organic compounds
Ethyl (E)-3-(anthracen-9-yl)prop-2-enoate
aInstitute of Inorganic Chemistry, University of Hamburg, Hamburg, Germany, bDepartment of Chemical Engineering, United Arab Emirates University, Al Ain, Abu Dhabi, United Arab Emirates, and cDepartment of Chemistry, United Arab Emirates University, AL Ain, Abu Dhabi, United Arab Emirates
*Correspondence e-mail: thies@uaeu.ac.ae
In the 19H16O2, there are two symmetry-independent molecules (A and B) that differ in the conformation of the ester ethoxy group. In the crystal, the molecules form inversion dimers via pairs of C—H⋯O interactions. Within the dimers, the anthracenyl units have interplanar distances of 0.528 (2) and 0.479 (2) Å for dimers of molecules A and B, respectively. Another short C—H⋯O contact between symmetry-independent dimers links them into columns parallel to [10-1]. These columns are arranged into (111) layers and there are π–π stacking interactions [centroid–centroid distances = 3.6446 (15) and 3.6531 (15) Å] between the anthracenyl units from the neighbouring columns. In addition, there are C—H⋯π interactions between the anthracenyl unit of dimers A and dimers B within the same column.
of the title compound, CRelated literature
For an analogous preparation of the title compound, see: Nguyen & Weizman (2007). For modeling of the title compound at the B3LYP/6–31G* level, see: Coleman (2007). For crystal structures of photodimerizable arylenes, see: Vishnumurthy et al. (2002); Mascitti & Corey (2006); Sonoda (2011); Schmidt (1964). For the photodimerization of anthracenes in the crystal, see: Schmidt (1971); Ihmels et al. (2000).
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis PRO (Agilent, 2012); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within OLEX2 (Dolomanov et al., 2009); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 and PLATON.
Supporting information
https://doi.org/10.1107/S1600536812051033/gk2545sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812051033/gk2545Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812051033/gk2545Isup3.cml
A solventless mixture of 9-anthracenylcarbaldehyde (1.00 g, 4.85 mmol) and ethoxycarbonylmethylidenephosphorane (2.70 g, 7.76 mmol) is heated at 130°C for 3 h. Thereafter, an additional amount of phosphorane (1.00 g, 2.87 mmol) is added and the reaction mixture heated for another hour at 135°C. The cooled solution is subjected directly to ν 3049, 2978, 1718, 1632, 1166, 889, 733, 716 cm-1; δH (400 MHz, CDCl3) 1.35 (3H, t, 3J = 7.2 Hz), 4.31 (2H, q, 3J = 7.2 Hz, OCH2), 6.36 (1H, d, 3J = 16.0 Hz), 7.43 (4H, m), 7.95 (2H, m), 8.17 (2H, m), 8.39 (1H, s), 8.57 (1H, d, 3J = 16.0 Hz); δC (100.5 MHz, CDCl3) 14.5, 61.0, 125.2, 125.4, 127.2, 128.2, 128.8, 129.3, 129.4, 131.2, 141.9, 166.5; MS: Found: 299.1040 (C19H16O2+Na)+; Calcd. for C19H16O2Na: 299.1048. Crystals were grown from cold 2-propanol.
on silica gel (eluent: MtBE/CHCl3/hexane 1:1:7) to give the title compound (1.24 g, 93%) as a yellow solid; (m.p. 353.6 K). IR: (KBr)All carbon-bound hydrogen atoms were placed in calculated positions with C—H distances of 0.95 - 1.00 Å and refined as riding with Uiso(H) =xUeq(C), where x = 1.5 for methyl and x = 1.2 for all other H-atoms.
In our endeavor to carry out [2 + 2]-photocycloaddition of ethyl 3(E)-(9-anthracenyl)propenoate in the solid state, the authors grew single crystals of the title compound to identify intermolecular interactions of the molecule in the crystal, which could control the photocycloaddition (Sonoda, 2011; Schmidt, 1964). In the title compound, the alkyl group forms very different torsion angles with the carboxyl group of the ester function (C17—O2—C18—C19) in molecules A and B, respectively, namely of 178.3 (2) ° in molecule A, and of 87.3 (3) ° in molecule B. Pairs of molecules A and B respectively, are formed by C13A—H13A···O1A (Figure 2) close contact for pairs A, and by C3B—H3B···O1B close contact (Table 1) for pairs B, and with the ring planes of the anthracenyl units of the respective pairs in parallel, but at an offset of 0.528 (2) Å for molecules A and 0.479 (2) Å for molecules B. Pairs A and pairs B interact with each other by C18B—H18B···O2A close contact (Figure 2) to for the [10-1] column. Also, C6B—H6B··· π and C8B—H8B···π interactions (Figure 2) are formed between the pairs B and A in the column. Neighboring columns arranged into [111] layer show partial intercalation to form π–π interaction (Table 1) between the parallel anthracenyl units of the same molecules (A—A and B—B).
The double bonds of two molecules in one pair are aligned parallel to each other at a distance of 5.549 (3) Å for A and 5.627 (3) Å for B. This intermolecular distance between the olefinic moieties is larger than in many of those found for aryl-enes that undergo [2 + 2]-photodimerization readily (Vishnumurthy et al. 2002; Mascitti et al. 2006). However, the anthracenyl units are aligned parallel to each other with an interplanar distance (C1-C8) of 3.945 (3) Å for A molecules and 4.031 (3) Å for B molecules. This distance lies within the distance of less than 4.2 Å, reported for anthracenes in the crystal that undergo photodimerisation (Schmidt, 1971; Ihmels et al., 2000).
