Download citation
Download citation
link to html
(1E,4E)-1,5-Bis(2,6-di­fluoro­phen­yl)penta-1,4-dien-3-one, C17H10F4O, (I), dimerizes under sunlight in chloro­form solution to form the corresponding cyclo­butane derivative, (2E,2′E)-1,1′-[2,4-bis­(2,6-di­fluoro­phen­yl)cyclo­butane-1,3-di­yl]bis­[3-(2,6-di­fluoro­phen­yl)prop-2-en-1-one], C34H20F8O2, (II). The crystal structure of (I) explains why no topochemical di­merization can occur in the solid state. In the solid, mol­ecules of dimer (II) show the `truxillic acid'-type arrangement of crystallographic centres of inversion, with half a mol­ecule per asymmetric unit and cell dimensions closely related to those of the monomer. Inter­molecular inter­actions in both solids are dominated by C—H...O and C—H...F contacts and also comprise inter­actions with aromatic systems (C—H...π and π–π).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229613034232/eg3145sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229613034232/eg3145Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229613034232/eg3145IIsup3.hkl
Contains datablock II

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229613034232/eg3145Isup4.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229613034232/eg3145IIsup5.cml
Supplementary material

CCDC references: 742631; 978150

Introduction top

Dimerization of olefinic compounds is a common reaction principle in organic synthesis. The photoinduced [2+2] cyclo­addition as the basic mechanism allows the synthesis of natural products (Büchi & Goldman, 1957) and molecules with sophisticated topology otherwise only hardly accessible, e.g. cubanes (Eaton & Cole, 1964) or ladderanes (Hopf, 2003). Photochemical [2+2] cyclo­addition can also occur in the solid state if the double bonds are parallel and separated by less than 4.2 Å (Schmidt, 1971). Therefore, this kind of topochemical control is used rather broadly in the realm of crystal engineering (Biradha & Santra, 2013).

Di­benzyl­ideneacetone, as the parent compound, was investigated several times regarding its photochemical behavior both in solution and in the solid state. It photodimerizes in acetic acid in the presence of uranyl chloride to form a cyclo­butane derived `truxillic'-type dimer (Praetorius & Korn, 1910; Alcock et al., 1975). This kind of dimer is formed due to a head-to-tail orientation of the alkenes during the dimerisation process. In contrast, the 'truxinic' form is based on the head-to-head orientation. In these designations, the head is associated with the phenyl ring and the tail with the moiety containing the carbonyl group. The latter truxinic-type dimer of dibenzalacetone results from the reaction in an iso­propanol/benzene mixture under UV light (Recktenwald et al., 1953). In ethanol solution and using sunlight, a mixture of oligomeric and polymeric compounds and the truxinic form is isolated (Ciamician & Silber, 1909). Furthermore, the reaction in n-hexane solution under N2 atmosphere with a high pressure Hg lamp as light source leads to the truxinic type dimer (Shoppee et al., 1976).

In the solid state, di­benzyl­ideneacetone is light stable (Green & Schmidt, 1970) with respect to dimerization; rather, it undergoes a photo-induced rearrangement of the double bond (Turowska-Tyrk, 2003). The isomerism of the olefinic moiety with respect to the CO bond results in two different orientations of the whole molecule. However, adjacent double bonds are not located in a suitably parallel geometry for a [2+2] cyclo­addition in the s olid state.

Experimental top

Synthesis and crystallization top

The synthesis for compound (I) (Scheme 1) was similar to the process described by Williamson (1999) for unsubstituted di­benzyl­ideneacetone. Acetone (0.15 g, 2.5 mmol) and 2,6-di­fluoro­benzaldehyde (0.71 g, 5 mmol) were added to a solution of 0.5 g (12.5 mmol) sodium hydroxide in a mixture of water (5 ml) and ethanol (4 ml). Stirring of the reaction mixture for 30 min at room temperature gave a yellow solid material which was collected via suction filtration. To remove the sodium hydroxide, the raw product was washed with water. Crystallization from ethanol yielded 0.25 g (33%) of yellow crystals [m.p. 409–413 K (ethanol)]. Analysis calculated for C17H10F4O: C 66.67, H 3.29%; found: C 66.42, H 3.31%. IR (KBr, νmax, cm-1): 3053 (w, CArH), 1660 (s, CO), 1624 (s, CC), 1602 (s, Ph), 1584 (s, Ph). 1H NMR (400 MHz, CDCl3): δ 7.83 (2H, d, 2JHH = 16.4 Hz, CCHPh), 7.41–7.28 (4H, m, HCCHPh, Ph), 6.96 (4H, m, Ph). 13C NMR (100 MHz, CDCl3): δ 189.27 (s, CO), 160.66, 163.21 (d, 1JCF = -256.5 Hz, C-2), 131.29 (t, 3JCF = -11.1 Hz, CCPh), 130.84 (s, C=CPh), 129.82 (t, 3JCF = -8.3, C-4), 112.86 (t, 2JCF = 14.9 Hz, C-1), 111.88 (d, 2JCF = 26.6 Hz, C-3). 19F NMR (476 MHz, CDCl3): δ -110.31 (4F, m). MS (m/e) 306 [M]+, 167, 139, 119, 99.

