4,6,12,14-Tetra-tert-butyl-17-N-(6-methyl­pyridin-2-yl)-8,16-dioxa-17-aza­tetra­cyclo­[7.7.1.02,7.010,15]hepta­deca-2,4,6,10,12,14-hexa­ene methanol solvate

Xu, L.; Kim, Y.; Qi, X.; Kim, S.-J.

doi:10.1107/S1600536805041383

4,6,12,14-Tetra-tert-butyl-17-N-(6-methylpyridin-2-yl)-8,16-dioxa-17-azatetracyclo[7.7.1.0^2,7.0^10,15]heptadeca-2,4,6,10,12,14-hexaene methanol solvate

The molecule of the title compoumd, C₃₇H₅₂N₂O₃, exhibits a propeller-like conformation, influenced by one intramolecular C—H

N and four intramolecular C—H

O hydrogen bonds. In the crystal structure, there are four weak C—H

π interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805041383/wn6397sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805041383/wn6397Isup2.hkl Contains datablock I

CCDC reference: 287024

checkCIF report

Key indicators

Single-crystal X-ray study
T = 273 K
Mean (C-C) = 0.004 Å
Disorder in main residue
R factor = 0.044
wR factor = 0.082
Data-to-parameter ratio = 14.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT026_ALERT_3_B Ratio Observed / Unique Reflections too Low ....         32 Perc.
PLAT420_ALERT_2_B D-H Without Acceptor       O3S    -   H3S    ...          ?
PLAT601_ALERT_2_B Structure Contains Solvent Accessible VOIDS of .     117.00 A   3  

Alert level C
GOODF01_ALERT_2_C  The least squares goodness of fit parameter lies
            outside the range 0.80 <> 2.00
            Goodness of fit given =      0.616
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.57 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C7
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C8
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C16
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for       C177
PLAT301_ALERT_3_C Main Residue  Disorder .........................       7.00 Perc.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H16I   ..  CG1     ..       2.91 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H16D   ..  CG2     ..       3.06 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H73A   ..  CG2     ..       2.95 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          3
PLAT737_ALERT_1_C D...A   Calc    2.967(3), Rep    2.967(8) ......       2.67 su-Rat
              C162 -O2      1.555   1.555
PLAT737_ALERT_1_C D...A   Calc    3.033(4), Rep    3.033(9) ......       2.25 su-Rat
              C82  -O1      1.555   1.555
PLAT737_ALERT_1_C D...A   Calc    2.979(3), Rep    2.980(9) ......       3.00 su-Rat
              C83  -O1      1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      41.30 Deg.
              C171 -C17  -C178    1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      39.40 Deg.
              C174 -C17  -C173    1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      38.40 Deg.
              C179 -C17  -C173    1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      44.80 Deg.
              C172 -C17  -C175    1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      28.00 Deg.
              C178 -C17  -C175    1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      38.70 Deg.
              C179 -C17  -C176    1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      34.60 Deg.
              C172 -C17  -C176    1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      34.80 Deg.
              C174 -C17  -C177    1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      38.90 Deg.
              C171 -C17  -C177    1.555   1.555   1.555

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

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

Comment top

Multidentate Schiff base ligands and their metal complexes have been extensively studied for many years (Daier et al., 2004; Munro & Camp, 2003; Weber, 1967; Xu et al., 2001). Schiff bases can be prepared by condensation of different types of amines and carbonyl compounds; one of the most popular methods has been the use of salicylideneamines, which can serve as efficient models for biologically important systems (Long, 1995) in addition to their diverse chelating ability (Kim et al., 2001). The title compound, (I), was unexpectedly obtained in the reaction of 3,5-di-tert-butylsalicylaldehyde with 6-amino-2-methylpyridine.

The title compound, (I), possesses three aryl rings, viz. benzene ring 1 (atoms C1–C6; denoted R1), benzene ring 2 (C10–C15; R2) and pyridyl ring 3 (N2/C19–C23; R3). These are connected to the central polyhedron (N1/C9/C18/O1/O2/C3/C4/C10/C11) to give a propeller-like conformation, which is influenced by one intramolecular C—H···N and four intramolecular C—H···O hydrogen bonds (Fig. 3 and Table 1). The dihedral angles for R1/R2, R1/R3 and R2/R3 are 79.4 (1), 27.8 (1) and 73.0 (1)°, respectively. The bond lengths and angles are unexceptional.

C—H···π interactions often play an important role in the formation of crystal structures (Low et al., 2004; Sylvestre et al., 2005). In the case of (I), an extended crystal structure (Fig. 4) is formed through weak intermolecular C—H···π interactions (Table 1; Cg1 is the centroid of R1 and Cg2 is the centroid of R2).

