Crystal structure of 2-[9-(2-hy­droxy­phen­yl)-1,8-dioxo-1,2,3,4,5,6,7,8,9,10-deca­hydro­acridin-10-yl]acetic acid

Akkurt, M.; Jasinski, J.P.; Mohamed, S.K.; Allah, O.A.A.; Tamam, A.H.A.; Albayati, M.R.

doi:10.1107/S2056989015021611

Crystal structure of 2-[9-(2-hydroxyphenyl)-1,8-dioxo-1,2,3,4,5,6,7,8,9,10-decahydroacridin-10-yl]acetic acid

M. Akkurt, J. P. Jasinski, S. K. Mohamed, O. A. A. Allah, A. H. A. Tamam and M. R. Albayati

The title compound, C₂₁H₂₁NO₅, crystallizes with two molecules in the asymmetric unit. In each molecule, the central 1,4-dihydropyridine ring adopts a shallow sofa conformations (with the C atom bearing the phenol ring as the flap), whereas the pendant cyclohexene rings both have twisted-boat conformations. Each molecule features an intramolecular O—H

O hydrogen bond, which closes an S(8) ring. In the crystal, the molecules are linked by O—H

O, C—H

O and C—H

π interactions, forming a three-dimensional network.

Keywords: crystal structure; acridines; acetic acid; hydrogen bonding; C—H

π interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989015021611/hb7542sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989015021611/hb7542Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989015021611/hb7542Isup3.cml Supplementary material

CCDC reference: 1437049

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.004 Å
R factor = 0.079
wR factor = 0.229
Data-to-parameter ratio = 23.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O4     --  C15     ..        6.5 su
PLAT242_ALERT_2_C Low       Ueq as Compared to Neighbors for .....        C15 Check
PLAT410_ALERT_2_C Short Intra H...H Contact  H10D   ..  H14C    ..       1.97 Ang.
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......     16.183 Check
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      3.135 Check
PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Th(Min) ...          9 Report
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          3 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          8 Note
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          6 Note
PLAT793_ALERT_4_G The Model has Chirality at C7      (Centro SPGR)          S Verify
PLAT793_ALERT_4_G The Model has Chirality at C7'     (Centro SPGR)          S Verify
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          7 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600       1315 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   7 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  10 ALERT level G = General information/check it is not something unexpected

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

Comment top

Acridines and acridinium salts are highly fluorescent (Szymanska et al., 2000), and as electron acceptors in photochemical processes (Fox & Chanon, 1988). In addition, acridine derivatives have found application as antimalarial, and antitumour agents (Groundwater & Munawar, 1997; Cane et al., 1991). In this context, we report herein the synthesis and crystal structure of the title compound.

Fig. 1 shows two molecules (A and B) of the title compound in the asymmetric unit. In the molecules (A and B), the central 1,4-dihydropyridine rings (N1/C5–C9 and N1'/C5'–C9') of the 1,2,3,4,5,6,7,8,9,10-decahydroacridine ring systems (N1/C1–C13 and N1'/C1'–C13') adopt nearly a chair conformation [the puckering parameters are Q_T = 0.261 (2) Å, θ = 110.0 (4) °, φ = 360.0 (5) ° and Q_T = 0.337 (2) Å, θ = 108.1 (3) °, φ = 4.8 (4) °, repsectively], which the cyclohexene rings (C1–C6, C8–C13 and C1'–C6', C8'–C13') of the 1,2,3,4,5,6,7,8,9,10-decahydroacridine ring systems have a twisted-boat conformation [for molecule A, the puckering parameters are Q_T = 0.470 (4) Å, θ = 120.0 (4) °, φ = 286.9 (4) ° and Q_T = 0.460 (3) Å, θ = 60.2 (4) °, φ = 196.0 (4) °, repsectively, and for molecule B, Q_T = 0.465 (3) Å, θ = 120.0 (4) °, φ = 288.3 (4) ° and Q_T = 0.474 (3) Å, θ = 61.3 (4) °, φ = 194.8 (4) °, respectively].

In the crystal structure, adjacent molecules are connected by O—H···O, C—H···O and C—H···π interactions, forming a three-dimensional network (Table 1, Fig. 2).

Related literature top

For the industrial and pharmaceutical applications of acridine compounds, see: Szymanska et al. (2000); Fox & Chanon (1988); Groundwater & Munawar (1997); Cane et al. (1991).

Experimental top

A mixture of ethyl 2-[9-(2-hydroxyphenyl)-1,8-dioxo-2,3,4,5,6,7,8,9-octahydroacridin- 10(1H)-yl) acetate (2.0 g, 0.005 mol) and a solution of NaOH (0.4 g, 0.01 mol) in (40 ml) ethanol was heated under reflux for 5 h. The reaction mixture was poured onto cold water and acidified with conc. HCl. The separated solid was filtered off, dried and crystallized from ethanol to afford dark red prisms. Yield: 93.5%, mp. 511–513 K. IR (λ_max, cm^-1): 3356 (OH_acid), 3119 (OH_arom.), 3081 (CH_arom.) 2969–2852 (CH_aliph.), 1726 (C=O_acid), 1625 (C=O_{cyclic ketone}). ¹H-NMR (DMSO-d₆), δ p.p.m.: 13.39 (s, 1H, OH acid, disappeared by D₂O), 9.6 (s, 1H, OH_arom., disappeared by D₂O), 6.96–6.67 (m, 4H, CH_arom.), 4.99 (s, 1H, CH), 4.72 (s, 2H, CH₂COOH), 2.91 (t, 2H, CH₂C=O), 2.45 (t, 2H, CH₂CO), 2.29 (t, 4H, 2CH₂-C=C), 1.96 (m, 2H, CH₂—CH₂—CH₂), 1.81 (m, 2H, CH₂–CH₂–CH₂). ¹³C-NMR (DMSO-d₆), δ p.p.m.: 197.62, 171.23, 156.26, 153.83, 132.81, 128.46, 127.77, 120.23, 117.26, 114.83, 47.93, 36.06, 25.99, 25.67.

