Atalaphylline

The title acridone alkaloid [systematic name: 1,3,5-trihydr­oxy-2,4-bis­(3-methyl­but-2-en­yl)acridin-9(10H)-one], C₂₃H₂₅NO₄, known as atalaphylline, was isolated from Atalantia monophylla Corrêa, a mangrove plant. The mol­ecule contains three fused planar rings with an r.m.s. deviation of 0.026 (2) Å. Both 3-methyl­but-2-enyl substituents are in a (−)anticlinal conformation. An intra­molecular N—H...O hydrogen bond generates an S(5) ring motif, while an intra­molecular O—H...O hydrogen bond generates an S(6) ring motif. In the crystal structure, the mol­ecules are linked into screw chains along [010] by inter­molecular O—H...O hydrogen bonds. These chains are stacked along the a axis by π–π inter­actions with centroid–centroid distances of 3.6695 (13) and 3.6696 (13) Å.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.049
• wR factor = 0.118
• Data-to-parameter ratio = 12.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT420_ALERT_2_B D-H Without Acceptor       O4     -   H1O4   ...          ?

Alert level C
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          9
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          2

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           30.00
           From the CIF: _reflns_number_total               3142
           Count of symmetry unique reflns         3153
           Completeness (_total/calc)             99.65%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT960_ALERT_3_G Number of Intensities with I .LT. - 2*sig(I) ..           1
PLAT380_ALERT_4_G Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C17
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          4

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Acridone alkaloids display a variety of biological activities such as antiproliferative (Kawii et al., 1999a), induction of human promyelocytic leukemia cell (HL-60) differentiation (Kawii et al., 1999b) and cancer chemopreventive activities (Itoigawa et al., 2003). The title acridone alkaloid (I) known as atalaphylline (Basu & Basa, 1972) was isolated from Atalantia monophylla Corrêa, known locally in Thai as Manao Phi, a mangrove plant which was collected from Trang province in the southern part of Thailand. We previously reported the crystal structure of N-methylataphyllinine, an acridone alkaloid which was isolated from the same plant (Chukaew et al., 2007). As part of our research on the crystal structures of natural product compounds from Thai medicinal plants, the molecular and crystal structure of the title acridone alkaloid was investigated and is reported here.

The title molecule (Fig. 1) has a three-fused planar rings with an r.m.s. deviation of 0.026 (2) Å. The pyridine ring makes the dihedral angles of 1.82 (11) and 1.14 (11)° with the C1–C3/C11–C13 and C5–C10 benzene rings, respectively. All the three hydroxyl groups are co-planar with the attached benzene rings. All C atoms of each of the 3-methylbut-2-enyl substituents lie on the same plane with r.m.s. deviations of 0.018 (2) and 0.004 (3)Å for the C14/C15/C16/C17/C18 and C19/C20/C21/C22/C23 planes, respectively. These two planes make dihedral angles of 88.55 (13) (for the 3-methylbut-2-enyl unit at atom C1) and 69.66 (13)° (for the 3-methylbut-2-enyl unit at atom C12) with the C1–C3/C11–C13 benzene ring. The torsion angles C2–C1–C19–C20 and C13–C12–C14–C15 are -103.0 (3) and -120.8 (2)°, indicating an (-)anti-clinal conformation of both the 3-methylbut-2-enyl units. An intramolecular N—H···O hydrogen bond generates an S(5) ring while an intramolecular O—H···O hydrogen bond generates an S(6) ring motif (Bernstein et al., 1995); these help to maintain the planarity of the acridone skeleton. The bond lengths in (I) are within normal ranges (Allen et al., 1987) and comparable with those found in a related structure (Chukaew et al., 2007).

In the crystal packing (Fig. 2), the molecules are linked into screw chains along the [0 1 0] direction by O3—H1O3···O2 hydrogen bonds (Table 1). These chains are stacked along the a axis (Fig. 2) by π···π interactions with distances Cg₁···Cg₂ = 3.6696 (13) Å and Cg₂···Cg₃ = 3.6695 (13) Å (symmetry codes for the interactions: 1 + x, y, z and -1 + x, y, z respectively); Cg₁, Cg₂ and Cg₃ are the centroids of C3–C5/C10–C11/N1, C1–C3/C11–C13 and C5–C10 rings, respectively.

