Two optically active iso­quinoline derivatives

In the two title optically active tetra­hydro­iso­quinoline derivatives, namely 3-hydroxy­methyl-4-phenyl-1,2,3,4-tetra­hydro­isoquinolin-2-ium bromide methanol hemisolvate, C₁₆H₁₈NO⁺·Br^-·0.5CH₃OH, (IIb), and 2-formyl-3-hydroxy­methyl-4-phenyl-1,2,3,4-tetra­hydro­iso­quinoline, C₁₇H₁₇NO₂, (III), the absolute configurations have been confirmed as 3R,4R by structure refinement using Bijvoet-pair reflections. The hydroxy­methyl and phenyl groups in (IIb) are oriented in equatorial and pseudo-equatorial positions, respectively, whereas in (III), the corresponding groups are in axial and pseudo-axial positions, respectively; the hydroxy­methyl and phenyl groups are trans with respect to one another in both structures. The heterocyclic rings in (IIb) and (III) adopt envelope conformations inverted with respect to each other. In both structures, the mol­ecules are linked through hydrogen bonds.

S1. Comment

One of the steps in our synthesis of 4-phenyl-1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid (4-phenyl-Tic), (IV), from (+)-thiomicamine, (I), involved N-formylation of the intermediate 3-hydroxymethyl-4-phenyl-1,2,3,4-tetrahydroisoquinoline hydrobromide, (IIa), to give 2-formyl-3-hydroxymethyl-4-phenyl-1,2,3,4-tetrahydroisoquinoline, (III) (Brózda et al., 2000; see Scheme). The absolute configuration of both compounds, i.e. of (IIa) and (III), as 3R,4R was implied by the 1S,2S configuration of the starting material (+)-thiomicamine, (I), and mechanistic considerations (Brózda et al., 2000).

A half-chair or envelope conformation with a trans equatorial–pseudo-equatorial orientation of the C3 and C4 substituents in (IIa), respectively, was confirmed by the value of the coupling constant (J = 10.2 Hz) between atoms H3 and H4 in the ¹H NMR spectrum. This value corresponds to that of axial–pseudo-axial H atoms in cyclohexene derivatives (Ehil & Wilen, 1994) and also to those in other trans-3,4-disubstituted tetrahydroisoquinoline derivatives (Bohe et al., 1999; Pedrosa et al., 2001).

In the ¹H NMR spectrum of formamide (III), however, atoms H3 and H4 appear as singlets, suggesting a conformational inversion within the hydrogenated heterocyclic ring. We suspected that intramolecular hydrogen bonding involving the hydroxyl H and amide O atoms was responsible for this change (Brózda et al., 2000). Such a ring inversion would then place these H atoms in equatorial–pseudo-equatorial positions, respectively, with a torsion angle θ of ca 90°, for which, according to the Karplus equation, ³J ≈ 0. There was also a possibility of steric hindrance between the C3 substituent and the introduced N-formyl group, resulting in a change of conformation. In order to solve this problem, X-ray single-crystal analyses were performed on compounds (IIb) and (III).

The asymmetric unit of (IIb) contains one 3-hydroxymethyl-4-phenyl-1,2,3,4-tetrahydroisoquinoline molecule in the form of its ammonium cation (i.e. with an NH₂⁺ group), a Br^- anion and half a methanol molecule. In compound (III), the asymmetric unit contains two independent 2-formyl-3-hydroxymethyl-4-phenyl-1,2,3,4-tetrahydroisoquinoline molecules.

The results obtained for the title compounds confirm the absolute 3R,4R configuration of both compounds proposed earlier on the basis of ¹H NMR studies (Brózda et al., 2000). Moreover, upon formylation of (II), the distorted envelope conformation of the heterocyclic ring in the tetrahydroisoquinoline system [Cremer & Pople (1975) puckering parameters for (IIb): Q = 0.512 (3) Å, Θ = 132.4 (3)° and Φ = 131.9 (5)°; for (III): Q = 0.446 (2) Å, Θ = 52.1 (3)° and Φ = 310.6 (3)° (molecule A), and Q = 0.469 (2) Å, Θ = 53.5 (2)° and Φ = 302.1 (3)° (molecule B)] has undergone inversion, leading to a change in the mutual orientation of the substituents at C3 and C4. The deviation of atom C3 from the almost planar system of the other five atoms of the heterocyclic ring is 0.691 (4) Å for (IIb), 0.611 (2) Å for molecule A of (III) and 0.646 (2) Å for molecule B of (III) (Sheldrick, 1997). In (IIb), the substituents at C3 and C4 have a mutually trans equatorial–pseudo-equatorial orientation, but in (III), they have a trans axial-pseudo-axial orientation. A similar stereochemistry of the partially reduced isoquinoline core of (IIb) and (III) seems to be preserved in solution, as may be judged from the values of the coupling constants in their ¹H NMR spectra (see above). In (IIb), the torsion angle C11—C3—C4—C13 [-58.5 (3)°] indicates a synclinal conformation of the C11 atom in the hydroxymethyl group with respect to the C13 atom of the phenyl group, while in (III), the analogous angle C13—C3—C4—C15 [-157.89 (16)° (molecule A) and -161.42 (14)° (molecule B)] reveals a mutual orientation between anticlinal–antiperiplanar for atoms C13 and C15. It can be concluded that the above-mentioned inversion of the conformation of the hetrocyclic ring in the partially reduced isoquinoline core occurred as a result of a steric hindrance between the C3-hydroxymethyl substituent and the N-formyl group or/and a change in the state of hybridization of atom N2, which suggests a considerable contribution of the ionic form in the resonance hybrid of the amide group. The N2—C11 bond distance [1.324 (3) Å (molecule A) and 1.318 (2) Å (molecule B)] is somewhat shorter than a tertiary amide distance [1.346 (5) Å; Allen et al., 1987]. The sum of the valence angles around N2 is 359.8 (3)° for molecule A and 359.6 (3)° for molecule B.

In (IIb), the methanol solvate molecule lies near the twofold rotation axis, showing orientational disorder (see Experimental).

The hydroxyl group in molecule A of (III) also exhibits orientational disorder. Both positions of the hydroxyl group favour the formation of an intermolecular hydrogen bond with atom O12 of the carbonyl group of molecule B (Table 2).

In the crystal lattice of (IIb), the Br^- anion is involved in three hydrogen bonds as an H-atom acceptor. In these bonds, the H-atom donors are the N2 atoms from two different molecules and atom O12 of the hydroxyl group belonging to the third molecule (Table 1). Additionally, there is a possible intermolecular C—H···O hydrogen bond (Table 1). In this way, chains are formed parallel to the y axis.

