organic compounds
Bis{5-[(2-propyn-1-yloxy)methyl]-1,3-phenylene}-32-crown-10
aSchool of Chemistry and Environment, South China Normal University, Guangzhou 510006, People's Republic of China
*Correspondence e-mail: jiang6128@yahoo.com.cn
The molecule of the title compound {systematic name: 17,35-bis[(2-propyn-1-yloxy)methyl]-2,5,8,11,14,20,23,26,29,32-decaoxatricyclo[31.3.1.115,19]octatriaconta-1(37),15,17,19 (38),33,35-hexaene}, C36H48O12, has crystallographic inversion symmetry and adopts a chair-like conformation. The polyether bridges of the macrocycle adopt gauche conformations and the cavity of the macrocycle is collapsed. In the there are weak intermolecular C—H⋯O hydrogen bonds driven in part by the elevated acidity of acetylenyl H atoms.
Related literature
For applications of et al. (2004); Raymo et al. (1999) and of bisphenylene crown erthers, see: Loeb (2007); Fang et al. (2010); Kay et al. (2007). For cryptands, see: Zhang et al. (2010). For supramolecular interlocked structures, see: Xu et al. (2011) For the synthesis of bis(5-hydroxymethyl-1,3-phenylene)-32-crown-10, see: Gibson & Nagvekar (1997) and for the synthesis of the title compound, see: Xu et al. (2010).
see: GokelExperimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2008); cell SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536811046435/ld2029sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811046435/ld2029Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536811046435/ld2029Isup3.cml
The title compound was synthesized from bis(5-hydroxymethyl-1,3-phenylene)-32-crown-10 (Gibson, et al., 1997) which was reacted with sodium hydride and propargyl bromide (Xu et al.,2010). Colourless block crystal of the title compound suitable for X-ray
was obtained by slow evaporation of its acetone solution at room temperature.The H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.95 - 0.99 Å, and Uiso=1.2–1.5 Ueq(C).
Crown
are important building blocks in supramolecular chemistry and have been widely used in materials and biological sciences for sensors and switches (Gokel et al., 2004; Raymo et al., 1999). Recently, bisphenylene such as bisparaphenylene-34-crown-10 (BPP34C10) and bismetaphenylene-32-crown-10 (BMP32C10), attracted great interests and were extensively used for construction of interlocked molecules (Loeb, 2007), mechanically bonded macromolecules(Fang et al., 2010) and molecular machines(Kay et al., 2007). Their wide uses are mainly because bisphenylene crown erther hosts can form relatively stable molecular complexes with electron deficient paraquat derivatives by virtue of multiple noncovalent interactions, such as hydrogen bondging and charge-transfer interactions. As part of our project to explore novel crown ether-based cryptands (Zhang et al., 2010,) in supramolecular self-assembly (Xu et al., 2010) and interlocked structures(Xu et al., 2011), we tackled the synthesis of