Structure description top

In the crystal structure, adjacent molecules are connected by O—H···O, C—H···O and C—H···π interactions, forming a three-dimensional network (Table 1, Fig. 2).

For the industrial and pharmaceutical applications of acridine compounds, see: Szymanska et al. (2000); Fox & Chanon (1988); Groundwater & Munawar (1997); Cane et al. (1991).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. View of two molecules in the asymmetric unit of the title compound with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. View of the hydrogen bonding and packing of the title compounds down the [010] axis. H atoms not involved in hydrogen bonding have been omitted for clarity.

2-[9-(2-Hydroxyphenyl)-1,8-dioxo-1,2,3,4,5,6,7,8,9,10-decahydroacridin-10-yl]acetic acid top

Crystal data top

C₂₁H₂₁NO₅	F(000) = 1552
M_r = 367.39	D_x = 1.373 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4652 reflections
a = 19.4735 (7) Å	θ = 3.8–27.1°
b = 8.9773 (4) Å	µ = 0.10 mm⁻¹
c = 20.3414 (8) Å	T = 293 K
β = 91.619 (3)°	Prism, dark red
V = 3554.7 (2) Å³	0.26 × 0.22 × 0.12 mm
Z = 8

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	11946 independent reflections
Radiation source: Enhance (Mo) X-ray Source	6442 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
Detector resolution: 16.0416 pixels mm^-1	θ_max = 32.9°, θ_min = 2.9°
ω scans	h = −19→29
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −13→13
T_min = 0.901, T_max = 1.000	l = −30→30
33119 measured reflections

Refinement top

Refinement on F²	7 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.079	w = 1/[σ²(F_o²) + (0.092P)² + 1.4407P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.229	(Δ/σ)_max < 0.001
S = 1.01	Δρ_max = 0.36 e Å⁻³
11946 reflections	Δρ_min = −0.36 e Å⁻³
499 parameters

Crystal data top

C₂₁H₂₁NO₅	V = 3554.7 (2) Å³
M_r = 367.39	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 19.4735 (7) Å	µ = 0.10 mm⁻¹
b = 8.9773 (4) Å	T = 293 K
c = 20.3414 (8) Å	0.26 × 0.22 × 0.12 mm
β = 91.619 (3)°

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	11946 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	6442 reflections with I > 2σ(I)
T_min = 0.901, T_max = 1.000	R_int = 0.044
33119 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.079	499 parameters
wR(F²) = 0.229	7 restraints
S = 1.01	Δρ_max = 0.36 e Å⁻³
11946 reflections	Δρ_min = −0.36 e Å⁻³

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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) top

