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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 62| Part 4| April 2006| Pages o1452-o1454
https://doi.org/10.1107/S1600536806009184

Conformational isomers in (2RS,3SR,6SR)-3-ethyl-2,6-di­phenyl-1-phenyl­acetyl-4-piperidone determined from synchrotron data at 120 K

CROSSMARK_Color_square_no_text.svg
Kanagasabapathy Thanikasalam,a Ramasubbu Jeyaraman,a Krishnaswamy Panchanatheswaran,a John N. Lowb and Christopher Glidewellc*

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 9 March 2006; accepted 10 March 2006; online 17 March 2006)

In the title compound, C27H27NO2, the conformations of the two independent mol­ecules differ in the shape of the piperidone rings, the orientation of the N-acyl substituents and the axial/equatorial disposition of the ethyl and phenyl groups. The mol­ecules are linked into complex chains by four independent C—H⋯O hydrogen bonds.

Comment

In piperidone derivatives containing N-chloro­acetyl or N-ethoxy­carbonyl substituents, the piperidone rings generally adopt distorted boat conformations (Ponnuswamy et al., 2002[Ponnuswamy, S., Venkatraj, M., Jeyaraman, R., Sureshkumar, M., Kumaran, D. & Ponnuswamy, M. N. (2002). Ind. J. Chem. Sect. B, 41, 614-627.]; Nallini et al., 2003[Nallini, A. L., Saraboji, K., Ponnuswamy, M. N., Venkatraj, M. & Jeyaraman, R. (2003). Mol. Cryst. Liq. Cryst. 403, 49-56.]). This study of the title compound, (I)[link] (Figs. 1[link] and 2[link]), was undertaken to investigate the effect of an N-phenyl­acetyl substituent upon the mol­ecular conformation of the piperidone ring.

[Scheme 1]

Compound (I)[link] forms extremely small crystals of rather indifferent quality, and synchrotron radiation was necessary to obtain usable diffraction data. It crystallizes with Z′ = 2 in the space group P21/c (Figs. 1[link] and 2[link]): mol­ecules 1 and 2 contain atoms N11 and N21, respectively. The conformations of the two independent mol­ecules are significantly different. Firstly, the ring-puckering parameters (Cremer & Pople, 1975[Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.]) for the piperidone rings are, for the atom sequences Nn1—Cn2—Cn3—Cn4—Cn5—Cn6, θ = 94.0 (8)° and φ = 254.6 (8)° when n = 1, and θ = 88.3 (7)° and φ = 124.1 (7)° when n = 2, indicating an almost ideal twist-boat conformation in mol­ecule 2, but a conformation midway between boat and twist-boat for mol­ecule 1. Secondly, the orientation of the N-acyl substituent is entirely different in the two mol­ecules, as indicated by the leading torsion angles (Table 1[link]). Finally, in mol­ecule 1, the substituents at C12 and C13 are axial and that at C16 is equatorial; in mol­ecule 2 the substituents at C22 and C23 are equatorial and that at C26 is axial (Figs. 1[link] and 2[link], and Table 1[link]). The two mol­ecules are thus conformational isomers and this in itself precludes the possibility of any additional crystallographic symmetry.

The mol­ecules are linked into rather complex chains by a combination of four C—H⋯O hydrogen bonds (Table 2[link]). Atoms C22 and C28 in the type 2 mol­ecule at (x, y, z) both act as hydrogen-bond donors to atom O24 in the type 2 mol­ecule at (x, [{3\over 2}] − y, [{1\over 2}] + z), so forming a C(4)C(5)[R21(7)] chain of rings (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) along [001]. This chain is formed by type 2 mol­ecule only and the type 1 mol­ecules are pendent from it. Atoms C13 and C222 at (x, y, z) act as hydrogen-bond donors respectively to atoms O24 and O14 at (1 − x, 1 − y, 1 − z), so forming a non-centrosymmetric R22(11) ring (Fig. 3[link]). Anti­parallel pairs of these chains, related to one another by inversion, are weakly linked by a single C—H⋯π(arene) inter­action (Table 2[link]).

[Figure 1]
Figure 1
The RSS enanti­omer of mol­ecule 1 of compound (I)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 20% probability level.
[Figure 2]
Figure 2
The RSS enanti­omer of mol­ecule 2 of compound (I)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 20% probability level.
[Figure 3]
Figure 3
Stereoview of part of the crystal structure of compound (I)[link], showing the formation of a [001] chain of rings containing only type 2 mol­ecules, with type 1 mol­ecules pendent from the chain. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.

Experimental

The title compound was prepared by the condensation of equimolar quanti­ties of phenyl­acetyl chloride and 3-ethyl-2,6-diphenyl­piperidin-4-one in anhydrous benzene, in the presence of triethyl­amine as the base. Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in aqueous ethanol (m.p. 368–371 K).