Related literature

For hydrogen-bond motifs, see Bernstein et al. (1995). For bond-length data, see: Allen et al. (1987). For details of acridone alkaloids and their biological activity, see: Basu & Basa (1972); Itoigawa et al. (2003); Kawaii et al. (1999a,b). For a related structure, see: Chukaew et al. (2007). For the stability of the temperature controller used in the data collection, see Cosier & Glazer, (1986).

S2. Experimental

The air-dried and pulverized root of A. monophylla (6.0 kg) was exhaustively extracted with methylene chloride (2 × 20 l for one week) at room temperature. Removal of the solvent from the methylene chloride extract under reduced pressure gave a yellow viscous residue (52.5 g) which was subjected to quick column chromatography over silica gel using solvents of increasing polarity from n-hexane through EtOAc. The eluents were separated into 18 fractions (F1–F18) on the basis of TLC analysis. Fraction F12 (4.3 g) was further separated by quick column chromatography (QCC) with a gradient of acetone-hexane to afford 6 subfractions (12 A-12 F). Subfraction 12 C (385.0 mg) was further purified by QCC with a gradient of acetone-hexane to give the title compound (22.0 mg). Brown plate-shaped single crystals of the title compound suitable for X-ray structure determination were recrystallized from CHCl₃/CH₃OH (9:1, v/v) after several days, m.p. 518–520 K.

S3. Refinement

All H atoms were positioned geometrically and allowed to ride on their parent atoms, with d(O—H) = 0.82 Å, d(N—H) = 0.86 Å and d(C—H) = 0.93 Å for aromatic and CH, 0.97 for CH₂ and 0.96 Å for CH₃ atoms. The U_iso values were constrained to be 1.5U_eq of the carrier atom for hydroxy and methyl H atoms and 1.2U_eq for the remaining H atoms. A rotating group model was used for the methyl groups. The highest residual electron density peak is located at 0.68 Å from C5 and the deepest hole is located at 1.28 Å from C10. A total of 2260 Friedel pairs were merged before final refinement as there is no large anomalous dispersion for the determination of the absolute configuration.

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The asymmetric unit of (I), showing 50% probability displacement ellipsoids and the atomic numbering scheme. Intramolecular hydrogen bonds are shown as dashed lines.
	Fig. 2. The crystal packing of (I) view along the a axis. Hydrogen bonds are drawn as dashed lines.

1,3,5-trihydroxy-2,4-bis(3-methylbut-2-enyl)acridin-9(10H)-one

Crystal data

C23H25NO4	Dx = 1.348 Mg m^−3
Mr = 379.44	Melting point = 518–520 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3142 reflections
a = 5.0650 (1) Å	θ = 1.6–30.0°
b = 15.0131 (4) Å	µ = 0.09 mm^−1
c = 24.5813 (5) Å	T = 100 K
V = 1869.20 (7) Å^3	Plate, brown
Z = 4	0.40 × 0.21 × 0.04 mm
F(000) = 808

Data collection

Bruker APEXII CCD area-detector diffractometer	3142 independent reflections
Radiation source: sealed tube	2525 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
ϕ and ω scans	θmax = 30.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −6→7
Tmin = 0.964, Tmax = 0.996	k = −21→15
17852 measured reflections	l = −34→34

