	C10—C11—C18—C8	41.5 (4)
C4—C5—C7—C17	70.9 (4)	O1—C11—C18—C19	55.5 (4)
C6—C5—C7—C8	13.3 (3)	C10—C11—C18—C19	170.9 (3)
C4—C5—C7—C8	−170.3 (3)	C13—C14—C19—C20	178.7 (3)
C9—N1—C8—C18	44.2 (4)	C15—C14—C19—C20	−1.8 (4)
C6—N1—C8—C18	−107.8 (3)	C13—C14—C19—C18	59.5 (4)
C9—N1—C8—C7	167.9 (3)	C15—C14—C19—C18	−121.0 (3)
C6—N1—C8—C7	16.0 (3)	C8—C18—C19—C14	59.6 (3)
C5—C7—C8—N1	−17.0 (3)	C11—C18—C19—C14	−67.6 (4)
C21—C7—C8—N1	−141.8 (3)	C8—C18—C19—C20	−61.1 (3)
C17—C7—C8—N1	103.5 (3)	C11—C18—C19—C20	171.6 (3)
C5—C7—C8—C18	99.2 (3)	C14—C19—C20—C21	−55.9 (3)
C21—C7—C8—C18	−25.5 (4)	C18—C19—C20—C21	68.2 (3)
C17—C7—C8—C18	−140.2 (3)	C19—C20—C21—N2	62.7 (3)
C6—N1—C9—O2	−21.4 (5)	C19—C20—C21—C7	−56.1 (4)
C8—N1—C9—O2	−168.8 (3)	C15—N2—C21—C20	−10.6 (3)
C6—N1—C9—C10	159.6 (3)	C16—N2—C21—C20	−135.7 (3)
C8—N1—C9—C10	12.2 (4)	C15—N2—C21—C7	114.4 (3)
O2—C9—C10—C11	137.3 (3)	C16—N2—C21—C7	−10.7 (3)
N1—C9—C10—C11	−43.7 (4)	C5—C7—C21—C20	−84.0 (3)
C12—O1—C11—C18	−66.7 (4)	C17—C7—C21—C20	153.1 (3)
C12—O1—C11—C10	174.5 (3)	C8—C7—C21—C20	33.5 (4)
C9—C10—C11—O1	136.4 (3)	C5—C7—C21—N2	154.4 (3)
C9—C10—C11—C18	14.0 (4)	C17—C7—C21—N2	31.6 (3)
C11—O1—C12—C13	88.7 (4)	C8—C7—C21—N2	−88.0 (3)
O1—C12—C13—C14	−66.1 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H22···O1W	0.93	1.95	2.758 (4)	145
N2—H22···O4	0.93	2.27	3.004 (5)	135
N2—H22···O4A	0.93	2.50	3.073 (10)	120
O1W—H11W···O6^i	0.86	1.97	2.709 (5)	143
O1W—H11W···O6A^i	0.86	2.43	3.238 (12)	158
O1W—H12W···O5^ii	0.86	1.98	2.791 (5)	156
O1W—H12W···O6A^ii	0.86	2.42	3.244 (12)	159

Symmetry codes: (i) −x, y+1/2, −z+1; (ii) x, y+1, z.

(II) Strychninium hydrogen sulfate (VI) dihydrate

Crystal data

C21H23N2O2^+·HO4S^−·2H2O	F(000) = 496
Mr = 468.51	Dx = 1.507 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1886 reflections
a = 7.7884 (8) Å	θ = 3.5–27.5°
b = 7.6686 (8) Å	µ = 0.21 mm^−1
c = 17.5780 (18) Å	T = 100 K
β = 100.388 (7)°	Needle, colourles
V = 1032.66 (18) Å^3	0.35 × 0.25 × 0.15 mm
Z = 2

Data collection

Kuma KM-4 CCD diffractometer	3552 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.076
Graphite monochromator	θmax = 27.5°, θmin = 3.5°
ω scans	h = −10→9
6972 measured reflections	k = −9→9
4009 independent reflections	l = −18→22

