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The indole and pyrrolidine ring systems of the title compound, C24H22N2O3S, are essentially coplanar. The angle between the planes of the phenyl­sulfonyl group and the indole ring system is 89.1 (2)°, which is characteristic of 1-(phenyl­sulfonyl)­indoles. The benzyl ring is nearly perpendicular to the pyrroloindole unit, with an angle between the planes of 82.2 (2)°.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032436/fl2139sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032436/fl2139Isup2.hkl
Contains datablock I

CCDC reference: 657695

Key indicators

  • Single-crystal X-ray study
  • T = 296 K
  • Mean [sigma](C-C) = 0.009 Å
  • R factor = 0.061
  • wR factor = 0.283
  • Data-to-parameter ratio = 17.4

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT026_ALERT_3_B Ratio Observed / Unique Reflections too Low .... 34 Perc. PLAT230_ALERT_2_B Hirshfeld Test Diff for C21 - C24 .. 8.14 su PLAT230_ALERT_2_B Hirshfeld Test Diff for C24 - C25 .. 14.62 su PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for C24 PLAT413_ALERT_2_B Short Inter XH3 .. XHn H20 .. H22 .. 1.95 Ang.
Alert level C RFACR01_ALERT_3_C The value of the weighted R factor is > 0.25 Weighted R factor given 0.283 PLAT031_ALERT_4_C Refined Extinction Parameter within Range ...... 2.74 Sigma PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT084_ALERT_2_C High R2 Value .................................. 0.28 PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT150_ALERT_1_C Volume as Calculated Differs from that Given ... 2063.60 Ang-3 PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.16 Ratio PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C11 PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 10 PLAT360_ALERT_2_C Short C(sp3)-C(sp3) Bond C24 - C25 ... 1.35 Ang. PLAT362_ALERT_2_C Short C(sp3)-C(sp2) Bond C21 - C24 ... 1.33 Ang.
0 ALERT level A = In general: serious problem 5 ALERT level B = Potentially serious problem 11 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 9 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The title compound, (I), was synthesized as a precursor to the corresponding pyrrolo[3,4-b]indole as a stable synthetic analogue of indole-2,3-quinodimethane and having a readily removable 4-methoxybenzyl protecting group. The X-ray crystallographic analysis confirms the molecular structure and atom connectivity for (I) that we had proposed for this compound based on NMR spectroscopy and chemical reactions (Kishbaugh & Gribble, 2002).

The pyrrolidine nitrogen N2 has bond angles totaling 337.8 (4)°, indicating slight flattening from a purely pyramidal nitrogen, which is 324° for ammonia with H—N—H bond angles of 108°, and is consistent with the inductive electron-withdrawing properties of a benzyl group.

Related literature top

For the synthesis of the title compound and related chemistry, see: Gribble (2003); Gribble et al. (2005); Roy, Kishbaugh et al. (2007); Roy, Pelkey et al. (2007); Kishbaugh & Gribble (2002); Mohanakrishnan & Srinivasan (1995). For a related structure, see: Kishbaugh et al. (2007).

Experimental top

To a refluxing solution of 2,3-dibromomethyl-1-(phenylsulfonyl)indole (415 mg, 0.937 mmol) (Mohanakrishnan & Srinivasan, 1995) and K2CO3 (397 mg, 2.80 mmol) in tetrahydrofuran (20 ml) was added a solution of 4-methoxybenzylamine (150 µL, 1.15 mmol) in tetrahydrofuran (20 ml) slowly via addition funnel. After 10 h, the opaque solution was filtered through a Celite pad with ethyl acetate rinses. The resulting yellow solution was concentrated in vacuo to yield a pale yellow solid which was purified by column chromatography (2:1 hexanes: ethyl acetate) to yield (I) as a white solid (290 mg, 74% yield): m.p. 391–391.5 K. As (I) was unstable toward oxidation, an elemental analysis was not attempted. Recrystallization from hexane–dichloromethane (3:1) yielded crystals that were suitable for X-ray crystallography.

Refinement top

The H atoms were included in the riding model approximation with C—H = 0.93–0.97 Å, and with Uiso(H) = 1.19–1.20Ueq(C).

