Literature DB >> 21203147

5',6-Dichloro-1',3',3'-trimethyl-spiro-[2H-1-benzopyran-2,2'-indoline].

Nameer Alhashimy, Helge Müller-Bunz, Benjamin Schazmann, Dermot Diamond.   

Abstract

In the crystal structure of the title compound, C(19)H(17)Cl(2)NO, the indoline and benzopyran ring systems are approximately perpendicular to each other. The indoline ring is in an envelope conformation with the spiro C atom as the flap. The N atom of the indoline ring forms a pyramidal environment, the sum of the angles at this atom being 352.46°.

Entities:  

Year:  2008        PMID： 21203147      PMCID： PMC2962063          DOI： 10.1107/S1600536808018722

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For related literature, see: Crano & Guglielmetti (1999 ▶); Kholmanskii & Dyumanev (1987 ▶); Tamai & Miyasaka (2000 ▶); Krongauz et al. (2000 ▶); Minkin (2004 ▶); Crano et al. (1996 ▶); Dvornikov et al. (1994 ▶); Tamai & Miyasaka (2000 ▶); Yoshida & Morinaka (1994 ▶); Willner et al. (1993 ▶); Byrne et al. (2006a ▶,b ▶); Raić-Malić et al. (2004 ▶); Aldoshin & Atovmyan (1985 ▶); Aldoshin et al. (1987 ▶); Mannschreeck et al. (1999 ▶). For the synthesis of the title compound, see: Martin et al. (1998 ▶).