Compound (II) was prepared via irradiation of (I) in chloro­form solution using sunlight. Crystals suitable for X-ray diffraction were grown from ethyl acetate in an optically opaque sample tube. IR (KBr, νmax, cm-1): 3100, 3063 (w, C—H), 1690 (s, CO), 1622 (s, CC), 1602 (s, Ph), 1585 (s, Ph). 1H NMR (400 MHz, CDCl3): δ 7.53 (2H, d, JHH = 20 Hz, CCHPh), 7.38–6.77 (14H, m, HCCHPh, Ph), 5.24 (2H, m, CH), 4.65 (2H, m, CH). 13C NMR (100 MHz, CDCl3): δ 198.0 (s, CO); 163.1/160.5, 162.8/160.3 (d, 1JCF = -256, 1JCF = 248 Hz, C1, C5, C13, C17); 131.2–128.6 (m, CCPh, CCPh, Ph); 115.3–111.4 (m, Ph); 49.9, 31.6 (s, C10, C11). 19F NMR (476 MHz, CDCl3): δ -110.5 (4F, m), -112.6 (4F, m).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. For compounds (I) and (II), H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.95 Å for aryl and olefinic CH groups [Uiso(H) = 1.2Ueq(C)], and C—H = 1.00 Å for aliphatic CH groups [Uiso(H) = 1.5Ueq(C)].

Results and discussion top

Although the crystal structure of 1,5-bis­(2,6-di­fluoro­phenyl)­penta-1,4-dien-3-one, (I), has been described previously (Huang et al., 2011), we decided to recollect intensity data at low temperature. We can confirm the previous results in principle, but the higher resolution and lower data collection temperature result in more accurate data; in the following discussion of the photodimerisation process, we therefore refer to our own results. The tetra­fluorinated di­benzyl­ideneacetone crystallizes in the space group P21/n with one molecule of C1 symmetry (Fig. 1a) in general position. The dimer of (I), namely (2E,2'E)-1,1'-[2,4-bis­(2,6-di­fluoro­phenyl)­cyclo­butane-1,3-diyl]bis­[3-(2,6-di­fluoro­phenyl)­prop-2-en-1-one], (II), was found to crystallize in the same space group with similar cell dimensions and the molecule on a centre of inversion (Fig. 2a). The comparison of the cell constants shows the following ratio: aI ~aII, bI \sim cII and cI ~bII. The similarities aI versus aII and bI versus cII are more pronounced than the relationship between cI and bII.

The crystal packing of (I) is dominated by C—H···O and C—H···F inter­actions forming several zigzag chains in the range of 2.3–2.6 Å for the hydrogen-acceptor distance (θ = 145–174°; Table 2). In addition, a ππ stacking inter­action between two adjacent phenyl rings generates molecular dimers. A distance of 3.72 Å and a slippage of 1.47 Å is revealed. These inter­molecular inter­actions have already been observed in the structure reported previously (Huang et al., 2011), but have not been discussed in detail or regarding a photodimerization process. In addition, the bond lengths and therefore the inter­molecular inter­actions are more precise and were found shorter. Furthermore, an additional C—H···F contact is observed existing in the structure (C14—H14···F2; Table 2).

As mentioned above, parallel orientation of the potentially active double bonds and a maximum separation of 4.2 Å have been defined as the basic conditions for a [2+2] cyclo­addition (Schmidt, 1971). The molecular arrangement of di­benzyl­ideneacetone (I) in the solid state does not meet these requirements, and thus this solid is not suitable for a [2+2] cyclo­addition. Instead, the double bonds are located adjacent to an aromatic moiety with a distance of about 3.38 Å and not to a second double bond (Fig. 2a). Therefore, a topochemical transformation of (I) to (II) in the solid state was not expected to be successful. Indeed, crystalline (I) proves to be light stable under sunlight and a UV Hg pressure lamp (100 W). Also, an intended dimerization of compound (I) in CH2Cl2 solution using the same conditions under inert atmosphere did not lead to the formation of a dimer but undefined oligo- and polymeric material. A corresponding behavior was found for the irradiation of the parent di­benzyl­ideneacetone in ethanol solution (Ciamician & Silber, 1909). Finally, irradiation of (I) in chloro­form solution using only sunlight gave the dimer. As indicated by the NMR data, two different configurations occur, but only the syn-head–tail orientation could be isolated and proved via single crystal X-ray diffraction (Fig. 2a). Fig. 3 shows the 13C NMR spectroscopic data of (I) and (II) in chloro­form for comparison. Signals of the cyclo­butane moiety appear at 49.9 and 31.6 p.p.m., and the chemical shift of the carbonyl group changes from 189.3 to 198.0 p.p.m. in the course of dimerization. In the case of (II), all signals are not distinctly sharp in shape and therefore indicate the formation of at least two different configurations. The crystallographically confirmed configuration of (II) can best be described by the syn-head–tail arrangement of the substituents at the cyclo­butane ring with the aryl group being defined as the head and the carbonyl group containing moiety as the tail (Fig. 2a). All bond lengths and angles are within the range of the expected values both for the cyclo­butane ring and the attached substitutents. The phenyl rings A and B are twisted are twisted with respect to each other with an angle of 63.52 (4)°, whereas the aryl moieties related by an inversion centre (A/A' and B/B') show a parallel orientation for reasons of symmetry.

