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(1RS,2SR,7RS,8RS)-N-Benzoyl­tri­cyclo­[6.2.2.02,7]­dodeca-9,11-diene-1,10-dicarbox­imide

aSchool of Chemical Sciences, Dublin City University, Dublin 9, Ireland, and bDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
*Correspondence e-mail: r.a.howie@abdn.ac.uk

(Received 20 January 2005; accepted 25 January 2005; online 5 February 2005)

The title 1,4-photoadduct, C21H19NO3, was formed on irra­diation of N-benzoyl­phthal­imide in di­chloro­methane con­tain­ing cyclo­hexene. The bond lengths and angles are generally within the normal ranges. A notable feature of the mol­ecule is the presence within it of four contiguous chiral centres.

Comment

The photochemistry of phthal­imides has been studied extensively and has been reviewed by Kanaoka (1978[Kanaoka, Y. (1978). Acc. Chem. Res. 11, 407-413.]), Coyle (1984[Coyle, J. D. (1984). Synthetic Organic Photochemistry, edited by W. M. Horspool, pp. 259-284. New York: Plenum Press.]) and Oelgemöller & Griesbeck (2002[Oelgemöller, M. & Griesbeck, A. G. (2002). J. Photochem. Photobiol. C, 3, 109-127.]). Schwack (1987[Schwack, W. (1987). Tetrahedron Lett. 28, 1869-1871.]) has reported the photo-induced para-cyclo­addition of cyclo­hexene to N-tri­chloro­methyl­thio-, N-methyl- and N-phenyl­phthal­imides. Suau et al. (1989[Suau, R., Garcia-Segura, R. & Sosa-Olaya, F. (1989). Tetrahedron Lett. 30, 3225-3228.]) have reported the ortho- and para-photo­cyclo­addition of 3-methoxy-N-methyl­phthal­imide to 1-hexene and Kubo et al. (1989[Kubo, Y., Taniguchi, E. & Araki, T. (1989). Heterocycles, 29, 1857-1860.]) have reported analogous ortho- and para-cyclo­additions of N-methyl­phthal­imide to allyl­tri­methyl­silane. In each case, the para-cyclo­addition products are structurally analogous to the title compound, (I[link]). However, the structures were only elucidated by spectroscopic means and lack stereochemical certainty. The determination of the structure of (I[link]) presented here was undertaken in the context of a study of the photochemistry of N-benzoyl­phthal­imide but is clearly of significance in relation to the analogous compounds.[link]

[Scheme 1]

The mol­ecule of (I[link]) is shown in Fig. 1[link]. Selected bond lengths and angles are given in Table 1[link]. The bond lengths, along with those of the phenyl group R1 defined by C16–C21 in the range 1.361 (6)–1.389 (5) Å, are not unusual excepting, perhaps, the C2—C3 and C6—C7 bond lengths of 1.493 (5) and 1.481 (5) Å, respectively. Likewise, with the sole exception of the angle C9—C10—C14 of 134.1 (3)°, the bond angles, including the internal angles of the phenyl group in the range 117.9 (3)–121.1 (4)°, are as expected. The cyclo­hexane ring, R3, defined by C2–C7, adopts the chair conformation, with puckering parameters (Cremer & Pople, 1975[Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.]) Q = 0.564 (4) Å, θ = 168.5 (5) and φ = 151 (2)°. The dihedral angle between the least-squares planes of phenyl group R1 (r.m.s. displacement = 0.0006 Å) and five-membered ring R2, defined by C1/C10/C13–C14/N1 (r.m.s. displacement = 0.0143 Å) is 61.97 (15)°. Atom O3 is displaced from the least-squares planes of R1 and R2 by 0.145 (7) and 1.134 (6) Å, respectively. The packing of the mol­ecules of (I[link]) creates layers parallel to ([\overline 1]02) (Fig. 2[link]) in such a way as to generate the first two C—H⋯π interactions given in Table 2[link] (shown as dashed lines in Fig. 2[link]). The only contact between the layers, other than van der Waals interactions, is the third, longer, C—H⋯π contact given in Table 2[link].

The racemic nature of (I[link]), a prerequisite for the refinement of the structure in the centrosymmetric space group P21/c, is a natural consequence of the manner in which the compound has been formed from achiral reactants. In principle, given that the unsymmetrical 1,4-addition across the aromatic ring must of necessity be cis, there are four possible racemic products, two involving trans ring junctions at C2—C7 and two involving cis junctions at C2—C7. Formation of the single unsymmetrical product, (I[link]), suggests a favoured approach by the cyclo­hexene to the excited phthal­imide, possibly involving minimization of steric interactions between the N-benzoyl­imide and cyclo­hexene rings in the transition state. The stereochemistry at the C2—C7 ring junction is the outcome of overall trans addition across the cyclo­hexene double bond.

[Figure 1]
Figure 1
A view of (I[link]). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small circles of arbitrary radii.
[Figure 2]
Figure 2
A layer of mol­ecules of (I[link]). Displacement ellipsoids are drawn at the 20% probability level and H atoms involved in C—H..π contacts (dashed lines) are shown as small circles of arbitrary radii. [Symmetry codes (i) 1 − x, 1 − y, 1 − z; (ii) 1 + x, [{3 \over 2}] − y, [{1 \over 2}] +  z; (iv) 2 − x, y − [{1 \over 2}], [{3 \over 2}] − z; (v) x − 1, [{3 \over 2}] − y, z − [{1 \over 2}]; (vi) −x, y − [{1 \over 2}], [{1 \over 2}] − z.]