Experimental

Crystal data

C19H17Cl2NO M = 346.24 Monoclinic, a = 8.3105 (7) Å b = 18.2576 (16) Å c = 11.1921 (10) Å β = 104.770 (2)° V = 1642.1 (2) Å3 Z = 4 Mo Kα radiation μ = 0.40 mm−1 T = 100 (2) K 0.50 × 0.40 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer Absorption correction: multi-scan (; Sheldrick, 2000 ▶) T min = 0.740, T max = 0.980 16175 measured reflections 4312 independent reflections 3857 reflections with I > 2σ(I) R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.046 wR(F 2) = 0.122 S = 1.05 4312 reflections 276 parameters All H-atom parameters refined Δρmax = 0.96 e Å−3 Δρmin = −0.25 e Å−3 Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2008 ▶). Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808018722/nc2106sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536808018722/nc2106Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
C19H17Cl2NOF000 = 720
Mr = 346.24Dx = 1.401 Mg m−3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7373 reflections
a = 8.3105 (7) Åθ = 2.2–31.7º
b = 18.2576 (16) ŵ = 0.40 mm−1
c = 11.1921 (10) ÅT = 100 (2) K
β = 104.770 (2)ºPlate, colourless
V = 1642.1 (2) Å30.50 × 0.40 × 0.05 mm
Z = 4
Bruker SMART CCD area-detector diffractometer4312 independent reflections
Radiation source: fine-focus sealed tube3857 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.023
Detector resolution: 8.366 pixels mm-1θmax = 29.0º
T = 100(2) Kθmin = 2.2º
φ and ω scansh = −11→11
Absorption correction: multi-scan(SADABS; Sheldrick, 2000)k = −24→24
Tmin = 0.740, Tmax = 0.980l = −15→15
16175 measured reflections
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046All H-atom parameters refined
wR(F2) = 0.122  w = 1/[σ2(Fo2) + (0.0653P)2 + 1.2622P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.002
4312 reflectionsΔρmax = 0.96 e Å−3
276 parametersΔρmin = −0.25 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Experimental. 1H NMR δ(CDCl3); 1.190 (S, 3H, CH3), 1.30 (S, 3H, CH~3~),2.72 (S, 3H, CH3), 5.73 (d, 1H, J= 10.4 Hz, CH=CH), 6.46 ( d, H, J= 12.8 Hz, Ar-H), 6.67 (d, 1H, J =9.6 Hz, Ar-H), 6.83 (d, 1H, J = 16.4, Ar-H), 7.01-7.08 ( m, 2H, Ar-H), 7.15 ( d, 1H, J = 10.4 Hz, CH=CH).13C NMR δ(CDCl3); 19.95, 25.68, 29.04, 51.96, 104.60, 107.78, 116.33, 119.91,120.17, 122.11, 123.93, 124.85, 126.28, 127.37, 128.80, 129.50, 138.53, 146.73,152.80.M.S. (m/z ion) (m/z 346.2).
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.
xyzUiso*/Ueq
Cl11.29108 (6)0.46363 (2)0.01666 (4)0.02892 (13)
C11.2126 (2)0.38771 (9)0.07835 (15)0.0198 (3)
C21.0760 (2)0.39650 (9)0.12870 (15)0.0187 (3)
H21.029 (3)0.4437 (13)0.133 (2)0.025 (5)*
C31.01780 (19)0.33524 (8)0.17644 (14)0.0160 (3)
C41.09359 (19)0.26690 (8)0.17419 (14)0.0169 (3)
C51.2295 (2)0.25851 (9)0.12441 (16)0.0202 (3)
H51.284 (3)0.2115 (12)0.120 (2)0.020 (5)*
C61.2886 (2)0.32043 (10)0.07558 (16)0.0223 (3)
H61.381 (3)0.3155 (12)0.037 (2)0.024 (5)*
N1.01339 (17)0.21423 (7)0.22743 (13)0.0186 (3)
C71.0459 (2)0.13674 (9)0.21878 (17)0.0225 (3)
H7A1.015 (3)0.1214 (13)0.136 (2)0.029 (6)*
H7B0.989 (3)0.1089 (13)0.271 (2)0.030 (6)*
H7C1.163 (3)0.1284 (14)0.256 (2)0.038 (7)*
C80.88187 (19)0.32673 (8)0.24368 (14)0.0150 (3)
C90.9546 (2)0.34836 (9)0.37930 (15)0.0197 (3)
H9A0.989 (3)0.3981 (13)0.383 (2)0.024 (5)*
H9B0.870 (3)0.3426 (12)0.427 (2)0.027 (6)*
