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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): o1939.
Published online 2010 July 7. doi:  10.1107/S1600536810025833
PMCID: PMC3007235

9,9-Bis[4-(prop-2-yn­yloxy)phen­yl]-9H-fluorene

Abstract

In the title compound, C31H22O2, the bond angle at the C atom belonging to the five-membered ring of the fluorene system is opened to 112.64 (12)°. The two benzene rings are twisted with respect to the fluorene ring system at dihedral angles of 72.81 (6) and 81.83 (6)°. One Car­yl—O—C—C  fragment is extended, with a C—O—C—C torsion angle of −178.77 (13)°, but the other Car­yl—O—C—C  fragment is bent, with a C—O—C—C torsion angle of 64.78 (19)°. Inter­molecular weak C—H(...)O hydrogen bonding is present in the crystal structure.

Related literature

For the synthesis of copolyethers having 1,3,4-oxadiazole rings and fluorene groups from the polymerization of 9,9-bis­(4-propargyloxyphen­yl)fluorene, see: Hamciuc et al. (2009 [triangle]). For a related structure, see: Shah et al. (2010 [triangle]).

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Object name is e-66-o1939-scheme1.jpg

Experimental

Crystal data

  • C31H22O2
  • M r = 426.49
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1939-efi1.jpg
  • a = 11.0047 (8) Å
  • b = 12.9686 (9) Å
  • c = 15.4371 (11) Å
  • V = 2203.1 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 100 K
  • 0.35 × 0.25 × 0.15 mm

Data collection

  • Bruker SMART APEX diffractometer
  • 21245 measured reflections
  • 2861 independent reflections
  • 2658 reflections with I > 2σ(I)
  • R int = 0.042

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.082
  • S = 1.04
  • 2861 reflections
  • 306 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.18 e Å−3
  • Δρmin = −0.20 e Å−3
  • Absolute structure: 2204 Friedel pairs were merged
  • Flack parameter: ?
  • Rogers parameter: ?

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810025833/xu2792sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810025833/xu2792Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Higher Education Commission of Pakistan and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

9,9-Bis(4-propargyloxyphenyl)fluorene is the mononer required for the synthesis of other copolyethers (Hamciuc et al., 2009); these polymers typically possess good solubility in inorganic solvents, high thermal stability and high glass transition temperatures. The compound is readily synthesized from commercially available 9,9-bis(4-hydroxyphenyl)fluorene and propargyl bromide. A previous report detailed the structure of the product of its reaction with t-butyl bromoacetate (Shah et al., 2010). In the C31H22O2 molecule (Scheme I, Fig. 1), the angle at the carbon atom belonging to the five-membered fluorenyl ring that is connected to two p-phenylene rings is open to 116.1 (1) ° by the rings. One four-atom Caryl–O–C–C[equivalent] fragment is coplanar with the ring [C—O–C–C torsion angle 1.2 (1) °] but the other is bent [torsion angle 64.8 (2) °].

Experimental

9,9-Bis(4-hydroxyphenyl)fluorene (0.5 g, 1.4 mmol) was dissolved in acetone (25 ml) to give a clear solution. Potassium carbonate (0.7 g, 5 mmol) was added and the mixture stirred for an hour. Propargyl bromide (0.7 ml, 5 mmol) was added and stirring continued overnight. The mixture was filtered; prismatic crystals separated from the solution in 80% yield.

Refinement

The acetylenic H-atoms were located in a difference Fourier map, and were refined with a distance restraint of C–H 0.95±0.01 Å; their temperature factors were refined. Other H atoms were placed in calculated positions [C–H 0.95–0.99 Å, U(H) = 1.2U(C)] and were included in the refinement in the riding model approximation. Friedel pairs were merged as no significant anomalous scattering.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of C31H22O2 at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C31H22O2F(000) = 896
Mr = 426.49Dx = 1.286 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 7024 reflections
a = 11.0047 (8) Åθ = 2.3–27.7°
b = 12.9686 (9) ŵ = 0.08 mm1
c = 15.4371 (11) ÅT = 100 K
V = 2203.1 (3) Å3Block, colorless
Z = 40.35 × 0.25 × 0.15 mm

Data collection

Bruker SMART APEX diffractometer2658 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.042
graphiteθmax = 27.5°, θmin = 2.1°
ω scansh = −14→14
21245 measured reflectionsk = −16→16
2861 independent reflectionsl = −19→20

