Acta Cryst.(2001). E57, o163±o165 DOI: 101107/S160053680100085X Masood Parvezet al. C17H23N2O+C4H5O4ÿ
o163
organic papers
Acta Crystallographica Section E
Structure Reports Online
ISSN 1600-5368
Doxylamine hydrogen succinate
Masood Parvez,* Sean Dalrymple and Adrien Cote
Department of Chemistry, The University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study
T= 293 K
Mean(C±C) = 0.009 AÊ
Rfactor = 0.067
wRfactor = 0.243
Data-to-parameter ratio = 19.3
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2001 International Union of Crystallography Printed in Great Britain ± all rights reserved
The crystal structure of doxylamine hydrogen succinate or dimethyl{[1-phenyl-1-(2-pyridyl)ethoxy]ethyl]ammonium hydrogen succinate, C17H23N2O+C4H5O4ÿ, contains two
independent protonated molecules of doxylamine with different conformations and two succinate anions in an asymmetric unit. The structure is stabilized by hydrogen bonds involving the cations and the anions, with O O and N O distances in the range 2.536 (5)±2.853 (5) AÊ.
Comment
Doxylamine [dimethylaminoethoxy(methyl)benzylpyridine] is a chiral tertiary aminoalkyl ether, with antihistaminic actions on the H1-receptor site (Casy, 1991). The crystal structures of
the tetrachlorozincate(II), tetrachlorocobaltate(II) (Parvez & Sabir, 1998) and tetrachlorocuprate(II) (Braitenbach & Parvez, 2001) salts of doxylamine have been reported from our laboratory. The crystal structures of a number of compounds belonging to this class of ethers which possess antiallergic activities have been reported, e.g. diphenhy-dramine hydrochloride (Glaser & Maartmann-Moe, 1990), diphenhydramine thiourea complex (Wiedenfeld & Knoch, 1987), carbinoxamine maleate (Bertolasi et al., 1980) and clemastine hydrogen fumarate (Parvez & Wendling, 1991). The crystal structure of orphenadrine hydrochloride, a skeletal muscle relaxant, which is closely related to these compounds has also been reported (Glaser et al., 1992). Continuing our investigations on the conformation of this important antiallergic drug, we now report the crystal struc-ture of doxylamine hydrogen succinate, (I).
The asymmetric unit of (I) is composed of two cations of the antihistamine with different conformations and two hydrogen succinate ions (Fig. 1). The C9A±C12Aatoms in one of the phenyl rings and the O3A atom had large displacement parameters possibly re¯ecting a degree of disorder.
In both cations in (I), the pyridine rings are planar; they are inclined by 84.6 (2) and 85.9 (2) to the phenyl rings. The
corresponding angles in the tetrachlorozincate(II), tetra-chlorocobaltate(II) (Parvez & Sabir, 1998) and tetrachloro-cuprate(II) (Braitenbach & Parvez, 2001) salts of doxylamine were 87.68 (14), 88.1 (2) and 82.9 (3), respectively.
The orientations of the pyridyl rings in both cations in (I) are different from their conformations in the dihydrocationic salts of doxylamine mentioned above, wherein both lone electron pairs of ethereal O atoms were oriented towards ammonium and pyridinium H atoms. This difference in orientation is due to a lack of interactions between ethereal O and pyridyl N atoms in (I) and results in a rotation of approximately 180about the C5ÐC6 and C5AÐC6Abonds
in both cations of (I) as compared with those in the doxyl-amine moiety in the dihydro-cationic salts. Furthermore, the cations in (I) differ in the orientation of the aminomethyl
groups; the ammonium H atom of one of the cations has switched positions with a methyl group as compared to the other cation resulting in signi®cantly different intramolecular separations between the ethereal O and ammonium N atoms: N2 O1 3.095 (6) versus N2A O1A 2.870 (6) AÊ. The difference in the orientation of the aminomethyl groups in the two cations is evident from a comparison of the torsion angles O1ÐC14ÐC15ÐN2 76.9 (6) and O1AÐC14AÐC15AÐ
N2A 58.4 (6), and C14ÐC15ÐN2ÐC17 ÿ62.0 (6) and
C14AÐC15AÐN2AÐC17A 51.5 (6). The torsion angles
corresponding to C5ÐC6ÐO1ÐC14, C6ÐO1ÐC14ÐC15 and C14ÐC15ÐN2ÐC17 in the two molecules are close to 180 with values in the range 173.2 (4)±179.5 (5), with the
exception of C6ÐO1ÐC14ÐC15 of 155.7 (5) in one of the
cations.
In general, carboxylic acids tend to form cyclic dimersvia
hydrogen bonding. The crystal structure of (I) displays an extensive network of hydrogen bonding wherein the succinate ions are linked into chains in a zigzag fashion along thecaxis, with O5 O2A and O5A O2 being 2.538 (5) and 2.536 (5) AÊ, respectively. Only a few carboxylic acids appear to adopt this arrangement (Bernsteinet al., 1994),e.g.l-lysine succinate (Prasad & Vijayan, 1991). The cations are attached to the anion chains via ammonium H atoms involved in the NÐH O interactions with N2 O2 and N2A O2A
distances of 2.744 (5) and 2.853 (5) AÊ, respectively (see Table 1).
