In the rac isomer of the title compound, C34H28O2, the two C-Phdimethylphenyl bond axes make an angle of 58.7 (1)°. There is no short contact between the two 3,5-dimethylphenyl rings, although the dihedral angle between them is 4.93 (7)°. The meso isomer has a center of symmetry at the middle of the C=C bond, and the two C-Phdimethylphenyl bond axes are antiparallel to one another.
Supporting information
CCDC references: 217142; 217143
Compounds (I) and (II) were synthesized according to the method reported by Tanaka & Toda (2000). The rac-isomer, (I), and meso-isomer, (II), were separated by repeated recrystallization of the crude reaction products from dichloromethane solution. The crystals of (I) and (II) suitable for X-ray study were grown from dichloromethane solutions. For (I) (m.p. 509–515 K); IR: 1686 (C=O), 1604 (C=C) cm−1; UV: λ/nm (ε) 241 (9600), 302 (24000); 1H NMR: δ 2.25 (12H, s, CH3), 5.74 (2H, s, CH), 6.83–7.76 (14H, m, Ph). For (II) (m.p. 529–532 K); IR: 1685 (C=O), 1600 (C=C) cm−1; UV: λ/nm (ε) 241 (9900), 294 (24200); 1H NMR: δ 2.22 (12H, s, CH3), 5.88 (2H, s, CH), 6.75–7.75 (14H, m, Ph).
All H atoms were positioned geometrically and fixed, with Uiso(H) equal to 1.2Ueq(parent atom). Some methyl H-atom positional parameters were modified further based on difference density maps.
For both compounds, data collection: WinAFC Diffractometer Control Software (Rigaku, 1999); cell refinement: WinAFC Diffractometer Control Software (Rigaku, 1999); data reduction: TEXSAN (Molecular Structure Corporation, 2001); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.
Crystal data top
C34H28O2 | Z = 2 |
Mr = 468.59 | F(000) = 496 |
Triclinic, P1 | Dx = 1.239 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.7107 Å |
a = 11.392 (2) Å | Cell parameters from 25 reflections |
b = 13.9700 (18) Å | θ = 10.4–14.4° |
c = 9.2771 (13) Å | µ = 0.08 mm−1 |
α = 97.705 (11)° | T = 298 K |
β = 109.950 (12)° | Plate, yellow |
γ = 109.492 (11)° | 0.5 × 0.25 × 0.1 mm |
V = 1256.0 (4) Å3 | |
Data collection top
Rigaku AFC7R diffractometer | θmax = 27.5° |
ω–2θ scans | h = −14→14 |
6275 measured reflections | k = −18→6 |
5773 independent reflections | l = −12→12 |
3911 reflections with I > 2σ(I) | 3 standard reflections every 150 reflections |
Rint = 0.025 | intensity decay: none |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.050 | w = 1/[σ2(Fo2) + (0.0736P)2 + 0.2455P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.154 | (Δ/σ)max = 0.006 |
S = 1.03 | Δρmax = 0.21 e Å−3 |
5773 reflections | Δρmin = −0.25 e Å−3 |
325 parameters | |
Crystal data top
C34H28O2 | γ = 109.492 (11)° |
Mr = 468.59 | V = 1256.0 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.392 (2) Å | Mo Kα radiation |
b = 13.9700 (18) Å | µ = 0.08 mm−1 |
c = 9.2771 (13) Å | T = 298 K |
α = 97.705 (11)° | 0.5 × 0.25 × 0.1 mm |
β = 109.950 (12)° | |
Data collection top
Rigaku AFC7R diffractometer | Rint = 0.025 |
6275 measured reflections | 3 standard reflections every 150 reflections |
5773 independent reflections | intensity decay: none |
3911 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 325 parameters |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.21 e Å−3 |
5773 reflections | Δρmin = −0.25 e Å−3 |
Special details top
