The molecule of 3,3',4,4'-tetrakis(phenylethynyl)biphenyl, C44H26, is approximately planar and is located on a crystallographic inversion center. Bis[3,4-bis(phenylethynyl)phenyl] ether, C44H26O, has molecules located on twofold symmetry axes, whereas the molecule of 2,2-bis[3,4-bis(phenylethynyl)phenyl]propane, C47H32, does not exhibit any molecular symmetry.
Supporting information
CCDC references: 208008; 208009; 208010
Bis-ortho-diynylarylene (BODA) derivatives were synthesized as described previously (Smith et al., 1998). Monomers were prepared in three steps via ortho bromination and trifluoromethylsulfonate (trifluoromethanesulfonate) esterification, followed by Pd-catalyzed coupling of phenyl acetylene (Sonogashira et al., 1975) to give tetrayne (see reaction Scheme above). Solvents for recrystallization were hexane–ethyl acetate (1:1) for (I) and (II), and hexane for (III.
All H atoms, except those on atoms C22 and C23 of (III), were placed in idealized positions and were refined riding on their parent atoms. C—H distances of 0.98 and 0.99 Å were used for methyl and secondary C atoms, respectively. A distance of 0.93 Å was used for Csp2 atoms in structures (I) and (II), and 0.95 Å in structure (III). The H-atom displacement parameters were set at 1.2Ueq of the parent C atom and 1.5Ueq for the methyl C atoms.
Data collection: CrystalClear (Rigaku, 1998-2001) for (I), (II); SMART (Bruker, 1998) for (III). Cell refinement: CrystalClear for (I), (II); SMART and SAINT (Bruker, 1998) for (III). Data reduction: CrystalClear for (I), (II); SHELXTL (Bruker, 1998) for (III). Program(s) used to solve structure: SIR92 (Altomare et al., 1994) for (I), (II); SHELXTL for (III). Program(s) used to refine structure: SHELXTL (Bruker. 1998) for (I); SHELXTL (Bruker, 1998) for (II); SHELXTL for (III). For all compounds, molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Crystal data top
C44H26 | F(000) = 580.00 |
Mr = 554.65 | Dx = 1.254 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ybc | Cell parameters from 3530 reflections |
a = 13.299 (7) Å | θ = 1.0–26.5° |
b = 5.229 (3) Å | µ = 0.07 mm−1 |
c = 21.196 (11) Å | T = 300 K |
β = 92.540 (15)° | Platelet, colorless |
V = 1472.4 (14) Å3 | 0.30 × 0.15 × 0.10 mm |
Z = 2 | |
Data collection top
Rigaku Mercury CCD diffractometer | 3021 independent reflections |
Radiation source: X-ray tube | 1664 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.091 |
Detector resolution: 7.314 pixels mm-1 | θmax = 26.5°, θmin = 2.5° |
ω scans | h = −16→16 |
Absorption correction: multi-scan (Jacobson, 1998) | k = −6→6 |
Tmin = 0.987, Tmax = 0.993 | l = −26→26 |
14417 measured reflections | |
Refinement top
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)] = 0.079 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.182 | H-atom parameters constrained |
S = 1.15 | w = 1/[σ2(Fo2) + (0.0608P)2] where P = (Fo2 + 2Fc2)/3 |
3021 reflections | (Δ/σ)max < 0.001 |
200 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
Crystal data top
C44H26 | V = 1472.4 (14) Å3 |
Mr = 554.65 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.299 (7) Å | µ = 0.07 mm−1 |
b = 5.229 (3) Å | T = 300 K |
c = 21.196 (11) Å | 0.30 × 0.15 × 0.10 mm |
β = 92.540 (15)° | |
Data collection top
Rigaku Mercury CCD diffractometer | 3021 independent reflections |
Absorption correction: multi-scan (Jacobson, 1998) | 1664 reflections with I > 2σ(I) |
Tmin = 0.987, Tmax = 0.993 | Rint = 0.091 |
14417 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.079 | 0 restraints |
wR(F2) = 0.182 | H-atom parameters constrained |
S = 1.15 | Δρmax = 0.18 e Å−3 |
3021 reflections | Δρmin = −0.18 e Å−3 |
200 parameters | |
Special details top
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 | x | y | z | Uiso*/Ueq | |
C1 | 0.0200 (2) | 0.4834 (6) | 0.96801 (15) | 0.0323 (7) | |
C2 | 0.0893 (2) | 0.2930 (6) | 0.95569 (15) | 0.0352 (7) | |
H2 | 0.1096 | 0.1832 | 0.9883 | 0.042* | |
C3 | 0.1296 (2) | 0.2591 (6) | 0.89687 (15) | 0.0336 (7) | |
C4 | 0.0985 (2) | 0.4236 (6) | 0.84734 (14) | 0.0358 (8) | |
C5 | 0.0272 (2) | 0.6120 (6) | 0.85877 (16) | 0.0399 (8) | |
H5 | 0.0048 | 0.7191 | 0.8260 | 0.048* | |
C6 | −0.0104 (2) | 0.6414 (6) | 0.91780 (15) | 0.0373 (8) | |
H6 | −0.0573 | 0.7697 | 0.9244 | 0.045* | |
C7 | 0.2030 (2) | 0.0641 (7) | 0.88780 (14) | 0.0384 (8) | |
C8 | 0.2659 (2) | −0.0997 (6) | 0.88176 (15) | 0.0378 (8) | |
C9 | 0.3399 (2) | −0.2945 (6) | 0.87416 (15) | 0.0339 (7) | |
C10 | 0.3742 (2) | −0.4486 (6) | 0.92376 (16) | 0.0409 (8) | |
H10 | 0.3497 | −0.4242 | 0.9638 | 0.049* | |
C11 | 0.4446 (2) | −0.6385 (7) | 0.91435 (17) | 0.0442 (9) | |
H11 | 0.4669 | −0.7413 | 0.9479 | 0.053* | |
C12 | 0.4816 (2) | −0.6753 (6) | 0.85530 (17) | 0.0419 (9) | |
H12 | 0.5288 | −0.8030 | 0.8488 | 0.050* | |
C13 | 0.4482 (2) | −0.5215 (6) | 0.80574 (17) | 0.0429 (8) | |
H13 | 0.4732 | −0.5458 | 0.7658 | 0.051* | |
C14 | 0.3782 (2) | −0.3319 (6) | 0.81492 (16) | 0.0393 (8) | |
H14 | 0.3565 | −0.2287 | 0.7813 | 0.047* | |
C15 | 0.1405 (2) | 0.4116 (7) | 0.78612 (16) | 0.0392 (8) | |
C16 | 0.1763 (2) | 0.4203 (7) | 0.73519 (16) | 0.0406 (8) | |
C17 | 0.2190 (2) | 0.4426 (6) | 0.67546 (14) | 0.0349 (7) | |
C18 | 0.2918 (2) | 0.2725 (7) | 0.65654 (16) | 0.0426 (8) | |
H18 | 0.3141 | 0.1430 | 0.6838 | 0.051* | |
C19 | 0.3314 (3) | 0.2930 (7) | 0.59811 (16) | 0.0455 (9) | |
H19 | 0.3803 | 0.1777 | 0.5860 | 0.055* | |
C20 | 0.2992 (2) | 0.4831 (7) | 0.55715 (16) | 0.0437 (8) | |
H20 | 0.3257 | 0.4952 | 0.5173 | 0.052* | |
C21 | 0.2279 (2) | 0.6544 (7) | 0.57506 (17) | 0.0431 (8) | |
H21 | 0.2065 | 0.7833 | 0.5474 | 0.052* | |
C22 | 0.1875 (2) | 0.6373 (6) | 0.63388 (16) | 0.0413 (8) | |
