Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104019067/de1244sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104019067/de1244Isup2.hkl |
CCDC reference: 254920
The title compound was synthesized by the reaction of 7,8-benzocoumarin and phenylmagnesium bromide as described by Cottam et al. (1964).
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of (V), showing 50% probability displacement ellipsoids and the atom-numbering scheme. |
C27H22O3 | F(000) = 832 |
Mr = 394.45 | Dx = 1.299 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P2ybc | Cell parameters from 877 reflections |
a = 9.609 (3) Å | θ = 2.8–25.0° |
b = 15.799 (4) Å | µ = 0.08 mm−1 |
c = 13.426 (4) Å | T = 293 K |
β = 98.189 (5)° | Needle, colourless |
V = 2017.5 (10) Å3 | 0.22 × 0.20 × 0.18 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2445 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.037 |
Graphite monochromator | θmax = 26.4°, θmin = 2.0° |
ϕ and ω scans | h = −9→12 |
9496 measured reflections | k = −15→19 |
4105 independent reflections | l = −16→16 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0533P)2 + 0.1508P] where P = (Fo2 + 2Fc2)/3 |
4105 reflections | (Δ/σ)max < 0.001 |
273 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C27H22O3 | V = 2017.5 (10) Å3 |
Mr = 394.45 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.609 (3) Å | µ = 0.08 mm−1 |
b = 15.799 (4) Å | T = 293 K |
c = 13.426 (4) Å | 0.22 × 0.20 × 0.18 mm |
β = 98.189 (5)° |
Bruker SMART CCD area-detector diffractometer | 2445 reflections with I > 2σ(I) |
9496 measured reflections | Rint = 0.037 |
4105 independent reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.28 e Å−3 |
4105 reflections | Δρmin = −0.18 e Å−3 |
273 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 | ||
O1 | 0.87367 (13) | 0.04168 (8) | 0.27317 (10) | 0.0428 (4) | |
O2 | 0.77257 (15) | −0.10600 (9) | 0.36257 (11) | 0.0532 (4) | |
O3 | 0.47231 (15) | 0.09054 (9) | 0.35101 (11) | 0.0518 (4) | |
C1 | 0.72509 (19) | 0.05746 (12) | 0.27897 (14) | 0.0368 (5) | |
C2 | 0.67815 (19) | 0.13600 (12) | 0.22048 (14) | 0.0396 (5) | |
H2 | 0.6009 | 0.1656 | 0.2370 | 0.048* | |
C3 | 0.74264 (19) | 0.16476 (12) | 0.14621 (15) | 0.0394 (5) | |
H3 | 0.7068 | 0.2118 | 0.1095 | 0.047* | |
C4 | 0.86836 (18) | 0.12365 (11) | 0.12158 (14) | 0.0338 (4) | |
C5 | 0.93646 (19) | 0.14559 (12) | 0.03687 (14) | 0.0361 (5) | |
C6 | 0.8783 (2) | 0.20242 (12) | −0.03844 (15) | 0.0443 (5) | |
H6 | 0.7923 | 0.2280 | −0.0336 | 0.053* | |
C7 | 0.9461 (2) | 0.22055 (14) | −0.11840 (16) | 0.0542 (6) | |