The crystal packing of (II) is not only dominated by closed-packing and maximum symmetry but also by C—H···O (Desiraju & Steiner, 1999) and C—H···F contacts (Berger et al., 2011). These hydrogen-involved inter­actions are in the range 3.25–3.48 Å for the donor–acceptor distance (θ = 124.6–147.3°) are 2.54–2.65 Å for the hydrogen–acceptor distance. Moreover, there are F···F contacts (Schwarzer & Weber, 2008; Schwarzer et al., 2010) with distances close to the sum of the van der Waals radii [F1···F3(x+1/2, -y-1/2, z+1/2) = 2.9159 (12) Å and F1···F4(-x+3/2, y-1/2, -z+1/2) = 2.9302 (13) Å]. Hence, they might not significantly contribute to a stabilizing effect within the crystal packing. Compound (II) exhibits several aromatic moieties being able to inter­act in inter­molecular inter­actions. In addition to typical C—H···π contacts (Nishio, 2004), ππ stacking inter­actions (Dance, 2004) are localized. They occur between adjacent rings A (atoms C1–C6; symmetry code: -x+1, -y, -z+1), with a distance of 3.65 Å and a slippage of 0.970 Å. The distances of the C—H···π inter­actions are as follows: C7—H7···CgB(-x+1/2, y-1/2, -z+1/2) = 3.662 Å and 141.1°, where CgB as the centroid of the C12–C17 ring (Fig. 1). Relevant C—F···π inter­actions (Berger et al., 2011) are not present in the crystal structure of compound (II).

On the one hand, a comparison of the inter­molecular inter­actions of compounds (I) and (II) reveals minor differences. In both cases, the ortho-substituted H atoms inter­act with either the O atom or the F atom. On the other hand, the aliphatic hydrogen atoms in (II) seem to play a significant role in the packing of (II) as well as the described C–H···π inter­actions which are not present in (I). Moreover, F···F contacts of (II) are not observed in (I).

In conclusion, the light stability of compound (I) in the solid state is in agreement with its crystal structure and (I) readily dimerizes in chloro­form solution under sunlight and reacts under UV light to yield oligo- and polymeric compounds. The cyclo­butane-type dimer is formed with the syn–head–tail orientation, having two olefinic residues thus illustrating that under the given conditions two molecules of (I) have been transformed in a single [2+2] cyclo­addition reaction leaving the second olefinic bond of (I) untouched.

Related literature top

For related literature, see: Alcock et al. (1975); Büchi & Goldman (1957); Berger et al. (2011); Biradha & Santra (2013); Ciamician & Silber (1909); Dance (2004); Desiraju & Steiner (1999); Eaton & Cole (1964); Green & Schmidt (1970); Hopf (2003); Huang et al. (2011); Nishio (2004); Praetorius & Korn (1910); Recktenwald et al. (1953); Schmidt (1971); Schwarzer & Weber (2008); Schwarzer et al. (2010); Shoppee et al. (1976); Turowska-Tyrk (2003); Williamson (1999).

Computing details top

For both compounds, data collection: SMART (Bruker, 2007); cell refinement: SMART (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Bruker, 2007); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
(a) Perspective view of (I), showing 50% probability displacement ellipsoids for the non-H atoms. (b) The crystal packing of (I) illustrating the distances between the olefinic double bond and the aromatic unit (right), the bifurcated C—H..O interactions (middle) and the C—H···F interactions (top). [Symmetry codes: (i) -x+5/2, y-1/2, -z+3/2; (ii) -x+3/2, y+1/2, -z+3/2; (iii) -x+3/2, y-1/2, -z+1/2; (iv) -x+3/2, y+1/2, -z+1/2; (v) -x+3/2, y+1/2, -z+3/2; (vi) x+1/2, -y+5/2, z+1/2.]

(a) Perspective view of (II), showing 50% probability displacement ellipsoids for the non-H atoms. The syn-head–tail arrangement of the substituents at the cyclobutane ring is indicated with the aryl group being defined as the head and the carbonyl moiety as the tail. [Symmetry code: (i) -x+1, -y, -z.] (b) Crystal packing of (II) illustrating the intermolecular C—H···O and C—H···F interactions. [Symmetry codes: (iii) x+1/2, -y+1/2, z+1/2; (iv) -x+3/2, y+1/2, -z+1/2; (v) x+1, y+1, z; (vi) x-1/2, -y-1/2, z-1/2].