bisacetylene-substituted BMP32C10, an important precursor to cryptands. We envisioned that the title compound could be obtained by the reaction of bis(5-hydroxymethyl-1,3-phenylene)-32-crown-10 with propargyl bromide in the presence of sodium hydride.As shown in Fig. 1, the title compound has crystallographic inversion symmetry in the solid state. The phenyl rings are at a centroid-centroid distance of 9.422 Å and they are arranged in an edge-to-edge conformation rather than a face-to-face one. The polyether bridges of the macrocycle adopt a
conformation and the cavity of the macrocycle is collapsed. The molecule as a whole adopts a chair-like conformation. Weak intermolecular C—H···O hydrogen bonds driven by the elevated acidity of acetylene hydrogen were observed.For applications of
see: Gokel et al. (2004); Raymo et al. (1999) and of bisphenylene crown erthers, see: Loeb (2007); Fang et al. (2010); Kay et al. (2007). For cryptands, see: Zhang et al. (2010). For supramolecular interlocked structures, see: Xu et al. (2011) For the synthesis of bis(5-hydroxymethyl-1,3-phenylene)-32-crown-10, see: Gibson & Nagvekar (1997) and of the title compound, see: Xu et al. (2010).Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. View of the title compound showing the atom-labelling scheme. Ellipsoids are drawn at the 50% probability level. |
C36H48O12 | V = 883.9 (2) Å3 |
Mr = 672.74 | Z = 1 |
Triclinic, P1 | F(000) = 360 |
Hall symbol: -P 1 | Dx = 1.264 Mg m−3 |
a = 9.2256 (13) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.8561 (14) Å | µ = 0.09 mm−1 |
c = 10.0808 (14) Å | T = 298 K |
α = 97.213 (2)° | Block, colourless |
β = 98.658 (2)° | 0.64 × 0.32 × 0.10 mm |
γ = 99.226 (2)° |
Bruker APEXII CCD diffractometer | 3108 independent reflections |
Radiation source: fine-focus sealed tube | 2350 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
φ and ω scans | θmax = 25.2°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→10 |
Tmin = 0.965, Tmax = 0.991 | k = −7→11 |
4551 measured reflections | l = −12→10 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0506P)2 + 0.1259P] where P = (Fo2 + 2Fc2)/3 |
3108 reflections | (Δ/σ)max < 0.001 |
217 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C36H48O12 | γ = 99.226 (2)° |
Mr = 672.74 | V = 883.9 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.2256 (13) Å | Mo Kα radiation |
b = 9.8561 (14) Å | µ = 0.09 mm−1 |
c = 10.0808 (14) Å | T = 298 K |
α = 97.213 (2)° | 0.64 × 0.32 × 0.10 mm |
β = 98.658 (2)° |
Bruker APEXII CCD diffractometer | 3108 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2350 reflections with I > 2σ(I) |
Tmin = 0.965, Tmax = 0.991 | Rint = 0.020 |
4551 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.26 e Å−3 |
3108 reflections | Δρmin = −0.21 e Å−3 |
217 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.19258 (19) | 0.18786 (18) | 0.55393 (17) | 0.0405 (4) | |
