N-[(R)-1-(2-Hydr­oxy-5-methyl­phen­yl)­eth­yl]-N-[(R)-1-(2-meth­oxy-5-methyl­phen­yl)-2-phenyl­eth­yl]aminium chloride

The title compound, C₂₅H₃₀NO₂⁺·Cl⁻, has been synthesized, and the crystal structure shows that it is mainly stabilized through inter­molecular N—H...Cl and O—H...Cl and intra­molecular N—H...O hydrogen bonds. The absolute configuration of the new stereogenic center (the C atom adjacent to the N atom on the phenol side) was determined to have an R configuration.

S1. Comment

The synthesis of enantiopure amines is an important subject of research because this class of compounds has found widespread application in biological systems showing pharmacological activity, and these compounds are used as resolving agents, chiral bases and auxiliaries in asymmetric synthesis (Juraristi, 1997; Clifton et al., 1982; Palmieri, 1999, 2000; Cimarelli & Palmieri, 1998, 2000). Most of them have been derived from a few readily available natural products (Soai & Niwa, 1992; Ager et al., 1996). To increase the understanding of asymmetric reactions, the design and synthesis of chiral ligands from non-natural resources is an essential research area in the field of synthetic organic chemistry (Vidal-Ferran et al., 1997; Bolm et al., 1998; Reddy et al., 1999; Paleo et al., 2000; Nugent, 2002) and chiral aminoalkylphenols are gaining increasing importance (Palmieri, 2000; Vyskocil et al., 1998; Cardellicchio et al., 1998, 1999; Bernardinelli et al., 2000; Liu et al., 2001; Cimarelli et al., 2001; Zhang et al., 2003).

We report here the molecular structure of one example of this class of aminoalkylphenols, namely 2-{(R)-1-[(R)-1-(2-methoxy-5-methylphenyl)-2-phenylethylamino]ethyl}-4- methylphenol, (I). The aminoalkylphenol was prepared by conventional condensation of (R)-(-)-[(2-methoxy-5-methyl)-phenyl]-2- phenyl ethylamine with 2-hydroxy-5-methyl acetophenone (both purchased from J&K Chemical Ltd), andthen reduction using sodium borohydride in a tetrahydrofuran (THF)/ethanol (1:1, v/v) mixture. The (R,R)-diastereoisomer is obtained as the main product; the chemical yield of purified and isolated (R,R)-(I) and the diastereoisomeric excess, d.e. (determined by ¹HMR of the crude reaction mixture), are 89.2 and 99.0%, respectively. Generally, the reduction should take place after the boron coordinates the imine N atom, activating the C═ N double bond, which assumes predominantly an E configuration, to nucleophilic attack. Subsequently, an intramolecular hydride transfer from NaBH₄ to the C atom both on the si or re face of the C═N double bond takes place. Calculations were performed to find the energies of the transition states (R,R)–(I)—Ts and (S,R)–(I)–Ts, minimized at the PM3 semiempirical level, corresponding to the two different situations. Transition state (R,R)–(I)–Ts was more stable, with a difference of 1.35 kcal mol⁻¹, and this value is in satisfactory accordance with experimental d.e., which shows (R,R)–(I) as major product. This is in agreement with the fact that for si attack, the hydride enters on the less hindered side, on the same side of the H atom of the chiral auxiliary (R)-(2-methoxy-5-methyl)phenyl benzyl group. At the same time the N-atom lone pair is gauche between the (2-hydroxy-5-methyl)phenyl and the methyl group of the same chiral group, in a very favourable position. On the other hand, the attack on the re face is on the more hindered side (Me) and with the N-atom lone pair in a less convenient position between (2-hydroxy-5-methyl)phenyl and hydrogen.

It is noteworthy that a novel chiral aminoalkylphenol, (I), was synthesized. To confirm the structure of (I), an X-ray study of the title compound, (II), was carried out (Fig. 1).

The molecular structure of Despite the large number of hydrogen bonds within the asymmetric unit, t(II) is shown in Fig. 1. Thes C1–C6 and C11–C16 aromatic ring are approximately parallel (Fig. 2), the dihedral angle between their planes being 4.5°. The dihehral angle between the planes of the C1–C6 and C19–C24 aromatic rings is 20.0°, while the dihedral angle between the C11–C16 and C19–C24 planes is 14.0°.

