(+)-[1-(4-Methoxy­benz­yl)pyrrolidin-2-yl]diphenyl­methanol

Jin, J.; Xue, S.-J.; Li, X.-F.; Fang, Z.-K.

doi:10.1107/S1600536809011817

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1035

doi:10.1107/S1600536809011817

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(+)-[1-(4-Methoxybenzyl)pyrrolidin-2-yl]diphenylmethanol

Jia Jin,^a Si-Jia Xue,^a ^* Xue-Fei Li ^a and Zhi-Kun Fang ^a

^aDepartment of Chemistry, College of Life and Environmental Science, Shanghai Normal University, Shanghai, 200234, People's Republic of China
^*Correspondence e-mail: sjxue@sohu.com

(Received 25 March 2009; accepted 30 March 2009; online 18 April 2009)

The title compound, C₂₅H₂₇NO₂, was obtained as the product of a Grignard reagent and an intermediate ester synthesized from L-(-)-proline. The asymmetric unit contains two independent molecules, both of which feature an intramolecular O—H⋯N hydrogen bond. In one of the molecules, the pyrrolidine ring is disordered over two orientations in a 0.63 (3):0.37 (3) ratio.

Related literature

For the synthesis, see: Baker et al. (1991 ); Zhao et al. (1999 ). For background on the applications of this family of compounds, see: Kagabu et al. (2007 ).

Experimental

Crystal data

C₂₅H₂₇NO₂
M_r = 373.48
Monoclinic, C 2
a = 33.131 (4) Å
b = 5.9916 (7) Å
c = 21.472 (3) Å
β = 97.715 (3)°
V = 4223.8 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 292 K
0.20 × 0.10 × 0.04 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: none
20497 measured reflections
4093 independent reflections
2040 reflections with I > 2σ(I)
R_int = 0.107

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.179
S = 0.93
4093 reflections
536 parameters
7 restraints
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	2.32	2.673 (8)	106
O3—H3A⋯N2	0.82	2.33	2.672 (7)	106

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809011817/hb2936sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809011817/hb2936Isup2.hkl

checkCIF report

Comment top

Pyrrolidine derivatives have received much attention on their potential applications in chiral catalysis, medicine intermediate and pesticide (e.g. Kagabu et al., 2007). We report here the synthesis and crystal structure of the title compound (I).

There are four aromatic rings in one molecule structure (Figure 1), namely a pyrrolidine ring (N2/C39—C42), phenyl rings (C26—C31), (C32—C37), (C44—C49) (Fig 1). the phenyl ring (C26—C31) and phenyl ring (C32—C37) forms dihedral angle of 71.5 (8)°; the phenyl ring (C32—C37) and phenyl ring (C44—C49) forms dihedral angle of 83.4 (6)°; the phenyl ring (C26—C31) and phenyl ring (C44—C49) forms dihedral angle of 41.1 (6)°. It is interesting that the dihedral angle of the phenyl ring (C26—C31) and phenyl ring (C44—C49) are smaller than the other two dihedral angles. It probably because that the —OCH₃ effect the phenyl ring (C44—C49). Another structure feature that should be mentioned here is the N—C bond length data (C18—N1 1.45 Å and C43—N2 1.45 Å) in the crystal of compound (I) are between the standard C—N (1.47 Å) and C=N (1.26 Å), which shows that the nitrogen atom may have weak conjugation with the carbon atom (C18 and C43).

The title compound (I) belongs to monoclinic crystal system with space group C2. Each asymmetric unit contains two independent conformational isomer molecules, and two intramolecular hydrogen bonds (O3—H3A···N2) and (O1—H1···N1) are observed (Table 1) forming two five-membered rings (O1, H1, N1, C13, C14) and (O3, H3A, N2, C38, C39).

Related literature top

For the synthesis, see: Baker et al. (1991); Zhao et al. (1999). For background on the applications of this family of compounds, see: Kagabu et al. (2007).

Experimental top

The title compound was prepared by the literature method (Zhao et al., 1999; Baker et al., 1991) and crystals were grown using volatilization of dichloromethane and methanol solution at room temperature. ¹H NMR (DMSO-d₆, 400 MHz): 6.67–7.66 (m, 14H, Ph—H), 4.95(s, 1H, —OH),3.95(m, 1H, pyrrol N—H), 3.61(s, 3H, —OCH₃), 2.95(m, 2H, CH₂), 2.69(m, 1H, pyrrol N—H), 2.17(m, 1H, pyrrol N—H), 1.78(m, 1H, pyrrol N—H), 1.45(m, 3H, pyrrol N—H); Analysis calculated for C₂₅H₂₇NO₂: C 80.61, H 7.04, N 3.76%; found: C 80.40, H 7.29, N 3.75%. Colourless plates of (I) suitable for single-crystal X-ray diffraction were selected directly from the sample as prepared.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the N2 molecule (I), showing 30% displacement ellipsoids for the non-hydrogen atoms. The hydrogen bond is shown as a double dashed line.
	Fig. 2. Supplementary figure.