H7 | 0.9053 | 0.2578 | −0.1678 | 0.065* | |
C8 | 1.0758 (2) | 0.18400 (15) | −0.12710 (17) | 0.0564 (6) | |
H8 | 1.1212 | 0.1972 | −0.1818 | 0.068* | |
C9 | 1.1356 (2) | 0.12954 (14) | −0.05624 (17) | 0.0520 (6) | |
H9 | 1.2225 | 0.1058 | −0.0625 | 0.062* | |
C10 | 1.0684 (2) | 0.10796 (12) | 0.02724 (15) | 0.0401 (5) | |
C11 | 1.1277 (2) | 0.05034 (13) | 0.10097 (16) | 0.0472 (5) | |
H11 | 1.2151 | 0.0268 | 0.0959 | 0.057* | |
C12 | 1.0602 (2) | 0.02806 (13) | 0.17986 (15) | 0.0446 (5) | |
H12 | 1.1001 | −0.0112 | 0.2272 | 0.053* | |
C13 | 0.92984 (19) | 0.06501 (12) | 0.18875 (14) | 0.0364 (5) | |
C14 | 0.64300 (19) | −0.02174 (12) | 0.23763 (14) | 0.0344 (4) | |
C15 | 0.6709 (2) | −0.10172 (12) | 0.28110 (15) | 0.0385 (5) | |
C16 | 0.5971 (2) | −0.17206 (13) | 0.24112 (16) | 0.0475 (5) | |
H16 | 0.6160 | −0.2249 | 0.2705 | 0.057* | |
C17 | 0.4963 (2) | −0.16412 (14) | 0.15819 (18) | 0.0546 (6) | |
H17 | 0.4475 | −0.2118 | 0.1317 | 0.066* | |
C18 | 0.4668 (2) | −0.08695 (15) | 0.11417 (17) | 0.0534 (6) | |
H18 | 0.3985 | −0.0818 | 0.0580 | 0.064* | |
C19 | 0.5403 (2) | −0.01660 (13) | 0.15447 (15) | 0.0441 (5) | |
H19 | 0.5199 | 0.0359 | 0.1246 | 0.053* | |
C20 | 0.8105 (2) | −0.18649 (15) | 0.40466 (17) | 0.0615 (7) | |
H20A | 0.7293 | −0.2131 | 0.4250 | 0.092* | |
H20B | 0.8815 | −0.1797 | 0.4621 | 0.092* | |
H20C | 0.8464 | −0.2211 | 0.3553 | 0.092* | |
C21 | 0.7165 (2) | 0.07238 (11) | 0.39121 (14) | 0.0375 (5) | |
C22 | 0.5880 (2) | 0.09009 (12) | 0.42368 (15) | 0.0408 (5) | |
C23 | 0.5813 (3) | 0.10558 (13) | 0.52488 (16) | 0.0516 (6) | |
H23 | 0.4952 | 0.1172 | 0.5460 | 0.062* | |
C24 | 0.7017 (3) | 0.10376 (13) | 0.59352 (17) | 0.0565 (6) | |
H24 | 0.6966 | 0.1140 | 0.6611 | 0.068* | |
C25 | 0.8288 (3) | 0.08701 (14) | 0.56361 (17) | 0.0564 (6) | |
H25 | 0.9100 | 0.0860 | 0.6105 | 0.068* | |
C26 | 0.8361 (2) | 0.07149 (13) | 0.46285 (16) | 0.0465 (5) | |
H26 | 0.9229 | 0.0602 | 0.4427 | 0.056* | |
C27 | 0.3408 (2) | 0.11628 (15) | 0.37808 (18) | 0.0593 (6) | |
H27A | 0.3135 | 0.0778 | 0.4271 | 0.089* | |
H27B | 0.2709 | 0.1162 | 0.3194 | 0.089* | |
H27C | 0.3494 | 0.1723 | 0.4060 | 0.089* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0374 (8) | 0.0501 (9) | 0.0417 (8) | 0.0048 (6) | 0.0085 (6) | 0.0078 (6) |
O2 | 0.0635 (10) | 0.0407 (9) | 0.0503 (9) | 0.0048 (7) | −0.0099 (8) | 0.0078 (7) |
O3 | 0.0454 (9) | 0.0638 (10) | 0.0487 (9) | 0.0012 (7) | 0.0153 (7) | −0.0044 (7) |
C1 | 0.0334 (10) | 0.0399 (12) | 0.0381 (11) | 0.0013 (8) | 0.0083 (9) | 0.0000 (9) |
