9-(2-Chloro­ethyl­amino)­acridine monohydrate and its precursor 9-phenoxy­acridine

The title compounds, C₁₅H₁₃ClN₂·H₂O, (I), and C₁₉H₁₃NO, (II), form monoclinic crystals. Arranged in a `head-to-tail' manner, the mol­ecules of the amine form (I) lie along the b axis in layers that are linked by a network of hydrogen bonds involving the endocyclic N atom, the H atom at the exocyclic N atom and all the atoms of the solvent water mol­ecule. Molecules of (II), with the phenoxy group nearly perpendicular to the acridine moiety, are arranged in pairs related by a center of symmetry and stabilized via two C—H...N contacts; the latter are linked via a network of further C—H...N contacts and non-specific dispersive interactions.

S1. Comment

The practically and cognitively interesting 9-aminoacridine molecule has the potential to coexist, in the liquid and gaseous phases, in the amine and imine tautomeric forms (Rak et al., 1997), even though it has been established that only the amine tautomer is present in the crystalline phase (Chaudhuri, 1983). It has recently been found that the electron-withdrawing and -donating substituents at the exocyclic N atom have a greater affinity for, respectively, the imine and amine forms of 9-aminoacridines (Wróblewska et al., 2004). Two examples confirm this rule; molecules of the imine form are present in crystals of 9-(trichloroacetylimino)acridine (Meszko et al., 2002) and 9-(phenylsulfonylimino)acridine (Kuz'mina & Struchkov, 1981), both of which contain strongly electron-attracting substituents at the exocyclic N atom (the former compound crystallizes as a monohydrate). In order to obtain more evidence supporting the expected regularity, further 9-aminoacridine derivatives need to be synthesized and their structures and properties determined. This publication focuses on the refinement of the structure of (I), in which 9-aminoacridine is substituted at the exocyclic N atom with CH₂CH₂Cl – a substituent that, according to our recent work (Wróblewska et al., 2004), should display an affinity for the imine form of 9-aminoacridine (the logarithm of the equilibrium constant for the amine–imine tautomerization and the mean charge of CH₂CH₂Cl predicted for the gaseous phase are 1.59 and 0.14, respectively). The other compound investigated here, (II), the phenoxy-substituted acridine, serves as an intermediate in the syntheses of numerous acridine derivatives, among them 9-aminoacridines (Albert, 1966). Their biological relevance is well established, and 9-aminoacridines are capable of interacting specifically with adjacent molecules. The mechanisms of these interactions undoubtedly depend on the form in which the 9-aminoacridines occur (Barbe et al., 1996; Wróblewska et al., 2004). Investigation of these mechanisms? was the reason for undertaking the present work.

Crystals of (I) contain molecules of the amine form (Fig. 1), eight of which occupy the unit cell (Fig. 2). The acridine moiety is nearly planar in the crystalline phase (Table 1), with atoms C9, N10 and N15 arranged almost linearly [N10···C9—N15 = 176.7 (2) °]. The NCH₂CH₂Cl group is twisted relative to the acridine skeleton, at an angle of 22.8 (1)° (this is the angle between the plane containing atoms N15, C16 and C17 and the mean plane delineated by all the non-H atoms of the acridine nucleus). The value of the N15—C16—C17—Cl18 angle (Table 1) indicates that the conformation of the (NCH₂CH₂Cl) substituent is of the s-cis type. Molecules of (I) are arranged `head-to-tail' in layers along the b axis. Molecules of (I) and water are linked by a network of hydrogen bonds involving the endocylic N atom, the H atom at the exocyclic N atom and all three water atoms (Fig. 2 and Table 2). These multidirectional hydrogen bonds are the principal factor in stabilizing the lattice and, most probably, in forcing the introduction of (I) into the lattice in the amine tautometric form.