Experimental
Crystals of (I) (Sigma Inc.) were grown from a solution in ethanol by slow evaporation at room temperature.
Crystal data
C17H23N2O+C4H5O4ÿ
Mr= 388.45
Monoclinic,P21/c
a= 8.901 (3) AÊ
b= 21.075 (4) AÊ
c= 22.721 (5) AÊ
= 97.22 (2)
V= 4228.4 (19) AÊ3
Z= 8
Dx= 1.220 Mg mÿ3
MoKradiation Cell parameters from 25
re¯ections
= 10.0±15.0 = 0.09 mmÿ1
T= 293 (2) K Prism, colourless 0.400.300.30 mm
Data collection
Rigaku AFC-6Sdiffractometer
!/2scans
10 376 measured re¯ections 9763 independent re¯ections 2872 re¯ections withI> 2(I)
Rint= 0.06 max= 27.5
h= 0!11
k= 0!27
l=ÿ29!29 3 standard re¯ections
every 200 re¯ections intensity decay: <0.1%
Re®nement
Re®nement onF2
R(F) = 0.067
wR(F2) = 0.243
S= 1.04 9763 re¯ections 507 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0479P)2
+ 9.25P]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001 max= 0.42 e AÊÿ3 min=ÿ0.31 e AÊÿ3
Figure 1
ORTEPII (Johnson, 1976) drawing of one of the two independent cation± anion pairs in (I). Displacement ellipsoids have been plotted at the 50% probability level.
Figure 2
Table 1
Hydrogen-bonding geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
N2ÐH1 O2 0.91 1.85 2.744 (5) 166
N2AÐH2 O2A 0.91 2.01 2.853 (5) 153
O5ÐH3 O2Ai 0.82 1.73 2.538 (5) 171
O5AÐH4 O2ii 0.82 1.72 2.536 (5) 171
Symmetry codes: (i)ÿx;1ÿy;1ÿz; (ii)ÿx;yÿ1 2;12ÿz.
All H atoms were located from difference maps and were included at geometrically idealized positions, with OÐH = 0.82, NÐH = 0.91 and CÐH = 0.93±0.97 AÊ, in a riding mode with isotropic displace-ment parameters of 1.2 (non-methyl) and 1.5 (methyl) times the displacement parameters of the atoms to which they were attached. Data collection: MSC/AFC Diffractometer Control Software
(Molecular Structure Corporation, 1988); cell re®nement:MSC/AFC Diffractometer Control Software; data reduction:TEXSAN (Mole-cular Structure Corporation, 1994); program(s) used to solve struc-ture: SAPI91 (Fan, 1991); program(s) used to re®ne structure:
SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN; soft-ware used to prepare material for publication:SHELXL97 (Shel-drick, 1997).
The authors thank the Natural Sciences and Engineering Research Council (Canada) for providing the diffractometer through an equipment grant to the University of Calgary.
References
Bernstein, J., Etter, M. C. & Leiserowitz, L. (1994).Structure Correlation, edited by H.-B. BuÈrgi & J. D. Dunitz, Vol. 2, pp. 431±507. New York: VCH. Bertolasi, V., Borea, P. A., Gilli, G. & Sacerdoti, M. (1980).Acta Cryst.B36,
2287±2291.
Braitenbach, K. & Parvez, M. (2001).Acta Cryst.C57. In the press. Casy, A. F. (1991).Histamine and Histamine Antagonists, edited by B. Uvnas,
pp. 549±572. Berlin, Heidelberg: Springer-Verlag.
Glaser, R., Donnell, D. & Maartmann-Moe, K. (1992).J. Pharm. Sci.81, 858± 862.
Glaser, R. & Maartmann-Moe, K. (1990).J. Chem. Soc. Perkin Trans.II, pp. 1205±1210.
Fan, H.-F. (1991).SAPI91. Rigaku Corporation, Tokyo, Japan.
Johnson, C. K. (1976).ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.
Molecular Structure Corporation (1988).MSC/AFC Diffractometer Control Software. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA.
Molecular Structure Corporation (1994). TEXSAN. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA.
Parvez, M. & Sabir, A. P. (1998).Acta Cryst.C54, 933±935. Parvez, M. & Wendling, M. (1991).Acta Cryst.C47, 613±616. Prasad, G. S. & Vijayan, M. (1991).Acta Cryst.C47, 927±935.
Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Wiedenfeld, H. & Knoch, F. (1987).Acta Cryst.C43, 1359±1362.
supporting information
Acta Cryst. (2001). E57, o163–o165 [doi:10.1107/S160053680100085X]
Doxylamine hydrogen succinate
Masood Parvez, Sean Dalrymple and Adrien Cote
S1. Comment
Doxylamine [dimethylaminoethoxy(methyl)benzylpyridine] is a chiral tertiary aminoalkyl ether, with antihistaminic
actions on the H1-receptor site (Casy, 1991). The crystal structures of the tetrachlorozincate(II), tetrachlorocobaltate(II)
(Parvez & Sabir, 1998) and tetrachlorocuprate(II) (Braitenbach & Parvez, 2000) salts of doxylamine have been reported
from our laboratory. The crystal structures of a number of compounds belonging to this class of ethers which possess
antiallergic activities have been reported, e.g. diphenhydramine hydrochloride (Glaser & Maartmann-Moe, 1990),
diphenhydramine thiourea complex (Wiedenfeld & Knoch, 1987), carbinoxamine maleate (Bertolasi et al., 1980) and
clemastine hydrogen fumarate (Parvez & Wendling, 1991). The crystal structure of orphenadrine hydrochloride, a skeletal
muscle relaxant, which is closely related to these compounds has also been reported (Glaser et al., 1992). Continuing our
investigations on the conformation of this important antiallergic drug, we now report the crystal structure of doxylamine
hydrogen succinate, (I).
