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Treatment of 9-li­thia­ted fluorene with pivaloyl chloride provided ap-9-pivaloyl­fluorene, (1), the major product, and a minor product ultimately identified as the title compound, C23H26O2, (2). The latter was also formed directly, but slowly, from 9-li­thia­ted-(1) treated with pivaloyl chloride. Although (1) exists exclusively as its less sterically restricted ap rotamer, its sp2-hybridized anion sterically impedes reaction at the 9-position from either face. While 9-li­thia­ted-(1) is exclusively, but slowly, 9-methyl­ated with methyl iodide, reaction with pivaloyl chloride, also slow, leads only to the O-acyl­ated product, (2). The protons of the tert-butyl-C=C moiety approach a proton on the fluorene ring to well within the sum of their van der Waals radii, resulting in significant molecular compression, strain and distortion. For example, distortion in the moiety C=C(O)(C) is exhibited by the enlargement of C=C-C angle to 130.6 (2)° at the expense of the corresponding `equivalent' C=C-O angle, which is compressed to 116.46 (19)°.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100011197/bk1551sup1.cif
Contains datablocks global, 2

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100011197/bk15512sup2.hkl
Contains datablock 2

CCDC reference: 153913

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation,1996); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: PROCESS in TEXSAN (Molecular Structure Corporation, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: LS in TEXSAN and SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: TEXSAN, SHELXL97 and PLATON (Spek, 2000).

9-(2',2'-dimethyl-1'-pivaloxypropylidine)fluorene top
Crystal data top
C23H26O2Dx = 1.151 Mg m3
Mr = 334.44Melting point = 404–405 K
Monoclinic, P21/nMo Kα radiation, λ = 0.71069 Å
a = 11.1247 (15) ÅCell parameters from 24 reflections
b = 10.4604 (10) Åθ = 18.8–20.9°
c = 16.6259 (14) ŵ = 0.07 mm1
β = 93.951 (9)°T = 296 K
V = 1930.1 (4) Å3Prism, colorless
Z = 40.54 × 0.49 × 0.43 mm
F(000) = 720
Data collection top
Rigaku AFC-5S
diffractometer
Rint = 0.017
Radiation source: X-ray tubeθmax = 25.0°, θmin = 2.1°
Graphite monochromatorh = 013
ω scansk = 012
3589 measured reflectionsl = 1919
3401 independent reflections3 standard reflections every 100 reflections
2019 reflections with I > 2σ(I) intensity decay: 0.2%
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)] = 0.050H-atom parameters constrained