In the crystal lattice of (III), the A and B molecules are connected by hydrogen bonds (O141···O12Bⁱ, O142···O12Bⁱ and O14B···O12Aⁱⁱ; see Table 2 for symmetry codes), forming chains parallel to the y axis. A comparison of IR absorption in spectra of (III), recorded in the solid state (KBr) and in solution (CH₂Cl₂), suggests the existence of similar intermolecular interactions in both phases.

S2. Experimental

Compounds (IIb) and (III) were prepared according to the method of Brózda et al. (2000). Crystals of both compounds suitable for single-crystal X-ray diffraction analysis were selected directly from the analytical samples.

S3. Refinement

The positions of the H atoms bonded to N and O atoms in the partially reduced isoquinoline core of (IIb) were obtained from difference Fourier maps and were refined freely. For molecule A of (III), the hydroxyl group, which was disordered over two positions (O141 and O142, with occupation factors of 67 and 33%), was allowed to rotate freely around the C—O bond. Atoms H141/H142 was placed geometrically and they converged to a position that could be interpreted as a favourable conformation for the formation of a hydrogen bond. The remaining H atoms of (IIb) and (III) were positioned geometrically and refined with a riding model (O—H = 0.82 Å and C—H = 0.93–0.98 Å) and with U_iso values constrained to be 1.5 (for hydroxyl H atoms) or 1.2 (for all other Hatoms) times the U_eq value of the parent atom.

In (IIb), the methanol solvate molecule lies near the twofold axis and shows orientational disorder; the equivalent isotropic displacement parameter of atom O19 is high [0.211 (5) Ų], and is associated with an interatomic O19—C20 distance [1.247 (14) Å] shortened by about 11σ relative to the normal value for a Csp³—O single bond [1.413 (4) Å; Allen et al., 1987]. The position of atom O19 was fixed on the twofold axis, and atom C20 was introduced with a site-occupation factor of 50%. A significant degree of disorder of the methanol solvate molecule prevents identification of the positions of the H atoms, so making it difficult to perform a correct determination of the positions of the O and C atoms in the molecule. Nevertheless, the assumption of the inverse positions of the atoms leads to worse results.

Computing details

For both compounds, data collection: KM-4 Software (Kuma, 1991); cell refinement: KM-4 Software; data reduction: KM-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of (IIb), showing the atomic labeling scheme. Only one position of the disordered C20 atom is shown. Non-H atoms are drawn as 30% probability displacement ellipsoids and H atoms as spheres of an arbitrary size.
	Fig. 2. The molecular structure (a) molecule A and (b) molecule B of (III). Non-H atoms are drawn as 30% probability displacement ellipsoids and H atoms as spheres of an arbitrary size.

(IIb) 3-Hydroxymethyl-4-phenyl-1,2,3,4-tetrahydroisoquinoline hydrobromide methanol hemisolvate

Crystal data

C16H18NO^+·Br^−·0.5CH4O	F(000) = 692
Mr = 336.25	Dx = 1.435 Mg m^−3
Monoclinic, C2	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: C 2y	Cell parameters from 58 reflections
a = 20.5882 (14) Å	θ = 10.2–29.4°
b = 6.4413 (6) Å	µ = 3.58 mm^−1
c = 11.7354 (6) Å	T = 293 K
β = 91.004 (5)°	Block, colourless
V = 1556.0 (2) Å^3	0.43 × 0.14 × 0.10 mm
Z = 4

Data collection

Kuma KM-4 diffractometer	2713 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.020
Graphite monochromator	θmax = 70.1°, θmin = 3.8°
ω–1θ scans	h = −24→24
Absorption correction: ψ scan (North et al., 1968)	k = −7→7
Tmin = 0.395, Tmax = 0.699	l = 0→14
2953 measured reflections	2 standard reflections every 100 reflections
2827 independent reflections	intensity decay: 3.4%

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)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.081	w = 1/[σ^2(Fo^2) + (0.0498P)^2 + 0.8792P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.019
2827 reflections	Δρmax = 0.36 e Å^−3
198 parameters	Δρmin = −0.43 e Å^−3
1 restraint	Absolute structure: Flack (1983), 1205 Friedel reflections
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (2)

