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Appl. Sci. 2012, 2(1), 61-99; doi:10.3390/app2010061

Article
Novel Fluorinated Indanone, Tetralone and Naphthone Derivatives: Synthesis and Unique Structural Features
Joseph C. Sloop 1,*, Paul D. Boyle 2, Augustus W. Fountain 3, Cristina Gomez 4, James L. Jackson 5, William F. Pearman 4, Robert D. Schmidt 2 and Jonathan Weyand 4
1
School of Science and Technology, Georgia Gwinnett College, 1000 University Center Lane, Lawrenceville, GA 30043, USA
2
Department of Chemistry, North Carolina State University, P.O. Box 8204, Raleigh, NC 27695, USA; Email: boyle@ncsu.edu (P.D.B.); rdschmid@ncsu.edu (R.D.S.)
3
Edgewood Chemical and Biological Center, 5183 Blackhawk Road, Aberdeen Proving Ground, MD 21010, USA; Email: augustus.w.fountain@us.army.mil
4
Department of Chemistry and Life Science, United States Military Academy, 646 Swift Road, West Point, NY 10996, USA; Email: cristina.c.gomez@us.army.mil (C.G.); William.Pearman@usma.edu (W.F.P.); jon.weyand@us.army.mil (J.W.)
5
US Army Corps of Engineers, 101 West Oglethorpe Avenue, Savannah, GA 31401, USA; Email: James.L.Jackson@usace.army.mil
*
Author to whom correspondence should be addressed; Email: jsloop@ggc.edu; Tel.: +1-678-407-5022; Fax: +1-678-407-5938.
Received: 6 December 2011; in revised form: 12 January 2012 / Accepted: 16 January 2012 /
Published: 1 February 2012

Abstract

: Several fluorinated and trifluoromethylated indanone, tetralone and naphthone derivatives have been prepared via Claisen condensations and selective fluorinations in yields ranging from 22–60%. In addition, we report the synthesis of new, selectively fluorinated bindones in yields ranging from 72–92%. Of particular interest is the fluorination and trifluoroacetylation regiochemistry observed in these fluorinated products. We also note unusual transformations including a novel one pot, dual trifluoroacetylation, trifluoroacetylnaphthone synthesis via a deacetylation as well as an acetyl-trifluoroacetyl group exchange. Solid-state structural features exhibited by these compounds were investigated using crystallographic methods. Crystallographic results, supported by spectroscopic data, show that trifluoroacetylated ketones prefer a chelated cis-enol form whereas fluorinated bindone products exist primarily as the cross-conjugated triketo form.
Keywords:
2-trifluoroacetyl-1,3-Diketone; 1,3,5-triketone; tautomerism; X-ray crystallography

1. Introduction

Molecules which have medicinal, industrial and herbicidal properties are of continued interest to the pharmaceutical, chemical and agrochemical communities. For example, indanone derivatives have anticoagulant properties and are used in elaborating latent fingerprints, bindone variants comprise components of near infrared dyes while certain tetralones and naphthones, ketones similar in structure to those shown in Figure 1, have demonstrated bioactive properties [1,2,3,4,5,6]. Since bioactivity is known to be enhanced in many classes of fluorinated molecules [3,7], it is desirous to prepare fluorine-containing molecules with similar architecture and gain a better understanding of their structure-property relationships.

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Figure 1. Medicinally and industrially important ketones.

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Figure 1. Medicinally and industrially important ketones.
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Previously, we reported the preparation and structure-property relationships of acyclic fluorinated and trifluoromethylated β-diketones, precursors to a variety of heterocyclic molecules [8,9,10]. While the syntheses and properties of these molecules have been investigated thoroughly, the preparation and study of selectively fluorinated, cyclic ketones containing the structural features of the molecules depicted in Figure 1 remains relatively limited [11].

The molecules of interest in this study, shown in Scheme 1, provide this sort of molecular architecture. This paper addresses the design and synthetic approach to prepare these novel molecules, the interesting synthetic results and the unique solid-state structural features that differentiate these molecules.

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Scheme 1. Synthesis of fluorinated ketones.

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Scheme 1. Synthesis of fluorinated ketones.
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2. Experimental Section

2.1. Chemicals

All chemicals were obtained from the Aldrich Chemical Company, Eastman Kodak, or Fisher Chemical Company. All solvents (spectrophotometric grade) and starting materials were checked for purity by mass spectrometry prior to use.

2.2. Instrumentation

Melting points were obtained on a Mel-Temp melting point apparatus and are uncorrected. NMR data were collected using a Varian VXR-200 spectrometer with a broad band probe operating at 200.0 MHz for 1H, 188.2 MHz for 19F and 50.3 MHz for 13C, and/or a Brüker Avance 300 spectrometer operating at 300.0 MHz for 1H, 282.0 MHz for 19F and 75.4 MHz for 13C. Unless otherwise noted, CDCl3 was used as the solvent and internal standard for 1H and 13C NMR experiments while CFCl3 served as the internal standard for 19F NMR experiments. All X-ray measurements were made on a Bruker-Nonius X8 Apex2 diffractometer. See the appendix for complete crystallographic experimental details.

2.3. General Procedure for the Preparation of Trifluoromethyl-β–Diketones and Triketones [12]

A 100 mL round bottom flask equipped with a magnetic stirrer is charged with 50 mL diethyl ether and 60 mmol of sodium methoxide is added slowly. Then, 1eq (60 mmol) of trifluoromethyl ethyl acetate is added dropwise slowly while stirring. After 5 minutes, 1eq (60 mmol) of the ketone is added dropwise and stirred overnight at room temperature under a calcium chloride drying tube. The resulting solution is evaporated to dryness under reduced pressure and the solid residue dissolved in 30 mL 3M sulfuric acid. This solution is extracted with ether, and the organic layer dried over Na2SO4. The solvent is evaporated under reduced pressure and the crude diketone purified by radial chromatography.

2.4. General Procedure for the Preparation of Selectively Fluorinated Ketones [10,13]

A 100 mL round bottom flask equipped with a magnetic stirrer is charged with 40 mL CH3CN and the ketone (1 eq: 1–10 mmol). Then, Selectfluor® (1–3 eq (3–30 mmol)) dissolved in 30 mL CH3CN is added slowly while stirring. The solution is either allowed to stir at room temperature or refluxed as required. Times range from 10–30 h. The resulting solution is evaporated to dryness under reduced pressure and the solid residue taken up in distilled water. This solution is extracted with CH2Cl2, and the organic layer dried over Na2SO4. The solvent is evaporated under reduced pressure and the crude fluorinated ketone purified by radial chromatography.

2-fluoro-1,3-indanedione (1b). This compound was obtained in 60% yield as pale yellow crystals (EtOH), m.p. 97–99 °C lit [14] (m.p. 96–98 °C). NMR: 1H: δ 5.4 (d, 1JH-F = 51.0 Hz, 1H), 7.65–8.22 (m, 4H). 13C: δ 90.1 (d, 1JC-F = 211.2 Hz, CF), 125.3, 138.9, 141.9, 193.5 (d, 2JC-F = 24.0 Hz, C-CF). 19F: δ −207.3 (d, 1JF-H = 51.1 Hz, 1F). HRMS (ESI+) Calcd. for C9H5FO2: 164.02740. Found: 164.027580.

2,2-difluoro-1,3-indanedione (1c). This compound was obtained in 60% yield from fluorination of 1b as described in the general procedure above as yellowish-brown crystals (EtOH), m.p. 116–117 °C, lit [15] (m.p. 117–118 °C). NMR: 1H: δ 8.0–8.15 (m, 4H). 13C: δ 104.0 (t, 1JC-F = 264 Hz, CF2), 128.8, 138.2, 139.3 (t, 3JC-F = 4.3 Hz), 185.8(t, 2JC-F = 24.0Hz, C-CF2). 19F: δ −125.9 (s, 2F).

[Δ1,2'-Biindan]-1',3,3'-trione (1d). This compound was obtained in 72% yield as orange crystals (EtOH), m.p. 207–209 °C, lit [16] (m.p. 205–208 °C). NMR: 1H: δ 4.17 (s, 2H), 7.74–8.04 (m, 8H), 9.50 (d, J = 7.8 Hz, 1H). 13C: δ 43.4, 123.0, 123.4, 123.5, 125.8, 131.7, 134.2, 135.3, 135.4, 140.4, 141.2, 141.6, 145.9, 155.4, 189.5, 191.0, 201.2.

[Δ1,2'-Biindan]-2-fluoro-1',3,3'-trione (1e). This compound was obtained was obtained in 85% yield from fluorination of 1d as described in the general procedure above as orange crystals (EtOH), m.p. 165–168 °C (dec). NMR: 1H: δ 6.45 (d, 1JH-F = 46.1 Hz, 1H), 7.75–8.20 (m, 7H), 9.50 (d, J = 7.7 Hz, 1H). 13C: δ 70.8 (d, 1JC-F = 194 Hz, CF), 125.4, 126.6, 129.3, 130.1, 132.0, 137.7, 138.5, 166.3, 189.3, 191.2, 204.1 (d, 2JC-F = 24 Hz, C-CF). 19F: δ −182.4 (d, 1JF-H = 46.0 Hz, 1F). Analysis calcd for C18H9FO3: C, 73.97, H, 3.10. Found: C, 74.06, H, 3.21.

2-fluoro-2-(2’-fluoro-3'-oxoindenyl)-1,3-indanedione (1f). This compound was obtained in 92% yield from fluorination of 1e as described in the general procedure above as yellow crystals (EtOH), m.p. 126–129 °C. NMR: 1H: 7.8–8.25 (7H, m), 9.53 (1H, d, J = 6.9 Hz). 13C: δ 89.9, 125.1, 126.3, 129.5, 130.0, 132.2, 137.1, 138.0 (d, 1JC-F = 254 Hz, CF), 166.1, 185.9, 189.1. 19F: δ −137.3 (s, 1F), −176.7 (s, 1F). HRMS (ESI+) calcd for C18H8F2O3: 310.04415. Found: 310.04415.

1-trifluoroacetyl-2-indanone (2b). This compound was obtained in 52% yield as a brown oil. NMR: 1H: δ 3.73 (2H, s), 7.29 (2H, m), 7.60 (2H, m), 14.19 (1H, bs), 13C: δ 40.9, 111.5, 120.4 (CF3, q, 1JC-F = 277 Hz), 122.9, 123.0, 124.9, 127.7, 128.1, 128.8, 129.6, 154.5 (C-CF3, q, 2JC-F = 37 Hz), 203.0. 19F: −68.59 (s, 3F). Analysis calcd for C11H7F3O2: C, 57.90, H, 3.09. Found: C, 58.04, H, 3.02.

1,3-ditrifluoroacetyl-2-indanone (2c). To 30 mL dry Et2O in a round bottom flask equipped with a magnetic stirrer is added sodium methoxide (0.449 g, 8.32 mmol) all at once. Then, trifluoromethyl ethyl acetate (0.903 mL, 7.57 mmol) is added dropwise slowly while stirring. After 5 minutes, 2-indanone (1.00 g, 7.57 mmol) dissolved in 20 mL dry Et2O is added dropwise and stirred overnight at room temperature under a calcium chloride drying tube. After 24 h, another equivalent of trifluoromethyl ethyl acetate is added dropwise and stirred overnight at room temperature under a calcium chloride drying tube. The reaction mixture is acidifed with 30 mL 3M sulfuric acid. The organic layer was separated, washed with deionized water, and the organic layer dried over Na2SO4. The solvent was evaporated under reduced pressure, providing a yellow solid, which when recrystallized, yielded yellow crystals (cyclohexane), in 42% yield, m.p. 111–113 °C. NMR: 1H: δ 7.34 (2H, m), 7.65 (2H, m), 13.50 (2H, bs). 13C: δ 111.5, 118.4 (CF3, q, 1JC-F = 273 Hz), 119.6, 122.9, 126.7, 128.4, 128.9, 130.2, 168.5 (C-CF3, q, 2JC-F = 35 Hz), 177.0. 19F: −68.53 (s, 3F). HRMS (ESI+) calcd for C13H6F6O3: 324.02211, found: 324.02158.