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.118	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0588P)^2 + 0.5624P] where P = (Fo^2 + 2Fc^2)/3
3142 reflections	(Δ/σ)max < 0.001
257 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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	0.3340 (3)	0.33730 (11)	0.16280 (7)	0.0193 (4)
H1O1	0.4552	0.3307	0.1845	0.029*
O2	0.7218 (3)	0.37946 (11)	0.22404 (6)	0.0183 (4)
O3	0.9035 (4)	0.77231 (10)	0.22808 (6)	0.0187 (4)
H1O3	1.0112	0.8067	0.2415	0.028*
O4	−0.0692 (3)	0.56738 (12)	0.05943 (7)	0.0220 (4)
H1O4	−0.1545	0.5244	0.0487	0.026*
N1	0.6177 (4)	0.64068 (12)	0.18267 (8)	0.0150 (4)
H1N1	0.6002	0.6956	0.1734	0.018*
C1	0.1293 (5)	0.44831 (15)	0.11046 (9)	0.0149 (5)
C2	0.3171 (5)	0.42414 (15)	0.14846 (9)	0.0148 (5)
C3	0.4888 (4)	0.48744 (14)	0.17270 (9)	0.0137 (4)
C4	0.6867 (5)	0.46079 (15)	0.21169 (9)	0.0141 (4)
C5	0.8434 (5)	0.53044 (15)	0.23695 (9)	0.0152 (5)
C6	1.0356 (5)	0.51065 (15)	0.27656 (9)	0.0193 (5)
H6A	1.0648	0.4519	0.2868	0.023*
C7	1.1794 (5)	0.57750 (17)	0.29992 (10)	0.0226 (5)
H7A	1.3061	0.5639	0.3260	0.027*
C8	1.1368 (5)	0.66664 (16)	0.28480 (9)	0.0198 (5)
H8A	1.2342	0.7116	0.3014	0.024*
C9	0.9534 (5)	0.68805 (15)	0.24586 (9)	0.0159 (5)
C10	0.8024 (5)	0.61953 (15)	0.22133 (9)	0.0147 (4)
C11	0.4593 (4)	0.57851 (14)	0.15804 (9)	0.0143 (4)
C12	0.2707 (5)	0.60543 (15)	0.11958 (9)	0.0149 (5)
C13	0.1139 (5)	0.53968 (15)	0.09674 (9)	0.0167 (5)
C14	0.2242 (5)	0.70302 (15)	0.10646 (10)	0.0176 (5)
H14A	0.0747	0.7072	0.0819	0.021*
H14B	0.1765	0.7336	0.1398	0.021*
C15	0.4547 (5)	0.75103 (16)	0.08107 (9)	0.0185 (5)
H15A	0.5447	0.7210	0.0537	0.022*
C16	0.5433 (5)	0.83205 (16)	0.09377 (10)	0.0214 (5)
C17	0.7643 (6)	0.87496 (19)	0.06275 (13)	0.0337 (7)
H17A	0.8238	0.8353	0.0347	0.051*
H17B	0.9077	0.8877	0.0871	0.051*
H17C	0.7028	0.9294	0.0466	0.051*
C18	0.4340 (6)	0.88750 (17)	0.13926 (11)	0.0284 (6)
H18A	0.2903	0.8564	0.1562	0.043*
H18B	0.3717	0.9432	0.1250	0.043*
H18C	0.5700	0.8984	0.1656	0.043*
C19	−0.0597 (5)	0.38065 (15)	0.08666 (9)	0.0179 (5)
H19A	−0.0638	0.3287	0.1101	0.022*
H19B	−0.2358	0.4060	0.0862	0.022*
C20	0.0113 (5)	0.35141 (15)	0.02980 (9)	0.0190 (5)
H20A	0.1620	0.3164	0.0266	0.023*
C21	−0.1154 (5)	0.36960 (16)	−0.01649 (10)	0.0219 (5)
C22	−0.0143 (7)	0.3355 (2)	−0.07035 (10)	0.0323 (7)
H22A	0.1369	0.2982	−0.0643	0.049*