C2 | 0.0401 (11) | 0.0353 (11) | 0.0454 (12) | 0.0039 (9) | 0.0130 (9) | −0.0011 (9) |
C3 | 0.0401 (11) | 0.0350 (12) | 0.0432 (12) | 0.0010 (9) | 0.0066 (9) | 0.0007 (9) |
C4 | 0.0342 (10) | 0.0313 (11) | 0.0352 (11) | −0.0027 (8) | 0.0027 (8) | −0.0021 (9) |
C5 | 0.0373 (11) | 0.0353 (11) | 0.0361 (11) | −0.0075 (8) | 0.0065 (9) | −0.0077 (9) |
C6 | 0.0443 (12) | 0.0448 (13) | 0.0444 (13) | −0.0015 (9) | 0.0078 (10) | 0.0017 (10) |
C7 | 0.0639 (15) | 0.0569 (15) | 0.0437 (13) | −0.0018 (11) | 0.0142 (11) | 0.0061 (11) |
C8 | 0.0651 (16) | 0.0627 (15) | 0.0466 (14) | −0.0036 (12) | 0.0255 (12) | 0.0022 (12) |
C9 | 0.0481 (13) | 0.0561 (15) | 0.0553 (14) | 0.0000 (11) | 0.0192 (11) | −0.0064 (12) |
C10 | 0.0403 (12) | 0.0410 (12) | 0.0395 (12) | −0.0049 (9) | 0.0069 (9) | −0.0058 (9) |
C11 | 0.0352 (11) | 0.0546 (14) | 0.0532 (14) | 0.0055 (10) | 0.0106 (10) | −0.0036 (11) |
C12 | 0.0384 (12) | 0.0464 (13) | 0.0474 (13) | 0.0066 (9) | 0.0008 (10) | 0.0031 (10) |
C13 | 0.0351 (11) | 0.0384 (11) | 0.0361 (11) | −0.0060 (9) | 0.0066 (9) | −0.0061 (9) |
C14 | 0.0361 (11) | 0.0357 (11) | 0.0326 (11) | 0.0037 (8) | 0.0089 (9) | −0.0029 (9) |
C15 | 0.0401 (11) | 0.0393 (12) | 0.0362 (11) | 0.0040 (9) | 0.0063 (9) | 0.0006 (9) |
C16 | 0.0509 (13) | 0.0364 (13) | 0.0552 (14) | 0.0020 (10) | 0.0070 (11) | 0.0008 (10) |
C17 | 0.0496 (14) | 0.0437 (14) | 0.0684 (16) | −0.0034 (10) | 0.0013 (12) | −0.0113 (12) |
C18 | 0.0463 (13) | 0.0555 (15) | 0.0545 (14) | 0.0028 (11) | −0.0062 (11) | −0.0096 (12) |
C19 | 0.0446 (12) | 0.0409 (12) | 0.0464 (13) | 0.0073 (10) | 0.0045 (10) | 0.0008 (10) |
C20 | 0.0717 (17) | 0.0573 (15) | 0.0546 (15) | 0.0148 (12) | 0.0060 (13) | 0.0137 (12) |
C21 | 0.0457 (12) | 0.0308 (11) | 0.0368 (11) | −0.0048 (9) | 0.0088 (10) | 0.0003 (9) |
C22 | 0.0500 (13) | 0.0346 (12) | 0.0384 (12) | −0.0045 (9) | 0.0084 (10) | 0.0001 (9) |
C23 | 0.0683 (16) | 0.0442 (13) | 0.0469 (14) | 0.0026 (11) | 0.0240 (12) | 0.0012 (10) |
C24 | 0.0886 (19) | 0.0477 (14) | 0.0348 (13) | −0.0011 (12) | 0.0138 (13) | 0.0004 (10) |
C25 | 0.0724 (17) | 0.0533 (15) | 0.0411 (13) | −0.0071 (12) | −0.0002 (12) | 0.0060 (11) |
C26 | 0.0522 (14) | 0.0417 (13) | 0.0453 (13) | −0.0029 (10) | 0.0059 (11) | 0.0025 (10) |
C27 | 0.0477 (13) | 0.0617 (16) | 0.0732 (16) | −0.0001 (11) | 0.0248 (12) | −0.0006 (12) |
O1—C13 | 1.373 (2) | C12—C13 | 1.402 (3) |
O1—C1 | 1.462 (2) | C12—H12 | 0.9300 |
O2—C15 | 1.360 (2) | C14—C19 | 1.383 (3) |
O2—C20 | 1.418 (2) | C14—C15 | 1.402 (2) |
O3—C22 | 1.370 (2) | C15—C16 | 1.385 (3) |
O3—C27 | 1.423 (2) | C16—C17 | 1.374 (3) |