	x	y	z	U_iso*/U_eq
O1	0.54951 (10)	1.0494 (2)	0.80712 (11)	0.0622 (7)
O2	0.46153 (8)	0.56884 (17)	0.87478 (8)	0.0433 (5)
O3	0.36550 (14)	0.6857 (4)	0.58385 (13)	0.1172 (15)
O4	0.41939 (12)	0.6805 (4)	0.49001 (11)	0.0891 (9)
O5	0.44030 (11)	1.0230 (2)	0.87818 (9)	0.0565 (6)
N1	0.48876 (10)	0.6798 (2)	0.65174 (9)	0.0445 (6)
C1	0.54926 (12)	1.0057 (3)	0.75006 (15)	0.0496 (8)
O1'	0.39287 (9)	0.2869 (3)	0.52414 (10)	0.0675 (8)
C2	0.59167 (17)	1.0827 (4)	0.69950 (18)	0.0732 (13)
O2'	0.29880 (9)	0.7291 (2)	0.42658 (10)	0.0601 (7)
C3	0.5597 (2)	1.0692 (4)	0.63282 (18)	0.0815 (15)
O3'	0.10134 (9)	0.1149 (2)	0.42055 (10)	0.0653 (7)
C4	0.54754 (17)	0.9082 (3)	0.61352 (15)	0.0661 (10)
O4'	−0.00242 (8)	0.1429 (2)	0.46142 (8)	0.0472 (5)
C5	0.51323 (12)	0.8215 (3)	0.66776 (12)	0.0446 (7)
O5'	0.37299 (12)	0.5356 (3)	0.34753 (12)	0.0773 (9)
C6	0.50975 (11)	0.8746 (2)	0.72947 (11)	0.0401 (7)
C7	0.46943 (10)	0.7948 (2)	0.78090 (10)	0.0336 (6)
C8	0.46571 (10)	0.6316 (2)	0.76357 (10)	0.0341 (6)
C9	0.47006 (11)	0.5828 (2)	0.70101 (10)	0.0366 (6)
C10	0.45820 (13)	0.4225 (3)	0.68218 (12)	0.0473 (8)
C11	0.42648 (14)	0.3332 (3)	0.73625 (13)	0.0524 (8)
C12	0.46099 (16)	0.3626 (3)	0.80162 (13)	0.0533 (8)
C13	0.46154 (10)	0.5261 (2)	0.81698 (11)	0.0360 (6)
C14	0.48528 (14)	0.6324 (3)	0.58306 (12)	0.0538 (9)
C15	0.41689 (17)	0.6716 (4)	0.55438 (14)	0.0623 (10)
C16	0.39868 (11)	0.8636 (2)	0.78994 (10)	0.0355 (6)
C17	0.34257 (12)	0.8207 (3)	0.75127 (12)	0.0479 (8)
C18	0.27772 (14)	0.8762 (4)	0.76125 (15)	0.0654 (10)
C19	0.26799 (16)	0.9772 (4)	0.81090 (16)	0.0682 (11)
C20	0.32242 (17)	1.0251 (3)	0.84917 (14)	0.0609 (10)
C21	0.38832 (13)	0.9711 (3)	0.83864 (11)	0.0438 (7)
N1'	0.15357 (8)	0.3463 (2)	0.49752 (8)	0.0362 (5)
C1'	0.33538 (12)	0.2426 (3)	0.53659 (12)	0.0468 (8)
C2'	0.32463 (16)	0.1296 (4)	0.58950 (16)	0.0689 (11)
C3'	0.26161 (16)	0.0409 (4)	0.57678 (18)	0.0716 (11)
C4'	0.19809 (13)	0.1389 (3)	0.56772 (12)	0.0491 (8)
C5'	0.21077 (11)	0.2651 (2)	0.52069 (10)	0.0360 (6)
C6'	0.27448 (10)	0.3044 (2)	0.50276 (10)	0.0361 (6)
C7'	0.28481 (10)	0.4197 (2)	0.45054 (10)	0.0365 (6)
C8'	0.22693 (10)	0.5304 (2)	0.45338 (10)	0.0352 (6)
C9'	0.16270 (10)	0.4853 (2)	0.46978 (10)	0.0336 (6)
C10'	0.10140 (11)	0.5844 (3)	0.46075 (11)	0.0442 (7)
C11'	0.11568 (13)	0.7190 (3)	0.41893 (14)	0.0550 (9)
C12'	0.18185 (14)	0.7926 (3)	0.43997 (15)	0.0580 (9)
C13'	0.24005 (12)	0.6846 (3)	0.43923 (11)	0.0428 (7)
C14'	0.08462 (11)	0.2878 (3)	0.50771 (11)	0.0412 (7)
C15'	0.06362 (11)	0.1735 (2)	0.45782 (11)	0.0382 (6)
C16'	0.28966 (11)	0.3533 (3)	0.38153 (11)	0.0422 (7)
C17'	0.24941 (14)	0.2339 (4)	0.36209 (13)	0.0594 (9)
C18'	0.25191 (18)	0.1744 (5)	0.29965 (15)	0.0773 (13)
C19'	0.29600 (19)	0.2327 (5)	0.25536 (15)	0.0817 (13)
C20'	0.33619 (17)	0.3501 (4)	0.27253 (14)	0.0710 (13)
C21'	0.33296 (13)	0.4147 (3)	0.33476 (13)	0.0538 (9)