Refinement. Refinement using reflections with F2 > 0.0 σ(F2). The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | −0.1395 (1) | 0.0481 (1) | 0.0679 (2) | 0.0506 (3) | |
O2 | 0.1733 (1) | 0.2675 (1) | −0.1794 (2) | 0.0569 (4) | |
C3 | −0.0183 (2) | 0.0998 (1) | 0.1123 (2) | 0.0342 (3) | |
C4 | 0.0491 (2) | 0.1686 (1) | 0.0266 (2) | 0.0310 (3) | |
C5 | 0.2030 (2) | 0.2168 (1) | 0.1228 (2) | 0.0326 (3) | |
C6 | 0.2190 (2) | 0.1656 (1) | 0.2586 (2) | 0.0352 (3) | |
C7 | 0.0943 (2) | 0.1038 (1) | 0.2556 (2) | 0.0353 (3) | |
C8 | 0.0857 (2) | 0.0547 (2) | 0.3750 (2) | 0.0454 (4) | |
C9 | 0.2057 (2) | 0.0698 (2) | 0.4990 (2) | 0.0520 (5) | |
C10 | 0.3313 (2) | 0.1306 (2) | 0.5016 (2) | 0.0524 (5) | |
C11 | 0.3395 (2) | 0.1786 (1) | 0.3823 (2) | 0.0455 (4) | |
C12 | 0.0514 (2) | 0.2302 (1) | −0.2145 (2) | 0.0375 (4) | |
C13 | −0.0183 (2) | 0.1801 (1) | −0.1147 (2) | 0.0323 (3) | |
C14 | −0.1721 (2) | 0.1417 (1) | −0.2056 (2) | 0.0338 (3) | |
C15 | −0.1851 (2) | 0.1673 (1) | −0.3633 (2) | 0.0376 (4) | |
C16 | −0.0588 (2) | 0.2175 (1) | −0.3658 (2) | 0.0401 (4) | |
C17 | −0.0471 (2) | 0.2457 (2) | −0.5013 (2) | 0.0531 (5) | |
C18 | −0.1646 (3) | 0.2226 (2) | −0.6332 (2) | 0.0628 (6) | |
C19 | −0.2913 (2) | 0.1736 (2) | −0.6304 (2) | 0.0607 (6) | |
C20 | −0.3038 (2) | 0.1456 (2) | −0.4967 (2) | 0.0501 (4) | |
C21 | 0.2640 (2) | 0.3367 (1) | 0.1914 (2) | 0.0352 (3) | |
C22 | 0.2035 (2) | 0.3830 (1) | 0.2689 (2) | 0.0444 (4) | |
C23 | 0.2618 (2) | 0.4915 (2) | 0.3407 (2) | 0.0535 (5) | |
C24 | 0.3819 (2) | 0.5524 (2) | 0.3324 (3) | 0.0582 (5) | |
C25 | 0.4461 (2) | 0.5088 (2) | 0.2578 (3) | 0.0539 (5) | |
C26 | 0.3847 (2) | 0.4000 (1) | 0.1870 (2) | 0.0445 (4) | |
C27 | 0.1969 (3) | 0.5413 (2) | 0.4274 (4) | 0.0871 (8) | |
C28 | 0.5772 (3) | 0.5773 (2) | 0.2517 (4) | 0.0817 (8) | |
C29 | −0.2380 (2) | 0.1950 (1) | −0.1235 (2) | 0.0358 (3) | |
C30 | −0.1758 (2) | 0.3033 (1) | −0.0518 (2) | 0.0435 (4) | |
C31 | −0.2377 (2) | 0.3544 (2) | 0.0165 (2) | 0.0500 (4) | |
C32 | −0.3639 (2) | 0.2938 (2) | 0.0121 (2) | 0.0543 (5) | |
C33 | −0.4290 (2) | 0.1855 (2) | −0.0585 (2) | 0.0493 (5) | |
C34 | −0.3643 (2) | 0.1368 (1) | −0.1257 (2) | 0.0416 (4) | |
C35 | −0.1699 (3) | 0.4724 (2) | 0.0920 (3) | 0.0754 (7) | |
C36 | −0.5670 (2) | 0.1222 (2) | −0.0627 (3) | 0.0709 (7) | |
H5 | 0.2469 | 0.1977 | 0.0605 | 0.0381* | |
H8 | −0.0003 | 0.0121 | 0.3719 | 0.0538* | |
H9 | 0.2021 | 0.0385 | 0.5825 | 0.0614* | |
H10 | 0.4129 | 0.1394 | 0.5874 | 0.0618* | |
H11 | 0.4260 | 0.2196 | 0.3842 | 0.0537* | |
H14 | −0.2142 | 0.0674 | −0.2242 | 0.0391* | |
H17 | 0.0404 | 0.2802 | −0.5017 | 0.0619* | |
H18 | −0.1595 | 0.2402 | −0.7269 | 0.0743* | |
H19 | −0.3715 | 0.1586 | −0.7225 | 0.0713* | |
H20 | −0.3916 | 0.1132 | −0.4964 | 0.0592* | |
H22 | 0.1208 | 0.3399 | 0.2732 | 0.0517* | |
H24 | 0.4221 | 0.6265 | 0.3806 | 0.0685* | |
H26 | 0.4265 | 0.3685 | 0.1341 | 0.0525* | |
H27A | 0.2589 | 0.5733 | 0.5370 | 0.1026* | |
H27B | 0.1776 | 0.5939 | 0.3812 | 0.1026* | |
H27C | 0.1154 | 0.4886 | 0.4194 | 0.1026* | |
H28A | 0.5633 | 0.6293 | 0.2001 | 0.0982* | |
H28B | 0.6465 | 0.6105 | 0.3567 | 0.0982* | |
H28C | 0.6039 | 0.5337 | 0.1927 | 0.0982* | |
H30 | −0.0890 | 0.3435 | −0.0492 | 0.0507* | |
H32 | −0.4069 | 0.3275 | 0.0591 | 0.0642* | |
H34 | −0.4075 | 0.0628 | −0.1747 | 0.0495* | |
H35A | −0.0833 | 0.4898 | 0.1779 | 0.0886* | |
