(+) Escholinine perchlorate

Acta Cryst.(2002). E58, o1023±o1024 DOI: 10.1107/S160053680201512X Marek NecÏaset al. C₂₁H₂₆NO₄+ClO₄ÿ

o1023

organic papers

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

(+)-Escholinine perchlorate

Marek NecÏas,a_{* JirÏõÂ DostaÂl}b_and

JirÏõÂ SlavõÂkb

a_{Department of Inorganic Chemistry, Faculty of}

Science, Masaryk University, KotlaÂrÏska 2, 611 37 Brno, Czech Republic, andb_Department of Biochemistry, Faculty of Medicine, Masaryk University, KomenskeÂho naÂm. 2, 662 43 Brno, Czech Republic

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study T= 120 K

Mean(C±C) = 0.003 AÊ Rfactor = 0.028 wRfactor = 0.067

Data-to-parameter ratio = 11.2

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2002 International Union of Crystallography Printed in Great Britain ± all rights reserved

(+)-Escholinine perchlorate, C21H26NO4+ClO4ÿ, is a

quaternary benzyltetrahydroisoquinoline alkaloid isolated fromEschscholtzia californica. The partially saturated nitro-gen heterocycle has an almost regular half-chair conformation, with the N atom lying 0.666 (3) AÊ out of the plane of the other atoms. The two methoxy groups lie in the plane of their parent benzene ring. The dihedral angle between the two aromatic rings is 31.44 (7)_.

Comment

(+)-Escholinine, anN-methyl derivative of (+)-romneine, is a quaternary benzyltetrahydroisoquinoline alkaloid isolated (as its perchlorate) fromEschscholtzia californicaCham. (Papa-veraceae) (SlavõÂk & DolejsÏ, 1973). It is a minor component of the highly polar fraction of alkaloids from this source. Recently, it has been isolated fromRomneya coulteri Harv. (Valpuestaet al., 1999). The corresponding tertiary base (+)-romneine also occurs in the same plant species (Stermitzet al., 1966).

(+)-Escholinine perchlorate, (I), possesses a tetrahydroiso-quinoline skeleton with a substituted benzyl group attached to C1 (Fig. 1). All bond lengths and angles are within normal ranges. The bond lengths involving tetravalent nitrogen (N2Ð C1, N2ÐC3, N2ÐC16 and N2ÐC17) are 1.524 (2), 1.509 (3), 1.488 (3) and 1.496 (3) AÊ, respectively. These are somewhat longer than the corresponding NÐC distances in the tertiary tetrahydroisoquinoline alkaloids egenine and armepavine (Dokurno et al., 1993; Marek et al., 1997). The mean of the bond angles around N2 is 109.5_{, appropriate forsp}3

hybrid-ization. The two methoxy groups at C12 and C13 lie in the plane of their parent benzene ring. The partially saturated nitrogen heterocycle has an almost regular half-chair conformation, with atom N2 lying 0.666 (3) AÊ out of the least-squares plane C1/C8a/C4a/C4/C3. The dihedral angle between the aromatic rings of the isoquinoline moiety and the benzyl group is 31.44 (7)_.

The molecule of (I) contains one chiral centre, atom C1. From previous steric correlations, it is known that dextro-rotatory benzyltetrahydroisoquinoline alkaloids have the S

con®guration (SÆantavyÂ, 1979; Bentley, 1998). In accordance with previous investigations, and with the re®nement of the Flack (1983) parameter, the molecule of escholinine in Fig. 1 is depicted as theSenantiomer.

The perchlorate anion is a regular tetrahedron. The mean ClÐO bond length is 1.418 AÊ. There are no hydrogen bonds and the ions are held together by Coulombic and van der Waals interactions. The isoquinoline rings are stacked in columns parallel to the crystallographicaaxis.

Experimental

(+)-Escholinine was isolated as a perchlorate salt from the roots of

Eschscholtzia californicaCham. (SlavõÂk & DolejsÏ, 1973) and recrys-tallized from methanol; m.p. 482±483 K, []D25 = +74 (0.3M in

methanol).