H2A	0.59640	1.18720	0.71090	0.0880*
H2B	0.63720	1.03910	0.69970	0.0880*
H3A	0.58940	1.11560	0.60120	0.0980*
H3B	0.51620	1.12200	0.63150	0.0980*
H4	0.3763 (10)	0.686 (4)	0.4766 (17)	0.0850*
H4A	0.59110	0.86180	0.60400	0.0790*
H4B	0.51870	0.90450	0.57390	0.0790*
H5	0.4779 (12)	1.025 (4)	0.8603 (16)	0.0850*
H7	0.49510	0.80370	0.82280	0.0400*
H10A	0.50170	0.37770	0.67120	0.0570*
H10B	0.42820	0.41860	0.64330	0.0570*
H11A	0.37810	0.35810	0.73850	0.0630*
H11B	0.42990	0.22800	0.72610	0.0630*
H12A	0.50780	0.32580	0.80130	0.0640*
H12B	0.43700	0.30960	0.83560	0.0640*
H14A	0.49240	0.52570	0.58030	0.0640*
H14B	0.52100	0.68150	0.55880	0.0640*
H17	0.34880	0.75250	0.71760	0.0570*
H18	0.24080	0.84560	0.73460	0.0780*
H19	0.22410	1.01310	0.81850	0.0820*
H20	0.31550	1.09410	0.88240	0.0730*
H2'1	0.36400	0.06330	0.59220	0.0830*
H2'2	0.32130	0.18000	0.63150	0.0830*
H3'1	0.25500	−0.02650	0.61330	0.0860*
H4'	−0.013 (2)	0.088 (4)	0.4291 (15)	0.1160*
H3'2	0.26720	−0.01870	0.53750	0.0860*
H5'	0.353 (2)	0.590 (4)	0.3751 (18)	0.1160*
H4'1	0.16000	0.07900	0.55100	0.0590*
H4'2	0.18560	0.17920	0.61000	0.0590*
H7'	0.32790	0.47230	0.46090	0.0440*
H10C	0.08660	0.61730	0.50350	0.0530*
H10D	0.06410	0.52780	0.44040	0.0530*
H11C	0.11810	0.68890	0.37330	0.0660*
H11D	0.07830	0.78970	0.42240	0.0660*
H12C	0.19110	0.87480	0.41060	0.0700*
H12D	0.17770	0.83260	0.48400	0.0700*
H14C	0.05200	0.36940	0.50590	0.0490*
H14D	0.08310	0.24390	0.55120	0.0490*
H17'	0.21970	0.19230	0.39200	0.0710*
H18'	0.22370	0.09470	0.28780	0.0930*
H19'	0.29840	0.19180	0.21350	0.0980*
H20'	0.36650	0.38840	0.24230	0.0850*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0625 (12)	0.0388 (10)	0.0849 (14)	−0.0124 (9)	−0.0024 (10)	−0.0031 (10)
O2	0.0532 (9)	0.0330 (8)	0.0441 (8)	0.0069 (7)	0.0067 (7)	0.0040 (7)
O3	0.0716 (16)	0.201 (4)	0.0788 (16)	0.0340 (19)	−0.0036 (13)	−0.010 (2)
O4	0.0745 (15)	0.130 (2)	0.0619 (13)	−0.0260 (16)	−0.0121 (11)	0.0250 (14)
O5	0.0814 (13)	0.0385 (9)	0.0495 (10)	−0.0029 (10)	0.0027 (9)	−0.0070 (8)
N1	0.0530 (11)	0.0409 (11)	0.0402 (10)	0.0023 (9)	0.0120 (8)	0.0023 (8)
C1	0.0378 (12)	0.0308 (12)	0.0806 (18)	0.0008 (10)	0.0074 (11)	0.0099 (12)
O1'	0.0364 (9)	0.0949 (17)	0.0712 (12)	0.0032 (10)	0.0009 (8)	0.0210 (11)
C2	0.0665 (19)	0.0437 (16)	0.111 (3)	−0.0115 (14)	0.0289 (18)	0.0119 (16)
O2'	0.0464 (10)	0.0474 (11)	0.0862 (13)	−0.0130 (8)	−0.0034 (9)	0.0174 (10)
C3	0.102 (3)	0.0479 (17)	0.097 (3)	−0.0075 (17)	0.048 (2)	0.0218 (17)
O3'	0.0486 (10)	0.0677 (13)	0.0806 (13)	−0.0091 (9)	0.0210 (9)	−0.0326 (11)
C4	0.0743 (19)	0.0516 (17)	0.0743 (18)	0.0038 (15)	0.0354 (15)	0.0169 (14)
O4'	0.0376 (8)	0.0464 (10)	0.0579 (10)	−0.0082 (7)	0.0069 (7)	−0.0111 (8)
C5	0.0420 (12)	0.0351 (12)	0.0575 (14)	0.0033 (10)	0.0141 (10)	0.0122 (10)
O5'	0.0692 (13)	0.0725 (16)	0.0921 (16)	−0.0095 (12)	0.0374 (11)	0.0162 (12)