Four molecules of (II) (Fig. 3) occupy the unit cell (Fig.4). The acridine moiety is nearly planar in the crystalline phase (Table 3), with atoms C9, N10 and O15 arranged almost linearly [N10···C9—O15 = 176.0 (2)°]. The values of the C11—C9—O15—C16 and C13—C9—O15—C16 angles (Table 3) and the angle between mean planes delineated by all the non-H atoms of acridine and the phenyl nuclei [85.2 (1)°] testify to the almost perpendicular arrangement of the two fragments. Molecules of (II) are arranged in pairs stabilized by two C17—H17···N10 contacts (Table 4). Adjacent pairs, which form a herring-bone pattern in the crystal [the angle between these pairs – i.e. the mean planes delineated by the respective non-H atoms of the acridine nuclei – is 40.1 (2)°], are linked through a network of C19—H19···N10 contacts (Table 4) and non-specific dispersive interactions.

S2. Experimental

9-(2-Chloroethylamino)acridine was obtained by heating (1.5 h at 373 K) a mixture of 9-phenoxyacridine and 2-chloroethylamine in phenol (Dupre & Robinson, 1945). The product was purified chromatographically (silica gel 60, toluene/diethylamine, 10/1 v/v). Analysis found: C 65.56, H 5.32, N 10.22%; calculated: C 65.45, H 5.45, N 10.18%. Yellow crystals suitable for X-ray analysis were grown from cyclohexane (m.p. 348–350 K). 9-Phenoxyacridine was synthesized following the literature procedure (Albert, 1966). The product was purified chromatographically (silica gel 60, toluene/methanol, 10/1 v/v) and yellow crystals suitable for X-ray investigation were grown from toluene (m.p. 398–399 K).

S3. Refinement

All H atoms where found in difference Fourier maps and were refined without constraints [C—H = 0.92 (4)–0.98 (3) Å in (I) and 0.955 (15)–1.016 (15) Å in (II)]. Parameters of C—H···N contacts in (II) were calculated assuming a C—H bond length of 1.08 Å (Steiner, 1997).

Computing details

Data collection: KM-4 Software (Kuma Diffraction, 1989) for (I); KM4CCD Software (Kuma Diffraction, 1995–1999) for (II). Cell refinement: KM-4 Software for (I); KM4CCD Software for (II). Data reduction: KM-4 Software for (I); KM4CCD Software for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme and 50% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii. The N15—H15···O19 hydrogen bond is represented by a dashed line.
	Fig. 2. The arrangement of the molecules of (I) in the unit cell, viewed along the b axis. H atoms not involved in hydrogen bonds have been omitted. Hydrogen bonds are represented by dashed lines. Symmetry codes are as in Table 2.
	Fig. 3. The molecular structure of (II), showing the atom-labelling scheme and 50% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. The arrangement of the molecules of (II) in the unit cell, viewed along the a axis. H atoms not involved in C—H···N interactions have been omitted. The C—H···N interactions are represented by dashed lines. Symmetry codes are as in Table 4.

(I) 9-(2-chloroethylamino)acridine monohydrate

Crystal data

C15H13ClN2·H2O	F(000) = 1152
Mr = 274.74	Dx = 1.388 Mg m^−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 14.052 (3) Å	θ = 5–25°
b = 11.330 (2) Å	µ = 2.51 mm^−1
c = 17.283 (3) Å	T = 293 K
β = 107.20 (3)°	Prism, yellow
V = 2628.6 (10) Å^3	0.4 × 0.4 × 0.35 mm
Z = 8

Data collection

Kuma KM-4 diffractometer	Rint = 0.038
Radiation source: fine-focus sealed tube	θmax = 81.1°, θmin = 5.1°
Graphite monochromator	h = −18→8
θ/2θ scans	k = −10→14
5227 measured reflections	l = −21→22
2909 independent reflections	3 standard reflections every 200 reflections
1793 reflections with I > 2σ(I)	intensity decay: 2.5%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.045	All H-atom parameters refined
wR(F^2) = 0.136	w = 1/[σ^2(Fo^2) + (0.0538P)^2 + 2.9481P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
2909 reflections	Δρmax = 0.34 e Å^−3
228 parameters	Δρmin = −0.37 e Å^−3
0 restraints	Extinction correction: SHELXL97
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00079 (10)

