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In the isomeric compounds 2-benzyl-3-methyl-1-phenyl­benzo­[b]­furo­[2,3-c]­pyrrole and 2-benzyl-1-methyl-3-phenyl­benzo­[b]­furo­[2,3-c]­pyrrole, both C24H19NO, the pyrrole ring, although presumably somewhat strained, does not differ appreciably from N-methyl­pyrrole except for a relatively short C-C single bond in the pyrrole ring.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199016492/fr1233sup1.cif
Contains datablocks Global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199016492/fr1233Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199016492/fr1233IIsup3.hkl
Contains datablock II

CCDC references: 143272; 143273

Comment top

Fused heterocycles such as the title compounds, 2-benzyl-3-methyl-1-phenylbenzo[b]furo[2,3-c]pyrrole, (I), and 2-benzyl-1-methyl-3-phenylbenzo[b]furo[2,3-c]pyrrole, (II), are of great importance in the construction of more complex molecules, for example, by cycloaddition chemistry. In connection with our recent studies of these fused heterocycles, obtained by the reaction of mesoionic münchnones (1,3-oxazolium-5-olates) with 2-nitrobenzo[b]furan (Gribble et al., 1998), we needed to differentiate the two isomeric compounds, (I) and (II). The crystal structure determinations reported in the present paper support our isomer assignments reached using NMR techniques (Gribble et al., 1999). The only previous example of the benzo[b]furo[2,3-c]pyrrole ring system was reported by Sha et al. (1995), but a crystal structure was not described. \scheme

The tricyclic fused benzofuropyrrole ring system in both (I) and (II) is planar, as expected. The C1 phenyl ring in (I) is twisted 37.3 (2)°? out of planarity, while the corresponding C3 phenyl ring in (II) is twisted by 33.7 (1)°?, consistent with the greater interaction of the C1 phenyl in (I) with H8. The N-benzyl phenyl rings in (I) and (II) are twisted 85.5 (1)? and 82.5 (1)°? out of the plane of the benzofuropyrrole ring system, respectively. This is anticipated, since π-conjugation between these aromatic systems is not possible.

The unequal pyrrole C=C double bonds in (I) [C1—C8b 1.385 (6) Å and C3—C3a 1.353 (5) Å] and (II) [C1—C8b 1.385 (4) Å and C3—C3a 1.366 (4) Å] presumably reflect differing degrees of π-conjugation. For example, the larger C3—C3a bond length in (II) may be a consequence of π-conjugation in the benzofuran. Steric interaction on the C1—C8b bond, due to the phenyl ring in (I) or the methyl group in (II), appears minimal as the bond lengths are nearly identical [1.385 (6) in (I), 1.385 (4) Å in (II)]. By comparison, N-methylpyrrole itself has a C=C double bond length of 1.35 Å and a C3—C4 bond length of 1.43 Å (electron diffraction; Vilkov et al., 1962). On the other hand, N-benzylisoindole, which is a delocalized system like naphthalene, has an average pyrrole ring C=C double bond length of 1.384 Å (Bonnett et al., 1985).

That pyrrole ring distortion is present in both (I) and (II) is evident from several bond angles. Thus, in (I) and (II) the C1—C8b—C8a bond angles are 147.2 (3)° and 147.7 (3)°, respectively, while the C3—C3a—O4 bond angles are 135.1 (4)° and 135.1 (3)°, respectively. The comparable bond angle in pyrrole itself (C2—C3—H3) is 126° (Vilkov et al., 1962). Likewise, as a consequence of the two fused five-membered rings, the central C3a—C8b bond is very short for a C—C single bond in (I) and (II), at 1.394 (5) and 1.398 (4) Å, respectively. In N-methylpyrrole, the C3—C4 bond length is 1.43 Å (Vilkov et al., 1962), and this single bond length in N-benzylisoindole is 1.429 Å (Bonnett et al., 1985). The C1—N2 and N2—C3 bond lengths in (I) and (II) are 1.389 (4) and 1.403 (6) Å, respectively, for (I) and 1.384 (3) and 1.408 (4) Å, respectively, for (II). These compare with the corresponding bond lengths in N-methylpyrrole (1.40 Å; Vilkov et al., 1962) and N-benzylisoindole (1.362 Å; Bonnett et al., 1985). The mean deviation of the pyrrole nitrogen N2 from the plane of its nearest three neighbours, C1, C3 and C9, is -0.0095 Å in (I) and -0.0056 Å in (II). The internal bond angles in the pyrrole rings of (I) and (II) are quite similar to those found in N-benzylisoindole. For example, the C1—N2—C3 bond angles in (I) and (II) are 111.8 (3) and 111.6 (2)°, respectively. In N-benzylisoindole this angle is 111° (Bonnett et al., 1985). Likewise, the other internal pyrrole ring bond angles in (I) and (II) do not deviate much from those reported for N-benzylpyrrole. The least squares planes mean deviation for the benzofuropyrrole ring is 0.0134 in (I) and 0.0086 Å in (II).

In summary, the pyrrole rings in (I) and (II), which compounds are reactive as dienes in Diels-Alder reactions, although somewhat strained due to being fused to another five-membered ring, do not differ appreciably from that in N-methylpyrrole, except for a relatively short C—C single bond (C3a—C8b) in the pyrrole ring.