H1 | 0.0968 | 0.1897 | 0.5717 | 0.049* | |
C2 | 0.21585 (18) | 0.15530 (18) | 0.42298 (16) | 0.0393 (4) | |
C3 | 0.35977 (19) | 0.15509 (19) | 0.39575 (17) | 0.0428 (4) | |
H3 | 0.3744 | 0.1335 | 0.3068 | 0.051* | |
C5 | 0.45832 (19) | 0.21882 (18) | 0.63403 (17) | 0.0427 (4) | |
H5 | 0.5393 | 0.2404 | 0.7049 | 0.051* | |
C6 | 0.31507 (19) | 0.21810 (18) | 0.65978 (16) | 0.0392 (4) | |
C8 | −0.13388 (19) | 0.0898 (2) | 0.18269 (18) | 0.0472 (5) | |
H8A | −0.1242 | −0.0054 | 0.1536 | 0.057* | |
H8B | −0.2380 | 0.0914 | 0.1867 | 0.057* | |
C7 | −0.04096 (18) | 0.1423 (2) | 0.32005 (17) | 0.0456 (4) | |
H7A | −0.0407 | 0.2406 | 0.3455 | 0.055* | |
H7B | −0.0801 | 0.0923 | 0.3878 | 0.055* | |
C9 | −0.1580 (2) | 0.1224 (2) | −0.04624 (17) | 0.0513 (5) | |
H9A | −0.2653 | 0.1062 | −0.0510 | 0.062* | |
H9B | −0.1291 | 0.0348 | −0.0762 | 0.062* | |
C10 | 0.4014 (2) | 0.2810 (2) | 0.89901 (17) | 0.0519 (5) | |
H10A | 0.4619 | 0.3688 | 0.8916 | 0.062* | |
H10B | 0.4639 | 0.2107 | 0.8987 | 0.062* | |
C11 | 0.3400 (2) | 0.2938 (2) | 1.02859 (17) | 0.0520 (5) | |
H11A | 0.2712 | 0.2091 | 1.0311 | 0.062* | |
H11B | 0.4206 | 0.3065 | 1.1054 | 0.062* | |
C12 | 0.2334 (2) | 0.4423 (2) | 1.17067 (16) | 0.0492 (5) | |
H12A | 0.3250 | 0.4829 | 1.2333 | 0.059* | |
H12B | 0.1886 | 0.3588 | 1.2018 | 0.059* | |
C13 | 0.1296 (2) | 0.5426 (2) | 1.16786 (17) | 0.0513 (5) | |
H13A | 0.0356 | 0.4998 | 1.1098 | 0.062* | |
H13B | 0.1102 | 0.5687 | 1.2587 | 0.062* | |
C14 | 0.1140 (2) | 0.7742 (2) | 1.13577 (19) | 0.0553 (5) | |
H14A | 0.1367 | 0.8184 | 1.2299 | 0.066* | |
H14B | 0.0076 | 0.7388 | 1.1128 | 0.066* | |
C4 | 0.47982 (19) | 0.18667 (18) | 0.49997 (17) | 0.0408 (4) | |
C15 | 0.63517 (19) | 0.1857 (2) | 0.46986 (19) | 0.0492 (5) | |
H15A | 0.6738 | 0.1108 | 0.5088 | 0.059* | |
H15B | 0.6298 | 0.1666 | 0.3723 | 0.059* | |
C16 | 0.6984 (3) | 0.4263 (2) | 0.4602 (2) | 0.0663 (6) | |
H16A | 0.7603 | 0.5112 | 0.5111 | 0.080* | |
H16B | 0.5954 | 0.4319 | 0.4656 | 0.080* | |
C18 | 0.7341 (2) | 0.4114 (2) | 0.2047 (2) | 0.0671 (6) | |
H18 | 0.7476 | 0.4066 | 0.1147 | 0.081* | |
C17 | 0.7173 (2) | 0.4175 (2) | 0.3175 (2) | 0.0567 (5) | |
O6 | 0.73584 (14) | 0.31229 (15) | 0.52126 (12) | 0.0566 (4) | |
O1 | 0.10633 (13) | 0.11960 (14) | 0.31046 (11) | 0.0512 (4) | |
O3 | 0.28037 (13) | 0.24304 (13) | 0.78669 (11) | 0.0463 (3) | |
O4 | 0.26536 (15) | 0.40777 (14) | 1.03810 (11) | 0.0512 (3) | |
O5 | 0.19356 (13) | 0.66270 (14) | 1.11802 (12) | 0.0506 (3) | |
O2 | −0.08593 (13) | 0.17487 (13) | 0.08915 (11) | 0.0490 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0395 (9) | 0.0443 (10) | 0.0403 (10) | 0.0095 (8) | 0.0102 (7) | 0.0095 (8) |
C2 | 0.0433 (9) | 0.0424 (10) | 0.0335 (9) | 0.0107 (8) | 0.0051 (7) | 0.0089 (7) |
C3 | 0.0487 (10) | 0.0493 (11) | 0.0342 (9) | 0.0136 (8) | 0.0121 (8) | 0.0088 (8) |
C5 | 0.0413 (9) | 0.0467 (11) | 0.0391 (10) | 0.0050 (8) | 0.0047 (7) | 0.0095 (8) |