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3630 (2)	0.1946 (2)	0.43440 (14)	0.0478 (6)
H1	0.348 (2)	0.193 (2)	0.3781 (18)	0.053 (8)*
C2	0.3817 (2)	0.0902 (2)	0.47443 (16)	0.0540 (7)
H2	0.381 (2)	0.020 (3)	0.4454 (19)	0.068 (10)*
C3	0.4086 (2)	0.0873 (2)	0.55918 (16)	0.0510 (7)
H3	0.422 (2)	0.012 (3)	0.588 (2)	0.070 (10)*
C4	0.4179 (2)	0.1889 (2)	0.60156 (14)	0.0455 (6)
H4	0.438 (2)	0.189 (2)	0.6606 (18)	0.050 (7)*
C5	0.4175 (2)	0.6046 (2)	0.62351 (15)	0.0482 (6)
H5	0.439 (2)	0.591 (3)	0.681 (2)	0.066 (9)*
C6	0.4042 (2)	0.7146 (2)	0.59147 (18)	0.0548 (7)
H6	0.415 (3)	0.779 (3)	0.625 (2)	0.081 (11)*
C7	0.3730 (2)	0.7301 (3)	0.50762 (18)	0.0544 (7)
H7	0.358 (3)	0.806 (3)	0.484 (2)	0.088 (12)*
C8	0.3558 (2)	0.6354 (2)	0.45724 (15)	0.0446 (6)
H8	0.3310 (19)	0.648 (2)	0.3994 (16)	0.044 (7)*
C9	0.35264 (17)	0.41649 (19)	0.43715 (12)	0.0343 (5)
N10	0.41450 (16)	0.39637 (18)	0.60992 (11)	0.0409 (5)
C11	0.36840 (17)	0.3039 (2)	0.47552 (12)	0.0341 (5)
C12	0.39901 (17)	0.3003 (2)	0.56203 (13)	0.0361 (5)
C13	0.36966 (16)	0.5183 (2)	0.48793 (13)	0.0338 (5)
C14	0.40056 (18)	0.5032 (2)	0.57327 (13)	0.0367 (5)
N15	0.32497 (17)	0.43216 (19)	0.35597 (11)	0.0422 (5)
H15	0.333 (2)	0.499 (3)	0.3391 (18)	0.051 (8)*
C16	0.2696 (2)	0.3541 (2)	0.29262 (14)	0.0465 (6)
H16A	0.228 (2)	0.304 (2)	0.3142 (17)	0.051 (8)*
H16B	0.311 (3)	0.307 (3)	0.271 (2)	0.071 (10)*
C17	0.2099 (2)	0.4234 (3)	0.22029 (15)	0.0522 (7)
H17A	0.249 (2)	0.475 (3)	0.1963 (19)	0.058 (8)*
H17B	0.175 (2)	0.372 (3)	0.1778 (19)	0.062 (9)*
Cl18	0.12332 (6)	0.51965 (8)	0.24439 (5)	0.0699 (3)
O19	0.38779 (12)	0.63302 (15)	0.26947 (9)	0.0491 (4)
H19A	0.397 (3)	0.609 (4)	0.217 (2)	0.096 (12)*
H19B	0.451 (3)	0.628 (3)	0.301 (2)	0.082 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0681 (18)	0.0393 (13)	0.0302 (11)	0.0023 (12)	0.0056 (11)	−0.0024 (10)
C2	0.078 (2)	0.0357 (13)	0.0420 (13)	0.0035 (13)	0.0081 (13)	−0.0025 (11)
C3	0.0686 (19)	0.0376 (14)	0.0427 (13)	0.0021 (12)	0.0099 (12)	0.0074 (11)
C4	0.0592 (17)	0.0444 (14)	0.0314 (11)	0.0010 (12)	0.0112 (11)	0.0060 (10)
C5	0.0595 (17)	0.0446 (14)	0.0368 (12)	−0.0021 (12)	0.0088 (11)	−0.0073 (11)
C6	0.073 (2)	0.0388 (14)	0.0533 (15)	−0.0029 (13)	0.0197 (14)	−0.0115 (12)
C7	0.073 (2)	0.0375 (14)	0.0551 (16)	0.0009 (13)	0.0222 (14)	0.0014 (12)
C8	0.0569 (16)	0.0380 (13)	0.0392 (12)	0.0025 (11)	0.0148 (11)	0.0056 (10)
C9	0.0340 (12)	0.0381 (12)	0.0290 (10)	−0.0015 (9)	0.0066 (8)	0.0010 (9)
N10	0.0530 (13)	0.0397 (11)	0.0270 (8)	−0.0004 (9)	0.0073 (8)	0.0000 (8)
C11	0.0369 (12)	0.0353 (11)	0.0277 (10)	−0.0001 (9)	0.0059 (8)	0.0007 (8)
C12	0.0399 (13)	0.0374 (12)	0.0301 (10)	0.0003 (10)	0.0089 (9)	0.0020 (9)
C13	0.0334 (12)	0.0341 (11)	0.0331 (10)	−0.0001 (9)	0.0086 (9)	0.0007 (9)
C14	0.0387 (13)	0.0391 (13)	0.0308 (10)	−0.0007 (10)	0.0079 (9)	−0.0022 (9)
N15	0.0548 (13)	0.0392 (11)	0.0268 (9)	−0.0072 (9)	0.0028 (8)	0.0051 (8)
C16	0.0611 (18)	0.0442 (14)	0.0289 (11)	−0.0038 (13)	0.0053 (11)	−0.0001 (10)
C17	0.0627 (19)	0.0578 (17)	0.0284 (11)	−0.0055 (14)	0.0019 (11)	0.0038 (11)
Cl18	0.0613 (5)	0.0852 (6)	0.0608 (4)	0.0124 (4)	0.0142 (3)	0.0270 (4)
O19	0.0484 (10)	0.0600 (10)	0.0384 (8)	0.0005 (8)	0.0122 (7)	0.0057 (7)