(+)-[1-(4-Methoxybenzyl)pyrrolidin-2-yl]diphenylmethanol top

Crystal data top

C₂₅H₂₇NO₂	F(000) = 1600
M_r = 373.48	D_x = 1.175 Mg m⁻³
Monoclinic, C2	Melting point: 391 K
Hall symbol: C 2y	Mo Kα radiation, λ = 0.71073 Å
a = 33.131 (4) Å	Cell parameters from 1185 reflections
b = 5.9916 (7) Å	θ = 2.5–17.0°
c = 21.472 (3) Å	µ = 0.07 mm⁻¹
β = 97.715 (3)°	T = 292 K
V = 4223.8 (9) Å³	Plate, colourless
Z = 8	0.20 × 0.10 × 0.04 mm

Data collection top

Bruker SMART CCD diffractometer	2040 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.107
Graphite monochromator	θ_max = 25.0°, θ_min = 1.7°
ω scans	h = −39→39
20497 measured reflections	k = −7→7
4093 independent reflections	l = −25→25

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.067	H-atom parameters constrained
wR(F²) = 0.179	w = 1/[σ²(F_o²) + (0.0935P)²] where P = (F_o² + 2F_c²)/3
S = 0.93	(Δ/σ)_max < 0.001
4093 reflections	Δρ_max = 0.19 e Å⁻³
536 parameters	Δρ_min = −0.16 e Å⁻³
7 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0016 (4)

Crystal data top

C₂₅H₂₇NO₂	V = 4223.8 (9) Å³
M_r = 373.48	Z = 8
Monoclinic, C2	Mo Kα radiation
a = 33.131 (4) Å	µ = 0.07 mm⁻¹
b = 5.9916 (7) Å	T = 292 K
c = 21.472 (3) Å	0.20 × 0.10 × 0.04 mm
β = 97.715 (3)°