The asymmetric unit of (I) is composed of two cations of the antihistamine with different conformations and two
hydrogen succinate ions (Fig. 1). The C9A–C12A atoms in one of the phenyl rings and the O3A atom had large
displacement displacement parameters possibly reflecting a degree of disorder.
In both cations in (I), the pyridine rings are planar; they are inclined by 84.6 (2) and 85.9 (2)° to the phenyl rings. The
corresponding angles in the tetrachlorozincate(II), tetrachlorocobaltate(II) (Parvez & Sabir, 1998) and
tetrachloro-cuprate(II) (Braitenbach & Parvez, 2000) salts of doxylamine were 87.68 (14), 88.1 (2) and 82.9 (3)°, respectively.
The orientations of the pyridyl rings in both cations in (I) are different from their conformations in the dihydrocationic
salts of doxylamine mentioned above, wherein both lone electron pairs of ethereal O atoms were oriented towards
ammonium and pyridinium H atoms. This difference in orientation is due to a lack of interactions between ethereal O and
pyridyl N atoms in (I) and results in a rotation of approximately 180° about the C5—C6 and C5A—C6A bonds in both
cations of (I) as compared with those in the doxylamine moiety in the dihydrocationic salts. Furthermore, the cations in
(I) differ in the orientation of the aminomethyl groups; the ammonium H atom of one of the cations has switched
positions with a methyl group as compared to the other cation resulting in significantly different intramolecular
separations between the ethereal O and ammonium N atoms: N2···O1 3.095 (6) versus N2A···O1A 2.870 (6) Å. The
difference in the orientation of the aminomethyl groups in the two cations is evident from a comparison of the torsion
angles O1—C14—C15—N2 76.9 (6)° and O1A—C14A—C15A—N2A 58.4 (6)°, and C14—C15—N2—C17 - 62.0 (6)°
and C14A—C15A—N2A—C17A 51.5 (6)°. The torsion angles corresponding to C5—C6—O1—C14, C6—-O1–C14—
C15 and C14—C15—N2—C17 in the two molecules are close to 180° with values in the range 173.2 (4)–179.5 (5)°,
with the exception of C6—O1—C14—C15 of 155.7 (5)° in one of the cations.
In general, carboxylic acids tend to form cyclic dimers via hydrogen bonding. The crystal structure of (I) displays an
extensive network of hydrogenbonding wherein the succinate ions are linked into chains in a zigzag fashion along the c
supporting information
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Acta Cryst. (2001). E57, o163–o165
adopt this arrangement (Bernstein et al., 1994), e.g. L-lysine succinate (Prasad & Vijayan, 1991). The cations are attached
to the anion chains via ammonium H atoms involved in the N—H···O interactions with N2···O2 and N2A···O2A distances
of 2.744 (5) and 2.853 (5) Å, respectively (see Table 1).
S2. Experimental
Crystals of (I) (Sigma Inc.) were grown from a solution in ethanol by slow evaporation at room temperature.
S3. Refinement
All H atoms were located from difference maps and were included at geometrically idealized positions, with O—H =
0.82, N—H = 0.91 and C—H = 0.93–0.97 Å, in a riding mode with isotropic displacement parameters of 1.2
[image:5.610.125.487.213.456.2](non-methyl) and 1.5 ((non-methyl) times the displacement parameters of the atoms to which they were attached.
Figure 1
ORTEPII (Johnson, 1976) drawings of the two independent cations and anions in (I). Displacement ellipsoids have been
Figure 2
?