Geometric parameters (Å, º)

C9—C11	1.425 (3)	C5—C6	1.354 (4)
C9—C13	1.427 (3)	C5—C14	1.417 (3)
C9—N15	1.352 (3)	C5—H5	0.96 (3)
N10—C12	1.345 (3)	C6—C7	1.395 (4)
N10—C14	1.353 (3)	C6—H6	0.92 (4)
N15—H15	0.84 (3)	C7—C8	1.358 (4)
N15—C16	1.443 (3)	C7—H7	0.94 (4)
C16—C17	1.504 (3)	C8—C13	1.420 (3)
C17—Cl18	1.773 (3)	C8—H8	0.97 (3)
C1—C2	1.357 (4)	C11—C12	1.429 (3)
C1—C11	1.418 (3)	C13—C14	1.419 (3)
C1—H1	0.93 (3)	C16—H16A	0.97 (3)
C2—C3	1.401 (4)	C16—H16B	0.94 (4)
C2—H2	0.94 (3)	C17—H17A	0.98 (3)
C3—C4	1.350 (4)	C17—H17B	0.95 (3)
C3—H3	0.98 (3)	O19—H19A	1.00 (4)
C4—C12	1.422 (3)	O19—H19B	0.90 (4)
C4—H4	0.98 (3)
C9—N15—H15	117 (2)	C6—C7—H7	121 (2)
C9—N15—C16	129.2 (2)	C7—C8—C13	121.3 (2)
C11—C9—C13	117.6 (2)	C7—C8—H8	118.9 (16)
C11—C9—N15	123.9 (2)	C13—C8—H8	119.7 (16)
C12—N10—C14	117.4 (2)	C1—C11—C9	124.78 (19)
C13—C9—N15	118.5 (2)	C1—C11—C12	117.0 (2)
N15—C16—C17	110.7 (2)	C9—C11—C12	118.0 (2)
C16—C17—Cl18	112.2 (2)	N10—C12—C4	116.7 (2)
C2—C1—C11	122.2 (2)	N10—C12—C11	124.4 (2)
C2—C1—H1	117.6 (17)	C4—C12—C11	118.9 (2)
C11—C1—H1	120.2 (17)	C14—C13—C8	117.9 (2)
C1—C2—C3	120.3 (2)	C14—C13—C9	119.0 (2)
C1—C2—H2	120 (2)	C8—C13—C9	123.1 (2)
C3—C2—H2	120 (2)	N10—C14—C5	117.6 (2)
C4—C3—C2	120.0 (2)	N10—C14—C13	123.5 (2)
C4—C3—H3	120 (2)	C5—C14—C13	118.9 (2)
C2—C3—H3	120 (2)	C16—N15—H15	113 (2)
C3—C4—C12	121.4 (2)	N15—C16—H16A	108.7 (17)
C3—C4—H4	121.2 (16)	C17—C16—H16A	112.1 (17)
C12—C4—H4	117.4 (16)	N15—C16—H16B	113 (2)
C6—C5—C14	121.2 (2)	C17—C16—H16B	103 (2)
C6—C5—H5	122.3 (19)	H16A—C16—H16B	109 (3)
C14—C5—H5	116.5 (19)	C16—C17—H17A	115.2 (19)
C5—C6—C7	120.2 (3)	Cl18—C17—H17A	103.7 (18)
C5—C6—H6	120 (2)	C16—C17—H17B	110.9 (19)
C7—C6—H6	120 (2)	Cl18—C17—H17B	108.9 (19)
C8—C7—C6	120.5 (3)	H17A—C17—H17B	105 (3)
C8—C7—H7	118 (2)	H19A—O19—H19B	100 (3)