H35B | −0.1561 | 0.5077 | 0.0156 | 0.0886* | |
H35C | −0.2256 | 0.4936 | 0.1335 | 0.0886* | |
H36A | −0.5606 | 0.1290 | 0.0439 | 0.0834* | |
H36B | −0.6316 | 0.1484 | −0.1178 | 0.0834* | |
H36C | −0.5970 | 0.0501 | −0.1152 | 0.0834* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0329 (6) | 0.0610 (8) | 0.0545 (8) | 0.0115 (6) | 0.0176 (6) | 0.0268 (6) |
O2 | 0.0416 (7) | 0.0732 (9) | 0.0544 (8) | 0.0129 (7) | 0.0259 (6) | 0.0244 (7) |
C3 | 0.0343 (8) | 0.0358 (8) | 0.0349 (8) | 0.0144 (7) | 0.0165 (7) | 0.0108 (6) |
C4 | 0.0304 (7) | 0.0308 (7) | 0.0326 (8) | 0.0128 (6) | 0.0145 (6) | 0.0070 (6) |
C5 | 0.0297 (7) | 0.0328 (7) | 0.0347 (8) | 0.0120 (6) | 0.0141 (6) | 0.0075 (6) |
C6 | 0.0372 (8) | 0.0314 (7) | 0.0345 (8) | 0.0153 (7) | 0.0120 (7) | 0.0055 (6) |
C7 | 0.0388 (8) | 0.0341 (8) | 0.0350 (8) | 0.0165 (7) | 0.0158 (7) | 0.0095 (6) |
C8 | 0.050 (1) | 0.0506 (10) | 0.0419 (9) | 0.0222 (8) | 0.0220 (8) | 0.0198 (8) |
C9 | 0.065 (1) | 0.058 (1) | 0.0394 (10) | 0.031 (1) | 0.0201 (9) | 0.0214 (9) |
C10 | 0.052 (1) | 0.056 (1) | 0.0395 (10) | 0.0269 (9) | 0.0042 (8) | 0.0111 (8) |
C11 | 0.0369 (9) | 0.0434 (9) | 0.0437 (10) | 0.0136 (8) | 0.0070 (7) | 0.0069 (8) |
C12 | 0.0390 (9) | 0.0378 (8) | 0.0371 (8) | 0.0124 (7) | 0.0202 (7) | 0.0110 (7) |
C13 | 0.0340 (8) | 0.0312 (7) | 0.0331 (8) | 0.0126 (6) | 0.0163 (6) | 0.0085 (6) |
C14 | 0.0311 (8) | 0.0346 (8) | 0.0336 (8) | 0.0117 (6) | 0.0126 (6) | 0.0098 (6) |
C15 | 0.0442 (9) | 0.0368 (8) | 0.0325 (8) | 0.0191 (7) | 0.0147 (7) | 0.0084 (6) |
C16 | 0.0498 (10) | 0.0408 (9) | 0.0349 (8) | 0.0207 (8) | 0.0207 (8) | 0.0127 (7) |
C17 | 0.069 (1) | 0.062 (1) | 0.044 (1) | 0.031 (1) | 0.0327 (10) | 0.0238 (9) |
C18 | 0.091 (2) | 0.078 (1) | 0.039 (1) | 0.048 (1) | 0.032 (1) | 0.027 (1) |
C19 | 0.073 (1) | 0.073 (1) | 0.0341 (9) | 0.040 (1) | 0.0110 (9) | 0.0148 (9) |
C20 | 0.051 (1) | 0.056 (1) | 0.0397 (10) | 0.0253 (9) | 0.0113 (8) | 0.0110 (8) |
C21 | 0.0336 (8) | 0.0333 (8) | 0.0344 (8) | 0.0112 (6) | 0.0117 (7) | 0.0088 (6) |
C22 | 0.0463 (10) | 0.0385 (9) | 0.048 (1) | 0.0145 (8) | 0.0234 (8) | 0.0085 (8) |
C23 | 0.066 (1) | 0.0405 (9) | 0.051 (1) | 0.0204 (9) | 0.0240 (10) | 0.0061 (8) |
C24 | 0.063 (1) | 0.0336 (9) | 0.057 (1) | 0.0071 (9) | 0.015 (1) | 0.0045 (8) |
C25 | 0.044 (1) | 0.0419 (10) | 0.056 (1) | 0.0027 (8) | 0.0145 (9) | 0.0120 (9) |
C26 | 0.0358 (9) | 0.0424 (9) | 0.051 (1) | 0.0109 (7) | 0.0182 (8) | 0.0109 (8) |
C27 | 0.114 (2) | 0.058 (1) | 0.099 (2) | 0.038 (1) | 0.060 (2) | 0.001 (1) |
C28 | 0.055 (1) | 0.057 (1) | 0.105 (2) | −0.004 (1) | 0.031 (1) | 0.018 (1) |
C29 | 0.0342 (8) | 0.0439 (9) | 0.0322 (8) | 0.0187 (7) | 0.0133 (7) | 0.0137 (7) |
C30 | 0.0442 (10) | 0.0448 (9) | 0.0480 (10) | 0.0209 (8) | 0.0225 (8) | 0.0163 (8) |
C31 | 0.059 (1) | 0.052 (1) | 0.049 (1) | 0.0315 (9) | 0.0239 (9) | 0.0153 (9) |
C32 | 0.056 (1) | 0.078 (1) | 0.049 (1) | 0.043 (1) | 0.0277 (9) | 0.021 (1) |
C33 | 0.0373 (9) | 0.077 (1) | 0.0407 (10) | 0.0277 (9) | 0.0178 (8) | 0.0223 (9) |
C34 | 0.0339 (8) | 0.0517 (10) | 0.0373 (9) | 0.0158 (8) | 0.0134 (7) | 0.0143 (7) |
C35 | 0.093 (2) | 0.058 (1) | 0.086 (2) | 0.040 (1) | 0.043 (2) | 0.013 (1) |
C36 | 0.044 (1) | 0.109 (2) | 0.063 (1) | 0.028 (1) | 0.029 (1) | 0.023 (1) |
Geometric parameters (Å, º) top