C6 | 0.0464 (10) | 0.0416 (10) | 0.0313 (9) | 0.0067 (8) | 0.0113 (7) | 0.0076 (7) |
C8 | 0.0416 (9) | 0.0574 (12) | 0.0425 (10) | 0.0079 (9) | 0.0061 (8) | 0.0098 (9) |
C7 | 0.0414 (10) | 0.0587 (12) | 0.0398 (10) | 0.0125 (9) | 0.0097 (8) | 0.0122 (9) |
C9 | 0.0546 (11) | 0.0577 (12) | 0.0383 (10) | 0.0145 (9) | −0.0011 (8) | 0.0002 (9) |
C10 | 0.0512 (11) | 0.0671 (13) | 0.0349 (10) | 0.0101 (10) | 0.0029 (8) | 0.0043 (9) |
C11 | 0.0608 (12) | 0.0579 (12) | 0.0353 (10) | 0.0090 (10) | 0.0023 (8) | 0.0089 (9) |
C12 | 0.0623 (11) | 0.0568 (12) | 0.0271 (9) | 0.0020 (9) | 0.0092 (8) | 0.0103 (8) |
C13 | 0.0495 (10) | 0.0712 (14) | 0.0298 (9) | 0.0012 (10) | 0.0071 (8) | 0.0074 (9) |
C14 | 0.0589 (11) | 0.0735 (14) | 0.0369 (10) | 0.0245 (11) | 0.0067 (8) | 0.0070 (9) |
C4 | 0.0443 (10) | 0.0416 (10) | 0.0399 (10) | 0.0101 (8) | 0.0118 (8) | 0.0106 (8) |
C15 | 0.0441 (10) | 0.0566 (12) | 0.0510 (11) | 0.0109 (9) | 0.0140 (8) | 0.0148 (9) |
C16 | 0.0830 (15) | 0.0566 (13) | 0.0629 (14) | 0.0066 (12) | 0.0300 (12) | 0.0094 (11) |
C18 | 0.0694 (14) | 0.0862 (17) | 0.0565 (14) | 0.0202 (12) | 0.0215 (11) | 0.0315 (12) |
C17 | 0.0597 (12) | 0.0608 (13) | 0.0564 (13) | 0.0135 (10) | 0.0199 (10) | 0.0201 (10) |
O6 | 0.0530 (8) | 0.0709 (10) | 0.0438 (8) | −0.0001 (7) | 0.0092 (6) | 0.0150 (7) |
O1 | 0.0435 (7) | 0.0752 (9) | 0.0350 (7) | 0.0193 (6) | 0.0034 (5) | 0.0017 (6) |
O3 | 0.0456 (7) | 0.0607 (8) | 0.0307 (6) | 0.0048 (6) | 0.0077 (5) | 0.0051 (6) |
O4 | 0.0700 (8) | 0.0582 (8) | 0.0279 (6) | 0.0123 (7) | 0.0118 (6) | 0.0114 (6) |
O5 | 0.0489 (7) | 0.0630 (9) | 0.0454 (7) | 0.0154 (6) | 0.0136 (6) | 0.0163 (6) |
O2 | 0.0529 (7) | 0.0567 (8) | 0.0336 (7) | 0.0045 (6) | 0.0002 (5) | 0.0078 (6) |
C1—C2 | 1.376 (2) | C10—H10B | 0.9700 |
C1—C6 | 1.398 (2) | C11—O4 | 1.409 (2) |
C1—H1 | 0.9300 | C11—H11A | 0.9700 |
C2—O1 | 1.3682 (19) | C11—H11B | 0.9700 |
C2—C3 | 1.396 (2) | C12—O4 | 1.423 (2) |
C3—C4 | 1.373 (2) | C12—C13 | 1.482 (3) |
C3—H3 | 0.9300 | C12—H12A | 0.9700 |
C5—C6 | 1.384 (2) | C12—H12B | 0.9700 |
C5—C4 | 1.400 (2) | C13—O5 | 1.420 (2) |
C5—H5 | 0.9300 | C13—H13A | 0.9700 |
C6—O3 | 1.3672 (19) | C13—H13B | 0.9700 |
C8—O2 | 1.412 (2) | C14—O5 | 1.423 (2) |
C8—C7 | 1.497 (2) | C14—C9i | 1.492 (3) |
C8—H8A | 0.9700 | C14—H14A | 0.9700 |
C8—H8B | 0.9700 | C14—H14B | 0.9700 |
C7—O1 | 1.428 (2) | C4—C15 | 1.510 (2) |
C7—H7A | 0.9700 | C15—O6 | 1.418 (2) |
C7—H7B | 0.9700 | C15—H15A | 0.9700 |
C9—O2 | 1.418 (2) | C15—H15B | 0.9700 |
C9—C14i | 1.492 (3) | C16—O6 | 1.412 (3) |
C9—H9A | 0.9700 | C16—C17 | 1.468 (3) |
C9—H9B | 0.9700 | C16—H16A | 0.9700 |
C10—O3 | 1.431 (2) | C16—H16B | 0.9700 |
C10—C11 | 1.499 (2) | C18—C17 | 1.167 (3) |
C10—H10A | 0.9700 | C18—H18 | 0.9300 |
C2—C1—C6 | 118.97 (15) | C10—C11—H11B | 109.6 |
C2—C1—H1 | 120.5 | H11A—C11—H11B | 108.1 |
C6—C1—H1 | 120.5 | O4—C12—C13 | 109.57 (14) |
O1—C2—C1 | 125.21 (15) | O4—C12—H12A | 109.8 |
O1—C2—C3 | 114.18 (14) | C13—C12—H12A | 109.8 |