C6	0.0364 (11)	0.0285 (10)	0.0558 (13)	0.0020 (9)	0.0093 (9)	0.0064 (9)
C7	0.0352 (10)	0.0258 (10)	0.0398 (10)	−0.0001 (8)	0.0031 (8)	0.0020 (8)
C8	0.0320 (10)	0.0264 (10)	0.0441 (11)	0.0012 (8)	0.0062 (8)	0.0020 (8)
C9	0.0349 (10)	0.0320 (11)	0.0430 (11)	0.0026 (9)	0.0055 (8)	0.0022 (9)
C10	0.0545 (14)	0.0370 (12)	0.0507 (13)	0.0011 (11)	0.0063 (10)	−0.0064 (10)
C11	0.0601 (15)	0.0346 (13)	0.0624 (15)	−0.0088 (11)	0.0025 (12)	−0.0014 (11)
C12	0.0791 (18)	0.0262 (11)	0.0546 (14)	−0.0015 (12)	0.0040 (12)	0.0034 (10)
C13	0.0316 (10)	0.0284 (10)	0.0482 (12)	0.0025 (8)	0.0054 (8)	0.0035 (9)
C14	0.0625 (16)	0.0557 (16)	0.0435 (13)	0.0037 (13)	0.0095 (11)	0.0027 (11)
C15	0.0685 (19)	0.070 (2)	0.0484 (15)	−0.0049 (16)	0.0012 (13)	0.0032 (13)
C16	0.0408 (11)	0.0287 (10)	0.0375 (10)	0.0056 (9)	0.0088 (8)	0.0046 (8)
C17	0.0428 (12)	0.0545 (15)	0.0466 (12)	0.0086 (11)	0.0054 (10)	−0.0047 (11)
C18	0.0434 (14)	0.086 (2)	0.0669 (17)	0.0169 (15)	0.0031 (12)	0.0012 (16)
C19	0.0555 (17)	0.072 (2)	0.078 (2)	0.0292 (16)	0.0182 (15)	0.0098 (16)
C20	0.082 (2)	0.0421 (14)	0.0599 (16)	0.0219 (14)	0.0268 (14)	0.0026 (12)
C21	0.0616 (14)	0.0294 (11)	0.0409 (11)	0.0049 (10)	0.0095 (10)	0.0052 (9)
N1'	0.0292 (8)	0.0374 (10)	0.0422 (9)	−0.0049 (7)	0.0069 (7)	−0.0046 (7)
C1'	0.0410 (12)	0.0535 (15)	0.0459 (12)	0.0038 (11)	0.0018 (9)	0.0020 (11)
C2'	0.0591 (17)	0.075 (2)	0.0720 (19)	0.0043 (16)	−0.0084 (14)	0.0261 (16)
C3'	0.0713 (19)	0.0569 (18)	0.086 (2)	−0.0039 (15)	−0.0069 (16)	0.0285 (16)
C4'	0.0536 (14)	0.0469 (14)	0.0470 (13)	−0.0098 (12)	0.0071 (10)	0.0056 (11)
C5'	0.0376 (11)	0.0336 (11)	0.0369 (10)	−0.0030 (9)	0.0050 (8)	−0.0028 (8)
C6'	0.0345 (10)	0.0365 (11)	0.0375 (10)	0.0010 (9)	0.0046 (8)	−0.0014 (8)
C7'	0.0286 (9)	0.0361 (11)	0.0449 (11)	−0.0009 (9)	0.0040 (8)	0.0021 (9)
C8'	0.0315 (10)	0.0346 (11)	0.0395 (10)	−0.0018 (8)	0.0023 (8)	−0.0017 (8)
C9'	0.0326 (10)	0.0350 (11)	0.0334 (10)	−0.0015 (8)	0.0025 (7)	−0.0066 (8)
C10'	0.0339 (11)	0.0530 (14)	0.0458 (12)	0.0058 (10)	0.0029 (9)	−0.0017 (10)
C11'	0.0497 (14)	0.0535 (16)	0.0618 (15)	0.0157 (12)	0.0008 (11)	0.0033 (12)
C12'	0.0601 (16)	0.0362 (13)	0.0775 (18)	0.0065 (12)	−0.0011 (13)	−0.0008 (12)
C13'	0.0394 (12)	0.0369 (12)	0.0519 (13)	−0.0039 (10)	−0.0029 (9)	0.0011 (10)
C14'	0.0305 (10)	0.0420 (12)	0.0517 (12)	−0.0055 (9)	0.0109 (9)	−0.0070 (10)
C15'	0.0343 (10)	0.0329 (11)	0.0478 (12)	−0.0022 (9)	0.0065 (9)	−0.0018 (9)
C16'	0.0328 (10)	0.0492 (14)	0.0452 (12)	0.0106 (10)	0.0112 (9)	0.0049 (10)
C17'	0.0534 (15)	0.0712 (19)	0.0543 (15)	−0.0054 (14)	0.0167 (12)	−0.0141 (13)
C18'	0.074 (2)	0.098 (3)	0.0604 (17)	−0.0054 (19)	0.0126 (15)	−0.0292 (17)
C19'	0.087 (2)	0.108 (3)	0.0509 (17)	0.018 (2)	0.0158 (16)	−0.0081 (18)
C20'	0.0696 (19)	0.093 (3)	0.0521 (16)	0.0293 (19)	0.0298 (14)	0.0192 (16)
C21'	0.0456 (13)	0.0590 (17)	0.0575 (15)	0.0118 (12)	0.0157 (11)	0.0162 (12)