Experimental

Compound (I[link]) was one of the products of irradiation for 40 h of N-benzoyl­phthal­imide (2.90 g, 11.5 mmol) and cyclo­hexene (19.60 g, 239.0 mmol) in di­chloro­methane (300 ml) by a 400 W medium-pressure mercury vapour lamp fitted with a Pyrex filter. After removal of solvents under vacuum three products (previously detected by thin-layer chromatography) were isolated by means of a Chromatotron and a 4 mm silica plate with a mixture of di­chloro­methane and light petroleum (b.p. 313–333 K) (2:98 increased stepwise to 60:40) as eluant to yield: (i) recovered N-benzoyl­phthal­imide (2.75 g); (ii) a mixture of minor products as a colourless oil (12 mg); (iii) compound (I[link]), a white crystalline solid [160 mg, 80%; m.p. 411–413 K (from chloro­form/light petroleum, b.p. 363–373 K)], λmax (MeCN): 251 ( 20,208 dm3 mol−1 cm−1); νmax 2929 (aliphatic CH), 1717 and 1694 (C=O), 1297 and 1252 cm−1; δH (270 MHz, CDCl3): 7.89–7.47 (5H, m, ArH), 7.10 (1H, d, J 6.0 Hz, vinyl­ic H), 6.82 (1H, d of d, J 6.0 Hz, J 7.0 Hz, vinyl­ic H), 6.16 (1H, d, J 7.0 Hz, vinyl­ic H), 3.76 (1H, t, J 6.0 Hz), 2.10–1.11 (10H, m, cyclo­hexane derived moiety); δC (67.8 MHz, CDCl3): 173.0, 167.1, 162.3 (carbonyl C), 143.3, 141.7, 137.3, 134.8, 131.9, 130.4, 128.8, 123.5 (aromatic and vinyl­ic C), 56.2, 52.5, 50.7, 45.7, 32.7, 30.2, 27.7 and 27.4 (aliphatic C); analysis found: C 75.3, H 5.8, N 3.9%; C21H19NO3 requires: C 75.7, H 5.8, N 4.2%; m/e: 333 (1), 265 (47), 264 (31), 252 (56), 105 (100), 77 (63) and 67 (45%).

Crystal data
  • C21H19NO3

  • Mr = 333.37

  • Monoclinic, P21/c

  • a = 8.111 (3) Å

  • b = 12.999 (7) Å

  • c = 16.256 (5) Å

  • β = 100.76 (3)°

  • V = 1683.8 (12) Å3

  • Z = 4

  • Dx = 1.315 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 14 reflections

  • θ = 11.0–13.0°

  • μ = 0.09 mm−1

  • T = 298 (2) K

  • Block, colourless

  • 0.60 × 0.40 × 0.26 mm

Data collection
  • Nicolet P3 four-circle diffractometer

  • θ–2θ scans

  • Absorption correction: none

  • 3882 measured reflections

  • 3882 independent reflections

  • 1880 reflections with I > 2σ(I)

  • θmax = 30.1°

  • h = 0 → 11

  • k = 0 → 18

  • l = −22 → 22

  • 2 standard reflections every 50 reflections intensity decay: none

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.088

  • wR(F2) = 0.192

  • S = 1.03

  • 3882 reflections

  • 226 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0735P)2] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.32 e Å−3

  • Δρmin = −0.23 e Å−3

Table 1
Selected geometric parameters (Å, °)

N1—C13 1.408 (4)
N1—C14 1.425 (4)
N1—C15 1.444 (4)
O1—C13 1.203 (4)
O2—C14 1.200 (4)
O3—C15 1.194 (4)
C1—C11 1.500 (5)
C1—C13 1.504 (5)
C1—C10 1.504 (4)
C1—C2 1.571 (4)
C2—C3 1.493 (5)
C2—C7 1.514 (5)
C6—C7 1.481 (5)
C7—C8 1.584 (5)
C8—C9 1.506 (5)
C8—C12 1.519 (5)
C9—C10 1.330 (4)
C10—C14 1.462 (5)
C11—C12 1.323 (5)
C15—C16 1.473 (5)
C13—N1—C14 113.0 (3)
C13—N1—C15 121.3 (3)
C14—N1—C15 125.0 (3)
C11—C1—C13 118.0 (3)
C11—C1—C10 108.2 (3)
C13—C1—C10 103.4 (3)
C11—C1—C2 109.4 (3)
C13—C1—C2 114.3 (3)
C10—C1—C2 102.0 (3)
C3—C2—C7 110.4 (3)
C3—C2—C1 124.6 (3)
C7—C2—C1 107.4 (3)
C6—C7—C2 110.8 (3)
C6—C7—C8 122.4 (3)
C2—C7—C8 109.0 (3)
C9—C8—C12 108.3 (3)
C9—C8—C7 109.1 (3)
C12—C8—C7 100.8 (3)
C10—C9—C8 112.1 (3)
C9—C10—C14 134.1 (3)
C9—C10—C1 115.4 (3)
C14—C10—C1 110.3 (3)
C12—C11—C1 113.2 (3)
C11—C12—C8 114.5 (3)
O1—C13—N1 124.0 (3)
O1—C13—C1 127.9 (3)
N1—C13—C1 108.1 (3)
O2—C14—N1 123.9 (3)
O2—C14—C10 130.9 (3)
N1—C14—C10 105.1 (3)
O3—C15—N1 118.4 (3)
O3—C15—C16 123.8 (3)
N1—C15—C16 117.7 (3)
C11—C1—C2—C3 −86.5 (4)
C13—C1—C2—C3 48.3 (5)
C10—C1—C2—C3 159.1 (4)
C11—C1—C2—C7 44.9 (4)
C13—C1—C2—C7 179.7 (3)
C10—C1—C2—C7 −69.5 (3)
C1—C2—C3—C4 −171.5 (3)
C5—C6—C7—C8 −170.5 (4)
C3—C2—C7—C6 −65.8 (4)
C1—C2—C7—C6 155.5 (3)
C3—C2—C7—C8 156.7 (3)
C1—C2—C7—C8 18.0 (4)
C6—C7—C8—C9 −87.4 (4)
C2—C7—C8—C9 44.1 (4)
C6—C7—C8—C12 158.8 (4)
C2—C7—C8—C12 −69.7 (4)
C8—C9—C10—C14 178.1 (3)
C8—C9—C10—C1 3.3 (4)
C13—C1—C10—C9 179.5 (3)
C13—C1—C10—C14 3.4 (3)
C1—C11—C12—C8 3.4 (4)
C9—C8—C12—C11 −54.9 (4)
C7—C8—C12—C11 59.5 (4)