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.126	w = 1/[σ^2(Fo^2) + (0.0753P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
4009 reflections	Δρmax = 0.33 e Å^−3
289 parameters	Δρmin = −0.55 e Å^−3
1 restraint	Absolute structure: from known structure (Robertson & Beevers, 1951), Flack (1983), 1465 Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.14 (9)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	1.0840 (3)	0.4310 (3)	0.70225 (11)	0.0171 (4)
O2	0.9198 (3)	−0.0316 (3)	0.52768 (12)	0.0221 (5)
N1	0.8127 (3)	0.0140 (3)	0.63901 (13)	0.0146 (5)
N2	0.6123 (3)	0.2719 (3)	0.84398 (13)	0.0142 (5)
H22	0.5288	0.2624	0.8755	0.017*
C1	0.6044 (4)	−0.2025 (4)	0.56144 (16)	0.0177 (6)
H1	0.6780	−0.2299	0.5255	0.021*
C2	0.4418 (4)	−0.2786 (4)	0.55629 (17)	0.0192 (6)
H2	0.4034	−0.3581	0.5153	0.023*
C3	0.3318 (4)	−0.2436 (4)	0.60875 (17)	0.0195 (6)
H3	0.2206	−0.2980	0.6033	0.023*
C4	0.3875 (4)	−0.1268 (4)	0.66980 (16)	0.0166 (6)
H4	0.3151	−0.1024	0.7066	0.020*
C5	0.5502 (4)	−0.0471 (3)	0.67583 (15)	0.0130 (6)
C6	0.6565 (4)	−0.0836 (4)	0.62158 (14)	0.0155 (5)
C7	0.6405 (4)	0.0756 (4)	0.73712 (15)	0.0124 (5)
C8	0.7982 (4)	0.1442 (4)	0.70073 (15)	0.0114 (5)
H8	0.9073	0.1426	0.7407	0.014*
C9	0.9200 (4)	0.0542 (4)	0.58699 (16)	0.0156 (6)
C10	1.0394 (4)	0.2084 (4)	0.60997 (17)	0.0183 (6)
H10A	1.0911	0.2429	0.5647	0.022*
H10B	1.1362	0.1701	0.6511	0.022*
C11	0.9540 (4)	0.3712 (4)	0.63923 (15)	0.0135 (6)
H11	0.9353	0.4617	0.5976	0.016*
C12	1.0443 (4)	0.5923 (4)	0.73722 (17)	0.0191 (6)
H12A	0.9740	0.6676	0.6976	0.023*
H12B	1.1540	0.6545	0.7582	0.023*
C13	0.9443 (4)	0.5575 (4)	0.80131 (17)	0.0183 (6)
H13	0.9978	0.5824	0.8531	0.022*
C14	0.7839 (4)	0.4932 (4)	0.78758 (16)	0.0153 (6)
C15	0.6824 (4)	0.4573 (4)	0.85108 (16)	0.0169 (6)
H15A	0.5842	0.5407	0.8475	0.020*
H15B	0.7590	0.4730	0.9020	0.020*
C16	0.7524 (4)	0.1370 (4)	0.87069 (16)	0.0154 (6)
H16A	0.7501	0.1006	0.9245	0.018*
H16B	0.8694	0.1844	0.8681	0.018*
C17	0.7089 (4)	−0.0164 (4)	0.81521 (15)	0.0140 (5)
H17A	0.6183	−0.0921	0.8307	0.017*
H17B	0.8140	−0.0871	0.8126	0.017*
C18	0.7774 (4)	0.3227 (4)	0.66118 (15)	0.0129 (6)
H18	0.6960	0.3036	0.6110	0.016*
C19	0.6855 (4)	0.4564 (4)	0.70598 (15)	0.0130 (5)
H19	0.6716	0.5683	0.6763	0.016*
C20	0.5038 (4)	0.3836 (4)	0.70964 (16)	0.0140 (6)
H20A	0.4338	0.4726	0.7311	0.017*
H20B	0.4425	0.3528	0.6570	0.017*
C21	0.5242 (4)	0.2221 (4)	0.76095 (15)	0.0132 (6)
H21	0.4058	0.1732	0.7625	0.016*
S1	0.24975 (9)	−0.08189 (9)	0.89124 (4)	0.01541 (17)
O3	0.1683 (3)	−0.0051 (3)	0.81895 (12)	0.0218 (5)
O4	0.4044 (3)	0.0449 (3)	0.92333 (12)	0.0180 (5)
H4A	0.4634	0.0028	0.9639	0.027*
O5	0.3280 (3)	−0.2524 (3)	0.88275 (12)	0.0237 (5)
O6	0.1375 (3)	−0.0836 (3)	0.95010 (12)	0.0252 (5)
O1W	0.4017 (3)	0.4373 (3)	0.95295 (11)	0.0187 (4)
H11W	0.3137	0.3822	0.9646	0.028*
H12W	0.3714	0.5426	0.9398	0.028*
O2W	0.1496 (3)	0.2649 (3)	1.00627 (13)	0.0277 (5)
H21W	0.0551	0.3044	1.0189	0.042*
H22W	0.1282	0.1662	0.9831	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0173 (9)	0.0132 (9)	0.0206 (9)	−0.0015 (9)	0.0027 (8)	−0.0036 (9)
O2	0.0303 (11)	0.0207 (11)	0.0178 (10)	−0.0004 (10)	0.0108 (9)	−0.0050 (8)
N1	0.0197 (12)	0.0103 (11)	0.0146 (11)	−0.0012 (10)	0.0048 (10)	−0.0023 (9)
N2	0.0197 (12)	0.0105 (12)	0.0129 (11)	−0.0006 (10)	0.0044 (10)	−0.0013 (9)
C1	0.0288 (16)	0.0111 (14)	0.0128 (13)	0.0016 (13)	0.0026 (11)	0.0006 (11)
C2	0.0267 (16)	0.0137 (14)	0.0150 (13)	−0.0022 (13)	−0.0023 (12)	0.0007 (11)
C3	0.0227 (15)	0.0140 (14)	0.0199 (14)	−0.0022 (13)	−0.0012 (12)	0.0017 (12)
C4	0.0217 (15)	0.0104 (13)	0.0167 (13)	−0.0007 (12)	0.0006 (11)	0.0019 (10)
C5	0.0185 (13)	0.0082 (14)	0.0111 (11)	0.0023 (11)	−0.0002 (10)	0.0018 (10)
C6	0.0239 (14)	0.0091 (12)	0.0130 (11)	−0.0006 (13)	0.0018 (10)	0.0043 (12)
C7	0.0139 (13)	0.0102 (13)	0.0140 (12)	−0.0017 (11)	0.0048 (10)	−0.0015 (11)
C8	0.0151 (13)	0.0079 (12)	0.0113 (12)	−0.0027 (11)	0.0030 (10)	−0.0002 (10)
C9	0.0200 (14)	0.0135 (14)	0.0138 (13)	0.0015 (12)	0.0047 (11)	−0.0001 (11)
C10	0.0212 (14)	0.0141 (14)	0.0212 (14)	0.0008 (13)	0.0079 (12)	0.0000 (12)
C11	0.0182 (14)	0.0099 (13)	0.0130 (12)	0.0028 (11)	0.0041 (10)	0.0014 (10)
C12	0.0229 (16)	0.0120 (14)	0.0225 (15)	−0.0035 (13)	0.0041 (12)	−0.0030 (12)
C13	0.0252 (16)	0.0127 (14)	0.0164 (13)	−0.0030 (12)	0.0021 (12)	−0.0018 (11)
C14	0.0221 (14)	0.0094 (12)	0.0157 (13)	−0.0024 (12)	0.0064 (11)	−0.0003 (11)
C15	0.0229 (14)	0.0147 (14)	0.0145 (12)	−0.0043 (12)	0.0067 (11)	−0.0028 (11)
C16	0.0180 (14)	0.0131 (14)	0.0146 (13)	−0.0013 (12)	0.0014 (11)	0.0007 (11)
C17	0.0201 (14)	0.0083 (12)	0.0133 (12)	−0.0010 (11)	0.0021 (10)	0.0006 (10)
C18	0.0182 (14)	0.0094 (13)	0.0106 (12)	−0.0007 (11)	0.0008 (10)	0.0005 (10)
C19	0.0165 (12)	0.0086 (13)	0.0145 (12)	−0.0006 (11)	0.0045 (10)	0.0009 (10)
C20	0.0151 (13)	0.0100 (14)	0.0177 (13)	0.0003 (11)	0.0050 (10)	0.0037 (10)
C21	0.0170 (13)	0.0096 (13)	0.0121 (12)	0.0001 (11)	0.0000 (11)	0.0007 (10)
S1	0.0190 (3)	0.0114 (3)	0.0160 (3)	−0.0011 (3)	0.0037 (2)	0.0000 (3)
O3	0.0245 (11)	0.0222 (11)	0.0174 (10)	0.0046 (10)	0.0007 (8)	0.0040 (9)
O4	0.0220 (11)	0.0150 (11)	0.0169 (10)	−0.0033 (9)	0.0032 (8)	0.0015 (8)
O5	0.0317 (12)	0.0136 (11)	0.0242 (11)	0.0012 (10)	0.0007 (10)	−0.0019 (9)
O6	0.0277 (11)	0.0265 (12)	0.0245 (10)	−0.0122 (11)	0.0131 (9)	−0.0045 (10)
O1W	0.0214 (10)	0.0132 (10)	0.0224 (10)	0.0009 (9)	0.0067 (8)	0.0040 (9)
O2W	0.0295 (12)	0.0193 (12)	0.0383 (13)	−0.0025 (11)	0.0171 (11)	−0.0062 (10)

