1-Benzyl-2-[(2RS,3SR,6SR)-3-methyl-4-oxo-2,6-diphenyl­piperidin-1-ylcarbon­yl]-2-phenyl­ethenyl phenyl­acetate

Thanikasalam, K.; Jeyaraman, R.; Panchanatheswaran, K.; Low, J.N.; Glidewell, C.

doi:10.1107/S1600536806008804

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 62| Part 4| April 2006| Pages o1443-o1445

https://doi.org/10.1107/S1600536806008804

1-Benzyl-2-[(2RS,3SR,6SR)-3-methyl-4-oxo-2,6-diphenylpiperidin-1-ylcarbonyl]-2-phenylethenyl phenylacetate

Kanagasabapathy Thanikasalam,^a Ramasubbu Jeyaraman,^a Krishnaswamy Panchanatheswaran,^a John N. Low ^b and Christopher Glidewell ^c ^*

^aSchool of Chemistry, Bharathidasan University, Tiruchirappalli, Tamil Nadu 620 024, India, ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^cSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 8 March 2006; accepted 8 March 2006; online 17 March 2006)

Molecules of the title compound, C₄₂H₃₇NO₄, are weakly linked into chains by a C—H⋯O hydrogen bond and pairs of such chains are linked by a single aromatic π–π stacking interaction.

Comment

The reactions of acyl chlorides with piperidines in a 1:1 molar ratio in the presence of a suitable base yields the N-acyl derivatives, but the yields are sometimes low. This observation prompted us to carry out the reaction of 3-methyl-2,6-diphenylpiperidin-4-one with an excess of phenylacetyl chloride. The ¹³C NMR spectrum of the product contained three absorptions at 168, 170 and 210 p.p.m. indicative of the presence of three different carbonyl environments. The present investigation was therefore undertaken to establish the constitution, configuration and conformation of the product, the title compound, (I) (Fig. 1).

The piperidone ring adopts a boat conformation with a pseudo-mirror plane containing atoms C33 and C36; the ring-puckering parameters (Cremer & Pople, 1975 ) for the atom sequence N31–C32–C33–C34–C35–C36 are θ = 94.1 (2)° and φ = 122.0 (2)°, very close to the ideal values for a boat conformation of θ = 90° and φ = (60n)°. The substituents at C32 and C33 occupy equatorial sites and that at C36 occupies an axial site. In the selected reference molecule, the configuration at C22 is R and those at C33 and C36 are both S. The centrosymmetric space group accommodates equal numbers of the RSS and SRR enantiomers.

The presence of a vinylic ester is shown clearly by the geometry involving atoms C1 and C2 (Table 1). There are two C—H⋯O hydrogen bonds within the molecule, both involving atom O1 as the acceptor (Table 2), and these may have some influence on the overall molecular conformation. A third hydrogen bond (Table 2) links the molecules into chains: atom C47 at (x, y, z) acts as donor, via H47A, to atom O4 at (−1 + x, y, z), so generating by translation a C(12) (Bernstein et al., 1995 ) chain running parallel to the [100] direction (Fig. 2). Two such chains, related to one another by inversion, pass through each unit cell and these chains are linked by a π–π stacking interaction. The C61–C66 rings in the molecules at (x, y, z) and (1 − x, 1 − y, −z) are strictly parallel, with an interplanar spacing of 3.523 (2) Å; the ring-centroid separation is 3.868 (2) Å, corresponding to a ring offset of 1.597 (2) Å. Propagation of this interaction by translation and inversion then links a pair of [100] chains into a molecular ladder (Fig. 2).

Figure 1
The RSS enantiomer of (I)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
A stereoscopic view of part of the crystal structure of (I)

, showing the formation of a π-stacked pair of C(12) chains along [100]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.

Experimental

The title compound was prepared by heating under reflux a benzene solution of 3-methyl-2,6-diphenylpiperidin-4-one with a fourfold molar excess of phenylacetyl chloride in the presence of triethylamine. The resulting solid product was crystallized from aqueous ethanol, yielding crystals suitable for single-crystal X-ray diffraction (yield 48%, m.p. 419–421 K).