Table 2
Geometry (Å,°) of C—H⋯π contacts in (I)

C—H⋯Cga C—H H⋯Cg Hperpb γc C—H⋯Cg C⋯Cg
C6—H6ACg1i 0.97 2.80 2.69 16 149 3.68
C6—H6BCg1ii 0.97 3.03 2.93 15 135 3.79
C4—H4BCg2iii 0.97 3.34 3.28 11 120 3.92
Notes: (a) Cg1 and Cg2 are the centroids of the rings defined by C16–C21 and C1/C10/C13–C14/N1, respectively; (b) Hperp is the perpendicular distance of the H atom from the mean plane of the ring; (c) γ is the angle at hydrogen between Hperp and H⋯Cg. Symmetry codes (i) 1-x,1-y,1-z; (ii) [1+x,{\script{3\over 2}}-y, {\script{1\over 2}}+z]; (iii) 1+ x,y,z.

The incompleteness (84.9% complete for θfull = 25°) of the mid-1980s data set upon which this refinement is based is due to the suppression, during data reduction and contrary to current practice, of reflections with intensities measured as negative. As a consequence, the omissions are scattered throughout the data set although they are more prevalent at high θ. In the final stages of refinement, H atoms were introduced in calculated positions with C—H set at 0.93, 0.97 and 0.98 Å for aryl/alkene, methyl­ene and tertiary H atoms, respectively, and refined with a riding model, with Uiso(H) = 1.2Ueq(C) in all cases.

Data collection: Nicolet P3 Software (Nicolet, 1980[Nicolet. (1980). Nicolet P3/R3 Data Collection Operator's Manual. Nicolet XRD Corporation, Cupertino, California, USA.]); cell refinement: Nicolet P3 Software; data reduction: RDNIC (Howie, 1980[Howie, R. A. (1980). RDNIC. University of Aberdeen, Scotland.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]).

Supporting information


Comment top

The photochemistry of phthalimides has been studied extensively and has been reviewed by Kanaoka (1978), Coyle (1984) and Oelgemöller & Griesbeck (2002). Schwack (1987) has reported the photoinduced para-cycloaddition of cyclohexene to N-trichloromethylthio-, N-methyl- and N-phenylphthalimides. Suau et al. (1989) have reported the ortho- and para-photocycloaddition of 3-methoxy-N-methylphthalimide to 1-hexene and Kubo et al. (1989) have reported analogous ortho- and para-cycloadditions of N-methylphthalimide to allyltrimethylsilane. In each case, the para-cycloaddition products are structurally analogous to the title compound, (I). However, the structures were only elucidated by spectroscopic means and lack stereochemical certainty. The determination of the structure of (I) presented here was undertaken in the context of a study of the photochemistry of N-benzoylphthalimide but is clearly of significance in relation to the analogous compounds.

The molecule of (I) is shown in Fig. 1. Selected bond lengths and angles are given in Table 1. The bond lengths, along with those of the phenyl group R1 defined by C16–C21 in the range 1.361 (6)–1.389 (5) Å, are not unusual excepting, perhaps, the C2—C3 and C6—C7 bond lengths of 1.493 (5) and 1.481 (5) Å, respectively. Likewise, with the sole exception of the angle C9—C10—C14 of 134.1 (3)°, the bond angles, including the internal angles of the phenyl group in the range 117.9 (3)–121.1 (4)°, are as expected. The cyclohexane ring, R3, defined by C2–C7, adopts the chair conformation, with puckering parameters (Cremer & Pople, 1975) Q = 0.564 (4) Å, θ = 168.5 (5) and ϕ = 151 (2)°. The dihedral angle between the least-squares planes of phenyl group R1 (r.m.s. displacement = 0.0006 Å) and five-membered ring R2, defined by C1/C10/C13–C14/N1 (r.m.s. displacement = 0.0143 Å) is 61.97 (15)°. Atom O3 is displaced from the least-squares planes of R1 and R2 by 0.145 (7) and -1.134 (6) Å, respectively. The packing of the molecules of (I) creates layers parallel to (102) (Fig. 2) in such a way as to create the first two C—H..π interactions given in Table 2 (shown as dashed lines in Fig. 2). The only contact between the layers, other than van der Waals interactions, is the third, longer, C—H..π contact given in Table 2.