O1—C3 | 1.211 (2) | C21—C22 | 1.387 (3) |
O2—C12 | 1.213 (2) | C21—C26 | 1.383 (3) |
C3—C4 | 1.508 (3) | C22—C23 | 1.392 (3) |
C3—C7 | 1.478 (2) | C22—H22 | 0.951 |
C4—C5 | 1.519 (2) | C23—C24 | 1.384 (3) |
C4—C13 | 1.337 (2) | C23—C27 | 1.509 (5) |
C5—C6 | 1.518 (3) | C24—C25 | 1.383 (4) |
C5—C21 | 1.526 (2) | C24—H24 | 0.950 |
C5—H5 | 0.949 | C25—C26 | 1.393 (3) |
C6—C7 | 1.383 (2) | C25—C28 | 1.506 (4) |
C6—C11 | 1.391 (2) | C26—H26 | 0.951 |
C7—C8 | 1.393 (3) | C27—H27A | 0.953 |
C8—C9 | 1.381 (3) | C27—H27B | 0.949 |
C8—H8 | 0.950 | C27—H27C | 0.944 |
C9—C10 | 1.389 (3) | C28—H28A | 0.948 |
C9—H9 | 0.945 | C28—H28B | 0.948 |
C10—C11 | 1.383 (3) | C28—H28C | 0.954 |
C10—H10 | 0.952 | C29—C30 | 1.388 (2) |
C11—H11 | 0.953 | C29—C34 | 1.389 (3) |
C12—C13 | 1.509 (3) | C30—C31 | 1.388 (4) |
C12—C16 | 1.470 (2) | C30—H30 | 0.950 |
C13—C14 | 1.521 (2) | C31—C32 | 1.386 (3) |
C14—C15 | 1.523 (3) | C31—C35 | 1.509 (3) |
C14—C29 | 1.520 (3) | C32—C33 | 1.386 (3) |
C14—H14 | 0.948 | C32—H32 | 0.948 |
C15—C16 | 1.384 (3) | C33—C34 | 1.388 (3) |
C15—C20 | 1.392 (2) | C33—C36 | 1.509 (3) |
C16—C17 | 1.402 (3) | C34—H34 | 0.949 |
C17—C18 | 1.372 (3) | C35—H35A | 0.959 |
C17—H17 | 0.953 | C35—H35B | 0.943 |
C18—C19 | 1.387 (4) | C35—H35C | 0.948 |
C18—H18 | 0.950 | C36—H36A | 0.955 |
C19—C20 | 1.387 (3) | C36—H36B | 0.954 |
C19—H19 | 0.948 | C36—H36C | 0.946 |
C20—H20 | 0.951 | | |
| | | |
O1—C3—C4 | 126.7 (2) | C5—C21—C22 | 120.1 (2) |
O1—C3—C7 | 127.4 (2) | C5—C21—C26 | 120.9 (2) |
C4—C3—C7 | 105.9 (1) | C22—C21—C26 | 118.9 (2) |
C3—C4—C5 | 109.0 (1) | C21—C22—C23 | 121.1 (2) |
C3—C4—C13 | 124.2 (1) | C21—C22—H22 | 119.5 |
C5—C4—C13 | 126.7 (2) | C23—C22—H22 | 119.4 |
C4—C5—C6 | 102.6 (1) | C22—C23—C24 | 118.3 (2) |
C4—C5—C21 | 113.6 (2) | C22—C23—C27 | 120.9 (2) |
C4—C5—H5 | 110.4 | C24—C23—C27 | 120.8 (2) |
C6—C5—C21 | 109.3 (1) | C23—C24—C25 | 122.2 (2) |
C6—C5—H5 | 110.3 | C23—C24—H24 | 118.8 |
C21—C5—H5 | 110.4 | C25—C24—H24 | 119.0 |
C5—C6—C7 | 112.2 (1) | C24—C25—C26 | 117.9 (2) |
C5—C6—C11 | 128.0 (2) | C24—C25—C28 | 120.9 (2) |
C7—C6—C11 | 119.8 (2) | C26—C25—C28 | 121.2 (2) |
C3—C7—C6 | 110.0 (2) | C21—C26—C25 | 121.6 (2) |
C3—C7—C8 | 128.4 (2) | C21—C26—H26 | 119.1 |
C6—C7—C8 | 121.6 (2) | C25—C26—H26 | 119.3 |
C7—C8—C9 | 118.3 (2) | C23—C27—H27A | 109.2 |
C7—C8—H8 | 121.1 | C23—C27—H27B | 109.3 |
C9—C8—H8 | 120.6 | C23—C27—H27C | 109.3 |
C8—C9—C10 | 120.4 (2) | H27A—C27—H27B | 109.2 |
C8—C9—H9 | 119.7 | H27A—C27—H27C | 109.7 |
C10—C9—H9 | 119.9 | H27B—C27—H27C | 110.1 |
C9—C10—C11 | 121.2 (2) | C25—C28—H28A | 109.7 |
C9—C10—H10 | 119.2 | C25—C28—H28B | 109.7 |
C11—C10—H10 | 119.6 | C25—C28—H28C | 108.7 |
C6—C11—C10 | 118.8 (2) | H28A—C28—H28B | 109.8 |
C6—C11—H11 | 120.5 | H28A—C28—H28C | 109.4 |
C10—C11—H11 | 120.7 | H28B—C28—H28C | 109.5 |
O2—C12—C13 | 126.5 (2) | C14—C29—C30 | 120.5 (2) |
O2—C12—C16 | 127.3 (2) | C14—C29—C34 | 120.4 (1) |
C13—C12—C16 | 106.0 (1) | C30—C29—C34 | 119.1 (2) |
C4—C13—C12 | 123.3 (1) | C29—C30—C31 | 121.4 (2) |
C4—C13—C14 | 127.6 (2) | C29—C30—H30 | 119.5 |
C12—C13—C14 | 109.0 (1) | C31—C30—H30 | 119.2 |
C13—C14—C15 | 102.5 (1) | C30—C31—C32 | 118.0 (2) |
C13—C14—C29 | 114.3 (1) | C30—C31—C35 | 120.8 (2) |
C13—C14—H14 | 109.4 | C32—C31—C35 | 121.2 (3) |
C15—C14—C29 | 111.2 (2) | C31—C32—C33 | 122.2 (2) |