Crystal data

C₄₂H₃₇NO₄
M_r = 619.73
Triclinic, $[P \overline 1]$
a = 9.3027 (3) Å
b = 12.1333 (5) Å
c = 14.5927 (6) Å
α = 88.7510 (17)°
β = 78.574 (3)°
γ = 85.653 (2)°
V = 1609.79 (11) Å³
Z = 2
D_x = 1.279 Mg m⁻³
Mo Kα radiation
Cell parameters from 7258 reflections
θ = 2.9–27.5°
μ = 0.08 mm⁻¹
T = 120 (2) K
Plate, colourless
0.13 × 0.07 × 0.03 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003 )T_min = 0.985, T_max = 0.997
34829 measured reflections
7423 independent reflections
4485 reflections with I > 2σ(I)
R_int = 0.091
θ_max = 27.7°
h = −12 → 10
k = −15 → 15
l = −19 → 18

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.153
S = 1.01
7423 reflections
425 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0577P)² + 0.6078P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

C1—C2	1.332 (3)
C1—O1	1.415 (2)
C1—C17	1.494 (3)
C2—C3	1.519 (3)
C2—C21	1.485 (3)

C2—C1—O1	114.70 (18)
C2—C1—C17	130.9 (2)
O1—C1—C17	114.38 (17)
C1—C2—C3	116.53 (19)
C1—C2—C21	127.73 (19)
C3—C2—C21	115.55 (17)

O1—C1—C2—C3	−7.7 (3)
O1—C1—C2—C21	177.47 (18)
C17—C1—C2—C21	−1.3 (4)
C17—C1—C2—C3	173.5 (2)
C36—N31—C32—C51	−115.6 (2)
N31—C32—C33—C37	165.83 (19)
C34—C35—C36—C61	−77.2 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯O1	0.95	2.42	3.075 (3)	126
C47—H47A⋯O4ⁱ	0.99	2.59	3.571 (3)	172
C66—H66⋯O1	0.95	2.53	3.469 (3)	172
Symmetry code: (i) x-1, y, z.

All H atoms were located in difference maps and then treated as riding atoms, with C—H = 0.95 (aromatic), 0.98 (CH₃), 0.99 (CH₂) or 1.00 Å (aliphatic CH), and with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C).

Data collection: COLLECT (Hooft, 1999 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003 ) and SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536806008804/lh2020sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806008804/lh2020Isup2.hkl

Computing details top

Data collection: COLLECT (Hooft, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

1-Benzyl-2-[(2RS,3SR,6SR)-3-methyl-4-oxo-2,6-diphenylpiperidin-1-ylcarbonyl]- 2-phenylethenyl phenylacetate top

Crystal data top

C₄₂H₃₇NO₄	Z = 2
M_r = 619.73	F(000) = 656
Triclinic, P1	D_x = 1.279 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3027 (3) Å	Cell parameters from 7258 reflections
b = 12.1333 (5) Å	θ = 2.9–27.5°
c = 14.5927 (6) Å	µ = 0.08 mm⁻¹
α = 88.7510 (17)°	T = 120 K
β = 78.574 (3)°	Plate, colourless
γ = 85.653 (2)°	0.13 × 0.07 × 0.03 mm
V = 1609.79 (11) Å³

Data collection top

Bruker–Nonius KappaCCD diffractometer	7423 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	4485 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.091
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.7°, θ_min = 3.0°
φ and ω scans	h = −12→10
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −15→15
T_min = 0.985, T_max = 0.997	l = −19→18
34829 measured reflections