H22 | 0.1395 | 0.7552 | 0.6458 | 0.050* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0273 (14) | 0.0376 (16) | 0.0321 (16) | −0.0031 (13) | 0.0026 (12) | −0.0055 (14) |
C2 | 0.0335 (16) | 0.0390 (17) | 0.0334 (17) | 0.0007 (14) | 0.0027 (14) | −0.0010 (15) |
C3 | 0.0291 (15) | 0.0379 (17) | 0.0339 (17) | −0.0017 (14) | 0.0041 (13) | −0.0077 (15) |
C4 | 0.0282 (15) | 0.046 (2) | 0.0336 (18) | −0.0030 (14) | 0.0036 (13) | −0.0069 (15) |
C5 | 0.0406 (18) | 0.0456 (19) | 0.0333 (18) | 0.0062 (15) | 0.0013 (14) | 0.0034 (16) |
C6 | 0.0366 (17) | 0.0414 (19) | 0.0342 (18) | 0.0065 (14) | 0.0041 (14) | −0.0003 (15) |
C7 | 0.0391 (17) | 0.0456 (19) | 0.0311 (18) | −0.0015 (16) | 0.0082 (14) | −0.0096 (16) |
C8 | 0.0349 (16) | 0.0427 (18) | 0.0362 (18) | −0.0044 (15) | 0.0072 (14) | −0.0088 (16) |
C9 | 0.0271 (15) | 0.0344 (16) | 0.0405 (19) | −0.0014 (13) | 0.0054 (14) | −0.0070 (15) |
C10 | 0.0425 (18) | 0.0413 (19) | 0.0396 (19) | −0.0039 (16) | 0.0096 (15) | −0.0027 (16) |
C11 | 0.0439 (19) | 0.0409 (19) | 0.048 (2) | −0.0003 (15) | 0.0006 (17) | 0.0036 (16) |
C12 | 0.0333 (17) | 0.0395 (19) | 0.053 (2) | 0.0030 (14) | 0.0049 (16) | −0.0059 (17) |
C13 | 0.0393 (17) | 0.0452 (19) | 0.045 (2) | 0.0011 (16) | 0.0117 (15) | −0.0118 (17) |
C14 | 0.0385 (17) | 0.0416 (18) | 0.0380 (19) | 0.0008 (15) | 0.0050 (15) | −0.0044 (16) |
C15 | 0.0342 (17) | 0.046 (2) | 0.038 (2) | −0.0019 (15) | 0.0052 (15) | −0.0068 (16) |
C16 | 0.0394 (18) | 0.047 (2) | 0.0350 (19) | 0.0005 (15) | 0.0031 (16) | −0.0047 (16) |
C17 | 0.0350 (16) | 0.0431 (18) | 0.0267 (16) | −0.0054 (15) | 0.0017 (13) | −0.0047 (15) |
C18 | 0.0477 (19) | 0.0421 (19) | 0.0381 (19) | 0.0060 (16) | 0.0019 (16) | 0.0063 (16) |
C19 | 0.049 (2) | 0.051 (2) | 0.037 (2) | 0.0089 (17) | 0.0114 (16) | −0.0012 (17) |
C20 | 0.0477 (19) | 0.054 (2) | 0.0296 (17) | −0.0048 (17) | 0.0035 (15) | 0.0026 (16) |
C21 | 0.0410 (18) | 0.0458 (19) | 0.043 (2) | 0.0029 (16) | 0.0015 (16) | 0.0086 (17) |
C22 | 0.0365 (17) | 0.0427 (19) | 0.045 (2) | 0.0040 (15) | 0.0054 (15) | −0.0018 (17) |
Geometric parameters (Å, º) top
C1—C2 | 1.388 (4) | C11—H11 | 0.9300 |
C1—C6 | 1.392 (4) | C12—C13 | 1.380 (5) |
C1—C1i | 1.486 (6) | C12—H12 | 0.9300 |
C2—C3 | 1.388 (4) | C13—C14 | 1.379 (4) |
C2—H2 | 0.9300 | C13—H13 | 0.9300 |
C3—C4 | 1.404 (4) | C14—H14 | 0.9300 |
C3—C7 | 1.430 (4) | C15—C16 | 1.198 (4) |
C4—C5 | 1.395 (4) | C16—C17 | 1.413 (4) |
C4—C15 | 1.435 (4) | C17—C18 | 1.386 (4) |
C5—C6 | 1.375 (4) | C17—C22 | 1.398 (4) |
C5—H5 | 0.9300 | C18—C19 | 1.369 (5) |
C6—H6 | 0.9300 | C18—H18 | 0.9300 |
C7—C8 | 1.207 (4) | C19—C20 | 1.375 (5) |
C8—C9 | 1.430 (4) | C19—H19 | 0.9300 |
C9—C10 | 1.385 (4) | C20—C21 | 1.369 (5) |
C9—C14 | 1.387 (4) | C20—H20 | 0.9300 |
C10—C11 | 1.384 (5) | C21—C22 | 1.380 (5) |
C10—H10 | 0.9300 | C21—H21 | 0.9300 |
C11—C12 | 1.377 (5) | C22—H22 | 0.9300 |
| | | |
C2—C1—C6 | 117.1 (3) | C11—C12—C13 | 119.6 (3) |
C2—C1—C1i | 121.4 (4) | C11—C12—H12 | 120.2 |
C6—C1—C1i | 121.6 (3) | C13—C12—H12 | 120.2 |
C1—C2—C3 | 123.0 (3) | C14—C13—C12 | 120.6 (3) |
C1—C2—H2 | 118.5 | C14—C13—H13 | 119.7 |
C3—C2—H2 | 118.5 | C12—C13—H13 | 119.7 |
C2—C3—C4 | 118.6 (3) | C13—C14—C9 | 120.3 (3) |
C2—C3—C7 | 120.2 (3) | C13—C14—H14 | 119.8 |
C4—C3—C7 | 121.1 (3) | C9—C14—H14 | 119.8 |
C5—C4—C3 | 118.9 (3) | C16—C15—C4 | 175.3 (4) |
C5—C4—C15 | 118.8 (3) | C15—C16—C17 | 177.4 (4) |
C3—C4—C15 | 122.3 (3) | C18—C17—C22 | 118.6 (3) |
C6—C5—C4 | 120.9 (3) | C18—C17—C16 | 121.1 (3) |
C6—C5—H5 | 119.6 | C22—C17—C16 | 120.2 (3) |
C4—C5—H5 | 119.6 | C19—C18—C17 | 120.7 (3) |
C5—C6—C1 | 121.5 (3) | C19—C18—H18 | 119.6 |
C5—C6—H6 | 119.2 | C17—C18—H18 | 119.6 |
C1—C6—H6 | 119.2 | C18—C19—C20 | 120.3 (3) |
C8—C7—C3 | 178.3 (3) | C18—C19—H19 | 119.8 |
C7—C8—C9 | 179.5 (4) | C20—C19—H19 | 119.8 |
C10—C9—C14 | 118.8 (3) | C21—C20—C19 | 119.9 (3) |
C10—C9—C8 | 122.3 (3) | C21—C20—H20 | 120.0 |
C14—C9—C8 | 118.9 (3) | C19—C20—H20 | 120.0 |
C11—C10—C9 | 120.7 (3) | C20—C21—C22 | 120.5 (3) |
C11—C10—H10 | 119.7 | C20—C21—H21 | 119.7 |
C9—C10—H10 | 119.7 | C22—C21—H21 | 119.7 |
C12—C11—C10 | 120.1 (3) | C21—C22—C17 | 119.9 (3) |
C12—C11—H11 | 120.0 | C21—C22—H22 | 120.1 |
C10—C11—H11 | 120.0 | C17—C22—H22 | 120.1 |
| | | |
C6—C1—C2—C3 | 1.2 (4) | C9—C10—C11—C12 | 0.3 (5) |
C1i—C1—C2—C3 | −178.8 (4) | C10—C11—C12—C13 | 0.1 (5) |
C1—C2—C3—C4 | −0.4 (5) | C11—C12—C13—C14 | −0.1 (5) |
C1—C2—C3—C7 | 178.1 (3) | C12—C13—C14—C9 | −0.4 (5) |
C2—C3—C4—C5 | −1.1 (4) | C10—C9—C14—C13 | 0.8 (5) |
C7—C3—C4—C5 | −179.5 (3) | C8—C9—C14—C13 | −178.7 (3) |
C2—C3—C4—C15 | 176.4 (3) | C22—C17—C18—C19 | −0.7 (5) |
C7—C3—C4—C15 | −2.1 (5) | C16—C17—C18—C19 | 178.8 (3) |
C3—C4—C5—C6 | 1.7 (5) | C17—C18—C19—C20 | −0.1 (5) |
C15—C4—C5—C6 | −175.9 (3) | C18—C19—C20—C21 | 0.6 (5) |
C4—C5—C6—C1 | −0.8 (5) | C19—C20—C21—C22 | −0.3 (5) |
C2—C1—C6—C5 | −0.6 (5) | C20—C21—C22—C17 | −0.5 (5) |
C1i—C1—C6—C5 | 179.4 (4) | C18—C17—C22—C21 | 1.0 (5) |
C14—C9—C10—C11 | −0.7 (5) | C16—C17—C22—C21 | −178.5 (3) |
C8—C9—C10—C11 | 178.8 (3) | | |
Symmetry code: (i) −x, −y+1, −z+2. |
Crystal data top
C44H26O | F(000) = 1192.00 |
Mr = 570.65 | Dx = 1.209 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -C 2yc | Cell parameters from 4736 reflections |
a = 35.483 (10) Å | θ = 0.6–26.5° |
b = 5.8875 (15) Å | µ = 0.07 mm−1 |
c = 15.919 (5) Å | T = 300 K |
β = 109.932 (6)° | Block, colorless |
V = 3126.4 (14) Å3 | 0.30 × 0.20 × 0.20 mm |
Z = 4 | |
Data collection top
Rigaku Mercury CCD diffractometer | 3203 independent reflections |
Radiation source: X-ray tube | 1964 reflections with I > 2.00σ(I) |
Graphite monochromator | Rint = 0.052 |
Detector resolution: 7.314 pixels mm-1 | θmax = 26.5°, θmin = 3.5° |