Geometric parameters (Å, º)

O1—C11	1.435 (3)	C12—C13	1.504 (4)
O1—C12	1.439 (4)	C12—H12A	0.9900
O2—C9	1.233 (3)	C12—H12B	0.9900
N1—C9	1.380 (3)	C13—C14	1.324 (4)
N1—C6	1.414 (4)	C13—H13	0.9500
N1—C8	1.493 (3)	C14—C15	1.505 (4)
N2—C16	1.515 (4)	C14—C19	1.526 (4)
N2—C15	1.520 (4)	C15—H15A	0.9900
N2—C21	1.545 (3)	C15—H15B	0.9900
N2—H22	0.9300	C16—C17	1.527 (4)
C1—C2	1.383 (4)	C16—H16A	0.9900
C1—C6	1.399 (4)	C16—H16B	0.9900
C1—H1	0.9500	C17—H17A	0.9900
C2—C3	1.393 (4)	C17—H17B	0.9900
C2—H2	0.9500	C18—C19	1.545 (4)
C3—C4	1.405 (4)	C18—H18	1.0000
C3—H3	0.9500	C19—C20	1.534 (4)
C4—C5	1.393 (4)	C19—H19	1.0000
C4—H4	0.9500	C20—C21	1.523 (4)
C5—C6	1.399 (4)	C20—H20A	0.9900
C5—C7	1.506 (4)	C20—H20B	0.9900
C7—C21	1.548 (4)	C21—H21	1.0000
C7—C17	1.550 (4)	S1—O3	1.440 (2)
C7—C8	1.574 (4)	S1—O5	1.462 (2)
C8—C18	1.531 (4)	S1—O6	1.470 (2)
C8—H8	1.0000	S1—O4	1.572 (2)
C9—C10	1.513 (4)	O4—H4A	0.8400
C10—C11	1.546 (4)	O1W—H11W	0.86
C10—H10A	0.9900	O1W—H12W	0.86
C10—H10B	0.9900	O2W—H21W	0.86
C11—C18	1.539 (4)	O2W—H22W	0.86
C11—H11	1.0000
C11—O1—C12	115.4 (2)	C13—C12—H12B	109.6
C9—N1—C6	125.1 (2)	H12A—C12—H12B	108.1
C9—N1—C8	117.8 (2)	C14—C13—C12	121.9 (3)
C6—N1—C8	109.7 (2)	C14—C13—H13	119.1
C16—N2—C15	112.7 (2)	C12—C13—H13	119.1
C16—N2—C21	107.3 (2)	C13—C14—C15	122.5 (3)
C15—N2—C21	113.6 (2)	C13—C14—C19	122.5 (2)
C16—N2—H22	107.7	C15—C14—C19	114.9 (2)
C15—N2—H22	107.7	C14—C15—N2	109.8 (2)
C21—N2—H22	107.7	C14—C15—H15A	109.7
C2—C1—C6	117.5 (3)	N2—C15—H15A	109.7
C2—C1—H1	121.2	C14—C15—H15B	109.7
C6—C1—H1	121.2	N2—C15—H15B	109.7
C1—C2—C3	122.7 (3)	H15A—C15—H15B	108.2
C1—C2—H2	118.6	N2—C16—C17	105.3 (2)
C3—C2—H2	118.6	N2—C16—H16A	110.7
C2—C3—C4	119.1 (3)	C17—C16—H16A	110.7
C2—C3—H3	120.5	N2—C16—H16B	110.7
C4—C3—H3	120.5	C17—C16—H16B	110.7
C5—C4—C3	119.3 (3)	H16A—C16—H16B	108.8
C5—C4—H4	120.4	C16—C17—C7	102.5 (2)
C3—C4—H4	120.4	C16—C17—H17A	111.3
C4—C5—C6	120.1 (3)	C7—C17—H17A	111.3
C4—C5—C7	129.0 (2)	C16—C17—H17B	111.3
C6—C5—C7	110.8 (2)	C7—C17—H17B	111.3
C1—C6—C5	121.2 (3)	H17A—C17—H17B	109.2
C1—C6—N1	129.0 (2)	C8—C18—C11	107.7 (2)
C5—C6—N1	109.8 (2)	C8—C18—C19	112.5 (2)
C5—C7—C21	115.2 (2)	C11—C18—C19	119.0 (2)
C5—C7—C17	113.0 (2)	C8—C18—H18	105.5
C21—C7—C17	102.4 (2)	C11—C18—H18	105.5
C5—C7—C8	102.5 (2)	C19—C18—H18	105.5
C21—C7—C8	113.9 (2)	C14—C19—C20	109.8 (2)
C17—C7—C8	110.1 (2)	C14—C19—C18	113.7 (2)
N1—C8—C18	106.5 (2)	C20—C19—C18	107.2 (2)
N1—C8—C7	103.8 (2)	C14—C19—H19	108.7
C18—C8—C7	117.2 (2)	C20—C19—H19	108.7
N1—C8—H8	109.7	C18—C19—H19	108.7
C18—C8—H8	109.7	C21—C20—C19	108.8 (2)
C7—C8—H8	109.7	C21—C20—H20A	109.9
O2—C9—N1	122.2 (3)	C19—C20—H20A	109.9
O2—C9—C10	123.4 (3)	C21—C20—H20B	109.9
N1—C9—C10	114.5 (2)	C19—C20—H20B	109.9
C9—C10—C11	116.1 (2)	H20A—C20—H20B	108.3
C9—C10—H10A	108.3	C20—C21—N2	109.9 (2)
C11—C10—H10A	108.3	C20—C21—C7	115.7 (2)
C9—C10—H10B	108.3	N2—C21—C7	104.6 (2)