H22B	0.0349	0.3850	−0.0929	0.049*
H22C	−0.1502	0.3017	−0.0880	0.049*
C23	−0.3584 (6)	0.4259 (2)	−0.02118 (12)	0.0333 (6)
H23A	−0.4316	0.4356	0.0143	0.050*
H23B	−0.4859	0.3961	−0.0436	0.050*
H23C	−0.3134	0.4821	−0.0373	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0209 (8)	0.0137 (8)	0.0235 (8)	−0.0020 (7)	−0.0046 (7)	0.0007 (7)
O2	0.0205 (8)	0.0100 (7)	0.0243 (8)	−0.0001 (7)	−0.0030 (7)	0.0012 (7)
O3	0.0236 (9)	0.0098 (7)	0.0227 (8)	−0.0018 (7)	−0.0055 (7)	−0.0001 (6)
O4	0.0206 (8)	0.0205 (8)	0.0251 (9)	−0.0028 (8)	−0.0084 (7)	0.0007 (7)
N1	0.0153 (9)	0.0083 (9)	0.0214 (9)	0.0004 (8)	−0.0029 (8)	0.0009 (7)
C1	0.0155 (10)	0.0137 (10)	0.0155 (10)	−0.0026 (9)	0.0010 (9)	−0.0029 (9)
C2	0.0167 (11)	0.0107 (10)	0.0169 (11)	−0.0015 (9)	0.0031 (9)	−0.0020 (9)
C3	0.0143 (10)	0.0110 (9)	0.0158 (10)	−0.0010 (9)	0.0004 (9)	−0.0014 (8)
C4	0.0147 (10)	0.0133 (10)	0.0141 (10)	0.0009 (9)	−0.0006 (9)	−0.0013 (9)
C5	0.0169 (11)	0.0121 (10)	0.0164 (10)	−0.0003 (9)	0.0003 (9)	−0.0013 (9)
C6	0.0255 (12)	0.0112 (10)	0.0213 (12)	0.0022 (10)	−0.0066 (10)	0.0013 (9)
C7	0.0264 (13)	0.0179 (11)	0.0236 (12)	0.0013 (11)	−0.0108 (11)	0.0011 (10)
C8	0.0246 (12)	0.0135 (11)	0.0211 (12)	−0.0040 (10)	−0.0063 (10)	−0.0031 (9)
C9	0.0194 (11)	0.0113 (10)	0.0170 (11)	−0.0017 (9)	0.0008 (10)	−0.0021 (9)
C10	0.0152 (10)	0.0144 (10)	0.0145 (10)	0.0006 (9)	0.0003 (9)	−0.0003 (9)
C11	0.0125 (10)	0.0115 (9)	0.0190 (11)	−0.0019 (9)	0.0013 (9)	−0.0006 (9)
C12	0.0161 (10)	0.0099 (10)	0.0186 (11)	0.0000 (9)	−0.0008 (9)	0.0011 (9)
C13	0.0159 (11)	0.0176 (11)	0.0167 (10)	0.0012 (10)	0.0006 (9)	0.0014 (9)
C14	0.0154 (11)	0.0121 (10)	0.0252 (12)	−0.0004 (9)	−0.0036 (10)	0.0024 (9)
C15	0.0200 (11)	0.0174 (11)	0.0181 (11)	0.0026 (10)	−0.0021 (9)	0.0023 (9)
C16	0.0192 (11)	0.0191 (11)	0.0258 (12)	−0.0022 (10)	−0.0084 (10)	0.0073 (10)
C17	0.0237 (13)	0.0263 (14)	0.0510 (18)	−0.0056 (13)	−0.0017 (14)	0.0111 (13)
C18	0.0376 (15)	0.0150 (11)	0.0326 (14)	−0.0031 (12)	−0.0083 (13)	−0.0037 (11)
C19	0.0172 (11)	0.0155 (10)	0.0211 (11)	−0.0045 (10)	−0.0004 (9)	0.0005 (9)
C20	0.0202 (11)	0.0148 (10)	0.0220 (12)	−0.0034 (10)	0.0012 (10)	−0.0033 (9)
C21	0.0283 (13)	0.0170 (11)	0.0205 (12)	−0.0085 (11)	0.0017 (11)	−0.0007 (10)
C22	0.0453 (17)	0.0313 (14)	0.0204 (13)	−0.0074 (15)	0.0010 (13)	−0.0022 (11)
C23	0.0268 (14)	0.0446 (17)	0.0287 (14)	−0.0006 (14)	−0.0086 (12)	0.0017 (13)