wR(F2) = 0.153 w = 1/[σ2(Fo2) + (0.0734P)2 + 0.2129P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
3401 reflectionsΔρmax = 0.17 e Å3
233 parametersΔρmin = 0.16 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.017 (2)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.07492 (13)0.97025 (15)0.23828 (8)0.0542 (4)
O20.07343 (17)1.11034 (18)0.25097 (13)0.0863 (6)
C10.2022 (2)1.0212 (2)0.39161 (15)0.0614 (7)
C20.2759 (2)1.0701 (3)0.45469 (17)0.0702 (7)
C30.2670 (2)1.0289 (3)0.53221 (16)0.0723 (7)
C40.1846 (2)0.9361 (3)0.54869 (15)0.0653 (7)
C4a0.11190 (19)0.8851 (2)0.48594 (13)0.0506 (6)
C4b0.0220 (2)0.7845 (2)0.48720 (14)0.0532 (6)
C50.0122 (2)0.7134 (3)0.55244 (16)0.0714 (7)
C60.0997 (3)0.6225 (3)0.54009 (18)0.0825 (9)
C70.1534 (3)0.6026 (3)0.46414 (19)0.0839 (9)
C80.1208 (2)0.6735 (3)0.39891 (17)0.0725 (7)
C8a0.0296 (2)0.7640 (2)0.40863 (14)0.0539 (6)
C90.02719 (19)0.8556 (2)0.35357 (13)0.0493 (6)
C9a0.11783 (19)0.9285 (2)0.40658 (13)0.0489 (6)
C100.0060 (2)0.8737 (2)0.27363 (14)0.0531 (6)
C110.0221 (2)1.0863 (2)0.22611 (14)0.0604 (7)
C120.0955 (2)1.1787 (3)0.17876 (16)0.0688 (7)
C130.1308 (5)1.2902 (3)0.2346 (2)0.1435 (18)
C140.2080 (3)1.1203 (3)0.1491 (2)0.1080 (12)
C150.0162 (4)1.2248 (4)0.1072 (3)0.1449 (18)
C160.0764 (2)0.8021 (3)0.21199 (15)0.0667 (7)
C170.0594 (3)0.8474 (3)0.12516 (17)0.0990 (11)
C180.2096 (2)0.8281 (3)0.22818 (19)0.0893 (9)
C190.0433 (3)0.6589 (3)0.21374 (18)0.0888 (9)
H10.20941.05050.33940.074*
H20.33261.13210.44420.084*
H30.31681.06370.57380.087*
H40.17790.90810.60130.078*
H50.02400.72760.60380.086*
H60.12300.57390.58320.099*
H70.21280.54040.45650.101*
H80.16000.66050.34830.087*
H13a0.18181.34800.20770.215*
H13b0.05961.33440.24860.215*
H13c0.17331.25840.28270.215*
H14a0.25991.09260.19430.162*
H14b0.18671.04820.11520.162*
H14c0.24921.18270.11870.162*
H15a0.06021.28460.07670.217*
H15b0.00801.15330.07370.217*
H15c0.05401.26580.12570.217*
H17a0.02360.83840.11390.148*
H17b0.10870.79650.08780.148*
H17c0.08280.93550.11970.148*
H18a0.23040.91400.21250.134*
H18b0.26060.76920.19750.134*
H18c0.22030.81710.28460.134*
H19a0.03540.62970.26860.133*
H19b0.10560.61110.18440.133*
H19c0.03160.64670.18940.133*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0550 (9)0.0568 (10)0.0514 (9)0.0031 (8)0.0090 (7)0.0059 (7)
O20.0751 (12)0.0803 (13)0.1077 (15)0.0211 (11)0.0376 (11)0.0208 (11)
C10.0666 (16)0.0596 (15)0.0583 (15)0.0078 (13)0.0059 (12)0.0020 (12)
C20.0697 (17)0.0651 (17)0.0751 (18)0.0168 (13)0.0007 (14)0.0015 (14)
C30.0712 (17)0.0804 (19)0.0637 (17)0.0082 (16)0.0079 (13)0.0042 (15)