Structure description top

The title compound, (I), was synthesized as a precursor to the corresponding pyrrolo[3,4-b]indole as a stable synthetic analogue of indole-2,3-quinodimethane and having a readily removable 4-methoxybenzyl protecting group. The X-ray crystallographic analysis confirms the molecular structure and atom connectivity for (I) that we had proposed for this compound based on NMR spectroscopy and chemical reactions (Kishbaugh & Gribble, 2002).

The pyrrolidine nitrogen N2 has bond angles totaling 337.8 (4)°, indicating slight flattening from a purely pyramidal nitrogen, which is 324° for ammonia with H—N—H bond angles of 108°, and is consistent with the inductive electron-withdrawing properties of a benzyl group.

For the synthesis of the title compound and related chemistry, see: Gribble (2003); Gribble et al. (2005); Roy, Kishbaugh et al. (2007); Roy, Pelkey et al. (2007); Kishbaugh & Gribble (2002); Mohanakrishnan & Srinivasan (1995). For a related structure, see: Kishbaugh et al. (2007).

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1994); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: CrystalStructure (Rigaku/MSC, 2005); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: CrystalStructure.

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) showing atom labelling and 50% probability displacement ellipsoids.
2-(4-Methoxybenzyl)-4-(phenylsulfonyl)-1,2,3,4-tetrahydropyrrolo[3,4-b]indole top
Crystal data top
C25H24N2O2SF(000) = 880
Mr = 416.52Dx = 1.341 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71069 Å
a = 11.929 (7) ÅCell parameters from 20 reflections
b = 9.397 (7) Åθ = 6.2–7.8°
c = 19.198 (4) ŵ = 0.18 mm1
β = 106.47 (3)°T = 296 K
V = 2063.6 (19) Å3Prism, colourless
Z = 40.50 × 0.40 × 0.20 mm
Data collection top
Rigaku AFC-6S
diffractometer
1590 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tubeRint = 0.000
Graphite monochromatorθmax = 27.5°, θmin = 1.8°
ω/2θ scansh = 015
Absorption correction: ψ scan
(North et al., 1968)
k = 012
Tmin = 0.915, Tmax = 0.965l = 2423
4739 measured reflections3 standard reflections every 150 reflections
4739 independent reflections intensity decay: none
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)] = 0.061H-atom parameters constrained
wR(F2) = 0.284 w = 1/[σ2(Fo2) + (0.1351P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
4739 reflectionsΔρmax = 0.48 e Å3
273 parametersΔρmin = 0.38 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0052 (19)
Crystal data top
C25H24N2O2SV = 2063.6 (19) Å3
Mr = 416.52Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.929 (7) ŵ = 0.18 mm1
b = 9.397 (7) ÅT = 296 K
c = 19.198 (4) Å0.50 × 0.40 × 0.20 mm
β = 106.47 (3)°
Data collection top
Rigaku AFC-6S
diffractometer
1590 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.000
Tmin = 0.915, Tmax = 0.9653 standard reflections every 150 reflections
4739 measured reflections intensity decay: none
4739 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0610 restraints
wR(F2) = 0.284H-atom parameters constrained
S = 1.03Δρmax = 0.48 e Å3
4739 reflectionsΔρmin = 0.38 e Å3
273 parameters
Special details top