Selected bond lengths and angles, including those of the new stereogenic carbon center (C17), are reported in Table 1. The absolute configuration of (I) and (II) is (R,R), as shown in Fig. 1.

N—H···O hydrogen bonds are present within the asymmetric unit; atom N1 act as a hydrogen-bond donor to phenolyl atom O2 (Fig. 2 and Table 2). The molecular structure depends on two further pairs of N—H···Cl and O—H···Cl hydrogen bonds, from atoms N1 and O2 in the cation to atom Cl1 (Fig. 2 and Table 2).

S2. Experimental

(R)-(-)-[(2-methoxy-5-methyl)phenyl]-2-phenyl ethylamine (3 mmol) and 2-hydroxy-5-methyl acetophenone (3 mmol) (both purchased from J&K Chemical Ltd) were dissolved in me thanol (20 ml) and reacted at room temperature for 12 h. Solvent was removed and NaBH₄ (15 mmol) was added to the solution in an THF/ethanol (20 ml, 1:1 v/v) mixture. The reaction was allowed to stand and was monitored by thin-layer chromatography and gel chromatography. After a variable period, the reaction was stopped at constant conversion of starting material. 6 M HCl was then added dropwise to the reaction mixture until hydrogen production ceased, and the mixture was then neutralized with Na₂CO₃. The aqueous solution was extracted with CHCl₃. The organic layer was dried with anhydrous sodium sulfate and filtered. The solvent was removed under reduced pressure. Further purification was carried out by thin-layer silica gel chromatography [first time: chloroform/methanol (40:1 v/v); second time: chloroform/methanol (60:1, v/v)] to give chiral 2-{(R)-1-[(R)-1-(2-methoxy-5-methylphenyl)-2-phenylethyl- amino]ethyl}-4-methylphenol (canary oil, 89.2%, [a]_D¹⁸= −19.5(c 1/2, CHCl₃)). Since only the major diastereoisomer was obtained pure by thin-lay silica gel chromatography, the ¹H NMR signals for the minor diastereoisomer was deduced from the spectra of the crude reaction mixture. Compound (I) and concentrated HCl were reacted at room temperature, and a white solid was precipitated. The solvent was removed and the solid residue was recrystallized from ethanol to yield compound (II) (m.p. 473.0–473.2 K).

S3. Refinement

H atoms were visible in difference maps and were subsequently treated as riding atoms, with C—H distances of 0.93 (aromatic H atoms), 0.96 (CH₃), 0.97 (CH₂) and 0.98 Å (CH).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1995); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of (II), with the atom-numbering scheme for non-H atoms. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted.
	Fig. 2. A view of the packing in (II). Hydrogen bonds are shown as dashed lines For clarity, H atoms have been omitted.

N-[(R)-1-(2-Hydroxy-5-methylphenyl)ethyl]-N-[(R)-1-(2-methoxy-5- methylphenyl)-2-phenylethyl]aminium chloride

Crystal data

C25H30NO2^+·Cl^−	Dx = 1.173 Mg m^−3
Mr = 411.95	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 3690 reflections
a = 9.227 (3) Å	θ = 2.5–22.3°
b = 15.323 (6) Å	µ = 0.18 mm^−1
c = 16.504 (6) Å	T = 298 K
V = 2333.4 (15) Å^3	Block, colorless
Z = 4	0.43 × 0.35 × 0.31 mm
F(000) = 880

Data collection

Bruker SMART CCD area-detector diffractometer	4115 independent reflections
Radiation source: fine-focus sealed tube	3080 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ϕ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.926, Tmax = 0.946	k = −18→18
12327 measured reflections	l = −19→14