C40.0685 (16)0.0742 (17)0.0521 (14)0.0015 (15)0.0027 (12)0.0044 (13)
C4a0.0506 (13)0.0511 (13)0.0503 (14)0.0083 (11)0.0043 (10)0.0002 (11)
C4b0.0522 (13)0.0517 (14)0.0563 (15)0.0053 (11)0.0085 (11)0.0033 (11)
C50.0798 (18)0.0733 (18)0.0617 (16)0.0046 (15)0.0093 (14)0.0113 (14)
C60.096 (2)0.0776 (19)0.076 (2)0.0152 (18)0.0180 (17)0.0204 (16)
C70.091 (2)0.0726 (19)0.090 (2)0.0280 (16)0.0166 (17)0.0048 (17)
C80.0834 (18)0.0679 (17)0.0663 (17)0.0174 (15)0.0063 (14)0.0017 (14)
C8a0.0553 (14)0.0495 (13)0.0574 (14)0.0016 (11)0.0080 (11)0.0005 (11)
C90.0511 (13)0.0482 (13)0.0487 (13)0.0018 (11)0.0045 (10)0.0009 (10)
C9a0.0490 (13)0.0455 (13)0.0522 (13)0.0025 (10)0.0043 (10)0.0009 (10)
C100.0500 (13)0.0543 (14)0.0552 (14)0.0011 (11)0.0058 (11)0.0009 (11)
C110.0623 (16)0.0621 (16)0.0577 (15)0.0074 (13)0.0103 (12)0.0043 (12)
C120.0775 (18)0.0687 (17)0.0619 (16)0.0042 (14)0.0175 (13)0.0131 (14)
C130.237 (5)0.078 (2)0.125 (3)0.052 (3)0.080 (3)0.009 (2)
C140.098 (2)0.102 (2)0.131 (3)0.003 (2)0.057 (2)0.024 (2)
C150.123 (3)0.181 (4)0.131 (3)0.012 (3)0.012 (3)0.094 (3)
C160.0684 (16)0.0749 (18)0.0555 (15)0.0093 (14)0.0046 (12)0.0033 (13)
C170.118 (3)0.120 (3)0.0560 (18)0.028 (2)0.0086 (16)0.0042 (18)
C180.0679 (18)0.099 (2)0.099 (2)0.0127 (17)0.0129 (16)0.0041 (18)
C190.107 (2)0.081 (2)0.078 (2)0.0122 (18)0.0004 (17)0.0214 (16)
Geometric parameters (Å, º) top
O1—C111.358 (3)C1—H10.9300
O1—C101.420 (3)C2—H20.9300
O2—C111.194 (3)C3—H30.9300
C1—C21.384 (3)C4—H40.9300
C1—C9a1.384 (3)C5—H50.9300
C2—C31.369 (4)C6—H60.9300
C3—C41.375 (4)C7—H70.9300
C4—C4a1.383 (3)C8—H80.9300
C4a—C9a1.401 (3)C13—H13a0.9600
C4a—C4b1.453 (3)C13—H13b0.9600
C4b—C51.389 (3)C13—H13c0.9600
C4b—C8a1.407 (3)C14—H14a0.9600
C5—C61.366 (4)C14—H14b0.9600
C6—C71.375 (4)C14—H14c0.9600
C7—C81.383 (4)C15—H15a0.9600
C8—C8a1.388 (3)C15—H15b0.9600
C8a—C91.495 (3)C15—H15c0.9600
C9—C101.347 (3)C17—H17a0.9600
C9—C9a1.501 (3)C17—H17b0.9600
C10—C161.524 (3)C17—H17c0.9600
C11—C121.519 (3)C18—H18a0.9600
C12—C141.507 (4)C18—H18b0.9600
C12—C151.511 (4)C18—H18c0.9600
C12—C131.526 (5)C19—H19a0.9600
C16—C191.542 (4)C19—H19b0.9600
C16—C171.543 (4)C19—H19c0.9600
C16—C181.548 (4)
C8a—C9—C10129.9 (2)C4—C3—H3119.9
C9a—C9—C10125.0 (2)C3—C4—H4120.5
C9—C10—C16130.6 (2)C4a—C4—H4120.5
C9—C10—O1116.46 (19)C6—C5—H5120.5
C18—C16—C19113.4 (2)C4b—C5—H5120.5
C17—C16—C19105.8 (2)C5—C6—H6119.9
C17—C16—C18106.8 (2)C7—C6—H6119.9
C10—C16—C17111.8 (2)C6—C7—H7119.4
C10—C16—C18109.6 (2)C8—C7—H7119.4
C10—C16—C19109.5 (2)C7—C8—H8119.9
C13—C12—C14108.9 (3)C8a—C8—H8119.9
C15—C12—C14108.9 (3)C12—C13—H13b109.5