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.082w = 1/[σ2(Fo2) + (0.0504P)2 + 0.3105P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
2861 reflectionsΔρmax = 0.18 e Å3
306 parametersΔρmin = −0.20 e Å3
2 restraintsAbsolute structure: 2204 Friedel pairs were merged
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O11.24715 (9)0.37529 (9)1.06380 (7)0.0184 (3)
O20.72277 (11)0.74489 (10)0.66169 (7)0.0228 (3)
C10.84334 (14)0.71897 (12)1.07308 (10)0.0146 (3)
C20.93879 (15)0.78830 (12)1.08005 (11)0.0174 (3)
H21.00720.78321.04280.021*
C30.93255 (15)0.86561 (13)1.14272 (11)0.0200 (3)
H30.99790.91301.14880.024*
C40.83115 (16)0.87398 (13)1.19668 (11)0.0205 (3)
H40.82780.92761.23850.025*
C50.73513 (16)0.80494 (13)1.18992 (11)0.0188 (3)
H50.66600.81111.22640.023*
C60.74238 (14)0.72624 (13)1.12841 (10)0.0156 (3)
C70.65875 (14)0.64169 (13)1.10835 (10)0.0169 (3)
C80.54672 (15)0.61615 (14)1.14465 (11)0.0206 (3)
H80.51280.65651.19000.025*
C90.48567 (15)0.52999 (15)1.11285 (12)0.0226 (4)
H90.40970.51091.13720.027*
C100.53482 (15)0.47162 (14)1.04579 (12)0.0211 (4)
H100.49220.41291.02510.025*
C110.64577 (15)0.49837 (13)1.00872 (11)0.0189 (3)
H110.67820.45930.96210.023*
C120.70800 (14)0.58268 (13)1.04078 (10)0.0157 (3)
C130.82912 (13)0.62794 (12)1.01042 (10)0.0143 (3)
C140.93668 (14)0.55407 (12)1.02154 (10)0.0145 (3)
C150.93030 (15)0.46837 (13)1.07548 (11)0.0167 (3)
H150.85530.45191.10270.020*
C161.03105 (14)0.40609 (13)1.09059 (10)0.0170 (3)
H161.02480.34771.12750.020*
C171.14088 (14)0.43008 (13)1.05113 (11)0.0151 (3)
C181.14950 (14)0.51457 (12)0.99593 (11)0.0160 (3)
H181.22430.53030.96820.019*
C191.04803 (14)0.57562 (12)0.98172 (10)0.0160 (3)
H191.05420.63340.94410.019*
C201.23372 (16)0.26883 (13)1.08654 (12)0.0210 (4)
H20A1.19070.23131.03990.025*
H20B1.18590.26231.14060.025*
C211.35523 (17)0.22575 (14)1.09882 (11)0.0222 (4)
C221.4531 (2)0.19125 (17)1.11001 (14)0.0342 (5)
C230.81257 (14)0.66357 (13)0.91600 (10)0.0153 (3)
C240.76842 (14)0.76168 (13)0.89833 (10)0.0163 (3)
H240.75880.80920.94470.020*
C250.73786 (15)0.79255 (13)0.81480 (11)0.0186 (3)
H250.70750.86000.80430.022*
C260.75237 (15)0.72339 (14)0.74710 (10)0.0182 (3)
C270.79946 (15)0.62612 (15)0.76239 (11)0.0210 (4)
H270.81190.57990.71550.025*
C280.82856 (15)0.59607 (13)0.84623 (11)0.0192 (3)
H280.85970.52880.85630.023*
C290.67080 (16)0.84363 (14)0.64399 (11)0.0221 (4)
H29A0.66280.85180.58050.027*
H29B0.72720.89770.66490.027*