3-trifluoroacetyl-2-tetralone (3b) and 1-trifluoroacetyl-2-tetralone (3c). These compounds were obtained as a 4:3 mixture of 3b:3c. Radial chromatography (100% CH2Cl2–50/50 CH2Cl2/MeOH) afforded two product fractions. Fraction 1: 3b as orange crystals (hexane), in 40% yield, m.p. 123–126 °C. NMR: 1H: δ, 3.76 (2H, s), 3.81 (2H, s), 7.25–8.05 (4H, m), 15.01 (1H, bs). 13C: δ 27.8, 38.3, 103.7, 117.5 (CF3, q, 1JC-F = 281 Hz), 127.1, 127.3, 127.8, 127.9, 130.5, 133.4, 157.3, 174.8 (C-CF3, q, 2JC-F = 35 Hz), 191.0. 19F (C6F6 ext. std.): δ−70.62 (s, 3F). HRMS (ESI+) calcd for C12H9F3O2: 242.04470, found: 242.04436. Fraction 2: 3c (30%) as an orange solid, m.p. 88–91 °C. 3c: NMR: 1H: δ 2.72 (2H, t, 2J = 1.9 Hz), 3.01 (2H, t, 2J = 1.9 Hz), 7.25 (4H, m), 14.98 (1H, bs). 13C: δ 25.0, 30.3, 102.9, 118.6 (CF3, q, 1JC-F = 282 Hz), 126.6, 126.9, 127.3, 128.1, 130.2, 133.8, 158.1, 175.4 (C-CF3, q, 2JC-F = 35 Hz), 189.1. 19F (C6F6 ext. std.): δ−67.70 (s, 3F). HRMS (ESI+) calcd for C12H9F3O2: 242.04470, found: 242.04442.

3-trifluoroacetyl-2-naphthol (3d). A round bottom flask equipped with a magnetic stirrer containing 30 mL dry Et2O is charged with 1 equivalent NaOCH3. Then, 1 equivalent ethyl trifluoroacetate is added dropwise slowly and stirred for 15 min. To this solution is added a 4:3 mixture of compounds 3b:3c dissolved in 20 mL Et2O. The reaction mixture is stirred overnight at room temperature under a calcium chloride drying tube. The solvent is removed under reduced pressure while heating at 60 °C for 20 min. The solid residue is acidified with 30 mL 3M sulfuric acid and extracted with 3–15 mL portions of Et2O. The organic layers were combined, washed with deionized water, and the organic layer dried over Na2SO4. The solvent was evaporated under reduced pressure, providing a orange solid, which when subjected to radial chromatography, gave a fraction which upon recrystallization, yielded pale, orange crystals (CH2Cl2), 3d, in 45% yield, m.p. 80–83 °C. An additional fraction was collected which contained unreacted 3b and 3c. 3d: NMR: 1H: δ, 7.25–8.05 (6H, m), 14.83 (1H, bs). 13C: δ 119.3 (CF3, q, 1JC-F = 284 Hz), 124.9, 125.4, 126.9, 129.9, 130.1, 130.4, 131.4, 135.1, 139.1, 157.3, 184.6 (C-CF3, q, 2JC-F = 35 Hz). 19F (C6F6 ext. std.): δ −74.25 (s, 3F). Analysis calcd for C12H7F3O2: C, 60.01, H, 2.94. Found: C, 60.13, H, 2.88.

4,4,4-trifluoro-1-(1-oxotetrahydronaphthyl)-1,3-butanedione (4b) [17]. A 100 mL round bottom flask is charged with 50 mL dry Et2O, 5 mL dry diisopropylamine, equipped with a magnetic stir bar and placed under N2 at 0 °C. To this is added LDA (6.0 mL, 0.0120 mol) and stirred for fifteen minutes. Then, a solution of 4a (0.752 g, 0.004 mol) in 15 mL dry Et2O is added dropwise slowly via syringe. After 8 h, ethyl trifluoroacetate (0.96 mL, 0.008 mol) is delivered dropwise slowly via syringe, the reaction mixture is stirred overnight and allowed to warm to rt. A third equivalent of ethyl trifluoroacetate (0.004 mol) is added after 24 hours and the solution is left to stir again overnight. The reaction mixture is acidifed with 30 mL 3M sulfuric acid. The organic layer was separated, washed with deionized water, and the organic layer dried over Na2SO4. The solvent was evaporated under reduced pressure, and subjected to radial chromatography. After recrystallization from cyclohexane, 4b was obtained as reddish-brown crystals in 27% yield, mp 133–135 °C. 4b: NMR: 1H: δ 2.85 (2H, t, 7.6 Hz), 2.93 (2H, t, 7.6 Hz), 6.76 (s, 1H), 7.37–7.77 (4H, m), 15.68 (2H, bs). 13C: δ 20.9, 22.7, 104.6, 118.4 (CF3, q, 1JC-F = 270 Hz), 125.9, 126.8, 127.3, 127.4, 128.2, 128.5, 128.6, 129.9, 133.9, 142.8, 177.0 (C-CF3, q, 2JC-F = 36 Hz), 182.2. 19F (C6F6 ext. std.): δ −72.04 (s, 3F). Analysis calcd for C14H11F3O3: C, 59.16, H, 3.90. Found: C, 58.99, H, 4.01.

2-trifluoroacetyl-1-tetralone (4c). This compound was obtained as off-white crystals, 4c, in 53% yield, m.p. 50–52 °C lit [18] (m.p. 51–52 °C). 4c: NMR: 1H: δ 2.75 (2H, t, 9.0 Hz), 2.88 (2H, t, 9.0 Hz), 7.16–7.87 (4H, m), 15.62 (1H, bs). 13C: δ 21.0, 27.8, 38.3, 103.7, 117.5 (CF3, q, 1JC-F = 285 Hz), 127.1, 127.3, 127.8, 127.9, 130.5, 133.4, 157.3, 174.8 (C-CF3, q, 2JC-F = 35 Hz), 185.0. 19F (C6F6 ext. std.): δ −70.61 (s, 3F). HRMS (ESI+) calcd for C12H9F3O2: 242.04470, found: 242.04436.

4,4,4-trifluoro-1-(1-hydroxynaphthyl)-1,3-butanedione (5b) [17]. A 100 mL RBF equipped with a magnetic stir bar is charged with 50 mL dry Et2O, 5 mL dry diisopropylamine (DIPA) and placed under N2 at 0 °C. To this is added LDA (6.0 mL, 0.0120 mol) and stirred for fifteen minutes. Then, a solution of 5a (0.740 g, 0.004 mol) in 15 mL dry Et2O is added dropwise slowly via syringe. After 8 h, ethyl trifluoroacetate (0.96 mL, 0.008 mol) is delivered dropwise slowly via syringe and the reaction mixture is stirred overnight and allowed to warm to rt. After 24 h, another equivalent of ethyl trifluoroacetate (0.46 mL, 0.004 mol) is added all at once. The reaction is stirred for an additional 24 h. The reaction mixture is acidifed with 30 mL 3M sulfuric acid. The organic layer was separated, washed with deionized water, and the organic layer dried over Na2SO4. The solvent was evaporated under reduced pressure, and subjected to radial chromatography. After recrystallization (cyclohexane) 5b was obtained as brown crystals, in 22% yield, m.p. 154–157 °C. 5b: NMR: 1H: δ 6.90 (s, 1H), 7.51–8.50 (6H, m), 14.44 (1H, bs), 15.70 (1H, bs). 13C: δ 111.9, 115.7 (CF3, q, 1JC-F = 271 Hz), 127.1, 127.3, 127.8, 127.9, 130.5, 133.4, 157.3, 174.8 (C-CF3, q, 2JC-F = 35 Hz), 185.0. 19F (C6F6 ext. std.): δ −71.60 (s, 3F). Analysis calcd for C14H9F3O3: C, 59.59, H, 3.21. Found: C, 59.86, H, 3.16.

2-acetyl-4-fluoro-1-naphthol (5c) and 2-acetyl-3-fluoro-1-naphthol (5d). These compounds were obtained as a 5:1 mixture of 5c:5d. Radial chromatography (100% CH2Cl2–50/50 CH2Cl2/MeOH) afforded 5c as brown crystals (51%, m.p. 93–95 °C) and 5d as a tan solid (13%, m.p. 88–91 °C). 5c: NMR: 1H: δ 2.71 (3H, s), 7.31–8.48 (5H, m), 14.01 (1H, bs). 13C: δ 26.9, 113.1, 118.3, 124.9, 126.0, 127.4, 130.1, 137.4, 150.5 (Ar-F, d, 1JC-F = 243 Hz), 162.4, 204.2. 19F (C6F6 ext. std.): δ −134.0 (s, 1F). Analysis calcd for C12H9FO2: C, 70.59, H, 4.44. Found: C, 70.77, H, 4.31. 5d: NMR: 1H: δ 2.63 (3H, s), 7.40–8.00 (5H, m), 13.82 (1H, bs). 13C: δ 27.6, 111.3, 120.3, 124.6, 125.1, 126.9, 128.6, 130.2, 130.3, 155.5 (Ar-F, d, 1JC-F = 244 Hz), 158.7, 203.4. 19F (C6F6 ext. std.): δ −134.2 (s, 1F). Analysis calcd for C12H9FO2: C, 70.59, H, 4.44. Found: C, 70.44, H, 4.49.

3. Results and Discussion

3.1. Synthesis

Compounds 1a-5a are commercially available and were used without further purification. Compounds 1b and 1c have been previously described, but were prepared according to a different method [14,15]. Compound 1d is known and was synthesized via a previously described method [12,16]. The remaining compounds were prepared using a modified Claisen condensation or direct fluorination with Selectfluor® [10,12,13,18,19]. See Scheme 1.

Recent work by our group showed that regioselective monofluorination and geminal difluorination of acyclic β-diketones could be effected with Selectfluor® under mild conditions without the necessity of specialized glassware or safety precautions [10,14,15]. The current synthetic investigation sought to take advantage of this earlier work by probing Selectfluor®’s efficiency and effectiveness in the mono- and difluorination of 1,3-indanedione and bindone. Our efforts revealed some unexpected findings. The monofluorination of 1a proceeded with little difficulty to give 2-fluoro-1,3-indanedione (1b) in the diketonic form (as evidenced by a doublet signal (JF-H = 51.1 Hz) in the 19F NMR at −207.3 ppm), albeit in slightly lower yield compared to fluorination achieved with 5% F2 in N2 [10]. Diketone 1b was also successfully fluorinated (as evidenced by a singlet signal in the 19F NMR at −125.9 ppm), delivering the geminally difluorinated product 1c in good overall yield.

We then examined whether bindone, the aldol self-condensation product of 1,3-indanedione, would react similarly to treatment with Selectfluor®. As expected, monofluorination was achieved in high yield to give 1e as an enantiomeric triketone pair (19F NMR: −182.4 ppm, JF-H = 46.0 Hz), but the site of fluorination was the α-carbon adjacent to the isolated ketone rather than fluorination between the 1,3-diketone residue. Subsequent fluorination of 1e likewise yielded interesting results. Particularly noteworthy were the fluorination regioselectivity and alkene rearrangement observed during the formation of triketone 1f. We expected an outcome similar to the fluorination of 1b, but the occurrence of two distinct signals in the 19F NMR at −137.3 ppm and −176.7 ppm ruled out geminal difluorination. Evidently, the alkene in 1e retains sufficient nucleophilic nature to permit electrophilic fluorination between the β-dicarbonyl residue. This addition, coupled with a concomitant E1-like elimination leads to 1f, rather than formation of [Δ1,2'-Biindan]-2,2-difluoro-1',3,3'-trione, shown in Scheme 1.

While preparing 2b and 2c, the previously undescribed one-pot, twin trifluoroacetylation of 2-indanone gave the dual exocyclic enol 2c in moderate yield (confirmed by the presence of a single 19F NMR resonance at −68.5 ppm) and no 2c, Figure 2. In this case, the ethoxide base present following the condensation apparently deprotonates the unsubstituted benzylic α-hydrogen (H3) rather than the more acidic α-hydrogen H1.

There are several possible explanations for the formation of 2c and the failure to obtain 2c. The most plausible scenario involves initial formation of 2c. Given the basic reaction conditions, however, we surmise that upon attachment of the second COCF3 group, 2c may undergo nucleophilic acyl substitution by ethoxide, reverting 2c back to enolate A. A second possibility for the failure to obtain 2c may be larger steric demands in the transition state leading to enolate A formation relative to that leading to enolate B. Finally, a base-promoted tautomerization from enolate A to enolate B could occur before formation of 2c, ultimately leading to 2c.

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Figure 2. Formation of 1,3-ditrifluoroacetyl-2-indanone (2c).

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Figure 2. Formation of 1,3-ditrifluoroacetyl-2-indanone (2c).
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We then attempted a similar strategy with β-tetralone (3a) to ascertain whether this ditrifluoroacetylation methodology could be generalized to other ketones with two acidic α-hydrogen sets. Sequential treatment of 3a with two equivalents of ethyl trifluoroacetate followed by neutralization at room temperature led to a mixture of the 3- and 1-trifluoroacetyl-2-tetralone endocyclic enols 3b and 3c, respectively; the formation of 1,3-ditrifluoroacetyl-2-tetralone was not observed. Assignment of the endocyclic enolic structures was based on the observation of a single 19F NMR resonance at −70.6 ppm for 3b and −67.7 ppm for 3c. When the reaction workup conditions were modified by subjecting the enols 3b and 3c to an additional equivalent of base and ethyl trifluoroacetate followed by in vacuo removal of solvent at elevated temperature, we were surprised to find that aromatization occurred to give the trifluoroacetylated naphthol 3d in moderate overall yield. Figure 3 depicts a plausible route to naphthol 3d. We surmise that deprotonation of the less sterically hindered α-hydrogen enroute to 3b occurs rather than abstraction of the more acidic, benzylic α-hydrogen. Detrifluoroacetylation of triketone I followed by tautomerization of diketone II under acidic workup provides naphthol 3d.