Data collection top

Bruker SMART CCD diffractometer	2040 reflections with I > 2σ(I)
20497 measured reflections	R_int = 0.107
4093 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	7 restraints
wR(F²) = 0.179	H-atom parameters constrained
S = 0.93	Δρ_max = 0.19 e Å⁻³
4093 reflections	Δρ_min = −0.16 e Å⁻³
536 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.08941 (17)	0.3509 (11)	0.3865 (3)	0.0601 (17)
C2	0.0964 (2)	0.1590 (16)	0.4202 (3)	0.099 (2)
H2	0.1087	0.0383	0.4030	0.119*
C3	0.0852 (3)	0.143 (2)	0.4800 (4)	0.122 (3)
H3	0.0911	0.0115	0.5026	0.146*
C4	0.0666 (3)	0.303 (2)	0.5063 (4)	0.112 (3)
H4	0.0585	0.2841	0.5458	0.135*
C5	0.0596 (3)	0.4983 (19)	0.4745 (3)	0.114 (3)
H5	0.0472	0.6161	0.4928	0.136*
C6	0.0709 (2)	0.5235 (14)	0.4141 (3)	0.097 (3)
H6	0.0659	0.6577	0.3927	0.117*
C7	0.04379 (19)	0.6188 (11)	0.2672 (3)	0.0637 (17)
H7	0.0527	0.7343	0.2945	0.076*
C8	0.0106 (2)	0.6517 (14)	0.2239 (3)	0.0721 (18)
H8	−0.0030	0.7877	0.2226	0.087*
C9	−0.0031 (2)	0.4887 (18)	0.1823 (3)	0.088 (2)
H9	−0.0257	0.5126	0.1523	0.106*
C10	0.0170 (2)	0.2886 (14)	0.1852 (4)	0.090 (2)
H10	0.0079	0.1755	0.1571	0.109*
C11	0.0506 (2)	0.2531 (12)	0.2294 (3)	0.0760 (19)
H11	0.0640	0.1163	0.2305	0.091*
C12	0.06482 (16)	0.4176 (10)	0.2720 (2)	0.0485 (15)
C13	0.10208 (18)	0.3747 (12)	0.3204 (3)	0.0633 (17)
C14	0.13520 (17)	0.5563 (14)	0.3190 (2)	0.073 (2)
H14	0.1237	0.7068	0.3201	0.087*
C17	0.2001 (3)	0.488 (5)	0.2787 (6)	0.099 (7)	0.63 (3)
H17A	0.2148	0.6269	0.2761	0.119*	0.63 (3)
H17B	0.2100	0.3793	0.2510	0.119*	0.63 (3)
C16	0.2048 (4)	0.401 (5)	0.3470 (5)	0.091 (7)	0.63 (3)
H16A	0.2019	0.2403	0.3482	0.109*	0.63 (3)
H16B	0.2310	0.4428	0.3698	0.109*	0.63 (3)
C15	0.1699 (8)	0.519 (5)	0.3738 (15)	0.077 (8)	0.63 (3)
H15A	0.1791	0.6605	0.3923	0.093*	0.63 (3)
H15B	0.1604	0.4271	0.4061	0.093*	0.63 (3)
C15'	0.1681 (16)	0.600 (12)	0.379 (3)	0.117 (17)	0.37 (3)
H15C	0.1632	0.7412	0.3986	0.140*	0.37 (3)
H15D	0.1681	0.4811	0.4093	0.140*	0.37 (3)
C16'	0.2083 (9)	0.605 (11)	0.3506 (11)	0.134 (16)	0.37 (3)
H16C	0.2252	0.7290	0.3676	0.161*	0.37 (3)
H16D	0.2233	0.4673	0.3597	0.161*	0.37 (3)
C17'	0.1961 (6)	0.633 (6)	0.2798 (10)	0.089 (10)	0.37 (3)
H17C	0.1942	0.7899	0.2690	0.107*	0.37 (3)
H17D	0.2163	0.5642	0.2572	0.107*	0.37 (3)
C18	0.14033 (19)	0.6485 (12)	0.2070 (3)	0.0732 (19)
H18A	0.1475	0.8043	0.2138	0.088*
H18B	0.1108	0.6383	0.2003	0.088*
C19	0.15663 (18)	0.5684 (12)	0.1493 (3)	0.0616 (17)
C20	0.18472 (19)	0.6911 (13)	0.1207 (3)	0.0732 (19)
H20	0.1933	0.8296	0.1369	0.088*
C21	0.2001 (2)	0.6082 (14)	0.0680 (3)	0.077 (2)
H21	0.2196	0.6895	0.0505	0.092*
C22	0.1868 (2)	0.4085 (14)	0.0416 (3)	0.0696 (19)
C23	0.15938 (19)	0.2875 (12)	0.0687 (3)	0.0729 (18)
H23	0.1500	0.1518	0.0514	0.087*
C24	0.14537 (19)	0.3664 (13)	0.1223 (3)	0.0725 (19)
H24	0.1274	0.2779	0.1412	0.087*
C25	0.1898 (2)	0.1469 (16)	−0.0416 (3)	0.110 (3)
H25A	0.1958	0.0253	−0.0128	0.165*
H25B	0.2034	0.1238	−0.0778	0.165*
H25C	0.1609	0.1544	−0.0545	0.165*
C26	0.33222 (18)	0.4931 (11)	0.3688 (3)	0.0618 (16)
C27	0.3166 (2)	0.6886 (14)	0.3858 (4)	0.097 (2)
H27	0.3166	0.8109	0.3592	0.117*