C15—C14—H14 | 109.7 | C31—C32—H32 | 118.9 |
C29—C14—H14 | 109.5 | C33—C32—H32 | 118.9 |
C14—C15—C16 | 112.0 (1) | C32—C33—C34 | 118.3 (2) |
C14—C15—C20 | 128.2 (2) | C32—C33—C36 | 120.8 (2) |
C16—C15—C20 | 119.8 (2) | C34—C33—C36 | 120.9 (2) |
C12—C16—C15 | 110.4 (2) | C29—C34—C33 | 121.0 (2) |
C12—C16—C17 | 128.1 (2) | C29—C34—H34 | 119.5 |
C15—C16—C17 | 121.5 (2) | C33—C34—H34 | 119.5 |
C16—C17—C18 | 118.4 (2) | C31—C35—H35A | 109.0 |
C16—C17—H17 | 120.8 | C31—C35—H35B | 109.9 |
C18—C17—H17 | 120.9 | C31—C35—H35C | 109.5 |
C17—C18—C19 | 120.3 (2) | H35A—C35—H35B | 109.3 |
C17—C18—H18 | 120.0 | H35A—C35—H35C | 108.9 |
C19—C18—H18 | 119.7 | H35B—C35—H35C | 110.3 |
C18—C19—C20 | 121.8 (2) | C33—C36—H36A | 109.6 |
C18—C19—H19 | 119.1 | C33—C36—H36B | 109.7 |
C20—C19—H19 | 119.2 | C33—C36—H36C | 110.0 |
C15—C20—C19 | 118.3 (2) | H36A—C36—H36B | 108.7 |
C15—C20—H20 | 121.1 | H36A—C36—H36C | 109.4 |
C19—C20—H20 | 120.6 | H36B—C36—H36C | 109.5 |
| | | |
C3—C4—C13—C12 | −166.8 (2) | C4—C5—C6—C7 | −5.2 (2) |
C3—C4—C13—C14 | 9.5 (3) | C5—C4—C3—C7 | −1.9 (2) |
C5—C4—C13—C12 | 10.1 (3) | C12—C13—C14—C15 | 2.8 (2) |
C5—C4—C13—C14 | −173.6 (2) | C12—C16—C15—C14 | 0.6 (2) |
C3—C4—C5—C6 | 4.1 (2) | C13—C12—C16—C15 | 1.3 (2) |
C3—C7—C6—C5 | 4.3 (2) | C13—C14—C15—C16 | −2.1 (2) |
C4—C3—C7—C6 | −1.5 (2) | C14—C13—C12—C16 | −2.6 (2) |
Crystal data top
C34H28O2 | F(000) = 496 |
Mr = 468.59 | Dx = 1.204 Mg m−3 |
Monoclinic, P21/a | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2yab | Cell parameters from 25 reflections |
a = 19.230 (2) Å | θ = 10.1–12.8° |
b = 8.0506 (10) Å | µ = 0.07 mm−1 |
c = 8.4461 (11) Å | T = 298 K |
β = 98.802 (10)° | Needle, yellow |
V = 1292.2 (3) Å3 | 0.5 × 0.2 × 0.2 mm |
Z = 2 | |
Data collection top
Rigaku AFC7R diffractometer | θmax = 27.5° |
ω–2θ scans | h = −24→24 |
3542 measured reflections | k = 0→10 |
2969 independent reflections | l = −10→4 |
1870 reflections with I > 2σ(I) | 3 standard reflections every 150 reflections |
Rint = 0.013 | intensity decay: none |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.054 | w = 1/[σ2(Fo2) + (0.0887P)2 + 0.4121P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.195 | (Δ/σ)max = 0.004 |
S = 1.21 | Δρmax = 0.29 e Å−3 |
2969 reflections | Δρmin = −0.28 e Å−3 |
164 parameters | |
Crystal data top
C34H28O2 | V = 1292.2 (3) Å3 |
Mr = 468.59 | Z = 2 |
Monoclinic, P21/a | Mo Kα radiation |
a = 19.230 (2) Å | µ = 0.07 mm−1 |
b = 8.0506 (10) Å | T = 298 K |
c = 8.4461 (11) Å | 0.5 × 0.2 × 0.2 mm |
β = 98.802 (10)° | |
Data collection top
Rigaku AFC7R diffractometer | Rint = 0.013 |
3542 measured reflections | 3 standard reflections every 150 reflections |
2969 independent reflections | intensity decay: none |
1870 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.054 | 164 parameters |
wR(F2) = 0.195 | H-atom parameters constrained |
S = 1.21 | Δρmax = 0.29 e Å−3 |
2969 reflections | Δρmin = −0.28 e Å−3 |
Special details top
Refinement. Refinement using reflections with F2 > 0.0 σ(F2). The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.46758 (9) | −0.2628 (2) | 0.6626 (2) | 0.0568 (5) | |
C2 | 0.46117 (9) | −0.1124 (3) | 0.6735 (2) | 0.0402 (5) | |
C3 | 0.48116 (9) | 0.0159 (2) | 0.5584 (2) | 0.0367 (4) | |
C4 | 0.45392 (9) | 0.1841 (3) | 0.6041 (2) | 0.0388 (5) | |