Crystal data

  • C27H27NO2

  • Mr = 397.50

  • Monoclinic, P 21 /c

  • a = 19.355 (6) Å

  • b = 22.944 (8) Å

  • c = 9.959 (3) Å

  • β = 97.905 (6)°

  • V = 4381 (2) Å3

  • Z = 8

  • Dx = 1.205 Mg m−3

  • Synchrotron radiation

  • λ = 0.6712 Å

  • Cell parameters from 1257 reflections

  • θ = 2.6–18.5°

  • μ = 0.08 mm−1

  • T = 120 (2) K

  • Lath, colourless

  • 0.08 × 0.02 × 0.002 mm
Data collection

  • Bruker SMART APEX2 CCD diffractometer

  • Fine–slice ω scans

  • Absorption correction: none

  • 16316 measured reflections

  • 5346 independent reflections

  • 2533 reflections with I > 2σ(I)

  • Rint = 0.123

  • θmax = 20.7°

  • h = −19 → 20

  • k = −24 → 24

  • l = −10 → 10
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.108

  • wR(F2) = 0.338

  • S = 1.04

  • 5346 reflections

  • 526 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.195P)2] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.002

  • Δρmax = 0.81 e Å−3

  • Δρmin = −0.29 e Å−3

  • Extinction correction: SHELXL97

  • Extinction coefficient: 0.030 (5)

Table 1
Selected torsion angles (°)

C12—C13—C137—C138 67.5 (11)
N11—C12—C111—C112 130.2 (10)
N11—C16—C121—C122 −41.2 (10)
C12—N11—C17—C18 173.3 (7)
N11—C17—C18—C131 −162.0 (7)
C17—C18—C131—C132 98.1 (9)
C22—C23—C237—C238 154.9 (7)
N21—C22—C211—C212 57.0 (10)
N21—C26—C221—C222 −118.6 (9)
C22—N21—C27—C28 −4.2 (9)
N21—C27—C28—C231 158.6 (6)
C27—C28—C231—C232 79.2 (8)

Table 2
Hydrogen-bond geometry (Å, °)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C13—H13⋯O24i 1.00 2.35 3.232 (10) 147
C22—H22⋯O27ii 1.00 2.19 3.190 (10) 175
C28—H28A⋯O27ii 0.99 2.52 3.486 (9) 165
C222—H222⋯O14i 0.95 2.54 3.478 (10) 169
C123—H123⋯Cgiii 0.95 2.89 3.811 (10) 165
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) [x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]; (iii) x, y, z+1. Cg is the centroid of ring (C221–C226)

Diffraction data were collected at the Daresbury SRS, station 9.8, UK (Cernik et al., 1997[Cernik, R. J., Clegg, W., Catlow, C. R. A., Bushnell-Wye, G., Flaherty, J. V., Greaves, G. N., Hamichi, M., Burrows, I., Taylor, D. J. & Teat, S. J. (1997). J. Synchotron Rad. 4, 279-286; corrigendum: J. Synchotron Rad. 7, 40.]; Clegg, 2000[Clegg, W. (2000). J. Chem. Soc. Dalton Trans. pp. 3223-3232.]). The very small crystal size and weak diffraction led to a relatively high Rint and to a low 2θmax for the data used in the refinement. 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 Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for the methyl groups.

Data collection: APEX2 (Bruker, 2003[Bruker (2003). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: APEX2 and SAINT (Bruker, 2001[Bruker (2001). SAINT. Version 6.02. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: OSCAIL (McArdle, 2003[McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.]) and SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536806009184/lh2021sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806009184/lh2021Isup2.hkl


Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: APEX2 and SAINT (Bruker, 2001); data reduction: SAINT; 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).

