Crystal structures of (E)-(3-ethyl-1-methyl-2,6-di­phenyl­piperidin-4-yl­idene)amino phenyl carbonate and (E)-(3-isopropyl-1-methyl-2,6-di­phenyl­piperidin-4-yl­idene)amino phenyl carbonate

The title compounds are the 3-ethyl, (I), and 3-isopropyl, (II), derivatives of (1-methyl-2,6-diphenylpiperidin-4-ylidene)amino phenyl carbonate. The main difference in the conformation of the two compounds is the angle of inclination of the phenoxycarbonyl ring with respect to the piperidine ring mean plane, with a dihedral angle of 2.05 (8)° in (I) and 45.24 (13)° in (II).

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.047
• wR factor = 0.132
• Data-to-parameter ratio = 21.4

Structure: II

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.052
• wR factor = 0.145
• Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level A
PLAT015_ALERT_5_A No _shelx_hkl_file record in SHELXL20xy CIF ...      Please Do !

Alert level B
            Crystal system given = monoclinic
PLAT230_ALERT_2_B Hirshfeld Test Diff for    C15    --  C16     ..        7.3 su

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT793_ALERT_4_G The Model has Chirality at C2      .............          S Verify
PLAT793_ALERT_4_G The Model has Chirality at C5      .............          R Verify
PLAT793_ALERT_4_G The Model has Chirality at C6      .............          R Verify
PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) .....          1 Report
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         15 Note

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

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




Datablock: II


Alert level C
THETM01_ALERT_3_C  The value of sine(theta_max)/wavelength is less than 0.590
            Calculated sin(theta_max)/wavelength =    0.5859
PLAT242_ALERT_2_C Low       Ueq as Compared to Neighbors for .....         N1 Check
PLAT242_ALERT_2_C Low       Ueq as Compared to Neighbors for .....        C22 Check
PLAT331_ALERT_2_C Small Average Phenyl   C-C Dist. C13    -C18           1.37 Ang.
PLAT331_ALERT_2_C Small Average Phenyl   C-C Dist. C23    -C28           1.36 Ang.
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      3.337 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.586         27 Report

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT793_ALERT_4_G The Model has Chirality at C2      .............          S Verify
PLAT793_ALERT_4_G The Model has Chirality at C5      .............          R Verify
PLAT793_ALERT_4_G The Model has Chirality at C6      .............          R Verify
PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) .....          4 Report

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

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

---

S1. Chemical context

Piperidine derivatives are one of the simplest heterocyclic units found in nature, for example in several alkaloids. Such compounds have been used as anti­histamines, anaesthetics, tranquilizers and hypotensive agents (Robinson, 1973). The synthesis and biological activity of piperidin-4-one derivatives has received considerable attention (Parthiban et al., 2009; Narayanan et al., 2012). Both natural and synthetic piperidine derivatives have high pharmaceutical value, hence our inter­est in the synthesis of 2,6-disubstituted piperidine derivatives. We report herein on the synthesis and crystal structures of (E)-(3-ethyl-1-methyl-2,6-di­phenyl­piperidin-4-yl­idene)amino phenyl carbonate, (I), and (E)-(3-iso­propyl-1-methyl-2,6-di­phenyl­piperidin-4-yl­idene)amino phenyl carbonate, (II).

S2. Structural commentary

The molecular structure of compound (I) is shown in Fig. 1. The piperidine ring adopts a chair conformation. The attached phenyl rings (C7–C12 and C13–C18) are twisted away from the mean plane of the piperidine ring by 85.82 (8) and 85.84 (7)°. The two phenyl rings are oriented to each other with a dihedral angle of 52.87 (8)°. The phen­oxy ring (C22–C27) is almost coplanar with the piperidine ring mean plane with a dihedral angle of 2.05 (8)°. The sum of the bond angles around atom N1 (331.9°) is in accordance with sp³ hybridization. The ethyl group substituted at position 5 of the piperidine moiety is in an equatorial orientation.

The molecular structure of compound (II) is shown in Fig. 2. The piperidine ring also adopts a chair conformation. The attached phenyl rings (C7—C12 and C13—C18) are twisted away from the mean plane of the piperidine ring by 87.98 (12) and 86.42 (13) °. The two phenyl rings are oriented to each other with a dihedral angle of 60.51 (14)°. In (II) the phen­oxy ring (C23–C28) is no longer coplanar with the mean plane of the piperidine ring but inclined to it by 45.24 (13)°. The sum of the bond angles around atom N1 (335.6°) is in accordance with sp³ hybridization. The iso­propyl group substituted at position 5 of the piperidine moiety is in an equatorial orientation.

For both compounds (I) and (II), the bond lengths and bond angles are comparable with the values reported for the 3-methyl derivative (III), (E)-3-methyl-1-methyl-2,6-di­phenyl­piperidin-4-one O-phen­oxy­carbonyl oxime (Raghuvarman et al., 2014). The overall conformation of compound (III) is very similar to that of compound (II), with the phen­oxy ring inclined to the mean plane of the piperidine ring by 32.79 (9)°, compared to 45.24 (13)° in (II).

S3. Supra­molecular features

In the crystal of (I), pairs of C—H···O hydrogen bonds link the molecules, forming inversion dimers with R₂²(14) loops. The dimers are linked via C—H···π inter­actions, forming a three-dimensional network (Fig. 3 and Table 1).

In the crystal of (II), there are no significant inter­molecular inter­actions present. This is similar to the situation in the crystal of compound (III).

S4. Database survey

A search of the Cambridge Structural Database (Version 53.5, last update May 2014; Allen, 2002) revealed the presence of 25 structures with the substructure 2,6-di­phenyl-4-piperidine oxime. Of these, 16 have the piperidine ring in a chair conformation, while seven have a boat conformation and two a screw-boat conformation. In the various structures, the di­phenyl rings are inclined to one another by dihedral angles varying from ca. 44.9° in a very similar compound to those studied here, viz (E)-{[(3-iso­propyl-1-methyl-2,6-di­phenyl­piperidin-4-yl­idene)amino]­oxy}(pyridin-3-yl)methanone (CCDC refcode: HOFFIT; Vinuchakkaravarthy et al., 2014), to ca. 80.7° in t-3-benzyl-r-2,c-6-bis­(4-meth­oxy­phenyl)­piperidin-4-one oxime (CCDC refcode: HODGAU; Jayabharathi et al., 2008).