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)
Br	0.323588 (14)	0.25337 (7)	−0.15463 (2)	0.06295 (12)
C1	0.28368 (17)	0.2903 (5)	0.1680 (3)	0.0604 (8)
H1A	0.3026	0.1649	0.1370	0.072*
H1B	0.2368	0.2753	0.1644	0.072*
N2	0.30286 (13)	0.4706 (4)	0.0966 (2)	0.0525 (6)
H2A	0.2754 (17)	0.580 (7)	0.107 (3)	0.061 (10)*
H2B	0.2984 (19)	0.429 (7)	0.016 (4)	0.067 (11)*
C3	0.37024 (15)	0.5458 (5)	0.1205 (2)	0.0534 (6)
H3	0.4001	0.4277	0.1161	0.064*
C4	0.37215 (14)	0.6309 (5)	0.2436 (2)	0.0493 (6)
H4	0.3419	0.7483	0.2468	0.059*
C5	0.36770 (16)	0.4695 (6)	0.4407 (3)	0.0597 (7)
H5	0.3965	0.5710	0.4666	0.072*
C6	0.34464 (19)	0.3246 (6)	0.5162 (3)	0.0682 (10)
H6	0.3588	0.3272	0.5919	0.082*
C7	0.30071 (18)	0.1759 (6)	0.4806 (3)	0.0676 (9)
H7	0.2845	0.0800	0.5321	0.081*
C8	0.28108 (16)	0.1708 (5)	0.3681 (3)	0.0600 (7)
H8	0.2513	0.0709	0.3437	0.072*
C9	0.30511 (14)	0.3130 (4)	0.2904 (2)	0.0499 (7)
C10	0.34859 (14)	0.4670 (5)	0.3258 (2)	0.0491 (6)
C11	0.38801 (18)	0.7016 (6)	0.0308 (3)	0.0647 (9)
H11A	0.4312	0.7559	0.0465	0.078*
H11B	0.3880	0.6357	−0.0435	0.078*
O12	0.34219 (15)	0.8648 (4)	0.0314 (2)	0.0747 (7)
H12	0.359 (2)	0.920 (8)	−0.022 (4)	0.084 (14)*
C13	0.44004 (14)	0.7130 (5)	0.2732 (2)	0.0510 (7)
C14	0.49443 (18)	0.5933 (6)	0.2602 (3)	0.0664 (8)
H14	0.4903	0.4572	0.2346	0.080*
C15	0.55589 (19)	0.6736 (9)	0.2851 (4)	0.0808 (13)
H15	0.5924	0.5918	0.2739	0.097*
C16	0.5630 (2)	0.8698 (9)	0.3255 (4)	0.0803 (12)
H16	0.6042	0.9224	0.3422	0.096*
C17	0.5083 (2)	0.9908 (8)	0.3415 (4)	0.0885 (12)
H17	0.5125	1.1244	0.3708	0.106*
C18	0.44771 (18)	0.9135 (6)	0.3141 (3)	0.0680 (8)
H18	0.4113	0.9971	0.3233	0.082*
O19	0.5000	0.147 (2)	1.0000	0.211 (5)
C20	0.4793 (8)	0.315 (2)	0.9614 (13)	0.117 (4)	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br	0.07771 (19)	0.06541 (19)	0.04600 (15)	−0.00797 (19)	0.00925 (11)	0.00064 (17)
C1	0.0795 (18)	0.056 (2)	0.0457 (13)	−0.0045 (15)	−0.0041 (12)	0.0025 (13)
N2	0.0694 (15)	0.0497 (14)	0.0383 (12)	0.0023 (12)	−0.0028 (10)	−0.0003 (10)
C3	0.0625 (16)	0.0552 (16)	0.0427 (14)	0.0047 (13)	0.0033 (12)	0.0001 (12)
C4	0.0551 (14)	0.0528 (16)	0.0402 (13)	0.0048 (12)	0.0015 (11)	−0.0014 (11)
C5	0.0672 (18)	0.071 (2)	0.0408 (14)	−0.0028 (15)	−0.0016 (12)	−0.0006 (13)
C6	0.0727 (19)	0.090 (3)	0.0421 (15)	0.0030 (17)	0.0018 (13)	0.0080 (14)
C7	0.074 (2)	0.077 (2)	0.0527 (16)	0.0012 (16)	0.0091 (14)	0.0180 (15)
C8	0.0648 (17)	0.0600 (17)	0.0553 (17)	−0.0001 (14)	0.0017 (13)	0.0055 (13)
C9	0.0572 (14)	0.0486 (18)	0.0439 (14)	0.0058 (11)	0.0022 (11)	0.0009 (10)
C10	0.0541 (14)	0.0538 (16)	0.0396 (13)	0.0094 (12)	0.0022 (11)	0.0008 (11)
C11	0.0749 (18)	0.077 (3)	0.0427 (13)	−0.0031 (16)	0.0054 (12)	0.0031 (14)
O12	0.0894 (17)	0.0693 (15)	0.0655 (15)	0.0041 (13)	0.0053 (13)	0.0205 (13)
C13	0.0585 (14)	0.051 (2)	0.0439 (12)	−0.0008 (12)	0.0010 (10)	0.0072 (12)
C14	0.0695 (19)	0.066 (2)	0.0639 (19)	0.0081 (16)	−0.0017 (16)	−0.0035 (16)
C15	0.0599 (19)	0.112 (3)	0.070 (2)	0.016 (2)	−0.0014 (17)	0.007 (2)
C16	0.068 (2)	0.092 (3)	0.080 (3)	−0.011 (2)	−0.0111 (19)	0.006 (2)
C17	0.096 (3)	0.072 (2)	0.097 (3)	−0.017 (2)	−0.014 (2)	−0.002 (2)
C18	0.071 (2)	0.057 (2)	0.076 (2)	0.0044 (15)	−0.0050 (17)	−0.0091 (17)
O19	0.170 (8)	0.141 (8)	0.324 (17)	0.000	0.022 (9)	0.000
C20	0.141 (11)	0.093 (9)	0.118 (9)	0.016 (7)	0.013 (7)	−0.008 (6)

Geometric parameters (Å, º)