Experimental top

The title compound was synthesized by the reaction of 3,5-di-tert-butylsalicylaldehyde and 6-methyl-2-aminopyridine, under a nitrogen atmosphere. A mixture of 3,5-di-tertbutylsalicylaldehyde (4 mmol) and 2-amino-6-methylpyridine (4.4 mmol) in ethanol (20 ml) was heated under reflux for 24 h, after adding formic acid as a catalyst. It was then allowed to stand at room temperature overnight. The solid product was isolated by filtration, and purified by thin-layer chromatography. Pale-yellow single crystals suitable for X-ray diffraction were obtained by evaporation of a methanol solution of the product.

Computing details top

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 (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. The structure of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme. Only one component of the disordered tert-butyl group is shown. The solvent molecule has been omitted for the sake of clarity.
	Fig. 2. The structure of (I), showing the propeller-like conformation.
	Fig. 3. [Please provide description of figure]. The intramolecular hydrogen bonds are indicated by dashed lines.
	Fig. 4. The packing of (I), viewed along the a axis, showing the intermolecular C—H···π interactions as dashed lines.

4,6,12,14-Tetra-tert-butyl-17-N-(6-methylpyridin-2-yl)-8,16-dioxa-17- azatetracyclo[7.7.1.0^2,7.0^10,15]heptadeca-2,4,6,10,12,14-hexaene methanol solvate top