S5. Synthesis and crystallization

Compounds (I) and (II) were synthesized by Mannich condensation using benzaldehyde (2 mol), ammonium acetate (1 mol) and methyl propyl ketone (1 mol) for (I), and methyl iso­butyl ketone (1 mol) for (II), in absolute ethanol. The mixtures were warmed for 30 min and stirred overnight at room temperature. The products obtained were treated with methyl iodide (1.5 mol) in the presence of potassium carbonate (2 mol) in acetone (10 ml) and refluxed to give 1-methyl-3-ethyl-2,6-di­phenyl­piperidin-4-one and 1-methyl-3-iso­propyl-2,6-di­phenyl­piperidin-4-one, respectively. The oximations were carried out using hydroxyl­amine hydro­chloride (2 mol) in the presence of sodium acetate (2 mol) in ethanol (10 ml) and refluxed. To the resulting oximes, (0.5 g, 1.62 mmol) for the precursor of (I) and (0.5 g, 1.55 mmol) for the precursor of (II), in dry tetra­hydro­furan (10 ml), was added potassium carbonate (0.48 g, 3.24 mmol) followed by tetra­butyl­ammonium bromide (0.58 g, 1.62 mmol). After stirring for 15 min, phenyl chloro­formate (0.38 g, 2.43 mmol) was added dropwise to the reaction mixtures over a period of 15 min. The mixtures were stirred at ambient temperature for 2 h and progress of the reactions was monitored by thin-layer chromatography. Upon completion of the reactions, the reaction mixtures were diluted with water (20 ml) and extracted with di­chloro­methane (2 × 20 ml). The combined organic layers were washed with water (2 × 20 ml), brine solution (20 ml), dried over anhydrous sodium sulfate (5 g), filtered and concentrated under reduced pressure. The crude products were purified by column chromatography over silica gel (100–200 mesh) eluted with a solvent system of ethyl acetate–petroleum ether (2:98). The pure fractions were collected and concentrated under reduced pressure to give white solids of (I) (yield 0.60 g, 86%) and (II) (yield 0.56 g, 82%), which were recrystallized from a DMF–water mixture (9:1) to give colourless block-like crystals of (I) and (II), respectively.

S6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The C-bound H atoms were positioned geometrically and allowed to ride on their parent atoms: C–H = 0.93–0.98 Å with U_iso(H) = 1.5U_eq(C-methyl) and = 1.2U_eq(C) for other H atoms.

Related literature

For related literature, see: Allen (2002); Jayabharathi et al. (2008); Narayanan et al. (2012); Parthiban et al. (2009); Raghuvarman et al. (2014); Robinson (1973); Vinuchakkaravarthy et al. (2014).

Computing details

For both compounds, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008). Program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008) for (I); SHELXL97 (Sheldrick, 2008) for (II). For both compounds, molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of compound (I), with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The molecular structure of compound (II), with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. A view along the a axis of the crystal packing of compound (I). The C—H···O hydrogen bonds are shown as dashed lines (see Table 1 for details).
	Fig. 4. A view along the a axis of the crystal packing of compound (II).

(I) (E)-(3-Ethyl-1-methyl-2,6-diphenylpiperidin-4-ylidene)amino phenyl carbonate

Crystal data

C27H28N2O3	F(000) = 912
Mr = 428.51	Dx = 1.237 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.3844 (5) Å	Cell parameters from 3960 reflections
b = 17.8121 (8) Å	θ = 2.3–29.2°
c = 14.4077 (7) Å	µ = 0.08 mm^−1
β = 107.216 (2)°	T = 293 K
V = 2300.4 (2) Å^3	Block, colourless
Z = 4	0.26 × 0.23 × 0.19 mm

Data collection

Bruker SMART APEXII CCD diffractometer	6225 independent reflections
Radiation source: fine-focus sealed tube	3960 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
ω and ϕ scans	θmax = 29.2°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −11→12
Tmin = 0.979, Tmax = 0.985	k = −14→24
27700 measured reflections	l = −19→18