C1—N2	1.490 (4)	C8—H8	0.93
C1—C9	1.503 (4)	C9—C10	1.395 (4)
C1—H1A	0.97	C11—O12	1.412 (5)
C1—H1B	0.97	C11—H11A	0.97
N2—C3	1.491 (4)	C11—H11B	0.97
N2—H2A	0.92 (4)	O12—H12	0.81 (5)
N2—H2B	0.99 (4)	C13—C14	1.370 (5)
C3—C11	1.505 (4)	C13—C18	1.386 (5)
C3—C4	1.545 (4)	C14—C15	1.393 (6)
C3—H3	0.98	C14—H14	0.93
C4—C10	1.515 (4)	C15—C16	1.357 (7)
C4—C13	1.529 (4)	C15—H15	0.93
C4—H4	0.98	C16—C17	1.386 (7)
C5—C6	1.377 (5)	C16—H16	0.93
C5—C10	1.398 (4)	C17—C18	1.376 (6)
C5—H5	0.93	C17—H17	0.93
C6—C7	1.378 (5)	C18—H18	0.93
C6—H6	0.93	O19—C20^i	1.247 (14)
C7—C8	1.374 (5)	O19—C20	1.247 (14)
C7—H7	0.93	C20—C20^i	1.23 (3)
C8—C9	1.390 (4)
N2—C1—C9	112.7 (3)	C9—C8—H8	119.6
N2—C1—H1A	109.1	C8—C9—C10	120.5 (3)
C9—C1—H1A	109.1	C8—C9—C1	117.5 (3)
N2—C1—H1B	109.1	C10—C9—C1	122.0 (3)
C9—C1—H1B	109.1	C9—C10—C5	117.6 (3)
H1A—C1—H1B	107.8	C9—C10—C4	121.2 (2)
C1—N2—C3	113.7 (2)	C5—C10—C4	121.2 (3)
C1—N2—H2A	111 (2)	O12—C11—C3	108.8 (3)
C3—N2—H2A	107 (2)	O12—C11—H11A	109.9
C1—N2—H2B	108 (2)	C3—C11—H11A	109.9
C3—N2—H2B	110 (2)	O12—C11—H11B	109.9
H2A—N2—H2B	107 (3)	C3—C11—H11B	109.9
N2—C3—C11	108.8 (2)	H11A—C11—H11B	108.3
N2—C3—C4	107.4 (2)	C11—O12—H12	91 (4)
C11—C3—C4	114.5 (3)	C14—C13—C18	118.3 (3)
N2—C3—H3	108.7	C14—C13—C4	121.7 (3)
C11—C3—H3	108.7	C18—C13—C4	119.9 (3)
C4—C3—H3	108.7	C13—C14—C15	120.6 (4)
C10—C4—C13	113.5 (2)	C13—C14—H14	119.7
C10—C4—C3	110.2 (2)	C15—C14—H14	119.7
C13—C4—C3	110.1 (2)	C16—C15—C14	120.8 (4)
C10—C4—H4	107.6	C16—C15—H15	119.6
C13—C4—H4	107.6	C14—C15—H15	119.6
C3—C4—H4	107.6	C15—C16—C17	119.2 (4)
C6—C5—C10	121.2 (3)	C15—C16—H16	120.4
C6—C5—H5	119.4	C17—C16—H16	120.4
C10—C5—H5	119.4	C18—C17—C16	120.1 (4)
C5—C6—C7	120.5 (3)	C18—C17—H17	120.0
C5—C6—H6	119.7	C16—C17—H17	120.0
C7—C6—H6	119.7	C17—C18—C13	121.0 (4)
C8—C7—C6	119.3 (3)	C17—C18—H18	119.5
C8—C7—H7	120.4	C13—C18—H18	119.5
C6—C7—H7	120.4	C20^i—O19—C20	59.3 (15)
C7—C8—C9	120.8 (3)	C20^i—C20—O19	60.4 (7)
C7—C8—H8	119.6
C9—C1—N2—C3	42.5 (4)	C6—C5—C10—C4	177.9 (3)
C1—N2—C3—C11	170.4 (3)	C13—C4—C10—C9	−151.1 (3)
C1—N2—C3—C4	−65.2 (3)	C3—C4—C10—C9	−27.2 (4)
N2—C3—C4—C10	54.8 (3)	C13—C4—C10—C5	31.4 (4)
C11—C3—C4—C10	175.7 (3)	C3—C4—C10—C5	155.3 (3)
N2—C3—C4—C13	−179.4 (2)	N2—C3—C11—O12	57.6 (3)
C11—C3—C4—C13	−58.5 (3)	C4—C3—C11—O12	−62.6 (4)
C10—C5—C6—C7	−1.6 (6)	C10—C4—C13—C14	70.6 (4)
C5—C6—C7—C8	1.3 (6)	C3—C4—C13—C14	−53.4 (4)
C6—C7—C8—C9	0.2 (5)	C10—C4—C13—C18	−109.5 (3)
C7—C8—C9—C10	−1.5 (5)	C3—C4—C13—C18	126.5 (3)
C7—C8—C9—C1	177.1 (3)	C18—C13—C14—C15	−1.5 (5)
N2—C1—C9—C8	170.0 (3)	C4—C13—C14—C15	178.4 (3)
N2—C1—C9—C10	−11.5 (4)	C13—C14—C15—C16	1.8 (6)
C8—C9—C10—C5	1.2 (4)	C14—C15—C16—C17	−0.2 (7)
C1—C9—C10—C5	−177.3 (3)	C15—C16—C17—C18	−1.5 (8)
C8—C9—C10—C4	−176.3 (3)	C16—C17—C18—C13	1.7 (7)
C1—C9—C10—C4	5.1 (4)	C14—C13—C18—C17	−0.2 (6)
C6—C5—C10—C9	0.3 (5)	C4—C13—C18—C17	179.9 (4)

Symmetry code: (i) −x+1, y, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Br^ii	0.91 (4)	2.40 (4)	3.259 (3)	157 (3)
N2—H2B···Br	0.99 (5)	2.37 (5)	3.298 (2)	158 (3)
O12—H12···Br^iii	0.80 (5)	2.74 (5)	3.339 (3)	132 (4)
C1—H1A···O12^iv	0.97	2.44	3.406 (4)	171

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

(III) 2-Formyl-3-hydroxymethyl-4-phenyl-1,2,3,4-tetrahydroisoquinoline

Crystal data

C17H17NO2	F(000) = 1136
Mr = 267.32	Dx = 1.248 Mg m^−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 45 reflections
a = 11.097 (2) Å	θ = 14.9–26.1°
b = 11.742 (2) Å	µ = 0.65 mm^−1
c = 21.829 (4) Å	T = 293 K
V = 2844.3 (9) Å^3	Prism, colourless
Z = 8	0.52 × 0.16 × 0.11 mm

Data collection

Kuma KM-4 diffractometer	Rint = 0.028
Radiation source: fine-focus sealed tube	θmax = 70.1°, θmin = 4.1°
Graphite monochromator	h = 0→13
ω–2θ scans	k = 0→14
5771 measured reflections	l = −26→26
5213 independent reflections	2 standard reflections every 100 reflections
4350 reflections with I > 2σ(I)	intensity decay: 6.8%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.033	w = 1/[σ^2(Fo^2) + (0.0599P)^2 + 0.1727P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.099	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.28 e Å^−3
5213 reflections	Δρmin = −0.14 e Å^−3
375 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.0054 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 2181 Friedel reflections
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.1 (2)