Crystal data top

C₃₆H₄₈N₂O₂·CH₄O	Z = 2
M_r = 572.81	F(000) = 624
Triclinic, P1	D_x = 1.091 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.282 (2) Å	Cell parameters from 877 reflections
b = 12.775 (3) Å	θ = 2.3–18.5°
c = 15.601 (3) Å	µ = 0.07 mm⁻¹
α = 66.313 (4)°	T = 273 K
β = 82.711 (4)°	Block, pale yellow
γ = 68.295 (4)°	0.30 × 0.20 × 0.15 mm
V = 1743.0 (7) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	1913 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.049
Graphite monochromator	θ_max = 25.0°, θ_min = 2.1°
ϕ and ω scans	h = −12→12
9105 measured reflections	k = −15→13
6047 independent reflections	l = −18→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H-atom parameters constrained
S = 0.62	w = 1/[σ²(F_o²) + (0.0568P)²] where P = (F_o² + 2F_c²)/3
6047 reflections	(Δ/σ)_max = 0.015
408 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₃₆H₄₈N₂O₂·CH₄O	γ = 68.295 (4)°
M_r = 572.81	V = 1743.0 (7) Å³
Triclinic, P1	Z = 2
a = 10.282 (2) Å	Mo Kα radiation
b = 12.775 (3) Å	µ = 0.07 mm⁻¹
c = 15.601 (3) Å	T = 273 K
α = 66.313 (4)°	0.30 × 0.20 × 0.15 mm
β = 82.711 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1913 reflections with I > 2σ(I)
9105 measured reflections	R_int = 0.049
6047 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.082	H-atom parameters constrained
S = 0.62	Δρ_max = 0.27 e Å⁻³
6047 reflections	Δρ_min = −0.32 e Å⁻³
408 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	0.6021 (3)	−0.1768 (2)	0.42805 (17)	0.0470 (8)
H1	0.6285	−0.2396	0.4866	0.056*
C2	0.7072 (3)	−0.1602 (2)	0.36449 (18)	0.0403 (7)
C3	0.6611 (3)	−0.0647 (2)	0.27628 (18)	0.0378 (7)
C4	0.5223 (3)	0.0071 (2)	0.25645 (17)	0.0349 (7)
C5	0.4230 (3)	−0.0129 (2)	0.32417 (18)	0.0399 (7)
H5	0.3297	0.0378	0.3107	0.048*
C6	0.4599 (3)	−0.1068 (3)	0.41119 (18)	0.0416 (8)
C7	0.3553 (3)	−0.1365 (3)	0.48789 (19)	0.0511 (8)
C71	0.2052 (3)	−0.0515 (3)	0.45589 (17)	0.0764 (10)
H71A	0.1822	−0.0569	0.4004	0.115*
H71B	0.1968	0.0309	0.4426	0.115*
H71C	0.1423	−0.0752	0.5045	0.115*
C72	0.3638 (3)	−0.2678 (3)	0.51308 (19)	0.0886 (11)
H72A	0.3481	−0.2772	0.4577	0.133*
H72B	0.2938	−0.2852	0.5578	0.133*
H72C	0.4549	−0.3233	0.5395	0.133*
C73	0.3894 (3)	−0.1228 (3)	0.57513 (18)	0.0717 (10)
H73A	0.3275	−0.1473	0.6243	0.107*
H73B	0.3775	−0.0392	0.5601	0.107*
H73C	0.4845	−0.1735	0.5955	0.107*
C8	0.8613 (3)	−0.2395 (3)	0.38920 (19)	0.0523 (8)
C81	0.8822 (3)	−0.3311 (2)	0.49233 (17)	0.0823 (11)
H81A	0.8499	−0.2872	0.5330	0.123*
H81B	0.9798	−0.3794	0.5052	0.123*
H81C	0.8298	−0.3835	0.5028	0.123*
C82	0.9172 (3)	−0.3130 (3)	0.32641 (19)	0.0804 (10)
H82A	0.8649	−0.3654	0.3365	0.121*
H82B	1.0143	−0.3616	0.3416	0.121*
H82C	0.9072	−0.2579	0.2619	0.121*
C83	0.9485 (3)	−0.1596 (3)	0.37694 (18)	0.0757 (10)
H83A	0.9440	−0.1053	0.3125	0.114*
H83B	1.0442	−0.2107	0.3953	0.114*
H83C	0.9120	−0.1128	0.4153	0.114*
C9	0.4726 (3)	0.1021 (2)	0.15918 (17)	0.0385 (7)
H9	0.3888	0.0946	0.1423	0.046*
C10	0.5529 (3)	0.2521 (2)	0.16194 (16)	0.0344 (7)
C11	0.6870 (3)	0.1748 (2)	0.15559 (16)	0.0362 (7)
C12	0.8015 (3)	0.2019 (2)	0.16614 (16)	0.0415 (7)
H12	0.8912	0.1499	0.1617	0.050*