C11—C10—H10B	108.3	C20—C21—H21	108.8
H10A—C10—H10B	107.4	N2—C21—H21	108.8
O1—C11—C18	115.0 (2)	C7—C21—H21	108.8
O1—C11—C10	103.2 (2)	O3—S1—O5	113.66 (13)
C18—C11—C10	110.2 (2)	O3—S1—O6	113.67 (14)
O1—C11—H11	109.4	O5—S1—O6	112.05 (14)
C18—C11—H11	109.4	O3—S1—O4	104.52 (13)
C10—C11—H11	109.4	O5—S1—O4	106.49 (13)
O1—C12—C13	110.4 (2)	O6—S1—O4	105.53 (12)
O1—C12—H12A	109.6	S1—O4—H4A	109.5
C13—C12—H12A	109.6	H11W—O1W—H12W	109.4
O1—C12—H12B	109.6	H21W—O2W—H22W	109.2
C6—C1—C2—C3	−1.1 (4)	C12—C13—C14—C15	179.8 (3)
C1—C2—C3—C4	−0.2 (5)	C12—C13—C14—C19	−2.5 (5)
C2—C3—C4—C5	0.8 (4)	C13—C14—C15—N2	−128.5 (3)
C3—C4—C5—C6	−0.1 (4)	C19—C14—C15—N2	53.7 (3)
C3—C4—C5—C7	−177.3 (3)	C16—N2—C15—C14	75.3 (3)
C2—C1—C6—C5	1.9 (4)	C21—N2—C15—C14	−47.0 (3)
C2—C1—C6—N1	−178.7 (3)	C15—N2—C16—C17	−142.5 (2)
C4—C5—C6—C1	−1.3 (4)	C21—N2—C16—C17	−16.8 (3)
C7—C5—C6—C1	176.4 (3)	N2—C16—C17—C7	36.6 (3)
C4—C5—C6—N1	179.2 (2)	C5—C7—C17—C16	−166.8 (2)
C7—C5—C6—N1	−3.2 (3)	C21—C7—C17—C16	−42.2 (3)
C9—N1—C6—C1	22.2 (5)	C8—C7—C17—C16	79.2 (3)
C8—N1—C6—C1	171.0 (3)	N1—C8—C18—C11	−71.2 (3)
C9—N1—C6—C5	−158.3 (3)	C7—C8—C18—C11	173.2 (2)
C8—N1—C6—C5	−9.5 (3)	N1—C8—C18—C19	155.8 (2)
C4—C5—C7—C21	−44.9 (4)	C7—C8—C18—C19	40.2 (3)
C6—C5—C7—C21	137.7 (2)	O1—C11—C18—C8	−77.0 (3)
C4—C5—C7—C17	72.4 (4)	C10—C11—C18—C8	39.2 (3)
C6—C5—C7—C17	−105.0 (3)	O1—C11—C18—C19	52.5 (3)
C4—C5—C7—C8	−169.2 (3)	C10—C11—C18—C19	168.7 (2)
C6—C5—C7—C8	13.5 (3)	C13—C14—C19—C20	−179.8 (3)
C9—N1—C8—C18	44.4 (3)	C15—C14—C19—C20	−2.0 (3)
C6—N1—C8—C18	−107.0 (2)	C13—C14—C19—C18	60.1 (4)
C9—N1—C8—C7	168.7 (2)	C15—C14—C19—C18	−122.1 (3)
C6—N1—C8—C7	17.3 (3)	C8—C18—C19—C14	61.1 (3)
C5—C7—C8—N1	−17.9 (3)	C11—C18—C19—C14	−66.2 (3)
C21—C7—C8—N1	−143.1 (2)	C8—C18—C19—C20	−60.5 (3)
C17—C7—C8—N1	102.6 (2)	C11—C18—C19—C20	172.3 (2)
C5—C7—C8—C18	99.1 (3)	C14—C19—C20—C21	−56.1 (3)
C21—C7—C8—C18	−26.0 (3)	C18—C19—C20—C21	67.8 (3)
C17—C7—C8—C18	−140.4 (2)	C19—C20—C21—N2	62.1 (3)
C6—N1—C9—O2	−22.1 (5)	C19—C20—C21—C7	−56.0 (3)
C8—N1—C9—O2	−168.7 (3)	C16—N2—C21—C20	−134.5 (2)
C6—N1—C9—C10	159.3 (3)	C15—N2—C21—C20	−9.4 (3)
C8—N1—C9—C10	12.7 (4)	C16—N2—C21—C7	−9.7 (3)
O2—C9—C10—C11	135.6 (3)	C15—N2—C21—C7	115.4 (2)
N1—C9—C10—C11	−45.8 (3)	C5—C7—C21—C20	−83.9 (3)
C12—O1—C11—C18	−64.6 (3)	C17—C7—C21—C20	152.9 (2)
C12—O1—C11—C10	175.3 (2)	C8—C7—C21—C20	34.1 (3)
C9—C10—C11—O1	140.0 (2)	C5—C7—C21—N2	155.0 (2)
C9—C10—C11—C18	16.7 (3)	C17—C7—C21—N2	31.9 (3)
C11—O1—C12—C13	88.9 (3)	C8—C7—C21—N2	−86.9 (2)
O1—C12—C13—C14	−66.9 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H22···O4	0.93	2.17	2.900 (3)	134
N2—H22···O1W	0.93	2.26	3.017 (3)	138
O1W—H11W···O2W	0.86	1.82	2.673 (3)	170
O1W—H12W···O5^i	0.86	1.86	2.694 (3)	162
O2W—H21W···O6^ii	0.86	1.89	2.749 (3)	173
O2W—H22W···O6	0.86	2.01	2.845 (3)	164
O4—H4A···O1W^iii	0.84	1.71	2.551 (3)	174