C9—N15—H15—C16	−172 (2)	C14—N10—C12—C11	−0.4 (3)
C9—N15—C16—C17	149.7 (3)	C3—C4—C12—N10	−177.3 (3)
C11—C9—C13—C14	−0.4 (3)	C3—C4—C12—C11	0.7 (4)
C11—C9—N15—H15	−163 (2)	C1—C11—C12—N10	175.2 (2)
C11—C9—N15—C16	26.9 (4)	C9—C11—C12—N10	−0.3 (3)
C12—N10—C14—C13	0.8 (3)	C1—C11—C12—C4	−2.6 (3)
N15—C16—C17—Cl18	−59.9 (3)	C9—C11—C12—C4	−178.2 (2)
C11—C1—C2—C3	−0.8 (5)	C7—C8—C13—C14	1.0 (4)
C1—C2—C3—C4	−1.3 (5)	C7—C8—C13—C9	−179.9 (3)
C2—C3—C4—C12	1.3 (5)	N15—C9—C13—C14	−178.8 (2)
C14—C5—C6—C7	0.2 (5)	N15—C9—C13—C8	2.1 (3)
C5—C6—C7—C8	−0.2 (5)	C11—C9—C13—C8	−179.5 (2)
C6—C7—C8—C13	−0.5 (5)	C12—N10—C14—C5	−179.5 (2)
C2—C1—C11—C9	178.0 (3)	C6—C5—C14—N10	−179.3 (3)
C2—C1—C11—C12	2.7 (4)	C6—C5—C14—C13	0.4 (4)
N15—C9—C11—C1	3.9 (4)	C8—C13—C14—N10	178.7 (2)
C13—C9—C11—C1	−174.5 (2)	C9—C13—C14—N10	−0.4 (4)
N15—C9—C11—C12	179.1 (2)	C8—C13—C14—C5	−0.9 (3)
C13—C9—C11—C12	0.7 (3)	C9—C13—C14—C5	179.9 (2)
C14—N10—C12—C4	177.5 (2)	C13—C9—N15—C16	−154.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N15—H15···O19	0.84 (3)	2.21 (3)	2.996 (3)	157 (3)
O19—H19A···N10^i	1.00 (4)	1.93 (4)	2.908 (3)	166 (3)
O19—H19B···N10^ii	0.90 (4)	2.07 (4)	2.957 (3)	169 (3)

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

(II) 9-Phenoxyacridine

Crystal data

C19H13NO	F(000) = 568
Mr = 271.30	Dx = 1.301 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8411 reflections
a = 9.400 (3) Å	θ = 3.7–29.0°
b = 10.301 (3) Å	µ = 0.08 mm^−1
c = 14.955 (4) Å	T = 100 K
β = 106.89 (3)°	Prism, yellow
V = 1385.6 (7) Å^3	0.5 × 0.5 × 0.2 mm
Z = 4

Data collection

Kuma KM-4 CCD κ-geometry diffractometer	3308 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.038
Graphite monochromator	θmax = 29.0°, θmin = 3.7°
ω scans	h = −12→12
17261 measured reflections	k = −12→14
3641 independent reflections	l = −20→20