ω scans | h = −44→44 |
Absorption correction: multi-scan (Jacobson, 1998) | k = −7→7 |
Tmin = 0.983, Tmax = 0.986 | l = −19→19 |
15387 measured reflections | |
Refinement top
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)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.184 | H-atom parameters constrained |
S = 1.15 | w = 1/[σ2(Fo2) + (0.0853P)2] where P = (Fo2 + 2Fc2)/3 |
3202 reflections | (Δ/σ)max < 0.001 |
204 parameters | Δρmax = 0.13 e Å−3 |
0 restraints | Δρmin = −0.13 e Å−3 |
Crystal data top
C44H26O | V = 3126.4 (14) Å3 |
Mr = 570.65 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 35.483 (10) Å | µ = 0.07 mm−1 |
b = 5.8875 (15) Å | T = 300 K |
c = 15.919 (5) Å | 0.30 × 0.20 × 0.20 mm |
β = 109.932 (6)° | |
Data collection top
Rigaku Mercury CCD diffractometer | 3203 independent reflections |
Absorption correction: multi-scan (Jacobson, 1998) | 1964 reflections with I > 2.00σ(I) |
Tmin = 0.983, Tmax = 0.986 | Rint = 0.052 |
15387 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.065 | 0 restraints |
wR(F2) = 0.184 | H-atom parameters constrained |
S = 1.15 | Δρmax = 0.13 e Å−3 |
3202 reflections | Δρmin = −0.13 e Å−3 |
204 parameters | |
Special details top
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 | x | y | z | Uiso*/Ueq | |
O1 | 0.5000 | 1.2889 (4) | 0.2500 | 0.0760 (7) | |
C1 | 0.51935 (7) | 1.1672 (5) | 0.20143 (15) | 0.0637 (6) | |
C2 | 0.55477 (6) | 1.2509 (4) | 0.19903 (15) | 0.0590 (6) | |
H2 | 0.5656 | 1.3824 | 0.2303 | 0.071* | |
C3 | 0.57481 (6) | 1.1381 (4) | 0.14935 (14) | 0.0559 (6) | |
C4 | 0.55817 (7) | 0.9410 (4) | 0.10147 (15) | 0.0642 (6) | |
C5 | 0.52185 (8) | 0.8621 (5) | 0.10544 (19) | 0.0805 (8) | |
H5 | 0.5105 | 0.7315 | 0.0743 | 0.097* | |
C6 | 0.50241 (8) | 0.9740 (5) | 0.15469 (19) | 0.0821 (8) | |
H6 | 0.4781 | 0.9199 | 0.1565 | 0.098* | |
C7 | 0.61279 (7) | 1.2186 (4) | 0.14826 (14) | 0.0620 (6) | |
C8 | 0.64433 (7) | 1.2791 (4) | 0.14442 (14) | 0.0633 (6) | |
C9 | 0.68203 (6) | 1.3452 (4) | 0.13828 (13) | 0.0557 (6) | |
C10 | 0.69882 (7) | 1.5564 (5) | 0.16715 (16) | 0.0668 (6) | |
H10 | 0.6851 | 1.6604 | 0.1900 | 0.080* | |
C11 | 0.73565 (8) | 1.6124 (5) | 0.16205 (19) | 0.0769 (7) | |
H11 | 0.7468 | 1.7537 | 0.1817 | 0.092* | |
C12 | 0.75585 (8) | 1.4590 (6) | 0.1279 (2) | 0.0845 (9) | |
H12 | 0.7808 | 1.4962 | 0.1249 | 0.101* | |
C13 | 0.73938 (8) | 1.2529 (6) | 0.09850 (19) | 0.0821 (8) | |
H13 | 0.7531 | 1.1505 | 0.0749 | 0.098* | |
C14 | 0.70271 (7) | 1.1948 (5) | 0.10337 (16) | 0.0679 (6) | |
H14 | 0.6917 | 1.0534 | 0.0831 | 0.081* | |
C15 | 0.57749 (7) | 0.8224 (5) | 0.04879 (16) | 0.0682 (7) | |
C16 | 0.59235 (8) | 0.7199 (5) | 0.00317 (16) | 0.0681 (6) | |
C17 | 0.60854 (7) | 0.5880 (4) | −0.05270 (14) | 0.0605 (6) | |
C18 | 0.64050 (8) | 0.6618 (5) | −0.07597 (17) | 0.0705 (7) | |
H18 | 0.6525 | 0.8006 | −0.0550 | 0.085* | |
C19 | 0.65490 (8) | 0.5303 (6) | −0.13052 (18) | 0.0806 (8) | |
H19 | 0.6764 | 0.5814 | −0.1462 | 0.097* | |
C20 | 0.63756 (9) | 0.3255 (5) | −0.16143 (19) | 0.0810 (8) | |
H20 | 0.6472 | 0.2382 | −0.1984 | 0.097* | |
C21 | 0.60625 (8) | 0.2494 (5) | −0.13828 (18) | 0.0788 (8) | |
H21 | 0.5946 | 0.1097 | −0.1591 | 0.095* | |
C22 | 0.59170 (8) | 0.3799 (5) | −0.08370 (17) | 0.0730 (7) | |
H22 | 0.5704 | 0.3268 | −0.0678 | 0.088* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0736 (15) | 0.0784 (17) | 0.0938 (17) | 0.000 | 0.0515 (14) | 0.000 |
C1 | 0.0560 (12) | 0.0758 (17) | 0.0666 (13) | 0.0008 (12) | 0.0303 (11) | −0.0005 (12) |
C2 | 0.0575 (13) | 0.0661 (15) | 0.0592 (12) | −0.0047 (11) | 0.0272 (10) | −0.0003 (11) |
C3 | 0.0538 (12) | 0.0635 (15) | 0.0527 (11) | −0.0040 (10) | 0.0212 (9) | 0.0040 (10) |
C4 | 0.0626 (14) | 0.0742 (16) | 0.0604 (12) | −0.0027 (12) | 0.0271 (11) | −0.0039 (12) |
C5 | 0.0705 (16) | 0.090 (2) | 0.0870 (17) | −0.0235 (14) | 0.0339 (14) | −0.0258 (15) |
C6 | 0.0612 (15) | 0.100 (2) | 0.0946 (18) | −0.0221 (15) | 0.0383 (14) | −0.0219 (17) |
C7 | 0.0616 (14) | 0.0714 (16) | 0.0576 (12) | −0.0025 (12) | 0.0260 (11) | 0.0013 (11) |
C8 | 0.0585 (13) | 0.0762 (16) | 0.0601 (13) | −0.0022 (12) | 0.0268 (11) | 0.0017 (11) |
C9 | 0.0499 (11) | 0.0680 (15) | 0.0511 (11) | −0.0029 (10) | 0.0198 (9) | 0.0029 (10) |
C10 | 0.0637 (14) | 0.0678 (16) | 0.0725 (14) | −0.0020 (12) | 0.0277 (12) | −0.0034 (12) |
C11 | 0.0651 (15) | 0.0760 (19) | 0.0883 (17) | −0.0139 (13) | 0.0245 (13) | 0.0030 (14) |
C12 | 0.0605 (15) | 0.104 (2) | 0.0950 (19) | −0.0064 (15) | 0.0341 (14) | 0.0184 (18) |
C13 | 0.0735 (17) | 0.096 (2) | 0.0910 (18) | 0.0119 (16) | 0.0463 (15) | 0.0045 (16) |
C14 | 0.0676 (14) | 0.0706 (16) | 0.0701 (14) | −0.0031 (12) | 0.0295 (12) | −0.0013 (12) |
C15 | 0.0672 (15) | 0.0748 (17) | 0.0653 (13) | −0.0016 (12) | 0.0260 (12) | −0.0026 (13) |
C16 | 0.0704 (15) | 0.0718 (17) | 0.0636 (13) | −0.0042 (13) | 0.0247 (12) | −0.0046 (12) |
C17 | 0.0618 (13) | 0.0655 (16) | 0.0549 (11) | 0.0025 (11) | 0.0205 (10) | 0.0004 (11) |
C18 | 0.0694 (15) | 0.0720 (17) | 0.0718 (14) | −0.0069 (13) | 0.0263 (12) | −0.0009 (13) |
C19 | 0.0709 (17) | 0.098 (2) | 0.0827 (17) | 0.0005 (15) | 0.0386 (14) | 0.0057 (16) |
C20 | 0.0887 (19) | 0.084 (2) | 0.0778 (16) | 0.0136 (16) | 0.0385 (15) | −0.0062 (15) |
C21 | 0.0885 (19) | 0.0666 (18) | 0.0847 (17) | −0.0033 (14) | 0.0341 (15) | −0.0113 (14) |
C22 | 0.0734 (16) | 0.0769 (18) | 0.0740 (15) | −0.0100 (14) | 0.0319 (13) | −0.0078 (13) |
Geometric parameters (Å, º) top
O1—C1 | 1.395 (3) | C11—H11 | 0.9300 |
O1—C1i | 1.395 (3) | C12—C13 | 1.360 (4) |
C1—C2 | 1.363 (3) | C12—H12 | 0.9300 |
C1—C6 | 1.382 (4) | C13—C14 | 1.373 (3) |
C2—C3 | 1.399 (3) | C13—H13 | 0.9300 |
C2—H2 | 0.9300 | C14—H14 | 0.9300 |