C13	0.7854 (3)	0.3039 (3)	0.18296 (17)	0.0409 (7)
C14	0.6481 (3)	0.3817 (2)	0.18559 (15)	0.0444 (8)
H14	0.6356	0.4523	0.1949	0.053*
C15	0.5292 (3)	0.3597 (2)	0.17504 (16)	0.0360 (7)
C16	0.3817 (3)	0.4517 (2)	0.17389 (19)	0.0453 (8)
C161	0.2981 (2)	0.3937 (2)	0.25637 (17)	0.0644 (9)
H16A	0.2955	0.3208	0.2536	0.097*
H16B	0.2044	0.4504	0.2527	0.097*
H16C	0.3424	0.3737	0.3143	0.097*
C162	0.3047 (3)	0.4945 (2)	0.08056 (17)	0.0698 (10)
H16D	0.3534	0.5364	0.0298	0.105*
H16E	0.2109	0.5488	0.0817	0.105*
H16F	0.3018	0.4250	0.0721	0.105*
C163	0.3846 (3)	0.5655 (2)	0.1843 (2)	0.0855 (11)
H16G	0.4339	0.5413	0.2413	0.128*
H16H	0.2905	0.6188	0.1859	0.128*
H16I	0.4313	0.6075	0.1320	0.128*
C17	0.9119 (3)	0.3345 (3)	0.19624 (19)	0.0470 (8)
C171	1.0533 (6)	0.2400 (6)	0.1900 (6)	0.068 (2)*	0.50
H31	1.0582	0.2320	0.1310	0.101*	0.50
H32	1.0630	0.1627	0.2400	0.101*	0.50
H33	1.1274	0.2661	0.1951	0.101*	0.50
C172	0.9082 (7)	0.3419 (9)	0.2909 (4)	0.065 (2)*	0.50
H34	0.9884	0.3589	0.2988	0.097*	0.50
H35	0.9096	0.2656	0.3392	0.097*	0.50
H36	0.8243	0.4060	0.2948	0.097*	0.50
C173	0.9023 (7)	0.4610 (6)	0.1177 (5)	0.058 (2)*	0.50
H37	0.9800	0.4818	0.1246	0.088*	0.50
H38	0.8163	0.5223	0.1228	0.088*	0.50
H39	0.9048	0.4566	0.0575	0.088*	0.50
C174	0.9702 (16)	0.3859 (17)	0.1071 (8)	0.064 (4)*	0.25
H41	0.9027	0.4628	0.0700	0.096*	0.25
H42	0.9936	0.3311	0.0752	0.096*	0.25
H43	1.0530	0.3981	0.1166	0.096*	0.25
C175	0.9783 (15)	0.2427 (15)	0.2961 (8)	0.058 (4)*	0.25
H44	1.0083	0.1606	0.2993	0.086*	0.25
H45	0.9099	0.2526	0.3429	0.086*	0.25
H46	1.0574	0.2589	0.3072	0.086*	0.25
C176	0.8663 (12)	0.4237 (13)	0.2521 (11)	0.053 (4)*	0.25
H47	0.9463	0.4393	0.2622	0.080*	0.25
H48	0.8292	0.3858	0.3114	0.080*	0.25
H49	0.7959	0.4993	0.2162	0.080*	0.25
C177	1.0289 (11)	0.3055 (13)	0.1212 (8)	0.036 (3)*	0.25
H61	0.9892	0.3532	0.0590	0.054*	0.25
H62	1.0596	0.2203	0.1324	0.054*	0.25
H63	1.1072	0.3257	0.1277	0.054*	0.25
C178	1.0206 (15)	0.2143 (11)	0.2624 (12)	0.062 (5)*	0.25
H64	1.0601	0.1593	0.2307	0.093*	0.25
H65	0.9750	0.1771	0.3177	0.093*	0.25
H66	1.0937	0.2324	0.2797	0.093*	0.25
C179	0.8759 (11)	0.4668 (10)	0.1807 (12)	0.050 (4)*	0.25
H67	0.9597	0.4810	0.1852	0.075*	0.25
H68	0.8120	0.4855	0.2274	0.075*	0.25
H69	0.8331	0.5181	0.1197	0.075*	0.25
C18	0.7097 (3)	0.0671 (2)	0.12950 (17)	0.0388 (7)
H18	0.7789	0.0674	0.0801	0.047*
C19	0.5500 (3)	0.1264 (2)	−0.0019 (2)	0.0404 (7)
C20	0.4137 (3)	0.1884 (2)	−0.03731 (19)	0.0535 (9)
H20	0.3390	0.2046	0.0015	0.064*
C21	0.3925 (3)	0.2253 (2)	−0.1323 (2)	0.0616 (9)
H21	0.3021	0.2641	−0.1580	0.074*
C22	0.5046 (4)	0.2046 (3)	−0.1886 (2)	0.0597 (9)
H22	0.4913	0.2295	−0.2526	0.072*
C23	0.6366 (3)	0.1469 (3)	−0.1490 (2)	0.0537 (9)
C24	0.7648 (3)	0.1250 (3)	−0.20795 (18)	0.0815 (11)
H24A	0.8330	0.1480	−0.1902	0.122*
H24B	0.7389	0.1731	−0.2729	0.122*
H24C	0.8039	0.0401	−0.1982	0.122*
N1	0.5799 (2)	0.07651 (18)	0.09459 (15)	0.0387 (6)
N2	0.6617 (2)	0.10429 (19)	−0.05550 (17)	0.0477 (6)
O1	0.76077 (16)	−0.04700 (15)	0.20879 (11)	0.0432 (5)
O2	0.43683 (16)	0.22460 (15)	0.15522 (10)	0.0395 (5)
C3S	0.9833 (4)	0.8192 (3)	0.0525 (2)	0.1289 (17)