Symmetry codes: (i) x, y+1, z; (ii) −x, y+1/2, −z+2; (iii) −x+1, y−1/2, −z+2.

(III) Strychninium dihydrogen phosphate(V) dihydrate

Crystal data

C21H23N2O2^+·H2O4P^−·2H2O	F(000) = 496
Mr = 468.43	Dx = 1.477 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1674 reflections
a = 7.6407 (12) Å	θ = 3.5–27.0°
b = 7.6624 (9) Å	µ = 0.18 mm^−1
c = 17.992 (2) Å	T = 100 K
β = 91.203 (12)°	Plate, colourless
V = 1053.1 (2) Å^3	0.15 × 0.10 × 0.06 mm
Z = 2

Data collection

Kuma KM-4 CCD diffractometer	2421 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.056
Graphite monochromator	θmax = 27.0°, θmin = 3.5°
ω scans	h = −9→9
7082 measured reflections	k = −9→8
3353 independent reflections	l = −22→22

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.054	H-atom parameters constrained
wR(F^2) = 0.083	w = 1/[σ^2(Fo^2) + (0.0241P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
3353 reflections	Δρmax = 0.23 e Å^−3
289 parameters	Δρmin = −0.24 e Å^−3
1 restraint	Absolute structure: from known structure (Robertson & Beevers, 1951), Flack (1983), 886 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.05 (14)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	1.0260 (3)	0.3554 (3)	0.70326 (12)	0.0195 (6)
O2	0.9172 (3)	−0.0852 (3)	0.52588 (12)	0.0212 (6)
N1	0.7684 (3)	−0.0447 (4)	0.63359 (14)	0.0133 (7)
N2	0.4909 (3)	0.2025 (4)	0.83230 (14)	0.0143 (7)
H22	0.3939	0.1899	0.8622	0.017*
C1	0.5888 (5)	−0.2645 (5)	0.55887 (18)	0.0193 (8)
H1	0.6780	−0.2907	0.5246	0.023*
C2	0.4247 (5)	−0.3436 (5)	0.55375 (19)	0.0204 (9)
H2	0.4018	−0.4248	0.5148	0.024*
C3	0.2936 (5)	−0.3073 (5)	0.60392 (18)	0.0205 (9)
H3	0.1821	−0.3612	0.5983	0.025*
C4	0.3260 (5)	−0.1914 (5)	0.66256 (19)	0.0159 (8)
H4	0.2386	−0.1693	0.6982	0.019*
C5	0.4884 (4)	−0.1085 (5)	0.66822 (17)	0.0140 (8)
C6	0.6166 (4)	−0.1450 (4)	0.61658 (17)	0.0140 (8)
C7	0.5575 (4)	0.0136 (4)	0.72794 (19)	0.0132 (8)
C8	0.7318 (4)	0.0804 (4)	0.69469 (18)	0.0129 (8)
H8	0.8276	0.0742	0.7333	0.015*
C9	0.8962 (4)	−0.0026 (5)	0.5831 (2)	0.0160 (8)
C10	1.0105 (4)	0.1502 (5)	0.60675 (19)	0.0173 (8)
H10A	1.0752	0.1902	0.5628	0.021*
H10B	1.0981	0.1073	0.6437	0.021*
C11	0.9174 (4)	0.3096 (5)	0.64035 (18)	0.0160 (8)
H11	0.9167	0.4077	0.6037	0.019*
C12	0.9796 (5)	0.5157 (5)	0.7401 (2)	0.0213 (9)
H12A	0.9306	0.5991	0.7031	0.026*
H12B	1.0859	0.5688	0.7630	0.026*
C13	0.8476 (5)	0.4826 (5)	0.79900 (19)	0.0186 (9)
H13	0.8799	0.5029	0.8495	0.022*
C14	0.6865 (4)	0.4257 (4)	0.78276 (19)	0.0150 (8)
C15	0.5587 (4)	0.3869 (5)	0.84205 (18)	0.0175 (8)
H15A	0.4601	0.4705	0.8389	0.021*
H15B	0.6163	0.3993	0.8916	0.021*
C16	0.6245 (5)	0.0676 (4)	0.85649 (19)	0.0159 (8)
H16A	0.6050	0.0297	0.9083	0.019*
H16B	0.7448	0.1143	0.8529	0.019*
C17	0.5950 (4)	−0.0820 (5)	0.80253 (17)	0.0155 (8)
H17A	0.4941	−0.1546	0.8170	0.019*
H17B	0.7004	−0.1567	0.7995	0.019*
C18	0.7293 (4)	0.2622 (4)	0.65908 (19)	0.0146 (8)
H18	0.6661	0.2482	0.6102	0.018*
C19	0.6212 (4)	0.3947 (5)	0.70332 (18)	0.0141 (8)
H19A	0.6201	0.5086	0.6762	0.017*
C20	0.4340 (4)	0.3226 (5)	0.70426 (19)	0.0153 (8)
H20A	0.3540	0.4109	0.7249	0.018*