C28	0.3004 (3)	0.7125 (19)	0.4421 (5)	0.130 (4)
H28	0.2915	0.8520	0.4534	0.156*
C29	0.2977 (3)	0.545 (2)	0.4790 (4)	0.117 (3)
H29	0.2848	0.5598	0.5146	0.140*
C30	0.3142 (3)	0.343 (2)	0.4651 (4)	0.115 (3)
H30	0.3142	0.2237	0.4928	0.138*
C31	0.3311 (2)	0.3178 (14)	0.4090 (3)	0.093 (2)
H31	0.3416	0.1803	0.3991	0.112*
C32	0.39796 (18)	0.4804 (10)	0.3256 (2)	0.0550 (15)
C33	0.4203 (2)	0.3095 (12)	0.3570 (3)	0.0680 (18)
H33	0.4070	0.1805	0.3670	0.082*
C34	0.4615 (2)	0.3257 (13)	0.3735 (3)	0.0731 (19)
H34	0.4756	0.2096	0.3953	0.088*
C35	0.4820 (2)	0.5112 (17)	0.3582 (3)	0.085 (2)
H35	0.5101	0.5197	0.3689	0.102*
C36	0.4613 (2)	0.6840 (14)	0.3273 (3)	0.079 (2)
H36	0.4754	0.8106	0.3175	0.094*
C37	0.4193 (2)	0.6723 (11)	0.3103 (3)	0.0661 (18)
H37	0.4053	0.7902	0.2890	0.079*
C38	0.35166 (18)	0.4709 (10)	0.3084 (3)	0.0587 (16)
C39	0.33731 (17)	0.2594 (11)	0.2707 (2)	0.0595 (16)
H39	0.3512	0.1278	0.2904	0.071*
C40	0.29109 (17)	0.2231 (13)	0.2623 (3)	0.075 (2)
H40A	0.2846	0.0794	0.2793	0.090*
H40B	0.2779	0.3390	0.2839	0.090*
C41	0.2770 (2)	0.232 (2)	0.1931 (3)	0.126 (4)
H41A	0.2561	0.1207	0.1811	0.151*
H41B	0.2661	0.3781	0.1808	0.151*
C42	0.3128 (2)	0.1855 (15)	0.1642 (3)	0.093 (2)
H42A	0.3104	0.2513	0.1226	0.111*
H42B	0.3166	0.0258	0.1605	0.111*
C43	0.38595 (19)	0.1928 (12)	0.1945 (2)	0.0728 (19)
H43A	0.3843	0.0312	0.1946	0.087*
H43B	0.4064	0.2372	0.2289	0.087*
C44	0.39916 (18)	0.2683 (12)	0.1334 (3)	0.0614 (16)
C45	0.3946 (2)	0.1367 (12)	0.0805 (3)	0.0738 (19)
H45	0.3817	−0.0006	0.0819	0.089*
C46	0.4086 (2)	0.2006 (15)	0.0252 (3)	0.087 (2)
H46	0.4057	0.1063	−0.0095	0.105*
C47	0.4267 (2)	0.4038 (14)	0.0225 (3)	0.075 (2)
C48	0.4315 (2)	0.5416 (13)	0.0744 (3)	0.081 (2)
H48	0.4440	0.6801	0.0732	0.097*
C49	0.4172 (2)	0.4680 (13)	0.1279 (3)	0.075 (2)
H49	0.4201	0.5619	0.1627	0.090*
C50	0.4464 (3)	0.326 (2)	−0.0772 (4)	0.193 (6)
H50A	0.4671	0.2198	−0.0620	0.289*
H50B	0.4540	0.4015	−0.1132	0.289*
H50C	0.4210	0.2487	−0.0888	0.289*
N1	0.15568 (14)	0.5227 (11)	0.2625 (2)	0.0742 (16)
N2	0.34699 (14)	0.2840 (9)	0.20507 (19)	0.0600 (13)
O1	0.12066 (13)	0.1661 (8)	0.30748 (19)	0.0831 (14)
H1	0.1278	0.1705	0.2724	0.125*
O2	0.20340 (14)	0.3502 (10)	−0.0118 (2)	0.0925 (15)
O3	0.33741 (13)	0.6575 (7)	0.26944 (19)	0.0773 (13)
H3A	0.3482	0.6553	0.2372	0.116*
O4	0.44186 (16)	0.4827 (12)	−0.0294 (2)	0.1126 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.062 (4)	0.069 (5)	0.048 (3)	0.006 (4)	0.001 (3)	0.000 (4)
C2	0.128 (7)	0.098 (6)	0.069 (5)	0.007 (5)	0.002 (4)	0.027 (5)
C3	0.164 (9)	0.119 (9)	0.081 (6)	0.005 (8)	0.014 (6)	0.035 (6)
C4	0.133 (8)	0.138 (9)	0.068 (5)	0.000 (7)	0.023 (5)	0.023 (7)
C5	0.143 (7)	0.139 (9)	0.063 (5)	0.032 (7)	0.032 (5)	0.004 (6)
C6	0.153 (7)	0.082 (5)	0.065 (4)	0.040 (6)	0.047 (5)	0.014 (4)
C7	0.076 (4)	0.053 (4)	0.063 (4)	0.019 (4)	0.015 (4)	−0.007 (3)
C8	0.066 (4)	0.080 (5)	0.067 (4)	0.009 (4)	−0.003 (4)	0.000 (4)
C9	0.065 (4)	0.125 (8)	0.072 (5)	0.003 (5)	−0.002 (4)	0.011 (5)
C10	0.098 (6)	0.070 (5)	0.095 (5)	−0.005 (5)	−0.019 (5)	−0.020 (5)
C11	0.088 (5)	0.064 (5)	0.074 (4)	0.007 (4)	0.005 (4)	−0.008 (4)
C12	0.051 (3)	0.051 (4)	0.045 (3)	−0.010 (3)	0.009 (3)	−0.005 (3)