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)] = 0.038	Geom
wR(F^2) = 0.097	w = 1/[σ^2(Fo^2) + (0.0695P)^2 + 0.2951P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
4115 reflections	Δρmax = 0.14 e Å^−3
263 parameters	Δρmin = −0.13 e Å^−3
18 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (7)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on 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	Occ. (<1)
Cl1	0.54726 (8)	0.28032 (4)	0.32748 (4)	0.0603 (2)
N1	0.3272 (2)	−0.03250 (12)	0.18827 (11)	0.0386 (5)
H1A	0.3999	−0.0055	0.2146	0.046*
H1B	0.3549	−0.0880	0.1795	0.046*
O1	−0.0697 (2)	0.04598 (18)	0.24767 (15)	0.0941 (7)
O2	0.4320 (2)	0.13496 (10)	0.21243 (10)	0.0540 (5)
H2	0.4595	0.1745	0.2422	0.081*
C1	−0.0673 (3)	−0.0311 (2)	0.20648 (19)	0.0714 (9)
C2	0.0664 (3)	−0.07331 (18)	0.20186 (15)	0.0520 (7)
C3	0.0750 (3)	−0.15326 (19)	0.16279 (18)	0.0647 (8)
H3	0.1639	−0.1818	0.1610	0.078*
C4	−0.0439 (5)	−0.1925 (2)	0.1261 (2)	0.0829 (11)
C5	−0.1739 (5)	−0.1497 (3)	0.1314 (2)	0.0980 (14)
H5	−0.2555	−0.1748	0.1080	0.118*
C6	−0.1872 (4)	−0.0713 (3)	0.1698 (2)	0.0954 (13)
H6	−0.2772	−0.0441	0.1717	0.114*
C7	−0.0299 (5)	−0.2790 (3)	0.0838 (3)	0.1263 (17)
H7A	0.0689	−0.2984	0.0864	0.152*	0.50
H7B	−0.0583	−0.2728	0.0281	0.152*	0.50
H7C	−0.0914	−0.3211	0.1098	0.152*	0.50
H7D	−0.1228	−0.2964	0.0632	0.152*	0.50
H7E	0.0044	−0.3220	0.1215	0.152*	0.50
H7F	0.0375	−0.2738	0.0398	0.152*	0.50
C8	−0.1921 (4)	0.1014 (3)	0.2371 (3)	0.1235 (17)
H8A	−0.1803	0.1530	0.2693	0.148*	0.50
H8B	−0.2782	0.0711	0.2537	0.148*	0.50
H8C	−0.2003	0.1173	0.1810	0.148*	0.50
H8D	−0.2589	0.0746	0.2000	0.148*	0.50
H8E	−0.1610	0.1565	0.2156	0.148*	0.50
H8F	−0.2389	0.1103	0.2884	0.148*	0.50
C9	0.1955 (3)	−0.03336 (16)	0.24276 (15)	0.0452 (6)
H9	0.1714	0.0273	0.2559	0.054*
C10	0.2371 (3)	−0.07938 (16)	0.32176 (15)	0.0519 (7)
H10A	0.1544	−0.0790	0.3581	0.062*
H10B	0.2607	−0.1398	0.3100	0.062*
C11	0.3634 (3)	−0.03745 (16)	0.36337 (14)	0.0467 (6)
C12	0.3491 (4)	0.04298 (19)	0.40086 (17)	0.0645 (8)
H12	0.2592	0.0704	0.4017	0.077*
C13	0.4655 (5)	0.0828 (2)	0.43680 (19)	0.0817 (11)
H13	0.4537	0.1366	0.4620	0.098*
C14	0.5989 (5)	0.0439 (3)	0.4358 (2)	0.0869 (11)
H14	0.6780	0.0713	0.4598	0.104*
C15	0.6149 (4)	−0.0348 (3)	0.3995 (2)	0.0826 (10)
H15	0.7053	−0.0616	0.3991	0.099*
C16	0.4983 (3)	−0.07581 (19)	0.36311 (17)	0.0607 (8)
H16	0.5112	−0.1297	0.3383	0.073*
C17	0.3070 (3)	0.01147 (14)	0.10722 (14)	0.0381 (6)
H17	0.2360	−0.0225	0.0763	0.046*
C18	0.4506 (3)	0.00799 (17)	0.06186 (16)	0.0542 (7)
H18A	0.4375	0.0303	0.0080	0.065*
H18B	0.4837	−0.0513	0.0591	0.065*
H18C	0.5211	0.0428	0.0899	0.065*
C19	0.3103 (3)	0.16121 (14)	0.17134 (15)	0.0416 (6)
C20	0.2470 (3)	0.10201 (14)	0.11831 (14)	0.0378 (5)
