Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803001028/bt6228sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803001028/bt62282sup2.hkl |
CCDC reference: 204700
The title compound was prepared according to Witulski (1992) and was recrystallized from chloroform/pentane.
H atoms were included using a riding model with fixed C—H bond lengths (sp2 C—H = 0.95 Å and CH2 = 0.98 Å); Uiso(H) values were fixed at 1.2 times the Ueq values of the parent atom.
Data collection: P3 (Nicolet, 1987); cell refinement: P3; data reduction: XDISK (Nicolet, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.
C16H14O3 | F(000) = 536 |
Mr = 254.27 | Dx = 1.350 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.813 (3) Å | Cell parameters from 50 reflections |
b = 8.909 (3) Å | θ = 10–11° |
c = 10.658 (3) Å | µ = 0.09 mm−1 |
β = 107.44 (2)° | T = 178 K |
V = 1251.3 (6) Å3 | Prism, colourless |
Z = 4 | 0.7 × 0.4 × 0.4 mm |
Nicolet R3 diffractometer | Rint = 0.020 |
Radiation source: fine-focus sealed tube | θmax = 27.6°, θmin = 3.1° |
Graphite monochromator | h = −17→17 |
ω scans | k = −1→11 |
3018 measured reflections | l = 0→13 |
2857 independent reflections | 3 standard reflections every 147 reflections |
1807 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0502P)2 + 0.8067P] where P = (Fo2 + 2Fc2)/3 |
2857 reflections | (Δ/σ)max = 0.001 |
172 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C16H14O3 | V = 1251.3 (6) Å3 |
Mr = 254.27 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.813 (3) Å | µ = 0.09 mm−1 |
b = 8.909 (3) Å | T = 178 K |
c = 10.658 (3) Å | 0.7 × 0.4 × 0.4 mm |
β = 107.44 (2)° |
Nicolet R3 diffractometer | Rint = 0.020 |
3018 measured reflections | 3 standard reflections every 147 reflections |
2857 independent reflections | intensity decay: none |
1807 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.20 e Å−3 |
2857 reflections | Δρmin = −0.25 e Å−3 |
172 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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 13.2332 (0.0058) x + 0.0653 (0.0081) y − 5.9743 (0.0082) z = 2.0430 (0.0058) * 0.0274 (0.0010) O1 * −0.0223 (0.0011) C11 * 0.0086 (0.0011) C12 * 0.0080 (0.0011) C13 * −0.0217 (0.0011) C14 Rms deviation of fitted atoms = 0.0193 − 13.2926 (0.0065) x + 2.4116 (0.0098) y + 3.3331 (0.0111) z = 0.9787 (0.0087) Angle to previous plane (with approximate e.s.d.) = 21.99 (0.06) * 0.0005 (0.0010) C7 * −0.0005 (0.0010) C8 * 0.0005 (0.0010) C4 * −0.0005 (0.0010) C5 − 0.1600 (0.0029) C3 − 0.1695 (0.0029) C6 Rms deviation of fitted atoms = 0.0005 |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.36297 (15) | 0.7009 (2) | 0.5030 (2) | 0.0305 (5) | |
H1A | 0.3711 | 0.7682 | 0.4329 | 0.037* | |
H1B | 0.4242 | 0.7113 | 0.5799 | 0.037* | |