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0577P)² + 0.6078P] where P = (F_o² + 2F_c²)/3
7423 reflections	(Δ/σ)_max < 0.001
425 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.2356 (2)	0.43745 (17)	0.33712 (14)	0.0236 (5)
C17	0.1334 (2)	0.53735 (18)	0.36474 (14)	0.0255 (5)
C11	0.0816 (2)	0.60214 (18)	0.28508 (15)	0.0260 (5)
C12	0.0602 (3)	0.5520 (2)	0.20435 (16)	0.0335 (6)
C13	0.0064 (3)	0.6143 (2)	0.13589 (17)	0.0358 (6)
C14	−0.0288 (3)	0.7261 (2)	0.14681 (17)	0.0353 (6)
C15	−0.0094 (3)	0.7758 (2)	0.22692 (18)	0.0395 (6)
C16	0.0463 (3)	0.7141 (2)	0.29531 (17)	0.0340 (6)
O1	0.16875 (15)	0.34768 (12)	0.30674 (10)	0.0256 (3)
C4	0.0938 (2)	0.28122 (18)	0.37423 (16)	0.0261 (5)
O2	0.06080 (17)	0.30686 (13)	0.45492 (11)	0.0314 (4)
C47	0.0658 (3)	0.17689 (19)	0.32941 (16)	0.0319 (5)
C41	−0.0574 (2)	0.11470 (18)	0.38370 (15)	0.0267 (5)
C42	−0.1918 (3)	0.1688 (2)	0.42342 (17)	0.0351 (6)
C43	−0.3067 (3)	0.1106 (2)	0.47079 (18)	0.0392 (6)
C44	−0.2887 (3)	−0.0033 (2)	0.47951 (17)	0.0364 (6)
C45	−0.1564 (3)	−0.0582 (2)	0.44091 (17)	0.0367 (6)
C46	−0.0423 (3)	0.00086 (19)	0.39343 (17)	0.0337 (6)
C2	0.3793 (2)	0.41933 (17)	0.33484 (14)	0.0224 (5)
C21	0.4813 (2)	0.49775 (18)	0.35853 (14)	0.0232 (5)
C22	0.5994 (2)	0.4542 (2)	0.39704 (15)	0.0292 (5)
C23	0.7003 (3)	0.5218 (2)	0.41917 (16)	0.0352 (6)
C24	0.6862 (3)	0.6342 (2)	0.40385 (16)	0.0375 (6)
C25	0.5708 (3)	0.6784 (2)	0.36463 (16)	0.0346 (6)
C26	0.4689 (2)	0.61127 (18)	0.34235 (15)	0.0277 (5)
C3	0.4454 (2)	0.30227 (18)	0.31279 (15)	0.0240 (5)
O3	0.42009 (17)	0.22856 (12)	0.37155 (10)	0.0298 (4)
N31	0.53379 (19)	0.28357 (14)	0.22807 (12)	0.0237 (4)
C32	0.6095 (2)	0.17035 (17)	0.21216 (15)	0.0257 (5)
C51	0.5041 (2)	0.08504 (18)	0.19800 (16)	0.0287 (5)
C52	0.4433 (3)	0.0850 (2)	0.11868 (18)	0.0366 (6)
C53	0.3486 (3)	0.0059 (2)	0.1075 (2)	0.0452 (7)
C54	0.3135 (3)	−0.0740 (2)	0.1749 (2)	0.0490 (7)
C55	0.3730 (3)	−0.0747 (2)	0.2543 (2)	0.0461 (7)
C56	0.4681 (3)	0.0039 (2)	0.26610 (18)	0.0370 (6)
C33	0.7436 (2)	0.17069 (19)	0.13054 (16)	0.0301 (5)
C37	0.8405 (3)	0.0642 (2)	0.13068 (19)	0.0457 (7)
C34	0.8295 (3)	0.2720 (2)	0.12965 (16)	0.0338 (6)
O4	0.96224 (18)	0.26760 (16)	0.11562 (14)	0.0520 (5)
C35	0.7406 (2)	0.3808 (2)	0.14707 (16)	0.0316 (5)
C36	0.5752 (2)	0.37259 (18)	0.15922 (15)	0.0253 (5)
C61	0.5154 (2)	0.35869 (17)	0.07048 (14)	0.0243 (5)
C62	0.6029 (2)	0.35915 (19)	−0.01801 (15)	0.0295 (5)
C63	0.5429 (3)	0.3476 (2)	−0.09700 (16)	0.0342 (6)
C64	0.3938 (3)	0.3367 (2)	−0.08813 (16)	0.0340 (6)