For an analogous preparation of the title compound, see: Nguyen & Weizman (2007). For modeling of the title compound at the B3LYP/6–31G* level, see: Coleman (2007). For crystal structures of photodimerizable arylenes, see: Vishnumurthy et al. (2002); Mascitti et al. (2006); Sonoda (2011); Schmidt (1964). For the photodimerization of anthracenes in the crystal, see: Schmidt (1971); Ihmels et al. (2000).
Data collection: CrysAlis PRO (Agilent, 2012); cell
CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within OLEX2 (Dolomanov et al., 2009); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).Fig. 1. A view of molecules A and B of the title compound with the atom-numbering scheme. Displacement ellipsoids are shown at the 50% probability level. | |
Fig. 2. Intermolecular C—H···O, C—H···π, and π–π contacts between molecules of the title compound. [Symmetry codes: (i) -x,3 - y,1 - z; (ii) 1 - x,2 - y,1 - z; (iii) x,1 + y,z; (iv) 1 - x,2 - y,2 - z; (v) x,y,z; (vi) 2 - x,1 - y,2 - z; (vii) 2 - x,1 - y,1 - z; (viii) 1 + x,y,-1 + z] | |
Fig. 3. The crystal packing diagram showing the C—H···O intermolecular interactions (orange colored) and π–π stacking interactions between anthracenyl units of neighbouring [1 0 -1] columns indicated by yellow arrows. The A molecules are shown in blue. |
C19H16O2 | F(000) = 584 |
Mr = 276.32 | Dx = 1.306 Mg m−3 |
Triclinic, P1 | Melting point: 353.6 K |
a = 8.8700 (5) Å | Cu Kα radiation, λ = 1.5418 Å |
b = 12.8918 (7) Å | Cell parameters from 4999 reflections |
c = 13.1062 (7) Å | θ = 3.6–76.1° |
α = 84.389 (4)° | µ = 0.66 mm−1 |
β = 84.620 (4)° | T = 291 K |
γ = 70.771 (5)° | Block, translucent intense yellow |
V = 1405.28 (13) Å3 | 0.22 × 0.11 × 0.09 mm |
Z = 4 |
Agilent SuperNova Dual Atlas diffractometer | 4901 independent reflections |
Radiation source: SuperNova (Cu) X-ray Source | 4250 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.025 |
Detector resolution: 10.4127 pixels mm-1 | θmax = 66.0°, θmin = 3.6° |
ω scans | h = −10→10 |
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2012) | k = −10→15 |
Tmin = 0.889, Tmax = 0.942 | l = −15→15 |
11350 measured reflections |
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.171 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0665P)2 + 2.0996P] where P = (Fo2 + 2Fc2)/3 |
4901 reflections | (Δ/σ)max = 0.001 |
381 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C19H16O2 | γ = 70.771 (5)° |
Mr = 276.32 | V = 1405.28 (13) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.8700 (5) Å | Cu Kα radiation |
b = 12.8918 (7) Å | µ = 0.66 mm−1 |
c = 13.1062 (7) Å | T = 291 K |
α = 84.389 (4)° | 0.22 × 0.11 × 0.09 mm |
β = 84.620 (4)° |
Agilent SuperNova Dual Atlas diffractometer | 4901 independent reflections |
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2012) | 4250 reflections with I > 2σ(I) |
Tmin = 0.889, Tmax = 0.942 | Rint = 0.025 |
11350 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.171 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.29 e Å−3 |
4901 reflections | Δρmin = −0.26 e Å−3 |
381 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 | ||
C10A | 1.2110 (3) | 0.6510 (2) | 1.14911 (19) | 0.0233 (6) | |
C10B | 0.5292 (3) | 0.5977 (2) | 0.65022 (19) | 0.0226 (5) | |
C11A | 1.2162 (3) | 0.7552 (2) | 1.1299 (2) | 0.0248 (6) | |