The racemic nature of (I), a prerequisite for the refinement of the structure in the centrosymmetric space group P21/c, is a natural consequence of the manner in which the compound has been formed from achiral reactants. In principle, given that the unsymmetrical 1,4-addition across the aromatic ring must of necessity be cis, there are four possible racemic products, two involving trans ring junctions at C2—C7 and two involving cis junctions at C2—C7. Formation of the single unsymmetrical product, (I), suggests a favoured approach by the cyclohexene to the excited phthalimide, possibly involving minimization of steric interactions between the N-benzoylimide and cyclohexene rings in the transition state. The stereochemistry at the C2—C7 ring junction is the outcome of overall trans addition across the cyclohexene double bond.

Experimental top

Compound (I) was one of the products of irradiation for 40 h of N-benzoylphthalimide (2.90 g, 11.5 mmol) and cyclohexene (19.60 g, 239.0 mmol) in dichloromethane (300 ml) by a 400 W medium-pressure mercury vapour lamp fitted with a Pyrex filter. After removal of solvents under vacuum three products (previously detected by thin-layer chromatography) were isolated by means of a Chromatotron and a 4 mm silica plate with a mixture of dichloromethane and light petroleum (b.p. 313–333 K) (2:98 increased stepwise to 60:40) as eluant to yield: (i) recovered N-benzoylphthalimide (2.75 g); (ii) a mixture of minor products as a colourless oil (12 mg); (iii) compound (I), a white crystalline solid [160 mg, 80%; m.p. 411–413 K (from chloroform/light petroleum, b.p. 363–373 K)], λmax (MeCN): 251 (ε 20,208 dm3 mol-1 cm-1); νmax 2929 (aliphatic CH), 1717 and 1694 (CO), 1297 and 1252 cm-1; δH (270 MHz, CDCl3): 7.89–7.47 (5H, m, ArH), 7.10 (1H, d, J 6.0 Hz, vinylic H), 6.82 (1H, d of d, J 6.0 Hz, J 7.0 Hz, vinylic H), 6.16 (1H, d, J 7.0 Hz, vinylic H), 3.76 (1H, t, J 6.0 Hz), 2.10–1.11 (10H, m, cyclohexane derived moiety); δC (67.8 MHz, CDCl3): 173.0, 167.1, 162.3 (carbonyl C), 143.3, 141.7, 137.3, 134.8, 131.9, 130.4, 128.8, 123.5 (aromatic and vinylic C), 56.2, 52.5, 50.7, 45.7, 32.7, 30.2, 27.7 and 27.4 (aliphatic C); analysis found: C 75.3, H 5.8, N 3.9%; C21H19NO3 requires: C 75.7, H 5.8, N 4.2%; m/e: 333 (1), 265 (47), 264 (31), 252 (56), 105 (100), 77 (63) and 67 (45%).

Refinement top

The incompleteness (0.849 complete for θfull = 25°) of the mid-1980 s data set upon which this refinement is based is due to the suppression, during data reduction and contrary to current practice, of reflections with intensities measured as negative. As a consequence, the omissions are scattered throughout the data set although they are more prevalent at high θ. In the final stages of refinement, H atoms were introduced in calculated positions with C—H set at 0.93, 0.97 and 0.98 Å for aryl/alkene, methylene and tertiary H atoms, respectively, and refined with a riding model, with Uiso(H) = 1.2Ueq(C) in all cases.

Computing details top

Data collection: Nicolet P3 Software (Nicolet, 1980); cell refinement: Nicolet P3 Software; data reduction: RDNIC (Howie, 1980); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. A view of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small circles of arbitrary radii.
[Figure 2] Fig. 2. A layer of molecules of (I). Displacement ellipsoids are drawn at the 20% probability level and H atoms involved in C—H..π contacts (dashed lines) are shown as small circles of arbitrary radii. [Symmetry codes (i) 1 - x, 1 - y, 1 - z; (ii) 1 + x, 3/2 - y, 1/2 + z; (iv) 2 - x, y - 1/2, 32/-z; (v) x - 1, 3/2 - y, z - 1/2; (vi) -x, y - 1/2, 1/2 - z.]
(1RS,2SR,7RS,8RS)-N-Benzoyltricyclo[6.2.2.02,7]dodeca-9,11-diene-1,10- dicarboximide top
Crystal data top
C21H19NO3F(000) = 704
Mr = 333.37Dx = 1.315 Mg m3
Monoclinic, P21/cMelting point = 411–413 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 8.111 (3) ÅCell parameters from 14 reflections
b = 12.999 (7) Åθ = 11.0–13.0°
c = 16.256 (5) ŵ = 0.09 mm1
β = 100.76 (3)°T = 298 K
V = 1683.8 (12) Å3Block, colourless
Z = 40.60 × 0.40 × 0.26 mm
Data collection top
Nicolet P3 four-circle
diffractometer
Rint = 0.000
Radiation source: normal-focus sealed tubeθmax = 30.1°, θmin = 2.0°
Graphite monochromatorh = 011
θ–2θ scansk = 018
3882 measured reflectionsl = 2222
3882 independent reflections2 standard reflections every 50 reflections
1880 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.088Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.192H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0735P)2]
where P = (Fo2 + 2Fc2)/3
3882 reflections(Δ/σ)max < 0.001
226 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
C21H19NO3V = 1683.8 (12) Å3
Mr = 333.37Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.111 (3) ŵ = 0.09 mm1
b = 12.999 (7) ÅT = 298 K
c = 16.256 (5) Å0.60 × 0.40 × 0.26 mm
β = 100.76 (3)°
Data collection top
Nicolet P3 four-circle
diffractometer
Rint = 0.000
3882 measured reflections2 standard reflections every 50 reflections
3882 independent reflections intensity decay: none
1880 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0880 restraints
wR(F2) = 0.192H-atom parameters constrained
S = 1.03Δρmax = 0.32 e Å3
3882 reflectionsΔρmin = 0.23 e Å3
226 parameters
Special details top