Dimethylammoniumethoxy(methyl)benzylpyridine hydrogensuccinate
Crystal data
C17H23N2O+·C4H5O4− Mr = 388.45 Monoclinic, P21/c a = 8.901 (3) Å b = 21.075 (4) Å c = 22.721 (5) Å β = 97.22 (2)° V = 4228.4 (19) Å3 Z = 8
F(000) = 1664 Dx = 1.220 Mg m−3
Mo Kα radiation, λ = 0.71069 Å Cell parameters from 25 reflections θ = 10.0–15.0°
µ = 0.09 mm−1 T = 293 K Prism, colourless 0.40 × 0.30 × 0.30 mm
Data collection
Rigaku AFC-6S diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
ω/2θ scans
10376 measured reflections 9763 independent reflections 2872 reflections with I > 2σ(I)
Rint = 0.06
θmax = 27.5°, θmin = 2.0° h = 0→11
k = 0→27 l = −29→29
supporting information
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Acta Cryst. (2001). E57, o163–o165
Refinement
Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.067 wR(F2) = 0.243 S = 1.04 9763 reflections 507 parameters 0 restraints
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) + (0.0479P)2 + 9.25P] where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001 Δρmax = 0.42 e Å−3 Δρmin = −0.31 e Å−3
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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
O1 0.3343 (4) 0.47810 (18) 0.33285 (15) 0.0509 (10)
N1 0.4549 (6) 0.3162 (2) 0.3206 (2) 0.0599 (14)
N2 0.1845 (4) 0.6074 (2) 0.29755 (18) 0.0390 (11)
H1 0.0969 0.6050 0.3142 0.047*
C1 0.4878 (7) 0.2783 (3) 0.2761 (3) 0.0607 (18)
H1A 0.5174 0.2368 0.2854 0.073*
C2 0.4803 (7) 0.2974 (3) 0.2175 (3) 0.0585 (17)
H2A 0.5018 0.2695 0.1879 0.070*
C3 0.4403 (8) 0.3585 (3) 0.2050 (3) 0.070 (2)
H3A 0.4342 0.3731 0.1661 0.084*
C4 0.4084 (8) 0.3995 (3) 0.2495 (3) 0.0651 (19)
H4A 0.3825 0.4415 0.2410 0.078*
C5 0.4158 (6) 0.3768 (3) 0.3065 (2) 0.0416 (14)
C6 0.3850 (6) 0.4185 (3) 0.3589 (2) 0.0432 (14)
C7 0.5347 (7) 0.4286 (3) 0.3989 (2) 0.0429 (14)
C8 0.6468 (7) 0.4650 (3) 0.3784 (3) 0.0565 (17)
H8A 0.6287 0.4839 0.3412 0.068*
C9 0.7847 (8) 0.4735 (3) 0.4123 (3) 0.074 (2)
H9 0.8577 0.4990 0.3982 0.088*
C10 0.8152 (9) 0.4446 (4) 0.4667 (3) 0.076 (2)
H10A 0.9090 0.4496 0.4893 0.091*
C11 0.7057 (10) 0.4087 (3) 0.4867 (3) 0.070 (2)
H11A 0.7258 0.3895 0.5236 0.084*
C12 0.5650 (8) 0.3997 (3) 0.4540 (2) 0.0543 (16)
H12A 0.4922 0.3748 0.4688 0.065*
C13 0.2621 (7) 0.3887 (3) 0.3914 (3) 0.0654 (19)
H13A 0.2439 0.4154 0.4240 0.098*
H13C 0.1705 0.3845 0.3645 0.098*
C14 0.2963 (7) 0.5258 (3) 0.3720 (2) 0.0553 (17)
H14A 0.3629 0.5232 0.4091 0.066*
H14B 0.1930 0.5198 0.3803 0.066*
C15 0.3116 (6) 0.5902 (3) 0.3443 (2) 0.0469 (15)
H15A 0.3181 0.6221 0.3753 0.056*
H15B 0.4057 0.5914 0.3269 0.056*
C16 0.2011 (7) 0.6733 (3) 0.2778 (3) 0.0616 (18)
H16A 0.1183 0.6838 0.2482 0.092*
H16B 0.2948 0.6776 0.2614 0.092*
H16C 0.2011 0.7014 0.3111 0.092*
C17 0.1705 (6) 0.5638 (3) 0.2458 (2) 0.0454 (14)
H17A 0.0861 0.5765 0.2177 0.068*
H17B 0.1546 0.5213 0.2588 0.068*