C65	0.3051 (3)	0.3382 (2)	0.00000 (16)	0.0326 (5)
C66	0.3652 (2)	0.34915 (19)	0.07836 (16)	0.0296 (5)
H17A	0.1828	0.5878	0.3988	0.031*
H17B	0.0457	0.5139	0.4089	0.031*
H12	0.0826	0.4747	0.1961	0.040*
H13	−0.0063	0.5792	0.0808	0.043*
H14	−0.0658	0.7683	0.0998	0.042*
H15	−0.0342	0.8528	0.2356	0.047*
H16	0.0601	0.7498	0.3499	0.041*
H47A	0.0437	0.1957	0.2671	0.038*
H47B	0.1571	0.1274	0.3197	0.038*
H42	−0.2049	0.2469	0.4180	0.042*
H43	−0.3979	0.1488	0.4973	0.047*
H44	−0.3674	−0.0433	0.5120	0.044*
H45	−0.1433	−0.1362	0.4468	0.044*
H46	0.0486	−0.0378	0.3669	0.040*
H22	0.6106	0.3769	0.4082	0.035*
H23	0.7802	0.4905	0.4452	0.042*
H24	0.7549	0.6807	0.4200	0.045*
H25	0.5613	0.7557	0.3528	0.042*
H26	0.3898	0.6430	0.3158	0.033*
H32	0.6475	0.1485	0.2699	0.031*
H52	0.4668	0.1397	0.0716	0.044*
H53	0.3075	0.0067	0.0528	0.054*
H54	0.2486	−0.1282	0.1669	0.059*
H55	0.3487	−0.1295	0.3011	0.055*
H56	0.5090	0.0025	0.3209	0.044*
H33	0.7049	0.1723	0.0713	0.036*
H37A	0.9232	0.0644	0.0773	0.069*
H37B	0.7828	0.0010	0.1259	0.069*
H37C	0.8781	0.0585	0.1889	0.069*
H35A	0.7730	0.4312	0.0940	0.038*
H35B	0.7613	0.4140	0.2040	0.038*
H36	0.5272	0.4432	0.1885	0.030*
H62	0.7052	0.3675	−0.0249	0.035*
H63	0.6045	0.3471	−0.1573	0.041*
H64	0.3527	0.3282	−0.1420	0.041*
H65	0.2024	0.3317	0.0067	0.039*
H66	0.3032	0.3502	0.1385	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0292 (12)	0.0210 (11)	0.0216 (11)	−0.0050 (9)	−0.0061 (9)	−0.0001 (9)
C17	0.0254 (12)	0.0272 (12)	0.0237 (11)	−0.0018 (9)	−0.0046 (9)	−0.0010 (9)
C11	0.0192 (11)	0.0290 (13)	0.0299 (12)	−0.0029 (9)	−0.0048 (9)	0.0031 (10)
C12	0.0340 (13)	0.0337 (14)	0.0328 (13)	0.0056 (10)	−0.0093 (10)	−0.0022 (11)
C13	0.0361 (14)	0.0428 (15)	0.0304 (13)	0.0023 (11)	−0.0132 (11)	−0.0018 (11)
C14	0.0327 (13)	0.0391 (15)	0.0364 (14)	−0.0060 (11)	−0.0127 (11)	0.0114 (11)
C15	0.0467 (15)	0.0276 (14)	0.0475 (16)	−0.0042 (11)	−0.0177 (12)	0.0083 (12)
C16	0.0392 (14)	0.0305 (14)	0.0352 (13)	−0.0064 (11)	−0.0125 (11)	−0.0007 (11)
O1	0.0261 (8)	0.0255 (8)	0.0259 (8)	−0.0076 (6)	−0.0048 (6)	0.0006 (6)
C4	0.0216 (11)	0.0270 (12)	0.0297 (13)	−0.0027 (9)	−0.0049 (9)	0.0030 (10)
O2	0.0341 (9)	0.0326 (9)	0.0269 (9)	−0.0061 (7)	−0.0034 (7)	0.0005 (7)
C47	0.0313 (13)	0.0311 (13)	0.0335 (13)	−0.0067 (10)	−0.0049 (10)	−0.0009 (10)
C41	0.0285 (12)	0.0285 (13)	0.0252 (12)	−0.0057 (9)	−0.0093 (9)	0.0019 (10)
C42	0.0309 (13)	0.0271 (13)	0.0473 (15)	−0.0012 (10)	−0.0087 (11)	0.0053 (11)
C43	0.0276 (13)	0.0425 (16)	0.0462 (15)	−0.0024 (11)	−0.0038 (11)	0.0011 (12)