Experimental top

Compound (I) was prepared by our general method from 2-nitrobenzo[b]furan and N-benzyl-N-benzoylalanine (Gribble et al., 1998), and recrystallized from acetone-petroleum ether to give rhomboidal crystals (m.p. 389–391 K). Compound (II) was prepared similarly, from 2-nitrobenzo[b]furan and N-acetyl-N-benzyl-α-phenylglycine, and recrystallized from acetone-hexanes to give rhomboidal crystals (m.p. 426–427 K). The full synthetic details will be described separately (Gribble et al., 1999).

Computing details top

For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1994); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR97 (Altomare et al., 1997) and DIRDIF94 (Beurskens et al., 1994); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); software used to prepare material for publication: TEXSAN for Windows.

Figures top
[Figure 1] Fig. 1. An ORTEP (Johnson, 1965) diagram of (I) showing 30% probability displacement ellipsoids. H atoms are drawn as spheres of arbitrary radii.
[Figure 2] Fig. 2. An ORTEP (Johnson, 1965) diagram of (II) showing 30% probability displacement ellipsoids. H atoms are drawn as spheres of arbitrary radii.
(I) top
Crystal data top
C24H19NOZ = 2
Mr = 337.42F(000) = 356.00
Triclinic, P1Dx = 1.263 Mg m3
a = 10.405 (2) ÅMo Kα radiation, λ = 0.7107 Å
b = 11.524 (2) ÅCell parameters from 20 reflections
c = 9.177 (2) Åθ = 6.3–9.3°
α = 113.44 (1)°µ = 0.08 mm1
β = 113.94 (2)°T = 296 K
γ = 93.94 (2)°Prism, light orange
V = 887.4 (4) Å30.4 × 0.3 × 0.2 mm
Data collection top
Rigaku AFC-6S
diffractometer
Rint = 0.020
Radiation source: X-ray tubeθmax = 27.5°, θmin = 2.0°
Graphite monochromatorh = 013
ω/2θ scansk = 1414
4289 measured reflectionsl = 1110
4067 independent reflections3 standard reflections every 150 reflections
1420 reflections with I > 3σ(I) intensity decay: 0.6%
Refinement top
Refinement on F0 constraints
Least-squares matrix: fullH-atom parameters not refined
R[F2 > 2σ(F2)] = 0.049Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.00002|Fo|2]
wR(F2) = 0.225(Δ/σ)max = 0.050
S = 1.03Δρmax = 0.26 e Å3
4067 reflectionsΔρmin = 0.22 e Å3
236 parametersExtinction correction: Zachariasen (1967), equ (3) [Zachariasen, W. H. (1968). Acta Cryst. A24, p213.]
0 restraintsExtinction coefficient: 9.7 (7) × 10-7
Crystal data top
C24H19NOγ = 93.94 (2)°
Mr = 337.42V = 887.4 (4) Å3
Triclinic, P1Z = 2
a = 10.405 (2) ÅMo Kα radiation
b = 11.524 (2) ŵ = 0.08 mm1
c = 9.177 (2) ÅT = 296 K
α = 113.44 (1)°0.4 × 0.3 × 0.2 mm
β = 113.94 (2)°
Data collection top
Rigaku AFC-6S
diffractometer
Rint = 0.020
4289 measured reflections3 standard reflections every 150 reflections
4067 independent reflections intensity decay: 0.6%
1420 reflections with I > 3σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0490 restraints
wR(F2) = 0.225H-atom parameters not refined
S = 1.03Δρmax = 0.26 e Å3
4067 reflectionsΔρmin = 0.22 e Å3
236 parameters
Special details top

Experimental. The scan width was (1.37 + 0.34tanθ)° with an ω scan speed of 8° per minute [up to 5 scans to achieve I/σ(I) > 10]. Stationary background counts were recorded at each end of the scan, and the scan time to background time ratio was 2:1.