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.132	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.056P)^2 + 0.318P] where P = (Fo^2 + 2Fc^2)/3
6225 reflections	(Δ/σ)max = 0.001
291 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.21 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
O1	0.16033 (13)	0.69157 (5)	0.23258 (7)	0.0559 (3)
O2	0.18007 (13)	0.60763 (6)	0.11987 (8)	0.0600 (3)
O3	0.10502 (13)	0.57830 (5)	0.25107 (7)	0.0532 (3)
N1	0.43390 (12)	0.91971 (5)	0.30173 (7)	0.0375 (3)
N2	0.16780 (14)	0.75070 (6)	0.16364 (8)	0.0465 (3)
C2	0.40986 (16)	0.85353 (7)	0.35561 (9)	0.0390 (3)
H2	0.3156	0.8600	0.3709	0.047*
C3	0.39791 (17)	0.78357 (7)	0.29349 (10)	0.0453 (3)
H3A	0.4928	0.7742	0.2816	0.054*
H3B	0.3749	0.7407	0.3279	0.054*
C4	0.27994 (15)	0.79261 (7)	0.19955 (9)	0.0371 (3)
C5	0.29438 (15)	0.86167 (7)	0.14267 (9)	0.0359 (3)
H5	0.3881	0.8570	0.1262	0.043*
C6	0.31051 (15)	0.93034 (7)	0.21098 (9)	0.0363 (3)
H6	0.2174	0.9363	0.2279	0.044*
C7	0.33626 (15)	1.00074 (7)	0.15954 (9)	0.0382 (3)
C8	0.46668 (19)	1.01047 (8)	0.13590 (13)	0.0562 (4)
H8	0.5403	0.9738	0.1529	0.067*
C9	0.4899 (2)	1.07381 (9)	0.08742 (15)	0.0679 (5)
H9	0.5788	1.0793	0.0720	0.081*
C10	0.3841 (2)	1.12844 (9)	0.06185 (12)	0.0635 (5)
H10	0.3999	1.1708	0.0285	0.076*
C11	0.2546 (2)	1.12046 (9)	0.08567 (13)	0.0639 (5)
H11	0.1824	1.1579	0.0691	0.077*
C12	0.23004 (18)	1.05686 (8)	0.13439 (12)	0.0530 (4)
H12	0.1414	1.0520	0.1503	0.064*
C13	0.53352 (16)	0.84251 (7)	0.44998 (9)	0.0388 (3)
C14	0.49950 (18)	0.83362 (8)	0.53594 (10)	0.0473 (4)
H14	0.4008	0.8364	0.5365	0.057*
C15	0.6124 (2)	0.82040 (8)	0.62192 (11)	0.0625 (5)
H15	0.5894	0.8147	0.6800	0.075*
C16	0.7582 (2)	0.81580 (9)	0.62077 (13)	0.0657 (5)
H16	0.8340	0.8065	0.6780	0.079*
C17	0.7913 (2)	0.82486 (10)	0.53564 (14)	0.0670 (5)
H17	0.8899	0.8218	0.5350	0.080*
C18	0.68084 (17)	0.83849 (9)	0.45091 (12)	0.0542 (4)
H18	0.7053	0.8451	0.3934	0.065*
C19	0.17030 (17)	0.87159 (8)	0.04765 (10)	0.0471 (4)
H19A	0.0751	0.8691	0.0612	0.057*
H19B	0.1788	0.9213	0.0222	0.057*
C20	0.1705 (2)	0.81423 (9)	−0.02984 (11)	0.0596 (4)
H20A	0.1415	0.7662	−0.0112	0.089*
H20B	0.2688	0.8108	−0.0370	0.089*
H20C	0.1013	0.8294	−0.0905	0.089*
C21	0.15176 (16)	0.62395 (8)	0.19180 (10)	0.0438 (3)
C22	0.08654 (16)	0.50144 (7)	0.22919 (10)	0.0415 (3)
C23	0.14142 (17)	0.45367 (8)	0.30599 (11)	0.0482 (4)
H23	0.1928	0.4723	0.3670	0.058*
C24	0.11922 (19)	0.37755 (9)	0.29127 (13)	0.0585 (4)
H24	0.1565	0.3443	0.3425	0.070*
C25	0.0423 (2)	0.35073 (9)	0.20119 (13)	0.0602 (4)
H25	0.0282	0.2993	0.1914	0.072*
C26	−0.01384 (19)	0.39930 (9)	0.12579 (12)	0.0569 (4)
H26	−0.0666	0.3807	0.0650	0.068*
C27	0.00697 (18)	0.47570 (9)	0.13886 (11)	0.0501 (4)
H27	−0.0319	0.5089	0.0878	0.060*
C28	0.4511 (2)	0.98690 (8)	0.36280 (12)	0.0626 (5)
H28A	0.5327	0.9799	0.4208	0.094*
H28B	0.3610	0.9953	0.3799	0.094*
H28C	0.4707	1.0295	0.3277	0.094*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0890 (8)	0.0416 (5)	0.0359 (5)	−0.0271 (5)	0.0166 (5)	−0.0001 (4)
O2	0.0821 (8)	0.0514 (6)	0.0578 (7)	−0.0071 (6)	0.0380 (6)	0.0024 (5)
O3	0.0821 (8)	0.0388 (5)	0.0433 (6)	−0.0189 (5)	0.0258 (5)	−0.0009 (4)
N1	0.0464 (7)	0.0291 (5)	0.0335 (6)	−0.0036 (4)	0.0064 (5)	−0.0026 (4)
N2	0.0644 (8)	0.0388 (6)	0.0338 (6)	−0.0162 (5)	0.0108 (6)	0.0036 (5)
C2	0.0427 (8)	0.0385 (7)	0.0345 (7)	−0.0017 (5)	0.0093 (6)	0.0008 (5)
C3	0.0546 (9)	0.0320 (6)	0.0412 (8)	−0.0042 (6)	0.0016 (7)	0.0017 (5)
C4	0.0474 (8)	0.0297 (6)	0.0326 (7)	−0.0037 (5)	0.0095 (6)	−0.0024 (5)
C5	0.0422 (7)	0.0313 (6)	0.0333 (7)	−0.0044 (5)	0.0096 (6)	0.0002 (5)
C6	0.0408 (7)	0.0315 (6)	0.0359 (7)	−0.0017 (5)	0.0102 (6)	0.0001 (5)
C7	0.0438 (8)	0.0314 (6)	0.0360 (7)	−0.0048 (5)	0.0065 (6)	−0.0015 (5)
C8	0.0524 (9)	0.0402 (8)	0.0786 (12)	−0.0015 (7)	0.0235 (8)	0.0087 (7)
C9	0.0704 (12)	0.0517 (10)	0.0873 (13)	−0.0166 (8)	0.0323 (10)	0.0092 (9)
C10	0.0814 (13)	0.0418 (8)	0.0566 (10)	−0.0190 (8)	0.0036 (9)	0.0108 (7)
C11	0.0665 (11)	0.0374 (8)	0.0730 (11)	0.0046 (7)	−0.0019 (9)	0.0115 (7)
C12	0.0497 (9)	0.0410 (8)	0.0653 (10)	0.0018 (6)	0.0124 (8)	0.0048 (7)
C13	0.0453 (8)	0.0331 (6)	0.0352 (7)	−0.0026 (5)	0.0074 (6)	−0.0018 (5)
C14	0.0579 (9)	0.0423 (7)	0.0401 (8)	−0.0046 (6)	0.0122 (7)	−0.0001 (6)
C15	0.0953 (15)	0.0496 (9)	0.0355 (8)	−0.0136 (9)	0.0081 (9)	0.0062 (6)
C16	0.0688 (12)	0.0492 (9)	0.0561 (11)	−0.0042 (8)	−0.0172 (9)	0.0078 (7)
C17	0.0482 (10)	0.0697 (11)	0.0708 (13)	−0.0006 (8)	−0.0012 (9)	−0.0033 (9)
C18	0.0470 (9)	0.0641 (10)	0.0480 (9)	−0.0041 (7)	0.0087 (7)	−0.0036 (7)
C19	0.0609 (9)	0.0394 (7)	0.0355 (7)	−0.0061 (6)	0.0056 (7)	0.0029 (5)
C20	0.0873 (13)	0.0545 (9)	0.0352 (8)	−0.0124 (8)	0.0155 (8)	−0.0038 (6)
C21	0.0478 (8)	0.0434 (7)	0.0368 (7)	−0.0118 (6)	0.0074 (6)	0.0035 (6)
C22	0.0476 (8)	0.0368 (7)	0.0433 (8)	−0.0100 (6)	0.0185 (6)	−0.0007 (5)
C23	0.0514 (9)	0.0485 (8)	0.0426 (8)	−0.0086 (7)	0.0106 (7)	0.0026 (6)
C24	0.0666 (11)	0.0449 (8)	0.0633 (11)	0.0009 (8)	0.0183 (9)	0.0089 (7)
C25	0.0719 (11)	0.0402 (8)	0.0738 (12)	−0.0086 (7)	0.0296 (10)	−0.0065 (7)
C26	0.0642 (10)	0.0581 (9)	0.0509 (9)	−0.0185 (8)	0.0209 (8)	−0.0134 (7)
C27	0.0573 (9)	0.0504 (8)	0.0426 (8)	−0.0108 (7)	0.0149 (7)	0.0022 (6)
C28	0.0921 (13)	0.0391 (8)	0.0456 (9)	−0.0018 (8)	0.0035 (9)	−0.0097 (6)