(2RS,3SR,6SR)-3-ethyl-2,6-diphenyl-1-phenylacetyl-4-piperidone top
Crystal data top
C27H27NO2F(000) = 1696
Mr = 397.50Dx = 1.205 Mg m−3
Monoclinic, P21/cSynchrotron radiation, λ = 0.6712 Å
Hall symbol: -P 2ybcCell parameters from 1257 reflections
a = 19.355 (6) Åθ = 2.6–18.5°
b = 22.944 (8) ŵ = 0.08 mm−1
c = 9.959 (3) ÅT = 120 K
β = 97.905 (6)°Lath, colourless
V = 4381 (2) Å30.08 × 0.02 × 0.002 mm
Z = 8
Data collection top
Bruker SMART APEX2 CCD
diffractometer		2533 reflections with I > 2σ(I)
Radiation source: Daresbury SRS station 9.8Rint = 0.123
Silicon 111 monochromatorθmax = 20.7°, θmin = 2.5°
fine–slice ω scansh = −19→20
16316 measured reflectionsk = −24→24
5346 independent reflectionsl = −10→10
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.108H-atom parameters constrained
wR(F2) = 0.338 w = 1/[σ2(Fo2) + (0.195P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.002
5346 reflectionsΔρmax = 0.81 e Å−3
526 parametersΔρmin = −0.29 e Å−3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.030 (5)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N110.6763 (3)0.3221 (3)0.9826 (6)0.0563 (19)
C120.6095 (4)0.3205 (5)1.0347 (8)0.069 (3)
C1110.5988 (4)0.3713 (5)1.1295 (8)0.075 (3)
C1160.6501 (4)0.3807 (5)1.2418 (9)0.088 (3)
C1150.6409 (6)0.4260 (6)1.3317 (10)0.104 (4)
C1140.5824 (7)0.4597 (6)1.3165 (11)0.110 (4)
C1130.5314 (6)0.4504 (6)1.2081 (12)0.118 (4)
C1120.5390 (5)0.4058 (5)1.1154 (11)0.101 (4)
C130.5503 (4)0.3123 (5)0.9160 (9)0.071 (3)
C1370.5544 (5)0.2550 (5)0.8515 (10)0.079 (3)
C1380.5403 (6)0.2030 (5)0.9362 (11)0.104 (4)
C140.5511 (4)0.3595 (5)0.8117 (9)0.082 (3)
O140.4994 (3)0.3714 (3)0.7273 (6)0.099 (2)
C150.6148 (4)0.3930 (4)0.8189 (8)0.075 (3)
C160.6838 (4)0.3582 (4)0.8596 (8)0.058 (2)
C1210.7431 (4)0.4012 (3)0.8795 (8)0.054 (2)
C1220.7574 (4)0.4338 (4)1.0009 (8)0.059 (2)
C1230.8106 (5)0.4738 (4)1.0139 (10)0.070 (3)
C1240.8494 (4)0.4850 (4)0.9134 (10)0.063 (2)
C1250.8363 (4)0.4526 (4)0.7949 (9)0.062 (2)
C1260.7838 (4)0.4103 (4)0.7785 (8)0.060 (2)
C170.7275 (4)0.2832 (4)1.0293 (8)0.054 (2)
O170.7193 (3)0.2498 (3)1.1245 (6)0.0755 (19)
C180.7936 (4)0.2809 (3)0.9635 (8)0.056 (2)
C1310.8359 (4)0.2263 (4)0.9909 (8)0.054 (2)
C1320.8311 (4)0.1809 (4)0.8988 (9)0.066 (3)
C1330.8698 (5)0.1317 (4)0.9191 (9)0.075 (3)
C1340.9187 (4)0.1258 (4)1.0353 (9)0.068 (3)
C1350.9243 (4)0.1694 (4)1.1271 (9)0.061 (2)
C1360.8838 (4)0.2203 (4)1.1092 (8)0.059 (2)
N210.7780 (3)0.7033 (3)0.3650 (6)0.0510 (17)
C220.7804 (4)0.6604 (4)0.2513 (8)0.0643 (13)
C2110.8336 (4)0.6127 (3)0.2872 (8)0.048 (2)
C2120.8316 (5)0.5773 (4)0.3979 (8)0.061 (2)
C2130.8800 (5)0.5343 (4)0.4243 (9)0.072 (3)
C2140.9309 (5)0.5248 (4)0.3449 (10)0.068 (3)
C2150.9344 (4)0.5603 (3)0.2308 (8)0.056 (2)
C2160.8855 (4)0.6039 (3)0.2027 (8)0.050 (2)
C230.7057 (4)0.6369 (4)0.2075 (8)0.0643 (13)
C2370.7021 (4)0.6025 (4)0.0778 (8)0.064 (2)
C2380.6417 (5)0.5574 (5)0.0659 (10)0.096 (3)
C240.6532 (4)0.6883 (4)0.1948 (8)0.0643 (13)
O240.6163 (3)0.6997 (3)0.0870 (5)0.082 (2)
C250.6523 (4)0.7261 (4)0.3121 (7)0.0643 (13)
C260.7137 (4)0.7120 (4)0.4259 (7)0.057 (2)
C2210.7030 (4)0.6645 (4)0.5269 (7)0.062 (2)
C2260.7553 (4)0.6584 (4)0.6401 (8)0.063 (2)
C2250.7513 (5)0.6144 (4)0.7334 (9)0.072 (3)