C1—C2 | 1.503 (3) | C16—H16 | 0.9300 |
C1—C21 | 1.539 (3) | C17—C18 | 1.367 (3) |
C1—C14 | 1.540 (3) | C17—H17 | 0.9300 |
C2—C3 | 1.327 (3) | C18—C19 | 1.385 (3) |
C2—H2 | 0.9300 | C18—H18 | 0.9300 |
C3—C4 | 1.451 (2) | C19—H19 | 0.9300 |
C3—H3 | 0.9300 | C20—H20A | 0.9600 |
C4—C13 | 1.367 (3) | C20—H20B | 0.9600 |
C4—C5 | 1.433 (2) | C20—H20C | 0.9600 |
C5—C6 | 1.407 (3) | C21—C26 | 1.390 (3) |
C5—C10 | 1.423 (3) | C21—C22 | 1.395 (3) |
C6—C7 | 1.363 (3) | C22—C23 | 1.391 (3) |
C6—H6 | 0.9300 | C23—C24 | 1.373 (3) |
C7—C8 | 1.394 (3) | C23—H23 | 0.9300 |
C7—H7 | 0.9300 | C24—C25 | 1.365 (3) |
C8—C9 | 1.349 (3) | C24—H24 | 0.9300 |
C8—H8 | 0.9300 | C25—C26 | 1.386 (3) |
C9—C10 | 1.412 (3) | C25—H25 | 0.9300 |
C9—H9 | 0.9300 | C26—H26 | 0.9300 |
C10—C11 | 1.404 (3) | C27—H27A | 0.9600 |
C11—C12 | 1.365 (3) | C27—H27B | 0.9600 |
C11—H11 | 0.9300 | C27—H27C | 0.9600 |
C13—O1—C1 | 119.98 (14) | C15—C14—C1 | 121.64 (16) |
C15—O2—C20 | 118.64 (16) | O2—C15—C16 | 122.75 (18) |
C22—O3—C27 | 118.63 (17) | O2—C15—C14 | 116.91 (17) |
O1—C1—C2 | 109.61 (14) | C16—C15—C14 | 120.33 (18) |
O1—C1—C21 | 105.50 (15) | C17—C16—C15 | 120.3 (2) |
C2—C1—C21 | 109.34 (15) | C17—C16—H16 | 119.9 |
O1—C1—C14 | 107.23 (14) | C15—C16—H16 | 119.9 |
C2—C1—C14 | 112.48 (16) | C18—C17—C16 | 120.7 (2) |
C21—C1—C14 | 112.40 (15) | C18—C17—H17 | 119.7 |
C3—C2—C1 | 122.54 (17) | C16—C17—H17 | 119.7 |
C3—C2—H2 | 118.7 | C17—C18—C19 | 119.0 (2) |
C1—C2—H2 | 118.7 | C17—C18—H18 | 120.5 |
C2—C3—C4 | 120.74 (19) | C19—C18—H18 | 120.5 |
C2—C3—H3 | 119.6 | C14—C19—C18 | 122.3 (2) |
C4—C3—H3 | 119.6 | C14—C19—H19 | 118.9 |
C13—C4—C5 | 118.96 (17) | C18—C19—H19 | 118.9 |
C13—C4—C3 | 116.66 (17) | O2—C20—H20A | 109.5 |
C5—C4—C3 | 124.18 (18) | O2—C20—H20B | 109.5 |
C6—C5—C10 | 117.98 (17) | H20A—C20—H20B | 109.5 |
C6—C5—C4 | 123.03 (17) | O2—C20—H20C | 109.5 |
C10—C5—C4 | 118.99 (18) | H20A—C20—H20C | 109.5 |
C7—C6—C5 | 120.9 (2) | H20B—C20—H20C | 109.5 |
C7—C6—H6 | 119.5 | C26—C21—C22 | 117.87 (19) |
C5—C6—H6 | 119.5 | C26—C21—C1 | 121.44 (18) |
C6—C7—C8 | 120.8 (2) | C22—C21—C1 | 120.66 (18) |
C6—C7—H7 | 119.6 | O3—C22—C23 | 123.30 (19) |
C8—C7—H7 | 119.6 | O3—C22—C21 | 116.28 (17) |
C9—C8—C7 | 120.1 (2) | C23—C22—C21 | 120.4 (2) |
C9—C8—H8 | 120.0 | C24—C23—C22 | 120.0 (2) |
C7—C8—H8 | 120.0 | C24—C23—H23 | 120.0 |
C8—C9—C10 | 121.1 (2) | C22—C23—H23 | 120.0 |
C8—C9—H9 | 119.4 | C25—C24—C23 | 120.7 (2) |
C10—C9—H9 | 119.4 | C25—C24—H24 | 119.7 |
C11—C10—C9 | 122.05 (19) | C23—C24—H24 | 119.7 |
C11—C10—C5 | 118.93 (18) | C24—C25—C26 | 119.5 (2) |
C9—C10—C5 | 119.01 (19) | C24—C25—H25 | 120.2 |