Comparison of 13C NMR data of (I) and (II), indicating the cyclobutane ring formation. R1 represents 2,6-F2C6H4.
(I) 1,5-Bis(2,6-difluorophenyl)penta-1,4-dien-3-one top
Crystal data top
C17H10F4OF(000) = 624
Mr = 306.25Dx = 1.487 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ynCell parameters from 1695 reflections
a = 7.4793 (6) Åθ = 2.2–26.9°
b = 15.6410 (13) ŵ = 0.13 mm1
c = 12.0962 (11) ÅT = 93 K
β = 104.831 (5)°Needle, yellow
V = 1367.9 (2) Å30.51 × 0.36 × 0.32 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
1849 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.056
Graphite monochromatorθmax = 27.0°, θmin = 2.9°
phi and ω scansh = 98
10280 measured reflectionsk = 1919
2964 independent reflectionsl = 1215
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.059P)2]
where P = (Fo2 + 2Fc2)/3
2964 reflections(Δ/σ)max = 0.001
199 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C17H10F4OV = 1367.9 (2) Å3
Mr = 306.25Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.4793 (6) ŵ = 0.13 mm1
b = 15.6410 (13) ÅT = 93 K
c = 12.0962 (11) Å0.51 × 0.36 × 0.32 mm
β = 104.831 (5)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1849 reflections with I > 2σ(I)
10280 measured reflectionsRint = 0.056
2964 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.116H-atom parameters constrained
S = 0.99Δρmax = 0.22 e Å3
2964 reflectionsΔρmin = 0.25 e Å3
199 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
xyzUiso*/Ueq
O10.95990 (19)0.88009 (9)0.72219 (12)0.0311 (4)
F11.28188 (17)0.62221 (8)0.75771 (10)0.0408 (3)
F20.96248 (16)0.68269 (8)0.37687 (10)0.0375 (3)
F30.62824 (16)1.05282 (7)0.35881 (10)0.0320 (3)
F40.71941 (17)1.15006 (8)0.73743 (10)0.0416 (4)
C11.2344 (3)0.60131 (13)0.64476 (17)0.0279 (5)
C21.3041 (3)0.52711 (14)0.6123 (2)0.0326 (5)
H21.38210.49090.66700.039*
C31.2570 (3)0.50662 (14)0.4971 (2)0.0326 (5)
H31.30430.45570.47240.039*
C41.1418 (3)0.55928 (13)0.41686 (19)0.0298 (5)
H41.10930.54510.33790.036*
C51.0764 (3)0.63254 (13)0.45580 (18)0.0262 (5)
C61.1190 (2)0.65834 (13)0.56930 (16)0.0226 (4)
C71.0584 (2)0.73719 (12)0.61288 (17)0.0237 (4)
H71.09360.74350.69370.028*
C80.9598 (2)0.80204 (12)0.55473 (17)0.0227 (4)
H80.91720.79940.47380.027*
C90.9178 (2)0.87745 (12)0.61683 (17)0.0226 (4)
C100.8211 (2)0.94938 (12)0.54759 (17)0.0230 (4)
H100.79030.94650.46650.028*
C110.7772 (2)1.01847 (12)0.59975 (17)0.0226 (4)
H110.81471.01700.68090.027*
C120.6802 (2)1.09605 (12)0.55061 (16)0.0218 (4)
C130.6070 (2)1.11323 (13)0.43514 (16)0.0229 (4)
C140.5135 (3)1.18678 (13)0.39291 (17)0.0259 (5)
H140.46591.19490.31290.031*
C150.4906 (3)1.24870 (13)0.46984 (18)0.0275 (5)
H150.42611.29990.44230.033*
C160.5603 (3)1.23702 (13)0.58599 (18)0.0297 (5)
H160.54561.27970.63890.036*
C170.6515 (3)1.16191 (13)0.62293 (17)0.0267 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0375 (9)0.0309 (8)0.0231 (8)0.0021 (6)0.0045 (6)0.0002 (6)
F10.0500 (8)0.0379 (8)0.0266 (7)0.0059 (6)0.0045 (6)0.0035 (6)
F20.0419 (8)0.0433 (8)0.0243 (7)0.0150 (6)0.0028 (5)0.0012 (6)
F30.0388 (7)0.0344 (7)0.0223 (7)0.0067 (5)0.0069 (5)0.0022 (5)
F40.0522 (8)0.0454 (8)0.0236 (7)0.0103 (6)0.0034 (6)0.0069 (6)