Crystal data C21H26NO4+ClO4ÿ

Mr= 455.88

Monoclinic,P21

a= 7.450 (1) AÊ b= 17.010 (3) AÊ c= 9.038 (2) AÊ

= 114.32 (3) V= 1043.7 (3) AÊ3

Z= 2

Dx= 1.451 Mg mÿ3

MoKradiation Cell parameters from 500

re¯ections

= 4.5±27.8

= 0.23 mmÿ1

T= 120 (2) K Prism, colourless 0.400.400.20 mm Data collection

Kuma KM-4 CCD diffractometer

!scans

6727 measured re¯ections 3144 independent re¯ections 3001 re¯ections withI> 2(I)

Rint= 0.035

max= 25.0

h=ÿ8!8 k=ÿ20!19 l=ÿ10!9 Re®nement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.028}

wR(F2_{) = 0.067}

S= 1.04 3144 re¯ections 281 parameters

H-atom parameters constrained w= 1/[2_(F

o2) + (0.0353P)2

+ 0.1452P]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.001 max= 0.20 e AÊÿ3 min=ÿ0.20 e AÊÿ3

Extinction correction:SHELXTL Extinction coef®cient: 0.0106 (15) Absolute structure: Flack (1983),

1276 Friedel pairs Flack parameter =ÿ0.04 (5)

Data collection: Xcalibur (Oxford Diffraction Ltd, 2001); cell re®nement:Xcalibur; data reduction:Xcalibur; program(s) used to solve structure:SHELXTL(Bruker, 1997); program(s) used to re®ne

structure:SHELXTL; molecular graphics:SHELXTL; software used to prepare material for publication:SHELXTL.

This work was supported by the Ministry of Education of the Czech Republic (MSM 143100011) and by the Grant Agency of the Czech Republic (203/02/0436).

References

Bentley, K. W. (1998). The Isoquinoline Alkaloids, pp. 33±57. Amsterdam: Harwood Academic Publishers.

Bruker (1997). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.

Dokurno, P., Gdaniec, M., Kosturkiewicz, Z., Matecka, D. & Rozwadowska, M. D. (1993).Acta Cryst.C49, 517±519.

Flack, H. D. (1983).Acta Cryst.A39, 876±881.

Marek, R., Marek, J., DostaÂl, J. & SlavõÂk, J. (1997).Collect. Czech. Chem. Commun.62, 1623±1630.

Oxford Diffraction Ltd (2001).Xcalibur CCD System ± CrysAlis Software System. Version 1.166. Oxford Diffraction Ltd, Oxford, England. SlavõÂk, J. & DolejsÏ, L. (1973).Collect. Czech. Chem. Commun.38, 3514±3520. Stermitz, F. R., Chen, L. & White, J. I. (1966).Tetrahedron,22, 1095±1102. SÆantavyÂ, F. (1979).The Alkaloids, Vol. 17, edited by R. H. F. Manske & R. G.

A. Rodrigo, pp. 385±544. New York: Academic Press.

Valpuesta, M., Diaz, A. & Suau, R. (1999).Phytochemistry,51, 1157±1160. Figure 1

supporting information

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supporting information

Acta Cryst. (2002). E58, o1023–o1024 [doi:10.1107/S160053680201512X]

(+)-Escholinine perchlorate

Marek Ne

č

as, Ji

ří

Dost

á

l and Ji

ří

Slav

í

k

S1. Comment

(+)-Escholinine, an N-methyl derivative of (+)-romneine, is a quaternary benzyltetrahydroisoquinoline alkaloid isolated

(as the perchlorate of its protonated form) from Eschscholtzia californica Cham. (Papaveraceae) (Slavík & Dolejš, 1973).

It is a minor component of the highly polar fraction of alkaloids from this source. Recently, it has been isolated from

Romneya coulteri Harv. (Valpuesta et al., 1999). The corresponding tertiary base (+)-romneine also occurs in the same

plant species (Stermitz et al., 1966).