C2240.6975 (5)0.5751 (5)0.7195 (9)0.088 (3)
C2230.6433 (5)0.5819 (5)0.6104 (9)0.095 (4)
C2220.6475 (4)0.6263 (5)0.5169 (8)0.080 (3)
C270.8332 (4)0.7413 (4)0.4046 (8)0.052 (2)
O270.8300 (3)0.7766 (3)0.4954 (5)0.0628 (16)
C280.8982 (4)0.7358 (3)0.3368 (7)0.047 (2)
C2310.9411 (4)0.7912 (4)0.3484 (8)0.051 (2)
C2320.9853 (4)0.8049 (4)0.4697 (7)0.055 (2)
C2331.0237 (4)0.8554 (4)0.4775 (8)0.059 (2)
C2341.0202 (4)0.8941 (4)0.3692 (8)0.065 (2)
C2350.9773 (5)0.8794 (4)0.2489 (9)0.077 (3)
C2360.9397 (4)0.8286 (4)0.2419 (8)0.060 (2)
H120.61010.28441.09100.083*
H1160.69050.35671.25630.106*
H1150.67640.43351.40540.124*
H1140.57690.48951.38040.132*
H1130.49090.47431.19620.142*
H1120.50300.39901.04220.121*
H130.50490.31450.95290.085*
H13A0.60160.25070.82500.095*
H13B0.52060.25440.76730.095*
H13C0.49480.20740.96740.156*
H13D0.57670.20011.01480.156*
H13E0.54040.16740.88150.156*
H15A0.61280.42490.88520.090*
H15B0.61660.41110.72920.090*
H160.69100.33140.78350.069*
H1220.73050.42811.07270.071*
H1230.82070.49461.09690.083*
H1240.88460.51420.92370.076*
H1250.86350.45920.72380.074*
H1260.77620.38780.69770.073*
H18A0.78080.28510.86420.067*
H18B0.82320.31470.99550.067*
H1320.79930.18440.81760.080*
H1330.86360.10110.85430.089*
H1340.94710.09201.04930.082*
H1350.95700.16551.20700.073*
H1360.88870.25021.17600.071*
H220.79450.68240.17270.077*
H2120.79680.58280.45530.073*
H2130.87830.51010.50110.086*
H2140.96380.49430.36630.082*
H2150.96970.55450.17450.068*
H2160.88670.62820.12580.060*
H230.69370.61010.28010.077*
H23A0.74690.58190.07550.076*
H23B0.69490.6295−0.00050.076*
H23C0.65160.52800.13730.144*
H23D0.63740.5385−0.02300.144*
H23E0.59790.57740.07590.144*
H25A0.60750.72120.34820.077*
H25B0.65570.76730.28380.077*
H260.72150.74860.48070.069*
H2260.79350.68480.65210.076*
H2250.78680.61130.80920.087*
H2240.69660.54400.78220.106*
H2230.60440.55630.60080.114*
H2220.61080.63050.44370.096*
H28A0.88470.72620.23980.057*
H28B0.92710.70330.37910.057*
H2320.98840.77930.54520.066*
H2331.05350.86420.55900.071*
H2341.04600.92940.37660.078*
H2350.97430.90450.17250.093*
H2360.91150.81900.15900.072*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N110.033 (4)0.101 (5)0.031 (4)0.002 (4)−0.009 (3)0.010 (3)
C120.031 (5)0.127 (8)0.044 (5)0.000 (5)−0.012 (4)−0.004 (5)
C1110.042 (5)0.134 (9)0.045 (5)−0.002 (5)−0.009 (4)−0.014 (6)
C1160.047 (6)0.160 (10)0.055 (6)−0.012 (6)−0.004 (5)−0.016 (7)
C1150.078 (8)0.185 (12)0.047 (6)−0.011 (8)0.005 (5)−0.032 (7)
C1140.102 (9)0.154 (12)0.075 (8)0.012 (9)0.014 (7)−0.044 (7)
C1130.086 (8)0.176 (13)0.090 (9)0.022 (8)0.003 (7)−0.027 (9)
C1120.068 (7)0.148 (10)0.078 (8)0.019 (7)−0.019 (6)−0.039 (7)
C130.046 (5)0.110 (8)0.051 (6)−0.004 (5)−0.007 (4)−0.014 (6)
C1370.046 (5)0.098 (8)0.089 (7)0.004 (5)−0.006 (5)0.006 (7)
C1380.111 (9)0.103 (9)0.097 (9)0.001 (7)0.007 (7)0.016 (7)
C140.046 (6)0.158 (10)0.037 (5)0.009 (6)−0.016 (4)0.000 (6)
O140.061 (4)0.154 (7)0.070 (4)0.003 (4)−0.031 (4)0.007 (4)
C150.033 (5)0.137 (9)0.048 (5)0.015 (5)−0.020 (4)−0.006 (5)
C160.041 (5)0.094 (7)0.034 (5)0.004 (4)−0.008 (4)0.002 (4)
C1210.042 (5)0.071 (6)0.044 (5)0.009 (4)−0.014 (4)0.003 (4)
C1220.050 (5)0.081 (6)0.045 (5)0.010 (5)−0.002 (4)−0.011 (4)
C1230.055 (6)0.082 (7)0.066 (6)0.013 (5)−0.012 (5)−0.011 (5)