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Figure 3. Formation of 3-trifluoroacetyl-2-tetralone (3b) and 3-trifluoroacetyl-2-naphthol (3d).

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Figure 3. Formation of 3-trifluoroacetyl-2-tetralone (3b) and 3-trifluoroacetyl-2-naphthol (3d).
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Application of Light and Hauser’s method to 4a and 5a produced the cross-conjugated, dienolic 1,3,5-triketones 4b and 5b in modest yields [17]. Assignment of the enolic structures was based on a combination of resonances found in their NMR spectra—(4b) 1H: an alkene proton signal @ 6.76 ppm (1H), a broad, unresolvable singlet corresponding to the enol protons @ 15.68 ppm (2H) and 19F: a singlet @ −72.0 ppm (3F); for (5b) 1H: an alkene proton signal @ 6.90 ppm (1H), a singlet corresponding to the phenolic enol proton @ 14.44 (1H), a broader singlet @ 15.68 ppm (1H) corresponding to the enol adjacent to the CF3 group and 19F: a singlet @ −71.6 ppm (3F). Addition of D2O to the NMR samples of 4b and 5b resulted in rapid diminuation of the exchangeable enolic protons in the 1H NMR. Increasing the molar ratio of ethyl trifluoroacetate:diketone to >2:1, although necessary for triketone product formation, also led to O-trifluoroacetylated by-products. Fortunately, these were easily separated by chromatography from the desired 1,3,5-triketones. Additionally, we found that when 4a was subjected to standard Claisen reaction conditions, an unintended acetyl-trifluoroacetyl group exchange occurred to give 2-trifluoroacetyl-1-tetralone (4c) in good yield along with, to our surprise, naphthol 5a. A process similar to the detrifluoroacetylation depicted in Figure 2 may be operating in these cases as well.

Treatment of 5a with Selectfluor® demonstrated the fluorination preference of activated aromatic substrates over acetyl groups [19,20,21]. The fluorinated naphthols 5c and 5d were achieved in good overall yield and a 5:1 ratio of the para:meta isomers, respectively. Ring fluorination was confirmed by the observation of resonances in the 19F NMR spectra as singlets: −134.0 ppm (1F) and −134.2 ppm (1F) for 5c and 5d, respectively. Preferential para fluorination is in accord with the o-p directing ability of the hydroxyl group. Use of up to 5 equivalents of Selectfluor® to effect fluorination at the acetyl carbon provided only the monofluorinated naphthols 5c and 5d.

3.2. Solid State Structural Features: X-ray Crystallography

Several of the target molecules (1d, 2c, 3c and 4c) were examined by x-ray crystallography. Crystal data and structure refinement information for 1d and 2c are recorded in Figure 4 and Table 1 while Figure 5 and Table 2 contain data for 3d and 4c. Critical bond information is listed in Table 3. The crystallographic information files for these molecules have been uploaded to the Cambridge Crystallographic Data Center and have the following control numbers: 1d: 854704, 2c: 854697, 3d: 854705 and 4c: 854706.

Applsci 02 00061 g004 1024
Figure 4. ORTEP drawings of 1d and 2c. Ellipsoids are at the 50% probabilitylevel and hydrogen atoms were drawn with arbitrary radii for clarity.

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Figure 4. ORTEP drawings of 1d and 2c. Ellipsoids are at the 50% probabilitylevel and hydrogen atoms were drawn with arbitrary radii for clarity.
Applsci 02 00061 g004 1024
Table Table 1. Crystal data and structure refinement for 1d and 2c.

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Table 1. Crystal data and structure refinement for 1d and 2c.
Compound1d2c
FormulaC18H10O3C13H6F6O3
Formula Weight (g/mol)274.26324.18
Crystal Dimensions (mm)0.30 × 0.24 × 0.201.20 × 0.10 × 0.06
Crystal Color and Habitclear prismyellow needle
Crystal Systemorthorhombicmonoclinic
Space GroupF d d 2P 21/c
Temperature, K173173
a, Å18.0996(6)
b, Å 20.9271(7)18.6978(12)
c, Å 26.0789(8)13.8431(9)
α,°90.0090.0
β,°90.0098.964(3)
Compound1d2c
γ,°90.0090.0
V, Å39878.0(6)1218.11(14)
Reflections to determine final unit cell99759959
2θ range, °5.0, 56.845.28–57.7
Z324
F(000)4544648.71
ρ (g/cm)1.4751.768
λ, Å, (MoKα)0.710700.71073
μ, (cm−1)0.1010.18
Reflections collected10314626516
Unique reflections63603195
Rmerge0.04030.027
Cut off Threshold Expression>2sigma(I)Inet > 1.0sigma(Inet)
Refinement methodfull matrix least-sqs using F2full matrix least-sqs using F
Weighting Scheme1/[sigma2 (Fo2) + (0.0555P)2+3.0465P] where P = (Fo2 + 2Fc2)/31/(sigma2 (F) + 0.0005F2)
R1a0.03420.038
wR20.0846 b0.053 c
R1 (all data)0.04000.046
wR2 (all data)0.08800.054
GOF1.038 d1.74 e

a R1 = Σ(|Fo| − |Fc|)/Σ Fo; b wR2 = [Σ(w(Fo2 − Fc2)2)/Σ(wFo4)]½; c wR2 = [Σ(w(Fo2 − Fc2)2)/Σ(wFo4)]½; d GOF = [Σ(w(Fo2 − Fc2)2)/(# reflns − # params)]½; e GOF = [Σ(w( Fo2 − Fc2)2)/(No. reflns. No. params.)]½.

Applsci 02 00061 g005 1024
Figure 5. ORTEP drawings of 3d and 4c. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.

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Figure 5. ORTEP drawings of 3d and 4c. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.
Applsci 02 00061 g005 1024
Table Table 2. Crystal data and structure refinement for 3d and 4c.

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Table 2. Crystal data and structure refinement for 3d and 4c.
Compound3d4c
FormulaC12H7F3O2C12H9F3O2
Formula Weight (g/mol)240.18242.19
crystal size (mm)0.46 × 0.08 × 0.040.38 × 0.28 × 0.04
crystal color/shapeorange yellow needlecolourless plate
cryst systorthorhombictriclinic
space groupP n a 21P-1
temp, K110110
a, Å13.5923(5)7.3528(2)
b, Å 14.9695(5)7.9165(2)
c, Å 4.8381(2)9.7991(2)
α,°90.0073.0533(11)
β,°90.0085.3968(12)
γ,°90.0068.3581(11)
V, Å3984.41(6)506.92(2)
Reflections to final unit cell58596416
2θ range, °5.44–52.665.78–71.38
Z42
F(000)488248
ρ (g/cm)1.6211.587
λ, Å, (MoKα)0.710700.71073
μ, (cm1)0.1470.143
Reflections collected2156820479
Unique reflections26324691
Rmerge0.04440.0265
Cut off Threshold Expression>2sigma(I)>2sigma(I)
refinement methodfull matrix least-sqs using F2full matrix least-sqs using F2
Weighting Scheme1/[sigma2 (Fo2) + (0.0406P)2 + 0.0000P] where P = (Fo2 + 2Fc2)/31/[sigma2 (Fo2) + (0.0707P)2 + 0.0436P] where P = (Fo2 + 2Fc2)/3
R1a0.03700.0382
wR20.07120.1082
R1 (all data)b0.05380.0525
wR2 (all data)a0.07620.1220
GOF1.0351.048

a R1 = Σ(|Fo − Fc|)/Σ Fo, wR2 = [Σ(w(Fo − Fc)2)/Σ(Fo2)]½, GOF = [Σ(w(Fo − Fc)2)/(No. reflns. − No. params.)]½; b R1 = Σ(|Fo| − |Fc|)/Σ Fo, wR2 = [Σ(w(Fo2 − Fc2)2)/Σ(wFo4)]½, GOF = [Σ(w(Fo2 − Fc2)2)/(No. reflns. − No. params.)]½

Table Table 3. Selected interatomic distances and bond lengths of 1d, 2c, 3d and 4c.

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Table 3. Selected interatomic distances and bond lengths of 1d, 2c, 3d and 4c.
Interatomic Distances (Å)Bond Lengths (Å)Dihedral Applsci 02 00061 i002 (◦)
O….OO….HO-HC-OC-C
1dNANANAC1A-O1AC3A-C10AO3-C18-C10-C3
1.2143(17)1.3574(19)-2.4(11)
C11A-O2A
1.2212(17)
C18A-O3A
1.2143(17)
2cO1….O2O1….H2O2-H2C1-O1C1-C2O1-C1-C2-C10
2.5781(13)1.75(2)0.90(2)1.2576(15)1.4547(15)-1.91(11)
O1….O3O1….H3O3-H3C10-O2C2-C10
2.5926(14)1.81(2)0.88(2)1.3308(15)1.3593(17)
C12-O3C9-C12
1.3242(17)1.3602(17)
3dO1….O2O2….HO1-HC1-O1C1-C2O1-C1-C2-C11
2.6142(17)1.75(3)0.97(3)1.3588(19)1.438(2)1.9(2)
C11-O2C2-C11
1.2199(18)1.459(2)
4cO1….O2O2….HO1-H C1-O1C1-C2O1-C1-C2-C11
2.5063(9)1.72(2)0.855(19)1.3215(9)1.3895(10)-2.04(11)
C11-O2C2-C11
1.2476(10)1.4193(10)

In the case of compound 1d, the small O3-C10-C18-C3 dihedral angle of −2.4° shows bindone to be nearly planar across the ring bridge in the solid state. The C-O and C3-C10 bond lengths are consistent with those of typical carbonyls and alkenes, respectively and identify 1d as a cross-conjugated triketone in the solid state. For 2c, x-ray crystallography confirms the preference of a previously unreported structure in the solid state: a planar, exocyclic dienol shown in Figure 4. The weak intramolecular H-bonding normally observed in cyclic triketones is clearly supported for 2c by the interatomic O….H-O distances of 1.75Å and 1.81Å and very short O-H bond lengths of 0.88Å and 0.90Å [11,22]. The small O1-C1-C2-C10 dihedral angle of −1.91° attests to the planar nature of the cyclopentanone residue.

Likewise, 3-trifluoroacetyl-2-naphthol (3d) and 2-trifluoroacetyl-1-tetralone (4c) show trends consistent with a single endocyclic cis-enol tautomer having weak intramolecular H-bonding, e.g., interatomic O….H-O distances >1.7Å, O-H bond lengths < 1.0Å and small O1-C1-C2-C11 dihedral angles. For 3d, the aromatic ring introduces an additional structural constraint prohibiting tautomerism to either the diketo form or any other enolic structure.

Spectral data provided in the experimental section supports the solid-state structural data presented herein [8,9,10,23,24,25,26,27,28]. A detailed examination of the absorption, vibrational and magnetic resonance spectroscopy of these molecules is underway to discern the keto-enol and enol-enol behavior of these di- and triketones in various solvent systems and where applicable in the solid-state and/or neat liquid. Those results, along with a comparative ab initio component, will be presented in a future communication.

Acknowledgments

The views expressed in this academic research paper are those of the authors and do not necessarily reflect the official policy or position of the US Government, the Department of Defense, or any of its agencies. The authors wish to thank the NCSU X-ray Facility for crystallographic support and NCSU Mass Spectrometry Facility for high resolution mass spectroscopic support of this work. The authors also wish to thank the Department of Chemistry of NCSU and the State of North Carolina for funding the purchase of the Apex2 diffractometer. Joseph C. Sloop thanks the USMA (C&LS-02-07) and GGC SST Faculty Research Funds for providing financial support for this work.

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Appendix. X-Ray Experimental Procedures and Data

1. Compound 1d

Experimental for C18H10O3 (1d)

Data Collection and Processing. The sample 1d was submitted by Joseph Sloop of the Sloop research group at Georgia Gwinnett College. The sample was mounted on a nylon loop with a small amount of NVH immersion oil. All X-ray measurements were made on a Bruker-Nonius X8 Apex2 diffractometer at a temperature of 173 K. The unit cell dimensions were determined from a symmetry constrained fit of 9975 reflections with 5.0° < 2θ < 56.84°. The data collection strategy was a number of ω and ϕ scans which collected data up to 58.24° (2θ). The frame integration was performed using SAINT [29]. The resulting raw data was scaled and absorption corrected using a multi-scan averaging of symmetry equivalent data using SADABS [30].