C11B | 0.6625 (3) | 0.6286 (2) | 0.6358 (2) | 0.0252 (6) | |
C12A | 1.0823 (3) | 0.8399 (2) | 1.0900 (2) | 0.0247 (6) | |
C12B | 0.8112 (3) | 0.5498 (2) | 0.60494 (19) | 0.0232 (5) | |
C13A | 0.9467 (3) | 0.8181 (2) | 1.07279 (19) | 0.0217 (5) | |
C13B | 0.8205 (3) | 0.4465 (2) | 0.58699 (18) | 0.0211 (5) | |
C14A | 0.9348 (3) | 0.7097 (2) | 1.09399 (18) | 0.0185 (5) | |
C14B | 0.6822 (3) | 0.4108 (2) | 0.59782 (18) | 0.0188 (5) | |
C15A | 0.6563 (3) | 0.7738 (2) | 1.03919 (19) | 0.0189 (5) | |
C15B | 0.8340 (3) | 0.2220 (2) | 0.53924 (19) | 0.0192 (5) | |
C16A | 0.5756 (3) | 0.7705 (2) | 0.95986 (19) | 0.0195 (5) | |
C16B | 0.9259 (3) | 0.2403 (2) | 0.45797 (19) | 0.0192 (5) | |
C17A | 0.4367 (3) | 0.8650 (2) | 0.92781 (19) | 0.0187 (5) | |
C17B | 1.0714 (3) | 0.1530 (2) | 0.42227 (19) | 0.0186 (5) | |
C18A | 0.2639 (3) | 0.9408 (2) | 0.7928 (2) | 0.0241 (6) | |
C18B | 1.2700 (3) | 0.1079 (2) | 0.2833 (2) | 0.0253 (6) | |
C19A | 0.2370 (3) | 0.9096 (2) | 0.6907 (2) | 0.0287 (6) | |
C19B | 1.2224 (4) | 0.0354 (3) | 0.2187 (2) | 0.0381 (7) | |
C1A | 0.7963 (3) | 0.6843 (2) | 1.07686 (18) | 0.0179 (5) | |
C1B | 0.6856 (3) | 0.3039 (2) | 0.57936 (18) | 0.0192 (5) | |
C2A | 0.7926 (3) | 0.5751 (2) | 1.09581 (18) | 0.0182 (5) | |
C2B | 0.5461 (3) | 0.2731 (2) | 0.59795 (18) | 0.0187 (5) | |
C3A | 0.6545 (3) | 0.5437 (2) | 1.08596 (18) | 0.0205 (5) | |
C3B | 0.5413 (3) | 0.1676 (2) | 0.57712 (19) | 0.0218 (5) | |
C4A | 0.6582 (3) | 0.4370 (2) | 1.10317 (19) | 0.0238 (5) | |
C4B | 0.4033 (3) | 0.1420 (2) | 0.5929 (2) | 0.0242 (5) | |
C5A | 0.7991 (3) | 0.3526 (2) | 1.1330 (2) | 0.0257 (6) | |
C5B | 0.2589 (3) | 0.2189 (2) | 0.6321 (2) | 0.0234 (5) | |
C6A | 0.9315 (3) | 0.3792 (2) | 1.14713 (19) | 0.0234 (5) | |
C6B | 0.2578 (3) | 0.3206 (2) | 0.65261 (19) | 0.0218 (5) | |
C7A | 0.9337 (3) | 0.4898 (2) | 1.13063 (18) | 0.0208 (5) | |
C7B | 0.3988 (3) | 0.3521 (2) | 0.63505 (18) | 0.0191 (5) | |
C8A | 1.0680 (3) | 0.5168 (2) | 1.14721 (18) | 0.0213 (5) | |
C8B | 0.3970 (3) | 0.4574 (2) | 0.65117 (19) | 0.0213 (5) | |
C9A | 1.0724 (3) | 0.6240 (2) | 1.13095 (18) | 0.0195 (5) | |
C9B | 0.5332 (3) | 0.4892 (2) | 0.63321 (18) | 0.0197 (5) | |
H10A | 1.2994 | 0.5960 | 1.1746 | 0.028* | |
H10B | 0.4327 | 0.6487 | 0.6717 | 0.027* | |
H11A | 1.3071 | 0.7713 | 1.1428 | 0.030* | |
H11B | 0.6569 | 0.7002 | 0.6460 | 0.030* | |
H12A | 1.0872 | 0.9109 | 1.0755 | 0.030* | |
H12B | 0.9033 | 0.5700 | 0.5970 | 0.028* | |
H13A | 0.8604 | 0.8746 | 1.0468 | 0.026* | |
H13B | 0.9193 | 0.3970 | 0.5670 | 0.025* | |
H15A | 0.6218 | 0.8380 | 1.0739 | 0.023* | |
H15B | 0.8655 | 0.1523 | 0.5735 | 0.023* | |
H16A | 0.6070 | 0.7074 | 0.9237 | 0.023* | |
H16B | 0.8981 | 0.3095 | 0.4229 | 0.023* | |
H18A | 1.3367 | 0.0627 | 0.3362 | 0.030* | |
H18B | 1.3320 | 0.1471 | 0.2407 | 0.030* | |
H18C | 0.2929 | 1.0076 | 0.7845 | 0.029* | |
H18D | 0.1673 | 0.9538 | 0.8379 | 0.029* | |
H19A | 1.1467 | 0.0803 | 0.1714 | 0.057* | |
H19B | 1.1747 | −0.0112 | 0.2622 | 0.057* | |
H19C | 1.3155 | −0.0092 | 0.1811 | 0.057* | |
H19D | 0.3357 | 0.8908 | 0.6489 | 0.043* | |
H19E | 0.1588 | 0.9705 | 0.6572 | 0.043* | |
H19F | 0.1991 | 0.8474 | 0.7005 | 0.043* | |
H3A | 0.5599 | 0.5974 | 1.0674 | 0.025* | |
H3B | 0.6342 | 0.1153 | 0.5523 | 0.026* | |
H4A | 0.5668 | 0.4192 | 1.0952 | 0.029* | |