C21	0.1238 (3)	0.12697 (16)	0.07632 (15)	0.0465 (6)
H21	0.0808	0.0872	0.0411	0.056*
C22	0.0621 (3)	0.20900 (17)	0.08478 (16)	0.0571 (7)
C23	0.1256 (3)	0.26526 (17)	0.13990 (17)	0.0600 (8)
H23	0.0844	0.3199	0.1483	0.072*
C24	0.2482 (3)	0.24274 (15)	0.18272 (17)	0.0524 (7)
H24	0.2891	0.2820	0.2191	0.063*
C25	−0.0707 (4)	0.2348 (2)	0.0372 (2)	0.0946 (12)
H25A	−0.0988	0.1875	0.0024	0.114*	0.50
H25B	−0.0493	0.2853	0.0050	0.114*	0.50
H25C	−0.1484	0.2479	0.0739	0.114*	0.50
H25D	−0.0989	0.2930	0.0518	0.114*	0.50
H25E	−0.1484	0.1952	0.0492	0.114*	0.50
H25F	−0.0492	0.2326	−0.0197	0.114*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0633 (4)	0.0449 (3)	0.0726 (5)	−0.0110 (3)	−0.0108 (4)	−0.0020 (3)
N1	0.0369 (11)	0.0352 (10)	0.0437 (12)	0.0005 (8)	−0.0036 (9)	0.0017 (9)
O1	0.0617 (14)	0.128 (2)	0.0923 (17)	0.0378 (15)	0.0039 (14)	0.0002 (16)
O2	0.0532 (11)	0.0449 (9)	0.0639 (11)	−0.0038 (9)	−0.0171 (10)	−0.0082 (8)
C1	0.0463 (19)	0.108 (3)	0.0599 (19)	0.0007 (19)	0.0017 (16)	0.0267 (19)
C2	0.0386 (15)	0.0654 (17)	0.0519 (16)	−0.0092 (14)	−0.0011 (13)	0.0183 (13)
C3	0.0518 (17)	0.0684 (19)	0.074 (2)	−0.0231 (15)	−0.0078 (16)	0.0191 (17)
C4	0.081 (3)	0.094 (3)	0.073 (2)	−0.050 (2)	−0.022 (2)	0.0294 (19)
C5	0.069 (3)	0.144 (4)	0.081 (3)	−0.057 (3)	−0.020 (2)	0.041 (3)
C6	0.0409 (19)	0.164 (4)	0.081 (3)	−0.007 (2)	−0.0077 (19)	0.044 (3)
C7	0.162 (4)	0.097 (3)	0.120 (3)	−0.073 (3)	−0.043 (3)	0.013 (2)
C8	0.083 (3)	0.155 (4)	0.132 (4)	0.062 (3)	0.020 (3)	0.033 (3)
C9	0.0426 (14)	0.0461 (14)	0.0470 (15)	0.0000 (12)	0.0038 (12)	0.0056 (12)
C10	0.0558 (17)	0.0551 (15)	0.0450 (15)	−0.0053 (13)	0.0031 (14)	0.0097 (13)
C11	0.0620 (18)	0.0433 (14)	0.0348 (14)	−0.0007 (13)	−0.0002 (12)	0.0087 (11)
C12	0.090 (2)	0.0535 (17)	0.0507 (18)	0.0096 (17)	−0.0023 (17)	0.0027 (14)
C13	0.134 (4)	0.0563 (19)	0.055 (2)	−0.021 (2)	−0.010 (2)	−0.0042 (15)
C14	0.099 (3)	0.100 (3)	0.062 (2)	−0.041 (2)	−0.014 (2)	−0.004 (2)
C15	0.068 (2)	0.109 (3)	0.071 (2)	−0.004 (2)	−0.0105 (18)	−0.007 (2)
C16	0.066 (2)	0.0612 (17)	0.0547 (18)	0.0054 (15)	−0.0047 (14)	−0.0078 (14)
C17	0.0431 (14)	0.0352 (12)	0.0361 (14)	−0.0007 (11)	−0.0062 (11)	0.0005 (10)
C18	0.0598 (17)	0.0543 (15)	0.0485 (15)	0.0052 (14)	0.0049 (15)	0.0041 (12)
C19	0.0407 (14)	0.0394 (13)	0.0446 (14)	−0.0020 (10)	−0.0032 (13)	0.0031 (12)
C20	0.0452 (15)	0.0329 (12)	0.0353 (13)	−0.0010 (11)	0.0017 (12)	0.0021 (10)
C21	0.0514 (15)	0.0450 (14)	0.0432 (14)	0.0056 (12)	−0.0095 (13)	0.0006 (12)
C22	0.0638 (18)	0.0530 (16)	0.0544 (16)	0.0178 (15)	−0.0064 (15)	0.0009 (13)
C23	0.069 (2)	0.0445 (16)	0.0668 (19)	0.0164 (14)	0.0035 (16)	−0.0040 (14)
C24	0.0637 (18)	0.0387 (13)	0.0548 (16)	−0.0014 (12)	0.0030 (15)	−0.0079 (12)
C25	0.103 (3)	0.079 (2)	0.102 (3)	0.046 (2)	−0.040 (2)	−0.0132 (19)