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	All H-atom parameters refined
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0595P)^2 + 0.4293P] where P = (Fo^2 + 2Fc^2)/3
3641 reflections	(Δ/σ)max = 0.001
242 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.24 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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.40970 (12)	0.32673 (10)	0.45547 (7)	0.0199 (2)
H1	0.4607 (16)	0.3973 (15)	0.4322 (10)	0.030 (4)*
C2	0.25823 (12)	0.31650 (11)	0.42525 (7)	0.0228 (2)
H2	0.1995 (18)	0.3785 (16)	0.3778 (11)	0.036 (4)*
C3	0.18362 (11)	0.21753 (10)	0.46085 (7)	0.0220 (2)
H3	0.0744 (16)	0.2134 (14)	0.4382 (10)	0.027 (3)*
C4	0.26163 (11)	0.12980 (10)	0.52465 (7)	0.0193 (2)
H4	0.2114 (16)	0.0595 (15)	0.5508 (10)	0.030 (4)*
C5	0.71990 (12)	−0.04360 (10)	0.71688 (7)	0.0209 (2)
H5	0.6574 (16)	−0.1125 (15)	0.7363 (10)	0.029 (4)*
C6	0.87133 (12)	−0.04110 (11)	0.75046 (7)	0.0244 (2)
H6	0.9243 (17)	−0.1088 (15)	0.7969 (11)	0.032 (4)*
C7	0.95607 (12)	0.05573 (11)	0.72090 (8)	0.0245 (2)
H7	1.0661 (18)	0.0557 (15)	0.7467 (11)	0.034 (4)*
C8	0.88709 (11)	0.14837 (10)	0.65785 (7)	0.0212 (2)
H8	0.9454 (17)	0.2154 (15)	0.6364 (10)	0.031 (4)*
C9	0.64990 (11)	0.24061 (9)	0.55635 (6)	0.01609 (19)
N10	0.49290 (9)	0.04515 (8)	0.61944 (6)	0.01696 (18)
C11	0.49501 (10)	0.23634 (9)	0.52209 (6)	0.01595 (19)
C12	0.42091 (10)	0.13481 (9)	0.55682 (6)	0.01575 (19)
C13	0.72841 (11)	0.14904 (9)	0.62084 (6)	0.01678 (19)
C14	0.64269 (11)	0.05166 (9)	0.65066 (6)	0.01667 (19)
O15	0.72711 (8)	0.34171 (7)	0.53074 (5)	0.01975 (17)
C16	0.76284 (10)	0.33091 (9)	0.44710 (7)	0.01637 (19)
C17	0.72803 (10)	0.22247 (9)	0.38962 (7)	0.0181 (2)
H17	0.6705 (16)	0.1500 (14)	0.4045 (10)	0.026 (3)*
C18	0.77383 (11)	0.21988 (11)	0.30876 (7)	0.0232 (2)
H18	0.7512 (17)	0.1427 (16)	0.2698 (11)	0.033 (4)*