H9C1.051 (3)0.3191 (13)0.419 (2)0.029 (6)*
C100.7265 (2)0.37244 (10)0.18951 (16)0.0204 (3)
H10A0.687 (3)0.3635 (12)0.100 (2)0.022 (5)*
H10B0.756 (3)0.4243 (13)0.202 (2)0.028 (6)*
H10C0.647 (3)0.3607 (12)0.233 (2)0.023 (5)*
C110.85232 (19)0.24213 (9)0.23280 (14)0.0163 (3)
O0.73274 (14)0.23176 (6)0.11246 (10)0.0178 (2)
C120.7959 (2)0.20568 (9)0.33518 (15)0.0194 (3)
H120.853 (3)0.2181 (12)0.417 (2)0.025 (5)*
C130.6788 (2)0.15405 (9)0.31410 (15)0.0200 (3)
H130.651 (3)0.1291 (13)0.381 (2)0.028 (6)*
C140.5891 (2)0.13478 (8)0.18904 (15)0.0166 (3)
C150.61892 (19)0.17667 (8)0.09238 (14)0.0147 (3)
C160.52518 (19)0.16618 (9)−0.02828 (14)0.0159 (3)
H160.550 (3)0.1972 (12)−0.090 (2)0.021 (5)*
C170.4051 (2)0.11154 (9)−0.05435 (15)0.0185 (3)
H170.345 (2)0.1032 (11)−0.1356 (18)0.014 (5)*
C180.38016 (19)0.06811 (8)0.04128 (16)0.0183 (3)
Cl20.23079 (5)−0.00073 (2)0.00933 (4)0.02523 (13)
C190.4695 (2)0.07902 (9)0.16192 (16)0.0188 (3)
H190.452 (3)0.0512 (12)0.226 (2)0.022 (5)*
U11U22U33U12U13U23
Cl10.0321 (2)0.0223 (2)0.0349 (2)−0.00767 (16)0.01332 (18)0.00340 (17)
C10.0173 (7)0.0211 (8)0.0209 (7)−0.0046 (6)0.0047 (6)0.0022 (6)
C20.0180 (7)0.0160 (7)0.0208 (7)−0.0002 (6)0.0026 (6)−0.0016 (6)
C30.0129 (7)0.0172 (7)0.0165 (7)−0.0009 (5)0.0015 (5)−0.0014 (5)
C40.0145 (7)0.0176 (7)0.0171 (7)−0.0003 (5)0.0016 (5)−0.0016 (5)
C50.0152 (7)0.0200 (8)0.0248 (8)0.0016 (6)0.0041 (6)−0.0025 (6)
C60.0174 (8)0.0249 (8)0.0248 (8)−0.0022 (6)0.0061 (6)−0.0025 (6)
N0.0187 (6)0.0149 (6)0.0224 (7)0.0011 (5)0.0054 (5)−0.0002 (5)
C70.0284 (9)0.0143 (7)0.0252 (8)0.0031 (6)0.0078 (7)0.0011 (6)
C80.0141 (7)0.0149 (7)0.0158 (7)−0.0007 (5)0.0033 (5)−0.0021 (5)
C90.0205 (8)0.0199 (8)0.0178 (7)−0.0011 (6)0.0032 (6)−0.0037 (6)
C100.0157 (7)0.0213 (8)0.0240 (8)0.0019 (6)0.0048 (6)0.0012 (6)
C110.0179 (7)0.0166 (7)0.0134 (7)−0.0020 (5)0.0022 (5)−0.0011 (5)
O0.0204 (5)0.0194 (6)0.0125 (5)−0.0082 (4)0.0023 (4)0.0001 (4)
C120.0235 (8)0.0199 (7)0.0145 (7)−0.0006 (6)0.0045 (6)−0.0002 (6)
C130.0231 (8)0.0203 (8)0.0180 (7)−0.0001 (6)0.0080 (6)0.0026 (6)
C140.0169 (7)0.0147 (7)0.0190 (7)0.0010 (5)0.0058 (6)0.0003 (5)
C150.0133 (6)0.0134 (6)0.0182 (7)−0.0001 (5)0.0056 (5)−0.0013 (5)
C160.0132 (7)0.0173 (7)0.0171 (7)0.0004 (5)0.0039 (5)−0.0006 (5)
C170.0143 (7)0.0182 (7)0.0216 (8)0.0001 (6)0.0018 (6)−0.0028 (6)
C180.0122 (7)0.0117 (6)0.0308 (8)−0.0002 (5)0.0052 (6)−0.0012 (6)
Cl20.0158 (2)0.01421 (19)0.0436 (3)−0.00319 (13)0.00372 (17)0.00058 (15)
C190.0179 (7)0.0146 (7)0.0256 (8)0.0007 (6)0.0086 (6)0.0034 (6)
Cl1—C11.7474 (17)C9—H9C0.97 (2)
C1—C61.385 (2)C10—H10A0.98 (2)
C1—C21.399 (2)C10—H10B0.98 (2)
C2—C31.379 (2)C10—H10C0.94 (2)
C2—H20.95 (2)C11—O1.4680 (18)
C3—C41.401 (2)C11—C121.500 (2)
C3—C81.517 (2)O—C151.3596 (18)
C4—N1.388 (2)C12—C131.332 (2)
C4—C51.389 (2)C12—H120.94 (2)
C5—C61.398 (2)C13—C141.451 (2)
C5—H50.98 (2)C13—H130.95 (2)
C6—H60.98 (2)C14—C151.397 (2)
N—C111.448 (2)C14—C191.401 (2)
N—C71.448 (2)C15—C161.390 (2)
C7—H7A0.94 (2)C16—C171.389 (2)
C7—H7B0.98 (2)C16—H160.96 (2)
C7—H7C0.96 (3)C17—C181.389 (2)
C8—C101.527 (2)C17—H170.93 (2)
C8—C91.535 (2)C18—C191.379 (2)
C8—C111.564 (2)C18—Cl21.7384 (16)
C9—H9A0.95 (2)C19—H190.92 (2)
C9—H9B1.00 (2)
C6—C1—C2122.16 (15)H9B—C9—H9C107.9 (19)
C6—C1—Cl1118.44 (13)C8—C10—H10A109.9 (13)
C2—C1—Cl1119.41 (13)C8—C10—H10B108.3 (14)