Geometric parameters (Å, º)

O1—C21	1.3320 (17)	C13—C14	1.376 (2)
O1—N2	1.4635 (14)	C13—C18	1.380 (2)
O2—C21	1.1798 (17)	C14—C15	1.391 (2)
O3—C21	1.3433 (17)	C14—H14	0.9300
O3—C22	1.4041 (16)	C15—C16	1.376 (3)
N1—C2	1.4651 (16)	C15—H15	0.9300
N1—C28	1.4658 (17)	C16—C17	1.361 (3)
N1—C6	1.4799 (16)	C16—H16	0.9300
N2—C4	1.2690 (17)	C17—C18	1.369 (2)
C2—C13	1.5166 (18)	C17—H17	0.9300
C2—C3	1.5188 (18)	C18—H18	0.9300
C2—H2	0.9800	C19—C20	1.514 (2)
C3—C4	1.4820 (18)	C19—H19A	0.9700
C3—H3A	0.9700	C19—H19B	0.9700
C3—H3B	0.9700	C20—H20A	0.9600
C4—C5	1.5062 (17)	C20—H20B	0.9600
C5—C19	1.5224 (18)	C20—H20C	0.9600
C5—C6	1.5490 (17)	C22—C23	1.370 (2)
C5—H5	0.9800	C22—C27	1.373 (2)
C6—C7	1.5120 (17)	C23—C24	1.379 (2)
C6—H6	0.9800	C23—H23	0.9300
C7—C8	1.375 (2)	C24—C25	1.371 (2)
C7—C12	1.382 (2)	C24—H24	0.9300
C8—C9	1.378 (2)	C25—C26	1.366 (2)
C8—H8	0.9300	C25—H25	0.9300
C9—C10	1.361 (3)	C26—C27	1.380 (2)
C9—H9	0.9300	C26—H26	0.9300
C10—C11	1.365 (3)	C27—H27	0.9300
C10—H10	0.9300	C28—H28A	0.9600
C11—C12	1.388 (2)	C28—H28B	0.9600
C11—H11	0.9300	C28—H28C	0.9600
C12—H12	0.9300
C21—O1—N2	111.10 (10)	C13—C14—C15	120.16 (16)
C21—O3—C22	119.30 (11)	C13—C14—H14	119.9
C2—N1—C28	110.22 (11)	C15—C14—H14	119.9
C2—N1—C6	111.60 (10)	C16—C15—C14	119.82 (16)
C28—N1—C6	110.12 (10)	C16—C15—H15	120.1
C4—N2—O1	110.32 (10)	C14—C15—H15	120.1
N1—C2—C13	112.46 (10)	C17—C16—C15	119.78 (15)
N1—C2—C3	110.12 (11)	C17—C16—H16	120.1
C13—C2—C3	109.00 (11)	C15—C16—H16	120.1
N1—C2—H2	108.4	C16—C17—C18	120.69 (18)
C13—C2—H2	108.4	C16—C17—H17	119.7
C3—C2—H2	108.4	C18—C17—H17	119.7
C4—C3—C2	110.73 (11)	C17—C18—C13	120.63 (17)
C4—C3—H3A	109.5	C17—C18—H18	119.7
C2—C3—H3A	109.5	C13—C18—H18	119.7
C4—C3—H3B	109.5	C20—C19—C5	114.67 (13)
C2—C3—H3B	109.5	C20—C19—H19A	108.6
H3A—C3—H3B	108.1	C5—C19—H19A	108.6
N2—C4—C3	127.85 (12)	C20—C19—H19B	108.6
N2—C4—C5	117.13 (11)	C5—C19—H19B	108.6
C3—C4—C5	114.98 (11)	H19A—C19—H19B	107.6
C4—C5—C19	114.59 (11)	C19—C20—H20A	109.5
C4—C5—C6	107.87 (10)	C19—C20—H20B	109.5
C19—C5—C6	112.62 (11)	H20A—C20—H20B	109.5
C4—C5—H5	107.1	C19—C20—H20C	109.5
C19—C5—H5	107.1	H20A—C20—H20C	109.5
C6—C5—H5	107.1	H20B—C20—H20C	109.5
N1—C6—C7	110.03 (10)	O2—C21—O1	127.61 (13)
N1—C6—C5	111.35 (10)	O2—C21—O3	127.59 (13)
C7—C6—C5	110.07 (10)	O1—C21—O3	104.79 (12)
N1—C6—H6	108.4	C23—C22—C27	121.81 (13)
C7—C6—H6	108.4	C23—C22—O3	115.62 (12)
C5—C6—H6	108.4	C27—C22—O3	122.32 (13)
C8—C7—C12	118.01 (13)	C22—C23—C24	118.89 (14)
C8—C7—C6	120.60 (12)	C22—C23—H23	120.6
C12—C7—C6	121.39 (13)	C24—C23—H23	120.6
C7—C8—C9	120.97 (15)	C25—C24—C23	120.11 (15)
C7—C8—H8	119.5	C25—C24—H24	119.9
C9—C8—H8	119.5	C23—C24—H24	119.9
C10—C9—C8	120.72 (18)	C26—C25—C24	120.20 (15)
C10—C9—H9	119.6	C26—C25—H25	119.9
C8—C9—H9	119.6	C24—C25—H25	119.9
C9—C10—C11	119.35 (15)	C25—C26—C27	120.68 (15)
C9—C10—H10	120.3	C25—C26—H26	119.7
C11—C10—H10	120.3	C27—C26—H26	119.7
C10—C11—C12	120.40 (15)	C22—C27—C26	118.28 (14)
C10—C11—H11	119.8	C22—C27—H27	120.9
C12—C11—H11	119.8	C26—C27—H27	120.9
C7—C12—C11	120.54 (16)	N1—C28—H28A	109.5
C7—C12—H12	119.7	N1—C28—H28B	109.5
C11—C12—H12	119.7	H28A—C28—H28B	109.5
C14—C13—C18	118.92 (13)	N1—C28—H28C	109.5
C14—C13—C2	120.12 (13)	H28A—C28—H28C	109.5
C18—C13—C2	120.92 (13)	H28B—C28—H28C	109.5
C21—O1—N2—C4	−126.57 (13)	C8—C7—C12—C11	0.8 (2)
C28—N1—C2—C13	−56.10 (15)	C6—C7—C12—C11	−178.85 (13)
C6—N1—C2—C13	−178.80 (11)	C10—C11—C12—C7	0.0 (2)
C28—N1—C2—C3	−177.89 (12)	N1—C2—C13—C14	127.86 (13)
C6—N1—C2—C3	59.41 (14)	C3—C2—C13—C14	−109.72 (14)
N1—C2—C3—C4	−55.11 (16)	N1—C2—C13—C18	−54.52 (16)
C13—C2—C3—C4	−178.92 (12)	C3—C2—C13—C18	67.90 (16)
O1—N2—C4—C3	4.5 (2)	C18—C13—C14—C15	−0.3 (2)
O1—N2—C4—C5	−173.17 (11)	C2—C13—C14—C15	177.33 (12)
C2—C3—C4—N2	−124.04 (15)	C13—C14—C15—C16	−0.4 (2)
C2—C3—C4—C5	53.71 (17)	C14—C15—C16—C17	0.6 (2)
N2—C4—C5—C19	−0.37 (18)	C15—C16—C17—C18	0.0 (3)
C3—C4—C5—C19	−178.37 (12)	C16—C17—C18—C13	−0.7 (3)
N2—C4—C5—C6	125.92 (13)	C14—C13—C18—C17	0.9 (2)
C3—C4—C5—C6	−52.08 (15)	C2—C13—C18—C17	−176.78 (14)
C2—N1—C6—C7	177.77 (11)	C4—C5—C19—C20	−68.43 (17)
C28—N1—C6—C7	55.01 (15)	C6—C5—C19—C20	167.77 (12)
C2—N1—C6—C5	−59.91 (14)	N2—O1—C21—O2	16.9 (2)
C28—N1—C6—C5	177.34 (12)	N2—O1—C21—O3	−163.60 (11)
C4—C5—C6—N1	53.75 (14)	C22—O3—C21—O2	0.5 (2)
C19—C5—C6—N1	−178.81 (11)	C22—O3—C21—O1	−178.97 (12)
C4—C5—C6—C7	176.05 (11)	C21—O3—C22—C23	135.67 (14)
C19—C5—C6—C7	−56.51 (15)	C21—O3—C22—C27	−50.0 (2)
N1—C6—C7—C8	55.30 (17)	C27—C22—C23—C24	1.7 (2)
C5—C6—C7—C8	−67.78 (16)	O3—C22—C23—C24	176.06 (14)
N1—C6—C7—C12	−125.07 (14)	C22—C23—C24—C25	−0.5 (2)
C5—C6—C7—C12	111.85 (15)	C23—C24—C25—C26	−0.6 (3)
C12—C7—C8—C9	−0.9 (2)	C24—C25—C26—C27	0.5 (3)
C6—C7—C8—C9	178.77 (15)	C23—C22—C27—C26	−1.7 (2)
C7—C8—C9—C10	0.1 (3)	O3—C22—C27—C26	−175.70 (14)
C8—C9—C10—C11	0.7 (3)	C25—C26—C27—C22	0.6 (2)
C9—C10—C11—C12	−0.8 (3)