Refinement. The final cycle of full-matrix least-squares refinement (SHELXL93: Σw(Fo2-Fc2)2, where w = 1/[Σ2(Fo2) + (0.1P)2] and P = [Max(Fo2,0) + 2Fc2)/3], was based on 1420 (I) or 1789 (II) observed reflections and 236 (I) or 236 (II) variable parameters and converged [largest parameter shift was 0.07 (I) or 0.00 (II) times its esd] with unweighted and weighted agreement factors of: R1 = Σ||Fo| - |Fc||/Σ|Fo| = 0.049 (I), 0.045 (II); wR2 = [Σ(w(Fo2-Fc2)2)/Σw(Fo2)2]1/2 = 0.225(I), 0.197(II). The standard deviation of an observation of unit weight ([Σw(Fo2-Fc2)2/(No-Nv)]1/2, where No = number of observations and Nv = number of variables) was 1.03 (I) or 1.04 (II). The weighting scheme was based on counting statistics and included a factor [p = 0.010 (I) or 0.002 (II)] to downweight the intense reflections. The maximum and minimum peaks on the final difference Fourier map corresponded to 0.25 (I) and 0.24 (II), and -0.22 (I) and -0.23 (II) eÅ-3, respectively. Neutral atom scattering factors were taken from Cromer & Waber (1974). Anomalous dispersion effects were included in Fcalc (Ibers & Hamilton, 1964); the values for δf' and δf'' were those of Creagh & McAuley (1992). The values for the mass attenuation coefficients are those of Creagh & Hubbell (1992).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O40.0965 (3)0.4103 (2)0.1737 (3)0.0596 (8)
N20.1967 (3)0.3342 (3)0.0792 (4)0.0499 (9)
C10.0798 (4)0.2939 (3)0.0904 (4)0.046 (1)
C30.1564 (4)0.3864 (3)0.2157 (5)0.051 (1)
C3a0.0129 (4)0.3771 (3)0.1250 (5)0.051 (1)
C4a0.2179 (4)0.3747 (3)0.0099 (5)0.051 (1)
C50.3543 (4)0.3918 (3)0.0061 (5)0.062 (1)
C60.4664 (4)0.3478 (3)0.1790 (5)0.062 (1)
C70.4432 (4)0.2892 (3)0.3274 (5)0.063 (1)
C80.3069 (4)0.2760 (3)0.3095 (4)0.057 (1)
C8a0.1927 (4)0.3195 (3)0.1390 (5)0.046 (1)
C8b0.0370 (4)0.3225 (3)0.0602 (4)0.0465 (9)
C90.3442 (3)0.3236 (3)0.1190 (4)0.053 (1)
C100.2573 (4)0.4413 (3)0.4098 (4)0.071 (1)
C110.0865 (3)0.2385 (3)0.2605 (4)0.050 (1)
C120.0029 (4)0.2732 (3)0.3927 (5)0.060 (1)
C130.0020 (4)0.2199 (4)0.5598 (5)0.076 (1)
C140.0782 (5)0.1327 (4)0.5983 (5)0.081 (2)
C150.1622 (4)0.0969 (4)0.4709 (6)0.074 (1)
C160.1652 (4)0.1479 (3)0.3046 (5)0.060 (1)
C170.3734 (4)0.2031 (3)0.1426 (4)0.048 (1)
C180.5136 (4)0.1897 (3)0.1981 (4)0.058 (1)
C190.5445 (4)0.0806 (4)0.2209 (5)0.074 (1)
C200.4352 (5)0.0133 (4)0.1898 (6)0.085 (2)
C210.2959 (5)0.0016 (4)0.1334 (5)0.081 (1)
C220.2628 (4)0.1063 (3)0.1088 (5)0.067 (1)
H3A0.21850.41930.47870.090*
H3B0.35060.41690.44030.090*
H3C0.29180.54010.47670.090*
H50.37330.43360.10210.084*
H60.56390.35770.19790.077*
H70.52850.25430.45070.085*
H80.29250.23480.42130.077*
H9A0.36830.32500.02580.074*
H9B0.41960.40360.23070.074*
H100.16400.11140.06810.082*
H120.05780.33550.36650.081*
H140.07680.09790.71940.100*
H130.06730.24410.65550.092*
H150.22330.03480.49600.094*
H160.22940.12330.21210.076*
H180.59560.25860.22210.071*
H190.64790.07240.26080.097*
H200.46050.08960.20920.104*
H210.22010.07240.10960.092*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O40.070 (2)0.055 (2)0.054 (2)0.020 (1)0.031 (1)0.023 (1)
N20.043 (2)0.047 (2)0.053 (2)0.009 (2)0.014 (1)0.027 (2)
C10.049 (2)0.037 (2)0.052 (2)0.009 (2)0.021 (1)0.024 (2)
C30.055 (2)0.043 (2)0.053 (2)0.014 (2)0.022 (1)0.025 (2)
C30.058 (2)0.043 (2)0.054 (2)0.017 (2)0.029 (2)0.023 (2)
C40.059 (2)0.039 (2)0.060 (2)0.016 (2)0.028 (2)0.028 (2)