C44	0.0339 (14)	0.0398 (15)	0.0374 (14)	−0.0151 (11)	−0.0073 (11)	0.0045 (11)
C45	0.0413 (14)	0.0257 (13)	0.0446 (15)	−0.0090 (11)	−0.0097 (12)	0.0020 (11)
C46	0.0316 (13)	0.0287 (13)	0.0405 (14)	−0.0020 (10)	−0.0053 (10)	−0.0058 (11)
C2	0.0235 (11)	0.0232 (12)	0.0203 (11)	−0.0021 (8)	−0.0043 (8)	0.0020 (9)
C21	0.0229 (11)	0.0251 (12)	0.0213 (11)	−0.0033 (9)	−0.0034 (8)	−0.0005 (9)
C22	0.0248 (12)	0.0332 (13)	0.0293 (12)	−0.0007 (9)	−0.0054 (9)	−0.0004 (10)
C23	0.0268 (12)	0.0494 (17)	0.0318 (13)	−0.0053 (11)	−0.0105 (10)	−0.0003 (12)
C24	0.0332 (14)	0.0483 (17)	0.0326 (13)	−0.0167 (11)	−0.0048 (11)	−0.0055 (12)
C25	0.0417 (14)	0.0307 (14)	0.0319 (13)	−0.0118 (11)	−0.0045 (11)	−0.0012 (11)
C26	0.0307 (12)	0.0274 (13)	0.0264 (12)	−0.0052 (9)	−0.0078 (9)	0.0009 (10)
C3	0.0237 (11)	0.0239 (12)	0.0253 (11)	−0.0021 (9)	−0.0070 (9)	−0.0008 (9)
O3	0.0367 (9)	0.0245 (9)	0.0268 (8)	−0.0008 (7)	−0.0032 (7)	0.0038 (7)
N31	0.0265 (10)	0.0216 (10)	0.0225 (9)	−0.0010 (7)	−0.0039 (7)	−0.0001 (7)
C32	0.0268 (12)	0.0226 (12)	0.0266 (12)	0.0032 (9)	−0.0046 (9)	0.0000 (9)
C51	0.0298 (12)	0.0223 (12)	0.0320 (12)	0.0016 (9)	−0.0023 (10)	−0.0040 (10)
C52	0.0406 (14)	0.0281 (13)	0.0430 (15)	−0.0047 (11)	−0.0123 (11)	−0.0015 (11)
C53	0.0504 (16)	0.0360 (16)	0.0533 (17)	−0.0042 (12)	−0.0191 (13)	−0.0095 (13)
C54	0.0417 (16)	0.0321 (15)	0.073 (2)	−0.0103 (12)	−0.0070 (14)	−0.0118 (14)
C55	0.0496 (16)	0.0298 (15)	0.0543 (18)	−0.0061 (12)	0.0018 (13)	0.0003 (13)
C56	0.0411 (14)	0.0278 (13)	0.0403 (14)	−0.0004 (11)	−0.0043 (11)	−0.0018 (11)
C33	0.0266 (12)	0.0317 (13)	0.0310 (12)	0.0045 (10)	−0.0060 (10)	0.0003 (10)
C37	0.0413 (15)	0.0459 (17)	0.0470 (16)	0.0107 (12)	−0.0064 (12)	−0.0050 (13)
C34	0.0268 (13)	0.0456 (15)	0.0289 (13)	−0.0013 (10)	−0.0060 (10)	0.0050 (11)
O4	0.0228 (10)	0.0608 (13)	0.0701 (13)	−0.0009 (8)	−0.0059 (8)	0.0136 (10)
C35	0.0294 (13)	0.0370 (14)	0.0294 (12)	−0.0078 (10)	−0.0066 (10)	0.0026 (10)
C36	0.0256 (11)	0.0245 (12)	0.0259 (11)	−0.0043 (9)	−0.0050 (9)	0.0028 (9)
C61	0.0277 (12)	0.0216 (12)	0.0234 (11)	−0.0007 (9)	−0.0052 (9)	0.0026 (9)
C62	0.0262 (12)	0.0320 (13)	0.0296 (12)	−0.0011 (10)	−0.0044 (10)	0.0025 (10)
C63	0.0375 (14)	0.0386 (15)	0.0243 (12)	0.0001 (11)	−0.0020 (10)	0.0026 (10)
C64	0.0386 (14)	0.0370 (14)	0.0282 (13)	−0.0008 (11)	−0.0118 (10)	0.0002 (11)
C65	0.0304 (13)	0.0369 (14)	0.0310 (13)	−0.0007 (10)	−0.0084 (10)	0.0032 (11)
C66	0.0276 (12)	0.0343 (13)	0.0261 (12)	0.0014 (10)	−0.0051 (9)	0.0017 (10)