H20B	0.3935	0.2946	0.6530	0.018*
C21	0.4327 (4)	0.1595 (5)	0.75169 (18)	0.0160 (8)
H21	0.3108	0.1121	0.7521	0.019*
P1	0.16440 (15)	0.22066 (15)	0.98020 (6)	0.0333 (3)
O3	0.2926 (4)	0.2198 (4)	1.05036 (13)	0.0492 (9)
H3A	0.3945	0.2437	1.0370	0.074*
O4	0.2377 (3)	0.1028 (3)	0.92117 (13)	0.0276 (7)
O5	0.1703 (3)	0.4093 (4)	0.94618 (15)	0.0472 (9)
H5A	0.1079	0.4765	0.9713	0.071*
O6	−0.0144 (4)	0.1752 (4)	1.00773 (18)	0.0589 (10)
O1W	0.3748 (4)	−0.2095 (4)	0.97335 (14)	0.0510 (10)
H11W	0.3503	−0.1080	0.9557	0.077*
H12W	0.2802	−0.2634	0.9841	0.077*
O2W	0.0398 (3)	−0.1224 (4)	0.83054 (13)	0.0355 (7)
H21W	−0.0019	−0.1976	0.8609	0.053*
H22W	0.1036	−0.0482	0.8546	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0144 (13)	0.0220 (15)	0.0220 (14)	−0.0020 (11)	−0.0002 (10)	−0.0074 (12)
O2	0.0224 (14)	0.0238 (15)	0.0175 (14)	0.0002 (12)	0.0057 (11)	−0.0053 (12)
N1	0.0156 (16)	0.0123 (17)	0.0122 (15)	−0.0021 (13)	0.0032 (13)	−0.0005 (13)
N2	0.0131 (16)	0.0155 (18)	0.0144 (15)	0.0010 (14)	0.0055 (12)	−0.0007 (14)
C1	0.026 (2)	0.0161 (19)	0.0162 (19)	0.0013 (19)	0.0047 (16)	−0.0021 (17)
C2	0.033 (2)	0.014 (2)	0.0139 (19)	0.0014 (18)	−0.0048 (17)	−0.0003 (16)
C3	0.021 (2)	0.019 (2)	0.022 (2)	0.0004 (18)	−0.0029 (16)	0.0041 (17)
C4	0.0180 (19)	0.0125 (19)	0.0175 (19)	0.0007 (16)	0.0024 (16)	0.0012 (16)
C5	0.0182 (19)	0.0122 (19)	0.0115 (18)	−0.0004 (17)	0.0004 (15)	0.0014 (16)
C6	0.017 (2)	0.016 (2)	0.0084 (18)	0.0001 (17)	−0.0022 (15)	0.0054 (16)
C7	0.019 (2)	0.0102 (19)	0.0110 (18)	0.0022 (16)	0.0004 (15)	−0.0013 (15)
C8	0.0129 (19)	0.014 (2)	0.0120 (19)	−0.0023 (16)	0.0011 (15)	−0.0024 (16)
C9	0.015 (2)	0.015 (2)	0.018 (2)	0.0056 (17)	−0.0009 (16)	0.0039 (17)
C10	0.0126 (19)	0.019 (2)	0.021 (2)	−0.0021 (16)	0.0035 (16)	0.0019 (17)
C11	0.016 (2)	0.017 (2)	0.0149 (19)	−0.0015 (17)	0.0026 (16)	0.0031 (16)
C12	0.022 (2)	0.016 (2)	0.027 (2)	−0.0006 (18)	0.0001 (18)	−0.0068 (18)
C13	0.022 (2)	0.017 (2)	0.017 (2)	−0.0016 (17)	0.0025 (16)	−0.0044 (16)
C14	0.0179 (19)	0.0068 (19)	0.0206 (19)	−0.0013 (16)	0.0070 (16)	0.0002 (16)
C15	0.0179 (19)	0.014 (2)	0.020 (2)	−0.0030 (17)	0.0028 (16)	−0.0039 (17)
C16	0.021 (2)	0.013 (2)	0.014 (2)	−0.0005 (17)	−0.0017 (16)	0.0013 (16)
C17	0.0171 (19)	0.013 (2)	0.0164 (19)	0.0022 (17)	0.0043 (15)	0.0022 (16)
C18	0.016 (2)	0.015 (2)	0.0122 (17)	0.0001 (16)	−0.0024 (15)	−0.0025 (15)
C19	0.0138 (18)	0.0110 (19)	0.0174 (18)	0.0020 (16)	−0.0007 (15)	0.0028 (16)
C20	0.0111 (19)	0.015 (2)	0.020 (2)	−0.0004 (16)	−0.0002 (15)	0.0010 (16)
C21	0.0157 (19)	0.018 (2)	0.0144 (19)	0.0003 (16)	−0.0012 (15)	−0.0034 (16)
P1	0.0432 (7)	0.0283 (7)	0.0293 (6)	−0.0048 (6)	0.0221 (5)	−0.0039 (6)
O3	0.103 (3)	0.0310 (17)	0.0134 (14)	−0.022 (2)	0.0013 (15)	−0.0023 (15)
O4	0.0221 (15)	0.0384 (18)	0.0227 (15)	−0.0092 (13)	0.0088 (12)	−0.0097 (13)
O5	0.050 (2)	0.0336 (19)	0.059 (2)	0.0100 (17)	0.0330 (17)	0.0188 (17)
O6	0.055 (2)	0.034 (2)	0.090 (2)	−0.0016 (16)	0.0607 (18)	0.0010 (18)
O1W	0.057 (2)	0.048 (2)	0.0468 (19)	−0.0339 (17)	−0.0206 (16)	0.0231 (16)
O2W	0.0351 (16)	0.0399 (19)	0.0314 (16)	−0.0118 (15)	−0.0007 (13)	−0.0073 (15)