C50.074 (2)0.048 (2)0.087 (2)0.025 (2)0.053 (2)0.035 (2)
C60.054 (2)0.056 (3)0.093 (2)0.023 (2)0.040 (2)0.043 (2)
C70.054 (2)0.061 (3)0.082 (3)0.021 (2)0.029 (2)0.043 (2)
C80.056 (2)0.059 (2)0.058 (2)0.017 (2)0.024 (2)0.033 (2)
C8a0.049 (2)0.036 (2)0.052 (2)0.011 (2)0.020 (1)0.023 (2)
C8b0.045 (2)0.040 (2)0.055 (2)0.012 (2)0.021 (2)0.026 (2)
C90.041 (2)0.047 (2)0.064 (3)0.011 (2)0.017 (2)0.030 (2)
C100.079 (3)0.062 (3)0.056 (2)0.015 (2)0.019 (2)0.027 (2)
C110.044 (2)0.044 (2)0.059 (2)0.008 (2)0.019 (2)0.027 (2)
C120.065 (3)0.055 (3)0.063 (2)0.015 (2)0.027 (2)0.034 (2)
C130.084 (3)0.085 (3)0.063 (2)0.011 (2)0.029 (2)0.045 (3)
C140.087 (4)0.087 (4)0.070 (3)0.011 (2)0.051 (3)0.027 (3)
C150.066 (3)0.073 (3)0.080 (3)0.011 (2)0.042 (3)0.027 (2)
C160.056 (2)0.056 (2)0.066 (2)0.011 (2)0.029 (2)0.027 (2)
C170.052 (2)0.044 (2)0.046 (2)0.015 (2)0.020 (2)0.023 (2)
C180.062 (2)0.051 (2)0.053 (2)0.020 (2)0.022 (2)0.023 (2)
C190.081 (3)0.073 (3)0.070 (3)0.044 (2)0.030 (3)0.034 (3)
C200.134 (3)0.063 (3)0.078 (3)0.052 (3)0.053 (3)0.043 (3)
C210.112 (3)0.057 (3)0.093 (3)0.025 (2)0.056 (3)0.045 (2)
C220.072 (2)0.054 (3)0.086 (3)0.018 (2)0.039 (2)0.042 (2)
Geometric parameters (Å, º) top
O4—C3a1.407 (5)C10—H3B0.99
O4—C4a1.386 (4)C10—H3C1.00
N2—C11.389 (4)C11—C121.402 (6)
N2—C31.403 (6)C11—C161.406 (5)
N2—C91.453 (5)C12—C131.384 (6)
C1—C8b1.385 (6)C12—H121.01
C1—C111.466 (6)C13—C141.379 (7)
C3—C3a1.353 (5)C13—H131.02
C3—C101.474 (5)C14—C151.381 (7)
C3a—C8b1.394 (5)C14—H141.01
C4a—C51.402 (6)C15—C161.386 (7)
C4a—C8a1.401 (6)C15—H151.01
C5—C61.383 (5)C16—H161.00
C5—H51.03C17—C181.379 (5)
C6—C71.389 (7)C17—C221.387 (6)
C6—H60.98C18—C191.392 (6)
C7—C81.386 (6)C18—H181.01
C7—H71.00C19—C201.367 (7)
C8—C8a1.377 (4)C19—H191.01
C8—H81.02C20—C211.364 (7)
C8a—C8b1.473 (5)C20—H201.00
C9—C171.520 (6)C21—C221.392 (6)
C9—H9A0.99C21—H210.98
C9—H9B1.01C22—H100.96
C10—H3A0.97
O4···C12i3.222 (4)C15···C16iii3.489 (5)
C8···C19ii3.526 (5)C19···C19iv3.388 (8)
C14···C16iii3.524 (6)
C3a—O4—C4a103.2 (3)C3—C10—H3B115.4
C1—N2—C3111.8 (3)C3—C10—H3C114.4
C1—N2—C9126.4 (3)H3A—C10—H3B104.3
C3—N2—C9121.7 (3)H3A—C10—H3C103.2
N2—C1—C8b105.3 (3)H3B—C10—H3C102.1
N2—C1—C11125.4 (3)C1—C11—C12117.9 (3)
C8b—C1—C11129.3 (3)C1—C11—C16124.8 (4)
N2—C3—C3a103.6 (3)C12—C11—C16117.3 (4)
N2—C3—C10124.6 (3)C11—C12—C13121.2 (4)
C3a—C3—C10131.7 (4)C11—C12—H12119.0
O4—C3a—C3135.1 (4)C13—C12—H12119.7
O4—C3a—C8b113.0 (3)C12—C13—C14120.2 (4)
C3—C3a—C8b111.9 (4)C12—C13—H13119.4
O4—C4a—C5123.2 (4)C14—C13—H13120.3
O4—C4a—C8a114.1 (3)C13—C14—C15120.1 (5)
C5—C4a—C8a122.7 (3)C13—C14—H14119.0
C4a—C5—C6116.6 (4)C15—C14—H14120.8
C4a—C5—H5123.3C14—C15—C16120.0 (4)
C6—C5—H5120.0C14—C15—H15121.0
C5—C6—C7120.9 (4)C16—C15—H15119.1
C5—C6—H6120.0C11—C16—C15121.2 (4)
C7—C6—H6119.2C11—C16—H16119.7
C6—C7—C8122.0 (3)C15—C16—H16119.0
C6—C7—H7118.4C9—C17—C18118.9 (3)
C8—C7—H7119.6C9—C17—C22121.8 (3)
C7—C8—C8a118.5 (4)C18—C17—C22119.3 (4)
C7—C8—H8120.2C17—C18—C19120.5 (4)
C8a—C8—H8121.3C17—C18—H18120.6
C4a—C8a—C8119.2 (4)C19—C18—H18118.9
C4a—C8a—C8b104.2 (3)C18—C19—C20119.7 (4)
C8—C8a—C8b136.5 (4)C18—C19—H19119.2
C1—C8b—C3a107.3 (3)C20—C19—H19121.1
C1—C8b—C8a147.2 (3)C19—C20—C21120.3 (5)
C3a—C8b—C8a105.5 (4)C19—C20—H20118.1
N2—C9—C17114.0 (3)C21—C20—H20121.6
N2—C9—H9A111.3C20—C21—C22120.8 (4)
N2—C9—H9B111.5C20—C21—H21117.7
C17—C9—H9A109.4C22—C21—H21121.5
C17—C9—H9B108.0C17—C22—C21119.3 (4)