C3—C4 | 1.405 (3) | C15—C16 | 1.197 (3) |
C3—C7 | 1.434 (3) | C16—C17 | 1.440 (3) |
C4—C5 | 1.392 (3) | C17—C18 | 1.378 (3) |
C4—C15 | 1.433 (3) | C17—C22 | 1.380 (4) |
C5—C6 | 1.376 (4) | C18—C19 | 1.385 (4) |
C5—H5 | 0.9300 | C18—H18 | 0.9300 |
C6—H6 | 0.9300 | C19—C20 | 1.368 (4) |
C7—C8 | 1.196 (3) | C19—H19 | 0.9300 |
C8—C9 | 1.429 (3) | C20—C21 | 1.360 (4) |
C9—C14 | 1.383 (3) | C20—H20 | 0.9300 |
C9—C10 | 1.389 (3) | C21—C22 | 1.386 (4) |
C10—C11 | 1.377 (3) | C21—H21 | 0.9300 |
C10—H10 | 0.9300 | C22—H22 | 0.9300 |
C11—C12 | 1.376 (4) | | |
| | | |
C1—O1—C1i | 118.1 (3) | C13—C12—C11 | 120.1 (3) |
C2—C1—C6 | 121.3 (2) | C13—C12—H12 | 119.9 |
C2—C1—O1 | 117.5 (2) | C11—C12—H12 | 119.9 |
C6—C1—O1 | 121.1 (2) | C12—C13—C14 | 120.5 (3) |
C1—C2—C3 | 119.7 (2) | C12—C13—H13 | 119.7 |
C1—C2—H2 | 120.2 | C14—C13—H13 | 119.7 |
C3—C2—H2 | 120.2 | C13—C14—C9 | 120.4 (3) |
C2—C3—C4 | 120.0 (2) | C13—C14—H14 | 119.8 |
C2—C3—C7 | 120.7 (2) | C9—C14—H14 | 119.8 |
C4—C3—C7 | 119.4 (2) | C16—C15—C4 | 177.7 (3) |
C5—C4—C3 | 118.5 (2) | C15—C16—C17 | 177.0 (3) |
C5—C4—C15 | 119.9 (2) | C18—C17—C22 | 118.7 (2) |
C3—C4—C15 | 121.6 (2) | C18—C17—C16 | 122.3 (2) |
C6—C5—C4 | 121.1 (3) | C22—C17—C16 | 119.0 (2) |
C6—C5—H5 | 119.4 | C17—C18—C19 | 120.3 (3) |
C4—C5—H5 | 119.4 | C17—C18—H18 | 119.8 |
C5—C6—C1 | 119.5 (2) | C19—C18—H18 | 119.8 |
C5—C6—H6 | 120.3 | C20—C19—C18 | 120.2 (3) |
C1—C6—H6 | 120.3 | C20—C19—H19 | 119.9 |
C8—C7—C3 | 177.1 (3) | C18—C19—H19 | 119.9 |
C7—C8—C9 | 178.2 (3) | C21—C20—C19 | 120.2 (3) |
C14—C9—C10 | 118.8 (2) | C21—C20—H20 | 119.9 |
C14—C9—C8 | 119.4 (2) | C19—C20—H20 | 119.9 |
C10—C9—C8 | 121.9 (2) | C20—C21—C22 | 120.0 (3) |
C11—C10—C9 | 120.3 (2) | C20—C21—H21 | 120.0 |
C11—C10—H10 | 119.9 | C22—C21—H21 | 120.0 |
C9—C10—H10 | 119.9 | C17—C22—C21 | 120.6 (2) |
C12—C11—C10 | 119.9 (3) | C17—C22—H22 | 119.7 |
C12—C11—H11 | 120.0 | C21—C22—H22 | 119.7 |
C10—C11—H11 | 120.0 | | |
| | | |
C1i—O1—C1—C2 | −142.0 (2) | C8—C9—C10—C11 | 178.5 (2) |
C1i—O1—C1—C6 | 40.5 (2) | C9—C10—C11—C12 | 0.2 (4) |
C6—C1—C2—C3 | −0.9 (4) | C10—C11—C12—C13 | 0.5 (4) |
O1—C1—C2—C3 | −178.40 (19) | C11—C12—C13—C14 | −0.7 (4) |
C1—C2—C3—C4 | 0.7 (3) | C12—C13—C14—C9 | 0.0 (4) |
C1—C2—C3—C7 | −177.9 (2) | C10—C9—C14—C13 | 0.8 (4) |
C2—C3—C4—C5 | −0.4 (3) | C8—C9—C14—C13 | −178.7 (2) |
C7—C3—C4—C5 | 178.2 (2) | C22—C17—C18—C19 | 0.9 (4) |
C2—C3—C4—C15 | 179.1 (2) | C16—C17—C18—C19 | −179.5 (2) |
C7—C3—C4—C15 | −2.3 (3) | C17—C18—C19—C20 | −0.2 (4) |
C3—C4—C5—C6 | 0.2 (4) | C18—C19—C20—C21 | −0.4 (4) |
C15—C4—C5—C6 | −179.3 (3) | C19—C20—C21—C22 | 0.4 (4) |
C4—C5—C6—C1 | −0.4 (5) | C18—C17—C22—C21 | −1.0 (4) |
C2—C1—C6—C5 | 0.7 (4) | C16—C17—C22—C21 | 179.4 (2) |
O1—C1—C6—C5 | 178.1 (3) | C20—C21—C22—C17 | 0.3 (4) |
C14—C9—C10—C11 | −0.9 (3) | | |
Symmetry code: (i) −x+1, y, −z+1/2. |
Crystal data top
C47H32 | Z = 2 |
Mr = 596.73 | F(000) = 628 |
Triclinic, P1 | Dx = 1.187 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.323 (3) Å | Cell parameters from 54 reflections |
b = 14.575 (4) Å | θ = 2.0–25.0° |
c = 19.776 (4) Å | µ = 0.07 mm−1 |
α = 69.53 (3)° | T = 173 K |
β = 81.20 (4)° | Needle, colorless |
γ = 79.14 (4)° | 0.50 × 0.06 × 0.05 mm |
V = 1669.3 (10) Å3 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 5860 independent reflections |
Radiation source: normal-focus sealed tube | 3266 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
ω scans | θmax = 25.0°, θmin = 1.1° |
Absorption correction: empirical (using intensity measurements) (SADABS; Blessing, 1995) | h = −7→7 |
Tmin = 0.924, Tmax = 0.997 | k = −17→15 |
12148 measured reflections | l = −23→23 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.064 | H-atom parameters constrained |
wR(F2) = 0.150 | w = 1/[σ2(Fo2) + (0.0491P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
5860 reflections | Δρmax = 0.20 e Å−3 |
427 parameters | Δρmin = −0.19 e Å−3 |
0 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0095 (14) |
Crystal data top
C47H32 | γ = 79.14 (4)° |
Mr = 596.73 | V = 1669.3 (10) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.323 (3) Å | Mo Kα radiation |
b = 14.575 (4) Å | µ = 0.07 mm−1 |
c = 19.776 (4) Å | T = 173 K |
α = 69.53 (3)° | 0.50 × 0.06 × 0.05 mm |
β = 81.20 (4)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 5860 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Blessing, 1995) | 3266 reflections with I > 2σ(I) |
Tmin = 0.924, Tmax = 0.997 | Rint = 0.048 |
12148 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.064 | 0 restraints |
wR(F2) = 0.150 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.20 e Å−3 |
5860 reflections | Δρmin = −0.19 e Å−3 |
427 parameters | |
Special details top
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 | x | y | z | Uiso*/Ueq | |
C1 | −0.0457 (5) | 0.7671 (2) | 0.70667 (17) | 0.0372 (8) | |
C2 | −0.0915 (6) | 0.7211 (2) | 0.65219 (18) | 0.0495 (9) | |
H2A | −0.1636 | 0.6629 | 0.6782 | 0.074* | |
H2B | 0.0452 | 0.7012 | 0.6266 | 0.074* | |
H2C | −0.1852 | 0.7699 | 0.6171 | 0.074* | |
C3 | −0.2628 (5) | 0.8088 (3) | 0.7384 (2) | 0.0544 (10) | |
H3A | −0.3522 | 0.7558 | 0.7609 | 0.082* | |
H3B | −0.3372 | 0.8614 | 0.6996 | 0.082* | |
H3C | −0.2382 | 0.8358 | 0.7750 | 0.082* | |
C4 | 0.0834 (5) | 0.6863 (2) | 0.76476 (16) | 0.0334 (7) | |
C5 | 0.0058 (5) | 0.6542 (2) | 0.83755 (17) | 0.0421 (8) | |
H5A | −0.1310 | 0.6842 | 0.8529 | 0.051* | |
C6 | 0.1251 (6) | 0.5791 (2) | 0.88802 (18) | 0.0452 (9) | |
H6A | 0.0680 | 0.5583 | 0.9374 | 0.054* | |
C7 | 0.3250 (5) | 0.5339 (2) | 0.86818 (16) | 0.0365 (8) | |
C8 | 0.4056 (5) | 0.5647 (2) | 0.79428 (16) | 0.0325 (7) | |
C9 | 0.2852 (5) | 0.6411 (2) | 0.74483 (16) | 0.0333 (7) | |