H4B | 0.4034 | 0.0730 | 0.5777 | 0.029* | |
H5A | 0.8009 | 0.2798 | 1.1428 | 0.031* | |
H5B | 0.1661 | 0.1997 | 0.6436 | 0.028* | |
H6A | 1.0229 | 0.3239 | 1.1681 | 0.028* | |
H6B | 0.1635 | 0.3706 | 0.6785 | 0.026* | |
H8A | 1.1580 | 0.4614 | 1.1700 | 0.026* | |
H8B | 0.3018 | 0.5082 | 0.6747 | 0.026* | |
O1A | 0.3710 (2) | 0.94528 (14) | 0.97524 (14) | 0.0244 (4) | |
O1B | 1.1304 (2) | 0.06439 (14) | 0.46678 (14) | 0.0241 (4) | |
O2A | 0.3930 (2) | 0.84993 (14) | 0.83614 (13) | 0.0209 (4) | |
O2B | 1.1301 (2) | 0.18662 (14) | 0.33104 (13) | 0.0225 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C10A | 0.0158 (12) | 0.0318 (14) | 0.0185 (12) | −0.0022 (10) | −0.0003 (9) | −0.0036 (10) |
C10B | 0.0230 (13) | 0.0200 (12) | 0.0203 (12) | −0.0012 (10) | −0.0014 (10) | −0.0012 (10) |
C11A | 0.0168 (12) | 0.0328 (14) | 0.0258 (13) | −0.0079 (11) | 0.0003 (10) | −0.0077 (11) |
C11B | 0.0307 (14) | 0.0218 (13) | 0.0236 (13) | −0.0092 (11) | −0.0030 (11) | −0.0001 (10) |
C12A | 0.0240 (13) | 0.0235 (13) | 0.0272 (13) | −0.0084 (11) | 0.0023 (11) | −0.0064 (10) |
C12B | 0.0239 (13) | 0.0269 (13) | 0.0207 (12) | −0.0110 (11) | −0.0018 (10) | −0.0005 (10) |
C13A | 0.0178 (12) | 0.0215 (12) | 0.0227 (12) | −0.0022 (10) | 0.0005 (10) | −0.0030 (10) |
C13B | 0.0191 (12) | 0.0263 (13) | 0.0164 (12) | −0.0057 (10) | −0.0007 (9) | 0.0000 (10) |
C14A | 0.0174 (12) | 0.0194 (12) | 0.0155 (11) | −0.0019 (9) | 0.0009 (9) | −0.0027 (9) |
C14B | 0.0185 (12) | 0.0202 (12) | 0.0149 (11) | −0.0022 (10) | −0.0020 (9) | −0.0010 (9) |
C15A | 0.0156 (11) | 0.0167 (11) | 0.0228 (12) | −0.0040 (9) | 0.0015 (9) | −0.0005 (9) |
C15B | 0.0170 (12) | 0.0186 (12) | 0.0214 (12) | −0.0048 (9) | −0.0025 (9) | −0.0007 (9) |
C16A | 0.0166 (11) | 0.0178 (12) | 0.0231 (12) | −0.0049 (9) | 0.0019 (9) | −0.0025 (9) |
C16B | 0.0170 (12) | 0.0176 (12) | 0.0214 (12) | −0.0035 (9) | −0.0024 (9) | −0.0005 (9) |
C17A | 0.0167 (11) | 0.0187 (12) | 0.0214 (12) | −0.0079 (10) | 0.0006 (9) | 0.0003 (10) |
C17B | 0.0162 (11) | 0.0204 (12) | 0.0202 (12) | −0.0068 (10) | −0.0007 (9) | −0.0031 (10) |
C18A | 0.0193 (12) | 0.0204 (13) | 0.0289 (14) | −0.0016 (10) | −0.0061 (10) | 0.0026 (10) |
C18B | 0.0190 (12) | 0.0261 (13) | 0.0265 (13) | −0.0037 (10) | 0.0081 (10) | −0.0042 (11) |
C19A | 0.0302 (14) | 0.0285 (14) | 0.0266 (14) | −0.0084 (12) | −0.0083 (11) | 0.0044 (11) |
C19B | 0.0404 (17) | 0.0382 (17) | 0.0340 (16) | −0.0102 (14) | 0.0088 (13) | −0.0137 (13) |
C1A | 0.0163 (11) | 0.0180 (12) | 0.0161 (11) | −0.0013 (9) | 0.0014 (9) | −0.0028 (9) |
C1B | 0.0186 (12) | 0.0218 (12) | 0.0144 (11) | −0.0033 (10) | −0.0017 (9) | 0.0010 (9) |
C2A | 0.0181 (12) | 0.0191 (12) | 0.0137 (11) | −0.0016 (10) | 0.0008 (9) | −0.0006 (9) |
C2B | 0.0176 (12) | 0.0210 (12) | 0.0149 (11) | −0.0027 (10) | −0.0016 (9) | 0.0001 (9) |
C3A | 0.0194 (12) | 0.0221 (13) | 0.0176 (12) | −0.0037 (10) | 0.0002 (9) | −0.0011 (9) |
C3B | 0.0189 (12) | 0.0218 (13) | 0.0219 (12) | −0.0035 (10) | 0.0012 (10) | −0.0017 (10) |
C4A | 0.0279 (13) | 0.0266 (13) | 0.0187 (12) | −0.0119 (11) | 0.0018 (10) | −0.0026 (10) |
C4B | 0.0252 (13) | 0.0214 (13) | 0.0257 (13) | −0.0080 (11) | −0.0005 (10) | −0.0005 (10) |
C5A | 0.0322 (14) | 0.0194 (12) | 0.0239 (13) | −0.0075 (11) | 0.0039 (11) | −0.0021 (10) |