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)
C13A	0.2552 (2)	0.11568 (18)	0.06544 (10)	0.0761 (6)
H13A	0.2594	0.1469	0.0244	0.091*	0.67
H13B	0.3368	0.0980	0.0781	0.091*	0.67
H13C	0.1897	0.0663	0.0528	0.091*	0.33
H13D	0.2873	0.1519	0.0290	0.091*	0.33
O141	0.1926 (3)	0.01901 (19)	0.06332 (11)	0.0846 (7)	0.67
H141	0.1860	−0.0071	0.0980	0.127*	0.67
O142	0.3396 (5)	0.0537 (4)	0.0905 (2)	0.0858 (14)	0.33
H142	0.3171	0.0317	0.1243	0.129*	0.33
C1A	0.0593 (2)	0.2901 (2)	0.03364 (10)	0.0721 (6)
H1A	−0.0168	0.3305	0.0356	0.087*
H1B	0.0521	0.2316	0.0025	0.087*
N2A	0.08189 (15)	0.23617 (14)	0.09232 (8)	0.0602 (4)
C3A	0.20542 (18)	0.20721 (16)	0.10803 (9)	0.0576 (4)
H3A	0.2060	0.1770	0.1499	0.069*
C4A	0.28248 (15)	0.31543 (15)	0.10701 (8)	0.0501 (4)
H4A	0.3671	0.2916	0.1065	0.060*
C5A	0.34444 (19)	0.46413 (19)	0.03081 (9)	0.0662 (5)
H5A	0.4143	0.4736	0.0538	0.079*
C6A	0.3280 (2)	0.5295 (2)	−0.02021 (9)	0.0768 (6)
H6A	0.3858	0.5829	−0.0315	0.092*
C7A	0.2259 (2)	0.5160 (2)	−0.05456 (8)	0.0761 (6)
H7A	0.2140	0.5598	−0.0896	0.091*
C8A	0.1412 (2)	0.4376 (2)	−0.03704 (8)	0.0706 (6)
H8A	0.0722	0.4283	−0.0607	0.085*
C9A	0.15619 (17)	0.37149 (17)	0.01535 (7)	0.0546 (4)
C10A	0.26035 (17)	0.38422 (16)	0.04944 (7)	0.0512 (4)
C11A	−0.0091 (2)	0.20697 (19)	0.12830 (12)	0.0824 (7)
H11A	0.0089	0.1688	0.1645	0.099*
O12A	−0.11522 (18)	0.22665 (16)	0.11723 (11)	0.1083 (7)
C15A	0.26296 (16)	0.38446 (14)	0.16516 (7)	0.0497 (4)
C16A	0.33664 (17)	0.36730 (16)	0.21531 (8)	0.0543 (4)
H16A	0.3998	0.3154	0.2126	0.065*
C17A	0.3181 (2)	0.42578 (18)	0.26920 (8)	0.0633 (5)
H17A	0.3681	0.4121	0.3026	0.076*
C18A	0.2267 (2)	0.50394 (18)	0.27414 (8)	0.0667 (5)
H18A	0.2145	0.5436	0.3105	0.080*
C19A	0.1533 (2)	0.52245 (19)	0.22400 (10)	0.0718 (5)
H19A	0.0912	0.5754	0.2265	0.086*
C20A	0.1711 (2)	0.46338 (18)	0.17050 (8)	0.0641 (5)
H20A	0.1206	0.4767	0.1373	0.077*
C1B	0.62307 (18)	0.54871 (19)	0.23088 (8)	0.0622 (5)
H1C	0.6429	0.5952	0.2662	0.075*
H1D	0.5648	0.4921	0.2439	0.075*
N2B	0.73146 (13)	0.49106 (12)	0.20993 (6)	0.0497 (3)
C3B	0.73796 (16)	0.45876 (14)	0.14550 (7)	0.0498 (4)
H3B	0.8179	0.4263	0.1380	0.060*
C4B	0.72498 (16)	0.56558 (14)	0.10552 (7)	0.0486 (4)
H4B	0.7131	0.5401	0.0632	0.058*
C5B	0.5557 (2)	0.70084 (19)	0.08187 (10)	0.0678 (5)
H5B	0.5858	0.7063	0.0422	0.081*
C6B	0.4548 (2)	0.7618 (2)	0.09765 (13)	0.0834 (7)
H6B	0.4181	0.8091	0.0690	0.100*
C7B	0.40838 (19)	0.7529 (2)	0.15547 (13)	0.0756 (6)
H7B	0.3397	0.7938	0.1660	0.091*
C8B	0.46325 (17)	0.68334 (18)	0.19823 (9)	0.0622 (5)
H8B	0.4309	0.6771	0.2374	0.075*
C9B	0.56669 (15)	0.62259 (15)	0.18295 (8)	0.0511 (4)
C10B	0.61378 (16)	0.63103 (15)	0.12405 (8)	0.0511 (4)
C11B	0.81414 (19)	0.45985 (16)	0.24987 (9)	0.0610 (5)
H11B	0.8804	0.4200	0.2350	0.073*
O12B	0.81079 (15)	0.47911 (14)	0.30505 (7)	0.0798 (4)
C13B	0.6443 (2)	0.36826 (17)	0.12960 (9)	0.0635 (5)
H13E	0.5644	0.4000	0.1356	0.076*
H13F	0.6522	0.3485	0.0866	0.076*
O14B	0.65508 (16)	0.26995 (12)	0.16451 (8)	0.0815 (5)
H14B	0.7230	0.2435	0.1604	0.122*
C15B	0.83979 (16)	0.63570 (14)	0.10703 (7)	0.0475 (4)
C16B	0.93209 (18)	0.61088 (15)	0.06707 (8)	0.0574 (4)
H16B	0.9216	0.5541	0.0379	0.069*
C17B	1.04020 (19)	0.66921 (18)	0.06970 (10)	0.0668 (5)
H17B	1.1021	0.6505	0.0428	0.080*
C18B	1.05664 (18)	0.75407 (19)	0.11155 (11)	0.0692 (5)
H18B	1.1293	0.7934	0.1131	0.083*