H9A | 0.3429 | 0.6634 | 0.6956 | 0.040* | |
C10 | 0.4513 (6) | 0.4548 (3) | 0.91893 (17) | 0.0437 (9) | |
C11 | 0.5675 (6) | 0.3885 (3) | 0.95665 (17) | 0.0446 (9) | |
C12 | 0.7270 (6) | 0.3111 (2) | 0.99429 (16) | 0.0391 (8) | |
C13 | 0.9428 (6) | 0.3124 (2) | 0.96882 (17) | 0.0457 (9) | |
H13A | 0.9824 | 0.3660 | 0.9276 | 0.055* | |
C14 | 1.1023 (6) | 0.2384 (3) | 1.0014 (2) | 0.0558 (10) | |
H14A | 1.2499 | 0.2419 | 0.9835 | 0.067* | |
C15 | 1.0455 (7) | 0.1597 (3) | 1.0599 (2) | 0.0600 (11) | |
H15A | 1.1539 | 0.1075 | 1.0821 | 0.072* | |
C16 | 0.8329 (7) | 0.1563 (3) | 1.08630 (18) | 0.0589 (11) | |
H16A | 0.7949 | 0.1016 | 1.1268 | 0.071* | |
C17 | 0.6723 (6) | 0.2318 (3) | 1.05467 (17) | 0.0485 (9) | |
H17A | 0.5257 | 0.2293 | 1.0741 | 0.058* | |
C18 | 0.6045 (5) | 0.5131 (2) | 0.77096 (16) | 0.0350 (8) | |
C19 | 0.7627 (5) | 0.4637 (2) | 0.75351 (16) | 0.0370 (8) | |
C20 | 0.9517 (5) | 0.4035 (2) | 0.73393 (15) | 0.0327 (7) | |
C21 | 0.9460 (5) | 0.3554 (2) | 0.68436 (16) | 0.0373 (8) | |
H21A | 0.8158 | 0.3629 | 0.6633 | 0.045* | |
C22 | 1.1277 (5) | 0.2975 (2) | 0.66586 (16) | 0.0409 (8) | |
H22A | 1.1222 | 0.2653 | 0.6320 | 0.049* | |
C23 | 1.3182 (5) | 0.2855 (2) | 0.69609 (16) | 0.0406 (8) | |
H23A | 1.4438 | 0.2460 | 0.6827 | 0.049* | |
C24 | 1.3248 (5) | 0.3316 (2) | 0.74591 (17) | 0.0415 (8) | |
H24A | 1.4547 | 0.3226 | 0.7675 | 0.050* | |
C25 | 1.1434 (5) | 0.3907 (2) | 0.76449 (16) | 0.0401 (8) | |
H25A | 1.1500 | 0.4227 | 0.7984 | 0.048* | |
C26 | 0.0836 (5) | 0.8538 (2) | 0.66953 (16) | 0.0336 (7) | |
C27 | 0.1623 (5) | 0.8959 (2) | 0.71204 (15) | 0.0323 (7) | |
H27A | 0.1413 | 0.8678 | 0.7633 | 0.039* | |
C28 | 0.2708 (5) | 0.9779 (2) | 0.68199 (15) | 0.0303 (7) | |
C29 | 0.2980 (5) | 1.0220 (2) | 0.60597 (16) | 0.0348 (7) | |
C30 | 0.2235 (5) | 0.9786 (2) | 0.56352 (17) | 0.0429 (8) | |
H30A | 0.2448 | 1.0062 | 0.5122 | 0.052* | |
C31 | 0.1189 (5) | 0.8960 (2) | 0.59430 (17) | 0.0414 (8) | |
H31A | 0.0706 | 0.8677 | 0.5639 | 0.050* | |
C32 | 0.3652 (5) | 1.0140 (2) | 0.72833 (15) | 0.0334 (7) | |
C33 | 0.4540 (5) | 1.0385 (2) | 0.76692 (16) | 0.0353 (7) | |
C34 | 0.5688 (5) | 1.0676 (2) | 0.81134 (15) | 0.0325 (7) | |
C35 | 0.4803 (5) | 1.0693 (2) | 0.87957 (16) | 0.0409 (8) | |
H35A | 0.3415 | 1.0502 | 0.8978 | 0.049* | |
C36 | 0.5933 (6) | 1.0988 (3) | 0.92142 (17) | 0.0483 (9) | |
H36A | 0.5324 | 1.0987 | 0.9684 | 0.058* | |
C37 | 0.7926 (6) | 1.1282 (2) | 0.89541 (18) | 0.0479 (9) | |
H37A | 0.8684 | 1.1491 | 0.9240 | 0.057* | |
C38 | 0.8822 (5) | 1.1271 (2) | 0.82737 (17) | 0.0429 (8) | |
H38A | 1.0203 | 1.1471 | 0.8094 | 0.051* | |
C39 | 0.7728 (5) | 1.0972 (2) | 0.78537 (16) | 0.0378 (8) | |
H39A | 0.8359 | 1.0967 | 0.7387 | 0.045* | |
C40 | 0.4018 (5) | 1.1089 (2) | 0.57286 (16) | 0.0374 (8) | |
C41 | 0.4825 (5) | 1.1823 (2) | 0.54401 (16) | 0.0375 (8) | |
C42 | 0.5732 (5) | 1.2726 (2) | 0.51029 (16) | 0.0367 (8) | |
C43 | 0.7569 (6) | 1.2865 (3) | 0.53363 (17) | 0.0476 (9) | |
H43A | 0.8258 | 1.2353 | 0.5719 | 0.057* | |
C44 | 0.8403 (6) | 1.3746 (3) | 0.50135 (18) | 0.0534 (10) | |
H44A | 0.9657 | 1.3838 | 0.5179 | 0.064* | |
C45 | 0.7434 (6) | 1.4490 (3) | 0.44563 (18) | 0.0543 (10) | |
H45A | 0.8016 | 1.5093 | 0.4237 | 0.065* | |
C46 | 0.5609 (6) | 1.4359 (3) | 0.42161 (18) | 0.0505 (9) | |
H46A | 0.4931 | 1.4871 | 0.3832 | 0.061* | |
C47 | 0.4778 (5) | 1.3484 (2) | 0.45348 (17) | 0.0423 (8) | |
H47A | 0.3531 | 1.3395 | 0.4364 | 0.051* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0301 (18) | 0.0292 (17) | 0.0526 (19) | −0.0038 (14) | −0.0072 (15) | −0.0128 (16) |
C2 | 0.051 (2) | 0.042 (2) | 0.060 (2) | −0.0168 (17) | −0.0218 (19) | −0.0113 (18) |
C3 | 0.031 (2) | 0.044 (2) | 0.080 (3) | −0.0051 (17) | −0.0034 (19) | −0.011 (2) |
C4 | 0.0350 (19) | 0.0253 (16) | 0.0445 (18) | −0.0117 (14) | −0.0011 (15) | −0.0145 (15) |
C5 | 0.038 (2) | 0.0385 (19) | 0.049 (2) | −0.0037 (16) | 0.0068 (16) | −0.0191 (17) |
C6 | 0.056 (2) | 0.040 (2) | 0.0391 (19) | −0.0095 (18) | 0.0036 (17) | −0.0136 (17) |
C7 | 0.043 (2) | 0.0319 (17) | 0.0361 (18) | −0.0084 (16) | −0.0028 (16) | −0.0116 (15) |
C8 | 0.0355 (19) | 0.0256 (16) | 0.0379 (17) | −0.0066 (14) | −0.0036 (15) | −0.0112 (15) |
C9 | 0.0365 (19) | 0.0316 (17) | 0.0341 (16) | −0.0105 (15) | 0.0001 (14) | −0.0121 (15) |
C10 | 0.056 (2) | 0.043 (2) | 0.0345 (18) | −0.0101 (19) | −0.0043 (17) | −0.0139 (17) |
C11 | 0.058 (2) | 0.040 (2) | 0.0350 (18) | −0.0120 (19) | −0.0092 (18) | −0.0077 (17) |
C12 | 0.051 (2) | 0.0373 (19) | 0.0297 (16) | −0.0115 (17) | −0.0092 (16) | −0.0076 (15) |
C13 | 0.055 (2) | 0.042 (2) | 0.0395 (19) | −0.0151 (19) | −0.0044 (18) | −0.0082 (17) |
C14 | 0.055 (2) | 0.053 (2) | 0.061 (2) | −0.006 (2) | −0.017 (2) | −0.016 (2) |
C15 | 0.074 (3) | 0.047 (2) | 0.061 (2) | −0.004 (2) | −0.033 (2) | −0.011 (2) |
C16 | 0.089 (3) | 0.048 (2) | 0.039 (2) | −0.025 (2) | −0.026 (2) | 0.0020 (18) |
C17 | 0.058 (2) | 0.056 (2) | 0.0344 (18) | −0.023 (2) | −0.0070 (17) | −0.0104 (18) |
C18 | 0.039 (2) | 0.0283 (17) | 0.0365 (17) | −0.0093 (16) | −0.0045 (15) | −0.0063 (15) |
C19 | 0.038 (2) | 0.0296 (17) | 0.0406 (18) | −0.0091 (16) | −0.0033 (16) | −0.0063 (16) |
C20 | 0.0301 (18) | 0.0279 (16) | 0.0364 (17) | −0.0052 (14) | 0.0005 (14) | −0.0067 (15) |
C21 | 0.0318 (19) | 0.0397 (19) | 0.0379 (17) | −0.0061 (15) | −0.0049 (15) | −0.0085 (16) |
C22 | 0.045 (2) | 0.0385 (19) | 0.0406 (18) | −0.0072 (17) | −0.0030 (16) | −0.0144 (16) |
C23 | 0.037 (2) | 0.0322 (18) | 0.0433 (19) | −0.0018 (15) | 0.0005 (16) | −0.0041 (16) |
C24 | 0.0341 (19) | 0.043 (2) | 0.0457 (19) | −0.0079 (16) | −0.0077 (16) | −0.0093 (17) |
C25 | 0.040 (2) | 0.0412 (19) | 0.0418 (18) | −0.0113 (16) | −0.0034 (16) | −0.0144 (16) |