C1240.050 (5)0.060 (6)0.072 (7)0.003 (4)−0.018 (5)0.000 (5)
C1250.047 (5)0.080 (6)0.056 (6)0.005 (5)−0.001 (4)0.014 (5)
C1260.053 (5)0.086 (7)0.039 (5)0.016 (5)−0.005 (4)0.011 (4)
C170.039 (5)0.087 (6)0.032 (4)−0.009 (4)−0.007 (4)0.006 (5)
O170.047 (4)0.123 (5)0.051 (4)−0.015 (3)−0.012 (3)0.023 (4)
C180.050 (5)0.068 (6)0.046 (5)−0.006 (4)−0.009 (4)0.012 (4)
C1310.039 (5)0.069 (6)0.050 (5)−0.006 (4)−0.012 (4)0.016 (5)
C1320.060 (6)0.075 (7)0.053 (5)0.002 (5)−0.031 (4)0.006 (5)
C1330.080 (6)0.069 (6)0.064 (6)0.013 (5)−0.028 (5)−0.004 (5)
C1340.061 (6)0.064 (6)0.073 (7)0.006 (5)−0.015 (5)0.005 (5)
C1350.041 (5)0.081 (7)0.055 (5)−0.008 (5)−0.015 (4)0.019 (5)
C1360.054 (5)0.075 (6)0.045 (5)−0.007 (5)−0.008 (4)0.006 (4)
N210.032 (4)0.089 (5)0.031 (3)0.007 (3)0.000 (3)0.004 (3)
C220.037 (2)0.115 (4)0.037 (2)−0.006 (2)−0.0076 (19)0.001 (2)
C2110.046 (5)0.055 (5)0.037 (5)−0.004 (4)−0.013 (4)0.003 (4)
C2120.076 (6)0.069 (6)0.034 (5)0.005 (5)−0.006 (4)−0.001 (4)
C2130.096 (7)0.082 (7)0.034 (5)0.001 (6)−0.004 (5)−0.004 (5)
C2140.077 (7)0.055 (6)0.064 (6)0.009 (5)−0.023 (5)−0.007 (5)
C2150.055 (5)0.053 (5)0.054 (5)−0.002 (4)−0.017 (4)−0.007 (4)
C2160.033 (4)0.067 (6)0.044 (5)−0.006 (4)−0.015 (4)0.007 (4)
C230.037 (2)0.115 (4)0.037 (2)−0.006 (2)−0.0076 (19)0.001 (2)
C2370.050 (5)0.098 (7)0.041 (5)−0.002 (5)0.000 (4)−0.005 (4)
C2380.072 (7)0.127 (9)0.082 (7)−0.017 (6)−0.014 (5)−0.036 (6)
C240.037 (2)0.115 (4)0.037 (2)−0.006 (2)−0.0076 (19)0.001 (2)
O240.056 (4)0.139 (6)0.045 (3)0.001 (3)−0.014 (3)0.013 (3)
C250.037 (2)0.115 (4)0.037 (2)−0.006 (2)−0.0076 (19)0.001 (2)
C260.039 (5)0.099 (7)0.032 (4)0.006 (4)−0.002 (4)0.012 (4)
C2210.032 (5)0.120 (8)0.031 (5)−0.003 (5)−0.004 (4)0.004 (5)
C2260.048 (5)0.104 (7)0.034 (5)−0.004 (5)−0.007 (4)0.001 (5)
C2250.066 (6)0.108 (8)0.040 (5)−0.002 (6)−0.004 (4)0.002 (5)
C2240.097 (8)0.123 (9)0.041 (6)−0.022 (7)−0.002 (5)0.016 (5)
C2230.085 (7)0.151 (10)0.047 (6)−0.051 (7)−0.002 (5)0.005 (7)
C2220.052 (6)0.153 (10)0.033 (5)−0.018 (6)−0.005 (4)0.004 (6)
C270.041 (5)0.076 (6)0.036 (5)0.006 (4)−0.011 (4)0.016 (5)
O270.065 (4)0.084 (4)0.038 (3)0.009 (3)0.002 (3)−0.014 (3)
C280.044 (5)0.056 (5)0.038 (4)0.001 (4)−0.008 (4)−0.001 (4)
C2310.034 (4)0.069 (6)0.045 (5)0.006 (4)−0.007 (4)−0.012 (4)
C2320.044 (5)0.084 (6)0.033 (4)0.005 (5)−0.008 (4)−0.004 (4)
C2330.038 (5)0.091 (7)0.046 (5)−0.006 (5)−0.006 (4)−0.021 (5)
C2340.056 (5)0.080 (6)0.053 (6)−0.007 (5)−0.015 (4)−0.001 (5)
C2350.075 (6)0.082 (7)0.065 (6)−0.022 (5)−0.027 (5)0.011 (5)
C2360.063 (6)0.070 (6)0.039 (5)−0.010 (5)−0.020 (4)0.005 (5)
Geometric parameters (Å, º) top
N11—C171.366 (10)N21—C271.393 (10)
N11—C121.457 (9)N21—C261.473 (9)
N11—C161.502 (9)N21—C221.504 (10)
C12—C1111.531 (13)C22—C2111.512 (11)
C12—C131.541 (10)C22—C231.549 (10)
C12—H121.00C22—H221.00
C111—C1121.393 (13)C211—C2121.374 (11)
C111—C1161.407 (11)C211—C2161.410 (11)
C116—C1151.400 (14)C212—C2131.360 (12)
C116—H1160.95C212—H2120.95
C115—C1141.362 (14)C213—C2141.363 (12)
C115—H1150.95C213—H2130.95
C114—C1131.376 (15)C214—C2151.408 (12)
C114—H1140.95C214—H2140.95
C113—C1121.399 (15)C215—C2161.379 (10)
C113—H1130.95C215—H2150.95
C112—H1120.95C216—H2160.95
C13—C1371.469 (12)C23—C2371.507 (11)