Structure Solution and Refinement. The structure was solved by direct methods using the SIR92 program [31]. All non-hydrogen atoms were obtained from the initial E-map. The hydrogen atoms were introduced at idealized positions and were allowed to refine isotropically. The structural model was fit to the data using full matrix least-squares based on F2. The calculated structure factors included corrections for anomalous dispersion from the usual tabulation. The structure was refined using the XL program from SHELXTL [32], graphic plots were produced using the NRCVAX crystallographic program suite. Additional information and other relevant literature references can be found in the reference section of the Facility’s Web page (http://www.xray.ncsu.edu).

Applsci 02 00061 g006 1024
Figure 6. ORTEP drawing of 1d molecule A showing naming and numbering scheme. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.

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Figure 6. ORTEP drawing of 1d molecule A showing naming and numbering scheme. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.
Applsci 02 00061 g006 1024
Applsci 02 00061 g007 1024
Figure 7. ORTEP drawing of 1d molecule A. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.

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Figure 7. ORTEP drawing of 1d molecule A. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.
Applsci 02 00061 g007 1024
Applsci 02 00061 g008 1024
Figure 8. Stereoscopic ORTEP drawing of 1d molecule A. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.

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Figure 8. Stereoscopic ORTEP drawing of 1d molecule A. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.
Applsci 02 00061 g008 1024
Applsci 02 00061 g009 1024
Figure 9. ORTEP drawing of 1d molecule B showing naming and numbering scheme. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.

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Figure 9. ORTEP drawing of 1d molecule B showing naming and numbering scheme. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.
Applsci 02 00061 g009 1024
Applsci 02 00061 g010 1024
Figure 10. ORTEP drawing of 1d molecule B. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.

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Figure 10. ORTEP drawing of 1d molecule B. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.
Applsci 02 00061 g010 1024
Applsci 02 00061 g011 1024
Figure 11. Stereoscopic ORTEP drawing of 1d molecule B. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.

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Figure 11. Stereoscopic ORTEP drawing of 1d molecule B. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.
Applsci 02 00061 g011 1024

Table 4

Table Table 4. Summary of Crystal Data for 1d.

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Table 4. Summary of Crystal Data for 1d.
FormulaC18H10O3
Formula Weight (g/mol)274.26
Crystal Dimensions (mm )0.30 × 0.24 × 0.20
Crystal Color and Habitclear prism
Crystal Systemorthorhombic
Space GroupF d d 2
Temperature, K173
a, Å18.0996(6)
b, Å 20.9271(7)
c, Å 26.0789(8)
α,°90.00
β,°90.00
γ,°90.00
V, Å39878.0(6)
Number of reflections to determine final unit cell9975
Min and Max 2θ for cell determination, °5.0, 56.84
Z32
F(000)4544
ρ (g/cm)1.475
λ, Å, (MoKα)0.71070
μ, (cm−1)0.101
Diffractometer TypeBruker-Nonius X8 Apex2
Scan Type(s)omega and phi scans
Max 2θ for data collection, °58.24
Measured fraction of data1.000
Number of reflections measured103146
Unique reflections measured6360
Rmerge0.0403
Number of reflections included in refinement6360
Cut off Threshold Expression>2sigma(I)
Structure refined usingfull matrix least-squares using F2
Weighting Schemecalc w = 1/[sigma2(Fo2) + (0.0555P)2+ 3.0465P] where P=(Fo2+ 2Fc2)/3
Number of parameters in least-squares458
R10.0342
wR20.0846
R1 (all data)0.0400
wR2 (all data)0.0880
GOF1.038
Maximum shift/error0.000
Min & Max peak heights on final ΔF Map (e-/Å)−0.219, 0.216

Where: R1 = Σ( |Fo| − |Fc| )/Σ FowR2 = [ Σ( w( Fo2 − Fc2 )2 )/Σ(w Fo4) ] ½GOF = [ Σ( w( Fo2 − Fc2 )2 )/(No. of reflns. − No. of params. ) ]½

Table Table 5. Atomic Coordinates for 1d.

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Table 5. Atomic Coordinates for 1d.
AtomxyzUiso/equiv
O1A0.20028(6)0.13639(6)0.62634(6)0.0362(3)
O2A0.36237(6)0.01557(5)0.42200.0310(2)
O3A0.40033(6)−0.02683(5)0.59892(6)0.0329(2)
C1A0.23461(8)0.12010(7)0.58853(6)0.0257(3)
C2A0.29550(8)0.07078(7)0.58765(6)0.0265(3)
C3A0.31404(7)0.06171(6)0.53149(6)0.0215(2)
C4A0.27141(7)0.10937(6)0.50228(6)0.0214(2)
C5A0.27082(8)0.12548(7)0.45022(6)0.0246(3)
C6A0.22256(8)0.17252(7)0.43340(7)0.0271(3)
C7A0.17513(8)0.20411(7)0.46700(7)0.0283(3)
C8A0.17630(8)0.19033(7)0.51873(7)0.0279(3)
C9A0.22477(7)0.14322(7)0.53572(6)0.0234(3)
C10A0.36116(7)0.01514(6)0.51589(6)0.0217(2)
C11A0.38319(7)−0.00519(6)0.46328(6)0.0228(3)
C12A0.43567(7)−0.05931(6)0.46890(7)0.0231(3)
C13A0.47199(8)−0.09342(7)0.43109(7)0.0289(3)
C14A0.51888(9)−0.14212(8)0.44613(8)0.0328(3)
C15A0.52844(9)−0.15676(8)0.49786(8)0.0331(3)
C16A0.49169(8)−0.12272(7)0.53601(7)0.0293(3)
C17A0.44557(7)−0.07332(6)0.52064(7)0.0242(3)
C18A0.40165(7)−0.02813(7)0.55238(7)0.0237(3)
O1B0.14120(7)0.04113(5)0.35875(6)0.0349(2)
O2B0.25973(7)−0.11687(6)0.56110(5)0.0351(2)
O3B0.29954(7)−0.15569(6)0.38414(6)0.0367(3)
C1B0.15538(8)0.00789(7)0.39573(6)0.0270(3)
C2B0.20581(8)−0.04922(7)0.39627(6)0.0267(3)
C3B0.21160(8)−0.06899(7)0.45205(6)0.0233(3)
C4B0.16128(8)−0.02763(7)0.48137(7)0.0241(3)
C5B0.14109(8)−0.02690(8)0.53345(7)0.0286(3)
C6B0.09013(9)0.01792(8)0.54976(7)0.0314(3)
C7B0.05876(9)0.06238(8)0.51670(7)0.0318(3)
C8B0.07692(9)0.06178(7)0.46499(7)0.0298(3)
C9B0.12772(8)0.01681(7)0.44855(6)0.0255(3)
C10B0.25683(8)−0.11716(7)0.46724(6)0.0245(3)
C11B0.27541(8)−0.14057(7)0.52003(7)0.0259(3)
C12B0.32241(8)−0.19790(7)0.51345(7)0.0262(3)
C13B0.35157(9)−0.23821(8)0.55099(7)0.0322(3)
C14B0.39368(10)−0.28954(8)0.53526(8)0.0352(3)
C15B0.40794(9)−0.30056(8)0.48342(8)0.0352(3)
C16B0.37983(9)−0.25975(7)0.44609(7)0.0322(3)
C17B0.33643(8)−0.20886(7)0.46172(7)0.0264(3)
C18B0.29790(8)−0.15934(7)0.43065(7)0.0269(3)
H2A10.2800(10)0.0306(10)0.6041(7)0.038(5)
H2A20.3395(11)0.0877(9)0.6072(7)0.037(5)
H5A0.3041(10)0.1074(9)0.4261(8)0.033(4)
H6A0.2211(10)0.1858(9)0.3965(7)0.034(5)
H7A0.1431(11)0.2367(9)0.4567(7)0.036(5)
H8A0.1442(12)0.2130(10)0.5435(9)0.045(6)
H13A0.4637(10)−0.0835(9)0.3957(8)0.036(5)
H14A0.5436(10)−0.1635(9)0.4193(8)0.035(5)
H15A0.5585(12)−0.1908(10)0.5071(8)0.044(6)
H16A0.4962(11)−0.1324(10)0.5727(8)0.041(5)
H2B10.2541(12)−0.0384(10)0.3821(9)0.052(6)
H2B20.1831(10)−0.0855(9)0.3765(8)0.035(5)
H5B0.1623(10)−0.0581(9)0.5574(7)0.033(5)
H6B0.0744(12)0.0181(10)0.5865(9)0.049(6)
H7B0.0234(10)0.0921(9)0.5291(8)0.035(5)
H8B0.0572(10)0.0917(9)0.4398(8)0.038(5)
H13B0.3432(11)−0.2287(9)0.5847(8)0.036(5)
H14B0.4143(11)−0.3227(10)0.5586(8)0.039(5)
H15B0.4354(11)−0.3383(9)0.4722(8)0.043(5)
H16B0.3894(10)−0.2680(9)0.4103(7)0.029(4)
Table Table 6. Anisotropic Displacement Parameters for 1d.

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Table 6. Anisotropic Displacement Parameters for 1d.
Atomu11u22u33u12u13u23
O1A0.0362(6)0.0485(7)0.0238(5)0.0094(5)0.0051(4)−0.0015(5)
O2A0.0394(6)0.0338(6)0.0198(5)0.0040(4)0.0011(4)0.0012(4)
O3A0.0398(6)0.0369(6)0.0221(5)0.0069(5)−0.0075(4)−0.0029(4)
C1A0.0256(6)0.0301(7)0.0215(6)0.0000(5)−0.0008(5)−0.0014(5)
C2A0.0291(7)0.0326(7)0.0179(6)0.0040(6)−0.0015(5)−0.0015(5)
C3A0.0217(6)0.0238(6)0.0191(6)−0.0048(5)−0.0004(4)−0.0006(5)
C4A0.0218(6)0.0212(6)0.0213(6)−0.0030(5)−0.0006(4)−0.0007(5)
C5A0.0276(7)0.0253(7)0.0210(6)−0.0012(5)0.0020(5)0.0006(5)
C6A0.0332(7)0.0251(7)0.0230(6)−0.0029(5)0.0008(5)0.0032(5)
C7A0.0299(7)0.0245(7)0.0306(7)0.0028(5)−0.0008(6)0.0047(6)
C8A0.0283(7)0.0272(7)0.0282(7)0.0019(5)0.0025(5)−0.0001(6)
C9A0.0244(6)0.0250(6)0.0209(6)−0.0010(5)0.0003(5)−0.0001(5)
C10A0.0227(6)0.0235(6)0.0190(6)−0.0021(5)−0.0016(5)−0.0008(5)
C11A0.0232(6)0.0235(6)0.0217(6)−0.0034(5)0.0019(5)−0.0011(5)
C12A0.0223(6)0.0225(6)0.0247(6)−0.0031(5)0.0014(5)−0.0011(5)
C13A0.0300(7)0.0286(7)0.0282(7)−0.0032(6)0.0055(5)−0.0030(5)
C14A0.0305(7)0.0284(7)0.0396(8)−0.0010(6)0.0067(6)−0.0076(6)
C15A0.0266(7)0.0284(7)0.0443(9)0.0033(6)−0.0025(6)−0.0028(6)
C16A0.0279(7)0.0279(7)0.0321(8)0.0000(5)−0.0052(6)−0.0001(6)
C17A0.0225(6)0.0235(6)0.0264(6)−0.0046(5)−0.0021(5)−0.0016(5)
C18A0.0225(6)0.0249(7)0.0237(6)−0.0015(5)−0.0034(5)−0.0017(5)
O1B0.0463(6)0.0351(6)0.0235(5)−0.0023(5)−0.0037(4)0.0079(4)
O2B0.0415(6)0.0444(6)0.0192(5)0.0011(5)−0.0023(4)0.0013(4)
O3B0.0480(6)0.0425(6)0.0196(5)0.0073(5)−0.0015(4)0.0010(4)
C1B0.0292(7)0.0303(7)0.0214(6)−0.0089(5)−0.0038(5)0.0019(5)
C2B0.0287(7)0.0344(7)0.0168(6)−0.0024(6)−0.0015(5)0.0028(5)
C3B0.0240(6)0.0277(7)0.0181(6)−0.0080(5)−0.0024(5)0.0031(5)
C4B0.0252(6)0.0271(6)0.0200(6)−0.0078(5)−0.0020(5)0.0014(5)
C5B0.0309(7)0.0349(8)0.0200(6)−0.0068(6)−0.0009(5)0.0039(5)
C6B0.0326(8)0.0379(8)0.0238(7)−0.0048(6)0.0018(5)−0.0002(6)
C7B0.0329(7)0.0330(7)0.0296(7)−0.0032(6)0.0011(6)−0.0008(6)
C8B0.0328(7)0.0306(7)0.0261(7)−0.0037(6)−0.0026(6)0.0045(6)
C9B0.0270(7)0.0288(7)0.0207(6)−0.0068(5)−0.0034(5)0.0014(5)
C10B0.0261(7)0.0310(7)0.0163(6)−0.0071(5)−0.0015(5)0.0022(5)
C11B0.0273(7)0.0313(7)0.0190(6)−0.0078(5)−0.0020(5)0.0040(5)
C12B0.0268(6)0.0289(7)0.0227(7)−0.0089(5)−0.0046(5)0.0034(5)
C13B0.0367(8)0.0351(8)0.0247(7)−0.0091(6)−0.0067(6)0.0076(6)
C14B0.0410(9)0.0304(8)0.0344(8)−0.0063(6)−0.0125(7)0.0085(6)
C15B0.0378(8)0.0293(7)0.0386(9)−0.0001(6)−0.0093(6)0.0010(6)
C16B0.0373(8)0.0315(8)0.0279(8)−0.0012(6)−0.0054(6)−0.0008(6)
C17B0.0284(7)0.0281(7)0.0228(6)−0.0064(5)−0.0043(5)0.0020(5)
C18B0.0301(7)0.0304(7)0.0203(6)−0.0048(6)−0.0030(5)0.0016(5)
Table Table 7. Bond Lengths for 1d.