(+)-Escholinine perchlorate, (I), possesses a tetrahydroisoquinoline skeleton with a substituted benzyl group attached to

C1 (Fig. 1). All bond lengths and angles are within normal ranges. The bond lengths involving tetravalent nitrogen (N2—

C1, N2—C3, N2—C16 and N2—C17) are 1.524 (2), 1.509 (3), 1.488 (3) and 1.496 (3) Å, respectively. These are

somewhat longer than the corresponding N—C distances in the tertiary tetrahydroisoquinoline alkaloids egenine and

armepavine (Dokurno et al., 1993; Marek et al., 1997). The mean of the bond angles around N2 is 109.47°, appropriate

for sp3 _{hybridization. The two methoxy groups at C12 and C13 lie in the plane of their parent benzene ring. The partially}

saturated nitrogen heterocycle has an almost regular half-chair conformation, with atom N2 lying 0.666 (3) Å out of the

least-squares plane C1/C8a/C4a/C4/C3. The dihedral angle between the aromatic rings of the isoquinoline moiety and the

benzyl group is 31.44 (7)°.

The molecule of (I) contains one chiral centre, atom C1. From previous steric correlations, it is known that

dextrorotatory benzyltetrahydroisoquinoline alkaloids have the S configuration (Šantavý, 1979; Bentley, 1998). In

accordance with previous investigations, and with the refinement of the Flack (1983) parameter, the molecule of

escholinine in Fig. 1 is depicted as the S enantiomer.

The perchlorate anion is a regular tetrahedron. The mean Cl—O bond length is 1.418 Å. There are no hydrogen bonds

and the ions are held together by Coulombic and van der Waals interactions. The isoquinoline rings are stacked in

columns parallel to the crystallographic a axis.

S2. Experimental

(+)-Escholinine was isolated as a perchlorate salt from the roots of Eschscholtzia californica Cham. (Slavík & Dolejš,

Figure 1

A perspective view of (+)-escholinine perchlorate with the atom numbering. Ellipsoids are drawn at the 50% probability

level.

(I)

Crystal data C21H26NO4+·ClO4−

Mr = 455.88

Monoclinic, P21

a = 7.450 (1) Å b = 17.010 (3) Å c = 9.038 (2) Å β = 114.32 (3)° V = 1043.7 (3) Å3

Z = 2

F(000) = 480 Dx = 1.451 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 500 reflections θ = 4.5–27.8°

µ = 0.23 mm−1

T = 120 K Prism, colourless 0.40 × 0.40 × 0.20 mm

Data collection Kuma KM-4 CCD

diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

Detector resolution: 0.06 mm pixels mm-1

ω scans

6727 measured reflections

3144 independent reflections 3001 reflections with I > 2σ(I) Rint = 0.035

θmax = 25.0°, θmin = 3.4°

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Refinement Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.028}

wR(F2_{) = 0.067}

S = 1.04 3144 reflections 281 parameters 1 restraint

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained w = 1/[σ2_(F

o2) + (0.0353P)2 + 0.1452P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001

Δρmax = 0.20 e Å−3

Δρmin = −0.20 e Å−3

Extinction correction: SHELXTL, Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2θ)]-1/4

Extinction coefficient: 0.0106 (15)

Absolute structure: Flack (1983), 1276 Friedel pairs

Absolute structure parameter: −0.04 (5)

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 F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) is used}

only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2

are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq

Cl29 0.04206 (8) 0.06289 (3) 0.08370 (6) 0.02160 (14) O28 −0.0756 (3) 0.08890 (10) 0.1642 (2) 0.0433 (5) O27 0.0058 (3) 0.11044 (11) −0.05612 (19) 0.0371 (4) O26 0.2430 (2) 0.07085 (15) 0.19146 (19) 0.0560 (6) O25 −0.0030 (4) −0.01597 (11) 0.0364 (2) 0.0673 (7) C1 0.4345 (3) 0.03234 (12) 0.5776 (2) 0.0152 (4)

H1A 0.3487 0.0226 0.4605 0.018*

O22 0.4412 (2) −0.24707 (9) 0.90425 (18) 0.0277 (4) O21 0.4109 (2) −0.25527 (8) 0.64040 (18) 0.0250 (4) O24 0.9781 (2) −0.20592 (9) 0.39460 (16) 0.0217 (3) C5 0.4450 (3) −0.10299 (13) 0.9166 (2) 0.0209 (5)