Experimental. Scan rates, dependent on prescan intensity (Ip), were in the range 58.6 (Ip>2500) to 5.33 (Ip<150) degrees 2-theta per min. Scan widths, dependent on 2-theta, were in the range 2.4 to 2.7 degrees 2-theta. Stationary crystal, stationary counter background counts were taken on either side of the peak each for 25% of the total (peak plus background) count time.

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

- 7.2306 (0.0071) x + 5.8226 (0.0186) y + 1.6136 (0.0260) z = 1.6557 (0.0174)

* -0.0185 (0.0020) C1 * 0.0197 (0.0020) C10 * 0.0112 (0.0020) C13 * -0.0131 (0.0019) C14 * 0.0007 (0.0020) N1 0.0528 (0.0052) O1 - 0.0531 (0.0047) O2 - 1.1343 (0.0056) O3 - 0.1943 (0.0055) C15

Rms deviation of fitted atoms = 0.0143

- 0.6803 (0.0143) x + 10.2618 (0.0152) y - 9.4566 (0.0246) z = 2.4682 (0.0136)

Angle to previous plane (with approximate e.s.d.) = 61.97 (0.15)

* -0.0002 (0.0026) C16 * -0.0003 (0.0028) C17 * 0.0002 (0.0031) C18 * 0.0005 (0.0032) C19 * -0.0010 (0.0032) C20 * 0.0009 (0.0029) C21 - 0.0135 (0.0068) N1 0.1449 (0.0070) O3 0.0297 (0.0059) C15