C5 | 0.4314 (1) | 0.1468 (3) | 0.7662 (2) | 0.0442 (5) | |
C6 | 0.4335 (1) | −0.0209 (3) | 0.8005 (2) | 0.0424 (5) | |
C7 | 0.4133 (1) | −0.0830 (3) | 0.9415 (3) | 0.0533 (6) | |
C8 | 0.3919 (1) | 0.0286 (4) | 1.0465 (3) | 0.0645 (7) | |
C9 | 0.3905 (1) | 0.1961 (4) | 1.0139 (3) | 0.0713 (8) | |
C10 | 0.4102 (1) | 0.2596 (3) | 0.8741 (3) | 0.0613 (7) | |
C11 | 0.39113 (9) | 0.2488 (2) | 0.4869 (2) | 0.0364 (4) | |
C12 | 0.3349 (1) | 0.1450 (2) | 0.4324 (2) | 0.0398 (5) | |
C13 | 0.2765 (1) | 0.2031 (3) | 0.3299 (3) | 0.0449 (5) | |
C14 | 0.2751 (1) | 0.3700 (3) | 0.2862 (3) | 0.0505 (6) | |
C15 | 0.3296 (1) | 0.4762 (3) | 0.3400 (3) | 0.0513 (6) | |
C16 | 0.3882 (1) | 0.4133 (3) | 0.4396 (3) | 0.0448 (5) | |
C17 | 0.2169 (1) | 0.0880 (3) | 0.2664 (4) | 0.0674 (7) | |
C18 | 0.3266 (2) | 0.6564 (4) | 0.2912 (5) | 0.087 (1) | |
H4 | 0.4909 | 0.2636 | 0.6165 | 0.0460* | |
H7 | 0.4145 | −0.1989 | 0.9639 | 0.0623* | |
H8 | 0.3777 | −0.0099 | 1.1431 | 0.0768* | |
H9 | 0.3757 | 0.2707 | 1.0891 | 0.0840* | |
H10 | 0.4091 | 0.3758 | 0.8536 | 0.0729* | |
H12 | 0.3364 | 0.0325 | 0.4658 | 0.0474* | |
H14 | 0.2351 | 0.4117 | 0.2173 | 0.0590* | |
H16 | 0.4267 | 0.4850 | 0.4754 | 0.0530* | |
H17A | 0.1819 | 0.1484 | 0.1985 | 0.0794* | |
H17B | 0.2343 | 0.0010 | 0.2075 | 0.0794* | |
H17C | 0.1974 | 0.0427 | 0.3535 | 0.0794* | |
H18A | 0.3688 | 0.7102 | 0.3374 | 0.1035* | |
H18B | 0.3215 | 0.6641 | 0.1778 | 0.1035* | |
H18C | 0.2875 | 0.7082 | 0.3276 | 0.1035* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.066 (1) | 0.0450 (10) | 0.061 (1) | −0.0060 (8) | 0.0145 (8) | −0.0054 (8) |
C2 | 0.0303 (9) | 0.048 (1) | 0.042 (1) | −0.0009 (8) | 0.0037 (8) | −0.0064 (9) |
C3 | 0.0281 (8) | 0.041 (1) | 0.0396 (10) | 0.0035 (7) | −0.0002 (7) | −0.0079 (8) |
C4 | 0.0300 (9) | 0.041 (1) | 0.044 (1) | 0.0046 (8) | 0.0019 (8) | −0.0103 (9) |
C5 | 0.0333 (10) | 0.062 (1) | 0.035 (1) | 0.0114 (9) | −0.0025 (8) | −0.0094 (9) |
C6 | 0.0299 (9) | 0.058 (1) | 0.038 (1) | 0.0016 (9) | 0.0016 (8) | −0.0070 (9) |
C7 | 0.039 (1) | 0.079 (2) | 0.041 (1) | −0.004 (1) | 0.0026 (9) | −0.002 (1) |
C8 | 0.054 (1) | 0.102 (2) | 0.038 (1) | 0.010 (1) | 0.009 (1) | −0.004 (1) |
C9 | 0.067 (2) | 0.104 (2) | 0.043 (1) | 0.026 (2) | 0.012 (1) | −0.022 (1) |
C10 | 0.063 (1) | 0.072 (2) | 0.047 (1) | 0.026 (1) | 0.001 (1) | −0.014 (1) |
C11 | 0.0327 (9) | 0.0382 (10) | 0.0384 (9) | 0.0058 (8) | 0.0063 (7) | −0.0059 (8) |
C12 | 0.0368 (10) | 0.0370 (10) | 0.045 (1) | 0.0022 (8) | 0.0057 (8) | 0.0002 (9) |
C13 | 0.035 (1) | 0.051 (1) | 0.048 (1) | 0.0014 (9) | 0.0045 (9) | −0.0013 (10) |
C14 | 0.043 (1) | 0.056 (1) | 0.051 (1) | 0.0115 (10) | 0.0004 (9) | 0.005 (1) |
C15 | 0.057 (1) | 0.039 (1) | 0.058 (1) | 0.0091 (10) | 0.006 (1) | 0.002 (1) |
C16 | 0.043 (1) | 0.037 (1) | 0.054 (1) | −0.0007 (8) | 0.0052 (9) | −0.0084 (9) |
C17 | 0.045 (1) | 0.071 (2) | 0.080 (2) | −0.009 (1) | −0.011 (1) | 0.005 (1) |
C18 | 0.096 (2) | 0.048 (2) | 0.110 (3) | 0.009 (1) | −0.009 (2) | 0.017 (2) |
Geometric parameters (Å, º) top
O1—C2 | 1.222 (3) | C11—C12 | 1.389 (3) |
C2—C3 | 1.508 (3) | C11—C16 | 1.383 (3) |
C2—C6 | 1.467 (3) | C12—C13 | 1.389 (3) |
C3—C3i | 1.336 (4) | C12—H12 | 0.947 |
C3—C4 | 1.523 (3) | C13—C14 | 1.393 (3) |
C4—C5 | 1.527 (3) | C13—C17 | 1.507 (3) |
C4—C11 | 1.531 (2) | C14—C15 | 1.375 (3) |
C4—H4 | 0.950 | C14—H14 | 0.951 |