H17C 0.2617 0.5654 0.2273 0.068*
O1A −0.0540 (4) 0.15355 (18) 0.55067 (15) 0.0434 (9)
N1A 0.1792 (6) 0.0219 (2) 0.6138 (2) 0.0602 (14)
N2A −0.1818 (5) 0.2214 (2) 0.44678 (19) 0.0444 (12)
H2 −0.0861 0.2061 0.4471 0.053*
C1A 0.3225 (7) 0.0007 (3) 0.6089 (3) 0.0503 (15)
H1B 0.3588 −0.0339 0.6318 0.060*
C2A 0.4149 (6) 0.0276 (3) 0.5724 (3) 0.0522 (16)
H2B 0.5109 0.0112 0.5698 0.063*
C3A 0.3620 (6) 0.0797 (3) 0.5393 (3) 0.0533 (16)
H3B 0.4235 0.0991 0.5144 0.064*
C4A 0.2186 (6) 0.1032 (2) 0.5428 (2) 0.0388 (13)
H4B 0.1834 0.1386 0.5209 0.047*
C5A 0.1280 (6) 0.0732 (2) 0.5797 (2) 0.0363 (13)
C6A −0.0359 (6) 0.0951 (3) 0.5835 (2) 0.0441 (14)
C7A −0.0557 (7) 0.1076 (3) 0.6478 (3) 0.0566 (17)
C8A 0.0160 (9) 0.1556 (4) 0.6780 (3) 0.082 (2)
H8B 0.0791 0.1819 0.6593 0.098*
C9A −0.0030 (13) 0.1670 (5) 0.7386 (5) 0.122 (4)
H9B 0.0462 0.1999 0.7604 0.147*
C10A −0.0992 (14) 0.1258 (7) 0.7623 (4) 0.118 (5)
H10B −0.1201 0.1324 0.8009 0.142*
C11A −0.1640 (13) 0.0762 (6) 0.7316 (6) 0.143 (5)
H11B −0.2231 0.0481 0.7504 0.172*
C12A −0.1458 (8) 0.0665 (4) 0.6753 (4) 0.086 (2)
H12B −0.1931 0.0325 0.6545 0.103*
C13A −0.1420 (7) 0.0442 (3) 0.5536 (3) 0.077 (2)
H13D −0.2452 0.0567 0.5550 0.115*
H13E −0.1229 0.0046 0.5741 0.115*
H13F −0.1244 0.0394 0.5130 0.115*
C14A −0.1949 (6) 0.1853 (3) 0.5515 (2) 0.0506 (16)
H14C −0.2042 0.2004 0.5912 0.061*
H14D −0.2781 0.1565 0.5394 0.061*
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Acta Cryst. (2001). E57, o163–o165
H15C −0.2948 0.2627 0.5090 0.053*
H15D −0.1188 0.2699 0.5231 0.053*
C16A −0.1953 (8) 0.2785 (3) 0.4073 (3) 0.078 (2)
H16D −0.1834 0.2660 0.3675 0.117*
H16E −0.1180 0.3086 0.4213 0.117*
H16F −0.2931 0.2975 0.4078 0.117*
C17A −0.2867 (7) 0.1707 (4) 0.4233 (3) 0.078 (2)
H17D −0.2753 0.1348 0.4495 0.117*
H17E −0.2642 0.1582 0.3847 0.117*
H17F −0.3890 0.1860 0.4204 0.117*
O2 −0.1021 (4) 0.60452 (18) 0.32998 (15) 0.0422 (9)
O3 0.0240 (4) 0.6541 (2) 0.40586 (18) 0.0684 (14)
O4 −0.5046 (4) 0.7175 (2) 0.42707 (17) 0.0600 (12)
O5 −0.3921 (4) 0.7613 (2) 0.50865 (16) 0.0468 (10)
H3 −0.3054 0.7656 0.5252 0.070*
C18 −0.0953 (6) 0.6392 (3) 0.3759 (2) 0.0390 (13)
C19 −0.2458 (5) 0.6617 (3) 0.3933 (2) 0.0470 (15)
H19A −0.3005 0.6836 0.3597 0.056*
H19B −0.3048 0.6248 0.4014 0.056*
C20 −0.2360 (5) 0.7052 (3) 0.4464 (2) 0.0408 (14)
H20A −0.1730 0.7414 0.4396 0.049*
H20B −0.1875 0.6827 0.4809 0.049*
C21 −0.3894 (6) 0.7288 (3) 0.4591 (2) 0.0368 (13)
O2A 0.1334 (4) 0.21418 (19) 0.43556 (15) 0.0474 (10)
O3A 0.0024 (5) 0.1691 (3) 0.3592 (2) 0.123 (3)
O4A 0.5079 (4) 0.1128 (2) 0.30771 (16) 0.0513 (11)
O5A 0.3624 (4) 0.08584 (19) 0.22668 (16) 0.0448 (10)
H4 0.2765 0.0943 0.2112 0.067*
C18A 0.1233 (6) 0.1823 (3) 0.3878 (3) 0.0546 (17)
C19A 0.2684 (6) 0.1619 (3) 0.3656 (2) 0.0494 (16)
H19C 0.3215 0.1325 0.3937 0.059*
H19D 0.3327 0.1987 0.3632 0.059*
C20A 0.2417 (6) 0.1305 (3) 0.3054 (2) 0.0590 (19)