C13	0.068 (4)	0.069 (5)	0.054 (4)	0.005 (4)	0.010 (3)	−0.008 (3)
C14	0.060 (4)	0.110 (6)	0.050 (4)	−0.009 (4)	0.010 (3)	−0.018 (4)
C17	0.062 (9)	0.15 (2)	0.083 (10)	0.032 (10)	0.009 (7)	0.011 (11)
C16	0.058 (8)	0.146 (18)	0.061 (8)	0.001 (10)	−0.022 (6)	−0.004 (9)
C15	0.054 (10)	0.13 (2)	0.041 (9)	−0.009 (10)	0.001 (7)	−0.019 (12)
C15'	0.09 (3)	0.14 (4)	0.11 (4)	0.00 (2)	−0.03 (2)	−0.01 (3)
C16'	0.09 (2)	0.19 (5)	0.12 (2)	−0.02 (2)	0.001 (16)	0.01 (2)
C17'	0.046 (14)	0.14 (3)	0.082 (17)	0.044 (15)	0.026 (11)	−0.009 (18)
C18	0.081 (4)	0.074 (5)	0.067 (4)	−0.001 (4)	0.021 (4)	0.005 (4)
C19	0.059 (4)	0.069 (5)	0.057 (4)	0.002 (4)	0.008 (3)	−0.001 (4)
C20	0.076 (4)	0.074 (5)	0.071 (4)	−0.010 (4)	0.014 (4)	−0.001 (4)
C21	0.077 (5)	0.089 (6)	0.069 (4)	−0.006 (4)	0.025 (4)	0.014 (4)
C22	0.069 (4)	0.092 (6)	0.049 (4)	0.008 (4)	0.013 (3)	0.002 (4)
C23	0.090 (5)	0.066 (4)	0.064 (4)	−0.005 (4)	0.017 (4)	0.006 (4)
C24	0.079 (5)	0.083 (6)	0.057 (4)	−0.009 (4)	0.018 (3)	0.012 (4)
C25	0.122 (7)	0.120 (8)	0.089 (5)	0.013 (6)	0.020 (5)	−0.020 (6)
C26	0.076 (4)	0.053 (4)	0.058 (4)	−0.004 (4)	0.015 (3)	−0.003 (4)
C27	0.115 (6)	0.072 (6)	0.114 (6)	0.006 (5)	0.049 (5)	0.001 (5)
C28	0.157 (9)	0.114 (8)	0.139 (8)	−0.020 (7)	0.096 (7)	−0.042 (7)
C29	0.118 (7)	0.146 (10)	0.098 (7)	−0.047 (7)	0.055 (5)	−0.042 (8)
C30	0.158 (8)	0.121 (8)	0.070 (5)	−0.024 (7)	0.033 (5)	0.002 (6)
C31	0.134 (6)	0.092 (6)	0.059 (4)	0.001 (5)	0.033 (4)	0.005 (5)
C32	0.072 (4)	0.048 (4)	0.046 (3)	0.000 (4)	0.014 (3)	−0.004 (3)
C33	0.072 (5)	0.063 (5)	0.068 (4)	0.007 (4)	0.004 (3)	0.004 (4)
C34	0.077 (5)	0.084 (6)	0.058 (4)	0.000 (4)	0.009 (4)	0.003 (4)
C35	0.075 (5)	0.110 (7)	0.073 (5)	−0.011 (6)	0.018 (4)	−0.019 (5)
C36	0.085 (5)	0.080 (6)	0.078 (5)	−0.017 (5)	0.037 (4)	−0.015 (5)
C37	0.101 (6)	0.050 (4)	0.051 (4)	−0.006 (4)	0.023 (3)	−0.005 (3)
C38	0.081 (4)	0.046 (4)	0.051 (3)	0.009 (3)	0.018 (3)	0.013 (3)
C39	0.065 (4)	0.061 (4)	0.051 (3)	0.006 (3)	0.003 (3)	0.006 (3)
C40	0.074 (4)	0.093 (6)	0.058 (4)	0.003 (4)	0.002 (3)	−0.003 (4)
C41	0.082 (5)	0.213 (12)	0.082 (5)	−0.020 (7)	0.011 (4)	−0.027 (7)
C42	0.107 (6)	0.097 (6)	0.068 (4)	−0.016 (5)	−0.011 (4)	0.007 (5)
C43	0.095 (5)	0.078 (5)	0.045 (3)	0.029 (4)	0.006 (3)	0.009 (4)
C44	0.068 (4)	0.062 (5)	0.052 (4)	0.014 (4)	0.000 (3)	−0.002 (4)
C45	0.102 (5)	0.064 (4)	0.058 (4)	−0.005 (4)	0.018 (4)	−0.014 (4)
C46	0.108 (6)	0.109 (7)	0.046 (4)	−0.015 (5)	0.013 (4)	−0.025 (4)
C47	0.078 (5)	0.095 (6)	0.051 (4)	−0.015 (4)	0.008 (4)	0.003 (4)
C48	0.092 (5)	0.076 (5)	0.076 (5)	−0.005 (4)	0.017 (4)	−0.012 (5)
C49	0.080 (5)	0.080 (6)	0.063 (4)	0.009 (4)	0.003 (4)	−0.018 (4)
C50	0.250 (13)	0.238 (15)	0.107 (7)	−0.108 (12)	0.088 (8)	−0.051 (9)
N1	0.055 (3)	0.121 (5)	0.045 (3)	0.016 (3)	0.002 (2)	−0.005 (3)
N2	0.063 (3)	0.069 (4)	0.046 (3)	0.005 (3)	0.001 (2)	0.002 (3)
O1	0.098 (3)	0.072 (3)	0.076 (3)	0.037 (3)	−0.001 (2)	−0.019 (3)
O2	0.097 (3)	0.114 (4)	0.072 (3)	−0.005 (3)	0.028 (3)	−0.009 (3)
O3	0.104 (3)	0.056 (3)	0.071 (3)	0.017 (3)	0.010 (2)	0.019 (3)
O4	0.128 (4)	0.146 (5)	0.068 (3)	−0.026 (4)	0.028 (3)	0.001 (4)