H9A—C9—H9B102.0C17—C22—H10121.7
C3—C10—H3A115.6C21—C22—H10118.9
O4—C3a—C3—N2179.7 (4)C3a—C8b—C8a—C8177.6 (5)
O4—C3a—C3—C102.2 (8)C4a—O4—C3a—C8b0.3 (4)
O4—C3a—C8b—C1179.8 (3)C4a—C5—C6—C70.4 (6)
O4—C3a—C8b—C8a0.2 (4)C4a—C8a—C8—C70.4 (6)
O4—C4a—C5—C6178.1 (4)C5—C4a—C8a—C82.1 (6)
O4—C4a—C8a—C8177.7 (3)C5—C4a—C8a—C8b179.2 (4)
O4—C4a—C8a—C8b1.0 (4)C5—C6—C7—C82.1 (7)
N2—C1—C8b—C3a0.7 (4)C6—C5—C4a—C8a1.8 (6)
N2—C1—C8b—C8a180.0 (6)C6—C7—C8—C8a1.7 (6)
N2—C1—C11—C12142.6 (4)C7—C8—C8a—C8b178.5 (4)
N2—C1—C11—C1640.6 (6)C8a—C8b—C1—C112.4 (9)
N2—C3—C3a—C8b0.3 (4)C8b—C1—N2—C9179.2 (3)
N2—C9—C17—C18173.7 (3)C8b—C1—C11—C1234.6 (6)
N2—C9—C17—C226.7 (5)C8b—C1—C11—C16142.2 (4)
C1—N2—C3—C3a0.1 (4)C8b—C3a—C3—C10177.2 (4)
C1—N2—C3—C10177.9 (4)C9—N2—C1—C113.0 (6)
C1—N2—C9—C1796.7 (5)C9—N2—C3—C103.4 (6)
C1—C8b—C3a—C30.7 (5)C9—C17—C18—C19179.9 (3)
C1—C8b—C8a—C4a180.0 (6)C9—C17—C22—C21179.7 (4)
C1—C8b—C8a—C82 (1)C11—C12—C13—C141.1 (6)
C1—C11—C12—C13176.9 (3)C11—C16—C15—C141.5 (6)
C1—C11—C16—C15177.9 (3)C12—C11—C16—C151.2 (5)
C3—N2—C1—C8b0.5 (4)C12—C13—C14—C150.8 (7)
C3—N2—C1—C11178.3 (4)C13—C12—C11—C160.2 (5)
C3—N2—C9—C1781.9 (4)C13—C14—C15—C160.5 (6)
C3—C3a—O4—C4a179.0 (5)C17—C18—C19—C200.7 (6)
C3—C3a—C8b—C8a179.7 (3)C17—C22—C21—C200.1 (7)
C3a—O4—C4a—C5179.3 (4)C18—C17—C22—C210.7 (6)
C3a—O4—C4a—C8a0.8 (4)C18—C19—C20—C211.2 (7)
C3a—C3—N2—C9178.9 (3)C19—C18—C17—C220.3 (6)
C3a—C8b—C1—C11178.3 (4)C19—C20—C21—C220.8 (7)
C3a—C8b—C8a—C4a0.7 (4)
Symmetry codes: (i) x, y+1, z; (ii) x1, y, z1; (iii) x, y, z1; (iv) x+1, y, z.
(II) top
Crystal data top
C24H19NOZ = 2
Mr = 337.42F(000) = 356.00
Triclinic, P1Dx = 1.287 Mg m3
a = 9.956 (1) ÅMo Kα radiation, λ = 0.7107 Å
b = 11.329 (2) ÅCell parameters from 24 reflections
c = 8.939 (2) Åθ = 10.6–17.1°
α = 109.89 (1)°µ = 0.08 mm1
β = 107.06 (1)°T = 296 K
γ = 69.47 (1)°Prism, light brown
V = 870.3 (3) Å30.4 × 0.4 × 0.3 mm
Data collection top
Rigaku AFC-6S
diffractometer
1789 reflections with I > 3σ(I)
Radiation source: X-ray tubeRint = 0.018
Graphite monochromatorθmax = 27.5°, θmin = 2.0°
ω/2θ scansh = 012
Absorption correction: ψ scan
(North et al., 1968)
k = 1314
Tmin = 0.987, Tmax = 1.000l = 1111
4223 measured reflections3 standard reflections every 150 reflections
3991 independent reflections intensity decay: 1.4%
Refinement top
Refinement on F0 constraints
Least-squares matrix: fullH-atom parameters not refined
R[F2 > 2σ(F2)] = 0.045Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo)]
wR(F2) = 0.197(Δ/σ)max = 0.050
S = 1.04Δρmax = 0.24 e Å3
3991 reflectionsΔρmin = 0.23 e Å3
236 parametersExtinction correction: Zachariasen (1967), equ (3) [Zachariasen, W. H. (1968). Acta Cryst. A24, p213.]
0 restraintsExtinction coefficient: 2.06 (7) × 10-6
Crystal data top
C24H19NOγ = 69.47 (1)°
Mr = 337.42V = 870.3 (3) Å3
Triclinic, P1Z = 2
a = 9.956 (1) ÅMo Kα radiation
b = 11.329 (2) ŵ = 0.08 mm1
c = 8.939 (2) ÅT = 296 K
α = 109.89 (1)°0.4 × 0.4 × 0.3 mm
β = 107.06 (1)°
Data collection top
Rigaku AFC-6S
diffractometer
1789 reflections with I > 3σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.018
Tmin = 0.987, Tmax = 1.0003 standard reflections every 150 reflections
4223 measured reflections intensity decay: 1.4%
3991 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.197H-atom parameters not refined
S = 1.04Δρmax = 0.24 e Å3
3991 reflectionsΔρmin = 0.23 e Å3
236 parameters
Special details top