C19	0.85183 (12)	0.32302 (12)	0.28585 (7)	0.0259 (2)
H19	0.8829 (17)	0.3227 (15)	0.2292 (11)	0.033 (4)*
C20	0.88308 (11)	0.43128 (11)	0.34377 (8)	0.0238 (2)
H20	0.9370 (17)	0.5042 (16)	0.3258 (10)	0.034 (4)*
C21	0.83817 (10)	0.43659 (10)	0.42441 (7)	0.0200 (2)
H21	0.8585 (16)	0.5101 (15)	0.4651 (10)	0.027 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0240 (5)	0.0169 (4)	0.0197 (4)	0.0015 (4)	0.0078 (4)	0.0013 (3)
C2	0.0234 (5)	0.0221 (5)	0.0223 (5)	0.0052 (4)	0.0057 (4)	0.0026 (4)
C3	0.0181 (4)	0.0245 (5)	0.0232 (5)	0.0018 (4)	0.0055 (4)	−0.0019 (4)
C4	0.0183 (4)	0.0194 (4)	0.0216 (4)	−0.0012 (3)	0.0081 (4)	−0.0021 (3)
C5	0.0254 (5)	0.0196 (5)	0.0187 (4)	0.0026 (4)	0.0081 (4)	0.0010 (4)
C6	0.0269 (5)	0.0244 (5)	0.0199 (5)	0.0057 (4)	0.0036 (4)	0.0007 (4)
C7	0.0202 (5)	0.0264 (5)	0.0241 (5)	0.0014 (4)	0.0018 (4)	−0.0039 (4)
C8	0.0186 (5)	0.0214 (5)	0.0232 (5)	−0.0024 (4)	0.0051 (4)	−0.0045 (4)
C9	0.0202 (4)	0.0138 (4)	0.0161 (4)	−0.0025 (3)	0.0082 (3)	−0.0029 (3)
N10	0.0194 (4)	0.0166 (4)	0.0166 (4)	0.0003 (3)	0.0079 (3)	−0.0009 (3)
C11	0.0194 (4)	0.0147 (4)	0.0150 (4)	0.0002 (3)	0.0069 (3)	−0.0018 (3)
C12	0.0178 (4)	0.0158 (4)	0.0150 (4)	0.0001 (3)	0.0069 (3)	−0.0024 (3)
C13	0.0181 (4)	0.0166 (4)	0.0160 (4)	−0.0010 (3)	0.0056 (3)	−0.0036 (3)
C14	0.0205 (4)	0.0160 (4)	0.0148 (4)	0.0004 (3)	0.0071 (3)	−0.0022 (3)
O15	0.0246 (4)	0.0159 (3)	0.0208 (3)	−0.0060 (3)	0.0099 (3)	−0.0029 (3)
C16	0.0137 (4)	0.0166 (4)	0.0186 (4)	0.0004 (3)	0.0045 (3)	0.0017 (3)
C17	0.0170 (4)	0.0176 (4)	0.0198 (4)	−0.0016 (3)	0.0056 (3)	0.0000 (3)
C18	0.0214 (5)	0.0293 (5)	0.0190 (5)	0.0001 (4)	0.0059 (4)	−0.0018 (4)
C19	0.0202 (5)	0.0379 (6)	0.0206 (5)	0.0027 (4)	0.0077 (4)	0.0078 (4)
C20	0.0156 (4)	0.0254 (5)	0.0302 (5)	0.0010 (4)	0.0065 (4)	0.0126 (4)
C21	0.0149 (4)	0.0166 (4)	0.0270 (5)	−0.0010 (3)	0.0038 (4)	0.0033 (4)