H3S1	1.0050	0.8584	0.0871	0.193*
H3S2	1.0685	0.7644	0.0388	0.193*
H3S3	0.9249	0.7742	0.0890	0.193*
O3S	0.9177 (3)	0.9016 (3)	−0.0256 (2)	0.2240 (19)
H3S	0.8631	0.8780	−0.0403	0.336*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.052 (2)	0.044 (2)	0.0390 (19)	−0.0188 (18)	−0.0012 (16)	−0.0080 (15)
C2	0.0380 (19)	0.036 (2)	0.0437 (19)	−0.0104 (16)	−0.0015 (15)	−0.0138 (15)
C3	0.0384 (19)	0.038 (2)	0.0431 (19)	−0.0186 (16)	0.0120 (16)	−0.0197 (16)
C4	0.0336 (18)	0.0356 (19)	0.0392 (18)	−0.0142 (16)	0.0025 (15)	−0.0166 (15)
C5	0.0369 (18)	0.040 (2)	0.0473 (19)	−0.0143 (15)	−0.0003 (16)	−0.0195 (16)
C6	0.045 (2)	0.044 (2)	0.0408 (19)	−0.0216 (17)	0.0015 (16)	−0.0163 (15)
C7	0.048 (2)	0.064 (2)	0.043 (2)	−0.0282 (19)	0.0126 (16)	−0.0183 (17)
C71	0.051 (2)	0.104 (3)	0.061 (2)	−0.031 (2)	0.0135 (17)	−0.0198 (19)
C72	0.107 (3)	0.081 (3)	0.094 (3)	−0.063 (2)	0.041 (2)	−0.033 (2)
C73	0.075 (2)	0.090 (3)	0.049 (2)	−0.032 (2)	0.0113 (17)	−0.0261 (19)
C8	0.041 (2)	0.052 (2)	0.046 (2)	−0.0028 (18)	−0.0037 (15)	−0.0125 (17)
C81	0.059 (2)	0.075 (3)	0.067 (2)	0.000 (2)	−0.0101 (17)	0.0000 (19)
C82	0.075 (2)	0.064 (3)	0.079 (3)	0.004 (2)	0.0004 (19)	−0.031 (2)
C83	0.048 (2)	0.095 (3)	0.082 (2)	−0.026 (2)	−0.0049 (17)	−0.030 (2)
C9	0.0380 (19)	0.042 (2)	0.0435 (19)	−0.0207 (16)	0.0044 (15)	−0.0187 (16)
C10	0.0303 (18)	0.037 (2)	0.0372 (18)	−0.0182 (16)	−0.0001 (13)	−0.0090 (14)
C11	0.0320 (18)	0.0342 (19)	0.0388 (18)	−0.0117 (16)	0.0040 (14)	−0.0114 (14)
C12	0.0354 (18)	0.043 (2)	0.0413 (18)	−0.0150 (16)	−0.0010 (13)	−0.0104 (15)
C13	0.040 (2)	0.045 (2)	0.0410 (18)	−0.0232 (18)	0.0025 (14)	−0.0127 (15)
C14	0.0456 (19)	0.038 (2)	0.0529 (19)	−0.0179 (17)	0.0020 (15)	−0.0174 (15)
C15	0.0353 (19)	0.035 (2)	0.0383 (18)	−0.0144 (16)	0.0019 (14)	−0.0126 (14)
C16	0.0336 (18)	0.036 (2)	0.068 (2)	−0.0093 (16)	0.0015 (16)	−0.0240 (16)
C161	0.0451 (19)	0.077 (3)	0.076 (2)	−0.0208 (18)	0.0150 (17)	−0.0390 (18)
C162	0.058 (2)	0.057 (2)	0.073 (2)	−0.0055 (18)	−0.0156 (17)	−0.0121 (18)
C163	0.056 (2)	0.057 (3)	0.151 (3)	−0.0105 (19)	0.000 (2)	−0.055 (2)
C17	0.0386 (19)	0.049 (2)	0.052 (2)	−0.0182 (18)	−0.0018 (15)	−0.0144 (17)
C18	0.0390 (19)	0.042 (2)	0.0347 (18)	−0.0185 (16)	0.0064 (14)	−0.0126 (15)
C19	0.050 (2)	0.0311 (19)	0.044 (2)	−0.0186 (16)	0.0024 (18)	−0.0149 (15)
C20	0.056 (2)	0.059 (2)	0.044 (2)	−0.0205 (18)	−0.0025 (16)	−0.0164 (16)
C21	0.070 (2)	0.061 (2)	0.053 (2)	−0.029 (2)	−0.010 (2)	−0.0132 (19)
C22	0.084 (3)	0.062 (2)	0.044 (2)	−0.038 (2)	−0.001 (2)	−0.0202 (18)
C23	0.074 (3)	0.053 (2)	0.049 (2)	−0.035 (2)	0.012 (2)	−0.0260 (18)
C24	0.096 (3)	0.103 (3)	0.061 (2)	−0.046 (2)	0.031 (2)	−0.044 (2)
N1	0.0372 (15)	0.0437 (16)	0.0358 (16)	−0.0164 (13)	0.0015 (12)	−0.0141 (12)
N2	0.0599 (18)	0.0496 (17)	0.0429 (17)	−0.0266 (14)	0.0114 (14)	−0.0231 (13)
O1	0.0388 (12)	0.0395 (13)	0.0443 (12)	−0.0107 (10)	0.0035 (10)	−0.0128 (10)
O2	0.0348 (11)	0.0359 (13)	0.0513 (12)	−0.0144 (10)	0.0022 (9)	−0.0187 (9)
C3S	0.143 (4)	0.097 (4)	0.075 (3)	0.014 (3)	0.000 (3)	−0.014 (2)
O3S	0.208 (4)	0.216 (4)	0.126 (3)	0.071 (3)	−0.008 (2)	−0.074 (2)