C5—C6 | 1.381 (3) | C15—C16 | 1.395 (3) |
C5—C10 | 1.391 (3) | C15—C18 | 1.507 (4) |
C6—C7 | 1.400 (3) | C16—H16 | 0.950 |
C7—C8 | 1.370 (4) | C17—H17A | 0.950 |
C7—H7 | 0.952 | C17—H17B | 0.949 |
C8—C9 | 1.376 (5) | C17—H17C | 0.949 |
C8—H8 | 0.951 | C18—H18A | 0.949 |
C9—C10 | 1.391 (4) | C18—H18B | 0.950 |
C9—H9 | 0.949 | C18—H18C | 0.950 |
C10—H10 | 0.951 | | |
| | | |
O1—C2—C3 | 126.3 (2) | C4—C11—C12 | 120.5 (2) |
O1—C2—C6 | 127.2 (2) | C4—C11—C16 | 120.4 (2) |
C3—C2—C6 | 106.5 (2) | C12—C11—C16 | 119.1 (2) |
C2—C3—C3i | 124.5 (2) | C11—C12—C13 | 121.2 (2) |
C2—C3—C4 | 108.3 (2) | C11—C12—H12 | 119.3 |
C3i—C3—C4 | 127.2 (2) | C13—C12—H12 | 119.5 |
C3—C4—C5 | 102.0 (2) | C12—C13—C14 | 118.1 (2) |
C3—C4—C11 | 114.0 (2) | C12—C13—C17 | 120.8 (2) |
C3—C4—H4 | 110.3 | C14—C13—C17 | 121.0 (2) |
C5—C4—C11 | 110.0 (2) | C13—C14—C15 | 121.9 (2) |
C5—C4—H4 | 110.1 | C13—C14—H14 | 119.0 |
C11—C4—H4 | 110.1 | C15—C14—H14 | 119.1 |
C4—C5—C6 | 112.2 (2) | C14—C15—C16 | 118.6 (2) |
C4—C5—C10 | 127.7 (2) | C14—C15—C18 | 120.9 (2) |
C6—C5—C10 | 120.2 (2) | C16—C15—C18 | 120.5 (2) |
C2—C6—C5 | 109.9 (2) | C11—C16—C15 | 121.0 (2) |
C2—C6—C7 | 128.5 (2) | C11—C16—H16 | 119.6 |
C5—C6—C7 | 121.6 (2) | C15—C16—H16 | 119.4 |
C6—C7—C8 | 117.8 (2) | C13—C17—H17A | 109.4 |
C6—C7—H7 | 121.2 | C13—C17—H17B | 109.3 |
C8—C7—H7 | 121.0 | C13—C17—H17C | 109.3 |
C7—C8—C9 | 120.8 (2) | H17A—C17—H17B | 109.6 |
C7—C8—H8 | 119.8 | H17A—C17—H17C | 109.6 |
C9—C8—H8 | 119.5 | H17B—C17—H17C | 109.7 |
C8—C9—C10 | 122.0 (3) | C15—C18—H18A | 109.4 |
C8—C9—H9 | 119.0 | C15—C18—H18B | 109.4 |
C10—C9—H9 | 118.9 | C15—C18—H18C | 109.4 |
C5—C10—C9 | 117.5 (3) | H18A—C18—H18B | 109.6 |
C5—C10—H10 | 121.5 | H18A—C18—H18C | 109.5 |
C9—C10—H10 | 121.0 | H18B—C18—H18C | 109.5 |
| | | |
C2—C3—C4—C5 | 10.5 (2) | C3—C4—C5—C6 | −8.7 (2) |
C2—C6—C5—C4 | 3.4 (2) | C4—C3—C2—C6 | −9.1 (2) |
C3—C2—C6—C5 | 3.6 (2) | | |
Symmetry code: (i) −x+1, −y, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C34H28O2 | C34H28O2 |
Mr | 468.59 | 468.59 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/a |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 11.392 (2), 13.9700 (18), 9.2771 (13) | 19.230 (2), 8.0506 (10), 8.4461 (11) |
α, β, γ (°) | 97.705 (11), 109.950 (12), 109.492 (11) | 90, 98.802 (10), 90 |
V (Å3) | 1256.0 (4) | 1292.2 (3) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.07 |
Crystal size (mm) | 0.5 × 0.25 × 0.1 | 0.5 × 0.2 × 0.2 |
|
Data collection |
Diffractometer | Rigaku AFC7R diffractometer | Rigaku AFC7R diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6275, 5773, 3911 | 3542, 2969, 1870 |
Rint | 0.025 | 0.013 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.154, 1.03 | 0.054, 0.195, 1.21 |
No. of reflections | 5773 | 2969 |
No. of parameters | 325 | 164 |
No. of restraints | ? | ? |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.25 | 0.29, −0.28 |
Selected geometric parameters (Å, º) for (I) topO1—C3 | 1.211 (2) | C5—C21 | 1.526 (2) |
O2—C12 | 1.213 (2) | C12—C13 | 1.509 (3) |
C3—C4 | 1.508 (3) | C12—C16 | 1.470 (2) |
C3—C7 | 1.478 (2) | C13—C14 | 1.521 (2) |
C4—C5 | 1.519 (2) | C14—C15 | 1.523 (3) |
C4—C13 | 1.337 (2) | C14—C29 | 1.520 (3) |
C5—C6 | 1.518 (3) | | |
| | | |
C3—C4—C13—C12 | −166.8 (2) | C5—C4—C13—C14 | −173.6 (2) |