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Table 7. Bond Lengths for 1d.
O1A-C1A1.2143(17)O1B-C1B1.2166(17)
O2A-C11A1.2212(17)O2B-C11B1.2140(18)
O3A-C18A1.2143(17)O3B-C18B1.2159(17)
C1A-C9A1.4705(19)C1B-C9B1.4775(19)
C1A-C2A1.510(2)C1B-C2B1.504(2)
C2A-C3A1.5145(18)C2B-C3B1.5159(17)
C2A-H2A10.99(2)C2B-H2B10.98(2)
C2A-H2A21.01(2)C2B-H2B21.006(19)
C3A-C10A1.3574(19)C3B-C10B1.358(2)
C3A-C4A1.4733(19)C3B-C4B1.471(2)
C4A-C5A1.3989(18)C4B-C9B1.4025(19)
C4A-C9A1.4052(19)C4B-C5B1.4065(19)
C5A-C6A1.387(2)C5B-C6B1.383(2)
C5A-H5A0.95(2)C5B-H5B0.982(19)
C6A-C7A1.394(2)C6B-C7B1.390(2)
C6A-H6A1.001(19)C6B-H6B1.00(2)
C7A-C8A1.380(2)C7B-C8B1.388(2)
C7A-H7A0.94(2)C7B-H7B0.95(2)
C8A-C9A1.392(2)C8B-C9B1.384(2)
C8A-H8A0.99(2)C8B-H8B0.98(2)
C10A-C11A1.4908(18)C10B-C18B1.497(2)
C10A-C18A1.5043(19)C10B-C11B1.4995(18)
C11A-C12A1.4855(19)C11B-C12B1.481(2)
C12A-C13A1.383(2)C12B-C17B1.3916(19)
C12A-C17A1.3924(19)C12B-C13B1.396(2)
C13A-C14A1.383(2)C13B-C14B1.379(3)
C13A-H13A0.96(2)C13B-H13B0.91(2)
C14A-C15A1.394(2)C14B-C15B1.395(2)
C14A-H14A0.94(2)C14B-H14B1.00(2)
C15A-C16A1.393(2)C15B-C16B1.392(2)
C15A-H15A0.93(2)C15B-H15B0.98(2)
C16A-C17A1.388(2)C16B-C17B1.385(2)
C16A-H16A0.98(2)C16B-H16B0.965(19)
C17A-C18A1.4870(19)C17B-C18B1.489(2)
Table Table 8. Bond Angles for 1d.

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Table 8. Bond Angles for 1d.
O1A-C1A-C9A127.32(14)O1B-C1B-C9B126.54(14)
O1A-C1A-C2A125.28(13)O1B-C1B-C2B126.15(13)
C9A-C1A-C2A107.40(11)C9B-C1B-C2B107.30(11)
C1A-C2A-C3A105.20(11)C1B-C2B-C3B105.54(11)
C1A-C2A-H2A1111.6(11)C1B-C2B-H2B1110.9(13)
C3A-C2A-H2A1112.2(11)C3B-C2B-H2B1111.4(13)
C1A-C2A-H2A2109.2(11)C1B-C2B-H2B2110.3(11)
C3A-C2A-H2A2110.9(11)C3B-C2B-H2B2108.3(11)
H2A1-C2A-H2A2107.7(16)H2B1-C2B-H2B2110.2(18)
C10A-C3A-C4A131.31(12)C10B-C3B-C4B131.19(12)
C10A-C3A-C2A121.27(12)C10B-C3B-C2B121.63(13)
C4A-C3A-C2A107.40(11)C4B-C3B-C2B107.18(12)
C5A-C4A-C9A118.44(12)C9B-C4B-C5B118.01(13)
C5A-C4A-C3A131.98(13)C9B-C4B-C3B109.95(12)
C9A-C4A-C3A109.58(12)C5B-C4B-C3B132.01(13)
C6A-C5A-C4A118.86(13)C6B-C5B-C4B118.54(14)
C6A-C5A-H5A118.3(12)C6B-C5B-H5B121.1(11)
C4A-C5A-H5A122.8(12)C4B-C5B-H5B120.3(11)
C5A-C6A-C7A121.72(13)C5B-C6B-C7B122.40(14)
C5A-C6A-H6A121.2(11)C5B-C6B-H6B119.2(12)
C7A-C6A-H6A117.1(11)C7B-C6B-H6B118.4(12)
C8A-C7A-C6A120.41(14)C8B-C7B-C6B120.00(15)
C8A-C7A-H7A116.4(12)C8B-C7B-H7B119.7(12)
C6A-C7A-H7A123.2(12)C6B-C7B-H7B120.2(12)
C7A-C8A-C9A117.96(14)C9B-C8B-C7B117.68(14)
C7A-C8A-H8A121.9(13)C9B-C8B-H8B118.1(12)
C9A-C8A-H8A120.2(13)C7B-C8B-H8B124.2(12)
C8A-C9A-C4A122.55(13)C8B-C9B-C4B123.35(13)
C8A-C9A-C1A127.40(13)C8B-C9B-C1B126.87(13)
C4A-C9A-C1A110.03(12)C4B-C9B-C1B109.78(13)
C3A-C10A-C11A130.45(12)C3B-C10B-C18B123.44(12)
C3A-C10A-C18A123.28(12)C3B-C10B-C11B130.22(13)
C11A-C10A-C18A106.27(11)C18B-C10B-C11B106.33(12)
O2A-C11A-C12A123.76(13)O2B-C11B-C12B124.59(13)
O2A-C11A-C10A128.89(12)O2B-C11B-C10B128.62(14)
C12A-C11A-C10A107.32(11)C12B-C11B-C10B106.68(12)
C13A-C12A-C17A121.39(13)C17B-C12B-C13B120.75(14)
C13A-C12A-C11A128.82(13)C17B-C12B-C11B110.53(12)
C17A-C12A-C11A109.79(11)C13B-C12B-C11B128.72(14)
C14A-C13A-C12A118.02(15)C14B-C13B-C12B118.09(15)
C14A-C13A-H13A121.9(11)C14B-C13B-H13B123.2(12)
C12A-C13A-H13A120.1(11)C12B-C13B-H13B118.7(12)
C13A-C14A-C15A120.83(14)C13B-C14B-C15B121.28(15)
C13A-C14A-H14A115.4(12)C13B-C14B-H14B124.6(12)
C15A-C14A-H14A123.7(12)C15B-C14B-H14B114.1(12)
C16A-C15A-C14A121.30(15)C16B-C15B-C14B120.57(16)
C16A-C15A-H15A119.2(13)C16B-C15B-H15B118.2(12)
C14A-C15A-H15A119.5(13)C14B-C15B-H15B121.2(12)
C17A-C16A-C15A117.51(15)C17B-C16B-C15B118.27(15)
C17A-C16A-H16A119.1(12)C17B-C16B-H16B121.7(11)
C15A-C16A-H16A123.4(12)C15B-C16B-H16B120.0(11)
C16A-C17A-C12A120.94(13)C16B-C17B-C12B121.03(14)
C16A-C17A-C18A129.38(13)C16B-C17B-C18B129.85(14)
C12A-C17A-C18A109.68(11)C12B-C17B-C18B109.11(13)
O3A-C18A-C17A125.54(13)O3B-C18B-C17B125.12(14)
O3A-C18A-C10A127.53(13)O3B-C18B-C10B127.65(14)
C17A-C18A-C10A106.93(11)C17B-C18B-C10B107.22(11)
Table Table 9. Torsion Angles for 1d.

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Table 9. Torsion Angles for 1d.
O1A-C1A-C2A-C3A173.35(14)O1B-C1B-C2B-C3B173.77(14)
C9A-C1A-C2A-C3A−5.93(15)C9B-C1B-C2B-C3B−5.04(14)
C1A-C2A-C3A-C10A−172.45(12)C1B-C2B-C3B-C10B−175.90(12)
C1A-C2A-C3A-C4A6.20(14)C1B-C2B-C3B-C4B4.41(14)
C10A-C3A-C4A-C5A−6.6(2)C10B-C3B-C4B-C9B178.21(14)
C2A-C3A-C4A-C5A174.97(14)C2B-C3B-C4B-C9B−2.13(15)
C10A-C3A-C4A-C9A174.20(13)C10B-C3B-C4B-C5B−3.9(2)
C2A-C3A-C4A-C9A−4.26(15)C2B-C3B-C4B-C5B175.74(14)
C9A-C4A-C5A-C6A−2.2(2)C9B-C4B-C5B-C6B−0.83(19)
C3A-C4A-C5A-C6A178.62(13)C3B-C4B-C5B-C6B−178.57(14)
C4A-C5A-C6A-C7A0.3(2)C4B-C5B-C6B-C7B−0.5(2)
C5A-C6A-C7A-C8A1.6(2)C5B-C6B-C7B-C8B1.6(2)
C6A-C7A-C8A-C9A−1.5(2)C6B-C7B-C8B-C9B−1.3(2)
C7A-C8A-C9A-C4A−0.5(2)C7B-C8B-C9B-C4B0.0(2)
C7A-C8A-C9A-C1A−179.00(14)C7B-C8B-C9B-C1B−179.50(14)
C5A-C4A-C9A-C8A2.4(2)C5B-C4B-C9B-C8B1.1(2)
C3A-C4A-C9A-C8A−178.25(13)C3B-C4B-C9B-C8B179.32(13)
C5A-C4A-C9A-C1A−178.91(12)C5B-C4B-C9B-C1B−179.32(12)
C3A-C4A-C9A-C1A0.45(15)C3B-C4B-C9B-C1B−1.12(15)
O1A-C1A-C9A-C8A2.9(3)O1B-C1B-C9B-C8B4.7(2)
C2A-C1A-C9A-C8A−177.83(14)C2B-C1B-C9B-C8B−176.51(14)
O1A-C1A-C9A-C4A−175.70(15)O1B-C1B-C9B-C4B−174.87(14)
C2A-C1A-C9A-C4A3.56(15)C2B-C1B-C9B-C4B3.94(15)
C4A-C3A-C10A-C11A−2.9(2)C4B-C3B-C10B-C18B172.57(13)
C2A-C3A-C10A-C11A175.35(13)C2B-C3B-C10B-C18B−7.0(2)
C4A-C3A-C10A-C18A178.09(13)C4B-C3B-C10B-C11B−6.0(2)
C2A-C3A-C10A-C18A−3.6(2)C2B-C3B-C10B-C11B174.40(13)
C3A-C10A-C11A-O2A−1.1(2)C3B-C10B-C11B-O2B−8.6(2)
C18A-C10A-C11A-O2A177.98(14)C18B-C10B-C11B-O2B172.65(15)
C3A-C10A-C11A-C12A−179.17(13)C3B-C10B-C11B-C12B175.12(14)
C18A-C10A-C11A-C12A−0.06(14)C18B-C10B-C11B-C12B−3.62(14)
O2A-C11A-C12A-C13A2.9(2)O2B-C11B-C12B-C17B−173.55(14)
C10A-C11A-C12A-C13A−178.90(13)C10B-C11B-C12B-C17B2.91(15)
O2A-C11A-C12A-C17A−177.23(13)O2B-C11B-C12B-C13B6.2(2)
C10A-C11A-C12A-C17A0.94(15)C10B-C11B-C12B-C13B−177.33(14)
C17A-C12A-C13A-C14A−0.1(2)C17B-C12B-C13B-C14B−0.9(2)
C11A-C12A-C13A-C14A179.72(14)C11B-C12B-C13B-C14B179.39(14)
C12A-C13A-C14A-C15A0.7(2)C12B-C13B-C14B-C15B1.0(2)
C13A-C14A-C15A-C16A−0.5(2)C13B-C14B-C15B-C16B0.0(3)
C14A-C15A-C16A-C17A−0.5(2)C14B-C15B-C16B-C17B−1.2(2)
C15A-C16A-C17A-C12A1.1(2)C15B-C16B-C17B-C12B1.3(2)
C15A-C16A-C17A-C18A−177.97(13)C15B-C16B-C17B-C18B−178.14(15)
C13A-C12A-C17A-C16A−0.8(2)C13B-C12B-C17B-C16B−0.3(2)
C11A-C12A-C17A-C16A179.30(13)C11B-C12B-C17B-C16B179.50(13)
C13A-C12A-C17A-C18A178.41(12)C13B-C12B-C17B-C18B179.26(13)
C11A-C12A-C17A-C18A−1.45(15)C11B-C12B-C17B-C18B−0.96(16)
C16A-C17A-C18A-O3A1.4(2)C16B-C17B-C18B-O3B−0.8(2)
C12A-C17A-C18A-O3A−177.79(14)C12B-C17B-C18B-O3B179.73(14)
C16A-C17A-C18A-C10A−179.45(13)C16B-C17B-C18B-C10B178.11(15)
C12A-C17A-C18A-C10A1.39(15)C12B-C17B-C18B-C10B−1.38(15)
C3A-C10A-C18A-O3A−2.4(2)C3B-C10B-C18B-O3B3.1(2)
C11A-C10A-C18A-O3A178.39(14)C11B-C10B-C18B-O3B−178.05(15)
C3A-C10A-C18A-C17A178.42(12)C3B-C10B-C18B-C17B−175.76(12)
C11A-C10A-C18A-C17A−0.77(14)C11B-C10B-C18B-C17B3.10(14)