Geometric parameters (Å, º) top

C1—C2	1.388 (3)	C163—H16H	0.9600
C1—C6	1.396 (3)	C163—H16I	0.9600
C1—H1	0.9300	C17—C174	1.439 (11)
C2—C3	1.412 (3)	C17—C179	1.511 (11)
C2—C8	1.529 (3)	C17—C172	1.512 (6)
C3—C4	1.375 (3)	C17—C171	1.530 (6)
C3—O1	1.384 (2)	C17—C178	1.557 (13)
C4—C5	1.389 (3)	C17—C173	1.563 (6)
C4—C9	1.515 (3)	C17—C175	1.575 (12)
C5—C6	1.382 (3)	C17—C176	1.605 (12)
C5—H5	0.9300	C17—C177	1.617 (10)
C6—C7	1.531 (3)	C171—H31	0.9600
C7—C71	1.527 (3)	C171—H32	0.9600
C7—C72	1.532 (3)	C171—H33	0.9600
C7—C73	1.537 (3)	C172—H34	0.9601
C71—H71A	0.9600	C172—H35	0.9601
C71—H71B	0.9600	C172—H36	0.9601
C71—H71C	0.9600	C173—H37	0.9600
C72—H72A	0.9600	C173—H38	0.9600
C72—H72B	0.9600	C173—H39	0.9600
C72—H72C	0.9600	C174—H41	0.9602
C73—H73A	0.9600	C174—H42	0.9602
C73—H73B	0.9600	C174—H43	0.9602
C73—H73C	0.9600	C175—H44	0.9602
C8—C83	1.536 (3)	C175—H45	0.9602
C8—C82	1.540 (3)	C175—H46	0.9602
C8—C81	1.547 (3)	C176—H47	0.9602
C81—H81A	0.9600	C176—H48	0.9602
C81—H81B	0.9600	C176—H49	0.9602
C81—H81C	0.9600	C177—H61	0.9601
C82—H82A	0.9600	C177—H62	0.9601
C82—H82B	0.9600	C177—H63	0.9601
C82—H82C	0.9600	C178—H64	0.9601
C83—H83A	0.9600	C178—H65	0.9601
C83—H83B	0.9600	C178—H66	0.9601
C83—H83C	0.9600	C179—H67	0.9602
C9—N1	1.434 (3)	C179—H68	0.9602
C9—O2	1.445 (3)	C179—H69	0.9602
C9—H9	0.9800	C18—O1	1.442 (2)
C10—C11	1.387 (3)	C18—N1	1.451 (3)
C10—O2	1.390 (2)	C18—H18	0.9800
C10—C15	1.398 (3)	C19—N2	1.344 (3)
C11—C12	1.389 (3)	C19—C20	1.386 (3)
C11—C18	1.517 (3)	C19—N1	1.402 (3)
C12—C13	1.377 (3)	C20—C21	1.383 (3)
C12—H12	0.9300	C20—H20	0.9300
C13—C14	1.401 (3)	C21—C22	1.368 (3)
C13—C17	1.549 (3)	C21—H21	0.9300
C14—C15	1.394 (3)	C22—C23	1.369 (3)
C14—H14	0.9300	C22—H22	0.9300
C15—C16	1.535 (3)	C23—N2	1.359 (3)
C16—C163	1.538 (3)	C23—C24	1.512 (3)
C16—C161	1.538 (3)	C24—H24A	0.9600
C16—C162	1.542 (3)	C24—H24B	0.9600
C161—H16A	0.9600	C24—H24C	0.9600
C161—H16B	0.9600	C3S—O3S	1.304 (3)
C161—H16C	0.9600	C3S—H3S1	0.9600
C162—H16D	0.9600	C3S—H3S2	0.9600
C162—H16E	0.9600	C3S—H3S3	0.9600
C162—H16F	0.9600	O3S—H3S	0.8200
C163—H16G	0.9600