C12—C11—C10 | 121.63 (19) | C26—C25—H25 | 120.2 |
C12—C11—H11 | 119.2 | C25—C26—C21 | 121.5 (2) |
C10—C11—H11 | 119.2 | C25—C26—H26 | 119.3 |
C11—C12—C13 | 119.19 (19) | C21—C26—H26 | 119.3 |
C11—C12—H12 | 120.4 | O3—C27—H27A | 109.5 |
C13—C12—H12 | 120.4 | O3—C27—H27B | 109.5 |
C4—C13—O1 | 122.86 (16) | H27A—C27—H27B | 109.5 |
C4—C13—C12 | 122.23 (18) | O3—C27—H27C | 109.5 |
O1—C13—C12 | 114.79 (17) | H27A—C27—H27C | 109.5 |
C19—C14—C15 | 117.47 (18) | H27B—C27—H27C | 109.5 |
C19—C14—C1 | 120.88 (17) | ||
C13—O1—C1—C2 | −31.4 (2) | C21—C1—C14—C19 | 124.91 (19) |
C13—O1—C1—C21 | −149.03 (15) | O1—C1—C14—C15 | 59.1 (2) |
C13—O1—C1—C14 | 90.97 (18) | C2—C1—C14—C15 | 179.68 (16) |
O1—C1—C2—C3 | 23.9 (3) | C21—C1—C14—C15 | −56.4 (2) |
C21—C1—C2—C3 | 139.08 (19) | C20—O2—C15—C16 | 3.9 (3) |
C14—C1—C2—C3 | −95.3 (2) | C20—O2—C15—C14 | −175.88 (17) |
C1—C2—C3—C4 | −3.6 (3) | C19—C14—C15—O2 | 179.72 (17) |
C2—C3—C4—C13 | −11.4 (3) | C1—C14—C15—O2 | 1.0 (2) |
C2—C3—C4—C5 | 173.81 (18) | C19—C14—C15—C16 | −0.1 (3) |
C13—C4—C5—C6 | 177.16 (18) | C1—C14—C15—C16 | −178.80 (17) |
C3—C4—C5—C6 | −8.2 (3) | O2—C15—C16—C17 | −179.49 (19) |
C13—C4—C5—C10 | −2.3 (3) | C14—C15—C16—C17 | 0.3 (3) |
C3—C4—C5—C10 | 172.43 (17) | C15—C16—C17—C18 | −0.2 (3) |
C10—C5—C6—C7 | 0.3 (3) | C16—C17—C18—C19 | 0.0 (3) |
C4—C5—C6—C7 | −179.15 (18) | C15—C14—C19—C18 | −0.2 (3) |
C5—C6—C7—C8 | −0.7 (3) | C1—C14—C19—C18 | 178.55 (18) |
C6—C7—C8—C9 | 0.4 (3) | C17—C18—C19—C14 | 0.3 (3) |
C7—C8—C9—C10 | 0.5 (3) | O1—C1—C21—C26 | 1.7 (2) |
C8—C9—C10—C11 | 178.9 (2) | C2—C1—C21—C26 | −116.11 (19) |
C8—C9—C10—C5 | −0.9 (3) | C14—C1—C21—C26 | 118.23 (19) |
C6—C5—C10—C11 | −179.30 (17) | O1—C1—C21—C22 | 179.54 (15) |
C4—C5—C10—C11 | 0.1 (3) | C2—C1—C21—C22 | 61.7 (2) |
C6—C5—C10—C9 | 0.5 (3) | C14—C1—C21—C22 | −63.9 (2) |
C4—C5—C10—C9 | 179.99 (16) | C27—O3—C22—C23 | 6.5 (3) |
C9—C10—C11—C12 | −178.13 (19) | C27—O3—C22—C21 | −173.94 (17) |
C5—C10—C11—C12 | 1.7 (3) | C26—C21—C22—O3 | 179.92 (17) |
C10—C11—C12—C13 | −1.4 (3) | C1—C21—C22—O3 | 2.0 (2) |
C5—C4—C13—O1 | 178.45 (16) | C26—C21—C22—C23 | −0.5 (3) |
C3—C4—C13—O1 | 3.4 (3) | C1—C21—C22—C23 | −178.41 (17) |
C5—C4—C13—C12 | 2.6 (3) | O3—C22—C23—C24 | 179.76 (19) |
C3—C4—C13—C12 | −172.44 (17) | C21—C22—C23—C24 | 0.2 (3) |
C1—O1—C13—C4 | 19.7 (3) | C22—C23—C24—C25 | 0.1 (3) |
C1—O1—C13—C12 | −164.20 (16) | C23—C24—C25—C26 | −0.2 (3) |
C11—C12—C13—C4 | −0.8 (3) | C24—C25—C26—C21 | −0.1 (3) |
C11—C12—C13—O1 | −176.95 (17) | C22—C21—C26—C25 | 0.5 (3) |
O1—C1—C14—C19 | −119.59 (18) | C1—C21—C26—C25 | 178.37 (18) |