Geometric parameters (Å, º) top

O1—C1	1.225 (4)	C11—H11A	0.9700
O2—C13	1.237 (3)	C11—H11B	0.9700
O3—C15	1.188 (4)	C12—H12A	0.9700
O4—C15	1.314 (4)	C12—H12B	0.9700
O5—C21	1.357 (3)	C14—H14A	0.9700
N1—C5	1.394 (3)	C14—H14B	0.9700
N1—C9	1.384 (3)	C17—H17	0.9300
N1—C14	1.460 (3)	C18—H18	0.9300
O4—H4	0.88 (2)	C19—H19	0.9300
O5—H5	0.83 (3)	C20—H20	0.9300
C1—C6	1.461 (3)	C1'—C6'	1.463 (3)
C1—C2	1.505 (4)	C1'—C2'	1.498 (4)
O1'—C1'	1.221 (3)	C2'—C3'	1.480 (5)
C2—C3	1.481 (5)	C3'—C4'	1.525 (4)
O2'—C13'	1.246 (3)	C4'—C5'	1.508 (3)
C3—C4	1.515 (5)	C5'—C6'	1.350 (3)
O3'—C15'	1.193 (3)	C6'—C7'	1.501 (3)
C4—C5	1.520 (4)	C7'—C16'	1.531 (3)
O4'—C15'	1.319 (3)	C7'—C8'	1.505 (3)
C5—C6	1.346 (3)	C8'—C13'	1.438 (3)
O5'—C21'	1.357 (4)	C8'—C9'	1.365 (3)
C6—C7	1.507 (3)	C9'—C10'	1.496 (3)
C7—C16	1.526 (3)	C10'—C11'	1.508 (4)
C7—C8	1.508 (3)	C11'—C12'	1.500 (4)
C8—C9	1.351 (3)	C12'—C13'	1.492 (4)
C8—C13	1.445 (3)	C14'—C15'	1.492 (3)
C9—C10	1.505 (3)	C16'—C21'	1.402 (3)
C10—C11	1.507 (4)	C16'—C17'	1.379 (4)
C11—C12	1.496 (4)	C17'—C18'	1.380 (4)
C12—C13	1.501 (3)	C18'—C19'	1.366 (5)
C14—C15	1.481 (4)	C19'—C20'	1.353 (5)
C16—C17	1.383 (3)	C20'—C21'	1.395 (4)
C16—C21	1.402 (3)	C2'—H2'1	0.9700
C17—C18	1.378 (4)	C2'—H2'2	0.9700
C18—C19	1.374 (5)	C3'—H3'1	0.9700
C19—C20	1.367 (4)	C3'—H3'2	0.9700
C20—C21	1.394 (4)	C4'—H4'1	0.9700
N1'—C5'	1.402 (3)	C4'—H4'2	0.9700
N1'—C9'	1.383 (3)	C7'—H7'	0.9800
N1'—C14'	1.462 (3)	C10'—H10C	0.9700
C2—H2A	0.9700	C10'—H10D	0.9700
C2—H2B	0.9700	C11'—H11C	0.9700
C3—H3A	0.9700	C11'—H11D	0.9700
C3—H3B	0.9700	C12'—H12C	0.9700
C4—H4A	0.9700	C12'—H12D	0.9700
C4—H4B	0.9700	C14'—H14C	0.9700
O4'—H4'	0.84 (3)	C14'—H14D	0.9700
O5'—H5'	0.85 (4)	C17'—H17'	0.9300
C7—H7	0.9800	C18'—H18'	0.9300
C10—H10B	0.9700	C19'—H19'	0.9300
C10—H10A	0.9700	C20'—H20'	0.9300