C300.55120 (16)0.86010 (14)0.68398 (11)0.0203 (3)
C310.45729 (17)0.87683 (15)0.71807 (12)0.0254 (4)
H221.5337 (13)0.167 (2)1.1183 (19)0.073 (10)*
H310.3818 (13)0.8907 (17)0.7453 (13)0.036 (6)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0141 (5)0.0153 (6)0.0257 (6)0.0011 (5)0.0006 (5)0.0027 (5)
O20.0289 (6)0.0249 (6)0.0146 (5)0.0056 (5)−0.0034 (5)0.0000 (5)
C10.0168 (7)0.0140 (7)0.0130 (7)0.0024 (6)−0.0032 (6)0.0020 (6)
C20.0182 (7)0.0176 (8)0.0164 (8)−0.0001 (6)−0.0016 (6)0.0003 (6)
C30.0233 (8)0.0157 (8)0.0209 (8)−0.0031 (7)−0.0052 (7)0.0008 (7)
C40.0292 (8)0.0168 (8)0.0154 (7)0.0034 (7)−0.0040 (7)−0.0016 (6)
C50.0212 (8)0.0205 (8)0.0147 (7)0.0045 (7)−0.0007 (6)0.0001 (7)
C60.0161 (7)0.0167 (8)0.0140 (7)0.0031 (6)−0.0021 (6)0.0020 (6)
C70.0165 (7)0.0184 (8)0.0159 (7)0.0021 (6)−0.0024 (6)0.0027 (6)
C80.0160 (7)0.0267 (9)0.0192 (8)0.0023 (7)−0.0003 (6)0.0019 (7)
C90.0140 (7)0.0283 (9)0.0256 (9)−0.0019 (7)0.0001 (7)0.0063 (8)
C100.0167 (7)0.0196 (8)0.0269 (9)−0.0035 (6)−0.0053 (7)0.0031 (7)
C110.0171 (7)0.0181 (8)0.0215 (8)0.0007 (6)−0.0025 (7)0.0006 (7)
C120.0145 (7)0.0161 (8)0.0164 (7)0.0017 (6)−0.0026 (6)0.0036 (6)
C130.0144 (7)0.0131 (7)0.0153 (7)0.0007 (6)−0.0004 (6)0.0003 (6)
C140.0146 (7)0.0151 (8)0.0138 (7)0.0007 (6)−0.0012 (6)−0.0017 (6)
C150.0154 (7)0.0188 (8)0.0158 (8)−0.0021 (6)0.0008 (6)0.0007 (6)
C160.0186 (7)0.0163 (8)0.0159 (8)−0.0001 (6)−0.0007 (6)0.0031 (6)
C170.0149 (7)0.0142 (8)0.0162 (7)0.0000 (6)−0.0018 (6)−0.0032 (6)
C180.0154 (7)0.0160 (8)0.0166 (8)−0.0025 (6)0.0014 (6)−0.0009 (6)
C190.0192 (7)0.0126 (7)0.0160 (8)−0.0018 (6)0.0005 (6)0.0012 (6)
C200.0219 (8)0.0149 (8)0.0263 (9)−0.0003 (7)−0.0036 (7)0.0033 (7)
C210.0292 (9)0.0181 (8)0.0195 (8)0.0046 (7)0.0028 (7)0.0010 (7)
C220.0337 (10)0.0411 (12)0.0279 (10)0.0200 (10)0.0063 (9)0.0081 (9)
C230.0137 (7)0.0172 (8)0.0151 (7)−0.0003 (6)−0.0010 (6)−0.0002 (6)
C240.0173 (7)0.0151 (8)0.0165 (7)0.0005 (6)−0.0011 (6)−0.0031 (6)
C250.0203 (8)0.0151 (8)0.0205 (8)0.0011 (7)−0.0041 (7)0.0005 (7)
C260.0172 (7)0.0227 (8)0.0149 (7)−0.0005 (6)−0.0009 (6)−0.0002 (7)
C270.0224 (8)0.0235 (9)0.0169 (8)0.0036 (7)−0.0017 (6)−0.0040 (7)
C280.0208 (8)0.0161 (8)0.0206 (8)0.0037 (6)−0.0023 (7)−0.0021 (7)
C290.0247 (8)0.0233 (9)0.0184 (8)0.0012 (7)−0.0012 (7)0.0044 (7)
C300.0265 (8)0.0175 (8)0.0170 (8)−0.0020 (7)−0.0052 (7)0.0025 (7)
C310.0265 (9)0.0253 (10)0.0243 (9)−0.0038 (8)0.0013 (7)−0.0011 (8)