C2—C1—C14—C19 | 1.0 (2) |
Experimental details
Crystal data | |
Chemical formula | C27H22O3 |
Mr | 394.45 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 9.609 (3), 15.799 (4), 13.426 (4) |
β (°) | 98.189 (5) |
V (Å3) | 2017.5 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.22 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9496, 4105, 2445 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.121, 1.00 |
No. of reflections | 4105 |
No. of parameters | 273 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.18 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
O1—C13 | 1.373 (2) | C1—C14 | 1.540 (3) |
O1—C1 | 1.462 (2) | C2—C3 | 1.327 (3) |
C1—C2 | 1.503 (3) | C3—C4 | 1.451 (2) |
C1—C21 | 1.539 (3) | C4—C13 | 1.367 (3) |
C13—O1—C1 | 119.98 (14) | C3—C2—C1 | 122.54 (17) |
O1—C1—C2 | 109.61 (14) | C2—C3—C4 | 120.74 (19) |
O1—C1—C21 | 105.50 (15) | C13—C4—C3 | 116.66 (17) |
C2—C1—C21 | 109.34 (15) | C4—C13—O1 | 122.86 (16) |
O1—C1—C14 | 107.23 (14) | C26—C21—C1 | 121.44 (18) |
C2—C1—C14 | 112.48 (16) | C22—C21—C1 | 120.66 (18) |
C21—C1—C14 | 112.40 (15) | ||
C13—O1—C1—C2 | −31.4 (2) | O1—C1—C14—C19 | −119.59 (18) |
C13—O1—C1—C21 | −149.03 (15) | C2—C1—C14—C19 | 1.0 (2) |
C13—O1—C1—C14 | 90.97 (18) | O1—C1—C14—C15 | 59.1 (2) |
O1—C1—C2—C3 | 23.9 (3) | C2—C1—C14—C15 | 179.68 (16) |
C21—C1—C2—C3 | 139.08 (19) | O1—C1—C21—C26 | 1.7 (2) |
C14—C1—C2—C3 | −95.3 (2) | C2—C1—C21—C26 | −116.11 (19) |
C1—C2—C3—C4 | −3.6 (3) | C2—C1—C21—C22 | 61.7 (2) |
C1—O1—C13—C4 | 19.7 (3) |
2,2-Diphenylchromene derivatives are a special kind of photochromic compound. In contrast to other classes of photochromic compounds, such as spiropyrans and spirooxazines, 2H-chromenes do not contain a spiro-heterocyclic fragment. Nevertheless, some chromenes are photoactive and have found commercial application (Malatesta, 1999). Aldoshin et al. (1995, 1996, 1998) have discussed the structures and photochemical properties of 2,2-diphenylchromene derivatives (I), (II), (III) and (IV), and show that in those compounds the pyran Csp3—O1 bond, the rupture of which is responsible for the compounds' photochemical properties, is elongated as a result of steric interactions. Thus, any factor that affects the Csp3—O1 bond length and the planarity of the pyran ring will affect the photochemical properties of the compound. Moreover, substituents on the phenyl groups of 3,3-diphenyl-3H-naphtho[2,1-b]pyran compounds have a substantial effect on colour intensity and fade rate (Ligas et al., 1991). Our interest in this subject