C10.0238 (11)0.0340 (12)0.0236 (11)0.0050 (8)0.0017 (8)0.0035 (9)
C20.0227 (11)0.0294 (12)0.0414 (14)0.0004 (9)0.0006 (9)0.0059 (10)
C30.0213 (11)0.0308 (12)0.0478 (15)0.0001 (8)0.0125 (10)0.0026 (10)
C40.0264 (11)0.0346 (12)0.0307 (12)0.0007 (9)0.0114 (9)0.0022 (10)
C50.0187 (10)0.0302 (12)0.0294 (12)0.0026 (8)0.0057 (8)0.0057 (9)
C60.0136 (10)0.0280 (11)0.0261 (11)0.0033 (7)0.0052 (8)0.0025 (8)
C70.0165 (10)0.0310 (11)0.0236 (11)0.0067 (8)0.0049 (8)0.0008 (9)
C80.0164 (10)0.0298 (11)0.0219 (11)0.0052 (8)0.0047 (8)0.0003 (8)
C90.0144 (10)0.0290 (11)0.0242 (11)0.0082 (8)0.0048 (8)0.0012 (9)
C100.0188 (10)0.0288 (11)0.0214 (10)0.0052 (8)0.0050 (8)0.0015 (8)
C110.0177 (10)0.0298 (11)0.0209 (10)0.0078 (8)0.0058 (8)0.0007 (8)
C120.0132 (9)0.0269 (11)0.0261 (11)0.0053 (7)0.0068 (8)0.0001 (8)
C130.0186 (10)0.0274 (11)0.0246 (11)0.0069 (8)0.0087 (8)0.0042 (8)
C140.0216 (10)0.0314 (12)0.0250 (11)0.0032 (8)0.0063 (8)0.0025 (9)
C150.0198 (11)0.0265 (11)0.0375 (13)0.0020 (8)0.0098 (9)0.0020 (9)
C160.0287 (12)0.0294 (12)0.0328 (13)0.0035 (9)0.0114 (9)0.0072 (9)
C170.0240 (11)0.0343 (12)0.0208 (11)0.0039 (8)0.0039 (8)0.0053 (9)
Geometric parameters (Å, º) top
O1—C91.233 (2)C8—C91.475 (3)
F1—C11.361 (2)C8—H80.9500
F2—C51.355 (2)C9—C101.477 (3)
F3—C131.359 (2)C10—C111.334 (3)
F4—C171.360 (2)C10—H100.9500
C1—C21.370 (3)C11—C121.460 (3)
C1—C61.404 (3)C11—H110.9500
C2—C31.385 (3)C12—C131.390 (3)
C2—H20.9500C12—C171.403 (3)
C3—C41.391 (3)C13—C141.375 (3)
C3—H30.9500C14—C151.384 (3)
C4—C51.375 (3)C14—H140.9500
C4—H40.9500C15—C161.380 (3)
C5—C61.388 (3)C15—H150.9500
C6—C71.458 (3)C16—C171.374 (3)
C7—C81.342 (3)C16—H160.9500
C7—H70.9500
F1—C1—C2118.09 (18)C8—C9—C10117.24 (17)
F1—C1—C6117.34 (18)C11—C10—C9119.53 (18)
C2—C1—C6124.6 (2)C11—C10—H10120.2
C1—C2—C3117.9 (2)C9—C10—H10120.2
C1—C2—H2121.1C10—C11—C12129.61 (19)
C3—C2—H2121.1C10—C11—H11115.2
C2—C3—C4121.2 (2)C12—C11—H11115.2
C2—C3—H3119.4C13—C12—C17113.64 (17)
C4—C3—H3119.4C13—C12—C11126.63 (18)
C5—C4—C3117.7 (2)C17—C12—C11119.72 (18)
C5—C4—H4121.1F3—C13—C14117.79 (17)
C3—C4—H4121.1F3—C13—C12117.66 (17)
F2—C5—C4117.09 (18)C14—C13—C12124.55 (18)
F2—C5—C6118.20 (17)C13—C14—C15118.33 (19)
C4—C5—C6124.71 (19)C13—C14—H14120.8
C5—C6—C1113.95 (18)C15—C14—H14120.8
C5—C6—C7126.13 (18)C16—C15—C14120.82 (19)
C1—C6—C7119.91 (18)C16—C15—H15119.6
C8—C7—C6129.02 (19)C14—C15—H15119.6
C8—C7—H7115.5C17—C16—C15118.10 (19)
C6—C7—H7115.5C17—C16—H16121.0
C7—C8—C9119.84 (18)C15—C16—H16121.0
C7—C8—H8120.1F4—C17—C16118.19 (18)
C9—C8—H8120.1F4—C17—C12117.25 (18)
O1—C9—C8121.46 (18)C16—C17—C12124.56 (19)
O1—C9—C10121.30 (18)
F1—C1—C2—C3179.28 (18)O1—C9—C10—C110.4 (3)
C6—C1—C2—C30.3 (3)C8—C9—C10—C11178.90 (16)
C1—C2—C3—C40.4 (3)C9—C10—C11—C12178.86 (17)
C2—C3—C4—C50.2 (3)C10—C11—C12—C131.9 (3)
C3—C4—C5—F2179.23 (17)C10—C11—C12—C17179.01 (18)
C3—C4—C5—C60.9 (3)C17—C12—C13—F3179.93 (15)
F2—C5—C6—C1178.63 (17)C11—C12—C13—F30.7 (3)
C4—C5—C6—C11.5 (3)C17—C12—C13—C140.5 (3)
F2—C5—C6—C72.6 (3)C11—C12—C13—C14178.73 (18)
C4—C5—C6—C7177.34 (18)F3—C13—C14—C15179.83 (16)
F1—C1—C6—C5179.83 (17)C12—C13—C14—C150.4 (3)
C2—C1—C6—C51.1 (3)C13—C14—C15—C160.2 (3)
F1—C1—C6—C71.3 (3)C14—C15—C16—C170.6 (3)