C5B | 0.0178 (12) | 0.0277 (13) | 0.0246 (13) | −0.0081 (10) | −0.0006 (10) | 0.0005 (10) |
C6A | 0.0253 (13) | 0.0190 (12) | 0.0198 (12) | −0.0002 (10) | 0.0013 (10) | 0.0009 (10) |
C6B | 0.0168 (12) | 0.0252 (13) | 0.0198 (12) | −0.0027 (10) | −0.0003 (9) | −0.0004 (10) |
C7A | 0.0213 (12) | 0.0213 (12) | 0.0150 (11) | −0.0017 (10) | 0.0029 (9) | −0.0008 (9) |
C7B | 0.0170 (12) | 0.0226 (12) | 0.0145 (11) | −0.0025 (10) | −0.0005 (9) | −0.0003 (9) |
C8A | 0.0175 (12) | 0.0223 (12) | 0.0174 (12) | 0.0020 (10) | 0.0005 (9) | −0.0004 (9) |
C8B | 0.0182 (12) | 0.0215 (12) | 0.0179 (12) | 0.0023 (10) | −0.0003 (9) | −0.0024 (9) |
C9A | 0.0169 (12) | 0.0228 (12) | 0.0158 (11) | −0.0026 (10) | 0.0012 (9) | −0.0022 (9) |
C9B | 0.0200 (12) | 0.0220 (12) | 0.0143 (11) | −0.0028 (10) | −0.0034 (9) | 0.0001 (9) |
O1A | 0.0202 (9) | 0.0223 (9) | 0.0282 (10) | −0.0021 (7) | −0.0034 (7) | −0.0047 (7) |
O1B | 0.0199 (9) | 0.0215 (9) | 0.0264 (9) | −0.0022 (7) | 0.0016 (7) | 0.0017 (7) |
O2A | 0.0182 (8) | 0.0202 (9) | 0.0213 (9) | −0.0021 (7) | −0.0036 (7) | 0.0004 (7) |
O2B | 0.0188 (9) | 0.0225 (9) | 0.0222 (9) | −0.0033 (7) | 0.0046 (7) | −0.0006 (7) |
C10A—C11A | 1.358 (4) | C1A—C15A | 1.476 (3) |
C10A—H10A | 0.9300 | C1A—C14A | 1.414 (4) |
C10B—H10B | 0.9300 | C1A—C2A | 1.415 (4) |
C11A—H11A | 0.9300 | C1B—C15B | 1.479 (3) |
C11B—C10B | 1.359 (4) | C2A—C3A | 1.432 (4) |
C11B—H11B | 0.9300 | C2A—C7A | 1.445 (3) |
C12A—C11A | 1.424 (4) | C2B—C3B | 1.429 (4) |
C12A—H12A | 0.9300 | C2B—C7B | 1.443 (3) |
C12B—C11B | 1.426 (4) | C2B—C1B | 1.413 (4) |
C12B—C13B | 1.350 (4) | C3A—H3A | 0.9300 |
C12B—H12B | 0.9300 | C3B—H3B | 0.9300 |
C13A—C12A | 1.364 (4) | C4A—C5A | 1.418 (4) |
C13A—H13A | 0.9300 | C4A—C3A | 1.362 (4) |
C13B—H13B | 0.9300 | C4A—H4A | 0.9300 |
C14A—C13A | 1.434 (4) | C4B—C3B | 1.362 (4) |
C14A—C9A | 1.436 (3) | C4B—C5B | 1.424 (4) |
C14B—C13B | 1.436 (4) | C4B—H4B | 0.9300 |
C14B—C9B | 1.442 (3) | C5A—H5A | 0.9300 |
C14B—C1B | 1.412 (4) | C5B—H5B | 0.9300 |
C15A—C16A | 1.328 (4) | C6A—C5A | 1.360 (4) |
C15A—H15A | 0.9300 | C6A—H6A | 0.9300 |
C15B—H15B | 0.9300 | C6B—C5B | 1.361 (4) |
C16A—C17A | 1.478 (3) | C6B—H6B | 0.9300 |
C16A—H16A | 0.9300 | C7A—C6A | 1.427 (4) |
C16B—C17B | 1.478 (3) | C7B—C8B | 1.389 (4) |
C16B—C15B | 1.330 (4) | C7B—C6B | 1.429 (4) |
C16B—H16B | 0.9300 | C8A—C7A | 1.387 (4) |
C18A—C19A | 1.497 (4) | C8A—H8A | 0.9300 |
C18A—H18D | 0.9700 | C8B—H8B | 0.9300 |
C18A—H18C | 0.9700 | C9A—C10A | 1.428 (4) |
C18B—C19B | 1.500 (4) | C9A—C8A | 1.391 (4) |
C18B—H18B | 0.9700 | C9B—C10B | 1.427 (4) |
C18B—H18A | 0.9700 | C9B—C8B | 1.392 (4) |
C19A—H19F | 0.9600 | O1A—C17A | 1.207 (3) |
C19A—H19E | 0.9600 | O1B—C17B | 1.205 (3) |
C19A—H19D | 0.9600 | O2A—C18A | 1.454 (3) |
C19B—H19C | 0.9600 | O2A—C17A | 1.347 (3) |
C19B—H19B | 0.9600 | O2B—C18B | 1.453 (3) |
C19B—H19A | 0.9600 | O2B—C17B | 1.349 (3) |
C10A—C11A—H11A | 120.0 | C2B—C3B—H3B | 119.4 |
C10A—C11A—C12A | 120.0 (2) | C2B—C1B—C15B | 118.4 (2) |
C10A—C9A—C14A | 119.1 (2) | C3A—C4A—C5A | 121.2 (3) |
C10B—C11B—H11B | 120.4 | C3A—C4A—H4A | 119.4 |
C10B—C11B—C12B | 119.1 (2) | C3A—C2A—C7A | 117.1 (2) |
C10B—C9B—C14B | 119.0 (2) | C3B—C4B—C5B | 121.3 (2) |
C11A—C12A—H12A | 119.7 | C3B—C4B—H4B | 119.4 |
C11A—C10A—H10A | 119.4 | C3B—C2B—C7B | 117.5 (2) |
C11A—C10A—C9A | 121.3 (2) | C4A—C5A—H5A | 120.3 |