C13—C141.501 (13)C23—C241.552 (12)
C13—H131.00C23—H231.00
C137—C1381.509 (13)C237—C2381.554 (12)
C137—H13A0.99C237—H23A0.99
C137—H13B0.99C237—H23B0.99
C138—H13C0.98C238—H23C0.98
C138—H13D0.98C238—H23D0.98
C138—H13E0.98C238—H23E0.98
C14—O141.246 (9)C24—O241.233 (9)
C14—C151.446 (12)C24—C251.457 (11)
C15—C161.562 (11)C25—C261.559 (10)
C15—H15A0.99C25—H25A0.99
C15—H15B0.99C25—H25B0.99
C16—C1211.506 (11)C26—C2211.517 (11)
C16—H161.00C26—H261.00
C121—C1261.376 (11)C221—C2221.380 (12)
C121—C1221.417 (11)C221—C2261.415 (10)
C122—C1231.372 (12)C226—C2251.382 (11)
C122—H1220.95C226—H2260.95
C123—C1241.356 (12)C225—C2241.370 (12)
C123—H1230.95C225—H2250.95
C124—C1251.389 (11)C224—C2231.411 (13)
C124—H1240.95C224—H2240.95
C125—C1261.400 (11)C223—C2221.390 (13)
C125—H1250.95C223—H2230.95
C126—H1260.95C222—H2220.95
C17—O171.246 (9)C27—O271.221 (9)
C17—C181.517 (11)C27—C281.514 (11)
C18—C1311.502 (11)C28—C2311.514 (10)
C18—H18A0.99C28—H28A0.99
C18—H18B0.99C28—H28B0.99
C131—C1321.382 (11)C231—C2361.361 (11)
C131—C1361.401 (10)C231—C2321.417 (10)
C132—C1331.354 (11)C232—C2331.373 (11)
C132—H1320.95C232—H2320.95
C133—C1341.397 (11)C233—C2341.390 (11)
C133—H1330.95C233—H2330.95
C134—C1351.349 (11)C234—C2351.402 (11)
C134—H1340.95C234—H2340.95
C135—C1361.405 (11)C235—C2361.371 (11)
C135—H1350.95C235—H2350.95
C136—H1360.95C236—H2360.95
C17—N11—C12120.0 (7)C27—N21—C26117.1 (7)
C17—N11—C16119.3 (6)C27—N21—C22121.4 (6)
C12—N11—C16119.6 (6)C26—N21—C22121.0 (6)
N11—C12—C111113.8 (7)N21—C22—C211112.7 (6)
N11—C12—C13109.4 (7)N21—C22—C23108.4 (6)
C111—C12—C13114.6 (7)C211—C22—C23113.1 (7)
N11—C12—H12106.1N21—C22—H22107.5
C111—C12—H12106.1C211—C22—H22107.5
C13—C12—H12106.1C23—C22—H22107.5
C112—C111—C116118.6 (9)C212—C211—C216119.7 (7)
C112—C111—C12123.5 (7)C212—C211—C22121.7 (8)
C116—C111—C12117.7 (9)C216—C211—C22118.6 (7)
C115—C116—C111118.9 (10)C213—C212—C211119.3 (9)
C115—C116—H116120.5C213—C212—H212120.4
C111—C116—H116120.5C211—C212—H212120.4
C114—C115—C116121.9 (9)C212—C213—C214122.5 (9)
C114—C115—H115119.0C212—C213—H213118.7
C116—C115—H115119.0C214—C213—H213118.7
C115—C114—C113119.6 (11)C213—C214—C215119.6 (8)
C115—C114—H114120.2C213—C214—H214120.2
C113—C114—H114120.2C215—C214—H214120.2
C114—C113—C112120.1 (11)C216—C215—C214118.4 (8)
C114—C113—H113119.9C216—C215—H215120.8
C112—C113—H113119.9C214—C215—H215120.8
C111—C112—C113120.7 (9)C215—C216—C211120.5 (7)
C111—C112—H112119.7C215—C216—H216119.8
C113—C112—H112119.7C211—C216—H216119.8
C137—C13—C14109.7 (8)C237—C23—C22110.8 (7)
C137—C13—C12111.5 (8)C237—C23—C24112.1 (6)
C14—C13—C12111.4 (8)C22—C23—C24109.4 (7)
C137—C13—H13108.0C237—C23—H23108.1
C14—C13—H13108.0C22—C23—H23108.1
C12—C13—H13108.0C24—C23—H23108.1
C13—C137—C138116.0 (9)C23—C237—C238111.0 (7)
C13—C137—H13A108.3C23—C237—H23A109.4
C138—C137—H13A108.3C238—C237—H23A109.4
C13—C137—H13B108.3C23—C237—H23B109.4
C138—C137—H13B108.3C238—C237—H23B109.4
H13A—C137—H13B107.4H23A—C237—H23B108.0
C137—C138—H13C109.5C237—C238—H23C109.5
C137—C138—H13D109.5C237—C238—H23D109.5
H13C—C138—H13D109.5H23C—C238—H23D109.5
C137—C138—H13E109.5C237—C238—H23E109.5
H13C—C138—H13E109.5H23C—C238—H23E109.5
H13D—C138—H13E109.5H23D—C238—H23E109.5
O14—C14—C15121.2 (10)O24—C24—C25120.1 (8)