Geometric parameters (Å, º) top

C1—C2	1.362 (10)	C25—O2	1.421 (10)
C1—C6	1.376 (9)	C25—H25A	0.9600
C1—C13	1.540 (8)	C25—H25B	0.9600
C2—C3	1.388 (11)	C25—H25C	0.9600
C2—H2	0.9300	C26—C27	1.350 (9)
C3—C4	1.308 (12)	C26—C31	1.362 (9)
C3—H3	0.9300	C26—C38	1.529 (8)
C4—C5	1.359 (13)	C27—C28	1.394 (10)
C4—H4	0.9300	C27—H27	0.9300
C5—C6	1.404 (9)	C28—C29	1.291 (13)
C5—H5	0.9300	C28—H28	0.9300
C6—H6	0.9300	C29—C30	1.375 (14)
C7—C8	1.357 (8)	C29—H29	0.9300
C7—C12	1.389 (8)	C30—C31	1.403 (10)
C7—H7	0.9300	C30—H30	0.9300
C8—C9	1.360 (10)	C31—H31	0.9300
C8—H8	0.9300	C32—C33	1.384 (8)
C9—C10	1.369 (11)	C32—C37	1.411 (8)
C9—H9	0.9300	C32—C38	1.530 (8)
C10—C11	1.379 (9)	C33—C34	1.366 (8)
C10—H10	0.9300	C33—H33	0.9300
C11—C12	1.383 (8)	C34—C35	1.364 (11)
C11—H11	0.9300	C34—H34	0.9300
C12—C13	1.525 (8)	C35—C36	1.363 (10)
C13—O1	1.437 (8)	C35—H35	0.9300
C13—C14	1.548 (9)	C36—C37	1.394 (9)
C14—N1	1.482 (7)	C36—H36	0.9300
C14—C15	1.55 (4)	C37—H37	0.9300
C14—C15'	1.59 (8)	C38—O3	1.438 (7)
C14—H14	0.9800	C38—C39	1.545 (9)
C17—N1	1.481 (8)	C39—N2	1.493 (7)
C17—C16	1.542 (9)	C39—C40	1.533 (8)
C17—H17A	0.9700	C39—H39	0.9800
C17—H17B	0.9700	C40—C41	1.499 (8)
C16—C15	1.531 (10)	C40—H40A	0.9700
C16—H16A	0.9700	C40—H40B	0.9700
C16—H16B	0.9700	C41—C42	1.437 (9)
C15—H15A	0.9700	C41—H41A	0.9700
C15—H15B	0.9700	C41—H41B	0.9700
C15'—C16'	1.535 (11)	C42—N2	1.461 (8)
C15'—H15C	0.9700	C42—H42A	0.9700
C15'—H15D	0.9700	C42—H42B	0.9700
C16'—C17'	1.528 (10)	C43—N2	1.447 (7)
C16'—H16C	0.9700	C43—C44	1.507 (8)
C16'—H16D	0.9700	C43—H43A	0.9700
C17'—N1	1.493 (10)	C43—H43B	0.9700
C17'—H17C	0.9700	C44—C49	1.349 (9)
C17'—H17D	0.9700	C44—C45	1.375 (8)
C18—N1	1.444 (7)	C45—C46	1.384 (8)
C18—C19	1.496 (8)	C45—H45	0.9300
C18—H18A	0.9700	C46—C47	1.362 (10)
C18—H18B	0.9700	C46—H46	0.9300
C19—C24	1.371 (9)	C47—O4	1.367 (7)
C19—C20	1.392 (8)	C47—C48	1.378 (9)
C20—C21	1.392 (8)	C48—C49	1.374 (9)
C20—H20	0.9300	C48—H48	0.9300
C21—C22	1.372 (9)	C49—H49	0.9300
C21—H21	0.9300	C50—O4	1.415 (12)
C22—C23	1.353 (9)	C50—H50A	0.9600
C22—O2	1.381 (7)	C50—H50B	0.9600
C23—C24	1.381 (8)	C50—H50C	0.9600
C23—H23	0.9300	O1—H1	0.8200
C24—H24	0.9300	O3—H3A	0.8200