Geometric parameters (Å, °)

O1—C171.3824 (18)C14—C191.399 (2)
O1—C201.432 (2)C15—C161.391 (2)
O2—C261.387 (2)C15—H150.9500
O2—C291.429 (2)C16—C171.389 (2)
C1—C21.387 (2)C16—H160.9500
C1—C61.405 (2)C17—C181.391 (2)
C1—C131.534 (2)C18—C191.386 (2)
C2—C31.395 (2)C18—H180.9500
C2—H20.9500C19—H190.9500
C3—C41.397 (2)C20—C211.462 (2)
C3—H30.9500C20—H20A0.9900
C4—C51.389 (2)C20—H20B0.9900
C4—H40.9500C21—C221.179 (3)
C5—C61.396 (2)C22—H220.949 (10)
C5—H50.9500C23—C241.389 (2)
C6—C71.465 (2)C23—C281.399 (2)
C7—C81.394 (2)C24—C251.391 (2)
C7—C121.403 (2)C24—H240.9500
C8—C91.393 (3)C25—C261.386 (2)
C8—H80.9500C25—H250.9500
C9—C101.392 (3)C26—C271.384 (2)
C9—H90.9500C27—C281.389 (2)
C10—C111.392 (2)C27—H270.9500
C10—H100.9500C28—H280.9500
C11—C121.382 (2)C29—C301.469 (2)
C11—H110.9500C29—H29A0.9900
C12—C131.530 (2)C29—H29B0.9900
C13—C141.532 (2)C30—C311.180 (3)
C13—C231.540 (2)C31—H310.949 (10)
C14—C151.390 (2)
C17—O1—C20116.28 (12)C14—C15—H15119.2
C26—O2—C29117.13 (13)C16—C15—H15119.2
C2—C1—C6120.56 (15)C17—C16—C15119.34 (15)
C2—C1—C13128.68 (14)C17—C16—H16120.3
C6—C1—C13110.75 (13)C15—C16—H16120.3
C1—C2—C3118.85 (15)O1—C17—C16124.00 (14)
C1—C2—H2120.6O1—C17—C18115.70 (14)
C3—C2—H2120.6C16—C17—C18120.29 (15)
C2—C3—C4120.58 (16)C19—C18—C17119.46 (15)
C2—C3—H3119.7C19—C18—H18120.3
C4—C3—H3119.7C17—C18—H18120.3
C5—C4—C3120.86 (15)C18—C19—C14121.46 (15)
C5—C4—H4119.6C18—C19—H19119.3
C3—C4—H4119.6C14—C19—H19119.3
C4—C5—C6118.61 (15)O1—C20—C21107.81 (14)
C4—C5—H5120.7O1—C20—H20A110.1
C6—C5—H5120.7C21—C20—H20A110.1
C5—C6—C1120.52 (15)O1—C20—H20B110.1
C5—C6—C7130.92 (15)C21—C20—H20B110.1
C1—C6—C7108.56 (14)H20A—C20—H20B108.5
C8—C7—C12120.73 (16)C22—C21—C20179.0 (2)
C8—C7—C6130.43 (16)C21—C22—H22177 (2)
C12—C7—C6108.84 (14)C24—C23—C28117.77 (15)
C9—C8—C7118.38 (17)C24—C23—C13120.14 (14)
C9—C8—H8120.8C28—C23—C13121.74 (14)
C7—C8—H8120.8C23—C24—C25122.01 (15)
C8—C9—C10120.73 (16)C23—C24—H24119.0
C8—C9—H9119.6C25—C24—H24119.0
C10—C9—H9119.6C26—C25—C24118.99 (15)
C11—C10—C9120.73 (17)C26—C25—H25120.5
C11—C10—H10119.6C24—C25—H25120.5
C9—C10—H10119.6C27—C26—O2115.68 (15)
C12—C11—C10118.97 (16)C27—C26—C25120.28 (15)
C12—C11—H11120.5O2—C26—C25124.04 (15)
C10—C11—H11120.5C26—C27—C28120.06 (16)
C11—C12—C7120.44 (15)C26—C27—H27120.0
C11—C12—C13128.72 (15)C28—C27—H27120.0
C7—C12—C13110.80 (14)C27—C28—C23120.85 (16)
C12—C13—C14113.50 (13)C27—C28—H28119.6
C12—C13—C1101.01 (12)C23—C28—H28119.6