C2 | 0.26770 (17) | 0.7519 (3) | 0.5432 (2) | 0.0357 (5) | |
H2A | 0.2750 | 0.7206 | 0.6347 | 0.043* | |
H2B | 0.2614 | 0.8626 | 0.5382 | 0.043* | |
C3 | 0.17481 (15) | 0.6804 (2) | 0.4505 (2) | 0.0299 (5) | |
C4 | 0.14551 (15) | 0.5396 (2) | 0.4837 (2) | 0.0307 (5) | |
H4 | 0.1552 | 0.5149 | 0.5733 | 0.037* | |
C5 | 0.10238 (15) | 0.4359 (2) | 0.3864 (2) | 0.0319 (5) | |
H5 | 0.0822 | 0.3404 | 0.4095 | 0.038* | |
C6 | 0.08832 (14) | 0.4708 (3) | 0.2543 (2) | 0.0314 (5) | |
C7 | 0.09492 (15) | 0.6218 (3) | 0.2224 (2) | 0.0339 (5) | |
H7 | 0.0696 | 0.6534 | 0.1335 | 0.041* | |
C8 | 0.13823 (16) | 0.7255 (2) | 0.3199 (2) | 0.0330 (5) | |
H8 | 0.1430 | 0.8278 | 0.2973 | 0.040* | |
C9 | 0.09989 (16) | 0.3466 (3) | 0.1640 (2) | 0.0378 (5) | |
H9A | 0.0568 | 0.3670 | 0.0731 | 0.045* | |
H9B | 0.0783 | 0.2498 | 0.1928 | 0.045* | |
C10 | 0.21438 (15) | 0.3378 (2) | 0.16808 (18) | 0.0288 (4) | |
H10A | 0.2290 | 0.2354 | 0.1425 | 0.035* | |
H10B | 0.2261 | 0.4087 | 0.1026 | 0.035* | |
C11 | 0.28641 (14) | 0.3739 (2) | 0.30027 (18) | 0.0238 (4) | |
C12 | 0.33825 (14) | 0.2944 (2) | 0.40904 (18) | 0.0256 (4) | |
C13 | 0.38312 (14) | 0.4047 (2) | 0.50973 (18) | 0.0269 (4) | |
C14 | 0.35553 (14) | 0.5427 (2) | 0.45512 (18) | 0.0250 (4) | |
C15 | 0.34562 (17) | 0.1312 (2) | 0.4167 (2) | 0.0351 (5) | |
H15 | 0.3895 | 0.0887 | 0.4949 | 0.042* | |
C16 | 0.44465 (15) | 0.3810 (3) | 0.6452 (2) | 0.0348 (5) | |
H16 | 0.4665 | 0.4672 | 0.6988 | 0.042* | |
O1 | 0.30085 (9) | 0.52387 (15) | 0.32557 (12) | 0.0236 (3) | |
O2 | 0.30005 (15) | 0.04553 (19) | 0.33102 (17) | 0.0506 (5) | |
O3 | 0.47008 (12) | 0.2588 (2) | 0.69465 (15) | 0.0484 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0300 (10) | 0.0294 (11) | 0.0316 (10) | −0.0066 (9) | 0.0082 (8) | −0.0055 (9) |
C2 | 0.0429 (12) | 0.0313 (11) | 0.0356 (11) | −0.0013 (10) | 0.0162 (10) | −0.0089 (9) |
C3 | 0.0292 (10) | 0.0301 (11) | 0.0347 (11) | 0.0053 (8) | 0.0157 (8) | −0.0033 (9) |
C4 | 0.0315 (10) | 0.0350 (12) | 0.0292 (10) | 0.0012 (9) | 0.0145 (8) | 0.0002 (9) |
C5 | 0.0251 (10) | 0.0359 (12) | 0.0370 (11) | −0.0036 (9) | 0.0128 (8) | 0.0004 (9) |
C6 | 0.0180 (9) | 0.0420 (12) | 0.0322 (10) | −0.0006 (9) | 0.0046 (8) | −0.0026 (9) |
C7 | 0.0240 (10) | 0.0452 (13) | 0.0310 (10) | 0.0100 (9) | 0.0061 (8) | 0.0078 (10) |
C8 | 0.0308 (10) | 0.0285 (11) | 0.0433 (12) | 0.0099 (9) | 0.0167 (9) | 0.0073 (9) |
C9 | 0.0285 (11) | 0.0492 (14) | 0.0330 (11) | −0.0058 (10) | 0.0051 (9) | −0.0065 (10) |
C10 | 0.0303 (10) | 0.0311 (11) | 0.0248 (9) | −0.0031 (9) | 0.0078 (8) | −0.0031 (8) |
C11 | 0.0239 (9) | 0.0221 (9) | 0.0282 (9) | −0.0008 (8) | 0.0120 (8) | −0.0020 (8) |
C12 | 0.0250 (9) | 0.0254 (10) | 0.0288 (10) | 0.0017 (8) | 0.0116 (8) | 0.0004 (8) |
C13 | 0.0216 (9) | 0.0337 (11) | 0.0268 (9) | 0.0010 (8) | 0.0092 (7) | 0.0018 (8) |