C5—N1—C9	120.01 (18)	C17—C18—H18	120.00
C5—N1—C14	119.74 (19)	C20—C19—H19	120.00
C9—N1—C14	120.22 (18)	C18—C19—H19	120.00
C15—O4—H4	105 (2)	C19—C20—H20	120.00
C21—O5—H5	114 (2)	C21—C20—H20	120.00
C2—C1—C6	118.0 (3)	C2'—C1'—C6'	117.8 (2)
O1—C1—C2	120.9 (3)	O1'—C1'—C2'	121.1 (2)
O1—C1—C6	121.2 (2)	O1'—C1'—C6'	121.0 (2)
C1—C2—C3	111.3 (3)	C1'—C2'—C3'	111.8 (3)
C2—C3—C4	112.0 (3)	C2'—C3'—C4'	112.1 (3)
C3—C4—C5	111.7 (3)	C3'—C4'—C5'	111.3 (2)
N1—C5—C4	116.9 (2)	N1'—C5'—C4'	117.47 (19)
N1—C5—C6	121.0 (2)	N1'—C5'—C6'	120.06 (17)
C4—C5—C6	122.0 (2)	C4'—C5'—C6'	122.42 (19)
C1—C6—C5	120.8 (2)	C1'—C6'—C5'	120.84 (19)
C5—C6—C7	121.33 (19)	C5'—C6'—C7'	120.94 (18)
C1—C6—C7	117.7 (2)	C1'—C6'—C7'	118.12 (18)
C8—C7—C16	112.57 (16)	C8'—C7'—C16'	110.98 (17)
C6—C7—C16	112.41 (16)	C6'—C7'—C16'	113.18 (17)
C6—C7—C8	108.79 (16)	C6'—C7'—C8'	108.23 (16)
C7—C8—C9	122.10 (17)	C7'—C8'—C9'	120.39 (16)
C7—C8—C13	117.66 (17)	C7'—C8'—C13'	119.37 (18)
C9—C8—C13	120.13 (17)	C9'—C8'—C13'	120.24 (18)
N1—C9—C8	120.19 (17)	N1'—C9'—C8'	119.77 (17)
C8—C9—C10	122.45 (18)	C8'—C9'—C10'	121.81 (18)
N1—C9—C10	117.31 (18)	N1'—C9'—C10'	118.38 (18)
C9—C10—C11	112.7 (2)	C9'—C10'—C11'	112.74 (18)
C10—C11—C12	111.8 (2)	C10'—C11'—C12'	111.3 (2)
C11—C12—C13	111.0 (2)	C11'—C12'—C13'	111.0 (2)
O2—C13—C12	120.08 (19)	O2'—C13'—C12'	119.7 (2)
O2—C13—C8	120.85 (17)	O2'—C13'—C8'	121.3 (2)
C8—C13—C12	118.99 (19)	C8'—C13'—C12'	119.0 (2)
N1—C14—C15	108.9 (2)	N1'—C14'—C15'	112.69 (18)
O3—C15—C14	126.0 (3)	O3'—C15'—C14'	125.0 (2)
O4—C15—C14	110.4 (3)	O4'—C15'—C14'	110.75 (18)
O3—C15—O4	123.5 (3)	O3'—C15'—O4'	124.2 (2)
C17—C16—C21	117.8 (2)	C17'—C16'—C21'	117.3 (2)
C7—C16—C17	121.36 (18)	C7'—C16'—C17'	121.1 (2)
C7—C16—C21	120.82 (19)	C7'—C16'—C21'	121.6 (2)
C16—C17—C18	121.9 (2)	C16'—C17'—C18'	122.0 (3)
C17—C18—C19	119.5 (3)	C17'—C18'—C19'	119.9 (4)
C18—C19—C20	120.4 (3)	C18'—C19'—C20'	119.9 (3)
C19—C20—C21	120.4 (3)	C19'—C20'—C21'	121.2 (3)
C16—C21—C20	120.0 (2)	C16'—C21'—C20'	119.7 (3)
O5—C21—C16	122.4 (2)	O5'—C21'—C16'	122.5 (2)
O5—C21—C20	117.6 (2)	O5'—C21'—C20'	117.8 (3)
C5'—N1'—C9'	119.76 (16)	C1'—C2'—H2'1	109.00
C5'—N1'—C14'	119.33 (18)	C1'—C2'—H2'2	109.00
C9'—N1'—C14'	120.74 (17)	C3'—C2'—H2'1	109.00
C3—C2—H2B	109.00	C3'—C2'—H2'2	109.00
H2A—C2—H2B	108.00	H2'1—C2'—H2'2	108.00
C1—C2—H2A	109.00	C2'—C3'—H3'1	109.00
C1—C2—H2B	109.00	C2'—C3'—H3'2	109.00
C3—C2—H2A	109.00	C4'—C3'—H3'1	109.00
C2—C3—H3A	109.00	C4'—C3'—H3'2	109.00
C2—C3—H3B	109.00	H3'1—C3'—H3'2	108.00
C4—C3—H3A	109.00	C3'—C4'—H4'1	109.00
C4—C3—H3B	109.00	C3'—C4'—H4'2	109.00
H3A—C3—H3B	108.00	C5'—C4'—H4'1	109.00
C3—C4—H4B	109.00	C5'—C4'—H4'2	109.00
H4A—C4—H4B	108.00	H4'1—C4'—H4'2	108.00
C5—C4—H4A	109.00	C6'—C7'—H7'	108.00
C5—C4—H4B	109.00	C8'—C7'—H7'	108.00
C3—C4—H4A	109.00	C16'—C7'—H7'	108.00
C15'—O4'—H4'	107 (3)	C9'—C10'—H10C	109.00
C21'—O5'—H5'	108 (3)	C9'—C10'—H10D	109.00
C8—C7—H7	108.00	C11'—C10'—H10C	109.00
C16—C7—H7	108.00	C11'—C10'—H10D	109.00
C6—C7—H7	108.00	H10C—C10'—H10D	108.00
C9—C10—H10B	109.00	C10'—C11'—H11C	109.00
C9—C10—H10A	109.00	C10'—C11'—H11D	109.00
H10A—C10—H10B	108.00	C12'—C11'—H11C	109.00
C11—C10—H10A	109.00	C12'—C11'—H11D	109.00
C11—C10—H10B	109.00	H11C—C11'—H11D	108.00
C10—C11—H11A	109.00	C11'—C12'—H12C	109.00
H11A—C11—H11B	108.00	C11'—C12'—H12D	109.00
C12—C11—H11B	109.00	C13'—C12'—H12C	110.00
C10—C11—H11B	109.00	C13'—C12'—H12D	109.00
C12—C11—H11A	109.00	H12C—C12'—H12D	108.00
C13—C12—H12A	109.00	N1'—C14'—H14C	109.00
C11—C12—H12B	109.00	N1'—C14'—H14D	109.00
C11—C12—H12A	109.00	C15'—C14'—H14C	109.00
C13—C12—H12B	109.00	C15'—C14'—H14D	109.00
H12A—C12—H12B	108.00	H14C—C14'—H14D	108.00
C15—C14—H14A	110.00	C16'—C17'—H17'	119.00
C15—C14—H14B	110.00	C18'—C17'—H17'	119.00
N1—C14—H14B	110.00	C17'—C18'—H18'	120.00
N1—C14—H14A	110.00	C19'—C18'—H18'	120.00
H14A—C14—H14B	108.00	C18'—C19'—H19'	120.00
C16—C17—H17	119.00	C20'—C19'—H19'	120.00
C18—C17—H17	119.00	C19'—C20'—H20'	119.00
C19—C18—H18	120.00	C21'—C20'—H20'	119.00