Geometric parameters (Å, º)

O1—C11	1.433 (4)	C12—C13	1.500 (5)
O1—C12	1.443 (4)	C12—H12A	0.9900
O2—C9	1.222 (4)	C12—H12B	0.9900
N1—C9	1.385 (4)	C13—C14	1.333 (4)
N1—C6	1.419 (4)	C13—H13	0.9500
N1—C8	1.490 (4)	C14—C15	1.491 (4)
N2—C16	1.511 (4)	C14—C19	1.522 (4)
N2—C15	1.514 (4)	C15—H15A	0.9900
N2—C21	1.543 (4)	C15—H15B	0.9900
N2—H22	0.9300	C16—C17	1.516 (5)
C1—C2	1.394 (5)	C16—H16A	0.9900
C1—C6	1.397 (5)	C16—H16B	0.9900
C1—H1	0.9500	C17—H17A	0.9900
C2—C3	1.391 (5)	C17—H17B	0.9900
C2—H2	0.9500	C18—C19	1.540 (4)
C3—C4	1.397 (5)	C18—H18	1.0000
C3—H3	0.9500	C19—C20	1.534 (4)
C4—C5	1.396 (5)	C19—H19A	1.0000
C4—H4	0.9500	C20—C21	1.513 (5)
C5—C6	1.393 (4)	C20—H20A	0.9900
C5—C7	1.511 (5)	C20—H20B	0.9900
C7—C21	1.537 (4)	C21—H21	1.0000
C7—C17	1.550 (4)	P1—O6	1.504 (3)
C7—C8	1.558 (5)	P1—O4	1.511 (3)
C8—C18	1.534 (4)	P1—O5	1.570 (3)
C8—H8	1.0000	P1—O3	1.582 (3)
C9—C10	1.516 (5)	O3—H3A	0.8400
C10—C11	1.543 (5)	O5—H5A	0.8400
C10—H10A	0.9900	O1W—H11W	0.86
C10—H10B	0.9900	O1W—H12W	0.86
C11—C18	1.527 (4)	O2W—H21W	0.86
C11—H11	1.0000	O2W—H22W	0.86
C11—O1—C12	115.3 (3)	H12A—C12—H12B	108.1
C9—N1—C6	124.7 (3)	C14—C13—C12	122.2 (3)
C9—N1—C8	118.7 (3)	C14—C13—H13	118.9
C6—N1—C8	110.0 (2)	C12—C13—H13	118.9
C16—N2—C15	112.2 (3)	C13—C14—C15	121.6 (3)
C16—N2—C21	107.7 (2)	C13—C14—C19	122.7 (3)
C15—N2—C21	113.5 (2)	C15—C14—C19	115.7 (3)
C16—N2—H22	107.7	C14—C15—N2	109.3 (3)
C15—N2—H22	107.7	C14—C15—H15A	109.8
C21—N2—H22	107.7	N2—C15—H15A	109.8
C2—C1—C6	117.2 (3)	C14—C15—H15B	109.8
C2—C1—H1	121.4	N2—C15—H15B	109.8
C6—C1—H1	121.4	H15A—C15—H15B	108.3
C3—C2—C1	122.0 (3)	N2—C16—C17	104.0 (3)
C3—C2—H2	119.0	N2—C16—H16A	110.9
C1—C2—H2	119.0	C17—C16—H16A	110.9
C2—C3—C4	119.9 (3)	N2—C16—H16B	110.9
C2—C3—H3	120.0	C17—C16—H16B	110.9
C4—C3—H3	120.0	H16A—C16—H16B	109.0
C5—C4—C3	119.2 (3)	C16—C17—C7	102.7 (3)
C5—C4—H4	120.4	C16—C17—H17A	111.2
C3—C4—H4	120.4	C7—C17—H17A	111.2
C6—C5—C4	119.8 (3)	C16—C17—H17B	111.2
C6—C5—C7	111.0 (3)	C7—C17—H17B	111.2
C4—C5—C7	129.1 (3)	H17A—C17—H17B	109.1
C5—C6—C1	122.0 (3)	C11—C18—C8	107.7 (3)
C5—C6—N1	109.3 (3)	C11—C18—C19	118.3 (3)
C1—C6—N1	128.7 (3)	C8—C18—C19	112.6 (3)
C5—C7—C21	116.0 (3)	C11—C18—H18	105.7
C5—C7—C17	112.3 (3)	C8—C18—H18	105.7
C21—C7—C17	102.0 (3)	C19—C18—H18	105.7
C5—C7—C8	102.7 (3)	C14—C19—C20	109.5 (3)
C21—C7—C8	114.1 (3)	C14—C19—C18	114.8 (3)
C17—C7—C8	110.1 (3)	C20—C19—C18	106.2 (3)
N1—C8—C18	106.1 (2)	C14—C19—H19A	108.8
N1—C8—C7	104.3 (3)	C20—C19—H19A	108.8
C18—C8—C7	117.1 (3)	C18—C19—H19A	108.8
N1—C8—H8	109.7	C21—C20—C19	108.7 (3)
C18—C8—H8	109.7	C21—C20—H20A	109.9
C7—C8—H8	109.7	C19—C20—H20A	109.9
O2—C9—N1	122.6 (3)	C21—C20—H20B	109.9
O2—C9—C10	123.4 (3)	C19—C20—H20B	109.9
N1—C9—C10	114.0 (3)	H20A—C20—H20B	108.3
C9—C10—C11	117.0 (3)	C20—C21—C7	115.6 (3)
C9—C10—H10A	108.1	C20—C21—N2	110.4 (3)
C11—C10—H10A	108.1	C7—C21—N2	104.4 (3)
C9—C10—H10B	108.1	C20—C21—H21	108.7
C11—C10—H10B	108.1	C7—C21—H21	108.7