Geometric parameters (Å, º)

O1—C2	1.353 (3)	C12—C14	1.519 (3)
O1—H1O1	0.8200	C14—C15	1.508 (3)
O2—C4	1.271 (3)	C14—H14A	0.9700
O3—C9	1.362 (3)	C14—H14B	0.9700
O3—H1O3	0.8200	C15—C16	1.334 (3)
O4—C13	1.369 (3)	C15—H15A	0.9300
O4—H1O4	0.8200	C16—C17	1.500 (4)
N1—C10	1.371 (3)	C16—C18	1.500 (4)
N1—C11	1.372 (3)	C17—H17A	0.9600
N1—H1N1	0.8600	C17—H17B	0.9600
C1—C2	1.381 (3)	C17—H17C	0.9600
C1—C13	1.415 (3)	C18—H18A	0.9600
C1—C19	1.514 (3)	C18—H18B	0.9600
C2—C3	1.419 (3)	C18—H18C	0.9600
C3—C11	1.422 (3)	C19—C20	1.508 (3)
C3—C4	1.443 (3)	C19—H19A	0.9700
C4—C5	1.452 (3)	C19—H19B	0.9700
C5—C10	1.407 (3)	C20—C21	1.335 (3)
C5—C6	1.408 (3)	C20—H20A	0.9300
C6—C7	1.366 (3)	C21—C23	1.497 (4)
C6—H6A	0.9300	C21—C22	1.509 (3)
C7—C8	1.406 (3)	C22—H22A	0.9600
C7—H7A	0.9300	C22—H22B	0.9600
C8—C9	1.372 (3)	C22—H22C	0.9600
C8—H8A	0.9300	C23—H23A	0.9600
C9—C10	1.417 (3)	C23—H23B	0.9600
C11—C12	1.404 (3)	C23—H23C	0.9600
C12—C13	1.386 (3)
C2—O1—H1O1	109.5	C12—C14—H14A	108.4
C9—O3—H1O3	109.5	C15—C14—H14B	108.4
C13—O4—H1O4	109.5	C12—C14—H14B	108.4
C10—N1—C11	123.20 (19)	H14A—C14—H14B	107.5
C10—N1—H1N1	118.4	C16—C15—C14	126.8 (2)
C11—N1—H1N1	118.4	C16—C15—H15A	116.6
C2—C1—C13	117.0 (2)	C14—C15—H15A	116.6
C2—C1—C19	121.4 (2)	C15—C16—C17	121.6 (3)
C13—C1—C19	121.6 (2)	C15—C16—C18	123.8 (2)
O1—C2—C1	118.2 (2)	C17—C16—C18	114.6 (2)
O1—C2—C3	119.8 (2)	C16—C17—H17A	109.5
C1—C2—C3	122.0 (2)	C16—C17—H17B	109.5
C2—C3—C11	118.2 (2)	H17A—C17—H17B	109.5
C2—C3—C4	121.2 (2)	C16—C17—H17C	109.5
C11—C3—C4	120.5 (2)	H17A—C17—H17C	109.5
O2—C4—C3	121.5 (2)	H17B—C17—H17C	109.5
O2—C4—C5	120.9 (2)	C16—C18—H18A	109.5
C3—C4—C5	117.64 (19)	C16—C18—H18B	109.5
C10—C5—C6	119.4 (2)	H18A—C18—H18B	109.5
C10—C5—C4	119.1 (2)	C16—C18—H18C	109.5
C6—C5—C4	121.4 (2)	H18A—C18—H18C	109.5
C7—C6—C5	120.3 (2)	H18B—C18—H18C	109.5
C7—C6—H6A	119.9	C20—C19—C1	113.73 (19)
C5—C6—H6A	119.9	C20—C19—H19A	108.8
C6—C7—C8	120.4 (2)	C1—C19—H19A	108.8
C6—C7—H7A	119.8	C20—C19—H19B	108.8
C8—C7—H7A	119.8	C1—C19—H19B	108.8
C9—C8—C7	120.8 (2)	H19A—C19—H19B	107.7
C9—C8—H8A	119.6	C21—C20—C19	128.0 (2)
C7—C8—H8A	119.6	C21—C20—H20A	116.0
O3—C9—C8	124.5 (2)	C19—C20—H20A	116.0
O3—C9—C10	116.0 (2)	C20—C21—C23	125.2 (2)
C8—C9—C10	119.5 (2)	C20—C21—C22	121.0 (2)