H5A 0.4541 −0.1003 1.0244 0.025*

C7 0.4145 (3) −0.17829 (11) 0.6841 (2) 0.0176 (5) C19 0.9865 (3) −0.20774 (14) 0.8413 (2) 0.0248 (5)

H19A 1.0528 −0.2557 0.8975 0.037*

H19B 0.8494 −0.2082 0.8285 0.037*

H19C 1.0541 −0.1617 0.9052 0.037*

C9 0.6428 (3) 0.04954 (12) 0.5914 (2) 0.0176 (5)

H9A 0.6384 0.0966 0.5256 0.021*

H9B 0.7289 0.0618 0.7060 0.021*

C14 0.8057 (3) −0.08073 (12) 0.3299 (2) 0.0197 (5)

O23 0.9913 (2) −0.20434 (9) 0.68597 (16) 0.0199 (3) N2 0.3486 (3) 0.10224 (10) 0.63232 (19) 0.0172 (4) C12 0.9047 (3) −0.14084 (12) 0.5923 (2) 0.0149 (4) C4A 0.4422 (3) −0.03480 (13) 0.8294 (2) 0.0169 (5) C8A 0.4248 (3) −0.03982 (12) 0.6714 (2) 0.0145 (4) C6 0.4344 (3) −0.17285 (13) 0.8421 (2) 0.0187 (5) C10 0.7314 (3) −0.01735 (12) 0.5362 (2) 0.0160 (4) C11 0.8279 (3) −0.07786 (12) 0.6423 (2) 0.0173 (5)

H11A 0.8410 −0.0757 0.7513 0.021*

C18 0.3916 (4) −0.29875 (13) 0.7679 (3) 0.0275 (6)

H18A 0.4813 −0.3446 0.7974 0.033*

H18B 0.2548 −0.3180 0.7328 0.033*

C16 0.3633 (4) 0.17594 (12) 0.5492 (3) 0.0240 (5)

H16A 0.3069 0.2196 0.5867 0.036*

H16B 0.2905 0.1697 0.4316 0.036*

H16C 0.5019 0.1870 0.5746 0.036*

C15 0.7207 (3) −0.01961 (12) 0.3804 (2) 0.0189 (5)

H15A 0.6542 0.0212 0.3064 0.023*

C20 0.9804 (4) −0.20572 (15) 0.2381 (3) 0.0298 (6)

H20A 1.0419 −0.2542 0.2231 0.045*

H20B 1.0558 −0.1603 0.2284 0.045*

H20C 0.8450 −0.2025 0.1550 0.045*

C8 0.4067 (3) −0.11286 (13) 0.5944 (2) 0.0172 (4)

H8A 0.3898 −0.1166 0.4845 0.021*

C4 0.4411 (3) 0.04292 (12) 0.9072 (2) 0.0233 (5)

H4A 0.5522 0.0440 1.0159 0.028*

H4B 0.3177 0.0472 0.9231 0.028*

C17 0.1346 (3) 0.08731 (13) 0.5874 (3) 0.0228 (5)

H17A 0.0779 0.1319 0.6219 0.034*

H17B 0.1196 0.0394 0.6414 0.034*

H17C 0.0662 0.0809 0.4695 0.034*

C13 0.8959 (3) −0.14161 (12) 0.4341 (2) 0.0171 (4) C3 0.4571 (3) 0.11353 (13) 0.8127 (2) 0.0200 (5)