H10A—C10—H10B	107.3	N2—C21—H21	108.7
O1—C11—C18	114.6 (3)	O6—P1—O4	116.46 (17)
O1—C11—C10	103.9 (3)	O6—P1—O5	112.05 (17)
C18—C11—C10	110.0 (3)	O4—P1—O5	105.20 (15)
O1—C11—H11	109.4	O6—P1—O3	106.72 (19)
C18—C11—H11	109.4	O4—P1—O3	109.02 (17)
C10—C11—H11	109.4	O5—P1—O3	107.02 (17)
O1—C12—C13	110.8 (3)	P1—O3—H3A	109.5
O1—C12—H12A	109.5	P1—O5—H5A	109.5
C13—C12—H12A	109.5	H11W—O1W—H12W	109.9
O1—C12—H12B	109.5	H21W—O2W—H22W	109.7
C13—C12—H12B	109.5
C6—C1—C2—C3	−0.5 (5)	C12—C13—C14—C15	177.6 (3)
C1—C2—C3—C4	−1.5 (5)	C12—C13—C14—C19	−1.9 (5)
C2—C3—C4—C5	2.4 (5)	C13—C14—C15—N2	−125.8 (3)
C3—C4—C5—C6	−1.4 (5)	C19—C14—C15—N2	53.7 (4)
C3—C4—C5—C7	−176.5 (3)	C16—N2—C15—C14	74.7 (3)
C4—C5—C6—C1	−0.6 (5)	C21—N2—C15—C14	−47.7 (3)
C7—C5—C6—C1	175.4 (3)	C15—N2—C16—C17	−144.8 (3)
C4—C5—C6—N1	179.6 (3)	C21—N2—C16—C17	−19.2 (3)
C7—C5—C6—N1	−4.4 (4)	N2—C16—C17—C7	38.8 (3)
C2—C1—C6—C5	1.5 (5)	C5—C7—C17—C16	−168.6 (3)
C2—C1—C6—N1	−178.8 (3)	C21—C7—C17—C16	−43.7 (3)
C9—N1—C6—C5	−157.6 (3)	C8—C7—C17—C16	77.7 (3)
C8—N1—C6—C5	−6.8 (4)	O1—C11—C18—C8	−74.2 (3)
C9—N1—C6—C1	22.6 (5)	C10—C11—C18—C8	42.3 (3)
C8—N1—C6—C1	173.4 (3)	O1—C11—C18—C19	55.0 (4)
C6—C5—C7—C21	138.1 (3)	C10—C11—C18—C19	171.5 (3)
C4—C5—C7—C21	−46.5 (5)	N1—C8—C18—C11	−71.8 (3)
C6—C5—C7—C17	−105.2 (3)	C7—C8—C18—C11	172.4 (3)
C4—C5—C7—C17	70.3 (5)	N1—C8—C18—C19	155.9 (3)
C6—C5—C7—C8	13.0 (4)	C7—C8—C18—C19	40.0 (4)
C4—C5—C7—C8	−171.6 (3)	C13—C14—C19—C20	177.7 (3)
C9—N1—C8—C18	43.1 (4)	C15—C14—C19—C20	−1.9 (4)
C6—N1—C8—C18	−109.7 (3)	C13—C14—C19—C18	58.4 (5)
C9—N1—C8—C7	167.4 (3)	C15—C14—C19—C18	−121.1 (3)
C6—N1—C8—C7	14.6 (3)	C11—C18—C19—C14	−66.4 (4)
C5—C7—C8—N1	−16.0 (3)	C8—C18—C19—C14	60.5 (4)
C21—C7—C8—N1	−142.3 (3)	C11—C18—C19—C20	172.6 (3)
C17—C7—C8—N1	103.7 (3)	C8—C18—C19—C20	−60.6 (3)
C5—C7—C8—C18	100.9 (3)	C14—C19—C20—C21	−55.8 (4)
C21—C7—C8—C18	−25.5 (4)	C18—C19—C20—C21	68.6 (3)
C17—C7—C8—C18	−139.4 (3)	C19—C20—C21—C7	−57.1 (4)
C6—N1—C9—O2	−20.9 (5)	C19—C20—C21—N2	61.1 (3)
C8—N1—C9—O2	−169.4 (3)	C5—C7—C21—C20	−84.8 (4)
C6—N1—C9—C10	161.1 (3)	C17—C7—C21—C20	152.9 (3)
C8—N1—C9—C10	12.6 (4)	C8—C7—C21—C20	34.2 (4)
O2—C9—C10—C11	138.8 (3)	C5—C7—C21—N2	153.7 (3)
N1—C9—C10—C11	−43.2 (4)	C17—C7—C21—N2	31.4 (3)
C12—O1—C11—C18	−67.2 (4)	C8—C7—C21—N2	−87.3 (3)
C12—O1—C11—C10	172.8 (2)	C16—N2—C21—C20	−133.0 (3)
C9—C10—C11—O1	136.0 (3)	C15—N2—C21—C20	−8.1 (3)
C9—C10—C11—C18	12.9 (4)	C16—N2—C21—C7	−8.1 (3)
C11—O1—C12—C13	88.5 (3)	C15—N2—C21—C7	116.7 (3)
O1—C12—C13—C14	−65.0 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H22···O4	0.93	1.75	2.648 (3)	163
O1W—H11W···O4	0.86	1.93	2.768 (4)	166
O1W—H12W···O6^i	0.86	2.09	2.919 (4)	161
O2W—H21W···O6^i	0.86	2.56	3.307 (4)	146
O2W—H22W···O4	0.86	1.94	2.797 (3)	172
O3—H3A···O1W^ii	0.84	1.81	2.642 (4)	169
O5—H5A···O6^iii	0.84	1.73	2.510 (4)	154

Symmetry codes: (i) −x, y−1/2, −z+2; (ii) −x+1, y+1/2, −z+2; (iii) −x, y+1/2, −z+2.