C2—C1—C6	125.3 (2)	C179—C17—C171	129.5 (5)
C2—C1—H1	117.4	C172—C17—C171	107.4 (4)
C6—C1—H1	117.4	C174—C17—C13	110.3 (5)
C1—C2—C3	115.0 (2)	C179—C17—C13	113.7 (4)
C1—C2—C8	122.0 (2)	C172—C17—C13	110.4 (3)
C3—C2—C8	123.0 (2)	C171—C17—C13	113.2 (3)
C4—C3—O1	120.5 (2)	C174—C17—C178	111.8 (7)
C4—C3—C2	121.9 (2)	C179—C17—C178	132.3 (7)
O1—C3—C2	117.6 (2)	C172—C17—C178	71.9 (6)
C3—C4—C5	120.0 (2)	C171—C17—C178	41.3 (5)
C3—C4—C9	121.3 (2)	C13—C17—C178	107.4 (5)
C5—C4—C9	118.5 (2)	C174—C17—C173	39.4 (6)
C6—C5—C4	121.3 (2)	C179—C17—C173	38.4 (5)
C6—C5—H5	119.4	C172—C17—C173	109.3 (4)
C4—C5—H5	119.4	C171—C17—C173	108.4 (4)
C5—C6—C1	116.5 (3)	C13—C17—C173	108.1 (3)
C5—C6—C7	124.0 (3)	C178—C17—C173	141.1 (6)
C1—C6—C7	119.5 (2)	C174—C17—C175	133.5 (7)
C71—C7—C6	111.8 (2)	C179—C17—C175	113.5 (7)
C71—C7—C72	108.3 (2)	C172—C17—C175	44.8 (5)
C6—C7—C72	108.9 (2)	C171—C17—C175	68.3 (6)
C71—C7—C73	107.9 (2)	C13—C17—C175	106.9 (5)
C6—C7—C73	110.2 (2)	C178—C17—C175	28.0 (6)
C72—C7—C73	109.7 (2)	C173—C17—C175	142.7 (6)
C7—C71—H71A	109.5	C174—C17—C176	112.0 (7)
C7—C71—H71B	109.5	C179—C17—C176	38.7 (5)
H71A—C71—H71B	109.5	C172—C17—C176	34.6 (4)
C7—C71—H71C	109.5	C171—C17—C176	131.3 (5)
H71A—C71—H71C	109.5	C13—C17—C176	110.2 (4)
H71B—C71—H71C	109.5	C178—C17—C176	104.8 (7)
C7—C72—H72A	109.5	C173—C17—C176	77.0 (5)
C7—C72—H72B	109.5	C175—C17—C176	79.1 (7)
H72A—C72—H72B	109.5	C174—C17—C177	34.8 (6)
C7—C72—H72C	109.5	C179—C17—C177	107.3 (6)
H72A—C72—H72C	109.5	C172—C17—C177	137.3 (5)
H72B—C72—H72C	109.5	C171—C17—C177	38.9 (4)
C7—C73—H73A	109.5	C13—C17—C177	108.5 (4)
C7—C73—H73B	109.5	C178—C17—C177	80.2 (6)
H73A—C73—H73B	109.5	C173—C17—C177	74.0 (5)
C7—C73—H73C	109.5	C175—C17—C177	106.6 (7)
H73A—C73—H73C	109.5	C176—C17—C177	137.1 (6)
H73B—C73—H73C	109.5	C17—C171—H31	109.5
C2—C8—C83	110.3 (2)	C17—C171—H32	109.4
C2—C8—C82	109.9 (2)	C17—C171—H33	109.5
C83—C8—C82	109.9 (2)	C17—C172—H34	109.5
C2—C8—C81	111.8 (2)	C17—C172—H35	109.5
C83—C8—C81	106.9 (2)	C17—C172—H36	109.4
C82—C8—C81	107.9 (3)	C17—C173—H37	109.5
C8—C81—H81A	109.5	C17—C173—H38	109.5
C8—C81—H81B	109.5	C17—C173—H39	109.4
H81A—C81—H81B	109.5	C17—C174—H41	109.6
C8—C81—H81C	109.5	C17—C174—H42	109.4
H81A—C81—H81C	109.5	H41—C174—H42	109.5
H81B—C81—H81C	109.5	C17—C174—H43	109.5
C8—C82—H82A	109.5	H41—C174—H43	109.5
C8—C82—H82B	109.5	H42—C174—H43	109.4
H82A—C82—H82B	109.5	C17—C175—H44	109.6
C8—C82—H82C	109.5	C17—C175—H45	109.4
H82A—C82—H82C	109.5	H44—C175—H45	109.5
H82B—C82—H82C	109.5	C17—C175—H46	109.4
C8—C83—H83A	109.5	H44—C175—H46	109.5
C8—C83—H83B	109.5	H45—C175—H46	109.5
H83A—C83—H83B	109.5	C17—C176—H47	109.4
C8—C83—H83C	109.5	C17—C176—H48	109.6
H83A—C83—H83C	109.5	H47—C176—H48	109.5
H83B—C83—H83C	109.5	C17—C176—H49	109.4
N1—C9—O2	111.51 (19)	H47—C176—H49	109.5
N1—C9—C4	108.4 (2)	H48—C176—H49	109.5
O2—C9—C4	111.7 (2)	C17—C177—H61	109.5
N1—C9—H9	108.4	C17—C177—H62	109.4
O2—C9—H9	108.4	C17—C177—H63	109.5
C4—C9—H9	108.4	C17—C178—H64	109.5