C26 | 0.0288 (18) | 0.0291 (17) | 0.0429 (18) | −0.0021 (14) | −0.0080 (15) | −0.0112 (15) |
C27 | 0.0312 (17) | 0.0317 (17) | 0.0334 (16) | −0.0029 (14) | −0.0058 (14) | −0.0096 (15) |
C28 | 0.0289 (17) | 0.0250 (16) | 0.0374 (17) | −0.0002 (13) | −0.0063 (14) | −0.0114 (14) |
C29 | 0.0360 (18) | 0.0279 (17) | 0.0412 (18) | −0.0063 (14) | −0.0047 (15) | −0.0109 (15) |
C30 | 0.055 (2) | 0.0390 (19) | 0.0354 (17) | −0.0118 (17) | −0.0079 (16) | −0.0089 (16) |
C31 | 0.047 (2) | 0.0367 (19) | 0.047 (2) | −0.0087 (16) | −0.0109 (17) | −0.0176 (17) |
C32 | 0.0360 (18) | 0.0289 (17) | 0.0338 (16) | −0.0068 (14) | 0.0018 (15) | −0.0097 (15) |
C33 | 0.0415 (19) | 0.0294 (17) | 0.0349 (17) | −0.0080 (15) | −0.0035 (15) | −0.0091 (15) |
C34 | 0.0375 (19) | 0.0276 (16) | 0.0321 (16) | −0.0049 (14) | −0.0074 (14) | −0.0078 (14) |
C35 | 0.0382 (19) | 0.047 (2) | 0.0391 (18) | −0.0085 (16) | −0.0025 (15) | −0.0153 (17) |
C36 | 0.054 (2) | 0.059 (2) | 0.0357 (18) | −0.0078 (19) | −0.0056 (17) | −0.0194 (18) |
C37 | 0.053 (2) | 0.051 (2) | 0.048 (2) | −0.0102 (18) | −0.0152 (18) | −0.0211 (18) |
C38 | 0.036 (2) | 0.046 (2) | 0.047 (2) | −0.0089 (16) | −0.0111 (16) | −0.0107 (17) |
C39 | 0.0371 (19) | 0.0387 (19) | 0.0363 (17) | −0.0065 (15) | −0.0075 (15) | −0.0085 (16) |
C40 | 0.0402 (19) | 0.0360 (19) | 0.0371 (17) | −0.0044 (16) | −0.0034 (15) | −0.0139 (16) |
C41 | 0.046 (2) | 0.0349 (19) | 0.0325 (16) | −0.0100 (17) | 0.0013 (15) | −0.0121 (15) |
C42 | 0.040 (2) | 0.0398 (19) | 0.0337 (16) | −0.0114 (16) | 0.0043 (15) | −0.0161 (16) |
C43 | 0.055 (2) | 0.053 (2) | 0.0354 (18) | −0.0191 (19) | −0.0070 (17) | −0.0088 (17) |
C44 | 0.059 (2) | 0.065 (3) | 0.047 (2) | −0.033 (2) | 0.0015 (19) | −0.024 (2) |
C45 | 0.079 (3) | 0.044 (2) | 0.042 (2) | −0.028 (2) | 0.009 (2) | −0.0131 (18) |
C46 | 0.063 (2) | 0.040 (2) | 0.0409 (19) | −0.0085 (19) | −0.0047 (18) | −0.0031 (17) |
C47 | 0.044 (2) | 0.042 (2) | 0.0427 (18) | −0.0098 (17) | −0.0035 (16) | −0.0137 (17) |
Geometric parameters (Å, º) top
C1—C3 | 1.528 (4) | C35—C36 | 1.388 (4) |
C1—C4 | 1.534 (4) | C36—C37 | 1.373 (5) |
C1—C26 | 1.536 (4) | C37—C38 | 1.382 (4) |
C1—C2 | 1.539 (4) | C38—C39 | 1.379 (4) |
C4—C9 | 1.388 (4) | C40—C41 | 1.192 (4) |
C4—C5 | 1.390 (4) | C41—C42 | 1.435 (4) |
C5—C6 | 1.385 (4) | C42—C43 | 1.386 (4) |
C6—C7 | 1.379 (4) | C42—C47 | 1.391 (4) |
C7—C8 | 1.413 (4) | C43—C44 | 1.383 (4) |
C7—C10 | 1.436 (5) | C44—C45 | 1.373 (5) |
C8—C9 | 1.387 (4) | C45—C46 | 1.381 (5) |
C8—C18 | 1.438 (4) | C46—C47 | 1.373 (4) |
C10—C11 | 1.194 (4) | C3—H3B | 0.98 |
C11—C12 | 1.434 (5) | C25—H25A | 0.95 |
C12—C13 | 1.382 (4) | C3—H3C | 0.98 |
C12—C17 | 1.393 (4) | C27—H27A | 0.95 |
C13—C14 | 1.378 (5) | C5—H5A | 0.95 |
C14—C15 | 1.373 (5) | C30—H30A | 0.95 |
C15—C16 | 1.369 (5) | C6—H6A | 0.95 |
C16—C17 | 1.387 (5) | C31—H31A | 0.95 |
C18—C19 | 1.197 (4) | C9—H9A | 0.95 |
C19—C20 | 1.432 (4) | C35—H35A | 0.95 |
C20—C25 | 1.389 (4) | C13—H13A | 0.95 |
C20—C21 | 1.398 (4) | C36—H36A | 0.95 |
C21—C22 | 1.374 (4) | C14—H14A | 0.95 |
C22—C23 | 1.381 (4) | C37—H37A | 0.95 |
C23—C24 | 1.381 (4) | C15—H15A | 0.95 |
C24—C25 | 1.383 (4) | C38—H38A | 0.95 |
C26—C27 | 1.391 (4) | C16—H16A | 0.95 |
C26—C31 | 1.397 (4) | C39—H39A | 0.95 |
C27—C28 | 1.392 (4) | C17—H17A | 0.95 |
C28—C29 | 1.411 (4) | C43—H43A | 0.95 |
C28—C32 | 1.448 (4) | C21—H21A | 0.95 |
C29—C30 | 1.390 (4) | C44—H44A | 0.95 |
C29—C40 | 1.436 (4) | C22—H22A | 0.95 |
C30—C31 | 1.387 (4) | C45—H45A | 0.95 |
C32—C33 | 1.193 (4) | C23—H23A | 0.95 |
C33—C34 | 1.432 (4) | C46—H46A | 0.95 |
C34—C35 | 1.386 (4) | C24—H24A | 0.95 |
C34—C39 | 1.402 (4) | C47—H47A | 0.95 |
| | | |
C3—C1—C4 | 112.4 (3) | C44—C45—C46 | 119.7 (3) |
C3—C1—C26 | 107.3 (3) | C47—C46—C45 | 119.8 (3) |
C4—C1—C26 | 109.6 (2) | C46—C47—C42 | 121.1 (3) |
C3—C1—C2 | 107.9 (3) | C5—C6—H6A | 119.28 |
C4—C1—C2 | 108.1 (2) | C7—C6—H6A | 119.26 |
C26—C1—C2 | 111.6 (3) | C4—C9—H9A | 118.82 |
C9—C4—C5 | 117.6 (3) | C8—C9—H9A | 118.83 |
C9—C4—C1 | 119.6 (3) | C12—C13—H13A | 118.99 |
C5—C4—C1 | 122.8 (3) | C14—C13—H13A | 119.02 |
C6—C5—C4 | 121.0 (3) | C13—C14—H14A | 120.30 |
C7—C6—C5 | 121.4 (3) | C15—C14—H14A | 120.46 |
C6—C7—C8 | 118.4 (3) | C14—C15—H15A | 119.95 |
C6—C7—C10 | 122.9 (3) | C16—C15—H15A | 119.98 |
C8—C7—C10 | 118.7 (3) | C15—C16—H16A | 119.57 |
C9—C8—C7 | 119.1 (3) | C17—C16—H16A | 119.58 |
C9—C8—C18 | 121.1 (3) | C12—C17—H17A | 120.20 |
C7—C8—C18 | 119.7 (3) | C16—C17—H17A | 120.08 |
C8—C9—C4 | 122.4 (3) | C1—C2—H2A | 109.43 |
C11—C10—C7 | 174.9 (4) | C20—C21—H21A | 119.78 |
C10—C11—C12 | 172.8 (4) | C1—C2—H2B | 109.51 |
C13—C12—C17 | 118.1 (3) | C22—C21—H21A | 119.84 |
C13—C12—C11 | 119.4 (3) | C1—C2—H2C | 109.43 |
C17—C12—C11 | 122.4 (3) | C21—C22—H22A | 119.70 |
C14—C13—C12 | 122.0 (3) | H2A—C2—H2B | 109.46 |
C15—C14—C13 | 119.3 (4) | C23—C22—H22A | 119.66 |
C16—C15—C14 | 120.0 (4) | H2A—C2—H2C | 109.52 |
C15—C16—C17 | 120.9 (3) | C22—C23—H23A | 120.30 |
C16—C17—C12 | 119.7 (4) | H2B—C2—H2C | 109.48 |
C19—C18—C8 | 175.0 (3) | C24—C23—H23A | 120.24 |
C18—C19—C20 | 179.0 (3) | C1—C3—H3A | 109.41 |
C25—C20—C21 | 118.7 (3) | C23—C24—H24A | 119.76 |
C25—C20—C19 | 120.7 (3) | C1—C3—H3B | 109.46 |
C21—C20—C19 | 120.6 (3) | C25—C24—H24A | 119.84 |
C22—C21—C20 | 120.4 (3) | C1—C3—H3C | 109.47 |
C21—C22—C23 | 120.6 (3) | C20—C25—H25A | 119.84 |
C22—C23—C24 | 119.5 (3) | H3A—C3—H3B | 109.45 |
C23—C24—C25 | 120.4 (3) | C24—C25—H25A | 119.78 |
C24—C25—C20 | 120.4 (3) | H3A—C3—H3C | 109.50 |
C27—C26—C31 | 117.6 (3) | C26—C27—H27A | 118.89 |
C27—C26—C1 | 119.1 (3) | H3B—C3—H3C | 109.54 |
C31—C26—C1 | 123.2 (3) | C28—C27—H27A | 118.87 |
C26—C27—C28 | 122.2 (3) | C4—C5—H5A | 119.50 |
C27—C28—C29 | 119.5 (3) | C29—C30—H30A | 119.22 |