Geometric parameters (Å, º)

N1—C17	1.509 (3)	C10—H10B	0.9700
N1—C9	1.512 (3)	C11—C16	1.377 (4)
N1—H1A	0.9000	C11—C12	1.385 (4)
N1—H1B	0.9000	C12—C13	1.370 (5)
O1—C1	1.363 (4)	C12—H12	0.9300
O1—C8	1.423 (4)	C13—C14	1.368 (5)
O2—C19	1.372 (3)	C13—H13	0.9300
O2—H2	0.8200	C14—C15	1.354 (5)
C1—C2	1.395 (4)	C14—H14	0.9300
C1—C6	1.404 (5)	C15—C16	1.383 (4)
C2—C3	1.387 (4)	C15—H15	0.9300
C2—C9	1.500 (3)	C16—H16	0.9300
C3—C4	1.389 (4)	C17—C20	1.505 (3)
C3—H3	0.9300	C17—C18	1.523 (4)
C4—C5	1.369 (6)	C17—H17	0.9800
C4—C7	1.505 (5)	C18—H18A	0.9600
C5—C6	1.363 (6)	C18—H18B	0.9600
C5—H5	0.9300	C18—H18C	0.9600
C6—H6	0.9300	C19—C24	1.387 (3)
C7—H7A	0.9600	C19—C20	1.389 (3)
C7—H7B	0.9600	C20—C21	1.385 (3)
C7—H7C	0.9600	C21—C22	1.387 (3)
C7—H7D	0.9600	C21—H21	0.9300
C7—H7E	0.9600	C22—C23	1.384 (4)
C7—H7F	0.9600	C22—C25	1.508 (4)
C8—H8A	0.9600	C23—C24	1.377 (4)
C8—H8B	0.9600	C23—H23	0.9300
C8—H8C	0.9600	C24—H24	0.9300
C8—H8D	0.9600	C25—H25A	0.9600
C8—H8E	0.9600	C25—H25B	0.9600
C8—H8F	0.9600	C25—H25C	0.9600
C9—C10	1.531 (3)	C25—H25D	0.9600
C9—H9	0.9800	C25—H25E	0.9600
C10—C11	1.497 (4)	C25—H25F	0.9600
C10—H10A	0.9700
C17—N1—C9	115.59 (18)	C11—C10—H10A	109.0
C17—N1—H1A	108.4	C9—C10—H10A	109.0
C9—N1—H1A	108.4	C11—C10—H10B	109.0
C17—N1—H1B	108.4	C9—C10—H10B	109.0
C9—N1—H1B	108.4	H10A—C10—H10B	107.8
H1A—N1—H1B	107.4	C16—C11—C12	117.8 (3)
C1—O1—C8	117.9 (3)	C16—C11—C10	121.3 (2)
C19—O2—H2	109.5	C12—C11—C10	120.9 (3)
O1—C1—C2	116.3 (3)	C13—C12—C11	121.0 (3)
O1—C1—C6	125.7 (3)	C13—C12—H12	119.5
C2—C1—C6	118.0 (4)	C11—C12—H12	119.5
C3—C2—C1	119.1 (3)	C14—C13—C12	120.4 (3)
C3—C2—C9	121.6 (2)	C14—C13—H13	119.8
C1—C2—C9	119.3 (3)	C12—C13—H13	119.8
C2—C3—C4	122.6 (3)	C15—C14—C13	119.4 (3)
C2—C3—H3	118.7	C15—C14—H14	120.3
C4—C3—H3	118.7	C13—C14—H14	120.3
C5—C4—C3	117.2 (4)	C14—C15—C16	120.8 (3)
C5—C4—C7	121.8 (4)	C14—C15—H15	119.6
C3—C4—C7	121.0 (4)	C16—C15—H15	119.6
C6—C5—C4	122.0 (4)	C11—C16—C15	120.5 (3)
C6—C5—H5	119.0	C11—C16—H16	119.7
C4—C5—H5	119.0	C15—C16—H16	119.7
C5—C6—C1	121.1 (4)	C20—C17—N1	110.44 (19)