Rms deviation of fitted atoms = 0.0006

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
xyzUiso*/Ueq
N10.3644 (3)0.6274 (2)0.39508 (16)0.0392 (7)
O10.4530 (3)0.7657 (2)0.32558 (15)0.0603 (8)
O20.3050 (3)0.51618 (19)0.49727 (15)0.0500 (7)
O30.4287 (3)0.5436 (2)0.28269 (16)0.0619 (8)
C10.4954 (4)0.7640 (3)0.47789 (19)0.0373 (8)
C20.6906 (4)0.7617 (3)0.5097 (2)0.0414 (8)
H20.71720.68840.51710.050*
C30.8167 (5)0.8014 (4)0.4613 (2)0.0713 (13)
H3A0.80870.87570.45670.086*
H3B0.79570.77250.40530.086*
C40.9903 (5)0.7707 (4)0.5070 (3)0.0714 (13)
H4A1.00380.69720.50050.086*
H4B1.07310.80490.48070.086*
C51.0262 (5)0.7962 (4)0.5997 (3)0.0722 (13)
H5A1.04520.86960.60630.087*
H5B1.12860.76150.62570.087*
C60.8865 (5)0.7655 (4)0.6452 (2)0.0690 (13)
H6A0.88220.69120.64980.083*
H6B0.90750.79430.70120.083*
C70.7247 (4)0.8045 (3)0.5978 (2)0.0476 (9)
H70.74470.87790.59040.057*
C80.5568 (4)0.8011 (3)0.6343 (2)0.0489 (10)
H80.57520.81660.69440.059*
C90.4719 (4)0.6989 (3)0.6132 (2)0.0442 (9)
H90.44730.65280.65300.053*
C100.4362 (4)0.6823 (3)0.5311 (2)0.0375 (8)
C110.4270 (4)0.8654 (3)0.4999 (2)0.0481 (9)
H110.37110.91110.46020.058*
C120.4543 (4)0.8834 (3)0.5814 (2)0.0523 (10)
H120.41390.94160.60440.063*
C130.4398 (4)0.7243 (3)0.3902 (2)0.0423 (8)
C140.3603 (4)0.5969 (3)0.4789 (2)0.0387 (8)
C150.3223 (4)0.5619 (3)0.3224 (2)0.0428 (9)
C160.1475 (4)0.5261 (3)0.2993 (2)0.0418 (8)
C170.0221 (4)0.5567 (3)0.3415 (2)0.0548 (11)
H170.04750.60060.38730.066*
C180.1412 (5)0.5220 (4)0.3155 (3)0.0674 (12)
H180.22500.54260.34400.081*
C190.1789 (5)0.4577 (4)0.2485 (3)0.0709 (13)
H190.28840.43460.23110.085*
C200.0557 (6)0.4274 (4)0.2069 (3)0.0730 (13)
H200.08220.38330.16120.088*
C210.1079 (5)0.4610 (3)0.2314 (2)0.0594 (11)
H210.19050.43990.20240.071*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0374 (15)0.0425 (17)0.0380 (16)0.0070 (14)0.0082 (12)0.0007 (14)
O10.0765 (19)0.0623 (18)0.0420 (15)0.0096 (15)0.0103 (13)0.0145 (14)
O20.0512 (15)0.0449 (15)0.0555 (16)0.0120 (13)0.0138 (12)0.0067 (13)
O30.0498 (16)0.084 (2)0.0578 (17)0.0057 (14)0.0247 (13)0.0184 (15)
C10.0352 (18)0.042 (2)0.0345 (18)0.0005 (16)0.0055 (14)0.0031 (16)
C20.0350 (18)0.048 (2)0.043 (2)0.0049 (16)0.0131 (15)0.0030 (17)
C30.055 (3)0.114 (4)0.050 (2)0.020 (3)0.022 (2)0.007 (2)
C40.043 (2)0.102 (4)0.075 (3)0.012 (2)0.026 (2)0.016 (3)
C50.038 (2)0.103 (4)0.076 (3)0.004 (2)0.011 (2)0.013 (3)
C60.054 (3)0.104 (4)0.047 (2)0.002 (3)0.0052 (19)0.015 (2)
C70.0389 (19)0.063 (3)0.043 (2)0.0021 (18)0.0137 (16)0.0008 (19)
C80.048 (2)0.060 (3)0.042 (2)0.0055 (19)0.0191 (17)0.0104 (19)
C90.042 (2)0.053 (2)0.041 (2)0.0024 (17)0.0180 (16)0.0046 (18)
C100.0336 (17)0.041 (2)0.0398 (19)0.0024 (16)0.0119 (14)0.0032 (17)
C110.039 (2)0.043 (2)0.062 (3)0.0039 (17)0.0101 (17)0.007 (2)
C120.045 (2)0.050 (2)0.068 (3)0.0012 (19)0.0238 (19)0.011 (2)
C130.0377 (19)0.049 (2)0.041 (2)0.0005 (17)0.0084 (15)0.0081 (18)
C140.0303 (17)0.040 (2)0.048 (2)0.0008 (16)0.0134 (15)0.0039 (17)
C150.044 (2)0.047 (2)0.039 (2)0.0005 (17)0.0102 (17)0.0019 (17)
C160.0396 (19)0.051 (2)0.0351 (19)0.0026 (17)0.0070 (15)0.0000 (17)
C170.043 (2)0.072 (3)0.049 (2)0.003 (2)0.0085 (17)0.014 (2)
C180.039 (2)0.100 (4)0.065 (3)0.011 (2)0.0138 (19)0.008 (3)
C190.050 (2)0.099 (4)0.060 (3)0.030 (3)0.001 (2)0.001 (3)
C200.075 (3)0.088 (4)0.051 (3)0.023 (3)0.001 (2)0.016 (2)
C210.064 (3)0.068 (3)0.047 (2)0.015 (2)0.0128 (19)0.009 (2)
Geometric parameters (Å, º) top
N1—C131.408 (4)C6—H6B0.9700
N1—C141.425 (4)C7—C81.584 (5)
N1—C151.444 (4)C7—H70.9800
O1—C131.203 (4)C8—C91.506 (5)
O2—C141.200 (4)C8—C121.519 (5)
O3—C151.194 (4)C8—H80.9800