Experimental. The scan width was (1.68 + 0.34tanθ)° with an ω scan speed of 8° per minute [up to 5 scans to achieve I/σ(I) > 10]. Stationary background counts were recorded at each end of the scan, and the scan time:background time ratio was 2:1.

Refinement. The final cycle of full-matrix least-squares refinement (SHELXL93: Σw(Fo2-Fc2)2, where w = 1/[Σ2(Fo2) + (0.1P)2] and P = [Max(Fo2,0) + 2Fc2)/3], was based on 1420 (I) or 1789 (II) observed reflections and 236 (I) or 236 (II) variable parameters and converged [largest parameter shift was 0.07 (I) or 0.00 (II) times its esd] with unweighted and weighted agreement factors of: R1 = Σ||Fo| - |Fc||/Σ|Fo| = 0.049 (I), 0.045 (II); wR2 = [Σ(w(Fo2-Fc2)2)/Σw(Fo2)2]1/2 = 0.225(I), 0.197(II). The standard deviation of an observation of unit weight ([Σw(Fo2-Fc2)2/(No-Nv)]1/2, where No = number of observations and Nv = number of variables) was 1.03 (I) or 1.04 (II). The weighting scheme was based on counting statistics and included a factor [p = 0.010 (I) or 0.002 (II)] to downweight the intense reflections. The maximum and minimum peaks on the final difference Fourier map corresponded to 0.25 (I) and 0.24 (II), and -0.22 (I) and -0.23 (II) eÅ-3, respectively. Neutral atom scattering factors were taken from Cromer & Waber (1974). Anomalous dispersion effects were included in Fcalc (Ibers & Hamilton, 1964); the values for δf' and δf'' were those of Creagh & McAuley (1992). The values for the mass attenuation coefficients are those of Creagh & Hubbell (1992).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O40.6976 (2)0.2718 (2)0.9049 (2)0.0479 (7)
N20.3141 (2)0.3291 (2)0.8599 (3)0.0423 (8)
C10.3604 (3)0.3780 (2)1.0247 (3)0.045 (1)
C30.4312 (3)0.2770 (2)0.7770 (3)0.0407 (9)
C3a0.5486 (3)0.2980 (2)0.8976 (3)0.0422 (9)
C4a0.7531 (3)0.3177 (3)1.0691 (3)0.045 (1)
C50.9000 (3)0.3083 (3)1.1313 (4)0.051 (1)
C60.9387 (3)0.3589 (3)1.2978 (4)0.056 (1)
C70.8335 (3)0.4155 (3)1.3947 (3)0.058 (1)
C80.6875 (3)0.4226 (3)1.3300 (3)0.053 (1)
C8a0.6448 (3)0.3725 (2)1.1644 (3)0.0432 (9)
C8b0.5098 (3)0.3581 (2)1.0497 (3)0.0435 (9)
C90.1633 (3)0.3304 (3)0.7836 (3)0.0453 (9)
C100.2604 (3)0.4394 (3)1.1410 (3)0.060 (1)
C110.4257 (3)0.2202 (2)0.6021 (3)0.0407 (9)
C120.3354 (3)0.1421 (3)0.5005 (3)0.051 (1)
C130.3443 (3)0.0852 (3)0.3386 (4)0.060 (1)
C140.4452 (4)0.1024 (3)0.2756 (3)0.063 (1)
C150.5366 (3)0.1773 (3)0.3735 (4)0.061 (1)
C160.5265 (3)0.2369 (3)0.5351 (3)0.052 (1)
C170.1214 (3)0.2129 (2)0.7814 (3)0.0392 (9)
C180.2114 (3)0.1256 (3)0.8706 (3)0.054 (1)
C190.1681 (3)0.0206 (3)0.8663 (4)0.062 (1)
C200.0374 (4)0.0015 (3)0.7747 (4)0.064 (1)
C210.0524 (3)0.0876 (3)0.6851 (4)0.062 (1)
C220.0108 (3)0.1928 (3)0.6889 (3)0.051 (1)
H50.97860.26871.06420.066*
H61.04520.35391.34890.066*
H70.87160.45001.51260.070*
H80.62210.46081.40680.066*
H9A0.09350.41160.83560.052*
H9B0.14130.33740.67020.052*
H10A0.16360.41851.10010.068*
H10B0.29610.41851.24450.068*
H10C0.22820.53701.17020.068*
H120.25860.12770.54200.061*
H130.27670.03060.26640.068*
H140.44990.05950.16090.073*
H150.60820.19300.32790.068*
H160.59440.29090.60470.054*
H180.30440.13730.93290.058*
H190.22800.04090.93160.067*
H200.00460.07300.77180.065*
H210.14440.07300.61270.066*
H220.07760.25460.62160.053*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O40.041 (1)0.055 (1)0.048 (1)0.018 (1)0.010 (1)0.009 (1)