C1—C2—C3 | 120.60 (15) | O4—C12—H12B | 109.8 |
C4—C3—C2 | 120.15 (15) | C13—C12—H12B | 109.8 |
C4—C3—H3 | 119.9 | H12A—C12—H12B | 108.2 |
C2—C3—H3 | 119.9 | O5—C13—C12 | 109.56 (15) |
C6—C5—C4 | 119.21 (15) | O5—C13—H13A | 109.8 |
C6—C5—H5 | 120.4 | C12—C13—H13A | 109.8 |
C4—C5—H5 | 120.4 | O5—C13—H13B | 109.8 |
O3—C6—C5 | 124.27 (15) | C12—C13—H13B | 109.8 |
O3—C6—C1 | 114.76 (14) | H13A—C13—H13B | 108.2 |
C5—C6—C1 | 120.95 (15) | O5—C14—C9i | 109.25 (15) |
O2—C8—C7 | 109.34 (15) | O5—C14—H14A | 109.8 |
O2—C8—H8A | 109.8 | C9i—C14—H14A | 109.8 |
C7—C8—H8A | 109.8 | O5—C14—H14B | 109.8 |
O2—C8—H8B | 109.8 | C9i—C14—H14B | 109.8 |
C7—C8—H8B | 109.8 | H14A—C14—H14B | 108.3 |
H8A—C8—H8B | 108.3 | C3—C4—C5 | 120.11 (15) |
O1—C7—C8 | 106.52 (14) | C3—C4—C15 | 119.87 (15) |
O1—C7—H7A | 110.4 | C5—C4—C15 | 120.02 (16) |
C8—C7—H7A | 110.4 | O6—C15—C4 | 113.54 (15) |
O1—C7—H7B | 110.4 | O6—C15—H15A | 108.9 |
C8—C7—H7B | 110.4 | C4—C15—H15A | 108.9 |
H7A—C7—H7B | 108.6 | O6—C15—H15B | 108.9 |
O2—C9—C14i | 108.95 (16) | C4—C15—H15B | 108.9 |
O2—C9—H9A | 109.9 | H15A—C15—H15B | 107.7 |
C14i—C9—H9A | 109.9 | O6—C16—C17 | 113.58 (17) |
O2—C9—H9B | 109.9 | O6—C16—H16A | 108.8 |
C14i—C9—H9B | 109.9 | C17—C16—H16A | 108.8 |
H9A—C9—H9B | 108.3 | O6—C16—H16B | 108.8 |
O3—C10—C11 | 109.13 (15) | C17—C16—H16B | 108.8 |
O3—C10—H10A | 109.9 | H16A—C16—H16B | 107.7 |
C11—C10—H10A | 109.9 | C17—C18—H18 | 180.0 |
O3—C10—H10B | 109.9 | C18—C17—C16 | 179.1 (2) |
C11—C10—H10B | 109.9 | C16—O6—C15 | 113.57 (15) |
H10A—C10—H10B | 108.3 | C2—O1—C7 | 119.54 (13) |
O4—C11—C10 | 110.25 (15) | C6—O3—C10 | 117.49 (13) |
O4—C11—H11A | 109.6 | C11—O4—C12 | 112.09 (13) |
C10—C11—H11A | 109.6 | C13—O5—C14 | 112.83 (14) |
O4—C11—H11B | 109.6 | C8—O2—C9 | 112.47 (14) |
C6—C1—C2—O1 | 177.94 (16) | C5—C4—C15—O6 | −55.4 (2) |
C6—C1—C2—C3 | −1.3 (3) | O6—C16—C17—C18 | −90 (17) |
O1—C2—C3—C4 | −178.87 (15) | C17—C16—O6—C15 | −69.0 (2) |
C1—C2—C3—C4 | 0.4 (3) | C4—C15—O6—C16 | −64.9 (2) |
C4—C5—C6—O3 | 177.64 (16) | C1—C2—O1—C7 | 13.2 (3) |
C4—C5—C6—C1 | −1.0 (3) | C3—C2—O1—C7 | −167.59 (15) |
C2—C1—C6—O3 | −177.18 (15) | C8—C7—O1—C2 | −178.61 (15) |
C2—C1—C6—C5 | 1.5 (3) | C5—C6—O3—C10 | 4.2 (2) |
O2—C8—C7—O1 | −67.06 (18) | C1—C6—O3—C10 | −177.17 (16) |
O3—C10—C11—O4 | −67.2 (2) | C11—C10—O3—C6 | −176.06 (15) |
O4—C12—C13—O5 | −57.51 (19) | C10—C11—O4—C12 | −167.39 (15) |
C2—C3—C4—C5 | 0.2 (3) | C13—C12—O4—C11 | −168.70 (16) |
C2—C3—C4—C15 | 179.74 (16) | C12—C13—O5—C14 | −169.02 (14) |
C6—C5—C4—C3 | 0.1 (3) | C9i—C14—O5—C13 | −163.09 (15) |
C6—C5—C4—C15 | −179.47 (16) | C7—C8—O2—C9 | 173.50 (14) |
C3—C4—C15—O6 | 125.04 (18) | C14i—C9—O2—C8 | 173.71 (15) |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13B···O6ii | 0.97 | 2.49 | 3.247 (2) | 135 |
C18—H18···O4iii | 0.93 | 2.54 | 3.203 (2) | 128 |
C18—H18···O5iii | 0.93 | 2.52 | 3.431 (3) | 166 |
Symmetry codes: (ii) −x+1, −y+1, −z+2; (iii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C36H48O12 |