H3A 0.4031 0.1601 0.8461 0.024*

H3B 0.5978 0.1239 0.8392 0.024*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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C5 0.0194 (11) 0.0283 (13) 0.0147 (10) −0.0023 (10) 0.0068 (9) 0.0011 (9) C7 0.0117 (11) 0.0166 (11) 0.0255 (11) 0.0006 (9) 0.0087 (9) −0.0029 (9) C19 0.0278 (13) 0.0297 (13) 0.0210 (11) 0.0034 (11) 0.0141 (10) 0.0075 (10) C9 0.0195 (11) 0.0179 (12) 0.0179 (10) −0.0009 (9) 0.0102 (9) 0.0021 (9) C14 0.0192 (12) 0.0263 (12) 0.0143 (10) −0.0013 (9) 0.0077 (9) −0.0011 (9) O23 0.0223 (8) 0.0191 (8) 0.0196 (7) 0.0027 (7) 0.0099 (6) 0.0010 (6) N2 0.0177 (10) 0.0196 (10) 0.0146 (9) 0.0034 (7) 0.0071 (8) −0.0009 (7) C12 0.0116 (10) 0.0166 (11) 0.0162 (10) −0.0018 (9) 0.0054 (8) 0.0007 (9) C4A 0.0118 (11) 0.0240 (12) 0.0152 (10) −0.0005 (9) 0.0059 (8) −0.0002 (8) C8A 0.0110 (11) 0.0181 (11) 0.0152 (10) 0.0015 (9) 0.0060 (8) 0.0003 (8) C6 0.0151 (11) 0.0206 (12) 0.0200 (11) 0.0011 (9) 0.0069 (9) 0.0074 (9) C10 0.0128 (11) 0.0165 (11) 0.0195 (10) −0.0024 (8) 0.0076 (8) 0.0000 (8) C11 0.0167 (11) 0.0205 (12) 0.0156 (10) −0.0029 (9) 0.0076 (9) −0.0001 (8) C18 0.0362 (15) 0.0170 (12) 0.0346 (13) 0.0015 (10) 0.0201 (12) 0.0047 (10) C16 0.0283 (13) 0.0172 (12) 0.0287 (12) 0.0048 (10) 0.0138 (10) 0.0036 (10) C15 0.0201 (12) 0.0213 (12) 0.0166 (10) 0.0012 (9) 0.0089 (9) 0.0029 (9) C20 0.0382 (14) 0.0315 (13) 0.0278 (12) 0.0022 (12) 0.0217 (11) −0.0085 (11) C8 0.0152 (11) 0.0232 (12) 0.0159 (10) −0.0009 (9) 0.0093 (8) −0.0014 (9) C4 0.0287 (13) 0.0271 (14) 0.0180 (11) −0.0016 (10) 0.0136 (10) −0.0032 (9) C17 0.0162 (11) 0.0274 (13) 0.0257 (11) 0.0017 (9) 0.0096 (9) −0.0021 (9) C13 0.0155 (11) 0.0171 (11) 0.0199 (11) −0.0034 (9) 0.0086 (9) −0.0036 (9) C3 0.0192 (12) 0.0227 (12) 0.0175 (10) −0.0007 (10) 0.0071 (9) −0.0067 (9)

Geometric parameters (Å, º)

Cl29—O25 1.406 (2) N2—C16 1.488 (3)

Cl29—O26 1.4164 (18) N2—C17 1.496 (3)

Cl29—O28 1.4211 (17) N2—C3 1.504 (3)

Cl29—O27 1.4292 (17) C12—C11 1.376 (3)

C1—C8A 1.510 (3) C12—C13 1.404 (3)

C1—N2 1.526 (2) C4A—C8A 1.383 (3)

C1—C9 1.533 (3) C4A—C4 1.499 (3)

C1—H1A 1.000 C8A—C8 1.403 (3)

O22—C6 1.374 (2) C10—C15 1.378 (3)

O22—C18 1.433 (3) C10—C11 1.388 (3)

O21—C7 1.365 (2) C11—H11A 0.950

O21—C18 1.425 (3) C18—H18A 0.990

O24—C13 1.371 (2) C18—H18B 0.990

O24—C20 1.421 (3) C16—H16A 0.980

C5—C6 1.352 (3) C16—H16B 0.980

C5—C4A 1.397 (3) C16—H16C 0.980

C5—H5A 0.950 C15—H15A 0.950

C7—C8 1.364 (3) C20—H20A 0.980

C7—C6 1.377 (3) C20—H20B 0.980

C19—O23 1.420 (2) C20—H20C 0.980

C19—H19A 0.980 C8—H8A 0.950

C19—H19B 0.980 C4—C3 1.507 (3)

C9—C10 1.500 (3) C4—H4B 0.990

C9—H9A 0.990 C17—H17A 0.980

C9—H9B 0.990 C17—H17B 0.980

C14—C13 1.374 (3) C17—H17C 0.980

C14—C15 1.388 (3) C3—H3A 0.990

C14—H14A 0.950 C3—H3B 0.990

O23—C12 1.360 (2)