Hydrogen-bond geometry (Å, º)

Cg3 and Cg4 are the centroids of the C13–C18 and C22–C27 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C26—H26···O2^i	0.93	2.57	3.422 (2)	153
C6—H6···Cg4^ii	0.98	2.99	3.959 (2)	170
C10—H10···Cg3^iii	0.93	2.96	3.824 (2)	155

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

(II) (E)-(3-Isopropyl-1-methyl-2,6-diphenylpiperidin-4-ylidene)amino phenyl carbonate

Crystal data

C28H30N2O3	F(000) = 944
Mr = 442.54	Dx = 1.184 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2894 reflections
a = 10.3511 (5) Å	θ = 2.6–24.6°
b = 23.9398 (10) Å	µ = 0.08 mm^−1
c = 10.0587 (4) Å	T = 293 K
β = 94.997 (2)°	Block, colourless
V = 2483.11 (19) Å^3	0.28 × 0.25 × 0.20 mm
Z = 4

Data collection

Bruker SMART APEXII CCD diffractometer	4150 independent reflections
Radiation source: fine-focus sealed tube	2894 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω and ϕ scans	θmax = 24.6°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −12→11
Tmin = 0.979, Tmax = 0.985	k = −27→28
21076 measured reflections	l = −11→11

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.145	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0589P)^2 + 1.1855P] where P = (Fo^2 + 2Fc^2)/3
4150 reflections	(Δ/σ)max < 0.001
301 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.17 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.