N1—C10—C5	120.7 (2)	C23—C21—C22	113.8 (2)
N1—C10—C9	119.7 (2)	C21—C22—H22A	109.5
C5—C10—C9	119.6 (2)	C21—C22—H22B	109.5
N1—C11—C12	119.97 (19)	H22A—C22—H22B	109.5
N1—C11—C3	118.7 (2)	C21—C22—H22C	109.5
C12—C11—C3	121.3 (2)	H22A—C22—H22C	109.5
C13—C12—C11	117.3 (2)	H22B—C22—H22C	109.5
C13—C12—C14	120.8 (2)	C21—C23—H23A	109.5
C11—C12—C14	121.8 (2)	C21—C23—H23B	109.5
O4—C13—C12	116.3 (2)	H23A—C23—H23B	109.5
O4—C13—C1	119.5 (2)	C21—C23—H23C	109.5
C12—C13—C1	124.2 (2)	H23A—C23—H23C	109.5
C15—C14—C12	115.4 (2)	H23B—C23—H23C	109.5
C15—C14—H14A	108.4
C13—C1—C2—O1	179.2 (2)	O3—C9—C10—C5	179.3 (2)
C19—C1—C2—O1	2.1 (3)	C8—C9—C10—C5	−0.4 (3)
C13—C1—C2—C3	−0.3 (3)	C10—N1—C11—C12	178.7 (2)
C19—C1—C2—C3	−177.5 (2)	C10—N1—C11—C3	−0.6 (3)
O1—C2—C3—C11	−177.9 (2)	C2—C3—C11—N1	177.7 (2)
C1—C2—C3—C11	1.7 (3)	C4—C3—C11—N1	−1.7 (3)
O1—C2—C3—C4	1.4 (3)	C2—C3—C11—C12	−1.7 (3)
C1—C2—C3—C4	−179.0 (2)	C4—C3—C11—C12	179.0 (2)
C2—C3—C4—O2	3.0 (3)	N1—C11—C12—C13	−179.0 (2)
C11—C3—C4—O2	−177.7 (2)	C3—C11—C12—C13	0.3 (3)
C2—C3—C4—C5	−176.4 (2)	N1—C11—C12—C14	−3.6 (3)
C11—C3—C4—C5	2.9 (3)	C3—C11—C12—C14	175.7 (2)
O2—C4—C5—C10	178.7 (2)	C11—C12—C13—O4	179.85 (19)
C3—C4—C5—C10	−2.0 (3)	C14—C12—C13—O4	4.4 (3)
O2—C4—C5—C6	−1.2 (3)	C11—C12—C13—C1	1.2 (3)
C3—C4—C5—C6	178.2 (2)	C14—C12—C13—C1	−174.3 (2)
C10—C5—C6—C7	0.5 (4)	C2—C1—C13—O4	−179.8 (2)
C4—C5—C6—C7	−179.6 (2)	C19—C1—C13—O4	−2.7 (3)
C5—C6—C7—C8	0.1 (4)	C2—C1—C13—C12	−1.2 (3)
C6—C7—C8—C9	−0.9 (4)	C19—C1—C13—C12	176.0 (2)
C7—C8—C9—O3	−178.7 (2)	C13—C12—C14—C15	−120.8 (2)
C7—C8—C9—C10	1.0 (4)	C11—C12—C14—C15	64.0 (3)
C11—N1—C10—C5	1.6 (3)	C12—C14—C15—C16	−136.1 (2)
C11—N1—C10—C9	−178.3 (2)	C14—C15—C16—C17	−175.8 (2)
C6—C5—C10—N1	179.6 (2)	C14—C15—C16—C18	4.2 (4)
C4—C5—C10—N1	−0.2 (3)	C2—C1—C19—C20	−103.0 (3)
C6—C5—C10—C9	−0.4 (3)	C13—C1—C19—C20	79.9 (3)
C4—C5—C10—C9	179.7 (2)	C1—C19—C20—C21	−110.2 (3)
O3—C9—C10—N1	−0.7 (3)	C19—C20—C21—C23	1.2 (4)
C8—C9—C10—N1	179.6 (2)	C19—C20—C21—C22	179.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O2	0.82	1.82	2.554 (2)	149
O3—H1O3···O2^i	0.82	1.93	2.752 (2)	175
N1—H1N1···O3	0.86	2.34	2.692 (3)	105
C14—H14A···O4	0.97	2.29	2.773 (3)	110
C19—H19A···O1	0.97	2.40	2.811 (3)	105

Symmetry code: (i) −x+2, y+1/2, −z+1/2.