O14—C14—C13122.8 (9)O24—C24—C23121.8 (8)
C15—C14—C13116.0 (7)C25—C24—C23117.8 (7)
C14—C15—C16115.8 (8)C24—C25—C26111.6 (7)
C14—C15—H15A108.3C24—C25—H25A109.3
C16—C15—H15A108.3C26—C25—H25A109.3
C14—C15—H15B108.3C24—C25—H25B109.3
C16—C15—H15B108.3C26—C25—H25B109.3
H15A—C15—H15B107.4H25A—C25—H25B108.0
N11—C16—C121114.3 (6)N21—C26—C221112.0 (6)
N11—C16—C15108.5 (6)N21—C26—C25109.4 (6)
C121—C16—C15107.9 (7)C221—C26—C25118.1 (7)
N11—C16—H16108.6N21—C26—H26105.4
C121—C16—H16108.6C221—C26—H26105.4
C15—C16—H16108.6C25—C26—H26105.4
C126—C121—C122118.6 (8)C222—C221—C226117.4 (8)
C126—C121—C16120.3 (7)C222—C221—C26125.8 (7)
C122—C121—C16121.0 (8)C226—C221—C26116.8 (8)
C123—C122—C121119.4 (9)C225—C226—C221120.5 (8)
C123—C122—H122120.3C225—C226—H226119.8
C121—C122—H122120.3C221—C226—H226119.8
C124—C123—C122122.8 (8)C224—C225—C226121.7 (8)
C124—C123—H123118.6C224—C225—H225119.2
C122—C123—H123118.6C226—C225—H225119.2
C123—C124—C125118.1 (8)C225—C224—C223118.7 (10)
C123—C124—H124120.9C225—C224—H224120.7
C125—C124—H124120.9C223—C224—H224120.7
C124—C125—C126121.0 (9)C222—C223—C224119.4 (9)
C124—C125—H125119.5C222—C223—H223120.3
C126—C125—H125119.5C224—C223—H223120.3
C121—C126—C125120.0 (8)C221—C222—C223122.3 (8)
C121—C126—H126120.0C221—C222—H222118.9
C125—C126—H126120.0C223—C222—H222118.9
O17—C17—N11119.9 (7)O27—C27—N21120.7 (7)
O17—C17—C18120.7 (7)O27—C27—C28120.9 (7)
N11—C17—C18119.4 (7)N21—C27—C28118.2 (8)
C131—C18—C17115.0 (7)C27—C28—C231112.1 (6)
C131—C18—H18A108.5C27—C28—H28A109.2
C17—C18—H18A108.5C231—C28—H28A109.2
C131—C18—H18B108.5C27—C28—H28B109.2
C17—C18—H18B108.5C231—C28—H28B109.2
H18A—C18—H18B107.5H28A—C28—H28B107.9
C132—C131—C136117.5 (8)C236—C231—C232118.0 (8)
C132—C131—C18121.5 (7)C236—C231—C28121.2 (7)
C136—C131—C18121.0 (8)C232—C231—C28120.8 (8)
C133—C132—C131122.9 (7)C233—C232—C231119.6 (8)
C133—C132—H132118.6C233—C232—H232120.2
C131—C132—H132118.6C231—C232—H232120.2
C132—C133—C134120.1 (9)C232—C233—C234121.7 (7)
C132—C133—H133119.9C232—C233—H233119.1
C134—C133—H133119.9C234—C233—H233119.1
C135—C134—C133118.2 (8)C233—C234—C235118.0 (8)
C135—C134—H134120.9C233—C234—H234121.0
C133—C134—H134120.9C235—C234—H234121.0
C134—C135—C136122.6 (7)C236—C235—C234119.7 (8)
C134—C135—H135118.7C236—C235—H235120.1
C136—C135—H135118.7C234—C235—H235120.1
C131—C136—C135118.7 (8)C231—C236—C235122.9 (7)
C131—C136—H136120.6C231—C236—H236118.6
C135—C136—H136120.6C235—C236—H236118.6
C17—N11—C12—C111107.5 (9)C27—N21—C22—C21168.9 (9)
C16—N11—C12—C111−84.3 (8)C26—N21—C22—C211−119.5 (7)
C17—N11—C12—C13−122.9 (8)C27—N21—C22—C23−165.2 (6)
C16—N11—C12—C1345.3 (11)C26—N21—C22—C236.4 (10)
C12—C13—C137—C13867.5 (11)C22—C23—C237—C238154.9 (7)
N11—C12—C111—C112130.2 (10)N21—C22—C211—C21257.0 (10)
N11—C16—C121—C122−41.2 (10)N21—C26—C221—C222−118.6 (9)
C12—N11—C17—C18173.3 (7)C22—N21—C27—C28−4.2 (9)
N11—C17—C18—C131−162.0 (7)N21—C27—C28—C231158.6 (6)
C17—C18—C131—C13298.1 (9)C27—C28—C231—C23279.2 (8)
C13—C12—C111—C1123.3 (14)C23—C22—C211—C212−66.4 (9)
N11—C12—C111—C116−54.3 (11)N21—C22—C211—C216−124.2 (7)
C13—C12—C111—C116178.7 (9)C23—C22—C211—C216112.4 (8)
C112—C111—C116—C115−2.9 (16)C216—C211—C212—C2130.1 (11)
C12—C111—C116—C115−178.6 (9)C22—C211—C212—C213178.9 (7)