H20C 0.1876 0.1601 0.2777 0.071*
H20D 0.1767 0.0940 0.3082 0.071*
C21A 0.3829 (6) 0.1089 (3) 0.2802 (2) 0.0370 (13)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
O1 0.071 (3) 0.044 (2) 0.038 (2) 0.027 (2) 0.0075 (19) 0.0015 (19)
N1 0.078 (4) 0.037 (3) 0.065 (3) 0.012 (3) 0.009 (3) −0.002 (3)
N2 0.029 (2) 0.041 (3) 0.049 (3) 0.006 (2) 0.016 (2) 0.004 (2)
C1 0.077 (5) 0.034 (4) 0.070 (5) 0.013 (3) 0.009 (4) −0.008 (4)
C2 0.072 (4) 0.053 (4) 0.049 (4) 0.014 (4) 0.002 (3) −0.013 (3)
C3 0.095 (5) 0.066 (5) 0.048 (4) 0.032 (4) 0.007 (4) −0.004 (4)
C4 0.097 (5) 0.055 (4) 0.043 (4) 0.027 (4) 0.008 (3) 0.002 (3)
C6 0.056 (4) 0.037 (3) 0.037 (3) 0.011 (3) 0.009 (3) 0.004 (3)
C7 0.060 (4) 0.036 (3) 0.033 (3) 0.012 (3) 0.010 (3) 0.003 (3)
C8 0.065 (4) 0.050 (4) 0.052 (4) 0.006 (3) −0.001 (3) 0.008 (3)
C9 0.074 (5) 0.066 (5) 0.078 (5) −0.005 (4) −0.005 (4) 0.004 (4)
C10 0.088 (6) 0.062 (5) 0.070 (5) 0.006 (4) −0.022 (4) −0.014 (4)
C11 0.116 (6) 0.062 (5) 0.028 (3) 0.027 (5) −0.005 (4) −0.009 (3)
C12 0.087 (5) 0.039 (4) 0.037 (3) 0.011 (3) 0.011 (3) 0.004 (3)
C13 0.061 (4) 0.070 (5) 0.067 (4) −0.001 (4) 0.017 (3) 0.010 (4)
C14 0.073 (4) 0.054 (4) 0.041 (3) 0.023 (3) 0.017 (3) 0.001 (3)
C15 0.039 (3) 0.060 (4) 0.041 (3) 0.009 (3) 0.005 (3) −0.008 (3)
C16 0.067 (4) 0.047 (4) 0.073 (5) 0.007 (3) 0.020 (4) 0.008 (4)
C17 0.040 (3) 0.039 (3) 0.058 (4) 0.005 (3) 0.007 (3) −0.008 (3)
O1A 0.032 (2) 0.054 (3) 0.045 (2) 0.0058 (18) 0.0074 (16) 0.000 (2)
N1A 0.063 (4) 0.055 (4) 0.062 (3) 0.005 (3) 0.006 (3) −0.002 (3)
N2A 0.029 (2) 0.064 (3) 0.039 (3) 0.014 (2) 0.0016 (19) −0.005 (3)
C1A 0.058 (4) 0.041 (4) 0.051 (4) 0.013 (3) 0.000 (3) 0.005 (3)
C2A 0.039 (3) 0.057 (4) 0.061 (4) 0.011 (3) 0.006 (3) −0.002 (3)
C3A 0.036 (3) 0.067 (5) 0.059 (4) −0.001 (3) 0.012 (3) 0.002 (3)
C4A 0.037 (3) 0.030 (3) 0.049 (3) 0.002 (3) 0.004 (3) 0.004 (3)
C5A 0.038 (3) 0.034 (3) 0.038 (3) 0.005 (3) 0.006 (2) −0.003 (3)
C6A 0.034 (3) 0.046 (4) 0.054 (4) −0.003 (3) 0.012 (3) −0.002 (3)
C7A 0.059 (4) 0.068 (5) 0.046 (4) 0.026 (4) 0.018 (3) 0.007 (4)
C8A 0.107 (6) 0.098 (7) 0.037 (4) 0.037 (5) −0.002 (4) −0.012 (4)
C9A 0.137 (9) 0.128 (10) 0.095 (8) 0.064 (8) −0.008 (7) 0.006 (7)
C10A 0.156 (11) 0.152 (12) 0.052 (6) 0.081 (9) 0.032 (6) −0.003 (6)
C11A 0.158 (11) 0.158 (12) 0.133 (10) 0.040 (9) 0.096 (9) 0.049 (9)
C12A 0.080 (5) 0.101 (6) 0.088 (6) −0.008 (5) 0.049 (5) 0.019 (5)
C13A 0.053 (4) 0.054 (5) 0.125 (7) −0.018 (4) 0.018 (4) −0.023 (4)
C14A 0.034 (3) 0.072 (5) 0.046 (3) 0.016 (3) 0.007 (3) −0.003 (3)
C15A 0.031 (3) 0.059 (4) 0.040 (3) 0.012 (3) −0.002 (2) −0.005 (3)
C16A 0.096 (6) 0.084 (6) 0.058 (4) 0.038 (5) 0.020 (4) 0.012 (4)
C17A 0.057 (4) 0.108 (6) 0.066 (5) −0.011 (4) −0.007 (4) −0.043 (4)
O2 0.0319 (19) 0.058 (3) 0.038 (2) 0.0026 (18) 0.0084 (16) −0.0145 (19)
O3 0.029 (2) 0.115 (4) 0.058 (3) 0.012 (2) −0.0071 (19) −0.040 (3)