C19B	0.9655 (2)	0.78099 (19)	0.15125 (11)	0.0700 (5)
H19B	0.9760	0.8395	0.1795	0.084*
C20B	0.85793 (18)	0.72153 (17)	0.14958 (9)	0.0611 (5)
H20B	0.7972	0.7394	0.1773	0.073*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C13A	0.0903 (16)	0.0638 (12)	0.0744 (13)	0.0142 (12)	0.0135 (12)	−0.0090 (10)
O141	0.1097 (19)	0.0600 (13)	0.0839 (14)	−0.0124 (13)	0.0135 (14)	−0.0171 (11)
O142	0.077 (3)	0.084 (3)	0.097 (3)	0.032 (3)	0.005 (3)	−0.002 (3)
C1A	0.0571 (12)	0.0873 (15)	0.0720 (13)	−0.0061 (11)	−0.0037 (9)	−0.0105 (11)
N2A	0.0529 (9)	0.0579 (9)	0.0699 (10)	−0.0036 (7)	0.0124 (7)	−0.0074 (7)
C3A	0.0642 (12)	0.0540 (9)	0.0547 (9)	0.0041 (8)	0.0088 (8)	0.0002 (8)
C4A	0.0467 (9)	0.0574 (9)	0.0464 (8)	0.0032 (7)	−0.0011 (7)	0.0035 (7)
C5A	0.0602 (12)	0.0800 (13)	0.0584 (10)	−0.0109 (11)	0.0013 (9)	0.0102 (9)
C6A	0.0867 (16)	0.0845 (15)	0.0592 (11)	−0.0111 (13)	0.0122 (11)	0.0157 (10)
C7A	0.1014 (18)	0.0828 (14)	0.0440 (9)	0.0088 (13)	0.0081 (10)	0.0105 (9)
C8A	0.0714 (14)	0.0930 (15)	0.0474 (9)	0.0159 (12)	−0.0115 (9)	−0.0078 (10)
C9A	0.0526 (10)	0.0670 (11)	0.0442 (8)	0.0051 (9)	−0.0012 (7)	−0.0067 (7)
C10A	0.0500 (9)	0.0607 (10)	0.0429 (8)	0.0013 (8)	0.0033 (7)	0.0006 (7)
C11A	0.0759 (16)	0.0566 (12)	0.1148 (19)	−0.0038 (11)	0.0427 (14)	−0.0098 (12)
O12A	0.0683 (11)	0.0838 (11)	0.173 (2)	−0.0058 (9)	0.0463 (12)	−0.0091 (12)
C15A	0.0524 (9)	0.0509 (9)	0.0459 (8)	−0.0009 (8)	0.0005 (7)	0.0063 (7)
C16A	0.0528 (10)	0.0602 (10)	0.0498 (9)	−0.0021 (8)	−0.0039 (7)	0.0092 (7)
C17A	0.0719 (13)	0.0728 (12)	0.0454 (9)	−0.0092 (10)	−0.0044 (8)	0.0052 (8)
C18A	0.0878 (15)	0.0626 (11)	0.0497 (9)	−0.0085 (11)	0.0067 (9)	−0.0027 (8)
C19A	0.0820 (15)	0.0622 (11)	0.0713 (12)	0.0129 (11)	0.0076 (11)	−0.0021 (9)
C20A	0.0720 (13)	0.0685 (11)	0.0519 (9)	0.0144 (10)	−0.0066 (9)	0.0027 (8)
C1B	0.0579 (12)	0.0787 (13)	0.0501 (9)	0.0092 (10)	0.0036 (8)	−0.0005 (9)
N2B	0.0472 (8)	0.0517 (7)	0.0501 (7)	0.0030 (6)	−0.0010 (6)	0.0002 (6)
C3B	0.0479 (9)	0.0481 (8)	0.0534 (9)	−0.0016 (7)	0.0044 (7)	−0.0047 (7)
C4B	0.0495 (9)	0.0542 (9)	0.0421 (7)	−0.0036 (7)	0.0005 (7)	−0.0051 (7)
C5B	0.0621 (13)	0.0720 (13)	0.0695 (12)	0.0013 (10)	−0.0089 (9)	0.0117 (10)
C6B	0.0683 (15)	0.0827 (15)	0.0992 (18)	0.0117 (12)	−0.0204 (13)	0.0167 (13)
C7B	0.0489 (11)	0.0757 (14)	0.1022 (17)	0.0127 (10)	−0.0092 (11)	−0.0061 (12)
C8B	0.0437 (10)	0.0714 (12)	0.0715 (12)	0.0012 (9)	0.0016 (8)	−0.0090 (9)
C9B	0.0402 (8)	0.0568 (10)	0.0564 (9)	0.0006 (7)	−0.0030 (7)	−0.0048 (7)
C10B	0.0440 (9)	0.0533 (9)	0.0559 (9)	−0.0032 (7)	−0.0063 (7)	−0.0014 (8)
C11B	0.0605 (12)	0.0538 (10)	0.0687 (12)	0.0044 (9)	−0.0126 (9)	0.0007 (8)
O12B	0.0965 (12)	0.0782 (9)	0.0647 (8)	0.0145 (9)	−0.0252 (8)	−0.0028 (7)
C13B	0.0640 (12)	0.0591 (10)	0.0674 (11)	−0.0135 (9)	0.0057 (9)	−0.0060 (9)
O14B	0.0831 (11)	0.0587 (8)	0.1028 (11)	−0.0066 (8)	0.0300 (9)	0.0057 (8)
C15B	0.0489 (9)	0.0478 (8)	0.0457 (8)	0.0017 (7)	0.0012 (7)	0.0021 (7)
C16B	0.0609 (11)	0.0564 (10)	0.0550 (9)	0.0015 (9)	0.0116 (8)	0.0014 (8)
C17B	0.0549 (12)	0.0670 (12)	0.0786 (13)	0.0045 (9)	0.0186 (10)	0.0151 (10)
C18B	0.0492 (11)	0.0631 (11)	0.0954 (15)	−0.0030 (9)	−0.0045 (11)	0.0145 (11)
C19B	0.0586 (12)	0.0655 (12)	0.0861 (14)	−0.0058 (10)	−0.0078 (11)	−0.0151 (10)
C20B	0.0528 (11)	0.0608 (11)	0.0698 (11)	−0.0016 (9)	0.0040 (9)	−0.0145 (9)