Geometric parameters (Å, º) top

C1—C2	1.332 (3)	C25—H25	0.95
C1—O1	1.415 (2)	C26—H26	0.95
C1—C17	1.494 (3)	C3—O3	1.228 (2)
C17—C11	1.525 (3)	C3—N31	1.355 (3)
C17—H17A	0.99	N31—C36	1.479 (3)
C17—H17B	0.99	N31—C32	1.497 (3)
C11—C16	1.377 (3)	C32—C51	1.523 (3)
C11—C12	1.393 (3)	C32—C33	1.545 (3)
C12—C13	1.389 (3)	C32—H32	1.00
C12—H12	0.95	C51—C52	1.385 (3)
C13—C14	1.377 (3)	C51—C56	1.395 (3)
C13—H13	0.95	C52—C53	1.384 (3)
C14—C15	1.376 (3)	C52—H52	0.95
C14—H14	0.95	C53—C54	1.376 (4)
C15—C16	1.393 (3)	C53—H53	0.95
C15—H15	0.95	C54—C55	1.379 (4)
C16—H16	0.95	C54—H54	0.95
O1—C4	1.373 (3)	C55—C56	1.384 (4)
C4—O2	1.198 (3)	C55—H55	0.95
C4—C47	1.500 (3)	C56—H56	0.95
C47—C41	1.502 (3)	C33—C34	1.514 (3)
C47—H47A	0.99	C33—C37	1.518 (3)
C47—H47B	0.99	C33—H33	1.00
C41—C46	1.385 (3)	C37—H37A	0.98
C41—C42	1.391 (3)	C37—H37B	0.98
C42—C43	1.386 (3)	C37—H37C	0.98
C42—H42	0.95	C34—O4	1.209 (3)
C43—C44	1.385 (3)	C34—C35	1.502 (3)
C43—H43	0.95	C35—C36	1.524 (3)
C44—C45	1.376 (3)	C35—H35A	0.99
C44—H44	0.95	C35—H35B	0.99
C45—C46	1.386 (3)	C36—C61	1.525 (3)
C45—H45	0.95	C36—H36	1.00
C46—H46	0.95	C61—C62	1.384 (3)
C2—C3	1.519 (3)	C61—C66	1.392 (3)
C2—C21	1.485 (3)	C62—C63	1.390 (3)
C21—C26	1.392 (3)	C62—H62	0.95
C21—C22	1.395 (3)	C63—C64	1.384 (3)
C22—C23	1.380 (3)	C63—H63	0.95
C22—H22	0.95	C64—C65	1.383 (3)
C23—C24	1.378 (3)	C64—H64	0.95
C23—H23	0.95	C65—C66	1.382 (3)
C24—C25	1.382 (3)	C65—H65	0.95
C24—H24	0.95	C66—H66	0.95
C25—C26	1.386 (3)