C14 | 0.0207 (9) | 0.0299 (10) | 0.0253 (9) | −0.0021 (8) | 0.0081 (7) | −0.0010 (8) |
C15 | 0.0405 (12) | 0.0284 (11) | 0.0387 (12) | 0.0055 (9) | 0.0154 (10) | 0.0063 (10) |
C16 | 0.0257 (10) | 0.0479 (14) | 0.0303 (11) | 0.0016 (10) | 0.0077 (8) | 0.0050 (10) |
O1 | 0.0235 (7) | 0.0221 (7) | 0.0249 (7) | −0.0005 (5) | 0.0067 (5) | −0.0008 (5) |
O2 | 0.0725 (13) | 0.0277 (9) | 0.0516 (10) | −0.0050 (8) | 0.0184 (9) | −0.0010 (8) |
O3 | 0.0423 (9) | 0.0620 (12) | 0.0379 (9) | 0.0109 (8) | 0.0076 (7) | 0.0179 (9) |
C1—C14 | 1.492 (3) | C9—C10 | 1.571 (3) |
C1—C2 | 1.568 (3) | C9—H9A | 0.9900 |
C1—H1A | 0.9900 | C9—H9B | 0.9900 |
C1—H1B | 0.9900 | C10—C11 | 1.496 (3) |
C2—C3 | 1.506 (3) | C10—H10A | 0.9900 |
C2—H2A | 0.9900 | C10—H10B | 0.9900 |
C2—H2B | 0.9900 | C11—C12 | 1.364 (3) |
C3—C8 | 1.390 (3) | C11—O1 | 1.366 (2) |
C3—C4 | 1.396 (3) | C12—C13 | 1.450 (3) |
C4—C5 | 1.383 (3) | C12—C15 | 1.458 (3) |
C4—H4 | 0.9500 | C13—C14 | 1.365 (3) |
C5—C6 | 1.397 (3) | C13—C16 | 1.455 (3) |
C5—H5 | 0.9500 | C14—O1 | 1.371 (2) |
C6—C7 | 1.397 (3) | C15—O2 | 1.212 (3) |
C6—C9 | 1.507 (3) | C15—H15 | 0.9500 |
C7—C8 | 1.385 (3) | C16—O3 | 1.215 (3) |
C7—H7 | 0.9500 | C16—H16 | 0.9500 |
C8—H8 | 0.9500 | ||
C14—C1—C2 | 112.93 (16) | C6—C9—H9A | 110.0 |
C14—C1—H1A | 109.0 | C10—C9—H9A | 110.0 |
C2—C1—H1A | 109.0 | C6—C9—H9B | 110.0 |
C14—C1—H1B | 109.0 | C10—C9—H9B | 110.0 |
C2—C1—H1B | 109.0 | H9A—C9—H9B | 108.4 |
H1A—C1—H1B | 107.8 | C11—C10—C9 | 113.29 (16) |
C3—C2—C1 | 108.54 (16) | C11—C10—H10A | 108.9 |
C3—C2—H2A | 110.0 | C9—C10—H10A | 108.9 |
C1—C2—H2A | 110.0 | C11—C10—H10B | 108.9 |
C3—C2—H2B | 110.0 | C9—C10—H10B | 108.9 |
C1—C2—H2B | 110.0 | H10A—C10—H10B | 107.7 |
H2A—C2—H2B | 108.4 | C12—C11—O1 | 109.37 (16) |
C8—C3—C4 | 117.8 (2) | C12—C11—C10 | 136.10 (19) |
C8—C3—C2 | 121.16 (19) | O1—C11—C10 | 114.35 (16) |
C4—C3—C2 | 117.94 (19) | C11—C12—C13 | 106.02 (18) |
C5—C4—C3 | 120.21 (19) | C11—C12—C15 | 125.13 (19) |
C5—C4—H4 | 119.9 | C13—C12—C15 | 128.84 (19) |
C3—C4—H4 | 119.9 | C14—C13—C12 | 107.00 (17) |
C4—C5—C6 | 120.3 (2) | C14—C13—C16 | 124.02 (19) |
C4—C5—H5 | 119.8 | C12—C13—C16 | 129.0 (2) |
C6—C5—H5 | 119.8 | C13—C14—O1 | 108.56 (16) |
C7—C6—C5 | 117.4 (2) | C13—C14—C1 | 136.33 (18) |
C7—C6—C9 | 121.65 (19) | O1—C14—C1 | 114.88 (16) |
C5—C6—C9 | 118.1 (2) | O2—C15—C12 | 125.0 (2) |
C8—C7—C6 | 120.33 (19) | O2—C15—H15 | 117.5 |
C8—C7—H7 | 119.8 | C12—C15—H15 | 117.5 |
C6—C7—H7 | 119.8 | O3—C16—C13 | 124.6 (2) |
C7—C8—C3 | 120.3 (2) | O3—C16—H16 | 117.7 |
C7—C8—H8 | 119.9 | C13—C16—H16 | 117.7 |
C3—C8—H8 | 119.9 | C11—O1—C14 | 108.80 (14) |
C6—C9—C10 | 108.50 (17) | ||
C14—C1—C2—C3 | −36.1 (2) | O1—C11—C12—C15 | −176.28 (17) |
C1—C2—C3—C8 | −70.4 (2) | C10—C11—C12—C15 | 8.9 (4) |
C1—C2—C3—C4 | 89.4 (2) | C11—C12—C13—C14 | −0.1 (2) |