2. Compound 2c

Experimental for C13H6F6O3 (2c)

Data Collection and Processing. The sample 2c was submitted by Joseph Sloop of the Sloop research group at Georgia Gwinnett College. The sample was mounted on a nylon loop with a small amount of NVH immersion oil. All X-ray measurements were made on a Bruker-Nonius X8 Apex2 diffractometer at a temperature of 173 K. The unit cell dimensions were determined from a symmetry constrained fit of 9959 reflections with 5.28° < 2θ < 57.7°. The data collection strategy was a number of ω and ϕ scans which collected data up to 57.74° (2θ). The frame integration was performed using SAINT+ [29]. The resulting raw data was scaled and absorption corrected using a multi-scan averaging of symmetry equivalent data using SADABS [30].

Structure Solution and Refinement. The structure was solved by direct methods using the SIR92 program [31]. All non-hydrogen atoms were obtained from the initial E-map. The hydrogen atoms were introduced at idealized positions and were allowed to refine isotropically. The structural model was fit to the data using full matrix least-squares based on F. The calculated structure factors included corrections for anomalous dispersion from the usual tabulation. The structure was refined using the LSTSQ program from NRCVAX [33], graphic plots were produced using the NRCVAX crystallographic program suite. Additional information and other relevant literature references can be found in the reference section of the Facility’s Web page (http://www.xray.ncsu.edu).

Applsci 02 00061 g012 1024
Figure 12. ORTEP drawing of 2c showing naming and numbering scheme. Ellipsoids are at the 50%.

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Figure 12. ORTEP drawing of 2c showing naming and numbering scheme. Ellipsoids are at the 50%.
Applsci 02 00061 g012 1024
Applsci 02 00061 g013 1024
Figure 13. ORTEP drawing of 2c. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.

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Figure 13. ORTEP drawing of 2c. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.
Applsci 02 00061 g013 1024
Applsci 02 00061 g014 1024
Figure 14. Stereoscopic ORTEP drawing of 2c. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.

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Figure 14. Stereoscopic ORTEP drawing of 2c. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.
Applsci 02 00061 g014 1024
Table Table 10. Summary of Crystal Data for 2c.

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Table 10. Summary of Crystal Data for 2c.
FormulaC13H6F6O3
Formula Weight (g/mol)324.18
Crystal Dimensions (mm )1.20 × 0.10 × 0.06
Crystal Color and Habityellow needle
Crystal Systemmonoclinic
Space GroupP 21/c
Temperature, K173
a, Å4.7643(3)
b, Å 18.6978(12)
c, Å 13.8431(9)
α,°90.0
β,°98.964(3)
γ,°90.0
V, Å31218.11(14)
Number of reflections to determine final unit cell9959
Min and Max 2θ for cell determination, °5.28, 57.7
Z4
F(000)648.71
ρ (g/cm)1.768
λ, Å, (MoKα)0.71073
μ, (cm−1)0.18
Diffractometer TypeBruker-Nonius X8 Apex2
Scan Type(s)omega and phi scans
Max 2θ for data collection, °57.74
Measured fraction of data0.98
Number of reflections measured26516
Unique reflections measured3195
Rmerge0.027
Number of reflections included in refinement2755
Cut off Threshold ExpressionInet > 1.0 sigma(Inet)
Structure refined usingfull matrix least-squares using F
Weighting Scheme1/(sigma2(F) + 0.0005F2)
Number of parameters in least-squares223
Rf0.038
Rw0.053
Rf (all data)0.046
Rw (all data)0.054
GOF1.74
Maximum shift/error0.003
Min & Max peak heights on final ΔF Map (e−/Å)−0.30, 0.35

Where: Rf= Σ( |Fo− Fc| ) / Σ Fo Rw= [ Σ( w( Fo− Fc)2) / Σ( Fo2) ]½GOF = [ Σ( w( Fo− Fc)2) / (No. of reflns. − No. of params. ) ]½

Table Table 11. Atomic Coordinates for 2c.

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Table 11. Atomic Coordinates for 2c.
AtomxyzUiso/equiv
O10.81730(18)0.99675(5)0.07954(6)0.0316(4)
O20.77456(19)1.10306(5)−0.04046(7)0.0328(5)
O30.8507(2)0.90513(5)0.22145(8)0.0392(5)
C10.6645(2)1.03312(6)0.12739(8)0.0244(5)
C20.5495(2)1.10365(6)0.10029(9)0.0243(5)
C30.3836(2)1.12503(7)0.17672(8)0.0257(5)
C40.2245(3)1.18602(8)0.18650(10)0.0319(6)
C50.0812(3)1.19205(8)0.26621(11)0.0377(7)
C60.0964(3)1.13855(8)0.33508(11)0.0396(7)
C70.2560(3)1.07730(8)0.32738(10)0.0352(6)
C80.4020(2)1.07009(7)0.24809(9)0.0270(5)
C90.5808(2)1.01187(6)0.22025(8)0.0263(5)
C100.6161(2)1.13484(7)0.01809(9)0.0259(5)
C110.5253(3)1.20877(7)−0.01820(11)0.0337(6)
C120.6894(3)0.95005(7)0.26242(9)0.0311(6)
C130.6515(3)0.92528(8)0.36396(11)0.0401(7)
F10.61454(20)1.22376(5)−0.10179(7)0.0526(5)
F20.24328(16)1.21541(5)−0.03293(6)0.0430(4)
F30.62851(20)1.25846(5)0.04657(7)0.0526(5)
F40.8000(2)0.86675(5)0.39034(7)0.0592(6)
F50.7410(2)0.97545(6)0.43055(6)0.0548(5)
F60.38149(19)0.91237(6)0.37079(7)0.0579(5)
H20.822(4)1.0603(13)−0.0133(14)0.064(6)
H30.877(5)0.9223(11)0.1643(16)0.072(6)
H40.213(3)1.2212(8)0.1414(11)0.030(4)
H5−0.019(3)1.2318(8)0.2728(11)0.035(4)
H6−0.004(4)1.1455(9)0.3899(12)0.045(4)
H70.272(3)1.0418(9)0.3767(12)0.039(4)
Table Table 12. Anisotropic Displacement Parameters for 2c.

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Table 12. Anisotropic Displacement Parameters for 2c.
Atomu11u22u33u12u13u23
O10.0384(5)0.0291(5)0.0291(5)0.0065(4)0.0112(4)0.0003(4)
O20.0380(5)0.0333(5)0.0302(5)0.0053(4)0.0146(4)0.0045(4)
O30.0482(6)0.0321(5)0.0380(6)0.0067(4)0.0085(5)0.0061(4)
C10.0264(5)0.0255(6)0.0214(5)−0.0027(5)0.0040(4)−0.0019(4)
C20.0245(5)0.0243(6)0.0243(5)−0.0014(5)0.0042(4)−0.0029(4)
C30.0230(5)0.0294(6)0.0248(6)−0.0045(5)0.0042(4)−0.0063(5)
C40.0303(6)0.0330(7)0.0321(6)0.0012(5)0.0041(5)−0.0072(5)
C50.0313(6)0.0419(8)0.0407(7)0.0023(6)0.0084(6)−0.0160(6)
C60.0341(6)0.0531(9)0.0343(7)−0.0067(6)0.0139(6)−0.0166(7)
C70.0358(7)0.0441(8)0.0275(6)−0.0092(6)0.0112(5)−0.0064(6)
C80.0255(5)0.0316(6)0.0242(6)−0.0068(5)0.0051(4)−0.0053(5)
C90.0290(5)0.0282(6)0.0222(6)−0.0067(5)0.0054(5)−0.0015(4)
C100.0241(5)0.0270(6)0.0271(6)−0.0010(5)0.0051(4)0.0005(5)
C110.0293(6)0.0323(7)0.0409(7)0.0007(5)0.0096(5)0.0079(5)
C120.0324(6)0.0314(7)0.0291(6)−0.0071(5)0.0031(5)0.0023(5)
C130.0380(7)0.0444(8)0.0374(7)−0.0058(6)0.0045(6)0.0128(6)
F10.0516(5)0.0533(6)0.0594(6)0.0131(4)0.0287(5)0.0306(5)
F20.0296(4)0.0493(5)0.0507(5)0.0088(4)0.0084(4)0.0178(4)
F30.0538(5)0.0258(4)0.0750(7)0.0008(4)0.0006(5)−0.0021(4)
F40.0650(6)0.0577(6)0.0569(6)0.0082(5)0.0154(5)0.0322(5)
F50.0661(6)0.0702(7)0.0276(4)−0.0148(5)0.0057(4)0.0044(4)
F60.0427(5)0.0755(7)0.0574(6)−0.0133(5)0.0133(4)0.0236(5)
Table Table 13. Bond Lengths for 2c.

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Table 13. Bond Lengths for 2c.
O1-C11.2576(15)C6-C71.388(2)
O2-C101.3308(15)C6-H60.967(18)
O2-H20.90(2)C7-C81.3944(18)
O3-C121.3242(17)C7-H70.947(17)
O3-H30.88(2)C8-C91.4703(18)
C1-C21.4547(17)C9-C121.3602(18)
C1-C91.4590(17)C10-C111.5108(18)
C2-C31.4714(17)C11-F11.3235(16)
C2-C101.3593(17)C11-F21.3329(15)
C3-C41.3876(18)C11-F31.3311(17)
C3-C81.4186(18)C12-C131.5173(19)
C4-C51.3893(20)C13-F41.3233(18)
C4-H40.903(15)C13-F51.3375(18)
C5-C61.376(2)C13-F61.3267(17)
C5-H50.896(17)
Table Table 14. Bond Angles for 2c.

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Table 14. Bond Angles for 2c.
C10-O2-H2105.8(12)C3-C8-C9109.21(10)
C12-O3-H3109.1(14)C7-C8-C9131.18(12)
O1-C1-C2125.45(11)C1-C9-C8106.17(10)
O1-C1-C9125.23(11)C1-C9-C12118.14(11)
C2-C1-C9109.30(10)C8-C9-C12135.54(12)
C1-C2-C3106.48(10)O2-C10-C2123.15(11)
C1-C2-C10118.51(11)O2-C10-C11111.48(11)
C3-C2-C10134.99(11)C2-C10-C11125.36(11)
C2-C3-C4131.02(12)C10-C11-F1111.72(11)
C2-C3-C8108.80(10)C10-C11-F2111.45(10)
C4-C3-C8120.17(11)C10-C11-F3110.99(11)
C3-C4-C5119.18(14)F1-C11-F2107.46(11)
C3-C4-H4120.4(9)F1-C11-F3107.80(11)
C5-C4-H4120.4(9)F2-C11-F3107.21(11)
C4-C5-C6120.80(14)O3-C12-C9124.23(12)
C4-C5-H5119.0(10)O3-C12-C13111.34(12)
C6-C5-H5120.2(10)C9-C12-C13124.39(13)
C5-C6-C7121.13(13)C12-C13-F4111.87(13)
C5-C6-H6117.8(10)C12-C13-F5110.68(11)
C7-C6-H6121.0(10)C12-C13-F6112.22(11)
C6-C7-C8119.11(14)F4-C13-F5106.89(12)
C6-C7-H7120.5(9)F4-C13-F6108.20(12)
C8-C7-H7120.3(9)F5-C13-F6106.69(13)
C3-C8-C7119.60(12)
Table Table 15. Torsion Angles for 2c.