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
C2	0.0430 (2)	0.18137 (10)	−0.0563 (3)	0.0584 (6)
H2	0.0064	0.1957	0.0236	0.070*
C3	0.1492 (2)	0.22117 (10)	−0.0893 (3)	0.0608 (7)
H3A	0.1787	0.2114	−0.1752	0.073*
H3B	0.1151	0.2589	−0.0953	0.073*
C4	0.2604 (2)	0.21879 (9)	0.0150 (2)	0.0525 (6)
C5	0.3125 (2)	0.16055 (10)	0.0412 (2)	0.0536 (6)
H5	0.3350	0.1467	−0.0455	0.064*
C6	0.1996 (2)	0.12406 (10)	0.0777 (2)	0.0547 (6)
H6	0.1684	0.1396	0.1592	0.066*
C7	0.2425 (2)	0.06462 (9)	0.1082 (2)	0.0487 (6)
C8	0.2295 (2)	0.04233 (10)	0.2329 (2)	0.0585 (6)
H8	0.1936	0.0639	0.2972	0.070*
C9	0.2691 (3)	−0.01168 (12)	0.2631 (3)	0.0719 (8)
H9	0.2592	−0.0264	0.3471	0.086*
C10	0.3228 (3)	−0.04338 (11)	0.1694 (3)	0.0739 (8)
H10	0.3503	−0.0796	0.1897	0.089*
C11	0.3358 (3)	−0.02159 (11)	0.0459 (3)	0.0708 (8)
H11	0.3724	−0.0431	−0.0180	0.085*
C12	0.2955 (3)	0.03161 (11)	0.0155 (3)	0.0628 (7)
H12	0.3042	0.0457	−0.0695	0.075*
C13	−0.0643 (2)	0.18131 (9)	−0.1681 (2)	0.0532 (6)
C14	−0.0462 (3)	0.15994 (12)	−0.2912 (3)	0.0727 (8)
H14	0.0343	0.1453	−0.3070	0.087*
C15	−0.1438 (4)	0.15961 (15)	−0.3913 (3)	0.0894 (10)
H15	−0.1291	0.1448	−0.4742	0.107*
C16	−0.2622 (4)	0.18061 (14)	−0.3713 (4)	0.0901 (10)
H16	−0.3284	0.1803	−0.4400	0.108*
C17	−0.2831 (3)	0.20193 (14)	−0.2516 (4)	0.0878 (10)
H17	−0.3643	0.2161	−0.2371	0.105*
C18	−0.1845 (3)	0.20295 (12)	−0.1497 (3)	0.0721 (8)
H18	−0.1996	0.2185	−0.0677	0.086*
C19	0.4372 (2)	0.15494 (10)	0.1351 (2)	0.0551 (6)
H19	0.4554	0.1148	0.1414	0.066*
C20	0.5495 (3)	0.18046 (12)	0.0689 (3)	0.0746 (8)
H20A	0.5565	0.1628	−0.0159	0.112*
H20B	0.6284	0.1750	0.1248	0.112*
H20C	0.5345	0.2197	0.0559	0.112*
C21	0.4315 (3)	0.17488 (12)	0.2767 (3)	0.0756 (8)
H21A	0.4220	0.2148	0.2773	0.113*
H21B	0.5101	0.1646	0.3287	0.113*
H21C	0.3589	0.1579	0.3142	0.113*
C22	0.2968 (2)	0.35449 (9)	0.1078 (2)	0.0500 (6)
C23	0.2503 (2)	0.45192 (9)	0.1050 (2)	0.0498 (6)
C24	0.1424 (3)	0.48133 (11)	0.1271 (3)	0.0675 (7)
H24	0.0610	0.4647	0.1159	0.081*
C25	0.1551 (3)	0.53614 (13)	0.1665 (3)	0.0823 (9)
H25	0.0818	0.5569	0.1818	0.099*
C26	0.2743 (4)	0.56017 (12)	0.1832 (3)	0.0806 (9)
H26	0.2825	0.5973	0.2096	0.097*
C27	0.3816 (3)	0.52999 (12)	0.1614 (3)	0.0753 (8)
H27	0.4631	0.5465	0.1738	0.090*
C28	0.3704 (3)	0.47520 (11)	0.1212 (3)	0.0627 (7)
H28	0.4435	0.4545	0.1054	0.075*
C29	−0.0141 (3)	0.08902 (14)	0.0065 (4)	0.1030 (12)
H29A	−0.0487	0.1021	0.0863	0.155*
H29B	0.0178	0.0516	0.0201	0.155*
H29C	−0.0811	0.0894	−0.0658	0.155*
N1	0.09137 (17)	0.12532 (8)	−0.02577 (19)	0.0518 (5)
N2	0.31261 (19)	0.25920 (8)	0.0822 (2)	0.0552 (5)
O1	0.24663 (16)	0.31067 (6)	0.03989 (17)	0.0584 (4)