N20.040 (2)0.042 (2)0.048 (2)0.016 (1)0.009 (1)0.011 (1)
C10.049 (2)0.040 (2)0.051 (2)0.016 (2)0.017 (2)0.008 (2)
C30.041 (2)0.037 (2)0.048 (2)0.015 (1)0.009 (2)0.011 (1)
C3a0.040 (2)0.042 (2)0.048 (2)0.016 (1)0.012 (2)0.008 (1)
C4a0.054 (2)0.039 (2)0.043 (2)0.020 (2)0.005 (2)0.011 (1)
C50.048 (2)0.047 (2)0.063 (2)0.021 (2)0.006 (2)0.016 (2)
C60.055 (2)0.048 (2)0.065 (2)0.026 (2)0.010 (2)0.023 (2)
C70.075 (2)0.052 (2)0.048 (2)0.033 (2)0.005 (2)0.014 (2)
C80.072 (3)0.042 (2)0.050 (2)0.023 (2)0.012 (2)0.009 (2)
C8a0.052 (2)0.036 (2)0.045 (2)0.018 (2)0.007 (2)0.011 (1)
C8b0.050 (2)0.040 (2)0.045 (2)0.019 (1)0.012 (2)0.008 (1)
C90.039 (2)0.041 (2)0.059 (2)0.011 (1)0.007 (2)0.020 (2)
C100.061 (2)0.065 (2)0.059 (2)0.019 (2)0.027 (2)0.006 (2)
C110.044 (2)0.038 (2)0.043 (2)0.011 (1)0.008 (1)0.015 (1)
C120.052 (2)0.060 (2)0.046 (2)0.024 (2)0.009 (2)0.012 (2)
C130.057 (2)0.069 (2)0.049 (2)0.023 (2)0.002 (2)0.010 (2)
C140.073 (3)0.073 (2)0.041 (2)0.019 (2)0.009 (2)0.018 (2)
C150.074 (3)0.066 (2)0.058 (2)0.020 (2)0.024 (2)0.023 (2)
C160.059 (2)0.050 (2)0.055 (2)0.023 (2)0.014 (2)0.013 (2)
C170.038 (2)0.038 (2)0.044 (2)0.010 (1)0.013 (1)0.009 (1)
C180.047 (2)0.050 (2)0.067 (2)0.015 (2)0.003 (2)0.022 (2)
C190.072 (3)0.050 (2)0.073 (2)0.016 (2)0.010 (2)0.030 (2)
C200.079 (3)0.048 (2)0.078 (2)0.032 (2)0.023 (2)0.010 (2)
C210.056 (2)0.062 (2)0.073 (2)0.031 (2)0.006 (2)0.014 (2)
C220.043 (2)0.052 (2)0.057 (2)0.015 (2)0.004 (2)0.017 (2)
Geometric parameters (Å, º) top
O4—C3a1.392 (4)C10—H10A0.97
O4—C4a1.392 (3)C10—H10B1.00
N2—C11.384 (3)C11—C121.396 (4)
N2—C31.408 (4)C11—C161.402 (5)
N2—C91.452 (3)C12—C131.384 (4)
C1—C8b1.385 (4)C12—H121.02
C1—C101.478 (4)C13—C141.381 (6)
C3a—C31.366 (4)C13—H131.01
C3a—C8b1.398 (4)C14—C151.372 (5)
C3—C111.467 (4)C14—H140.98
C4a—C51.384 (4)C15—C161.388 (4)
C4a—C8a1.407 (4)C15—H151.01
C5—C61.389 (4)C16—H161.00
C5—H51.01C17—C181.383 (4)
C6—C71.392 (5)C17—C221.383 (4)
C6—H61.01C18—C191.386 (5)
C7—C81.382 (5)C18—H180.96
C7—H71.00C19—C201.365 (4)
C8a—C81.387 (4)C19—H190.98
C8a—C8b1.454 (4)C20—C211.375 (4)
C8—H80.97C20—H201.00
C9—C171.521 (5)C21—C221.380 (5)
C9—H9A1.00C21—H210.99
C9—H9B1.00C22—H221.01
C10—H10C1.01
O4···C21i3.293 (4)C8b···C8bii3.544 (7)
C1···C4aii3.542 (4)C11···C13iii3.531 (4)
C3···C8ii3.553 (4)C12···C13iii3.597 (4)
C6···C9ii3.571 (5)C21···C21iv3.476 (6)
C3a—O4—C4a103.7 (2)C1—C10—H10A116.6
C1—N2—C3111.6 (2)C1—C10—H10B114.7
C1—N2—C9123.7 (2)H10C—C10—H10A103.6
C3—N2—C9124.7 (2)H10C—C10—H10B101.3
N2—C1—C8b106.4 (3)H10A—C10—H10B104.2
N2—C1—C10123.3 (2)C3—C11—C12124.6 (3)
C8b—C1—C10130.3 (2)C3—C11—C16117.5 (3)
O4—C3a—C3135.1 (3)C12—C11—C16117.7 (3)
O4—C3a—C8b112.8 (2)C11—C12—C13120.8 (3)
C3—C3a—C8b112.1 (3)C11—C12—H12121.2
N2—C3—C3a103.3 (2)C13—C12—H12118.0
N2—C3—C11127.9 (2)C12—C13—C14120.5 (3)
C3a—C3—C11128.8 (3)C12—C13—H13119.7
O4—C4a—C5123.0 (3)C14—C13—H13119.8
O4—C4a—C8a113.0 (2)C13—C14—C15119.9 (3)
C5—C4a—C8a123.9 (2)C13—C14—H14118.5
C4a—C5—C6116.3 (3)C15—C14—H14121.6
C4a—C5—H5124.6C14—C15—C16120.0 (4)
C6—C5—H5119.1C14—C15—H15120.6
C5—C6—C7121.0 (3)C16—C15—H15119.4
C5—C6—H6119.1C11—C16—C15121.1 (3)
C7—C6—H6119.9C11—C16—H16120.0
C6—C7—C8121.7 (3)C15—C16—H16118.9
C6—C7—H7115.1C9—C17—C18121.9 (2)
C8—C7—H7123.2C9—C17—C22119.4 (2)
C4a—C8a—C8118.0 (3)C18—C17—C22118.7 (3)