C2—C1—C6	117.3 (6)	H25A—C25—H25B	109.5
C2—C1—C13	121.3 (6)	O2—C25—H25C	109.5
C6—C1—C13	121.4 (6)	H25A—C25—H25C	109.5
C1—C2—C3	120.3 (9)	H25B—C25—H25C	109.5
C1—C2—H2	119.9	C27—C26—C31	117.0 (6)
C3—C2—H2	119.9	C27—C26—C38	121.7 (6)
C4—C3—C2	123.1 (9)	C31—C26—C38	121.3 (6)
C4—C3—H3	118.4	C26—C27—C28	122.0 (8)
C2—C3—H3	118.4	C26—C27—H27	119.0
C3—C4—C5	118.3 (8)	C28—C27—H27	119.0
C3—C4—H4	120.9	C29—C28—C27	121.2 (9)
C5—C4—H4	120.9	C29—C28—H28	119.4
C4—C5—C6	120.5 (9)	C27—C28—H28	119.4
C4—C5—H5	119.7	C28—C29—C30	119.3 (8)
C6—C5—H5	119.7	C28—C29—H29	120.4
C1—C6—C5	120.4 (8)	C30—C29—H29	120.4
C1—C6—H6	119.8	C29—C30—C31	119.8 (9)
C5—C6—H6	119.8	C29—C30—H30	120.1
C8—C7—C12	122.0 (6)	C31—C30—H30	120.1
C8—C7—H7	119.0	C26—C31—C30	120.6 (8)
C12—C7—H7	119.0	C26—C31—H31	119.7
C7—C8—C9	120.9 (7)	C30—C31—H31	119.7
C7—C8—H8	119.5	C33—C32—C37	117.7 (6)
C9—C8—H8	119.5	C33—C32—C38	122.9 (6)
C8—C9—C10	118.8 (7)	C37—C32—C38	119.4 (6)
C8—C9—H9	120.6	C34—C33—C32	121.6 (6)
C10—C9—H9	120.6	C34—C33—H33	119.2
C9—C10—C11	120.7 (7)	C32—C33—H33	119.2
C9—C10—H10	119.7	C35—C34—C33	120.5 (7)
C11—C10—H10	119.7	C35—C34—H34	119.8
C10—C11—C12	121.1 (7)	C33—C34—H34	119.8
C10—C11—H11	119.5	C36—C35—C34	120.2 (7)
C12—C11—H11	119.5	C36—C35—H35	119.9
C11—C12—C7	116.5 (5)	C34—C35—H35	119.9
C11—C12—C13	120.2 (6)	C35—C36—C37	120.5 (7)
C7—C12—C13	123.3 (5)	C35—C36—H36	119.7
O1—C13—C12	110.1 (5)	C37—C36—H36	119.7
O1—C13—C1	105.9 (5)	C36—C37—C32	119.6 (6)
C12—C13—C1	110.4 (4)	C36—C37—H37	120.2
O1—C13—C14	106.5 (5)	C32—C37—H37	120.2
C12—C13—C14	112.3 (5)	O3—C38—C26	106.5 (5)
C1—C13—C14	111.4 (5)	O3—C38—C32	110.6 (5)
N1—C14—C15	103.1 (7)	C26—C38—C32	108.3 (5)
N1—C14—C13	108.9 (5)	O3—C38—C39	106.2 (4)
C15—C14—C13	109.8 (11)	C26—C38—C39	112.4 (5)
N1—C14—C15'	110.1 (12)	C32—C38—C39	112.7 (5)
C15—C14—C15'	18 (3)	N2—C39—C40	104.0 (4)
C13—C14—C15'	121 (2)	N2—C39—C38	108.9 (5)
N1—C14—H14	111.5	C40—C39—C38	114.2 (5)
C15—C14—H14	111.5	N2—C39—H39	109.9
C13—C14—H14	111.5	C40—C39—H39	109.9
C15'—C14—H14	93.2	C38—C39—H39	109.9
N1—C17—C16	104.0 (8)	C41—C40—C39	106.5 (5)
N1—C17—H17A	110.9	C41—C40—H40A	110.4
C16—C17—H17A	110.9	C39—C40—H40A	110.4
N1—C17—H17B	110.9	C41—C40—H40B	110.4
C16—C17—H17B	110.9	C39—C40—H40B	110.4
H17A—C17—H17B	109.0	H40A—C40—H40B	108.6
C15—C16—C17	102.5 (15)	C42—C41—C40	104.8 (6)
C15—C16—H16A	111.3	C42—C41—H41A	110.8
C17—C16—H16A	111.3	C40—C41—H41A	110.8
C15—C16—H16B	111.3	C42—C41—H41B	110.8
C17—C16—H16B	111.3	C40—C41—H41B	110.8
H16A—C16—H16B	109.2	H41A—C41—H41B	108.9
C16—C15—C14	107.7 (19)	C41—C42—N2	106.4 (6)
C16—C15—H15A	110.2	C41—C42—H42A	110.5
C14—C15—H15A	110.2	N2—C42—H42A	110.5
C16—C15—H15B	110.2	C41—C42—H42B	110.5
C14—C15—H15B	110.2	N2—C42—H42B	110.5
H15A—C15—H15B	108.5	H42A—C42—H42B	108.6
C16'—C15'—C14	103 (4)	N2—C43—C44	113.1 (5)
C16'—C15'—H15C	111.2	N2—C43—H43A	109.0
C14—C15'—H15C	111.2	C44—C43—H43A	109.0
C16'—C15'—H15D	111.2	N2—C43—H43B	109.0
C14—C15'—H15D	111.2	C44—C43—H43B	109.0
H15C—C15'—H15D	109.1	H43A—C43—H43B	107.8
C17'—C16'—C15'	105 (3)	C49—C44—C45	115.9 (6)
C17'—C16'—H16C	110.7	C49—C44—C43	121.7 (6)
C15'—C16'—H16C	110.7	C45—C44—C43	122.4 (7)
C17'—C16'—H16D	110.7	C44—C45—C46	122.6 (7)
C15'—C16'—H16D	110.7	C44—C45—H45	118.7
H16C—C16'—H16D	108.8	C46—C45—H45	118.7
N1—C17'—C16'	108.1 (18)	C47—C46—C45	118.9 (6)
N1—C17'—H17C	110.1	C47—C46—H46	120.5
C16'—C17'—H17C	110.1	C45—C46—H46	120.5
N1—C17'—H17D	110.1	C46—C47—O4	123.8 (7)
C16'—C17'—H17D	110.1	C46—C47—C48	120.3 (6)
H17C—C17'—H17D	108.4	O4—C47—C48	115.9 (7)
N1—C18—C19	112.9 (5)	C49—C48—C47	117.9 (7)
N1—C18—H18A	109.0	C49—C48—H48	121.0
C19—C18—H18A	109.0	C47—C48—H48	121.0
N1—C18—H18B	109.0	C44—C49—C48	124.4 (6)
C19—C18—H18B	109.0	C44—C49—H49	117.8
H18A—C18—H18B	107.8	C48—C49—H49	117.8
C24—C19—C20	116.1 (6)	O4—C50—H50A	109.5
C24—C19—C18	121.6 (6)	O4—C50—H50B	109.5
C20—C19—C18	122.2 (7)	H50A—C50—H50B	109.5
C19—C20—C21	120.6 (7)	O4—C50—H50C	109.5
C19—C20—H20	119.7	H50A—C50—H50C	109.5
C21—C20—H20	119.7	H50B—C50—H50C	109.5
C22—C21—C20	121.0 (6)	C18—N1—C17	119.8 (8)
C22—C21—H21	119.5	C18—N1—C14	117.1 (5)
C20—C21—H21	119.5	C17—N1—C14	112.0 (7)
C23—C22—C21	119.1 (6)	C18—N1—C17'	100.4 (13)
C23—C22—O2	126.0 (7)	C17—N1—C17'	34.3 (9)
C21—C22—O2	115.0 (7)	C14—N1—C17'	103.2 (10)
C22—C23—C24	119.7 (7)	C43—N2—C42	113.0 (5)
C22—C23—H23	120.1	C43—N2—C39	114.8 (4)
C24—C23—H23	120.1	C42—N2—C39	106.2 (5)
C19—C24—C23	123.4 (6)	C13—O1—H1	109.5
C19—C24—H24	118.3	C22—O2—C25	116.9 (6)
C23—C24—H24	118.3	C38—O3—H3A	109.5
O2—C25—H25A	109.5	C47—O4—C50	116.6 (8)
O2—C25—H25B	109.5