Mr | 672.74 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 9.2256 (13), 9.8561 (14), 10.0808 (14) |
α, β, γ (°) | 97.213 (2), 98.658 (2), 99.226 (2) |
V (Å3) | 883.9 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.64 × 0.32 × 0.10 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.965, 0.991 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4551, 3108, 2350 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.113, 1.05 |
No. of reflections | 3108 |
No. of parameters | 217 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.21 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13B···O6i | 0.97 | 2.49 | 3.247 (2) | 135.2 |
C18—H18···O4ii | 0.93 | 2.54 | 3.203 (2) | 128.4 |
C18—H18···O5ii | 0.93 | 2.52 | 3.431 (3) | 165.5 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y+1, −z+1. |
Acknowledgements
The authors gratefully acknowledge the support of the National Natural Science Foundation of China (No. 21072066) and the Natural Science Foundation of Guangdong Province of China (No. 8151063101000015).
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Crown ethers are important building blocks in supramolecular chemistry and have been widely used in materials and biological sciences for sensors and switches (Gokel et al., 2004; Raymo et al., 1999). Recently, bisphenylene crown ethers, such as bisparaphenylene-34-crown-10 (BPP34C10) and bismetaphenylene-32-crown-10 (BMP32C10), attracted great interests and were extensively used for construction of interlocked molecules (Loeb, 2007), mechanically bonded macromolecules(Fang et al., 2010) and molecular machines(Kay et al., 2007). Their wide uses are mainly because bisphenylene crown erther hosts can form relatively stable molecular complexes with electron deficient paraquat derivatives by virtue of multiple noncovalent interactions, such as hydrogen bondging and charge-transfer interactions. As part of our project to explore novel crown ether-based cryptands (Zhang et al., 2010,) in supramolecular self-assembly (Xu et al., 2010) and interlocked structures(Xu et al., 2011), we tackled the synthesis of bisacetylene-substituted BMP32C10, an important precursor to cryptands. We envisioned that the title compound could be obtained by the reaction of bis(5-hydroxymethyl-1,3-phenylene)-32-crown-10 with propargyl bromide in the presence of sodium hydride.
As shown in Fig. 1, the title compound has crystallographic inversion symmetry in the solid state. The phenyl rings are at a centroid-centroid distance of 9.422 Å and they are arranged in an edge-to-edge conformation rather than a face-to-face one. The polyether bridges of the macrocycle adopt a gauche conformation and the cavity of the macrocycle is collapsed. The molecule as a whole adopts a chair-like conformation. Weak intermolecular C—H···O hydrogen bonds driven by the elevated acidity of acetylene hydrogen were observed.