Experimental. 1H (CD2Cl2) δ 8.04 (d, 1H, 8 Hz), 7.88 (m, 2H), 7.24-7.56 (m, 8H), 6.95 (m, 2H), 4.32 (m, 2H), 4.00 (s, 2H), 3.96 (m, 2H), 3.86 (s, 3H); 13C (CD2Cl2) δ 159.2, 140.3, 139.8, 138.4, 134.3, 131.4, 130.2, 129.7, 129.3, 129.0, 128.8, 126.9, 126.7, 126.3, 124.0, 123.7, 119.6, 114.5, 114.4, 114.1, 60.1, 55.5, 54.9, 53.1; IR (film) λmax 3056, 2933, 2832, 1611, 1511, 1447, 1369, 1247, 1177, 996, 750, 723, 685 cm-1; UV (EtOH) λmax 224, 260 nm.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.29345 (13)0.16620 (16)0.82158 (8)0.0408 (4)
O10.3017 (3)0.0241 (4)0.7988 (2)0.0510 (11)
O20.3618 (3)0.2133 (5)0.8910 (2)0.0532 (12)
N10.3285 (4)0.2660 (5)0.7598 (2)0.0390 (11)
N20.3015 (4)0.1362 (5)0.5746 (2)0.0440 (13)
C10.3125 (6)0.0860 (6)0.6496 (3)0.0481 (15)
H10.24400.03320.65210.058*
H20.38160.02740.66810.058*
C20.3454 (6)0.2842 (7)0.5768 (3)0.0505 (16)
H30.29560.34150.53830.061*
H40.42470.28660.57290.061*
C30.3404 (5)0.3338 (6)0.6499 (3)0.0403 (14)
C40.3571 (5)0.4598 (6)0.6937 (3)0.0410 (14)
C50.3785 (5)0.6024 (7)0.6835 (4)0.0495 (16)
H50.38850.63330.63960.059*
C60.3850 (5)0.6982 (7)0.7393 (4)0.0539 (17)
H60.39980.79380.73310.065*
C70.3693 (5)0.6521 (7)0.8044 (3)0.0482 (15)
H70.37220.71880.84070.058*
C80.3498 (5)0.5120 (7)0.8177 (3)0.0481 (16)
H80.33980.48310.86190.058*
C90.3456 (4)0.4154 (6)0.7622 (3)0.0369 (13)
C100.3227 (4)0.2224 (6)0.6887 (3)0.0342 (12)
C110.1462 (5)0.2100 (6)0.8114 (3)0.0393 (13)
C120.0626 (6)0.1670 (8)0.7498 (4)0.0645 (19)
H90.08370.11280.71500.077*
C130.0525 (6)0.2044 (9)0.7397 (4)0.078 (2)
H100.10950.17630.69790.093*
C140.0823 (6)0.2839 (9)0.7920 (4)0.074 (2)
H110.16010.30870.78560.088*
C150.0002 (6)0.3265 (8)0.8529 (4)0.074 (2)
H120.02090.38010.88790.089*
C160.1157 (6)0.2897 (7)0.8625 (4)0.0613 (18)
H130.17270.31940.90390.074*
C170.3508 (6)0.0386 (7)0.5328 (3)0.0546 (17)
H140.42720.00830.56240.066*
H150.36140.08830.49090.066*
C180.2758 (5)0.0919 (7)0.5071 (3)0.0451 (15)
C190.3262 (6)0.2176 (7)0.4941 (3)0.0519 (16)
H160.40690.22410.50390.062*
C200.2568 (7)0.3341 (7)0.4664 (4)0.0613 (18)
H170.29220.41790.45770.074*
C210.1367 (6)0.3297 (7)0.4512 (3)0.0574 (17)
C220.0872 (6)0.2050 (7)0.4657 (4)0.0569 (18)
H180.00660.19900.45720.068*
C230.1563 (6)0.0897 (7)0.4924 (4)0.0565 (17)
H190.12060.00620.50100.068*
C240.0782 (5)0.4476 (5)0.4251 (3)0.0391 (14)
H200.10150.52070.46210.047*
H210.10390.47840.38390.047*
C250.0396 (10)0.4433 (9)0.4036 (5)0.109 (3)
H220.06890.46630.44390.131*
H230.06870.51100.36530.131*
H240.06500.34950.38630.131*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0453 (9)0.0433 (9)0.0367 (8)0.0029 (7)0.0163 (6)0.0038 (7)