C11B—C10B—H10B | 119.1 | C4A—C3A—H3A | 119.2 |
C11B—C10B—C9B | 121.8 (2) | C4A—C3A—C2A | 121.5 (2) |
C11B—C12B—H12B | 119.4 | C4B—C3B—H3B | 119.4 |
C12A—C11A—H11A | 120.0 | C4B—C3B—C2B | 121.2 (2) |
C12A—C13A—H13A | 119.4 | C4B—C5B—H5B | 120.3 |
C12A—C13A—C14A | 121.2 (2) | C5A—C6A—H6A | 119.1 |
C12B—C11B—H11B | 120.4 | C5A—C6A—C7A | 121.7 (2) |
C12B—C13B—H13B | 119.1 | C5A—C4A—H4A | 119.4 |
C12B—C13B—C14B | 121.9 (2) | C5B—C4B—H4B | 119.4 |
C13A—C12A—C11A | 120.7 (2) | C5B—C6B—H6B | 119.4 |
C13A—C12A—H12A | 119.7 | C5B—C6B—C7B | 121.2 (2) |
C13A—C14A—C9A | 117.7 (2) | C6A—C5A—H5A | 120.3 |
C13B—C12B—C11B | 121.1 (2) | C6A—C5A—C4A | 119.4 (2) |
C13B—C12B—H12B | 119.4 | C6A—C7A—C2A | 119.0 (2) |
C13B—C14B—C9B | 116.9 (2) | C6B—C5B—H5B | 120.3 |
C14A—C13A—H13A | 119.4 | C6B—C5B—C4B | 119.5 (2) |
C14A—C1A—C15A | 118.6 (2) | C6B—C7B—C2B | 119.3 (2) |
C14A—C1A—C2A | 120.5 (2) | C7A—C6A—H6A | 119.1 |
C14B—C13B—H13B | 119.1 | C7A—C8A—H8A | 118.9 |
C14B—C1B—C15B | 121.1 (2) | C7A—C8A—C9A | 122.2 (2) |
C14B—C1B—C2B | 120.5 (2) | C7B—C8B—H8B | 118.9 |
C15A—C16A—C17A | 121.4 (2) | C7B—C8B—C9B | 122.1 (2) |
C15A—C16A—H16A | 119.3 | C7B—C6B—H6B | 119.4 |
C15B—C16B—C17B | 121.4 (2) | C8A—C7A—C6A | 121.5 (2) |
C15B—C16B—H16B | 119.3 | C8A—C7A—C2A | 119.5 (2) |
C16A—C15A—H15A | 117.3 | C8A—C9A—C10A | 121.7 (2) |
C16A—C15A—C1A | 125.5 (2) | C8A—C9A—C14A | 119.2 (2) |
C16B—C15B—H15B | 117.5 | C8B—C9B—C10B | 121.4 (2) |
C16B—C15B—C1B | 125.0 (2) | C8B—C9B—C14B | 119.6 (2) |
C17A—C16A—H16A | 119.3 | C8B—C7B—C6B | 121.7 (2) |
C17A—O2A—C18A | 115.54 (19) | C8B—C7B—C2B | 119.1 (2) |
C17B—C16B—H16B | 119.3 | C9A—C10A—H10A | 119.4 |
C17B—O2B—C18B | 116.66 (19) | C9A—C8A—H8A | 118.9 |
C18A—C19A—H19F | 109.5 | C9B—C10B—H10B | 119.1 |
C18A—C19A—H19E | 109.5 | C9B—C8B—H8B | 118.9 |
C18A—C19A—H19D | 109.5 | H18A—C18B—H18B | 108.0 |
C18B—C19B—H19C | 109.5 | H18C—C18A—H18D | 108.5 |
C18B—C19B—H19B | 109.5 | H19A—C19B—H19C | 109.5 |
C18B—C19B—H19A | 109.5 | H19A—C19B—H19B | 109.5 |
C19A—C18A—H18D | 110.3 | H19B—C19B—H19C | 109.5 |
C19A—C18A—H18C | 110.3 | H19D—C19A—H19F | 109.5 |
C19B—C18B—H18B | 109.4 | H19D—C19A—H19E | 109.5 |
C19B—C18B—H18A | 109.4 | H19E—C19A—H19F | 109.5 |
C1A—C15A—H15A | 117.3 | O1A—C17A—C16A | 125.9 (2) |
C1A—C14A—C13A | 122.7 (2) | O1A—C17A—O2A | 123.9 (2) |
C1A—C14A—C9A | 119.6 (2) | O1B—C17B—C16B | 125.9 (2) |
C1A—C2A—C3A | 123.9 (2) | O1B—C17B—O2B | 124.2 (2) |
C1A—C2A—C7A | 119.0 (2) | O2A—C18A—C19A | 107.3 (2) |
C1B—C15B—H15B | 117.5 | O2A—C18A—H18D | 110.3 |
C1B—C2B—C3B | 122.9 (2) | O2A—C18A—H18C | 110.3 |
C1B—C2B—C7B | 119.6 (2) | O2A—C17A—C16A | 110.2 (2) |
C1B—C14B—C13B | 124.0 (2) | O2B—C18B—C19B | 111.0 (2) |
C1B—C14B—C9B | 119.1 (2) | O2B—C18B—H18B | 109.4 |
C2A—C3A—H3A | 119.2 | O2B—C18B—H18A | 109.4 |
C2A—C1A—C15A | 121.0 (2) | O2B—C17B—C16B | 109.9 (2) |
C10A—C9A—C8A—C7A | 179.5 (2) | C1A—C2A—C7A—C8A | 1.6 (3) |
C10B—C9B—C8B—C7B | −180.0 (2) | C1B—C2B—C3B—C4B | −177.8 (2) |
C11B—C12B—C13B—C14B | 0.1 (4) | C1B—C2B—C7B—C8B | 0.4 (3) |
C12B—C11B—C10B—C9B | −1.3 (4) | C1B—C2B—C7B—C6B | 179.3 (2) |
C13A—C12A—C11A—C10A | 1.4 (4) | C1B—C14B—C13B—C12B | 179.6 (2) |
C13A—C14A—C9A—C10A | 2.7 (3) | C1B—C14B—C9B—C10B | −179.0 (2) |
C13A—C14A—C9A—C8A | −176.7 (2) | C1B—C14B—C9B—C8B | 1.8 (3) |