C2—C1—O1	114.70 (18)	O3—C3—N31	122.12 (19)
C2—C1—C17	130.9 (2)	O3—C3—C2	119.98 (19)
O1—C1—C17	114.38 (17)	N31—C3—C2	117.89 (18)
C1—C17—C11	115.99 (18)	C3—N31—C36	123.03 (18)
C1—C17—H17A	108.3	C3—N31—C32	116.59 (17)
C11—C17—H17A	108.3	C36—N31—C32	119.65 (17)
C1—C17—H17B	108.3	N31—C32—C51	112.01 (17)
C11—C17—H17B	108.3	N31—C32—C33	111.09 (17)
H17A—C17—H17B	107.4	C51—C32—C33	111.77 (18)
C16—C11—C12	118.3 (2)	N31—C32—H32	107.2
C16—C11—C17	118.8 (2)	C51—C32—H32	107.2
C12—C11—C17	122.8 (2)	C33—C32—H32	107.2
C13—C12—C11	120.4 (2)	C52—C51—C56	118.7 (2)
C13—C12—H12	119.8	C52—C51—C32	121.8 (2)
C11—C12—H12	119.8	C56—C51—C32	119.5 (2)
C14—C13—C12	120.9 (2)	C53—C52—C51	120.5 (2)
C14—C13—H13	119.5	C53—C52—H52	119.7
C12—C13—H13	119.5	C51—C52—H52	119.7
C15—C14—C13	118.9 (2)	C54—C53—C52	120.5 (3)
C15—C14—H14	120.5	C54—C53—H53	119.7
C13—C14—H14	120.5	C52—C53—H53	119.7
C14—C15—C16	120.5 (2)	C53—C54—C55	119.5 (3)
C14—C15—H15	119.8	C53—C54—H54	120.2
C16—C15—H15	119.8	C55—C54—H54	120.2
C11—C16—C15	121.1 (2)	C54—C55—C56	120.4 (3)
C11—C16—H16	119.5	C54—C55—H55	119.8
C15—C16—H16	119.5	C56—C55—H55	119.8
C4—O1—C1	117.44 (16)	C55—C56—C51	120.3 (2)
O2—C4—O1	122.7 (2)	C55—C56—H56	119.8
O2—C4—C47	128.5 (2)	C51—C56—H56	119.8
O1—C4—C47	108.83 (18)	C34—C33—C37	112.1 (2)
C4—C47—C41	115.13 (19)	C34—C33—C32	112.89 (19)
C4—C47—H47A	108.5	C37—C33—C32	110.36 (19)
C41—C47—H47A	108.5	C34—C33—H33	107.1
C4—C47—H47B	108.5	C37—C33—H33	107.1
C41—C47—H47B	108.5	C32—C33—H33	107.1
H47A—C47—H47B	107.5	C33—C37—H37A	109.5
C46—C41—C42	117.7 (2)	C33—C37—H37B	109.5
C46—C41—C47	120.9 (2)	H37A—C37—H37B	109.5
C42—C41—C47	121.3 (2)	C33—C37—H37C	109.5
C43—C42—C41	121.1 (2)	H37A—C37—H37C	109.5
C43—C42—H42	119.5	H37B—C37—H37C	109.5
C41—C42—H42	119.5	O4—C34—C35	120.7 (2)
C44—C43—C42	120.0 (2)	O4—C34—C33	122.9 (2)
C44—C43—H43	120.0	C35—C34—C33	116.39 (19)
C42—C43—H43	120.0	C34—C35—C36	114.1 (2)
C45—C44—C43	119.7 (2)	C34—C35—H35A	108.7
C45—C44—H44	120.1	C36—C35—H35A	108.7
C43—C44—H44	120.1	C34—C35—H35B	108.7
C44—C45—C46	119.7 (2)	C36—C35—H35B	108.7
C44—C45—H45	120.1	H35A—C35—H35B	107.6
C46—C45—H45	120.1	N31—C36—C35	107.59 (17)
C41—C46—C45	121.7 (2)	N31—C36—C61	111.84 (17)
C41—C46—H46	119.2	C35—C36—C61	116.73 (18)
C45—C46—H46	119.2	N31—C36—H36	106.7
C1—C2—C3	116.53 (19)	C35—C36—H36	106.7
C1—C2—C21	127.73 (19)	C61—C36—H36	106.7
C3—C2—C21	115.55 (17)	C62—C61—C66	118.4 (2)
C26—C21—C22	118.0 (2)	C62—C61—C36	122.89 (19)
C26—C21—C2	124.25 (18)	C66—C61—C36	118.71 (19)
C22—C21—C2	117.74 (19)	C61—C62—C63	120.8 (2)
C23—C22—C21	121.0 (2)	C61—C62—H62	119.6
C23—C22—H22	119.5	C63—C62—H62	119.6
C21—C22—H22	119.5	C64—C63—C62	120.2 (2)
C24—C23—C22	120.6 (2)	C64—C63—H63	119.9
C24—C23—H23	119.7	C62—C63—H63	119.9
C22—C23—H23	119.7	C65—C64—C63	119.3 (2)
C23—C24—C25	119.1 (2)	C65—C64—H64	120.3
C23—C24—H24	120.4	C63—C64—H64	120.3
C25—C24—H24	120.4	C66—C65—C64	120.3 (2)
C24—C25—C26	120.7 (2)	C66—C65—H65	119.9
C24—C25—H25	119.7	C64—C65—H65	119.9
C26—C25—H25	119.7	C65—C66—C61	121.0 (2)
C25—C26—C21	120.6 (2)	C65—C66—H66	119.5
C25—C26—H26	119.7	C61—C66—H66	119.5
C21—C26—H26	119.7