O10.062 (3)0.039 (3)0.057 (3)0.007 (2)0.025 (2)0.007 (2)
O20.051 (3)0.070 (3)0.036 (2)0.008 (2)0.0096 (19)0.002 (2)
N10.045 (3)0.035 (3)0.040 (3)0.001 (2)0.018 (2)0.001 (2)
N20.056 (3)0.045 (3)0.035 (3)0.006 (2)0.020 (2)0.004 (2)
C10.058 (4)0.047 (4)0.044 (4)0.007 (3)0.022 (3)0.005 (3)
C20.065 (4)0.047 (4)0.044 (3)0.003 (3)0.022 (3)0.005 (3)
C30.045 (3)0.043 (3)0.036 (3)0.003 (3)0.017 (3)0.004 (3)
C40.033 (3)0.043 (4)0.050 (4)0.002 (3)0.015 (3)0.002 (3)
C50.042 (3)0.047 (4)0.060 (4)0.000 (3)0.016 (3)0.010 (3)
C60.046 (4)0.039 (4)0.074 (5)0.006 (3)0.011 (3)0.005 (3)
C70.047 (4)0.043 (4)0.053 (4)0.002 (3)0.011 (3)0.012 (3)
C80.051 (4)0.056 (4)0.038 (3)0.000 (3)0.012 (3)0.005 (3)
C90.029 (3)0.046 (4)0.033 (3)0.002 (3)0.006 (2)0.001 (3)
C100.036 (3)0.039 (3)0.030 (3)0.002 (2)0.012 (2)0.000 (3)
C110.041 (3)0.041 (3)0.039 (3)0.001 (3)0.016 (3)0.001 (3)
C120.050 (4)0.088 (5)0.056 (4)0.006 (4)0.016 (3)0.017 (4)
C130.048 (5)0.108 (7)0.071 (5)0.010 (4)0.006 (4)0.009 (5)
C140.040 (4)0.091 (6)0.090 (6)0.000 (4)0.018 (4)0.005 (5)
C150.055 (4)0.087 (6)0.090 (5)0.006 (4)0.036 (4)0.028 (5)
C160.055 (4)0.073 (5)0.057 (4)0.003 (4)0.017 (3)0.008 (4)
C170.068 (4)0.062 (4)0.038 (3)0.004 (4)0.022 (3)0.003 (3)
C180.052 (4)0.052 (4)0.035 (3)0.001 (3)0.018 (3)0.002 (3)
C190.054 (4)0.055 (4)0.051 (4)0.000 (3)0.021 (3)0.010 (3)
C200.081 (5)0.048 (4)0.058 (4)0.010 (4)0.025 (4)0.010 (4)
C210.069 (5)0.052 (4)0.051 (4)0.009 (4)0.017 (3)0.003 (3)
C220.049 (4)0.063 (5)0.060 (4)0.007 (3)0.017 (3)0.012 (4)
C230.064 (5)0.046 (4)0.062 (4)0.001 (3)0.022 (3)0.011 (3)
C240.042 (3)0.019 (3)0.052 (4)0.006 (3)0.006 (3)0.012 (3)
C250.168 (11)0.062 (6)0.087 (7)0.036 (6)0.018 (6)0.014 (5)
Geometric parameters (Å, º) top
S1—O11.416 (4)C12—C131.376 (9)
S1—O21.421 (4)C12—H90.9300
S1—N11.656 (5)C13—C141.377 (10)
S1—C111.760 (6)C13—H100.9300
N1—C101.407 (7)C14—C151.357 (10)
N1—C91.417 (7)C14—H110.9300
N2—C171.448 (7)C15—C161.380 (9)
N2—C21.482 (7)C15—H120.9300
N2—C11.485 (7)C16—H130.9300
C1—C101.474 (8)C17—C181.516 (8)
C1—H10.9700C17—H140.9700
C1—H20.9700C17—H150.9700
C2—C31.495 (8)C18—C231.373 (8)
C2—H30.9700C18—C191.380 (8)
C2—H40.9700C19—C201.384 (9)
C3—C101.336 (7)C19—H160.9300
C3—C41.433 (8)C20—C211.379 (9)
C4—C51.389 (8)C20—H170.9300
C4—C91.423 (7)C21—C241.330 (8)
C5—C61.385 (9)C21—C221.375 (9)
C5—H50.9300C22—C231.370 (8)
C6—C71.384 (9)C22—H180.9300
C6—H60.9300C23—H190.9300
C7—C81.373 (9)C24—C251.348 (11)
C7—H70.9300C24—H200.9700
C8—C91.390 (8)C24—H210.9700
C8—H80.9300C25—H220.9600
C11—C161.365 (8)C25—H230.9600
C11—C121.374 (8)C25—H240.9600
O1—S1—O2120.7 (3)C11—C12—C13119.9 (6)
O1—S1—N1105.0 (2)C11—C12—H9120.1