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Table 15. Torsion Angles for 2c.
O1-C1-C2-C3179.6(2)C8-C3-C4-C5−0.78(13)
O1-C1-C2-C10−1.91(11)C2-C3-C8-C7−178.6(3)
C9-C1-C2-C3−1.90(11)C2-C3-C8-C90.26(11)
C9-C1-C2-C10176.6(2)C4-C3-C8-C70.88(13)
O1-C1-C9-C8−179.4(3)C4-C3-C8-C9179.7(3)
O1-C1-C9-C124.37(11)C3-C4-C5-C60.17(13)
C2-C1-C9-C82.04(11)C4-C5-C6-C70.35(13)
C2-C1-C9-C12−174.2(3)C5-C6-C7-C8−0.25(13)
C1-C2-C3-C4−178.4(2)C6-C7-C8-C3−0.36(13)
C1-C2-C3-C81.00(11)C6-C7-C8-C9−178.9(3)
C10-C2-C3-C43.44(12)C3-C8-C9-C1−1.41(11)
C10-C2-C3-C8−177.2(3)C3-C8-C9-C12173.8(3)
C1-C2-C10-O22.08(10)C7-C8-C9-C1177.3(3)
C1-C2-C10-C11−177.3(2)C7-C8-C9-C12−7.50(13)
C3-C2-C10-O2−179.9(2)C1-C9-C12-O3−4.98(11)
C3-C2-C10-C110.67(11)C1-C9-C12-C13172.4(3)
C2-C3-C4-C5178.6(3)

3. Compound 3d

Experimental for C12H7F3O2 (3d)

Data Collection and Processing. The sample 3d was submitted by Joseph Sloop of the Sloop research group at Georgia Gwinnett College. The sample was mounted on a nylon loop with a small amount of NVH immersion oil. All X-ray measurements were made on a Bruker-Nonius X8 Apex2 diffractometer at a temperature of 110 K. The unit cell dimensions were determined from a symmetry constrained fit of 5859 reflections with 5.44° < 2θ < 52.66°. The data collection strategy was a number of ω and ϕ scans which collected data up to 62.92° (2θ). The frame integration was performed using SAINT [29]. The resulting raw data was scaled and absorption corrected using a multi-scan averaging of symmetry equivalent data using SADABS [30].

Structure Solution and Refinement. The structure was solved by direct methods using the SIR92 program [31]. All non-hydrogen atoms were obtained from the initial solution. The carbon bound hydrogen atoms were introduced at idealized positions while the hydroxy hydrogen atom position was obtained from a diffeence Fourier map. All hydrogen atoms were allowed to refine isotropically. The structural model was fit to the data using full matrix least-squares based on F2. The calculated structure factors included corrections for anomalous dispersion from the usual tabulation. The space group is achiral, therefore the structure has an absolute sense to it. However, the anomalous scattering signal is weak due to the absence of any atoms heavier than F, and the absolute structure could not be definitively determined. The structure was refined using the XL program from SHELXTL [32], graphic plots were produced using the NRCVAX crystallographic program suite. Additional information and other relevant literature references can be found in the reference section of the Facility’s Web page (http://www.xray.ncsu.edu).

Applsci 02 00061 g015 1024
Figure 15. ORTEP drawing of 3d showing naming and numbering scheme. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.

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Figure 15. ORTEP drawing of 3d showing naming and numbering scheme. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.
Applsci 02 00061 g015 1024
Applsci 02 00061 g016 1024
Figure 16. ORTEP drawing of 3d. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.

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Figure 16. ORTEP drawing of 3d. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.
Applsci 02 00061 g016 1024
Applsci 02 00061 g017 1024
Figure 17. Stereoscopic ORTEP drawing of 3d. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.

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Figure 17. Stereoscopic ORTEP drawing of 3d. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.
Applsci 02 00061 g017 1024
Table Table 16. Summary of Crystal Data for 3d.

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Table 16. Summary of Crystal Data for 3d.
FormulaC12H7F3O2
Formula Weight (g/mol)240.18
Crystal Dimensions (mm )0.46 × 0.08 × 0.04
Crystal Color and Habitorange yellow needle
Crystal Systemorthorhombic
Space GroupP n a 21
Temperature, K110
a, Å13.5923(5)
b, Å 14.9695(5)
c, Å 4.8381(2)
α,°90.00
β,°90.00
γ,°90.00
V, Å3984.41(6)
Number of reflections to determine final unit cell5859
Min and Max 2θ for cell determination, °5.44, 52.66
Z4
F(000)488
ρ (g/cm)1.621
λ, Å, (MoKα)0.71070
μ, (cm1)0.147
Diffractometer TypeBruker-Nonius X8 Apex2
Scan Type(s)omega and phi scans
Max 2θ for data collection, °62.92
Measured fraction of data0.874
Number of reflections measured21568
Unique reflections measured2632
Rmerge0.0444
Number of reflections included in refinement2632
Cut off Threshold Expression>2sigma(I)
Structure refined usingfull matrix least-squares using F2
Weighting Schemecalc w = 1/[sigma2(Fo2) + (0.0406P)2 + 0.0000P] where P=(Fo2 + 2Fc2)/3
Number of parameters in least-squares182
R10.0370
wR20.0712
R1 (all data)0.0538
wR2 (all data)0.0762
GOF1.035
Maximum shift/error0.000
Min & Max peak heights on final ΔF Map (e-/Å)−0.229, 0.183

Where: R1 = Σ( |Fo| − |Fc| ) / Σ Fo wR2 = [ Σ( w( Fo2 − Fc2 )2 ) / Σ(w Fo4 ) ]½GOF = [ Σ( w( Fo2 − Fc2 )2 ) / (No. of reflns. − No. of params. ) ]½

Table Table 17. Atomic Coordinates for 3d.

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Table 17. Atomic Coordinates for 3d.
AtomxyzUiso/equiv
O10.11391(8)0.26937(8)0.6424(3)0.0315(3)
O20.22469(8)0.37533(7)0.3464(3)0.0294(3)
C10.19885(11)0.24126(10)0.7623(4)0.0227(3)
C20.29250(11)0.27865(9)0.6863(4)0.0190(3)
C30.37673(11)0.24539(9)0.8101(4)0.0193(3)
C40.37205(11)0.17792(10)1.0120(4)0.0192(3)
C50.45775(12)0.14260(10)1.1386(4)0.0230(3)
C60.45137(13)0.07873(10)1.3373(4)0.0269(3)
C70.35837(14)0.04578(11)1.4184(4)0.0300(4)
C80.27466(13)0.07695(10)1.3003(4)0.0275(4)
C90.27804(11)0.14416(10)1.0917(4)0.0213(3)
C100.19325(12)0.17720(11)0.9629(4)0.0247(3)
C110.29517(12)0.35023(10)0.4818(4)0.0217(3)
C120.39217(11)0.40275(10)0.4367(4)0.0224(3)
F10.37724(7)0.47125(6)0.26750.0341(3)
F20.46266(6)0.35198(6)0.3256(3)0.0286(2)
F30.42682(6)0.43562(6)0.6742(3)0.0297(2)
H10.1301(19)0.3131(16)0.500(7)0.079(9)
H30.4391(12)0.2686(10)0.766(4)0.022(4)
H50.5197(14)0.1674(10)1.079(4)0.033(5)
H60.5078(13)0.0544(10)1.422(4)0.026(4)
H70.3543(13)0.0040(11)1.553(4)0.030(5)
H80.2120(15)0.0566(12)1.334(5)0.053(6)
Table Table 18. Anisotropic Displacement Parameters for 3d.

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Table 18. Anisotropic Displacement Parameters for 3d.
Atomu11u22u33u12u13u23
O10.0164(6)0.0433(7)0.0347(7)0.0007(5)−0.0018(5)0.0012(6)
O20.0251(6)0.0319(6)0.0312(6)0.0036(5)−0.0074(6)0.0048(6)
C10.0174(8)0.0271(8)0.0236(8)−0.0003(6)0.0012(6)−0.0060(7)
C20.0180(8)0.0211(7)0.0178(7)0.0006(6)0.0021(6)−0.0031(6)
C30.0174(8)0.0209(7)0.0196(7)−0.0016(6)0.0019(6)−0.0013(7)
C40.0199(8)0.0195(7)0.0182(7)−0.0011(6)0.0023(6)−0.0032(6)
C50.0249(9)0.0212(8)0.0229(8)0.0011(6)0.0005(7)−0.0006(6)
C60.0338(9)0.0226(8)0.0245(8)0.0051(7)−0.0020(7)0.0001(7)
C70.0471(11)0.0208(8)0.0223(9)−0.0038(7)0.0034(7)0.0020(7)
C80.0324(9)0.0256(8)0.0247(9)−0.0107(7)0.0084(8)−0.0037(7)
C90.0249(8)0.0193(7)0.0198(7)−0.0031(6)0.0041(6)−0.0060(6)
C100.0178(8)0.0300(8)0.0264(8)−0.0068(7)0.0072(7)−0.0062(7)
C110.0226(9)0.0230(8)0.0195(8)0.0020(6)0.0017(6)−0.0026(6)
C120.0238(8)0.0226(8)0.0208(7)0.0010(6)−0.0013(7)0.0006(6)
F10.0369(6)0.0279(5)0.0375(6)−0.0005(4)−0.0013(5)0.0126(5)
F20.0238(5)0.0291(5)0.0329(5)0.0011(4)0.0082(4)−0.0003(4)
F30.0309(5)0.0300(5)0.0282(5)−0.0080(4)−0.0005(4)−0.0051(4)
Table Table 19. Bond Lengths for 3d.

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Table 19. Bond Lengths for 3d.
O1-C11.3588(19)C6-C71.412(2)
O1-H10.97(3)C6-H60.941(18)
O2-C111.2199(18)C7-C81.356(2)
C1-C101.367(2)C7-H70.905(18)
C1-C21.438(2)C8-C91.426(2)
C2-C31.385(2)C8-H80.92(2)
C2-C111.459(2)C9-C101.400(2)
C3-C41.406(2)C10-H100.939(18)
C3-H30.941(16)C11-C121.551(2)
C4-C51.418(2)C12-F11.3278(18)
C4-C91.427(2)C12-F31.3356(19)
C5-C61.359(2)C12-F21.3359(18)
C5-H50.963(19)
Table Table 20. Bond Angles for 3d.

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Table 20. Bond Angles for 3d.
C1-O1-H1108.5(16)C8-C7-H7119.3(12)
O1-C1-C10118.24(14)C6-C7-H7119.8(12)
O1-C1-C2121.49(14)C7-C8-C9120.94(15)
C10-C1-C2120.25(14)C7-C8-H8126.2(13)
C3-C2-C1118.78(13)C9-C8-H8112.8(13)
C3-C2-C11122.46(13)C10-C9-C8122.53(15)
C1-C2-C11118.76(13)C10-C9-C4119.43(15)
C2-C3-C4121.41(13)C8-C9-C4118.04(15)
C2-C3-H3121.0(10)C1-C10-C9121.21(15)
C4-C3-H3117.5(10)C1-C10-H10116.9(11)
C3-C4-C5122.04(13)C9-C10-H10121.8(11)
C3-C4-C9118.85(13)O2-C11-C2124.81(14)
C5-C4-C9119.11(14)O2-C11-C12115.85(13)
C6-C5-C4121.03(15)C2-C11-C12119.28(13)
C6-C5-H5122.5(11)F1-C12-F3107.45(12)
C4-C5-H5116.5(11)F1-C12-F2107.51(13)
C5-C6-C7119.96(16)F3-C12-F2107.63(12)
C5-C6-H6121.7(10)F1-C12-C11110.39(12)
C7-C6-H6118.3(10)F3-C12-C11111.44(13)
C8-C7-C6120.91(16)F2-C12-C11112.21(12)
Table Table 21. Torsion Angles for 3d.