C2—C1—C17—C11	107.1 (3)	O3—C3—N31—C36	−175.01 (18)
O1—C1—C17—C11	−71.6 (2)	C2—C3—N31—C36	3.7 (3)
C1—C17—C11—C16	−151.1 (2)	O3—C3—N31—C32	−4.9 (3)
C1—C17—C11—C12	32.8 (3)	C2—C3—N31—C32	173.88 (17)
C16—C11—C12—C13	0.8 (3)	C3—N31—C32—C51	73.9 (2)
C17—C11—C12—C13	177.0 (2)	C36—N31—C32—C51	−115.6 (2)
C11—C12—C13—C14	−0.9 (4)	C3—N31—C32—C33	−160.30 (18)
C12—C13—C14—C15	0.2 (4)	C36—N31—C32—C33	10.2 (3)
C13—C14—C15—C16	0.7 (4)	N31—C32—C51—C52	69.2 (3)
C12—C11—C16—C15	0.0 (3)	C33—C32—C51—C52	−56.2 (3)
C17—C11—C16—C15	−176.3 (2)	N31—C32—C51—C56	−111.3 (2)
C14—C15—C16—C11	−0.7 (4)	C33—C32—C51—C56	123.2 (2)
C2—C1—O1—C4	99.5 (2)	C56—C51—C52—C53	0.1 (4)
C17—C1—O1—C4	−81.5 (2)	C32—C51—C52—C53	179.5 (2)
C1—O1—C4—O2	13.8 (3)	C51—C52—C53—C54	0.0 (4)
C1—O1—C4—C47	−165.53 (17)	C52—C53—C54—C55	0.2 (4)
O2—C4—C47—C41	21.6 (3)	C53—C54—C55—C56	−0.3 (4)
O1—C4—C47—C41	−159.19 (18)	C54—C55—C56—C51	0.3 (4)
C4—C47—C41—C46	−136.4 (2)	C52—C51—C56—C55	−0.2 (3)
C4—C47—C41—C42	45.5 (3)	C32—C51—C56—C55	−179.7 (2)
C46—C41—C42—C43	−0.3 (3)	N31—C32—C33—C34	39.5 (2)
C47—C41—C42—C43	177.8 (2)	C51—C32—C33—C34	165.45 (18)
C41—C42—C43—C44	0.2 (4)	N31—C32—C33—C37	165.83 (19)
C42—C43—C44—C45	0.0 (4)	C51—C32—C33—C37	−68.3 (2)
C43—C44—C45—C46	−0.2 (4)	C37—C33—C34—O4	11.0 (3)
C42—C41—C46—C45	0.1 (3)	C32—C33—C34—O4	136.4 (2)
C47—C41—C46—C45	−178.1 (2)	C37—C33—C34—C35	−169.2 (2)
C44—C45—C46—C41	0.1 (4)	C32—C33—C34—C35	−43.8 (3)
O1—C1—C2—C3	−7.7 (3)	O4—C34—C35—C36	177.4 (2)
O1—C1—C2—C21	177.47 (18)	C33—C34—C35—C36	−2.4 (3)
C17—C1—C2—C21	−1.3 (4)	C3—N31—C36—C35	114.8 (2)
C17—C1—C2—C3	173.5 (2)	C32—N31—C36—C35	−55.0 (2)
C1—C2—C21—C26	−33.8 (3)	C3—N31—C36—C61	−115.7 (2)
C3—C2—C21—C26	151.4 (2)	C32—N31—C36—C61	74.4 (2)
C1—C2—C21—C22	148.1 (2)	C34—C35—C36—N31	49.4 (2)
C3—C2—C21—C22	−26.7 (3)	C34—C35—C36—C61	−77.2 (2)
C26—C21—C22—C23	0.5 (3)	N31—C36—C61—C62	−127.9 (2)
C2—C21—C22—C23	178.8 (2)	C35—C36—C61—C62	−3.4 (3)
C21—C22—C23—C24	0.2 (3)	N31—C36—C61—C66	54.5 (3)
C22—C23—C24—C25	−1.0 (4)	C35—C36—C61—C66	179.0 (2)
C23—C24—C25—C26	1.1 (4)	C66—C61—C62—C63	−1.6 (3)
C24—C25—C26—C21	−0.4 (3)	C36—C61—C62—C63	−179.2 (2)
C22—C21—C26—C25	−0.4 (3)	C61—C62—C63—C64	0.8 (4)
C2—C21—C26—C25	−178.5 (2)	C62—C63—C64—C65	0.4 (4)
C1—C2—C3—O3	−72.9 (3)	C63—C64—C65—C66	−0.8 (4)
C21—C2—C3—O3	102.6 (2)	C64—C65—C66—C61	−0.1 (4)
C1—C2—C3—N31	108.3 (2)	C62—C61—C66—C65	1.3 (3)
C21—C2—C3—N31	−76.2 (2)	C36—C61—C66—C65	178.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O1	0.95	2.42	3.075 (3)	126
C47—H47A···O4ⁱ	0.99	2.59	3.571 (3)	172
C66—H66···O1	0.95	2.53	3.469 (3)	172

Symmetry code: (i) x−1, y, z.

Acknowledgements

X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England. The authors thank the staff for all their help and advice.

References

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