C13B—C12B—C11B—C10B | 1.9 (4) | C2A—C7A—C6A—C5A | −1.4 (4) |
C13B—C14B—C9B—C10B | 3.1 (3) | C2A—C1A—C15A—C16A | −49.8 (4) |
C13B—C14B—C9B—C8B | −176.1 (2) | C2A—C1A—C14A—C13A | 177.9 (2) |
C13B—C14B—C1B—C15B | −4.6 (4) | C2A—C1A—C14A—C9A | 0.0 (3) |
C13B—C14B—C1B—C2B | 176.0 (2) | C2B—C7B—C8B—C9B | −0.3 (4) |
C14A—C13A—C12A—C11A | −0.1 (4) | C2B—C7B—C6B—C5B | −2.0 (4) |
C14A—C9A—C10A—C11A | −1.5 (4) | C2B—C1B—C15B—C16B | 129.6 (3) |
C14A—C9A—C8A—C7A | −1.1 (4) | C3A—C4A—C5A—C6A | 1.6 (4) |
C14A—C1A—C15A—C16A | 130.4 (3) | C3A—C2A—C7A—C6A | 3.7 (3) |
C14A—C1A—C2A—C3A | 176.4 (2) | C3A—C2A—C7A—C8A | −176.3 (2) |
C14A—C1A—C2A—C7A | −1.4 (3) | C3B—C4B—C5B—C6B | 1.1 (4) |
C14B—C9B—C10B—C11B | −1.2 (4) | C3B—C2B—C7B—C8B | −176.8 (2) |
C14B—C9B—C8B—C7B | −0.7 (4) | C3B—C2B—C7B—C6B | 2.2 (3) |
C14B—C1B—C15B—C16B | −49.8 (4) | C3B—C2B—C1B—C15B | −1.7 (4) |
C15A—C16A—C17A—O2A | 169.2 (2) | C3B—C2B—C1B—C14B | 177.7 (2) |
C15A—C16A—C17A—O1A | −10.2 (4) | C5A—C4A—C3A—C2A | 0.9 (4) |
C15A—C1A—C14A—C13A | −2.3 (4) | C5B—C4B—C3B—C2B | −0.9 (4) |
C15A—C1A—C14A—C9A | 179.8 (2) | C6B—C7B—C8B—C9B | −179.3 (2) |
C15A—C1A—C2A—C3A | −3.5 (4) | C7A—C6A—C5A—C4A | −1.3 (4) |
C15A—C1A—C2A—C7A | 178.7 (2) | C7A—C2A—C3A—C4A | −3.5 (3) |
C15B—C16B—C17B—O2B | 171.2 (2) | C7B—C6B—C5B—C4B | 0.3 (4) |
C15B—C16B—C17B—O1B | −8.7 (4) | C7B—C2B—C3B—C4B | −0.8 (4) |
C17A—O2A—C18A—C19A | 178.4 (2) | C7B—C2B—C1B—C15B | −178.7 (2) |
C17B—C16B—C15B—C1B | −179.1 (2) | C7B—C2B—C1B—C14B | 0.7 (4) |
C17B—O2B—C18B—C19B | 87.3 (3) | C8A—C7A—C6A—C5A | 178.6 (2) |
C18A—O2A—C17A—C16A | −176.1 (2) | C8A—C9A—C10A—C11A | 177.9 (2) |
C18A—O2A—C17A—O1A | 3.3 (3) | C8B—C9B—C10B—C11B | 178.0 (2) |
C18B—O2B—C17B—C16B | −177.5 (2) | C8B—C7B—C6B—C5B | 176.9 (2) |
C18B—O2B—C17B—O1B | 2.4 (4) | C9A—C10A—C11A—C12A | −0.6 (4) |
C1A—C15A—C16A—C17A | −179.8 (2) | C9A—C8A—C7A—C6A | 179.6 (2) |
C1A—C14A—C13A—C12A | −179.9 (2) | C9A—C8A—C7A—C2A | −0.3 (4) |
C1A—C14A—C9A—C10A | −179.3 (2) | C9A—C14A—C13A—C12A | −1.9 (4) |
C1A—C14A—C9A—C8A | 1.3 (3) | C9B—C14B—C13B—C12B | −2.6 (4) |
C1A—C2A—C3A—C4A | 178.7 (2) | C9B—C14B—C1B—C15B | 177.6 (2) |
C1A—C2A—C7A—C6A | −178.4 (2) | C9B—C14B—C1B—C2B | −1.7 (3) |
Cg1 and Cg2 are the centroids of the C1A/C2A/C7A–C9A/C14A and C2A—C7A rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C13A—H13A···O1Ai | 0.93 | 2.56 | 3.455 (3) | 163 |
C18B—H18B···O2Aii | 0.97 | 2.56 | 3.422 (3) | 148 |
C3B—H3B···O1Biii | 0.93 | 2.57 | 3.470 (3) | 162 |
C6A—H6A···O2Biv | 0.93 | 2.67 | 3.438 (3) | 140 |
C19A—H19E···O1Bv | 0.96 | 2.66 | 3.409 (3) | 135 |
C6B—H6B···Cg1vi | 0.93 | 2.81 | 3.447 (3) | 126 |
C8B—H8B···Cg2vi | 0.93 | 2.82 | 3.439 (3) | 124 |
Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) −x+2, −y+1, −z+1; (iii) −x+2, −y, −z+1; (iv) x, y, z+1; (v) x−1, y+1, z; (vi) −x+1, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C19H16O2 |
Mr | 276.32 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 291 |
a, b, c (Å) | 8.8700 (5), 12.8918 (7), 13.1062 (7) |
α, β, γ (°) | 84.389 (4), 84.620 (4), 70.771 (5) |
V (Å3) | 1405.28 (13) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.66 |
Crystal size (mm) | 0.22 × 0.11 × 0.09 |
Data collection | |
Diffractometer | Agilent SuperNova Dual Atlas |
Absorption correction | Gaussian (CrysAlis PRO; Agilent, 2012) |