C4a—C8a—C8b104.7 (2)C17—C18—C19119.9 (3)
C8—C8a—C8b137.3 (3)C17—C18—H18119.4
C7—C8—C8a119.1 (3)C19—C18—H18120.6
C7—C8—H8116.3C18—C19—C20120.9 (3)
C8a—C8—H8124.6C18—C19—H19121.7
C1—C8b—C3a106.6 (2)C20—C19—H19117.4
C1—C8b—C8a147.7 (3)C19—C20—C21119.5 (4)
C3a—C8b—C8a105.7 (3)C19—C20—H20121.6
N2—C9—C17114.5 (2)C21—C20—H20118.9
N2—C9—H9A111.4C20—C21—C22120.1 (3)
N2—C9—H9B110.7C20—C21—H21121.1
C17—C9—H9A108.6C22—C21—H21118.7
C17—C9—H9B108.8C17—C22—C21120.8 (3)
H9A—C9—H9B102.1C17—C22—H22120.1
C1—C10—H10C114.6C21—C22—H22119.1
O4—C3a—C3—N2179.7 (3)C3—C3a—C8b—C8a179.4 (3)
O4—C3a—C3—C113.1 (6)C3—C11—C12—C13175.6 (2)
O4—C3a—C8b—C1179.8 (3)C3—C11—C16—C15174.7 (2)
O4—C3a—C8b—C8a0.4 (3)C4a—O4—C3a—C8b0.1 (3)
O4—C4a—C5—C6179.8 (3)C4a—C5—C6—C70.1 (5)
O4—C4a—C8a—C8179.4 (3)C4a—C8a—C8—C70.7 (5)
O4—C4a—C8a—C8b0.8 (3)C5—C4a—C8a—C81.4 (5)
N2—C1—C8b—C3a0.3 (3)C5—C4a—C8a—C8b178.4 (3)
N2—C1—C8b—C8a179.9 (5)C5—C6—C7—C80.5 (5)
N2—C3—C3a—C8b1.0 (3)C6—C5—C4a—C8a1.1 (5)
N2—C3—C11—C1238.1 (4)C6—C7—C8—C8a0.2 (5)
N2—C3—C11—C16147.3 (3)C7—C8—C8a—C8b179.0 (4)
N2—C9—C17—C1811.3 (4)C8a—C8b—C1—C100.7 (8)
N2—C9—C17—C22169.3 (2)C8b—C1—N2—C9179.5 (3)
C1—N2—C3—C3a0.8 (3)C8b—C3a—C3—C11178.2 (3)
C1—N2—C3—C11178.0 (3)C9—N2—C1—C101.2 (5)
C1—N2—C9—C1787.0 (3)C9—N2—C3—C112.8 (5)
C1—C8b—C3a—C30.8 (4)C9—C17—C18—C19179.3 (3)
C1—C8b—C8a—C4a179.7 (5)C9—C17—C22—C21179.6 (3)
C1—C8b—C8a—C80.0 (8)C11—C12—C13—C141.5 (4)
C3a—O4—C4a—C5178.7 (3)C11—C16—C15—C141.2 (4)
C3a—O4—C4a—C8a0.6 (3)C12—C11—C16—C150.3 (4)
C3a—C3—N2—C9180.0 (3)C12—C13—C14—C150.6 (4)
C3a—C3—C11—C12145.3 (3)C13—C12—C11—C161.0 (4)
C3a—C3—C11—C1629.3 (4)C13—C14—C15—C160.7 (4)
C3a—C8b—C1—C10178.9 (3)C17—C18—C19—C200.1 (5)
C3a—C8b—C8a—C4a0.7 (3)C17—C22—C21—C200.4 (4)
C3a—C8b—C8a—C8179.6 (4)C18—C17—C22—C210.1 (4)
C3—N2—C1—C8b0.3 (3)C18—C19—C20—C210.2 (5)
C3—N2—C1—C10179.6 (3)C19—C18—C17—C220.1 (4)
C3—N2—C9—C1792.2 (3)C19—C20—C21—C220.4 (5)
C3—C3a—O4—C4a178.6 (4)
Symmetry codes: (i) x+1, y, z; (ii) x+1, y+1, z+2; (iii) x+1, y, z+1; (iv) x, y, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC24H19NOC24H19NO
Mr337.42337.42
Crystal system, space groupTriclinic, P1Triclinic, P1
Temperature (K)296296
a, b, c (Å)10.405 (2), 11.524 (2), 9.177 (2)9.956 (1), 11.329 (2), 8.939 (2)
α, β, γ (°)113.44 (1), 113.94 (2), 93.94 (2)109.89 (1), 107.06 (1), 69.47 (1)
V3)887.4 (4)870.3 (3)
Z22
Radiation typeMo KαMo Kα
µ (mm1)0.080.08
Crystal size (mm)0.4 × 0.3 × 0.20.4 × 0.4 × 0.3
Data collection
DiffractometerRigaku AFC-6S
diffractometer
Rigaku AFC-6S
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.987, 1.000
No. of measured, independent and
observed [I > 3σ(I)] reflections
4289, 4067, 1420 4223, 3991, 1789
Rint0.0200.018
(sin θ/λ)max1)0.6500.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.225, 1.03 0.045, 0.197, 1.04
No. of reflections40673991
No. of parameters236236
H-atom treatmentH-atom parameters not refinedH-atom parameters not refined
Δρmax, Δρmin (e Å3)0.26, 0.220.24, 0.23

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1994), MSC/AFC Diffractometer Control Software, TEXSAN for Windows (Molecular Structure Corporation, 1999), SIR97 (Altomare et al., 1997) and DIRDIF94 (Beurskens et al., 1994), SHELXL93 (Sheldrick, 1993), TEXSAN for Windows.

 

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