C11—C10—O2	120.5 (2)	C17—C178—H65	109.4
C11—C10—C15	121.8 (2)	C17—C178—H66	109.6
O2—C10—C15	117.7 (2)	C17—C179—H67	109.5
C10—C11—C12	119.4 (3)	C17—C179—H68	109.6
C10—C11—C18	120.8 (2)	C17—C179—H69	109.4
C12—C11—C18	119.6 (2)	O1—C18—N1	108.79 (19)
C13—C12—C11	121.6 (3)	O1—C18—C11	111.3 (2)
C13—C12—H12	119.2	N1—C18—C11	110.4 (2)
C11—C12—H12	119.2	O1—C18—H18	108.8
C12—C13—C14	117.0 (2)	N1—C18—H18	108.8
C12—C13—C17	122.3 (3)	C11—C18—H18	108.8
C14—C13—C17	120.6 (3)	N2—C19—C20	123.3 (3)
C15—C14—C13	123.9 (3)	N2—C19—N1	115.1 (3)
C15—C14—H14	118.0	C20—C19—N1	121.6 (3)
C13—C14—H14	118.1	C21—C20—C19	117.8 (3)
C14—C15—C10	116.1 (2)	C21—C20—H20	121.1
C14—C15—C16	121.3 (3)	C19—C20—H20	121.1
C10—C15—C16	122.5 (2)	C22—C21—C20	120.0 (3)
C15—C16—C163	112.2 (2)	C22—C21—H21	120.0
C15—C16—C161	110.3 (2)	C20—C21—H21	120.0
C163—C16—C161	106.6 (2)	C21—C22—C23	118.9 (3)
C15—C16—C162	110.0 (2)	C21—C22—H22	120.6
C163—C16—C162	107.7 (2)	C23—C22—H22	120.6
C161—C16—C162	110.0 (2)	N2—C23—C22	123.0 (3)
C16—C161—H16A	109.5	N2—C23—C24	115.7 (3)
C16—C161—H16B	109.5	C22—C23—C24	121.3 (3)
H16A—C161—H16B	109.5	C23—C24—H24A	109.5
C16—C161—H16C	109.5	C23—C24—H24B	109.5
H16A—C161—H16C	109.5	H24A—C24—H24B	109.5
H16B—C161—H16C	109.5	C23—C24—H24C	109.5
C16—C162—H16D	109.5	H24A—C24—H24C	109.5
C16—C162—H16E	109.5	H24B—C24—H24C	109.5
H16D—C162—H16E	109.5	C19—N1—C9	120.9 (2)
C16—C162—H16F	109.5	C19—N1—C18	120.8 (2)
H16D—C162—H16F	109.5	C9—N1—C18	107.8 (2)
H16E—C162—H16F	109.5	C19—N2—C23	116.9 (3)
C16—C163—H16G	109.5	C3—O1—C18	113.10 (19)
C16—C163—H16H	109.5	C10—O2—C9	113.16 (19)
H16G—C163—H16H	109.5	O3S—C3S—H3S1	109.5
C16—C163—H16I	109.5	O3S—C3S—H3S2	109.5
H16G—C163—H16I	109.5	H3S1—C3S—H3S2	109.5
H16H—C163—H16I	109.5	O3S—C3S—H3S3	109.5
C174—C17—C179	75.4 (7)	H3S1—C3S—H3S3	109.5
C174—C17—C172	135.4 (6)	H3S2—C3S—H3S3	109.5
C179—C17—C172	72.0 (6)	C3S—O3S—H3S	109.5
C174—C17—C171	71.9 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18···N2	0.98	2.36	2.808 (3)	107
C161—H16A···O2	0.96	2.37	3.013 (6)	124
C162—H16F···O2	0.96	2.31	2.967 (8)	125
C82—H82C···O1	0.96	2.40	3.033 (9)	124
C83—H83A···O1	0.96	2.34	2.980 (9)	123
C163—H16I···Cg1ⁱ	0.96	2.91	3.565 (7)	127
C162—H16D···Cg2ⁱⁱ	0.96	3.06	3.893 (11)	146
C73—H73A···Cg2ⁱⁱⁱ	0.96	2.95	3.725 (9)	138
C24—H24B···Cg1ⁱ	0.96	2.65	3.147 (7)	113

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

Experimental details

Crystal data
Chemical formula	C₃₆H₄₈N₂O₂·CH₄O
M_r	572.81
Crystal system, space group	Triclinic, P1
Temperature (K)	273
a, b, c (Å)	10.282 (2), 12.775 (3), 15.601 (3)
α, β, γ (°)	66.313 (4), 82.711 (4), 68.295 (4)
V (Å³)	1743.0 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.30 × 0.20 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9105, 6047, 1913
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.082, 0.62
No. of reflections	6047
No. of parameters	408
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.32

Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.