Geometric parameters (Å, º)

C13A—O142	1.306 (5)	C19A—H19A	0.93
C13A—O141	1.331 (3)	C20A—H20A	0.93
C13A—C3A	1.525 (3)	C1B—N2B	1.454 (2)
C13A—H13A	0.97	C1B—C9B	1.496 (3)
C13A—H13B	0.97	C1B—H1C	0.97
C13A—H13C	0.97	C1B—H1D	0.97
C13A—H13D	0.97	N2B—C11B	1.318 (2)
O141—H141	0.82	N2B—C3B	1.458 (2)
O142—H142	0.82	C3B—C13B	1.526 (3)
C1A—N2A	1.451 (3)	C3B—C4B	1.535 (2)
C1A—C9A	1.493 (3)	C3B—H3B	0.98
C1A—H1A	0.97	C4B—C10B	1.509 (2)
C1A—H1B	0.97	C4B—C15B	1.517 (2)
N2A—C11A	1.324 (3)	C4B—H4B	0.98
N2A—C3A	1.453 (3)	C5B—C6B	1.373 (3)
C3A—C4A	1.532 (3)	C5B—C10B	1.391 (3)
C3A—H3A	0.98	C5B—H5B	0.93
C4A—C10A	1.514 (2)	C6B—C7B	1.367 (4)
C4A—C15A	1.522 (2)	C6B—H6B	0.93
C4A—H4A	0.98	C7B—C8B	1.382 (3)
C5A—C6A	1.365 (3)	C7B—H7B	0.93
C5A—C10A	1.384 (3)	C8B—C9B	1.392 (3)
C5A—H5A	0.93	C8B—H8B	0.93
C6A—C7A	1.368 (4)	C9B—C10B	1.391 (2)
C6A—H6A	0.93	C11B—O12B	1.226 (2)
C7A—C8A	1.370 (3)	C11B—H11B	0.93
C7A—H7A	0.93	C13B—O14B	1.388 (3)
C8A—C9A	1.392 (3)	C13B—H13E	0.97
C8A—H8A	0.93	C13B—H13F	0.97
C9A—C10A	1.383 (3)	O14B—H14B	0.82
C11A—O12A	1.224 (3)	C15B—C16B	1.377 (2)
C11A—H11A	0.93	C15B—C20B	1.385 (3)
C15A—C16A	1.381 (2)	C16B—C17B	1.383 (3)
C15A—C20A	1.382 (3)	C16B—H16B	0.93
C16A—C17A	1.378 (3)	C17B—C18B	1.364 (3)
C16A—H16A	0.93	C17B—H17B	0.93
C17A—C18A	1.372 (3)	C18B—C19B	1.369 (3)
C17A—H17A	0.93	C18B—H18B	0.93
C18A—C19A	1.382 (3)	C19B—C20B	1.383 (3)
C18A—H18A	0.93	C19B—H19B	0.93
C19A—C20A	1.373 (3)	C20B—H20B	0.93
O142—C13A—C3A	113.4 (3)	C20A—C19A—C18A	120.6 (2)
O141—C13A—C3A	115.7 (2)	C20A—C19A—H19A	119.7
O142—C13A—H13A	124.3	C18A—C19A—H19A	119.7
O141—C13A—H13A	108.4	C19A—C20A—C15A	121.13 (18)
C3A—C13A—H13A	108.4	C19A—C20A—H20A	119.4
O141—C13A—H13B	108.4	C15A—C20A—H20A	119.4
C3A—C13A—H13B	108.4	N2B—C1B—C9B	113.32 (14)
H13A—C13A—H13B	107.4	N2B—C1B—H1C	108.9
O142—C13A—H13C	108.9	C9B—C1B—H1C	108.9
C3A—C13A—H13C	108.9	N2B—C1B—H1D	108.9
H13A—C13A—H13C	89.9	C9B—C1B—H1D	108.9
H13B—C13A—H13C	130.8	H1C—C1B—H1D	107.7
O142—C13A—H13D	108.9	C11B—N2B—C1B	119.83 (15)
O141—C13A—H13D	122.5	C11B—N2B—C3B	122.09 (16)
C3A—C13A—H13D	108.9	C1B—N2B—C3B	117.73 (14)
H13B—C13A—H13D	89.1	N2B—C3B—C13B	111.51 (14)
H13C—C13A—H13D	107.7	N2B—C3B—C4B	109.34 (13)
C13A—O141—H141	109.5	C13B—C3B—C4B	112.07 (15)
C13A—O142—H142	109.5	N2B—C3B—H3B	107.9
N2A—C1A—C9A	113.03 (16)	C13B—C3B—H3B	107.9
N2A—C1A—H1A	109.0	C4B—C3B—H3B	107.9
C9A—C1A—H1A	109.0	C10B—C4B—C15B	113.85 (14)
N2A—C1A—H1B	109.0	C10B—C4B—C3B	109.91 (13)
C9A—C1A—H1B	109.0	C15B—C4B—C3B	110.63 (14)
H1A—C1A—H1B	107.8	C10B—C4B—H4B	107.4
C11A—N2A—C1A	120.3 (2)	C15B—C4B—H4B	107.4
C11A—N2A—C3A	121.2 (2)	C3B—C4B—H4B	107.4
C1A—N2A—C3A	118.24 (15)	C6B—C5B—C10B	121.3 (2)
N2A—C3A—C13A	111.27 (18)	C6B—C5B—H5B	119.4
N2A—C3A—C4A	109.20 (15)	C10B—C5B—H5B	119.4
C13A—C3A—C4A	111.95 (16)	C7B—C6B—C5B	120.0 (2)
N2A—C3A—H3A	108.1	C7B—C6B—H6B	120.0
C13A—C3A—H3A	108.1	C5B—C6B—H6B	120.0
C4A—C3A—H3A	108.1	C6B—C7B—C8B	120.2 (2)
C10A—C4A—C15A	112.65 (14)	C6B—C7B—H7B	119.9
C10A—C4A—C3A	111.36 (15)	C8B—C7B—H7B	119.9
C15A—C4A—C3A	110.51 (14)	C7B—C8B—C9B	120.3 (2)
C10A—C4A—H4A	107.3	C7B—C8B—H8B	119.9
C15A—C4A—H4A	107.3	C9B—C8B—H8B	119.9
C3A—C4A—H4A	107.3	C10B—C9B—C8B	119.65 (17)
C6A—C5A—C10A	122.1 (2)	C10B—C9B—C1B	122.04 (15)
C6A—C5A—H5A	119.0	C8B—C9B—C1B	118.32 (17)
C10A—C5A—H5A	119.0	C5B—C10B—C9B	118.67 (17)
C5A—C6A—C7A	119.5 (2)	C5B—C10B—C4B	120.10 (17)
C5A—C6A—H6A	120.2	C9B—C10B—C4B	121.23 (15)
C7A—C6A—H6A	120.2	O12B—C11B—N2B	125.28 (19)
C6A—C7A—C8A	119.53 (18)	O12B—C11B—H11B	117.4
C6A—C7A—H7A	120.2	N2B—C11B—H11B	117.4
C8A—C7A—H7A	120.2	O14B—C13B—C3B	113.28 (18)
C7A—C8A—C9A	121.47 (19)	O14B—C13B—H13E	108.9
C7A—C8A—H8A	119.3	C3B—C13B—H13E	108.9
C9A—C8A—H8A	119.3	O14B—C13B—H13F	108.9
C10A—C9A—C8A	118.81 (18)	C3B—C13B—H13F	108.9
C10A—C9A—C1A	121.81 (17)	H13E—C13B—H13F	107.7