O2	0.3785 (2)	0.35587 (7)	0.19522 (19)	0.0783 (6)
O3	0.22803 (16)	0.39771 (6)	0.05421 (17)	0.0614 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C2	0.0579 (15)	0.0519 (15)	0.0644 (15)	0.0002 (12)	−0.0010 (12)	0.0028 (12)
C3	0.0659 (16)	0.0453 (14)	0.0689 (16)	−0.0064 (12)	−0.0066 (13)	0.0039 (12)
C4	0.0537 (14)	0.0407 (13)	0.0622 (15)	−0.0064 (11)	−0.0007 (11)	0.0020 (11)
C5	0.0546 (14)	0.0428 (13)	0.0625 (15)	−0.0039 (11)	0.0004 (11)	−0.0012 (11)
C6	0.0556 (14)	0.0465 (13)	0.0607 (14)	−0.0052 (11)	−0.0035 (11)	0.0059 (11)
C7	0.0493 (13)	0.0426 (13)	0.0524 (13)	−0.0082 (10)	−0.0054 (11)	0.0023 (11)
C8	0.0667 (16)	0.0532 (15)	0.0554 (15)	−0.0121 (12)	0.0047 (12)	0.0002 (12)
C9	0.095 (2)	0.0556 (17)	0.0611 (16)	−0.0195 (15)	−0.0130 (15)	0.0153 (14)
C10	0.081 (2)	0.0407 (15)	0.094 (2)	−0.0037 (13)	−0.0266 (17)	0.0028 (16)
C11	0.0756 (19)	0.0509 (17)	0.085 (2)	−0.0036 (14)	0.0024 (15)	−0.0132 (15)
C12	0.0779 (18)	0.0539 (16)	0.0561 (15)	−0.0114 (13)	0.0033 (13)	−0.0013 (13)
C13	0.0513 (14)	0.0430 (13)	0.0640 (15)	0.0014 (11)	−0.0017 (11)	0.0025 (11)
C14	0.0610 (17)	0.0781 (19)	0.0781 (19)	0.0008 (14)	0.0005 (14)	−0.0201 (16)
C15	0.101 (3)	0.093 (2)	0.0714 (19)	−0.011 (2)	−0.0080 (18)	−0.0134 (17)
C16	0.084 (2)	0.086 (2)	0.094 (3)	−0.0046 (19)	−0.031 (2)	0.024 (2)
C17	0.0569 (18)	0.088 (2)	0.116 (3)	0.0213 (16)	−0.0047 (18)	0.024 (2)
C18	0.0718 (19)	0.0697 (18)	0.0758 (18)	0.0124 (15)	0.0129 (15)	0.0058 (15)
C19	0.0481 (13)	0.0451 (14)	0.0704 (16)	−0.0021 (11)	−0.0047 (11)	0.0002 (12)
C20	0.0632 (17)	0.0665 (18)	0.095 (2)	−0.0030 (14)	0.0126 (15)	−0.0041 (16)
C21	0.084 (2)	0.0757 (19)	0.0645 (17)	0.0037 (16)	−0.0079 (14)	−0.0003 (15)
C22	0.0591 (14)	0.0406 (13)	0.0501 (13)	−0.0032 (11)	0.0037 (12)	0.0031 (11)
C23	0.0626 (15)	0.0379 (12)	0.0478 (13)	−0.0020 (11)	−0.0006 (11)	0.0019 (10)
C24	0.0640 (17)	0.0564 (16)	0.0816 (18)	−0.0004 (13)	0.0029 (14)	0.0005 (14)
C25	0.089 (2)	0.0608 (19)	0.097 (2)	0.0181 (17)	0.0090 (18)	−0.0123 (16)
C26	0.108 (3)	0.0470 (16)	0.084 (2)	−0.0017 (17)	−0.0103 (18)	−0.0136 (14)
C27	0.081 (2)	0.0556 (17)	0.086 (2)	−0.0166 (15)	−0.0094 (16)	−0.0041 (15)
C28	0.0621 (16)	0.0511 (15)	0.0742 (17)	−0.0031 (12)	0.0010 (13)	−0.0046 (13)
C29	0.0671 (19)	0.087 (2)	0.149 (3)	−0.0271 (17)	−0.025 (2)	0.050 (2)
N1	0.0469 (11)	0.0426 (11)	0.0643 (12)	−0.0080 (9)	−0.0047 (9)	0.0060 (9)
N2	0.0603 (12)	0.0384 (11)	0.0657 (12)	0.0003 (9)	−0.0020 (10)	0.0038 (10)
O1	0.0662 (11)	0.0382 (9)	0.0683 (10)	−0.0025 (8)	−0.0081 (8)	−0.0025 (8)
O2	0.1028 (15)	0.0504 (11)	0.0750 (12)	−0.0003 (10)	−0.0308 (12)	0.0000 (9)
O3	0.0701 (11)	0.0395 (9)	0.0714 (11)	−0.0018 (8)	−0.0125 (9)	−0.0031 (8)