C8—C3—C4—C5 | 15.0 (3) | C15—C12—C13—C14 | 179.26 (19) |
C2—C3—C4—C5 | −145.5 (2) | C11—C12—C13—C16 | 178.82 (18) |
C3—C4—C5—C6 | 0.4 (3) | C15—C12—C13—C16 | −1.9 (3) |
C4—C5—C6—C7 | −15.7 (3) | C12—C13—C14—O1 | −2.9 (2) |
C4—C5—C6—C9 | 145.5 (2) | C16—C13—C14—O1 | 178.10 (16) |
C5—C6—C7—C8 | 15.7 (3) | C12—C13—C14—C1 | 171.1 (2) |
C9—C6—C7—C8 | −144.7 (2) | C16—C13—C14—C1 | −7.9 (3) |
C6—C7—C8—C3 | −0.5 (3) | C2—C1—C14—C13 | −91.1 (3) |
C4—C3—C8—C7 | −14.9 (3) | C2—C1—C14—O1 | 82.6 (2) |
C2—C3—C8—C7 | 145.0 (2) | C11—C12—C15—O2 | −6.3 (3) |
C7—C6—C9—C10 | 71.9 (2) | C13—C12—C15—O2 | 174.5 (2) |
C5—C6—C9—C10 | −88.4 (2) | C14—C13—C16—O3 | −179.6 (2) |
C6—C9—C10—C11 | 34.6 (2) | C12—C13—C16—O3 | 1.7 (3) |
C9—C10—C11—C12 | 92.9 (3) | C12—C11—O1—C14 | −5.0 (2) |
C9—C10—C11—O1 | −81.8 (2) | C10—C11—O1—C14 | 171.08 (15) |
O1—C11—C12—C13 | 3.1 (2) | C13—C14—O1—C11 | 4.91 (19) |
C10—C11—C12—C13 | −171.8 (2) | C1—C14—O1—C11 | −170.53 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···O3i | 0.99 | 2.45 | 3.393 (3) | 160 |
Symmetry code: (i) −x+1, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C16H14O3 |
Mr | 254.27 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 178 |
a, b, c (Å) | 13.813 (3), 8.909 (3), 10.658 (3) |
β (°) | 107.44 (2) |
V (Å3) | 1251.3 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.7 × 0.4 × 0.4 |
Data collection | |
Diffractometer | Nicolet R3 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3018, 2857, 1807 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.133, 1.02 |
No. of reflections | 2857 |
No. of parameters | 172 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.25 |
Computer programs: P3 (Nicolet, 1987), P3, XDISK (Nicolet, 1987), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···O3i | 0.99 | 2.45 | 3.393 (3) | 160 |
Symmetry code: (i) −x+1, y+1/2, −z+3/2. |
In our studies of the addition of highly reactive triple-bond dienophiles to strained aromatic compounds, we prepared the dinitrile (1) by the addition of cyanoacetylene to [2.2](2,5)furanoparacyclophane (Hopf & Witulski, 1995; Witulski, 1992). To utilize this adduct for further transformations, we have reduced the nitrile to the bis-aldehyde, (2) (Witulski, 1992).
The structure of (2) is shown in Fig. 1. The six-membered ring shows the flattened boat form typical of paracyclophanes, with atom C3 lying 0.160 (3) Å and C6 0.170 (3) Å out of the plane of the other four atoms. The interplanar angles between these four atoms and the furan ring (r.m.s. deviation 0.02 Å) is 22.0 (1)°.
The packing is determined by a short C1—H1b···O3 interaction (Table 2), which links adjacent molecules related by the 21 screw axis to form helical chains with an overall direction parallel to the y axis (Fig. 2). There are two such chains per cell.