C27—C28—C32 | 120.1 (3) | C6—C5—H5A | 119.53 |
C29—C28—C32 | 120.3 (3) | C31—C30—H30A | 119.25 |
C30—C29—C28 | 118.2 (3) | C26—C31—H31A | 119.54 |
C30—C29—C40 | 120.5 (3) | C38—C39—H39A | 119.85 |
C28—C29—C40 | 121.3 (3) | C30—C31—H31A | 119.64 |
C31—C30—C29 | 121.5 (3) | C42—C43—H43A | 119.87 |
C30—C31—C26 | 120.8 (3) | C34—C35—H35A | 119.85 |
C33—C32—C28 | 175.6 (3) | C44—C43—H43A | 119.91 |
C32—C33—C34 | 177.6 (3) | C36—C35—H35A | 119.79 |
C35—C34—C39 | 118.7 (3) | C43—C44—H44A | 119.75 |
C35—C34—C33 | 121.3 (3) | C35—C36—H36A | 119.75 |
C39—C34—C33 | 120.0 (3) | C45—C44—H44A | 119.68 |
C34—C35—C36 | 120.4 (3) | C37—C36—H36A | 119.71 |
C37—C36—C35 | 120.5 (3) | C44—C45—H45A | 120.12 |
C36—C37—C38 | 119.7 (3) | C36—C37—H37A | 120.21 |
C39—C38—C37 | 120.5 (3) | C46—C45—H45A | 120.10 |
C38—C39—C34 | 120.2 (3) | C38—C37—H37A | 120.17 |
C41—C40—C29 | 177.9 (3) | C45—C46—H46A | 120.15 |
C40—C41—C42 | 178.0 (4) | C37—C38—H38A | 119.73 |
C43—C42—C47 | 118.5 (3) | C47—C46—H46A | 120.05 |
C43—C42—C41 | 120.9 (3) | C39—C38—H38A | 119.73 |
C47—C42—C41 | 120.6 (3) | C42—C47—H47A | 119.43 |
C44—C43—C42 | 120.2 (3) | C34—C39—H39A | 119.95 |
C45—C44—C43 | 120.6 (3) | C46—C47—H47A | 119.46 |
| | | |
C3—C1—C4—C9 | −179.7 (3) | C3—C1—C26—C27 | 70.0 (3) |
C26—C1—C4—C9 | −60.5 (3) | C4—C1—C26—C27 | −52.3 (4) |
C2—C1—C4—C9 | 61.3 (3) | C2—C1—C26—C27 | −172.0 (3) |
C3—C1—C4—C5 | 1.3 (4) | C3—C1—C26—C31 | −107.1 (3) |
C26—C1—C4—C5 | 120.5 (3) | C4—C1—C26—C31 | 130.6 (3) |
C2—C1—C4—C5 | −117.6 (3) | C2—C1—C26—C31 | 10.9 (4) |
C9—C4—C5—C6 | −0.7 (4) | C31—C26—C27—C28 | 0.7 (4) |
C1—C4—C5—C6 | 178.3 (3) | C1—C26—C27—C28 | −176.5 (3) |
C4—C5—C6—C7 | 0.3 (5) | C26—C27—C28—C29 | 1.7 (4) |
C5—C6—C7—C8 | −1.0 (4) | C26—C27—C28—C32 | −174.9 (3) |
C5—C6—C7—C10 | −179.0 (3) | C27—C28—C29—C30 | −3.0 (4) |
C6—C7—C8—C9 | 2.1 (4) | C32—C28—C29—C30 | 173.6 (3) |
C10—C7—C8—C9 | −179.9 (3) | C27—C28—C29—C40 | 177.7 (3) |
C6—C7—C8—C18 | −174.5 (3) | C32—C28—C29—C40 | −5.7 (5) |
C10—C7—C8—C18 | 3.5 (4) | C28—C29—C30—C31 | 2.0 (5) |
C7—C8—C9—C4 | −2.6 (4) | C40—C29—C30—C31 | −178.7 (3) |
C18—C8—C9—C4 | 174.0 (3) | C29—C30—C31—C26 | 0.4 (5) |
C5—C4—C9—C8 | 1.9 (4) | C27—C26—C31—C30 | −1.7 (5) |
C1—C4—C9—C8 | −177.2 (2) | C1—C26—C31—C30 | 175.3 (3) |
C17—C12—C13—C14 | −0.2 (5) | C39—C34—C35—C36 | −0.7 (5) |
C11—C12—C13—C14 | −177.9 (3) | C33—C34—C35—C36 | −179.3 (3) |
C12—C13—C14—C15 | 1.5 (5) | C34—C35—C36—C37 | 1.1 (5) |
C13—C14—C15—C16 | −1.4 (5) | C35—C36—C37—C38 | −0.8 (5) |
C14—C15—C16—C17 | 0.0 (6) | C36—C37—C38—C39 | 0.3 (5) |
C15—C16—C17—C12 | 1.3 (5) | C37—C38—C39—C34 | 0.1 (5) |
C13—C12—C17—C16 | −1.2 (5) | C35—C34—C39—C38 | 0.1 (4) |
C11—C12—C17—C16 | 176.4 (3) | C33—C34—C39—C38 | 178.8 (3) |
C25—C20—C21—C22 | −0.6 (4) | C47—C42—C43—C44 | 0.9 (5) |
C19—C20—C21—C22 | −179.8 (3) | C41—C42—C43—C44 | −178.9 (3) |
C20—C21—C22—C23 | 0.2 (5) | C42—C43—C44—C45 | −0.4 (5) |
C21—C22—C23—C24 | 0.7 (5) | C43—C44—C45—C46 | 0.1 (5) |
C22—C23—C24—C25 | −1.2 (4) | C44—C45—C46—C47 | −0.1 (5) |
C23—C24—C25—C20 | 0.8 (5) | C45—C46—C47—C42 | 0.6 (5) |
C21—C20—C25—C24 | 0.1 (4) | C43—C42—C47—C46 | −1.0 (5) |
C19—C20—C25—C24 | 179.3 (3) | C41—C42—C47—C46 | 178.9 (3) |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C44H26 | C44H26O | C47H32 |
Mr | 554.65 | 570.65 | 596.73 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, C2/c | Triclinic, P1 |
Temperature (K) | 300 | 300 | 173 |
a, b, c (Å) | 13.299 (7), 5.229 (3), 21.196 (11) | 35.483 (10), 5.8875 (15), 15.919 (5) | 6.323 (3), 14.575 (4), 19.776 (4) |
α, β, γ (°) | 90, 92.540 (15), 90 | 90, 109.932 (6), 90 | 69.53 (3), 81.20 (4), 79.14 (4) |
V (Å3) | 1472.4 (14) | 3126.4 (14) | 1669.3 (10) |
Z | 2 | 4 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.07 | 0.07 | 0.07 |
Crystal size (mm) | 0.30 × 0.15 × 0.10 | 0.30 × 0.20 × 0.20 | 0.50 × 0.06 × 0.05 |
|
Data collection |
Diffractometer | Rigaku Mercury CCD diffractometer | Rigaku Mercury CCD diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (Jacobson, 1998) | Multi-scan (Jacobson, 1998) | Empirical (using intensity measurements) (SADABS; Blessing, 1995) |
Tmin, Tmax | 0.987, 0.993 | 0.983, 0.986 | 0.924, 0.997 |
No. of measured, independent and observed reflections | 14417, 3021, 1664 [I > 2σ(I)] | 15387, 3203, 1964 [I > 2.00σ(I)] | 12148, 5860, 3266 [I > 2σ(I)] |
Rint | 0.091 | 0.052 | 0.048 |
(sin θ/λ)max (Å−1) | 0.627 | 0.628 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.079, 0.182, 1.15 | 0.065, 0.184, 1.15 | 0.064, 0.150, 1.02 |
No. of reflections | 3021 | 3202 | 5860 |
No. of parameters | 200 | 204 | 427 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.18 | 0.13, −0.13 | 0.20, −0.19 |
Selected geometric parameters (Å, º) for (I) topC1—C1i | 1.486 (6) | C8—C9 | 1.430 (4) |
C3—C7 | 1.430 (4) | C15—C16 | 1.198 (4) |
C4—C15 | 1.435 (4) | C16—C17 | 1.413 (4) |
C7—C8 | 1.207 (4) | | |
| | | |
C2—C1—C6 | 117.1 (3) | C7—C8—C9 | 179.5 (4) |
C2—C1—C1i | 121.4 (4) | C10—C9—C14 | 118.8 (3) |
C6—C1—C1i | 121.6 (3) | C10—C9—C8 | 122.3 (3) |
C2—C3—C4 | 118.6 (3) | C14—C9—C8 | 118.9 (3) |
C2—C3—C7 | 120.2 (3) | C16—C15—C4 | 175.3 (4) |
C4—C3—C7 | 121.1 (3) | C15—C16—C17 | 177.4 (4) |
C5—C4—C3 | 118.9 (3) | C18—C17—C22 | 118.6 (3) |
C5—C4—C15 | 118.8 (3) | C18—C17—C16 | 121.1 (3) |
C3—C4—C15 | 122.3 (3) | C22—C17—C16 | 120.2 (3) |
C8—C7—C3 | 178.3 (3) | | |
Symmetry code: (i) −x, −y+1, −z+2. |
Selected geometric parameters (Å, º) for (II) topO1—C1 | 1.395 (3) | C8—C9 | 1.429 (3) |
C3—C7 | 1.434 (3) | C15—C16 | 1.197 (3) |
C4—C15 | 1.433 (3) | C16—C17 | 1.440 (3) |
C7—C8 | 1.196 (3) | | |
| | | |
C1—O1—C1i | 118.1 (3) | C5—C4—C15 | 119.9 (2) |
C2—C1—C6 | 121.3 (2) | C3—C4—C15 | 121.6 (2) |