O4 0.027 (2) 0.096 (4) 0.056 (3) 0.003 (2) 0.0038 (19) −0.026 (2)
O5 0.033 (2) 0.068 (3) 0.042 (2) 0.002 (2) 0.0118 (18) −0.014 (2)
C18 0.035 (3) 0.047 (4) 0.035 (3) 0.005 (3) 0.003 (2) −0.007 (3)
C19 0.028 (3) 0.062 (4) 0.051 (4) 0.002 (3) 0.006 (3) −0.022 (3)
C20 0.028 (3) 0.054 (4) 0.040 (3) 0.005 (3) 0.005 (2) −0.015 (3)
C21 0.031 (3) 0.047 (4) 0.034 (3) 0.001 (3) 0.011 (2) −0.007 (3)
O2A 0.040 (2) 0.068 (3) 0.035 (2) 0.005 (2) 0.0076 (17) −0.016 (2)
O3A 0.035 (3) 0.205 (7) 0.129 (5) 0.003 (3) 0.007 (3) −0.120 (5)
O4A 0.030 (2) 0.073 (3) 0.049 (2) 0.012 (2) −0.0050 (18) −0.010 (2)
O5A 0.033 (2) 0.062 (3) 0.039 (2) 0.010 (2) 0.0056 (16) −0.007 (2)
C18A 0.032 (3) 0.082 (5) 0.050 (4) 0.003 (3) 0.002 (3) −0.021 (4)
C19A 0.031 (3) 0.073 (5) 0.044 (3) 0.007 (3) 0.005 (2) −0.018 (3)
C20A 0.030 (3) 0.108 (6) 0.039 (3) 0.012 (3) 0.006 (2) −0.025 (4)
supporting information
sup-8
Acta Cryst. (2001). E57, o163–o165
Geometric parameters (Å, º)
O1—C14 1.411 (6) C1A—C2A 1.363 (8)
O1—C6 1.437 (6) C2A—C3A 1.380 (8)
N1—C1 1.349 (7) C3A—C4A 1.381 (7)
N1—C5 1.353 (7) C4A—C5A 1.385 (7)
N2—C16 1.472 (7) C5A—C6A 1.543 (7)
N2—C17 1.486 (6) C6A—C7A 1.517 (8)
N2—C15 1.496 (6) C6A—C13A 1.530 (8)
C1—C2 1.385 (8) C7A—C8A 1.339 (9)
C2—C3 1.357 (8) C7A—C12A 1.381 (9)
C3—C4 1.385 (8) C8A—C9A 1.426 (11)
C4—C5 1.373 (8) C9A—C10A 1.376 (14)
C5—C6 1.533 (7) C10A—C11A 1.345 (15)
C6—C13 1.528 (8) C11A—C12A 1.327 (12)
C6—C7 1.531 (8) C14A—C15A 1.509 (8)
C7—C8 1.385 (8) O2—C18 1.270 (6)
C7—C12 1.387 (7) O3—C18 1.227 (6)
C8—C9 1.375 (8) O4—C21 1.204 (6)
C9—C10 1.374 (9) O5—C21 1.320 (6)
C10—C11 1.355 (10) C18—C19 1.519 (7)
C11—C12 1.386 (9) C19—C20 1.508 (7)
C14—C15 1.509 (8) C20—C21 1.515 (7)
O1A—C14A 1.424 (6) O2A—C18A 1.269 (6)
O1A—C6A 1.438 (6) O3A—C18A 1.218 (6)
N1A—C1A 1.369 (7) O4A—C21A 1.209 (6)
N1A—C5A 1.375 (7) O5A—C21A 1.301 (6)
N2A—C17A 1.474 (7) C18A—C19A 1.508 (7)
N2A—C16A 1.497 (7) C19A—C20A 1.510 (7)
N2A—C15A 1.498 (6) C20A—C21A 1.515 (7)
C14—O1—C6 116.8 (4) C3A—C4A—C5A 118.9 (5)
C1—N1—C5 117.0 (5) N1A—C5A—C4A 121.6 (5)
C16—N2—C17 110.1 (4) N1A—C5A—C6A 116.9 (5)
C16—N2—C15 110.4 (4) C4A—C5A—C6A 121.6 (5)
C17—N2—C15 113.2 (4) O1A—C6A—C7A 109.4 (5)
N1—C1—C2 124.1 (6) O1A—C6A—C13A 110.3 (5)
C3—C2—C1 117.1 (6) C7A—C6A—C13A 114.1 (5)
C2—C3—C4 120.7 (6) O1A—C6A—C5A 105.8 (4)
C5—C4—C3 118.8 (6) C7A—C6A—C5A 109.4 (5)
N1—C5—C4 122.2 (5) C13A—C6A—C5A 107.5 (5)
N1—C5—C6 115.0 (5) C8A—C7A—C12A 120.5 (7)
C4—C5—C6 122.8 (5) C8A—C7A—C6A 121.3 (6)
O1—C6—C13 110.5 (5) C12A—C7A—C6A 118.1 (7)
O1—C6—C7 109.1 (5) C7A—C8A—C9A 121.0 (9)
C13—C6—C7 113.1 (5) C10A—C9A—C8A 115.3 (11)
O1—C6—C5 104.9 (4) C11A—C10A—C9A 122.3 (10)
C7—C6—C5 108.3 (4) C11A—C12A—C7A 119.3 (9)
C8—C7—C12 118.6 (6) O1A—C14A—C15A 107.8 (4)
C8—C7—C6 119.2 (5) N2A—C15A—C14A 113.5 (5)
C12—C7—C6 122.1 (6) O3—C18—O2 123.4 (5)
C9—C8—C7 120.9 (6) O3—C18—C19 120.4 (5)