C3—C2—C1117.62 (15)H10A—C10—H10B108.3 (18)
C3—C2—H2121.6 (14)C8—C10—H10C107.7 (14)
C1—C2—H2120.7 (14)H10A—C10—H10C113.3 (18)
C2—C3—C4120.77 (15)H10B—C10—H10C109.2 (19)
C2—C3—C8130.88 (14)N—C11—O109.47 (12)
C4—C3—C8108.24 (13)N—C11—C12110.36 (13)
N—C4—C5128.63 (15)O—C11—C12111.93 (13)
N—C4—C3110.00 (14)N—C11—C8102.84 (12)
C5—C4—C3121.37 (15)O—C11—C8104.77 (12)
C4—C5—C6118.05 (15)C12—C11—C8116.89 (13)
C4—C5—H5123.3 (13)C15—O—C11121.79 (12)
C6—C5—H5118.6 (13)C13—C12—C11122.36 (15)
C1—C6—C5120.02 (15)C13—C12—H12120.5 (14)
C1—C6—H6120.4 (13)C11—C12—H12117.0 (14)
C5—C6—H6119.5 (13)C12—C13—C14120.98 (15)
C4—N—C11108.93 (13)C12—C13—H13120.8 (14)
C4—N—C7122.00 (14)C14—C13—H13118.2 (14)
C11—N—C7122.46 (14)C15—C14—C19119.07 (15)
N—C7—H7A110.4 (14)C15—C14—C13117.73 (14)
N—C7—H7B109.9 (14)C19—C14—C13123.13 (15)
H7A—C7—H7B112 (2)O—C15—C16117.17 (14)
N—C7—H7C108.0 (16)O—C15—C14122.00 (14)
H7A—C7—H7C112 (2)C16—C15—C14120.72 (14)
H7B—C7—H7C104 (2)C17—C16—C15119.88 (15)
C3—C8—C10114.10 (13)C17—C16—H16123.2 (13)
C3—C8—C9107.98 (13)C15—C16—H16116.9 (13)
C10—C8—C9109.39 (13)C16—C17—C18119.23 (15)
C3—C8—C11100.63 (12)C16—C17—H17119.9 (12)
C10—C8—C11114.13 (13)C18—C17—H17120.8 (12)
C9—C8—C11110.21 (13)C19—C18—C17121.53 (15)
C8—C9—H9A109.3 (13)C19—C18—Cl2118.93 (13)
C8—C9—H9B110.6 (13)C17—C18—Cl2119.53 (13)
H9A—C9—H9B108.9 (19)C18—C19—C14119.48 (15)
C8—C9—H9C112.7 (14)C18—C19—H19121.8 (14)
H9A—C9—H9C107.3 (19)C14—C19—H19118.7 (14)
C6—C1—C2—C30.0 (2)C9—C8—C11—N−84.95 (15)
Cl1—C1—C2—C3179.99 (12)C3—C8—C11—O−85.57 (13)
C1—C2—C3—C40.0 (2)C10—C8—C11—O37.07 (17)
C1—C2—C3—C8175.66 (15)C9—C8—C11—O160.62 (12)
C2—C3—C4—N179.88 (14)C3—C8—C11—C12149.91 (14)
C8—C3—C4—N3.35 (17)C10—C8—C11—C12−87.45 (17)
C2—C3—C4—C50.2 (2)C9—C8—C11—C1236.10 (19)
C8—C3—C4—C5−176.36 (14)N—C11—O—C15102.17 (16)
N—C4—C5—C6179.99 (16)C12—C11—O—C15−20.53 (19)
C3—C4—C5—C6−0.4 (2)C8—C11—O—C15−148.14 (13)
C2—C1—C6—C5−0.2 (3)N—C11—C12—C13−104.55 (18)
Cl1—C1—C6—C5179.82 (13)O—C11—C12—C1317.6 (2)
C4—C5—C6—C10.4 (3)C8—C11—C12—C13138.45 (16)
C5—C4—N—C11−163.27 (16)C11—C12—C13—C14−5.4 (3)
C3—C4—N—C1117.04 (17)C12—C13—C14—C15−5.7 (2)
C5—C4—N—C7−11.2 (3)C12—C13—C14—C19177.48 (16)
C3—C4—N—C7169.10 (15)C11—O—C15—C16−172.39 (13)
C2—C3—C8—C1041.2 (2)C11—O—C15—C1411.3 (2)
C4—C3—C8—C10−142.78 (14)C19—C14—C15—O179.72 (14)
C2—C3—C8—C9−80.7 (2)C13—C14—C15—O2.8 (2)
C4—C3—C8—C995.37 (15)C19—C14—C15—C163.6 (2)
C2—C3—C8—C11163.81 (16)C13—C14—C15—C16−173.34 (14)
C4—C3—C8—C11−20.12 (15)O—C15—C16—C17−178.97 (14)
C4—N—C11—O81.89 (15)C14—C15—C16—C17−2.7 (2)
C7—N—C11—O−70.01 (18)C15—C16—C17—C180.2 (2)
C4—N—C11—C12−154.49 (13)C16—C17—C18—C191.4 (2)
C7—N—C11—C1253.62 (19)C16—C17—C18—Cl2−179.66 (12)
C4—N—C11—C8−29.08 (16)C17—C18—C19—C14−0.4 (2)
C7—N—C11—C8179.02 (14)Cl2—C18—C19—C14−179.39 (12)
C3—C8—C11—N28.87 (14)C15—C14—C19—C18−2.0 (2)
C10—C8—C11—N151.51 (13)C13—C14—C19—C18174.72 (15)
Atoms defining plane 1Atoms defining plane 2Interplanar angle (°)
C2, C6, C8, NC11, C19, O85.03 (4)
C3, C4, C8, NC8, C11, N28.9 (1)
C1, C2, C3, C4, C5, C6C3, C4, C8, N2.4 (1)
Table 1

Selected interplanar angles (°) for the title compound

Atoms defining plane 1Atoms defining plane 2Interplanar angle
C2, C6, C8, NC11, C19, O85.03 (4)
C3, C4, C8, NC8, C11, N28.9 (1)
C1, C2, C3, C4, C5, C6C3, C4, C8, N2.4 (1)
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