derives from the fact that derivatives of chromenes are easily synthesized, with potential for commercial application (Kou, Wang, Xiu, Meng & Weng, 2000). In order to understand how the substituents on the phenyl ring influence the photochromic properties, we prepared some chromene derivatives with substituted phenyl rings and determined the X-ray structure of the title compound, (V).
Fig. 1 shows that the pyran ring in (V) is non-planar, with folding along the O1···C2 and O1···C3 axes, in a similar manner to that reported for (II). The dihedral angle between the O1/C1/C2 and O1/C2/C3 planes is 20.0 (1)°, and between the O1/C2/C3 and O1/C3/C4 planes is 9.6 (2)°, while the corresponding values in (II) are 22.9 (2) and 10.0 (2)°, respectively (Aldoshin et al., 1998). The C1—O1 bond [1.462 (2) Å] is longer than a typical C—O bond in a six-membered heterocycle (1.41–1.43 Å; Birukov & Unkovskij, 1976), but is indistinguishable from those in (I)–(IV) [1.441 (2)–1.468 (2) Å]. Therefore chromenes (V) and (II) have similar pyran ring structures. The mutual arrangement of the phenyl rings in the molecules of (V) and (II) is similar. The dihedral angles between these fragments are 93.3 (2) and 96.6 (2)°, respectively. However, the arrangement of the phenyl rings with respect to the pyran ring differs. In a Newman projection along C1—Cph, atom O1 of the pyran ring in (V) is almost eclipsed with both phenyl rings [the O1—C1—C21—C26 torsion angle is 1.7 (2)° and C2—C1—C14—C15 is 179.68 (16)°]. In the (II), atom O1 is eclipsed with only one of the phenyl rings. The corresponding torsion angles along the C1—Cph bond are 14.2 (2) and 3.2 (2)°. The later conformation is partly stabilized by atom H27A forming π···H interactions with the phenyl rings of the other molecule. Thus, the conformations of the phenyl groups do not essentially affect the structure of the pyran fragment and Cspiro center. It might be expected that (V) and (II) have similar photochromic properties. However, the photochemical properties are different. Compared with (II), compound (V) has a dramatically enhanced optical density and slower rate of fade (Van Gemert et al., 1991). Apparently, the electron-donating substituent methoxyl group in the phenyl ring stabilizes the pyramidal carbocation at atom C1, which is formed upon elongation and rupture of the C1—O1 bond at the first stage of photoconversion. The steric effects of these groups hinder reversion to the closed-ring form, increasing the lifetime of the open-ring form of (V) and thus decreasing its fade rate.