C2—C1—C6—C7177.72 (18)C15—C16—C17—F4179.64 (17)
C5—C6—C7—C83.8 (3)C15—C16—C17—C120.4 (3)
C1—C6—C7—C8174.96 (19)C13—C12—C17—F4179.88 (16)
C6—C7—C8—C9178.40 (17)C11—C12—C17—F40.9 (3)
C7—C8—C9—O15.2 (3)C13—C12—C17—C160.0 (3)
C7—C8—C9—C10175.51 (17)C11—C12—C17—C16179.20 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O1i0.952.323.256 (3)168
C16—H16···O1ii0.952.313.255 (3)174
C4—H4···F3iii0.952.583.429 (2)149
C14—H14···F2iv0.952.493.314 (2)145
Symmetry codes: (i) x+5/2, y1/2, z+3/2; (ii) x+3/2, y+1/2, z+3/2; (iii) x+3/2, y1/2, z+1/2; (iv) x+3/2, y+1/2, z+1/2.
(II) (2E,2'E)-1,1'-[2,4-Bis(2,6-difluorophenyl)cyclobutane-1,3-diyl]bis[3-(2,6-difluorophenyl)prop-2-en-1-one] top
Crystal data top
C34H20F8O2F(000) = 624
Mr = 612.50Dx = 1.531 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ynCell parameters from 3206 reflections
a = 7.6508 (2) Åθ = 2.3–33.3°
b = 11.1075 (3) ŵ = 0.13 mm1
c = 15.6428 (3) ÅT = 93 K
β = 91.572 (1)°Splitter, colourless
V = 1328.84 (6) Å30.52 × 0.31 × 0.28 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer
2162 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.019
Graphite monochromatorθmax = 26.0°, θmin = 2.3°
phi and ω scansh = 99
6327 measured reflectionsk = 1311
2576 independent reflectionsl = 1919
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0464P)2 + 0.3848P]
where P = (Fo2 + 2Fc2)/3
2576 reflections(Δ/σ)max = 0.002
199 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.21 e Å3
Crystal data top
C34H20F8O2V = 1328.84 (6) Å3
Mr = 612.50Z = 2
Monoclinic, P21/nMo Kα radiation
a = 7.6508 (2) ŵ = 0.13 mm1
b = 11.1075 (3) ÅT = 93 K
c = 15.6428 (3) Å0.52 × 0.31 × 0.28 mm
β = 91.572 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2162 reflections with I > 2σ(I)
6327 measured reflectionsRint = 0.019
2576 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.090H-atom parameters constrained
S = 1.07Δρmax = 0.25 e Å3
2576 reflectionsΔρmin = 0.21 e Å3
199 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
xyzUiso*/Ueq
O10.55467 (13)0.20126 (9)0.12309 (6)0.0260 (2)
F10.72649 (12)0.25262 (8)0.41178 (5)0.0314 (2)
F20.61684 (12)0.15238 (8)0.33952 (5)0.0317 (2)
F30.18707 (11)0.11219 (8)0.06987 (5)0.0300 (2)
F40.42048 (12)0.26301 (8)0.15542 (5)0.0294 (2)
C10.72379 (18)0.13448 (13)0.43378 (9)0.0240 (3)
C20.7663 (2)0.10367 (15)0.51686 (9)0.0291 (3)
H20.80040.16310.55770.035*
C30.7578 (2)0.01675 (15)0.53920 (9)0.0297 (3)
H30.78680.04050.59620.036*
C40.7074 (2)0.10325 (14)0.47938 (9)0.0287 (3)
H40.69970.18570.49510.034*
C50.66876 (18)0.06713 (13)0.39694 (9)0.0241 (3)
C60.67639 (17)0.05240 (13)0.36965 (8)0.0212 (3)
C70.63852 (17)0.09570 (13)0.28284 (8)0.0210 (3)
H70.62280.18020.27710.025*
C80.62313 (17)0.03201 (13)0.21054 (8)0.0211 (3)
H80.63350.05320.21200.025*
C90.58980 (17)0.09461 (13)0.12804 (8)0.0201 (3)
C100.60172 (18)0.01498 (12)0.05015 (8)0.0196 (3)
H100.71630.02820.04920.023*
C110.44253 (17)0.07528 (12)0.03691 (8)0.0197 (3)
H110.48770.15850.02730.024*
C120.30823 (17)0.07749 (13)0.10586 (8)0.0209 (3)
C130.30348 (18)0.17197 (13)0.16430 (9)0.0232 (3)
C140.1914 (2)0.17843 (15)0.23155 (9)0.0288 (3)
H140.19390.24560.26920.035*