Geometric parameters (Å, º)

C1—C2	1.3671 (15)	C9—C13	1.3969 (14)
C1—C11	1.4278 (14)	C9—O15	1.3854 (11)
C1—H1	0.988 (15)	N10—C12	1.3490 (13)
C2—C3	1.4252 (15)	N10—C14	1.3502 (13)
C2—H2	0.994 (16)	O15—C16	1.3907 (12)
C3—C4	1.3632 (15)	C11—C12	1.4349 (13)
C3—H3	0.984 (14)	C13—C14	1.4364 (13)
C4—C12	1.4343 (14)	C16—C17	1.3893 (14)
C4—H4	1.004 (15)	C16—C21	1.3933 (13)
C5—C6	1.3652 (16)	C17—C18	1.3967 (14)
C5—C14	1.4327 (14)	C17—H17	0.984 (14)
C5—H5	1.016 (15)	C18—C19	1.3892 (16)
C6—C7	1.4247 (16)	C18—H18	0.973 (16)
C6—H6	1.008 (16)	C19—C20	1.3901 (17)
C7—C8	1.3657 (15)	C19—H19	0.974 (16)
C7—H7	0.993 (16)	C20—C21	1.3897 (15)
C8—C13	1.4322 (14)	C20—H20	0.986 (16)
C8—H8	0.991 (16)	C21—H21	0.955 (15)
C9—C11	1.3966 (14)
C2—C1—C11	120.02 (9)	C9—C11—C1	123.35 (9)
C2—C1—H1	120.4 (9)	C9—C11—C12	117.01 (8)
C11—C1—H1	119.6 (9)	C1—C11—C12	119.64 (9)
C1—C2—C3	120.66 (9)	N10—C12—C4	118.19 (9)
C1—C2—H2	119.7 (9)	N10—C12—C11	123.50 (9)
C3—C2—H2	119.6 (9)	C4—C12—C11	118.29 (9)
C4—C3—C2	120.84 (9)	C9—C13—C8	123.51 (9)
C4—C3—H3	120.5 (8)	C9—C13—C14	117.03 (9)
C2—C3—H3	118.7 (8)	C8—C13—C14	119.47 (9)
C3—C4—C12	120.52 (9)	N10—C14—C5	118.22 (9)
C3—C4—H4	122.2 (8)	N10—C14—C13	123.37 (9)
C12—C4—H4	117.3 (8)	C5—C14—C13	118.40 (9)
C6—C5—C14	120.40 (10)	C17—C16—C21	121.50 (9)
C6—C5—H5	122.4 (8)	O15—C16—C21	115.41 (9)
C14—C5—H5	117.2 (8)	C16—C17—C18	118.33 (9)
C5—C6—C7	121.08 (10)	C16—C17—H17	121.0 (8)
C5—C6—H6	119.6 (9)	C18—C17—H17	120.6 (8)
C7—C6—H6	119.3 (9)	C19—C18—C17	121.10 (10)
C8—C7—C6	120.49 (10)	C19—C18—H18	121.1 (9)
C8—C7—H7	120.0 (9)	C17—C18—H18	117.8 (9)
C6—C7—H7	119.5 (9)	C18—C19—C20	119.41 (10)
C7—C8—C13	120.16 (10)	C18—C19—H19	121.7 (9)
C7—C8—H8	120.9 (9)	C20—C19—H19	118.8 (9)
C13—C8—H8	118.9 (9)	C21—C20—C19	120.65 (9)
C9—O15—C16	118.11 (7)	C21—C20—H20	121.1 (9)
C11—C9—C13	121.15 (9)	C19—C20—H20	118.3 (9)
C11—C9—O15	119.76 (8)	C20—C21—C16	118.99 (10)
C12—N10—C14	117.93 (8)	C20—C21—H21	121.9 (9)
C13—C9—O15	118.97 (9)	C16—C21—H21	119.1 (9)
O15—C16—C17	123.08 (8)
C11—C1—C2—C3	1.13 (15)	C7—C8—C13—C9	179.87 (9)
C1—C2—C3—C4	−1.00 (16)	C7—C8—C13—C14	0.06 (14)
C2—C3—C4—C12	−0.45 (15)	C12—N10—C14—C5	−179.74 (8)
C14—C5—C6—C7	0.10 (15)	C6—C5—C14—N10	179.97 (9)
C5—C6—C7—C8	−0.13 (16)	C6—C5—C14—C13	0.02 (14)
C6—C7—C8—C13	0.05 (15)	C9—C13—C14—N10	0.13 (13)
O15—C9—C11—C1	4.72 (14)	C8—C13—C14—N10	179.96 (8)
C13—C9—C11—C1	−179.35 (9)	C9—C13—C14—C5	−179.92 (8)
O15—C9—C11—C12	−175.34 (8)	C8—C13—C14—C5	−0.09 (13)
C13—C9—C11—C12	0.59 (13)	C9—O15—C16—C17	−1.67 (13)
C2—C1—C11—C9	−179.91 (9)	C11—C9—C13—C14	−0.54 (13)
C2—C1—C11—C12	0.16 (14)	C11—C9—O15—C16	−84.92 (11)
C14—N10—C12—C4	−178.91 (8)	C12—N10—C14—C13	0.21 (13)
C14—N10—C12—C11	−0.15 (13)	C13—C9—O15—C16	99.06 (10)
C3—C4—C12—N10	−179.49 (9)	O15—C16—C17—C18	−177.76 (9)
C3—C4—C12—C11	1.69 (14)	C9—O15—C16—C21	178.92 (8)
C9—C11—C12—N10	−0.24 (13)	C21—C16—C17—C18	1.61 (14)
C1—C11—C12—N10	179.70 (9)	C16—C17—C18—C19	−0.21 (15)
C9—C11—C12—C4	178.52 (8)	C17—C18—C19—C20	−0.85 (16)
C1—C11—C12—C4	−1.55 (13)	C18—C19—C20—C21	0.54 (15)
O15—C9—C13—C8	−4.40 (14)	C19—C20—C21—C16	0.82 (15)
C11—C9—C13—C8	179.64 (8)	C17—C16—C21—C20	−1.92 (14)
O15—C9—C13—C14	175.42 (8)	O15—C16—C21—C20	177.50 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···N10^i	1.08	2.40	3.430 (2)	159
C19—H19···N10^ii	1.08	2.48	3.422 (2)	145

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