C10—C9—C8 120.5 (7) O2—C18—C19 116.2 (4)
C11—C10—C9 118.6 (7) C20—C19—C18 115.7 (4)
C10—C11—C12 122.5 (6) C19—C20—C21 112.9 (4)
C11—C12—C7 118.9 (6) O4—C21—O5 120.9 (5)
O1—C14—C15 109.7 (4) O4—C21—C20 122.6 (5)
N2—C15—C14 114.4 (5) O5—C21—C20 116.5 (4)
C14A—O1A—C6A 116.0 (4) O3A—C18A—O2A 122.7 (5)
C1A—N1A—C5A 117.1 (5) O3A—C18A—C19A 119.5 (5)
C17A—N2A—C16A 111.5 (5) O2A—C18A—C19A 117.8 (5)
C17A—N2A—C15A 113.6 (5) C18A—C19A—C20A 112.6 (4)
C16A—N2A—C15A 109.8 (4) C19A—C20A—C21A 115.5 (4)
C2A—C1A—N1A 123.7 (6) O4A—C21A—O5A 121.4 (5)
C1A—C2A—C3A 118.1 (5) O4A—C21A—C20A 122.5 (5)
C2A—C3A—C4A 120.6 (6) O5A—C21A—C20A 116.1 (4)
C5—N1—C1—C2 −1.6 (9) C1A—N1A—C5A—C6A 177.6 (5)
N1—C1—C2—C3 1.5 (10) C3A—C4A—C5A—N1A 1.9 (8)
C1—C2—C3—C4 −0.1 (10) C3A—C4A—C5A—C6A −177.2 (5)
C2—C3—C4—C5 −1.0 (11) C14A—O1A—C6A—C7A −58.1 (6)
C1—N1—C5—C4 0.4 (9) C14A—O1A—C6A—C13A 68.3 (6)
C1—N1—C5—C6 −177.9 (5) C14A—O1A—C6A—C5A −175.8 (4)
C3—C4—C5—N1 0.8 (10) N1A—C5A—C6A—O1A 172.3 (4)
C3—C4—C5—C6 179.0 (6) C4A—C5A—C6A—O1A −8.6 (7)
C14—O1—C6—C13 60.4 (6) N1A—C5A—C6A—C7A 54.6 (7)
C14—O1—C6—C7 −64.6 (6) C4A—C5A—C6A—C7A −126.3 (6)
C14—O1—C6—C5 179.5 (5) N1A—C5A—C6A—C13A −69.8 (6)
N1—C5—C6—O1 −175.4 (5) C4A—C5A—C6A—C13A 109.3 (6)
C4—C5—C6—O1 6.2 (7) O1A—C6A—C7A—C8A −48.1 (7)
N1—C5—C6—C13 −56.3 (6) C13A—C6A—C7A—C8A −172.2 (6)
C4—C5—C6—C13 125.3 (6) C5A—C6A—C7A—C8A 67.4 (7)
N1—C5—C6—C7 68.1 (6) O1A—C6A—C7A—C12A 134.3 (6)
C4—C5—C6—C7 −110.2 (6) C13A—C6A—C7A—C12A 10.1 (8)
O1—C6—C7—C8 −45.3 (7) C5A—C6A—C7A—C12A −110.3 (6)
C13—C6—C7—C8 −168.8 (5) C12A—C7A—C8A—C9A −2.3 (11)
C5—C6—C7—C8 68.4 (7) C6A—C7A—C8A—C9A −179.9 (6)
O1—C6—C7—C12 138.2 (5) C7A—C8A—C9A—C10A −0.4 (12)
C13—C6—C7—C12 14.7 (8) C8A—C9A—C10A—C11A 3.5 (15)
C5—C6—C7—C12 −108.1 (6) C9A—C10A—C11A—C12A −4.1 (18)
C12—C7—C8—C9 −1.3 (9) C10A—C11A—C12A—C7A 1.3 (16)
C6—C7—C8—C9 −177.9 (6) C8A—C7A—C12A—C11A 1.9 (12)
C7—C8—C9—C10 1.7 (10) C6A—C7A—C12A—C11A 179.6 (8)
C8—C9—C10—C11 −1.3 (11) C6A—O1A—C14A—C15A −173.2 (4)
supporting information
sup-10
Acta Cryst. (2001). E57, o163–o165
C10—C11—C12—C7 −0.2 (10) C16A—N2A—C15A—C14A 177.1 (5)
C8—C7—C12—C11 0.5 (8) O1A—C14A—C15A—N2A 58.4 (6)
C6—C7—C12—C11 177.1 (5) O3—C18—C19—C20 3.1 (8)
C6—O1—C14—C15 155.7 (5) O2—C18—C19—C20 −177.5 (5)
C16—N2—C15—C14 174.0 (4) C18—C19—C20—C21 176.7 (5)
C17—N2—C15—C14 −62.0 (6) C19—C20—C21—O4 −5.3 (8)
O1—C14—C15—N2 76.9 (6) C19—C20—C21—O5 172.7 (5)
C5A—N1A—C1A—C2A −0.1 (9) O3A—C18A—C19A—C20A 4.5 (10)
N1A—C1A—C2A—C3A 1.2 (9) O2A—C18A—C19A—C20A −173.9 (6)
C1A—C2A—C3A—C4A −0.8 (9) C18A—C19A—C20A—C21A 179.9 (6)
C2A—C3A—C4A—C5A −0.7 (9) C19A—C20A—C21A—O4A 4.3 (9)
C1A—N1A—C5A—C4A −1.5 (8) C19A—C20A—C21A—O5A −175.4 (5)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
N2—H1···O2 0.91 1.85 2.744 (5) 166
N2A—H2···O2A 0.91 2.01 2.853 (5) 153
O5—H3···O2Ai 0.82 1.73 2.538 (5) 171
O5A—H4···O2ii 0.82 1.72 2.536 (5) 171