C2—C1—O1 | 117.5 (2) | C14—C9—C10 | 118.8 (2) |
C6—C1—O1 | 121.1 (2) | C14—C9—C8 | 119.4 (2) |
C2—C3—C4 | 120.0 (2) | C10—C9—C8 | 121.9 (2) |
C2—C3—C7 | 120.7 (2) | C18—C17—C22 | 118.7 (2) |
C4—C3—C7 | 119.4 (2) | C18—C17—C16 | 122.3 (2) |
C5—C4—C3 | 118.5 (2) | C22—C17—C16 | 119.0 (2) |
| | | |
C1i—O1—C1—C2 | −142.0 (2) | | |
Symmetry code: (i) −x+1, y, −z+1/2. |
Selected geometric parameters (Å, º) for (III) topC1—C3 | 1.528 (4) | C18—C19 | 1.197 (4) |
C1—C4 | 1.534 (4) | C19—C20 | 1.432 (4) |
C1—C26 | 1.536 (4) | C28—C32 | 1.448 (4) |
C1—C2 | 1.539 (4) | C29—C40 | 1.436 (4) |
C7—C10 | 1.436 (5) | C32—C33 | 1.193 (4) |
C8—C18 | 1.438 (4) | C33—C34 | 1.432 (4) |
C10—C11 | 1.194 (4) | C40—C41 | 1.192 (4) |
C11—C12 | 1.434 (5) | C41—C42 | 1.435 (4) |
| | | |
C3—C1—C4 | 112.4 (3) | C10—C11—C12 | 172.8 (4) |
C3—C1—C26 | 107.3 (3) | C19—C18—C8 | 175.0 (3) |
C4—C1—C26 | 109.6 (2) | C18—C19—C20 | 179.0 (3) |
C3—C1—C2 | 107.9 (3) | C33—C32—C28 | 175.6 (3) |
C4—C1—C2 | 108.1 (2) | C32—C33—C34 | 177.6 (3) |
C26—C1—C2 | 111.6 (3) | C41—C40—C29 | 177.9 (3) |
C11—C10—C7 | 174.9 (4) | C40—C41—C42 | 178.0 (4) |
Selected perpendicular π-stacking distances (Å) and dihedral angles (°). The distances are measured from the centroid of the first ring to the least-squares plane of the second ring. top | Ring 1 | Ring 2 | Distance 1–2 | Distance 2–1 | Dihedral angle |
(I) | C1–C6 | C9–C14 | 3.451 | 3.429 | 2.1 (2) |
(I) | C17–C22 | C9–C14 | 2.630 | 3.416 | 9.7 (2) |
(II) | C1–C6 | C1–C6 | 3.519 | 3.519 | 0 |
(II) | C9–C14 | C17–C22 | 3.848 | 3.714 | 15.5 (2) |
Trans-alkyne distances (Å) in the title BODA molecules top | C11···C19 (C8···C16) | C33···C41 (C8···C16) |
(I) | 4.262 (5) | 4.262 (5) |
(II) | 4.061 (3) | 4.061 (3) |
(III) | 3.844 (4) | 4.159 (6) |
Bis-ortho-diynylarene (BODA) compounds are a new class of tetrayne monomers which undergo thermally induced Bergman cyclization (Bergman, 1973) to form processable precursors leading to polyarylene polymer networks (Smith et al., 1998). BODA-derived networks are targeted for applications such as high-temperature thin-film dielectrics, optoelectronic materials (Smith et al., 1998), matrix composite resins, and precursors to glassy carbon microstructures (Shah et al., 2000). Currently BODA monomers are polymerized in solution or melt. However, solid-state polymerization could occur with appropriate high melting crystals. We report here the crystal structures of a series of BODA compounds with melting points below their polymerization temperature (<473 K).
The molecule of compound (I) is located on an inversion center and is approximately planar, with an r.m.s displacement of the C atoms from the molecular plane of 0.131 Å and a maximum displacement of 0.230 (3) Å for atom C5. The molecules are stacked in the direction of the crystallographic b axis; the distances between benzene rings are reported in Table 4. The molecule of compound (II) is located on a twofold symmetry axis; both parts are planar with an r.m.s. displacement for the non-H atoms of 0.174 Å and a maximum displacement from the least-squares plane of 0.352 (3) Å for atom C13. For BODA molecules with terminal phenyl groups, π-stacking of the aromatic rings is an important factor in determining crystal packing. The π-stacking distances of all molecules reported here are in a narrow range. The almost planar stacking of molecules in (I) (as illustrated by low value of the dihedral angle between the stacked rings) indicates very efficient packing (Table 4). Rings I and I of the two adjacent molecules of BODA (II) are exactly parallel to each other. The other close contact between phenyl rings in the structure of (II) exhibits a slightly longer distance and a relatively large angle between the planes of the two interacting rings (Table 4). Reactivity-determining trans-alkyne distances are reported in Table 5. The variation of the distance in one of the molecule (III) is comparable to the variation between different molecules. Thus, it seems that packing plays as important role as the spacer group in determining the trans-alkyne distance in solid state.
For BODA compounds with terminal phenyl groups, π-stacking of the aromatic rings is an important factor in determining crystal packing. Apart from their potential application for network polyarenes, the monomers are good candidates for crystal engineering as robust and versatile building blocks for supramolecular assemblies.
The 1,2-bis(phenylethynyl)phenyl fragment present in all three compounds is relatively uncommon among structures reported in the Cambridge Structural Database (CSD; Allen, 2002). Most often, such fragments occur as part of a larger macrocycle consisting of alternating benzene rings and ethynylene bridges. Sometimes they also incorporate a transition metal atom in the center. There are only four structures reported in the CSD with a free standing 1,2-bis(phenylethynyl)phenyl fragment, namely 1,2-bis[2-(3-hydroxyphenyl)ethynyl]benzene (refcode ECACEQ; Schmittel et al., 2001), bis{2-[2-(trimethylsilylethynyl)phenylethynyl]phenyl}ethyne and bis{2-[2-(ethynyl)phenylethynyl]phenyl}ethyne (GOPMIH and GOPMON, respectively; Baldwin et al., 1998), and 1,2-bis[2-(2-ethynylphenyl)ethynyl]benzene (PIPYUI; Baldwin et al., 1993). In GOPMIH and GOPMON, only two of the aromatic rings are coplanar, the rest of the molecule being twisted as a result of bulky substituents. The atomic coordinates of PIPYUI were not reported in the CSD. The fourth structure, ECACEQ, is nearly planar, closely resembling the planar fragments in molecules (I) and (II) reported here. It forms a hemihydrate clathrate with two molecules encapsulating one water molecule.