C3—C4—C13—C14 | 9.5 (3) | C3—C7—C6—C5 | 4.3 (2) |
C5—C4—C13—C12 | 10.1 (3) | C4—C5—C6—C7 | −5.2 (2) |
Selected geometric parameters (Å, º) for (II) topO1—C2 | 1.222 (3) | C3—C4 | 1.523 (3) |
C2—C3 | 1.508 (3) | C4—C5 | 1.527 (3) |
C2—C6 | 1.467 (3) | C4—C11 | 1.531 (2) |
C3—C3i | 1.336 (4) | | |
| | | |
C2—C3—C4—C5 | 10.5 (2) | C4—C3—C2—C6 | −9.1 (2) |
Symmetry code: (i) −x+1, −y, −z+1. |
Organic photochromic compounds have received considerable attention in recent years because of their potential applications in many fields (Gemert, 1999). The title compounds, (I) and (II), were prepared in the course of a study of crystal photochromism of 3,3'-diaryl-3H,3'H-[2,2']biindenylidene-1,1'-diones (Tanaka & Toda, 2000; Tanaka et al., 2003). Compounds (I) and (II) are geometrical isomers, and they are not conclusively identifiable from spectroscopic data. The colour of crystals of both (I) and (II) changed from yellow to orange when they were irradiated with Hg light. This colour changed back to yellow in 30 min for (I) but has been stable for (II) for more than six months. The ESR spectra suggest that the photochromism of these crystals is due to the biradical caused by breaking the π-bond at the center of the biindenylidene moiety. In the present study, X-ray structure analyses of (I) and (II) have been carried out in order to investigate their molecular structures and π–π interactions.
In (I), each indene rings is approximately planar (Fig. 1). The dihedral angle between the C3/C4/C5 and C6–C11 planes is 3.12 (5)°, and that between the C12/C13/C14 and C15–C20 planes is 4.55 (6)°. The two indene rings are skewed with respect to each other by 13.29 (4)°. The two 3,5-dimethylphenyl rings are almost parallel and the dihedral angle between the C21–C26 and C29–C34 planes is 4.93 (7)°. However, there is no intramolecular short contact between these rings. The shortest distance between the non-H atoms is 3.964 (4) Å for C27···C35 and the second shortest is 3.986 (3) Å for C22···C30.
The meso-isomer, (II), has a center of symmetry (Fig. 2). Each indene ring is twisted a little, and the dihedral angle between the C2/C3/C4 and C5–C10 planes is 11.31 (7)°. The puckering? of the five-membered ring can be seen also from the C—C—C—C torsion angles of the ring, which are in the range −9.1 (2)–10.5 (2)° (Table 2). Non-planality of the five-membered rings in the biindenylidene moiety was also observed in crystals of 2,2'-biindenylidene-1,3,1',3'-tetraone (Khodorkovsky et al., 1994), the torsion angles in the five-membered rings being in the range −18.8–18.1°.
The densities of (I) and (II) are 1.239 and 1.204 Mg m−3, respectively, indicating that the meso-isomer has a lightly lower packing efficiency than the rac-isomer. The more flexible space around the molecule might be preferable for photochromism. In the crystals of (I), a pair of molecules related by center of symmetry show π–π interactions between the 6–5-5 rings of the biindenylidene moieties with, C3···C3' = 3.479 (4) Å, C8···C13' = 3.480 (3) Å and C9···C15' = 3.283 (3) Å [symmetry code: (') −x, −y, −z; Fig. 3). In (II), π–π stacking is observed between the terminal phenyl rings of the biindenylidene moieties, thus forming columns along c (Fig. 4), the shortest distance being 3.409 (3) Å for C6···C8 (1 − x, −y, 2 − z).