C14—C13—C1109.36 (12)O2—C29—C30114.11 (14)
C12—C13—C23107.59 (12)O2—C29—H29A108.7
C14—C13—C23112.64 (12)C30—C29—H29A108.7
C1—C13—C23112.21 (13)O2—C29—H29B108.7
C15—C14—C19117.84 (14)C30—C29—H29B108.7
C15—C14—C13121.86 (14)H29A—C29—H29B107.6
C19—C14—C13120.16 (14)C31—C30—C29177.1 (2)
C14—C15—C16121.61 (15)C30—C31—H31179.6 (16)
C6—C1—C2—C3−0.3 (2)C12—C13—C14—C15−17.1 (2)
C13—C1—C2—C3−179.70 (15)C1—C13—C14—C1594.84 (17)
C1—C2—C3—C4−0.9 (2)C23—C13—C14—C15−139.66 (15)
C2—C3—C4—C50.8 (3)C12—C13—C14—C19167.42 (14)
C3—C4—C5—C60.5 (2)C1—C13—C14—C19−80.65 (17)
C4—C5—C6—C1−1.7 (2)C23—C13—C14—C1944.9 (2)
C4—C5—C6—C7177.91 (16)C19—C14—C15—C160.7 (2)
C2—C1—C6—C51.6 (2)C13—C14—C15—C16−174.94 (15)
C13—C1—C6—C5−178.88 (14)C14—C15—C16—C170.2 (3)
C2—C1—C6—C7−178.09 (14)C20—O1—C17—C1627.2 (2)
C13—C1—C6—C71.44 (17)C20—O1—C17—C18−153.71 (14)
C5—C6—C7—C80.7 (3)C15—C16—C17—O1177.96 (15)
C1—C6—C7—C8−179.64 (16)C15—C16—C17—C18−1.1 (2)
C5—C6—C7—C12−179.73 (16)O1—C17—C18—C19−178.06 (14)
C1—C6—C7—C12−0.10 (18)C16—C17—C18—C191.0 (2)
C12—C7—C8—C90.7 (2)C17—C18—C19—C14−0.2 (2)
C6—C7—C8—C9−179.79 (16)C15—C14—C19—C18−0.7 (2)
C7—C8—C9—C10−0.7 (3)C13—C14—C19—C18174.99 (14)
C8—C9—C10—C11−0.3 (3)C17—O1—C20—C21−178.77 (13)
C9—C10—C11—C121.4 (3)C12—C13—C23—C2486.88 (17)
C10—C11—C12—C7−1.4 (2)C14—C13—C23—C24−147.28 (15)
C10—C11—C12—C13−178.96 (15)C1—C13—C23—C24−23.34 (19)
C8—C7—C12—C110.3 (2)C12—C13—C23—C28−86.21 (17)
C6—C7—C12—C11−179.24 (14)C14—C13—C23—C2839.6 (2)
C8—C7—C12—C13178.31 (14)C1—C13—C23—C28163.57 (15)
C6—C7—C12—C13−1.28 (18)C28—C23—C24—C251.5 (2)
C11—C12—C13—C14−63.3 (2)C13—C23—C24—C25−171.88 (15)
C7—C12—C13—C14118.92 (15)C23—C24—C25—C26−0.3 (2)
C11—C12—C13—C1179.74 (16)C29—O2—C26—C27178.32 (14)
C7—C12—C13—C11.99 (16)C29—O2—C26—C25−2.0 (2)
C11—C12—C13—C2362.0 (2)C24—C25—C26—C27−1.6 (2)
C7—C12—C13—C23−115.75 (15)C24—C25—C26—O2178.69 (15)
C2—C1—C13—C12177.43 (15)O2—C26—C27—C28−178.08 (15)
C6—C1—C13—C12−2.06 (16)C25—C26—C27—C282.2 (3)
C2—C1—C13—C1457.5 (2)C26—C27—C28—C23−0.9 (3)
C6—C1—C13—C14−121.99 (14)C24—C23—C28—C27−0.9 (2)
C2—C1—C13—C23−68.3 (2)C13—C23—C28—C27172.36 (15)
C6—C1—C13—C23112.26 (14)C26—O2—C29—C30−64.78 (19)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C29—H29A···O1i0.992.463.358 (2)151

Symmetry codes: (i) −x+2, y+1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2792).

References

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