C6—C1—C2—C3	−0.3 (11)	C33—C34—C35—C36	1.2 (10)
C13—C1—C2—C3	179.1 (7)	C34—C35—C36—C37	−0.8 (10)
C1—C2—C3—C4	2.2 (15)	C35—C36—C37—C32	0.4 (9)
C2—C3—C4—C5	−2.9 (16)	C33—C32—C37—C36	−0.5 (8)
C3—C4—C5—C6	1.9 (15)	C38—C32—C37—C36	178.4 (5)
C2—C1—C6—C5	−0.6 (11)	C27—C26—C38—O3	−18.6 (8)
C13—C1—C6—C5	180.0 (7)	C31—C26—C38—O3	163.5 (6)
C4—C5—C6—C1	−0.2 (14)	C27—C26—C38—C32	100.4 (7)
C12—C7—C8—C9	−1.2 (10)	C31—C26—C38—C32	−77.5 (7)
C7—C8—C9—C10	0.7 (10)	C27—C26—C38—C39	−134.5 (7)
C8—C9—C10—C11	−0.2 (11)	C31—C26—C38—C39	47.7 (8)
C9—C10—C11—C12	0.3 (11)	C33—C32—C38—O3	−172.7 (5)
C10—C11—C12—C7	−0.8 (9)	C37—C32—C38—O3	8.5 (7)
C10—C11—C12—C13	−180.0 (6)	C33—C32—C38—C26	70.9 (7)
C8—C7—C12—C11	1.2 (8)	C37—C32—C38—C26	−107.9 (6)
C8—C7—C12—C13	−179.6 (5)	C33—C32—C38—C39	−54.1 (7)
C11—C12—C13—O1	8.0 (7)	C37—C32—C38—C39	127.1 (5)
C7—C12—C13—O1	−171.2 (5)	O3—C38—C39—N2	46.9 (6)
C11—C12—C13—C1	−108.6 (6)	C26—C38—C39—N2	162.9 (5)
C7—C12—C13—C1	72.3 (7)	C32—C38—C39—N2	−74.3 (5)
C11—C12—C13—C14	126.5 (6)	O3—C38—C39—C40	−68.8 (6)
C7—C12—C13—C14	−52.6 (7)	C26—C38—C39—C40	47.2 (6)
C2—C1—C13—O1	−0.2 (8)	C32—C38—C39—C40	170.0 (5)
C6—C1—C13—O1	179.2 (6)	N2—C39—C40—C41	−0.7 (8)
C2—C1—C13—C12	118.9 (7)	C38—C39—C40—C41	117.9 (7)
C6—C1—C13—C12	−61.7 (8)	C39—C40—C41—C42	21.2 (10)
C2—C1—C13—C14	−115.7 (7)	C40—C41—C42—N2	−34.2 (10)
C6—C1—C13—C14	63.7 (8)	N2—C43—C44—C49	81.8 (7)
O1—C13—C14—N1	46.6 (6)	N2—C43—C44—C45	−100.0 (7)
C12—C13—C14—N1	−74.1 (6)	C49—C44—C45—C46	1.7 (10)
C1—C13—C14—N1	161.6 (5)	C43—C44—C45—C46	−176.6 (6)
O1—C13—C14—C15	−65.7 (10)	C44—C45—C46—C47	−1.5 (11)
C12—C13—C14—C15	173.7 (9)	C45—C46—C47—O4	179.4 (6)
C1—C13—C14—C15	49.4 (10)	C45—C46—C47—C48	0.9 (11)
O1—C13—C14—C15'	−82 (2)	C46—C47—C48—C49	−0.6 (11)
C12—C13—C14—C15'	157 (2)	O4—C47—C48—C49	−179.2 (6)
C1—C13—C14—C15'	33 (2)	C45—C44—C49—C48	−1.3 (10)
N1—C17—C16—C15	−31.8 (18)	C43—C44—C49—C48	177.0 (6)
C17—C16—C15—C14	29.8 (18)	C47—C48—C49—C44	0.8 (11)
N1—C14—C15—C16	−16.0 (18)	C19—C18—N1—C17	51.2 (15)
C13—C14—C15—C16	99.9 (16)	C19—C18—N1—C14	−167.6 (6)
C15'—C14—C15—C16	−130 (7)	C19—C18—N1—C17'	81.6 (13)
N1—C14—C15'—C16'	4 (5)	C16—C17—N1—C18	166.6 (10)
C15—C14—C15'—C16'	75 (5)	C16—C17—N1—C14	23.6 (17)
C13—C14—C15'—C16'	132 (3)	C16—C17—N1—C17'	105 (3)
C14—C15'—C16'—C17'	16 (5)	C15—C14—N1—C18	−149.1 (12)
C15'—C16'—C17'—N1	−31 (4)	C13—C14—N1—C18	94.3 (7)
N1—C18—C19—C24	69.7 (8)	C15'—C14—N1—C18	−131 (3)
N1—C18—C19—C20	−108.7 (7)	C15—C14—N1—C17	−5.0 (17)
C24—C19—C20—C21	−0.3 (9)	C13—C14—N1—C17	−121.6 (14)
C18—C19—C20—C21	178.2 (6)	C15'—C14—N1—C17	13 (3)
C19—C20—C21—C22	2.6 (10)	C15—C14—N1—C17'	−39.9 (18)
C20—C21—C22—C23	−2.4 (10)	C13—C14—N1—C17'	−156.5 (15)
C20—C21—C22—O2	177.7 (6)	C15'—C14—N1—C17'	−22 (3)
C21—C22—C23—C24	0.0 (10)	C16'—C17'—N1—C18	154 (2)
O2—C22—C23—C24	179.8 (6)	C16'—C17'—N1—C17	−77 (3)
C20—C19—C24—C23	−2.2 (10)	C16'—C17'—N1—C14	32 (2)
C18—C19—C24—C23	179.3 (6)	C44—C43—N2—C42	72.0 (7)
C22—C23—C24—C19	2.4 (10)	C44—C43—N2—C39	−166.0 (6)
C31—C26—C27—C28	0.8 (11)	C41—C42—N2—C43	161.0 (7)
C38—C26—C27—C28	−177.2 (7)	C41—C42—N2—C39	34.4 (8)
C26—C27—C28—C29	−3.8 (14)	C40—C39—N2—C43	−145.4 (6)
C27—C28—C29—C30	5.6 (15)	C38—C39—N2—C43	92.5 (6)
C28—C29—C30—C31	−4.6 (15)	C40—C39—N2—C42	−19.8 (7)
C27—C26—C31—C30	0.2 (11)	C38—C39—N2—C42	−141.9 (6)
C38—C26—C31—C30	178.1 (7)	C23—C22—O2—C25	1.6 (9)
C29—C30—C31—C26	1.7 (13)	C21—C22—O2—C25	−178.6 (6)
C37—C32—C33—C34	1.0 (8)	C46—C47—O4—C50	−13.6 (11)
C38—C32—C33—C34	−177.9 (6)	C48—C47—O4—C50	165.0 (8)
C32—C33—C34—C35	−1.4 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	2.32	2.673 (8)	106
O3—H3A···N2	0.82	2.33	2.672 (7)	106

Experimental details

Crystal data
Chemical formula	C₂₅H₂₇NO₂
M_r	373.48
Crystal system, space group	Monoclinic, C2
Temperature (K)	292
a, b, c (Å)	33.131 (4), 5.9916 (7), 21.472 (3)
β (°)	97.715 (3)
V (Å³)	4223.8 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.20 × 0.10 × 0.04

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	20497, 4093, 2040
R_int	0.107
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.179, 0.93
No. of reflections	4093
No. of parameters	536
No. of restraints	7
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.16

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	2.32	2.673 (8)	106
O3—H3A···N2	0.82	2.33	2.672 (7)	106

Acknowledgements

This research was supported by the National Natural Science Foundation of China (No. 20672073) and Shanghai Key Laboratory of Lanthanide Functional Materials (No. 07dz22303)

References

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