C8A—C9A—C1A	119.37 (18)	C13B—O14B—H14B	109.5
C9A—C10A—C5A	118.59 (16)	C16B—C15B—C20B	118.09 (17)
C9A—C10A—C4A	121.64 (16)	C16B—C15B—C4B	119.74 (15)
C5A—C10A—C4A	119.75 (17)	C20B—C15B—C4B	122.10 (16)
O12A—C11A—N2A	124.6 (3)	C15B—C16B—C17B	120.95 (18)
O12A—C11A—H11A	117.7	C15B—C16B—H16B	119.5
N2A—C11A—H11A	117.7	C17B—C16B—H16B	119.5
C16A—C15A—C20A	117.86 (16)	C18B—C17B—C16B	120.38 (19)
C16A—C15A—C4A	119.95 (16)	C18B—C17B—H17B	119.8
C20A—C15A—C4A	122.17 (15)	C16B—C17B—H17B	119.8
C17A—C16A—C15A	121.06 (18)	C17B—C18B—C19B	119.60 (19)
C17A—C16A—H16A	119.5	C17B—C18B—H18B	120.2
C15A—C16A—H16A	119.5	C19B—C18B—H18B	120.2
C18A—C17A—C16A	120.72 (17)	C18B—C19B—C20B	120.3 (2)
C18A—C17A—H17A	119.6	C18B—C19B—H19B	119.9
C16A—C17A—H17A	119.6	C20B—C19B—H19B	119.9
C17A—C18A—C19A	118.61 (17)	C19B—C20B—C15B	120.68 (18)
C17A—C18A—H18A	120.7	C19B—C20B—H20B	119.7
C19A—C18A—H18A	120.7	C15B—C20B—H20B	119.7
C9A—C1A—N2A—C11A	148.30 (19)	C4A—C15A—C20A—C19A	178.22 (19)
C9A—C1A—N2A—C3A	−36.5 (2)	C9B—C1B—N2B—C11B	154.36 (17)
C11A—N2A—C3A—C13A	109.6 (2)	C9B—C1B—N2B—C3B	−32.3 (2)
C1A—N2A—C3A—C13A	−65.5 (2)	C11B—N2B—C3B—C13B	107.4 (2)
C11A—N2A—C3A—C4A	−126.34 (19)	C1B—N2B—C3B—C13B	−65.7 (2)
C1A—N2A—C3A—C4A	58.5 (2)	C11B—N2B—C3B—C4B	−128.07 (18)
O142—C13A—C3A—N2A	−152.9 (3)	C1B—N2B—C3B—C4B	58.8 (2)
O141—C13A—C3A—N2A	−57.0 (3)	N2B—C3B—C4B—C10B	−52.17 (18)
O142—C13A—C3A—C4A	84.6 (3)	C13B—C3B—C4B—C10B	72.00 (17)
O141—C13A—C3A—C4A	−179.5 (2)	N2B—C3B—C4B—C15B	74.41 (17)
N2A—C3A—C4A—C10A	−47.57 (19)	C13B—C3B—C4B—C15B	−161.42 (14)
C13A—C3A—C4A—C10A	76.1 (2)	C10B—C5B—C6B—C7B	−1.2 (4)
N2A—C3A—C4A—C15A	78.43 (18)	C5B—C6B—C7B—C8B	0.5 (4)
C13A—C3A—C4A—C15A	−157.89 (16)	C6B—C7B—C8B—C9B	0.5 (3)
C10A—C5A—C6A—C7A	−0.4 (4)	C7B—C8B—C9B—C10B	−0.9 (3)
C5A—C6A—C7A—C8A	0.4 (4)	C7B—C8B—C9B—C1B	179.8 (2)
C6A—C7A—C8A—C9A	0.4 (3)	N2B—C1B—C9B—C10B	1.6 (3)
C7A—C8A—C9A—C10A	−1.4 (3)	N2B—C1B—C9B—C8B	−179.06 (16)
C7A—C8A—C9A—C1A	177.90 (19)	C6B—C5B—C10B—C9B	0.8 (3)
N2A—C1A—C9A—C10A	5.3 (3)	C6B—C5B—C10B—C4B	−179.6 (2)
N2A—C1A—C9A—C8A	−173.92 (18)	C8B—C9B—C10B—C5B	0.2 (3)
C8A—C9A—C10A—C5A	1.4 (3)	C1B—C9B—C10B—C5B	179.50 (18)
C1A—C9A—C10A—C5A	−177.85 (18)	C8B—C9B—C10B—C4B	−179.35 (16)
C8A—C9A—C10A—C4A	179.81 (17)	C1B—C9B—C10B—C4B	0.0 (3)
C1A—C9A—C10A—C4A	0.5 (3)	C15B—C4B—C10B—C5B	81.3 (2)
C6A—C5A—C10A—C9A	−0.6 (3)	C3B—C4B—C10B—C5B	−153.93 (17)
C6A—C5A—C10A—C4A	−179.0 (2)	C15B—C4B—C10B—C9B	−99.14 (19)
C15A—C4A—C10A—C9A	−103.66 (19)	C3B—C4B—C10B—C9B	25.6 (2)
C3A—C4A—C10A—C9A	21.1 (2)	C1B—N2B—C11B—O12B	−3.0 (3)
C15A—C4A—C10A—C5A	74.7 (2)	C3B—N2B—C11B—O12B	−176.03 (19)
C3A—C4A—C10A—C5A	−160.48 (18)	N2B—C3B—C13B—O14B	−57.9 (2)
C1A—N2A—C11A—O12A	−3.5 (3)	C4B—C3B—C13B—O14B	179.11 (15)
C3A—N2A—C11A—O12A	−178.5 (2)	C10B—C4B—C15B—C16B	−149.69 (16)
C10A—C4A—C15A—C16A	−143.10 (17)	C3B—C4B—C15B—C16B	85.96 (18)
C3A—C4A—C15A—C16A	91.6 (2)	C10B—C4B—C15B—C20B	33.5 (2)
C10A—C4A—C15A—C20A	38.4 (2)	C3B—C4B—C15B—C20B	−90.9 (2)
C3A—C4A—C15A—C20A	−86.9 (2)	C20B—C15B—C16B—C17B	0.6 (3)
C20A—C15A—C16A—C17A	0.9 (3)	C4B—C15B—C16B—C17B	−176.38 (17)
C4A—C15A—C16A—C17A	−177.66 (17)	C15B—C16B—C17B—C18B	−1.1 (3)
C15A—C16A—C17A—C18A	−0.9 (3)	C16B—C17B—C18B—C19B	0.3 (3)
C16A—C17A—C18A—C19A	0.3 (3)	C17B—C18B—C19B—C20B	0.9 (3)
C17A—C18A—C19A—C20A	0.3 (3)	C18B—C19B—C20B—C15B	−1.3 (3)
C18A—C19A—C20A—C15A	−0.3 (3)	C16B—C15B—C20B—C19B	0.6 (3)
C16A—C15A—C20A—C19A	−0.3 (3)	C4B—C15B—C20B—C19B	177.49 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O141—H141···O12B^i	0.82	2.12	2.912 (3)	161
O142—H142···O12B^i	0.82	2.18	2.958 (6)	158
O14B—H14B···O12A^ii	0.82	2.04	2.797 (3)	154
C3A—H3A···O12B^i	0.98	2.53	3.287 (3)	134
C3B—H3B···O12A^ii	0.98	2.50	3.235 (3)	132
C8B—H8B···O14B^iii	0.93	2.59	3.426 (3)	151

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