C111—C116—C115—C1142.6 (17)C211—C212—C213—C2140.0 (13)
C116—C115—C114—C113−2 (2)C212—C213—C214—C2150.1 (13)
C115—C114—C113—C1121 (2)C213—C214—C215—C216−0.4 (11)
C116—C111—C112—C1132.5 (17)C214—C215—C216—C2110.5 (10)
C12—C111—C112—C113177.9 (11)C212—C211—C216—C215−0.4 (11)
C114—C113—C112—C111−1.6 (19)C22—C211—C216—C215−179.2 (6)
N11—C12—C13—C13765.9 (11)N21—C22—C23—C237169.5 (7)
C111—C12—C13—C137−165.0 (8)C211—C22—C23—C237−64.8 (9)
N11—C12—C13—C14−57.0 (10)N21—C22—C23—C2445.4 (8)
C111—C12—C13—C1472.1 (10)C211—C22—C23—C24171.1 (7)
C14—C13—C137—C138−168.7 (8)C24—C23—C237—C238−82.5 (9)
C137—C13—C14—O1475.7 (12)C237—C23—C24—O24−3.3 (12)
C12—C13—C14—O14−160.4 (9)C22—C23—C24—O24120.1 (8)
C137—C13—C14—C15−107.3 (9)C237—C23—C24—C25−178.5 (7)
C12—C13—C14—C1516.6 (12)C22—C23—C24—C25−55.2 (10)
O14—C14—C15—C16−146.4 (9)O24—C24—C25—C26−167.3 (7)
C13—C14—C15—C1636.6 (11)C23—C24—C25—C268.0 (11)
C17—N11—C16—C121−66.1 (9)C27—N21—C26—C221−108.4 (8)
C12—N11—C16—C121125.7 (7)C22—N21—C26—C22179.6 (8)
C17—N11—C16—C15173.4 (7)C27—N21—C26—C25118.6 (7)
C12—N11—C16—C155.2 (10)C22—N21—C26—C25−53.3 (10)
C14—C15—C16—N11−48.2 (9)C24—C25—C26—N2143.3 (10)
C14—C15—C16—C121−172.7 (7)C24—C25—C26—C221−86.3 (9)
N11—C16—C121—C126139.8 (7)C25—C26—C221—C2229.9 (13)
C15—C16—C121—C126−99.3 (8)N21—C26—C221—C22660.5 (10)
C15—C16—C121—C12279.7 (8)C25—C26—C221—C226−171.0 (8)
C126—C121—C122—C1230.8 (11)C222—C221—C226—C2252.3 (13)
C16—C121—C122—C123−178.2 (7)C26—C221—C226—C225−176.9 (8)
C121—C122—C123—C1241.9 (12)C221—C226—C225—C2240.5 (14)
C122—C123—C124—C125−2.9 (12)C226—C225—C224—C223−3.0 (15)
C123—C124—C125—C1261.1 (11)C225—C224—C223—C2222.8 (16)
C122—C121—C126—C125−2.4 (11)C226—C221—C222—C223−2.5 (15)
C16—C121—C126—C125176.6 (7)C26—C221—C222—C223176.6 (9)
C124—C125—C126—C1211.5 (11)C224—C223—C222—C2210.0 (17)
C12—N11—C17—O17−6.0 (11)C26—N21—C27—O276.7 (10)
C16—N11—C17—O17−174.2 (7)C22—N21—C27—O27178.7 (7)
C16—N11—C17—C185.1 (10)C26—N21—C27—C28−176.1 (6)
O17—C17—C18—C13117.3 (11)O27—C27—C28—C231−24.2 (9)
C17—C18—C131—C136−84.2 (9)C27—C28—C231—C236−102.5 (8)
C136—C131—C132—C1330.7 (13)C236—C231—C232—C2331.6 (11)
C18—C131—C132—C133178.4 (8)C28—C231—C232—C233179.9 (7)
C131—C132—C133—C134−2.0 (15)C231—C232—C233—C2340.4 (12)
C132—C133—C134—C1352.0 (14)C232—C233—C234—C235−1.7 (13)
C133—C134—C135—C136−0.8 (13)C233—C234—C235—C2361.1 (14)
C132—C131—C136—C1350.6 (12)C232—C231—C236—C235−2.3 (13)
C18—C131—C136—C135−177.2 (7)C28—C231—C236—C235179.4 (8)
C134—C135—C136—C131−0.5 (12)C234—C235—C236—C2311.0 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C13—H13···O24i1.002.353.232 (10)147
C22—H22···O27ii1.002.193.190 (10)175
C28—H28A···O27ii0.992.523.486 (9)165
C222—H222···O14i0.952.543.478 (10)169
C123—H123···Cgiii0.952.893.811 (10)165
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+3/2, z−1/2; (iii) x, y, z+1.
 

Acknowledgements

X-ray data were collected through the EPSRC X-ray Crystallographic Service at Daresbury SRS station 9.8, UK. The authors thank the staff for all their help and advice.

References

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ISSN: 2056-9890
Volume 62| Part 4| April 2006| Pages o1452-o1454
https://doi.org/10.1107/S1600536806009184
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