O25—Cl29—O26 110.65 (16) C5—C6—C7 122.32 (19) O25—Cl29—O28 109.40 (13) O22—C6—C7 109.41 (18) O26—Cl29—O28 108.54 (12) C15—C10—C11 118.74 (19) O25—Cl29—O27 109.67 (12) C15—C10—C9 120.87 (18) O26—Cl29—O27 108.38 (11) C11—C10—C9 120.38 (17) O28—Cl29—O27 110.17 (11) C12—C11—C10 121.16 (18)

C8A—C1—N2 109.19 (15) C12—C11—H11A 119.4

C8A—C1—C9 112.95 (17) C10—C11—H11A 119.4

N2—C1—C9 111.74 (16) O21—C18—O22 107.50 (17)

C8A—C1—H1A 107.6 O21—C18—H18A 110.2

N2—C1—H1A 107.6 O22—C18—H18A 110.2

C9—C1—H1A 107.6 O21—C18—H18B 110.2

C6—O22—C18 105.02 (15) O22—C18—H18B 110.2 C7—O21—C18 105.11 (16) H18A—C18—H18B 108.5 C13—O24—C20 116.54 (17) N2—C16—H16A 109.5

C6—C5—C4A 117.70 (19) N2—C16—H16B 109.5

C6—C5—H5A 121.2 H16A—C16—H16B 109.5

C4A—C5—H5A 121.2 N2—C16—H16C 109.5

C8—C7—O21 128.32 (18) H16A—C16—H16C 109.5

C8—C7—C6 121.44 (19) H16B—C16—H16C 109.5

O21—C7—C6 110.21 (18) C10—C15—C14 120.94 (19)

O23—C19—H19A 109.5 C10—C15—H15A 119.5

O23—C19—H19B 109.5 C14—C15—H15A 119.5

H19A—C19—H19B 109.5 O24—C20—H20A 109.5

O23—C19—H19C 109.5 O24—C20—H20B 109.5

H19A—C19—H19C 109.5 H20A—C20—H20B 109.5

H19B—C19—H19C 109.5 O24—C20—H20C 109.5

C10—C9—C1 113.42 (17) H20A—C20—H20C 109.5

C10—C9—H9A 108.9 H20B—C20—H20C 109.5

C1—C9—H9A 108.9 C7—C8—C8A 117.13 (18)

C10—C9—H9B 108.9 C7—C8—H8A 121.4

C1—C9—H9B 108.9 C8A—C8—H8A 121.4

H9A—C9—H9B 107.7 C4A—C4—C3 114.85 (17)

C13—C14—C15 120.00 (18) C4A—C4—H4A 108.6

C13—C14—H14A 120.0 C3—C4—H4A 108.6

C15—C14—H14A 120.0 C4A—C4—H4B 108.6

C12—O23—C19 116.69 (16) C3—C4—H4B 108.6

C16—N2—C17 107.30 (16) H4A—C4—H4B 107.5

C16—N2—C3 108.72 (16) N2—C17—H17A 109.5

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C16—N2—C1 111.43 (15) H17A—C17—H17B 109.5

C17—N2—C1 108.78 (16) N2—C17—H17C 109.5

C3—N2—C1 109.92 (16) H17A—C17—H17C 109.5

O23—C12—C11 124.67 (17) H17B—C17—H17C 109.5 O23—C12—C13 115.96 (17) O24—C13—C14 124.60 (18) C11—C12—C13 119.37 (18) O24—C13—C12 115.73 (17) C8A—C4A—C5 120.3 (2) C14—C13—C12 119.66 (18) C8A—C4A—C4 121.51 (19) N2—C3—C4 112.33 (18)

C5—C4A—C4 118.00 (17) N2—C3—H3A 109.1

C4A—C8A—C8 121.06 (19) C4—C3—H3A 109.1

C4A—C8A—C1 121.58 (19) N2—C3—H3B 109.1

C8—C8A—C1 117.30 (17) C4—C3—H3B 109.1

C5—C6—O22 128.27 (18) H3A—C3—H3B 107.9