C15—C12—C13110.3 (3)C12—C13—H13a109.5
C11—O1—C10117.24 (17)H13a—C13—H13b109.5
C2—C1—C9a119.8 (2)C12—C13—H13c109.5
C3—C2—C1121.3 (2)H13a—C13—H13c109.5
C2—C3—C4120.1 (2)H13b—C13—H13c109.5
C3—C4—C4a119.0 (2)C12—C14—H14a109.5
C4—C4a—C9a121.5 (2)C12—C14—H14b109.5
C4—C4a—C4b129.5 (2)H14a—C14—H14b109.5
C9a—C4a—C4b108.99 (19)C12—C14—H14c109.5
C5—C4b—C8a121.9 (2)H14a—C14—H14c109.5
C5—C4b—C4a128.6 (2)H14b—C14—H14c109.5
C8a—C4b—C4a109.52 (19)C12—C15—H15a109.5
C6—C5—C4b119.0 (3)C12—C15—H15b109.5
C5—C6—C7120.2 (3)H15a—C15—H15b109.5
C6—C7—C8121.2 (3)C12—C15—H15c109.5
C7—C8—C8a120.2 (3)H15a—C15—H15c109.5
C8—C8a—C4b117.4 (2)H15b—C15—H15c109.5
C8—C8a—C9134.6 (2)C16—C17—H17a109.5
C4b—C8a—C9107.97 (19)C16—C17—H17b109.5
C8a—C9—C9a105.13 (18)H17a—C17—H17b109.5
C1—C9a—C4a118.2 (2)C16—C17—H17c109.5
C1—C9a—C9133.4 (2)H17a—C17—H17c109.5
C4a—C9a—C9108.38 (19)H17b—C17—H17c109.5
O1—C10—C16112.84 (19)C16—C18—H18a109.5
O2—C11—O1121.5 (2)C16—C18—H18b109.5
O2—C11—C12124.6 (2)H18a—C18—H18b109.5
O1—C11—C12113.8 (2)C16—C18—H18c109.5
C14—C12—C11113.6 (2)H18a—C18—H18c109.5
C15—C12—C11107.8 (2)H18b—C18—H18c109.5
C11—C12—C13107.2 (2)C16—C19—H19a109.5
C2—C1—H1120.1C16—C19—H19b109.5
C9a—C1—H1120.1H19a—C19—H19b109.5
C3—C2—H2119.3C16—C19—H19c109.5
C1—C2—H2119.3H19a—C19—H19c109.5
C2—C3—H3119.9H19b—C19—H19c109.5
C8a—C9—C10—C164.3 (4)C8—C8a—C9—C102.3 (4)
C9a—C9—C10—O10.6 (3)C4b—C8a—C9—C10178.8 (2)
C9a—C9—C10—C16175.6 (2)C4b—C8a—C9—C9a1.3 (2)
C8a—C9—C10—O1179.4 (2)C2—C1—C9a—C4a1.4 (3)
C8—C8a—C9—C9a177.8 (3)C4—C4a—C9a—C12.5 (3)
C8a—C9—C9a—C1176.5 (2)C4b—C4a—C9a—C1177.3 (2)
C2—C1—C9a—C9179.1 (2)C4—C4a—C9a—C9179.3 (2)
C9a—C1—C2—C30.2 (4)C4b—C4a—C9a—C91.0 (2)
C1—C2—C3—C40.7 (4)C10—C9—C9a—C13.5 (4)
C2—C3—C4—C4a0.3 (4)C10—C9—C9a—C4a178.7 (2)
C3—C4—C4a—C9a2.0 (4)C8a—C9—C9a—C4a1.4 (2)
C3—C4—C4a—C4b177.7 (2)C11—O1—C10—C998.2 (2)
C4—C4a—C4b—C50.8 (4)C11—O1—C10—C1684.9 (2)
C9a—C4a—C4b—C5178.9 (2)C10—O1—C11—O27.0 (3)
C4—C4a—C4b—C8a179.9 (2)C10—O1—C11—C12172.8 (2)
C9a—C4a—C4b—C8a0.1 (2)O2—C11—C12—C14175.4 (3)
C8a—C4b—C5—C61.1 (4)O1—C11—C12—C144.4 (3)
C4a—C4b—C5—C6180.0 (2)O2—C11—C12—C1554.6 (4)
C4b—C5—C6—C70.4 (4)O1—C11—C12—C15125.2 (3)
C5—C6—C7—C80.1 (5)O2—C11—C12—C1364.2 (4)
C6—C7—C8—C8a2.1 (5)O1—C11—C12—C13116.0 (3)
C7—C8—C8a—C4b3.4 (4)C9—C10—C16—C1956.3 (3)
C7—C8—C8a—C9179.6 (3)O1—C10—C16—C19120.0 (2)
C5—C4b—C8a—C82.9 (3)C9—C10—C16—C17173.2 (3)
C4a—C4b—C8a—C8177.9 (2)O1—C10—C16—C173.2 (3)
C5—C4b—C8a—C9179.9 (2)C9—C10—C16—C1868.6 (3)
C4a—C4b—C8a—C90.7 (2)O1—C10—C16—C18115.0 (2)
 

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