C5—C6—H6	119.5	C20—C17—C18	114.34 (19)
C1—C6—H6	119.5	N1—C17—C18	108.22 (19)
C4—C7—H7A	109.5	C20—C17—H17	107.9
C4—C7—H7B	109.5	N1—C17—H17	107.9
H7A—C7—H7B	109.5	C18—C17—H17	107.9
C4—C7—H7C	109.5	C17—C18—H18A	109.5
H7A—C7—H7C	109.5	C17—C18—H18B	109.5
H7B—C7—H7C	109.5	H18A—C18—H18B	109.5
C4—C7—H7D	109.5	C17—C18—H18C	109.5
H7A—C7—H7D	141.1	H18A—C18—H18C	109.5
H7B—C7—H7D	56.3	H18B—C18—H18C	109.5
H7C—C7—H7D	56.3	O2—C19—C24	122.4 (2)
C4—C7—H7E	109.5	O2—C19—C20	117.7 (2)
H7A—C7—H7E	56.3	C24—C19—C20	120.0 (2)
H7B—C7—H7E	141.1	C21—C20—C19	118.7 (2)
H7C—C7—H7E	56.3	C21—C20—C17	119.7 (2)
H7D—C7—H7E	109.5	C19—C20—C17	121.6 (2)
C4—C7—H7F	109.5	C20—C21—C22	122.5 (2)
H7A—C7—H7F	56.3	C20—C21—H21	118.8
H7B—C7—H7F	56.3	C22—C21—H21	118.8
H7C—C7—H7F	141.1	C23—C22—C21	117.2 (3)
H7D—C7—H7F	109.5	C23—C22—C25	121.6 (3)
H7E—C7—H7F	109.5	C21—C22—C25	121.2 (3)
O1—C8—H8A	109.5	C24—C23—C22	122.0 (2)
O1—C8—H8B	109.5	C24—C23—H23	119.0
H8A—C8—H8B	109.5	C22—C23—H23	119.0
O1—C8—H8C	109.5	C23—C24—C19	119.7 (2)
H8A—C8—H8C	109.5	C23—C24—H24	120.2
H8B—C8—H8C	109.5	C19—C24—H24	120.2
O1—C8—H8D	109.5	C22—C25—H25A	109.5
H8A—C8—H8D	141.1	C22—C25—H25B	109.5
H8B—C8—H8D	56.3	H25A—C25—H25B	109.5
H8C—C8—H8D	56.3	C22—C25—H25C	109.5
O1—C8—H8E	109.5	H25A—C25—H25C	109.5
H8A—C8—H8E	56.3	H25B—C25—H25C	109.5
H8B—C8—H8E	141.1	C22—C25—H25D	109.5
H8C—C8—H8E	56.3	H25A—C25—H25D	141.1
H8D—C8—H8E	109.5	H25B—C25—H25D	56.3
O1—C8—H8F	109.5	H25C—C25—H25D	56.3
H8A—C8—H8F	56.3	C22—C25—H25E	109.5
H8B—C8—H8F	56.3	H25A—C25—H25E	56.3
H8C—C8—H8F	141.1	H25B—C25—H25E	141.1
H8D—C8—H8F	109.5	H25C—C25—H25E	56.3
H8E—C8—H8F	109.5	H25D—C25—H25E	109.5
C2—C9—N1	112.0 (2)	C22—C25—H25F	109.5
C2—C9—C10	113.2 (2)	H25A—C25—H25F	56.3
N1—C9—C10	108.01 (19)	H25B—C25—H25F	56.3
C2—C9—H9	107.8	H25C—C25—H25F	141.1
N1—C9—H9	107.8	H25D—C25—H25F	109.5
C10—C9—H9	107.8	H25E—C25—H25F	109.5
C11—C10—C9	112.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.90	2.18	2.771 (3)	123
N1—H1B···Cl1^i	0.90	2.21	3.104 (2)	170
O2—H2···Cl1	0.82	2.29	3.114 (2)	177

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