Geometric parameters (Å, º)

C2—N1	1.456 (3)	C16—H16	0.9300
C2—C13	1.510 (3)	C17—C18	1.382 (4)
C2—C3	1.513 (3)	C17—H17	0.9300
C2—H2	0.9800	C18—H18	0.9300
C3—C4	1.490 (3)	C19—C21	1.508 (4)
C3—H3A	0.9700	C19—C20	1.517 (4)
C3—H3B	0.9700	C19—H19	0.9800
C4—N2	1.273 (3)	C20—H20A	0.9600
C4—C5	1.510 (3)	C20—H20B	0.9600
C5—C6	1.529 (3)	C20—H20C	0.9600
C5—C19	1.537 (3)	C21—H21A	0.9600
C5—H5	0.9800	C21—H21B	0.9600
C6—N1	1.462 (3)	C21—H21C	0.9600
C6—C7	1.514 (3)	C22—O2	1.166 (3)
C6—H6	0.9800	C22—O1	1.332 (3)
C7—C12	1.373 (3)	C22—O3	1.342 (3)
C7—C8	1.380 (3)	C23—C24	1.355 (3)
C8—C9	1.382 (4)	C23—C28	1.359 (3)
C8—H8	0.9300	C23—O3	1.406 (3)
C9—C10	1.365 (4)	C24—C25	1.374 (4)
C9—H9	0.9300	C24—H24	0.9300
C10—C11	1.365 (4)	C25—C26	1.359 (4)
C10—H10	0.9300	C25—H25	0.9300
C11—C12	1.366 (4)	C26—C27	1.359 (4)
C11—H11	0.9300	C26—H26	0.9300
C12—H12	0.9300	C27—C28	1.375 (4)
C13—C14	1.368 (4)	C27—H27	0.9300
C13—C18	1.375 (4)	C28—H28	0.9300
C14—C15	1.363 (4)	C29—N1	1.454 (3)
C14—H14	0.9300	C29—H29A	0.9600
C15—C16	1.355 (5)	C29—H29B	0.9600
C15—H15	0.9300	C29—H29C	0.9600
C16—C17	1.343 (5)	N2—O1	1.454 (2)
N1—C2—C13	111.92 (19)	C16—C17—C18	120.4 (3)
N1—C2—C3	112.6 (2)	C16—C17—H17	119.8
C13—C2—C3	109.8 (2)	C18—C17—H17	119.8
N1—C2—H2	107.4	C13—C18—C17	120.8 (3)
C13—C2—H2	107.4	C13—C18—H18	119.6
C3—C2—H2	107.4	C17—C18—H18	119.6
C4—C3—C2	110.7 (2)	C21—C19—C20	112.4 (2)
C4—C3—H3A	109.5	C21—C19—C5	116.9 (2)
C2—C3—H3A	109.5	C20—C19—C5	109.2 (2)
C4—C3—H3B	109.5	C21—C19—H19	105.8
C2—C3—H3B	109.5	C20—C19—H19	105.8
H3A—C3—H3B	108.1	C5—C19—H19	105.8
N2—C4—C3	127.6 (2)	C19—C20—H20A	109.5
N2—C4—C5	118.7 (2)	C19—C20—H20B	109.5
C3—C4—C5	113.6 (2)	H20A—C20—H20B	109.5
C4—C5—C6	107.51 (19)	C19—C20—H20C	109.5
C4—C5—C19	117.11 (19)	H20A—C20—H20C	109.5
C6—C5—C19	114.9 (2)	H20B—C20—H20C	109.5
C4—C5—H5	105.4	C19—C21—H21A	109.5
C6—C5—H5	105.4	C19—C21—H21B	109.5
C19—C5—H5	105.4	H21A—C21—H21B	109.5
N1—C6—C7	110.88 (19)	C19—C21—H21C	109.5
N1—C6—C5	111.81 (19)	H21A—C21—H21C	109.5
C7—C6—C5	111.7 (2)	H21B—C21—H21C	109.5
N1—C6—H6	107.4	O2—C22—O1	129.3 (2)
C7—C6—H6	107.4	O2—C22—O3	127.3 (2)
C5—C6—H6	107.4	O1—C22—O3	103.40 (19)
C12—C7—C8	118.1 (2)	C24—C23—C28	121.7 (2)
C12—C7—C6	122.0 (2)	C24—C23—O3	115.4 (2)
C8—C7—C6	119.9 (2)	C28—C23—O3	122.8 (2)
C7—C8—C9	120.7 (3)	C23—C24—C25	119.0 (3)
C7—C8—H8	119.6	C23—C24—H24	120.5
C9—C8—H8	119.6	C25—C24—H24	120.5
C10—C9—C8	120.0 (3)	C26—C25—C24	120.2 (3)
C10—C9—H9	120.0	C26—C25—H25	119.9
C8—C9—H9	120.0	C24—C25—H25	119.9
C9—C10—C11	119.6 (3)	C27—C26—C25	120.1 (3)
C9—C10—H10	120.2	C27—C26—H26	120.0
C11—C10—H10	120.2	C25—C26—H26	120.0
C10—C11—C12	120.5 (3)	C26—C27—C28	120.3 (3)
C10—C11—H11	119.7	C26—C27—H27	119.8
C12—C11—H11	119.7	C28—C27—H27	119.8
C11—C12—C7	121.1 (3)	C23—C28—C27	118.7 (3)
C11—C12—H12	119.5	C23—C28—H28	120.7
C7—C12—H12	119.5	C27—C28—H28	120.7
C14—C13—C18	117.4 (2)	N1—C29—H29A	109.5
C14—C13—C2	121.7 (2)	N1—C29—H29B	109.5
C18—C13—C2	121.0 (2)	H29A—C29—H29B	109.5
C15—C14—C13	121.3 (3)	N1—C29—H29C	109.5
C15—C14—H14	119.3	H29A—C29—H29C	109.5
C13—C14—H14	119.3	H29B—C29—H29C	109.5
C16—C15—C14	120.6 (3)	C29—N1—C2	110.3 (2)
C16—C15—H15	119.7	C29—N1—C6	111.9 (2)
C14—C15—H15	119.7	C2—N1—C6	113.42 (18)
C17—C16—C15	119.5 (3)	C4—N2—O1	108.79 (18)
C17—C16—H16	120.3	C22—O1—N2	111.42 (17)
C15—C16—H16	120.3	C22—O3—C23	120.09 (18)
N1—C2—C3—C4	−50.5 (3)	C14—C13—C18—C17	1.2 (4)
C13—C2—C3—C4	−175.9 (2)	C2—C13—C18—C17	−178.9 (3)
C2—C3—C4—N2	−125.4 (3)	C16—C17—C18—C13	−1.2 (5)
C2—C3—C4—C5	53.8 (3)	C4—C5—C19—C21	61.7 (3)
N2—C4—C5—C6	123.4 (2)	C6—C5—C19—C21	−65.9 (3)
C3—C4—C5—C6	−55.9 (3)	C4—C5—C19—C20	−67.4 (3)
N2—C4—C5—C19	−7.7 (3)	C6—C5—C19—C20	165.0 (2)
C3—C4—C5—C19	173.0 (2)	C28—C23—C24—C25	0.3 (4)
C4—C5—C6—N1	56.0 (3)	O3—C23—C24—C25	−174.8 (2)
C19—C5—C6—N1	−171.7 (2)	C23—C24—C25—C26	−0.2 (5)
C4—C5—C6—C7	−179.08 (19)	C24—C25—C26—C27	−0.2 (5)
C19—C5—C6—C7	−46.8 (3)	C25—C26—C27—C28	0.6 (5)
N1—C6—C7—C12	65.1 (3)	C24—C23—C28—C27	0.1 (4)
C5—C6—C7—C12	−60.4 (3)	O3—C23—C28—C27	174.9 (2)
N1—C6—C7—C8	−115.4 (2)	C26—C27—C28—C23	−0.6 (4)
C5—C6—C7—C8	119.1 (2)	C13—C2—N1—C29	−56.4 (3)
C12—C7—C8—C9	0.1 (4)	C3—C2—N1—C29	179.4 (2)
C6—C7—C8—C9	−179.4 (2)	C13—C2—N1—C6	177.2 (2)
C7—C8—C9—C10	0.5 (4)	C3—C2—N1—C6	53.0 (3)
C8—C9—C10—C11	−0.6 (4)	C7—C6—N1—C29	52.5 (3)
C9—C10—C11—C12	0.0 (4)	C5—C6—N1—C29	177.9 (3)
C10—C11—C12—C7	0.7 (4)	C7—C6—N1—C2	178.0 (2)
C8—C7—C12—C11	−0.8 (4)	C5—C6—N1—C2	−56.6 (3)
C6—C7—C12—C11	178.7 (2)	C3—C4—N2—O1	−0.8 (3)
N1—C2—C13—C14	−57.7 (3)	C5—C4—N2—O1	−179.95 (19)
C3—C2—C13—C14	68.0 (3)	O2—C22—O1—N2	−3.3 (4)
N1—C2—C13—C18	122.3 (3)	O3—C22—O1—N2	178.33 (17)
C3—C2—C13—C18	−111.9 (3)	C4—N2—O1—C22	179.5 (2)
C18—C13—C14—C15	−0.6 (4)	O2—C22—O3—C23	−0.9 (4)
C2—C13—C14—C15	179.5 (3)	O1—C22—O3—C23	177.43 (19)
C13—C14—C15—C16	0.0 (5)	C24—C23—O3—C22	−133.2 (2)
C14—C15—C16—C17	0.0 (5)	C28—C23—O3—C22	51.7 (3)
C15—C16—C17—C18	0.6 (5)