O2—S1—N1107.5 (3)C13—C12—H9120.1
O1—S1—C11109.9 (3)C12—C13—C14119.3 (7)
O2—S1—C11108.7 (3)C12—C13—H10120.4
N1—S1—C11103.5 (2)C14—C13—H10120.4
C10—N1—C9106.7 (4)C15—C14—C13120.9 (7)
C10—N1—S1125.2 (4)C15—C14—H11119.5
C9—N1—S1126.9 (4)C13—C14—H11119.5
C17—N2—C2114.5 (5)C14—C15—C16119.7 (7)
C17—N2—C1113.4 (5)C14—C15—H12120.2
C2—N2—C1109.7 (4)C16—C15—H12120.2
C10—C1—N2100.9 (4)C11—C16—C15120.0 (6)
C10—C1—H1111.6C11—C16—H13120.0
N2—C1—H1111.6C15—C16—H13120.0
C10—C1—H2111.6N2—C17—C18113.5 (5)
N2—C1—H2111.6N2—C17—H14108.9
H1—C1—H2109.4C18—C17—H14108.9
N2—C2—C3102.2 (5)N2—C17—H15108.9
N2—C2—H3111.3C18—C17—H15108.9
C3—C2—H3111.3H14—C17—H15107.7
N2—C2—H4111.3C23—C18—C19117.1 (6)
C3—C2—H4111.3C23—C18—C17122.5 (6)
H3—C2—H4109.2C19—C18—C17120.3 (5)
C10—C3—C4109.7 (5)C18—C19—C20120.2 (6)
C10—C3—C2109.5 (5)C18—C19—H16119.9
C4—C3—C2140.6 (5)C20—C19—H16119.9
C5—C4—C9118.9 (5)C21—C20—C19121.9 (6)
C5—C4—C3135.6 (6)C21—C20—H17119.0
C9—C4—C3105.5 (5)C19—C20—H17119.0
C6—C5—C4119.3 (6)C24—C21—C22125.2 (6)
C6—C5—H5120.3C24—C21—C20117.2 (6)
C4—C5—H5120.3C22—C21—C20117.6 (6)
C7—C6—C5120.2 (6)C23—C22—C21120.1 (6)
C7—C6—H6119.9C23—C22—H18119.9
C5—C6—H6119.9C21—C22—H18119.9
C8—C7—C6122.7 (6)C22—C23—C18123.0 (6)
C8—C7—H7118.6C22—C23—H19118.5
C6—C7—H7118.6C18—C23—H19118.5
C7—C8—C9117.0 (6)C21—C24—C25118.7 (6)
C7—C8—H8121.5C21—C24—H20107.6
C9—C8—H8121.5C25—C24—H20107.6
C8—C9—N1130.2 (5)C21—C24—H21107.6
C8—C9—C4121.7 (6)C25—C24—H21107.6
N1—C9—C4108.1 (5)H20—C24—H21107.1
C3—C10—N1110.0 (5)C24—C25—H22109.5
C3—C10—C1113.6 (5)C24—C25—H23109.5
N1—C10—C1136.2 (5)H22—C25—H23109.5
C16—C11—C12120.3 (6)C24—C25—H24109.5
C16—C11—S1120.6 (5)H22—C25—H24109.5
C12—C11—S1119.0 (5)H23—C25—H24109.5

Experimental details

Crystal data
Chemical formulaC25H24N2O2S
Mr416.52
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)11.929 (7), 9.397 (7), 19.198 (4)
β (°) 106.47 (3)
V3)2063.6 (19)
Z4
Radiation typeMo Kα
µ (mm1)0.18
Crystal size (mm)0.50 × 0.40 × 0.20
Data collection
DiffractometerRigaku AFC-6S
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.915, 0.965
No. of measured, independent and
observed [I > 2σ(I)] reflections
4739, 4739, 1590
Rint0.000
(sin θ/λ)max1)0.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.061, 0.284, 1.03
No. of reflections4739
No. of parameters273
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.48, 0.38

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1994), MSC/AFC Diffractometer Control Software, CrystalStructure (Rigaku/MSC, 2005), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), CrystalStructure.

 

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