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Table 21. Torsion Angles for 3d.
O1-C1-C2-C3−178.15(14)C3-C4-C9-C8−178.87(13)
C10-C1-C2-C33.2(2)C5-C4-C9-C81.1(2)
O1-C1-C2-C111.9(2)O1-C1-C10-C9178.95(14)
C10-C1-C2-C11−176.80(13)C2-C1-C10-C9−2.3(2)
C1-C2-C3-C4−1.6(2)C8-C9-C10-C1−179.58(14)
C11-C2-C3-C4178.34(13)C4-C9-C10-C1−0.1(2)
C2-C3-C4-C5179.37(14)C3-C2-C11-O2171.95(15)
C2-C3-C4-C9−0.7(2)C1-C2-C11-O2−8.1(2)
C3-C4-C5-C6178.62(14)C3-C2-C11-C12−11.0(2)
C9-C4-C5-C6−1.3(2)C1-C2-C11-C12168.99(13)
C4-C5-C6-C70.7(2)O2-C11-C12-F14.49(18)
C5-C6-C7-C80.1(2)C2-C11-C12-F1−172.83(12)
C6-C7-C8-C9−0.3(2)O2-C11-C12-F3123.80(14)
C7-C8-C9-C10179.23(15)C2-C11-C12-F3−53.51(17)
C7-C8-C9-C4−0.3(2)O2-C11-C12-F2−115.41(15)
C3-C4-C9-C101.6(2)C2-C11-C12-F267.28(18)
C5-C4-C9-C10−178.48(14)

4. Compound 4c

Experimental for C12H9F3O2 (4c)

Data Collection and Processing. The sample 4c was submitted by Joseph Sloop of the Sloop research group at Georgia Gwinnett College. The sample was mounted on a nylon loop with a small amount of Paratone N oil. All X-ray measurements were made on a Bruker-Nonius Kappa Axis X8 Apex2 diffractometer at a temperature of 110 K. The unit cell dimensions were determined from a symmetry constrained fit of 6416 reflections with 5.78° < 2θ < 71.38°. The data collection strategy was a number of ω and ϕ scans which collected data up to 71.58° (2θ). The frame integration was performed using SAINT [29]. The resulting raw data was scaled and absorption corrected using a multi-scan averaging of symmetry equivalent data using SADABS [30].

Structure Solution and Refinement. The structure was solved by direct methods using the XS program [31]. All non-hydrogen atoms were obtained from the initial solution. The hydrogen atoms were located from a difference Fourier map and were allowed to refine isotropically. The structural model was fit to the data using full matrix least-squares based on F2. The calculated structure factors included corrections for anomalous dispersion from the usual tabulation. The structure was refined using the XL program from SHELXTL [32], graphic plots were produced using the NRCVAX crystallographic program suite. Additional information and other relevant literature references can be found in the reference section of the Facility's Web page (http://www.xray.ncsu.edu).

Applsci 02 00061 g018 1024
Figure 18. ORTEP drawing of 4c showing naming and numbering scheme. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.

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Figure 18. ORTEP drawing of 4c showing naming and numbering scheme. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.
Applsci 02 00061 g018 1024
Applsci 02 00061 g019 1024
Figure 19. ORTEP drawing of 4c. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.

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Figure 19. ORTEP drawing of 4c. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.
Applsci 02 00061 g019 1024
Applsci 02 00061 g020 1024
Figure 20. Stereoscopic ORTEP drawing of 4c. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.

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Figure 20. Stereoscopic ORTEP drawing of 4c. Ellipsoids are at the 50% probability level and hydrogen atoms were drawn with arbitrary radii for clarity.
Applsci 02 00061 g020 1024
Table Table 22. Summary of Crystal Data for 4c.

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Table 22. Summary of Crystal Data for 4c.
FormulaC12H9F3O2
Formula Weight (g/mol)242.19
Crystal Dimensions (mm )0.38 × 0.28 × 0.04
Crystal Color and Habitcolourless plate
Crystal Systemtriclinic
Space GroupP -1
Temperature, K110
a, Å7.3528(2)
b, Å 7.9165(2)
c, Å 9.7991(2)
α,°73.0533(11)
β,°85.3968(12)
γ,°68.3581(11)
V, Å3506.92(2)
Reflections to determine final unit cell6416
Min and Max 2θ for cell determination, °5.78, 71.38
Z2
F(000)248
ρ (g/cm)1.587
λ, Å, (MoK )0.71073
μ, (cm1)0.143
Number of reflections measured20479
Unique reflections measured4691
Rmerge0.0265
Number of reflections included in refinement4691
Cut off Threshold Expression>2sigma(I)
Structure refined usingfull matrix least-squares using F2
Weighting Schemew = 1/[sigma2(Fo2) + (0.0707P)2 + 0.0436P] where P = (Fo2 + 2Fc2)/3
R10.0382
wR20.1082
R1 (all data)0.0525
wR2 (all data)0.1220
GOF1.048

Where:R1 = Σ( |Fo| − |Fc| ) / Σ FowR2 = [ Σ( w( Fo2 − Fc2 )2 ) / Σ(w Fo4 ) ] ½GOF = [ Σ( w( Fo2 − Fc2 )2 ) / (No. of reflns. − No. of params. ) ] ½

Table Table 23. Atomic Coordinates for 4c.

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Table 23. Atomic Coordinates for 4c.
AtomxyzUiso/equiv
O10.77448(8)0.28007(9)0.27345(6)0.01748(12)
O20.99446(9)0.28522(9)0.06442(6)0.02064(13)
C10.92164(10)0.26838(10)0.34926(7)0.01305(12)
C21.10003(10)0.26974(10)0.29126(8)0.01358(12)
C31.25154(11)0.27188(11)0.38557(8)0.01584(13)
C41.24786(11)0.15172(11)0.53827(8)0.01618(13)
C51.04451(11)0.19875(10)0.59451(8)0.01444(13)
C61.00916(12)0.18008(12)0.73914(8)0.01899(15)
C70.82002(13)0.21517(12)0.78875(9)0.02070(15)
C80.66361(12)0.26962(12)0.69526(9)0.01971(15)
C90.69574(11)0.28853(11)0.55100(8)0.01598(13)
C100.88579(10)0.25358(10)0.50052(7)0.01326(12)
C111.12232(11)0.27815(10)0.14448(8)0.01590(13)
C121.31898(12)0.27354(12)0.07494(9)0.02008(15)
F11.37562(8)0.40737(8)0.09309(6)0.02557(13)
F21.46211(8)0.10631(8)0.12997(6)0.03004(14)
F31.30731(9)0.29835(10)−0.06471(6)0.03180(15)
H10.818(3)0.282(3)0.190(2)0.066(5)
H3A1.2210(17)0.4028(17)0.3866(12)0.018(3)
H3B1.386(2)0.2261(18)0.3516(13)0.026(3)
H4A1.3333(19)0.1700(17)0.5989(13)0.021(3)
H4B1.2933(18)0.0209(17)0.5436(13)0.020(3)
H61.120(2)0.1395(19)0.8020(14)0.030(3)
H70.806(2)0.204(2)0.8859(17)0.041(4)
H80.526(2)0.304(2)0.7231(14)0.033(3)
H90.5882(18)0.3326(17)0.4836(13)0.019(3)
Table Table 24. Anisotropic Displacement Parameters for 4c.

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Table 24. Anisotropic Displacement Parameters for 4c.
Atomu11u22u33u12u13u23
O10.0149(2)0.0246(3)0.0147(2)−0.0091(2)−0.00183(19)−0.0048(2)
O20.0229(3)0.0269(3)0.0145(2)−0.0113(2)−0.0001(2)−0.0061(2)
C10.0127(3)0.0135(3)0.0133(3)−0.0052(2)−0.0005(2)−0.0035(2)
C20.0129(3)0.0155(3)0.0131(3)−0.0059(2)0.0007(2)−0.0042(2)
C30.0137(3)0.0189(3)0.0166(3)−0.0081(2)0.0007(2)−0.0046(2)
C40.0134(3)0.0184(3)0.0162(3)−0.0059(2)−0.0019(2)−0.0035(2)
C50.0151(3)0.0148(3)0.0143(3)−0.0062(2)0.0003(2)−0.0044(2)
C60.0226(4)0.0212(3)0.0144(3)−0.0091(3)−0.0007(3)−0.0051(3)
C70.0270(4)0.0225(3)0.0156(3)−0.0115(3)0.0055(3)−0.0078(3)
C80.0210(4)0.0215(3)0.0203(3)−0.0104(3)0.0077(3)−0.0097(3)
C90.0142(3)0.0171(3)0.0185(3)−0.0069(2)0.0030(2)−0.0068(2)
C100.0133(3)0.0143(3)0.0136(3)−0.0061(2)0.0012(2)−0.0047(2)
C110.0174(3)0.0162(3)0.0140(3)−0.0067(2)0.0021(2)−0.0038(2)
C120.0204(3)0.0226(4)0.0166(3)−0.0077(3)0.0049(3)−0.0058(3)
F10.0244(3)0.0283(3)0.0279(3)−0.0162(2)0.0068(2)−0.0065(2)
F20.0215(3)0.0254(3)0.0345(3)−0.0013(2)0.0080(2)−0.0070(2)
F30.0341(3)0.0473(4)0.0169(2)−0.0181(3)0.0108(2)−0.0115(2)
Table Table 25. Bond Lengths for 4c.

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Table 25. Bond Lengths for 4c.
O1-C11.3215(9)C5-C101.4016(10)
O1-H10.855(19)C6-C71.3903(12)
O2-C111.2476(10)C6-H60.960(14)
C1-C21.3895(10)C7-C81.3860(12)
C1-C101.4626(10)C7-H70.931(15)
C2-C111.4193(10)C8-C91.3877(11)
C2-C31.5112(10)C8-H80.984(14)
C3-C41.5255(11)C9-C101.3992(10)
C3-H3A0.979(12)C9-H90.964(12)
C3-H3B0.984(13)C11-C121.5408(11)
C4-C51.5016(10)C12-F31.3298(10)
C4-H4A0.972(12)C12-F11.3322(10)
C4-H4B0.950(12)C12-F21.3410(10)
C5-C61.3946(10)
Table Table 26. Bond Angles for 4c.

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Table 26. Bond Angles for 4c.
C1-O1-H1105.2(13)C7-C6-H6122.1(8)
O1-C1-C2123.08(7)C5-C6-H6117.4(8)
O1-C1-C10115.65(6)C8-C7-C6120.54(7)
C2-C1-C10121.28(6)C8-C7-H7123.4(9)
C1-C2-C11116.88(7)C6-C7-H7116.1(9)
C1-C2-C3118.29(6)C7-C8-C9119.86(7)
C11-C2-C3124.76(6)C7-C8-H8124.2(8)
C2-C3-C4111.06(6)C9-C8-H8115.9(8)
C2-C3-H3A108.3(7)C8-C9-C10119.82(7)
C4-C3-H3A108.5(7)C8-C9-H9121.1(7)
C2-C3-H3B113.2(7)C10-C9-H9119.0(7)
C4-C3-H3B108.2(8)C9-C10-C5120.59(7)
H3A-C3-H3B107.4(10)C9-C10-C1120.17(7)
C5-C4-C3112.07(6)C5-C10-C1119.22(6)
C5-C4-H4A110.3(7)O2-C11-C2125.09(7)
C3-C4-H4A109.1(7)O2-C11-C12115.47(7)
C5-C4-H4B105.9(7)C2-C11-C12119.42(7)
C3-C4-H4B111.1(7)F3-C12-F1107.53(7)
H4A-C4-H4B108.2(10)F3-C12-F2107.30(7)
C6-C5-C10118.70(7)F1-C12-F2107.24(7)
C6-C5-C4121.98(7)F3-C12-C11110.83(7)
C10-C5-C4119.24(6)F1-C12-C11112.56(6)
C7-C6-C5120.50(8)F2-C12-C11111.13(6)
Table Table 27. Torsion Angles for 4c.

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Table 27. Torsion Angles for 4c.
O1-C1-C2-C11−2.04(11)C4-C5-C10-C9176.58(7)
C10-C1-C2-C11177.93(6)C6-C5-C10-C1−178.26(7)
O1-C1-C2-C3175.03(7)C4-C5-C10-C1−1.57(10)
C10-C1-C2-C3−4.99(10)O1-C1-C10-C9−12.24(10)
C1-C2-C3-C436.71(9)C2-C1-C10-C9167.79(7)
C11-C2-C3-C4−146.47(7)O1-C1-C10-C5165.92(6)
C2-C3-C4-C5−49.62(8)C2-C1-C10-C5−14.06(10)
C3-C4-C5-C6−149.82(7)C1-C2-C11-O20.34(11)
C3-C4-C5-C1033.60(9)C3-C2-C11-O2−176.52(7)
C10-C5-C6-C70.04(11)C1-C2-C11-C12−178.03(6)
C4-C5-C6-C7−176.56(7)C3-C2-C11-C125.11(11)
C5-C6-C7-C8−0.13(12)O2-C11-C12-F36.60(10)
C6-C7-C8-C90.30(12)C2-C11-C12-F3−174.87(7)
C7-C8-C9-C10−0.37(11)O2-C11-C12-F1127.07(8)
C8-C9-C10-C50.28(11)C2-C11-C12-F1−54.40(10)
C8-C9-C10-C1178.41(7)O2-C11-C12-F2−112.62(8)
C6-C5-C10-C9−0.11(11)C2-C11-C12-F265.91(9)
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