C1—C111.500 (5)C9—C101.330 (4)
C1—C131.504 (5)C9—H90.9300
C1—C101.504 (4)C10—C141.462 (5)
C1—C21.571 (4)C11—C121.323 (5)
C2—C31.493 (5)C11—H110.9300
C2—C71.514 (5)C12—H120.9300
C2—H20.9800C15—C161.473 (5)
C3—C41.518 (6)C16—C211.380 (5)
C3—H3A0.9700C16—C171.387 (5)
C3—H3B0.9700C17—C181.389 (5)
C4—C51.516 (6)C17—H170.9300
C4—H4A0.9700C18—C191.361 (6)
C4—H4B0.9700C18—H180.9300
C5—C61.518 (6)C19—C201.366 (6)
C5—H5A0.9700C19—H190.9300
C5—H5B0.9700C20—C211.383 (5)
C6—C71.481 (5)C20—H200.9300
C6—H6A0.9700C21—H210.9300
C13—N1—C14113.0 (3)C9—C8—C12108.3 (3)
C13—N1—C15121.3 (3)C9—C8—C7109.1 (3)
C14—N1—C15125.0 (3)C12—C8—C7100.8 (3)
C11—C1—C13118.0 (3)C9—C8—H8112.7
C11—C1—C10108.2 (3)C12—C8—H8112.7
C13—C1—C10103.4 (3)C7—C8—H8112.7
C11—C1—C2109.4 (3)C10—C9—C8112.1 (3)
C13—C1—C2114.3 (3)C10—C9—H9123.9
C10—C1—C2102.0 (3)C8—C9—H9123.9
C3—C2—C7110.4 (3)C9—C10—C14134.1 (3)
C3—C2—C1124.6 (3)C9—C10—C1115.4 (3)
C7—C2—C1107.4 (3)C14—C10—C1110.3 (3)
C3—C2—H2104.1C12—C11—C1113.2 (3)
C7—C2—H2104.1C12—C11—H11123.4
C1—C2—H2104.1C1—C11—H11123.4
C2—C3—C4108.4 (3)C11—C12—C8114.5 (3)
C2—C3—H3A110.0C11—C12—H12122.8
C4—C3—H3A110.0C8—C12—H12122.8
C2—C3—H3B110.0O1—C13—N1124.0 (3)
C4—C3—H3B110.0O1—C13—C1127.9 (3)
H3A—C3—H3B108.4N1—C13—C1108.1 (3)
C5—C4—C3114.7 (3)O2—C14—N1123.9 (3)
C5—C4—H4A108.6O2—C14—C10130.9 (3)
C3—C4—H4A108.6N1—C14—C10105.1 (3)
C5—C4—H4B108.6O3—C15—N1118.4 (3)
C3—C4—H4B108.6O3—C15—C16123.8 (3)
H4A—C4—H4B107.6N1—C15—C16117.7 (3)
C4—C5—C6113.8 (3)C21—C16—C17119.3 (3)
C4—C5—H5A108.8C21—C16—C15117.9 (3)
C6—C5—H5A108.8C17—C16—C15122.8 (3)
C4—C5—H5B108.8C16—C17—C18120.1 (4)
C6—C5—H5B108.8C16—C17—H17119.9
H5A—C5—H5B107.7C18—C17—H17119.9
C7—C6—C5109.1 (4)C19—C18—C17120.2 (4)
C7—C6—H6A109.9C19—C18—H18119.9
C5—C6—H6A109.9C17—C18—H18119.9
C7—C6—H6B109.9C18—C19—C20119.8 (4)
C5—C6—H6B109.9C18—C19—H19120.1
H6A—C6—H6B108.3C20—C19—H19120.1
C6—C7—C2110.8 (3)C19—C20—C21121.1 (4)
C6—C7—C8122.4 (3)C19—C20—H20119.4
C2—C7—C8109.0 (3)C21—C20—H20119.4
C6—C7—H7104.3C16—C21—C20119.5 (4)
C2—C7—H7104.3C16—C21—H21120.3
C8—C7—H7104.3C20—C21—H21120.3
C11—C1—C2—C386.5 (4)C7—C8—C12—C1159.5 (4)
C13—C1—C2—C348.3 (5)C14—N1—C13—O1178.3 (3)
C10—C1—C2—C3159.1 (4)C15—N1—C13—O110.9 (5)
C11—C1—C2—C744.9 (4)C14—N1—C13—C10.9 (4)
C13—C1—C2—C7179.7 (3)C15—N1—C13—C1169.8 (3)
C10—C1—C2—C769.5 (3)C11—C1—C13—O157.3 (5)
C7—C2—C3—C458.4 (5)C10—C1—C13—O1176.6 (4)
C1—C2—C3—C4171.5 (3)C2—C1—C13—O173.4 (5)
C2—C3—C4—C549.9 (5)C11—C1—C13—N1121.9 (3)
C3—C4—C5—C646.7 (6)C10—C1—C13—N12.6 (3)
C4—C5—C6—C749.5 (5)C2—C1—C13—N1107.4 (3)
C5—C6—C7—C258.7 (5)C13—N1—C14—O2178.3 (3)
C5—C6—C7—C8170.5 (4)C15—N1—C14—O27.9 (5)
C3—C2—C7—C665.8 (4)C13—N1—C14—C101.3 (3)
C1—C2—C7—C6155.5 (3)C15—N1—C14—C10171.6 (3)
C3—C2—C7—C8156.7 (3)C9—C10—C14—O21.5 (6)
C1—C2—C7—C818.0 (4)C1—C10—C14—O2176.6 (3)
C6—C7—C8—C987.4 (4)C9—C10—C14—N1178.0 (4)
C2—C7—C8—C944.1 (4)C1—C10—C14—N12.9 (3)
C6—C7—C8—C12158.8 (4)C13—N1—C15—O351.8 (5)
C2—C7—C8—C1269.7 (4)C14—N1—C15—O3117.8 (4)
C12—C8—C9—C1050.0 (4)C13—N1—C15—C16125.1 (3)
C7—C8—C9—C1058.8 (4)C14—N1—C15—C1665.3 (4)
C8—C9—C10—C14178.1 (3)O3—C15—C16—C215.2 (6)
C8—C9—C10—C13.3 (4)N1—C15—C16—C21178.1 (3)
C11—C1—C10—C954.7 (4)O3—C15—C16—C17173.4 (4)
C13—C1—C10—C9179.5 (3)N1—C15—C16—C173.3 (5)
C2—C1—C10—C960.6 (4)C21—C16—C17—C180.0 (6)
C11—C1—C10—C14129.2 (3)C15—C16—C17—C18178.6 (4)
C13—C1—C10—C143.4 (3)C16—C17—C18—C190.0 (7)
C2—C1—C10—C14115.4 (3)C17—C18—C19—C200.1 (7)
C13—C1—C11—C12166.6 (3)C18—C19—C20—C210.2 (7)
C10—C1—C11—C1249.9 (4)C17—C16—C21—C200.1 (6)
C2—C1—C11—C1260.5 (4)C15—C16—C21—C20178.8 (4)
C1—C11—C12—C83.4 (4)C19—C20—C21—C160.2 (7)
C9—C8—C12—C1154.9 (4)