C5—N1—C9—C8	9.8 (3)	C5'—N1'—C9'—C8'	12.7 (3)
C14—N1—C9—C8	−172.4 (2)	C14'—N1'—C9'—C8'	−172.10 (19)
C5—N1—C14—C15	−90.8 (3)	C5'—N1'—C14'—C15'	−81.6 (2)
C9—N1—C14—C15	91.4 (3)	C9'—N1'—C14'—C15'	103.3 (2)
C14—N1—C5—C4	−11.2 (3)	C14'—N1'—C5'—C4'	−13.1 (3)
C9—N1—C5—C6	−9.8 (3)	C9'—N1'—C5'—C6'	−15.4 (3)
C14—N1—C5—C6	172.4 (2)	C14'—N1'—C5'—C6'	169.37 (19)
C9—N1—C5—C4	166.6 (2)	C9'—N1'—C5'—C4'	162.15 (19)
C5—N1—C9—C10	−167.6 (2)	C5'—N1'—C9'—C10'	−165.21 (18)
C14—N1—C9—C10	10.2 (3)	C14'—N1'—C9'—C10'	10.0 (3)
C6—C1—C2—C3	31.3 (4)	C6'—C1'—C2'—C3'	30.4 (4)
O1—C1—C2—C3	−150.7 (3)	O1'—C1'—C2'—C3'	−152.9 (3)
C2—C1—C6—C5	2.3 (3)	C2'—C1'—C6'—C5'	2.7 (3)
C2—C1—C6—C7	177.9 (2)	C2'—C1'—C6'—C7'	178.9 (2)
O1—C1—C6—C5	−175.7 (2)	O1'—C1'—C6'—C5'	−174.0 (2)
O1—C1—C6—C7	−0.1 (3)	O1'—C1'—C6'—C7'	2.2 (3)
C1—C2—C3—C4	−56.1 (4)	C1'—C2'—C3'—C4'	−55.5 (4)
C2—C3—C4—C5	47.8 (4)	C2'—C3'—C4'—C5'	47.8 (3)
C3—C4—C5—N1	169.3 (2)	C3'—C4'—C5'—N1'	167.6 (2)
C3—C4—C5—C6	−14.3 (4)	C3'—C4'—C5'—C6'	−14.9 (3)
N1—C5—C6—C1	165.4 (2)	N1'—C5'—C6'—C1'	167.06 (19)
C4—C5—C6—C1	−10.9 (4)	C4'—C5'—C6'—C1'	−10.4 (3)
N1—C5—C6—C7	−10.0 (3)	N1'—C5'—C6'—C7'	−9.1 (3)
C4—C5—C6—C7	173.7 (2)	C4'—C5'—C6'—C7'	173.51 (19)
C5—C6—C7—C16	−99.3 (2)	C5'—C6'—C7'—C16'	−91.8 (2)
C5—C6—C7—C8	26.1 (3)	C5'—C6'—C7'—C8'	31.6 (2)
C1—C6—C7—C8	−149.37 (19)	C1'—C6'—C7'—C8'	−144.58 (19)
C1—C6—C7—C16	85.3 (2)	C1'—C6'—C7'—C16'	92.0 (2)
C6—C7—C8—C9	−26.3 (3)	C6'—C7'—C8'—C9'	−34.2 (3)
C8—C7—C16—C17	−36.3 (3)	C8'—C7'—C16'—C17'	−84.2 (3)
C8—C7—C16—C21	142.7 (2)	C8'—C7'—C16'—C21'	93.2 (2)
C6—C7—C8—C13	149.89 (18)	C6'—C7'—C8'—C13'	145.26 (19)
C16—C7—C8—C9	99.0 (2)	C16'—C7'—C8'—C9'	90.6 (2)
C6—C7—C16—C21	−94.1 (2)	C6'—C7'—C16'—C21'	−144.9 (2)
C6—C7—C16—C17	87.0 (2)	C6'—C7'—C16'—C17'	37.7 (3)
C16—C7—C8—C13	−84.8 (2)	C16'—C7'—C8'—C13'	−90.0 (2)
C7—C8—C9—N1	10.0 (3)	C7'—C8'—C9'—N1'	14.1 (3)
C9—C8—C13—O2	175.8 (2)	C9'—C8'—C13'—O2'	177.3 (2)
C7—C8—C13—C12	−177.3 (2)	C7'—C8'—C13'—C12'	178.0 (2)
C13—C8—C9—N1	−166.08 (19)	C13'—C8'—C9'—N1'	−165.37 (19)
C9—C8—C13—C12	−1.0 (3)	C9'—C8'—C13'—C12'	−2.6 (3)
C7—C8—C9—C10	−172.69 (19)	C7'—C8'—C9'—C10'	−168.08 (19)
C7—C8—C13—O2	−0.5 (3)	C7'—C8'—C13'—O2'	−2.2 (3)
C13—C8—C9—C10	11.2 (3)	C13'—C8'—C9'—C10'	12.5 (3)
C8—C9—C10—C11	12.6 (3)	C8'—C9'—C10'—C11'	12.9 (3)
N1—C9—C10—C11	−170.1 (2)	N1'—C9'—C10'—C11'	−169.3 (2)
C9—C10—C11—C12	−45.5 (3)	C9'—C10'—C11'—C12'	−46.7 (3)
C10—C11—C12—C13	54.6 (3)	C10'—C11'—C12'—C13'	55.5 (3)
C11—C12—C13—C8	−32.0 (3)	C11'—C12'—C13'—C8'	−31.6 (3)
C11—C12—C13—O2	151.2 (2)	C11'—C12'—C13'—O2'	148.6 (2)
N1—C14—C15—O3	−26.1 (5)	N1'—C14'—C15'—O3'	12.6 (3)
N1—C14—C15—O4	157.7 (3)	N1'—C14'—C15'—O4'	−168.95 (18)
C7—C16—C17—C18	176.5 (2)	C7'—C16'—C17'—C18'	178.6 (3)
C21—C16—C17—C18	−2.5 (4)	C21'—C16'—C17'—C18'	1.1 (4)
C7—C16—C21—O5	2.4 (3)	C7'—C16'—C21'—O5'	0.1 (4)
C7—C16—C21—C20	−175.6 (2)	C7'—C16'—C21'—C20'	179.6 (2)
C17—C16—C21—O5	−178.6 (2)	C17'—C16'—C21'—O5'	177.6 (3)
C17—C16—C21—C20	3.5 (3)	C17'—C16'—C21'—C20'	−2.9 (4)
C16—C17—C18—C19	0.0 (5)	C16'—C17'—C18'—C19'	1.0 (5)
C17—C18—C19—C20	1.5 (5)	C17'—C18'—C19'—C20'	−1.1 (6)
C18—C19—C20—C21	−0.6 (5)	C18'—C19'—C20'—C21'	−0.8 (6)
C19—C20—C21—O5	179.9 (3)	C19'—C20'—C21'—O5'	−177.6 (3)
C19—C20—C21—C16	−2.0 (4)	C19'—C20'—C21'—C16'	2.9 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O2′	0.88 (2)	1.84 (3)	2.683 (3)	162 (3)
O4′—H4′···O2ⁱ	0.84 (3)	1.85 (3)	2.673 (2)	165 (3)
O5—H5···O1	0.83 (3)	1.80 (3)	2.616 (3)	168 (3)
O5′—H5′···O2′	0.85 (4)	1.96 (4)	2.797 (3)	171 (4)
C10—H10A···O5′ⁱⁱ	0.97	2.60	3.380 (3)	138
C14—H14B···O1′ⁱⁱ	0.97	2.43	3.347 (3)	158
C14′—H14D···O2ⁱⁱⁱ	0.97	2.36	3.241 (3)	151
C17′—H17′···O3′	0.93	2.49	3.326 (3)	149

Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z+1; (iii) −x+1/2, y−1/2, −z+3/2.