Tmin, Tmax | 0.889, 0.942 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11350, 4901, 4250 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.593 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.171, 1.10 |
No. of reflections | 4901 |
No. of parameters | 381 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.26 |
Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) within OLEX2 (Dolomanov et al., 2009), PLATON (Spek, 2009) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
Cg1 and Cg2 are the centroids of the C1A/C2A/C7A–C9A/C14A and C2A—C7A rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C13A—H13A···O1Ai | 0.930 | 2.56 | 3.455 (3) | 163 |
C18B—H18B···O2Aii | 0.970 | 2.56 | 3.422 (3) | 148 |
C3B—H3B···O1Biii | 0.930 | 2.57 | 3.470 (3) | 162 |
C6A—H6A···O2Biv | 0.930 | 2.67 | 3.438 (3) | 140 |
C19A—H19E···O1Bv | 0.960 | 2.66 | 3.409 (3) | 135 |
C6B—H6B···Cg1vi | 0.930 | 2.81 | 3.447 (3) | 126 |
C8B—H8B···Cg2vi | 0.930 | 2.82 | 3.439 (3) | 124 |
Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) −x+2, −y+1, −z+1; (iii) −x+2, −y, −z+1; (iv) x, y, z+1; (v) x−1, y+1, z; (vi) −x+1, −y+1, −z+2. |
Acknowledgements
The authors thank the UAEU interdisciplinary grant 31S036 for financial support. They also thank Thirumurugan Prakasam, NYU Abu Dhabi, for the
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In our endeavor to carry out [2 + 2]-photocycloaddition of ethyl 3(E)-(9-anthracenyl)propenoate in the solid state, the authors grew single crystals of the title compound to identify intermolecular interactions of the molecule in the crystal, which could control the photocycloaddition (Sonoda, 2011; Schmidt, 1964). In the title compound, the alkyl group forms very different torsion angles with the carboxyl group of the ester function (C17—O2—C18—C19) in molecules A and B, respectively, namely of 178.3 (2) ° in molecule A, and of 87.3 (3) ° in molecule B. Pairs of molecules A and B respectively, are formed by C13A—H13A···O1A (Figure 2) close contact for pairs A, and by C3B—H3B···O1B close contact (Table 1) for pairs B, and with the ring planes of the anthracenyl units of the respective pairs in parallel, but at an offset of 0.528 (2) Å for molecules A and 0.479 (2) Å for molecules B. Pairs A and pairs B interact with each other by C18B—H18B···O2A close contact (Figure 2) to for the [10-1] column. Also, C6B—H6B··· π and C8B—H8B···π interactions (Figure 2) are formed between the pairs B and A in the column. Neighboring columns arranged into [111] layer show partial intercalation to form π–π interaction (Table 1) between the parallel anthracenyl units of the same molecules (A—A and B—B).
The double bonds of two molecules in one pair are aligned parallel to each other at a distance of 5.549 (3) Å for A and 5.627 (3) Å for B. This intermolecular distance between the olefinic moieties is larger than in many of those found for aryl-enes that undergo [2 + 2]-photodimerization readily (Vishnumurthy et al. 2002; Mascitti et al. 2006). However, the anthracenyl units are aligned parallel to each other with an interplanar distance (C1-C8) of 3.945 (3) Å for A molecules and 4.031 (3) Å for B molecules. This distance lies within the distance of less than 4.2 Å, reported for anthracenes in the crystal that undergo photodimerisation (Schmidt, 1971; Ihmels et al., 2000).