C150.07498 (19)0.08464 (15)0.24295 (9)0.0291 (3)
H150.00420.08740.28870.035*
C160.07356 (19)0.01313 (14)0.18789 (9)0.0270 (3)
H160.00500.07820.19560.032*
C170.18906 (18)0.01376 (13)0.12149 (9)0.0234 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0352 (6)0.0227 (5)0.0202 (5)0.0017 (4)0.0020 (4)0.0007 (4)
F10.0456 (5)0.0243 (5)0.0242 (4)0.0058 (4)0.0025 (4)0.0020 (4)
F20.0485 (5)0.0240 (5)0.0224 (4)0.0019 (4)0.0051 (4)0.0015 (3)
F30.0363 (5)0.0256 (4)0.0286 (4)0.0060 (4)0.0112 (4)0.0044 (4)
F40.0388 (5)0.0242 (4)0.0253 (4)0.0022 (4)0.0051 (4)0.0054 (4)
C10.0248 (7)0.0247 (7)0.0226 (7)0.0001 (6)0.0012 (5)0.0015 (6)
C20.0321 (8)0.0337 (8)0.0212 (7)0.0007 (7)0.0028 (6)0.0049 (6)
C30.0353 (8)0.0357 (9)0.0179 (6)0.0060 (7)0.0026 (6)0.0002 (6)
C40.0358 (8)0.0276 (8)0.0227 (7)0.0042 (6)0.0006 (6)0.0039 (6)
C50.0270 (7)0.0251 (7)0.0202 (7)0.0005 (6)0.0002 (5)0.0043 (6)
C60.0199 (6)0.0258 (7)0.0179 (6)0.0012 (5)0.0022 (5)0.0011 (6)
C70.0201 (6)0.0233 (7)0.0199 (6)0.0006 (5)0.0026 (5)0.0004 (6)
C80.0214 (7)0.0222 (7)0.0196 (6)0.0013 (5)0.0012 (5)0.0001 (6)
C90.0181 (6)0.0237 (7)0.0186 (6)0.0012 (5)0.0033 (5)0.0004 (6)
C100.0218 (6)0.0211 (7)0.0160 (6)0.0001 (5)0.0027 (5)0.0003 (5)
C110.0240 (7)0.0191 (6)0.0161 (6)0.0000 (5)0.0022 (5)0.0007 (5)
C120.0238 (7)0.0235 (7)0.0153 (6)0.0049 (5)0.0010 (5)0.0019 (5)
C130.0274 (7)0.0232 (7)0.0190 (6)0.0036 (6)0.0002 (5)0.0004 (6)
C140.0329 (8)0.0339 (8)0.0196 (7)0.0089 (7)0.0012 (6)0.0052 (6)
C150.0263 (7)0.0419 (9)0.0194 (7)0.0085 (7)0.0066 (6)0.0028 (6)
C160.0238 (7)0.0333 (8)0.0241 (7)0.0024 (6)0.0046 (5)0.0038 (6)
C170.0263 (7)0.0237 (7)0.0205 (6)0.0041 (6)0.0021 (5)0.0007 (6)
Geometric parameters (Å, º) top
O1—C91.2168 (17)C8—H80.9500
F1—C11.3569 (17)C9—C101.5103 (18)
F2—C51.3571 (16)C10—C11i1.5468 (17)
F3—C171.3590 (16)C10—C111.5867 (19)
F4—C131.3601 (17)C10—H101.0000
C1—C21.374 (2)C11—C121.5102 (18)
C1—C61.396 (2)C11—C10i1.5468 (17)
C2—C31.384 (2)C11—H111.0000
C2—H20.9500C12—C171.389 (2)
C3—C41.388 (2)C12—C131.3929 (19)
C3—H30.9500C13—C141.377 (2)
C4—C51.3749 (19)C14—C151.385 (2)
C4—H40.9500C14—H140.9500
C5—C61.396 (2)C15—C161.386 (2)
C6—C71.4620 (18)C15—H150.9500
C7—C81.3365 (19)C16—C171.382 (2)
C7—H70.9500C16—H160.9500
C8—C91.4819 (18)
F1—C1—C2118.41 (13)C11i—C10—C1190.57 (10)
F1—C1—C6117.05 (12)C9—C10—H10111.4
C2—C1—C6124.54 (14)C11i—C10—H10111.4
C1—C2—C3117.88 (14)C11—C10—H10111.4
C1—C2—H2121.1C12—C11—C10i119.94 (11)
C3—C2—H2121.1C12—C11—C10116.87 (11)
C2—C3—C4120.84 (13)C10i—C11—C1089.43 (10)
C2—C3—H3119.6C12—C11—H11109.7
C4—C3—H3119.6C10i—C11—H11109.7
C5—C4—C3118.61 (14)C10—C11—H11109.7
C5—C4—H4120.7C17—C12—C13113.90 (12)
C3—C4—H4120.7C17—C12—C11125.20 (12)
F2—C5—C4117.95 (13)C13—C12—C11120.77 (13)
F2—C5—C6118.36 (12)F4—C13—C14117.68 (13)
C4—C5—C6123.68 (13)F4—C13—C12117.65 (12)
C5—C6—C1114.42 (12)C14—C13—C12124.66 (14)
C5—C6—C7126.00 (13)C13—C14—C15118.37 (14)
C1—C6—C7119.57 (13)C13—C14—H14120.8
C8—C7—C6128.50 (13)C15—C14—H14120.8
C8—C7—H7115.8C14—C15—C16120.22 (13)
C6—C7—H7115.8C14—C15—H15119.9
C7—C8—C9119.85 (13)C16—C15—H15119.9
C7—C8—H8120.1C17—C16—C15118.47 (14)
C9—C8—H8120.1C17—C16—H16120.8
O1—C9—C8123.00 (12)C15—C16—H16120.8
O1—C9—C10122.48 (12)F3—C17—C16116.98 (13)