Experimental details

Crystal data
Chemical formulaC21H19NO3
Mr333.37
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)8.111 (3), 12.999 (7), 16.256 (5)
β (°) 100.76 (3)
V3)1683.8 (12)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.60 × 0.40 × 0.26
Data collection
DiffractometerNicolet P3 four-circle
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3882, 3882, 1880
Rint0.000
(sin θ/λ)max1)0.705
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.088, 0.192, 1.03
No. of reflections3882
No. of parameters226
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.32, 0.23

Computer programs: Nicolet P3 Software (Nicolet, 1980), Nicolet P3 Software, RDNIC (Howie, 1980), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 and PLATON (Spek, 2003).

Selected geometric parameters (Å, º) top
N1—C131.408 (4)C3—C41.518 (6)
N1—C141.425 (4)C4—C51.516 (6)
N1—C151.444 (4)C5—C61.518 (6)
O1—C131.203 (4)C6—C71.481 (5)
O2—C141.200 (4)C7—C81.584 (5)
O3—C151.194 (4)C8—C91.506 (5)
C1—C111.500 (5)C8—C121.519 (5)
C1—C131.504 (5)C9—C101.330 (4)
C1—C101.504 (4)C10—C141.462 (5)
C1—C21.571 (4)C11—C121.323 (5)
C2—C31.493 (5)C15—C161.473 (5)
C2—C71.514 (5)
C13—N1—C14113.0 (3)C9—C8—C12108.3 (3)
C13—N1—C15121.3 (3)C9—C8—C7109.1 (3)
C14—N1—C15125.0 (3)C12—C8—C7100.8 (3)
C11—C1—C13118.0 (3)C10—C9—C8112.1 (3)
C11—C1—C10108.2 (3)C9—C10—C14134.1 (3)
C13—C1—C10103.4 (3)C9—C10—C1115.4 (3)
C11—C1—C2109.4 (3)C14—C10—C1110.3 (3)
C13—C1—C2114.3 (3)C12—C11—C1113.2 (3)
C10—C1—C2102.0 (3)C11—C12—C8114.5 (3)
C3—C2—C7110.4 (3)O1—C13—N1124.0 (3)
C3—C2—C1124.6 (3)O1—C13—C1127.9 (3)
C7—C2—C1107.4 (3)N1—C13—C1108.1 (3)
C2—C3—C4108.4 (3)O2—C14—N1123.9 (3)
C5—C4—C3114.7 (3)O2—C14—C10130.9 (3)
C4—C5—C6113.8 (3)N1—C14—C10105.1 (3)
C7—C6—C5109.1 (4)O3—C15—N1118.4 (3)
C6—C7—C2110.8 (3)O3—C15—C16123.8 (3)
C6—C7—C8122.4 (3)N1—C15—C16117.7 (3)
C2—C7—C8109.0 (3)
C11—C1—C2—C386.5 (4)C6—C7—C8—C12158.8 (4)
C13—C1—C2—C348.3 (5)C2—C7—C8—C1269.7 (4)
C10—C1—C2—C3159.1 (4)C12—C8—C9—C1050.0 (4)
C11—C1—C2—C744.9 (4)C7—C8—C9—C1058.8 (4)
C13—C1—C2—C7179.7 (3)C8—C9—C10—C14178.1 (3)
C10—C1—C2—C769.5 (3)C8—C9—C10—C13.3 (4)
C7—C2—C3—C458.4 (5)C11—C1—C10—C954.7 (4)
C1—C2—C3—C4171.5 (3)C13—C1—C10—C9179.5 (3)
C2—C3—C4—C549.9 (5)C2—C1—C10—C960.6 (4)
C3—C4—C5—C646.7 (6)C11—C1—C10—C14129.2 (3)
C4—C5—C6—C749.5 (5)C13—C1—C10—C143.4 (3)
C5—C6—C7—C258.7 (5)C2—C1—C10—C14115.4 (3)
C5—C6—C7—C8170.5 (4)C13—C1—C11—C12166.6 (3)
C3—C2—C7—C665.8 (4)C10—C1—C11—C1249.9 (4)
C1—C2—C7—C6155.5 (3)C2—C1—C11—C1260.5 (4)
C3—C2—C7—C8156.7 (3)C1—C11—C12—C83.4 (4)
C1—C2—C7—C818.0 (4)C9—C8—C12—C1154.9 (4)
C6—C7—C8—C987.4 (4)C7—C8—C12—C1159.5 (4)
C2—C7—C8—C944.1 (4)
Table 2. Geometry (Å, °) of C—H..π contacts in (I). top
C-H..CgaC—HH..CgHperpbγcC-H..CgC..Cg
C6-H6A-Cg1i0.972.802.69161493.68
C6-H6B-Cg1ii0.973.032.93151353.79
C4-H4B-Cg2iii0.973.343.28111203.92
Notes: (a) Cg1 and Cg2 are the centroids of the rings defined by C16-C21 and C1/C10/C13-C14/N1, respectively; (b) Hperp is the perpendicular distance of the H atom from the mean plane of the ring; (c) γ is the angle at hydrogen between Hperp and H..Cg. Symmetry codes (i) 1-x,1-y,1-z; (ii) 1+x,3/2-y,1/2+z; (iii) 1+x,y,z.
 

Acknowledgements

NM thanks Dublin City University for a studentship.

References

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