C8—C9—C10114.52 (12)F3—C17—C12118.62 (12)
C9—C10—C11i116.11 (11)C16—C17—C12124.38 (13)
C9—C10—C11114.34 (11)
F1—C1—C2—C3178.02 (13)C9—C10—C11—C124.49 (17)
C6—C1—C2—C31.5 (2)C11i—C10—C11—C12123.67 (14)
C1—C2—C3—C40.2 (2)C9—C10—C11—C10i119.18 (13)
C2—C3—C4—C51.1 (2)C11i—C10—C11—C10i0.0
C3—C4—C5—F2178.92 (13)C10i—C11—C12—C1735.36 (19)
C3—C4—C5—C60.4 (2)C10—C11—C12—C1770.83 (17)
F2—C5—C6—C1177.38 (12)C10i—C11—C12—C13149.23 (13)
C4—C5—C6—C11.2 (2)C10—C11—C12—C13104.58 (15)
F2—C5—C6—C72.1 (2)C17—C12—C13—F4177.66 (11)
C4—C5—C6—C7179.36 (14)C11—C12—C13—F41.76 (19)
F1—C1—C6—C5177.41 (12)C17—C12—C13—C140.8 (2)
C2—C1—C6—C52.2 (2)C11—C12—C13—C14176.71 (13)
F1—C1—C6—C72.09 (19)F4—C13—C14—C15178.12 (12)
C2—C1—C6—C7178.33 (13)C12—C13—C14—C150.4 (2)
C5—C6—C7—C814.1 (2)C13—C14—C15—C160.4 (2)
C1—C6—C7—C8166.42 (14)C14—C15—C16—C170.7 (2)
C6—C7—C8—C9177.94 (13)C15—C16—C17—F3178.53 (12)
C7—C8—C9—O19.0 (2)C15—C16—C17—C120.2 (2)
C7—C8—C9—C10171.38 (12)C13—C12—C17—F3177.80 (11)
O1—C9—C10—C11i2.97 (19)C11—C12—C17—F32.1 (2)
C8—C9—C10—C11i176.65 (11)C13—C12—C17—C160.5 (2)
O1—C9—C10—C11106.49 (15)C11—C12—C17—C16176.24 (13)
C8—C9—C10—C1173.12 (14)
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O1ii0.952.643.4817 (18)147
C14—H14···O1iii0.952.643.2766 (17)125
C2—H2···F3ii0.952.653.3232 (18)128
C3—H3···F4iv0.952.573.2733 (18)131
C11—H11···F1v1.002.563.2557 (16)127
C10—H10···F1v1.002.543.2452 (16)127
Symmetry codes: (ii) x+1/2, y1/2, z+1/2; (iii) x+1/2, y+1/2, z+1/2; (iv) x+1/2, y+1/2, z+1/2; (v) x+3/2, y+1/2, z+1/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC17H10F4OC34H20F8O2
Mr306.25612.50
Crystal system, space groupMonoclinic, P21/nMonoclinic, P21/n
Temperature (K)9393
a, b, c (Å)7.4793 (6), 15.6410 (13), 12.0962 (11)7.6508 (2), 11.1075 (3), 15.6428 (3)
β (°) 104.831 (5) 91.572 (1)
V3)1367.9 (2)1328.84 (6)
Z42
Radiation typeMo KαMo Kα
µ (mm1)0.130.13
Crystal size (mm)0.51 × 0.36 × 0.320.52 × 0.31 × 0.28
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Bruker SMART CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
10280, 2964, 1849 6327, 2576, 2162
Rint0.0560.019
(sin θ/λ)max1)0.6390.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.116, 0.99 0.032, 0.090, 1.07
No. of reflections29642576
No. of parameters199199
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.22, 0.250.25, 0.21

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Bruker, 2007), SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O1i0.952.323.256 (3)168.3
C16—H16···O1ii0.952.313.255 (3)174.2
C4—H4···F3iii0.952.583.429 (2)148.7
C14—H14···F2iv0.952.493.314 (2)144.5
Symmetry codes: (i) x+5/2, y1/2, z+3/2; (ii) x+3/2, y+1/2, z+3/2; (iii) x+3/2, y1/2, z+1/2; (iv) x+3/2, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O1i0.952.643.4817 (18)147.3
C14—H14···O1ii0.952.643.2766 (17)124.6
C2—H2···F3i0.952.653.3232 (18)128.2
C3—H3···F4iii0.952.573.2733 (18)130.9
C11—H11···F1iv1.002.563.2557 (16)126.6
C10—H10···F1iv1.002.543.2452 (16)126.9
Symmetry codes: (i) x+1/2, y1/2, z+1/2; (ii) x+1/2, y+1/2, z+1/2; (iii) x+1/2, y+1/2, z+1/2; (iv) x+3/2, y+1/2, z+1/2.
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds