Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011202447X/fg3250sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011202447X/fg3250Isup2.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S010827011202447X/fg3250Isup5.cml | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011202447X/fg3250IIsup3.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S010827011202447X/fg3250IIsup6.cml | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011202447X/fg3250IIIsup4.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S010827011202447X/fg3250IIIsup7.cml |
CCDC references: 893489; 893490; 893491
The title compounds were synthesized by heating together under reflux for 15 min cyclohexane-1,2-dicarboxylic anhydride (1 mmol) and, respectively, 2-, 3- or 4-fluoroaniline (1 mmol) in ethanol–water (50 ml, 1:1 v/v). After reducing the volume to 30 ml, the solutions were filtered while hot and allowed the evaporate to incipient dryness at room temperature over a period of several weeks, giving either colourless plates [for (I) and (II)] or prisms [for (III)] [Block in CIF for (I) and (III) - please clarify] from which specimens were cleaved for the X-ray analyses.
The H atoms involved in hydrogen-bonding interactions in (II) (H11 and H22) were located by difference methods and their positional and isotropic displacement parameters were refined. The other H atoms in all structures were included in the respective refinements at calculated positions (C—H = 0.93–0.97 Å), with Uiso(H) = 1.2Ueq(C), using a riding-model approximation. For (II), atom F31 was found to be disordered, having a rotationally related component F51 [site-occupancy factors for F31:F51 refined to 0.784 (4):0.216 (4)].
For all compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).
C14H14FNO2 | Z = 2 |
Mr = 247.26 | F(000) = 260 |
Triclinic, P1 | Dx = 1.390 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0316 (4) Å | Cell parameters from 3763 reflections |
b = 8.1702 (4) Å | θ = 3.3–28.8° |
c = 9.2085 (5) Å | µ = 0.10 mm−1 |
α = 98.595 (4)° | T = 200 K |
β = 93.324 (4)° | Block, colourless |
γ = 97.260 (4)° | 0.40 × 0.30 × 0.25 mm |
V = 590.86 (5) Å3 |
Oxford Gemini-S CCD area-detector diffractometer | 2305 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 1783 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
Detector resolution: 16.077 pixels mm-1 | θmax = 26.0°, θmin = 3.3° |
ω scans | h = −9→9 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | k = −10→10 |
Tmin = 0.969, Tmax = 0.989 | l = −11→11 |
7051 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0572P)2] where P = (Fo2 + 2Fc2)/3 |
2305 reflections | (Δ/σ)max < 0.001 |
163 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C14H14FNO2 | γ = 97.260 (4)° |
Mr = 247.26 | V = 590.86 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.0316 (4) Å | Mo Kα radiation |
b = 8.1702 (4) Å | µ = 0.10 mm−1 |
c = 9.2085 (5) Å | T = 200 K |
α = 98.595 (4)° | 0.40 × 0.30 × 0.25 mm |
β = 93.324 (4)° |
Oxford Gemini-S CCD area-detector diffractometer | 2305 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 1783 reflections with I > 2σ(I) |
Tmin = 0.969, Tmax = 0.989 | Rint = 0.022 |
7051 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.24 e Å−3 |
2305 reflections | Δρmin = −0.20 e Å−3 |
163 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
F21 | 0.74386 (11) | 0.59410 (12) | 0.94457 (10) | 0.0446 (3) | |
O1 | 0.46040 (12) | 0.13876 (12) | 0.70637 (11) | 0.0335 (3) | |
O3 | 0.87098 (12) | 0.55671 (12) | 0.64213 (11) | 0.0326 (3) | |
N2 | 0.64353 (13) | 0.37625 (13) | 0.69026 (12) | 0.0246 (3) | |
C1 | 0.59322 (17) | 0.20271 (16) | 0.67222 (15) | 0.0249 (4) | |
C3 | 0.80782 (17) | 0.41573 (17) | 0.65001 (15) | 0.0250 (4) | |
C4 | 0.99212 (18) | 0.25073 (18) | 0.77153 (17) | 0.0337 (5) | |
C5 | 1.02424 (19) | 0.07392 (19) | 0.78648 (18) | 0.0371 (5) | |
C6 | 0.85789 (19) | −0.03854 (18) | 0.78468 (17) | 0.0343 (5) | |
C7 | 0.75306 (18) | −0.05104 (17) | 0.63997 (16) | 0.0313 (4) | |
C8 | 0.73070 (17) | 0.11964 (17) | 0.59760 (15) | 0.0269 (4) | |
C9 | 0.88515 (17) | 0.25640 (17) | 0.62776 (16) | 0.0270 (4) | |
C11 | 0.54230 (16) | 0.49939 (16) | 0.74467 (15) | 0.0245 (4) | |
C21 | 0.59667 (17) | 0.61008 (18) | 0.87238 (15) | 0.0280 (4) | |
C31 | 0.5055 (2) | 0.73352 (18) | 0.92780 (17) | 0.0371 (5) | |
C41 | 0.3533 (2) | 0.74495 (19) | 0.85443 (18) | 0.0390 (5) | |
C51 | 0.29473 (19) | 0.63391 (19) | 0.72814 (18) | 0.0356 (5) | |
C61 | 0.38940 (17) | 0.51205 (18) | 0.67305 (16) | 0.0290 (4) | |
H4A | 1.09910 | 0.32120 | 0.77310 | 0.0400* | |
H4B | 0.93440 | 0.29530 | 0.85510 | 0.0400* | |
H5A | 1.08700 | 0.03050 | 0.70580 | 0.0440* | |
H5B | 1.09100 | 0.07560 | 0.87800 | 0.0440* | |
H6A | 0.79530 | 0.00570 | 0.86510 | 0.0410* | |
H6B | 0.87970 | −0.14920 | 0.79940 | 0.0410* | |
H7A | 0.64300 | −0.11220 | 0.64720 | 0.0380* | |
H7B | 0.80660 | −0.11400 | 0.56240 | 0.0380* | |
H8 | 0.69970 | 0.10150 | 0.49130 | 0.0320* | |
H9 | 0.95450 | 0.25210 | 0.54350 | 0.0320* | |
H31 | 0.54540 | 0.80780 | 1.01290 | 0.0440* | |
H41 | 0.29000 | 0.82780 | 0.89020 | 0.0470* | |
H51 | 0.19140 | 0.64120 | 0.68010 | 0.0430* | |
H61 | 0.35010 | 0.43830 | 0.58750 | 0.0350* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F21 | 0.0431 (6) | 0.0479 (6) | 0.0397 (5) | 0.0032 (4) | −0.0095 (4) | 0.0047 (4) |
O1 | 0.0284 (5) | 0.0289 (6) | 0.0404 (6) | −0.0046 (4) | 0.0056 (4) | 0.0028 (5) |
O3 | 0.0297 (5) | 0.0233 (5) | 0.0458 (6) | 0.0012 (4) | 0.0051 (4) | 0.0100 (5) |
N2 | 0.0228 (6) | 0.0206 (6) | 0.0300 (6) | 0.0025 (5) | 0.0024 (5) | 0.0034 (5) |
C1 | 0.0276 (7) | 0.0223 (7) | 0.0231 (7) | 0.0005 (6) | −0.0018 (6) | 0.0025 (5) |
C3 | 0.0226 (7) | 0.0263 (8) | 0.0261 (7) | 0.0015 (6) | 0.0006 (5) | 0.0058 (6) |
C4 | 0.0278 (8) | 0.0284 (8) | 0.0439 (9) | −0.0010 (6) | −0.0049 (6) | 0.0099 (7) |
C5 | 0.0354 (8) | 0.0353 (9) | 0.0427 (9) | 0.0085 (7) | −0.0032 (7) | 0.0124 (7) |
C6 | 0.0448 (9) | 0.0233 (8) | 0.0367 (9) | 0.0067 (7) | 0.0041 (7) | 0.0091 (6) |
C7 | 0.0365 (8) | 0.0198 (7) | 0.0363 (8) | 0.0025 (6) | 0.0040 (6) | 0.0010 (6) |
C8 | 0.0311 (8) | 0.0241 (7) | 0.0246 (7) | 0.0035 (6) | 0.0011 (6) | 0.0015 (6) |
C9 | 0.0269 (7) | 0.0254 (7) | 0.0306 (8) | 0.0047 (6) | 0.0075 (6) | 0.0076 (6) |
C11 | 0.0245 (7) | 0.0213 (7) | 0.0286 (8) | 0.0026 (6) | 0.0062 (6) | 0.0057 (6) |
C21 | 0.0277 (7) | 0.0282 (8) | 0.0274 (8) | −0.0005 (6) | 0.0003 (6) | 0.0064 (6) |
C31 | 0.0493 (10) | 0.0277 (8) | 0.0325 (9) | 0.0014 (7) | 0.0113 (7) | −0.0006 (7) |
C41 | 0.0433 (9) | 0.0316 (8) | 0.0470 (10) | 0.0137 (7) | 0.0194 (7) | 0.0087 (7) |
C51 | 0.0277 (8) | 0.0374 (9) | 0.0464 (10) | 0.0092 (7) | 0.0079 (7) | 0.0157 (7) |
C61 | 0.0257 (7) | 0.0307 (8) | 0.0305 (8) | 0.0020 (6) | 0.0020 (6) | 0.0062 (6) |
F21—C21 | 1.3529 (16) | C31—C41 | 1.383 (2) |
O1—C1 | 1.2071 (17) | C41—C51 | 1.382 (2) |
O3—C3 | 1.2128 (17) | C51—C61 | 1.383 (2) |
N2—C1 | 1.4065 (17) | C4—H4A | 0.9700 |
N2—C3 | 1.4026 (17) | C4—H4B | 0.9700 |
N2—C11 | 1.4239 (17) | C5—H5A | 0.9700 |
C1—C8 | 1.5133 (19) | C5—H5B | 0.9700 |
C3—C9 | 1.504 (2) | C6—H6A | 0.9700 |
C4—C5 | 1.524 (2) | C6—H6B | 0.9700 |
C4—C9 | 1.546 (2) | C7—H7A | 0.9700 |
C5—C6 | 1.521 (2) | C7—H7B | 0.9700 |
C6—C7 | 1.517 (2) | C8—H8 | 0.9800 |
C7—C8 | 1.532 (2) | C9—H9 | 0.9800 |
C8—C9 | 1.543 (2) | C31—H31 | 0.9300 |
C11—C21 | 1.3836 (19) | C41—H41 | 0.9300 |
C11—C61 | 1.3829 (19) | C51—H51 | 0.9300 |
C21—C31 | 1.375 (2) | C61—H61 | 0.9300 |
C1—N2—C3 | 112.11 (11) | C9—C4—H4B | 109.00 |
C1—N2—C11 | 124.71 (11) | H4A—C4—H4B | 108.00 |
C3—N2—C11 | 123.17 (11) | C4—C5—H5A | 110.00 |
O1—C1—N2 | 124.13 (12) | C4—C5—H5B | 110.00 |
O1—C1—C8 | 128.71 (12) | C6—C5—H5A | 110.00 |
N2—C1—C8 | 107.09 (11) | C6—C5—H5B | 110.00 |
O3—C3—N2 | 123.50 (13) | H5A—C5—H5B | 108.00 |
O3—C3—C9 | 128.95 (13) | C5—C6—H6A | 109.00 |
N2—C3—C9 | 107.49 (11) | C5—C6—H6B | 109.00 |
C5—C4—C9 | 112.18 (12) | C7—C6—H6A | 109.00 |
C4—C5—C6 | 110.01 (12) | C7—C6—H6B | 109.00 |
C5—C6—C7 | 111.31 (13) | H6A—C6—H6B | 108.00 |
C6—C7—C8 | 113.14 (12) | C6—C7—H7A | 109.00 |
C1—C8—C7 | 114.60 (11) | C6—C7—H7B | 109.00 |
C1—C8—C9 | 103.51 (11) | C8—C7—H7A | 109.00 |
C7—C8—C9 | 116.97 (12) | C8—C7—H7B | 109.00 |
C3—C9—C4 | 107.17 (12) | H7A—C7—H7B | 108.00 |
C3—C9—C8 | 103.24 (11) | C1—C8—H8 | 107.00 |
C4—C9—C8 | 113.19 (12) | C7—C8—H8 | 107.00 |
N2—C11—C21 | 119.82 (12) | C9—C8—H8 | 107.00 |
N2—C11—C61 | 121.70 (12) | C3—C9—H9 | 111.00 |
C21—C11—C61 | 118.48 (13) | C4—C9—H9 | 111.00 |
F21—C21—C11 | 118.31 (12) | C8—C9—H9 | 111.00 |
F21—C21—C31 | 119.57 (13) | C21—C31—H31 | 121.00 |
C11—C21—C31 | 122.12 (13) | C41—C31—H31 | 121.00 |
C21—C31—C41 | 118.65 (14) | C31—C41—H41 | 120.00 |
C31—C41—C51 | 120.34 (15) | C51—C41—H41 | 120.00 |
C41—C51—C61 | 120.13 (14) | C41—C51—H51 | 120.00 |
C11—C61—C51 | 120.27 (14) | C61—C51—H51 | 120.00 |
C5—C4—H4A | 109.00 | C11—C61—H61 | 120.00 |
C5—C4—H4B | 109.00 | C51—C61—H61 | 120.00 |
C9—C4—H4A | 109.00 | ||
C3—N2—C1—O1 | 176.24 (13) | C5—C4—C9—C8 | 45.91 (16) |
C11—N2—C1—O1 | −3.0 (2) | C9—C4—C5—C6 | −58.99 (16) |
C3—N2—C1—C8 | −6.50 (15) | C4—C5—C6—C7 | 62.01 (16) |
C11—N2—C1—C8 | 174.29 (12) | C5—C6—C7—C8 | −51.82 (16) |
C11—N2—C3—C9 | 168.84 (12) | C6—C7—C8—C1 | −81.64 (15) |
C1—N2—C11—C21 | 119.11 (15) | C6—C7—C8—C9 | 39.78 (17) |
C3—N2—C11—C21 | −60.02 (18) | C1—C8—C9—C4 | 90.39 (13) |
C1—N2—C11—C61 | −60.88 (19) | C7—C8—C9—C3 | −152.18 (12) |
C1—N2—C3—O3 | 172.17 (13) | C7—C8—C9—C4 | −36.67 (17) |
C11—N2—C3—O3 | −8.6 (2) | C1—C8—C9—C3 | −25.12 (13) |
C1—N2—C3—C9 | −10.39 (15) | N2—C11—C21—F21 | −1.96 (19) |
C3—N2—C11—C61 | 119.99 (15) | N2—C11—C21—C31 | 178.57 (13) |
O1—C1—C8—C7 | −34.4 (2) | C61—C11—C21—F21 | 178.03 (12) |
N2—C1—C8—C7 | 148.47 (12) | C61—C11—C21—C31 | −1.4 (2) |
N2—C1—C8—C9 | 19.94 (14) | N2—C11—C61—C51 | −179.48 (13) |
O1—C1—C8—C9 | −162.98 (14) | C21—C11—C61—C51 | 0.5 (2) |
N2—C3—C9—C8 | 22.21 (14) | F21—C21—C31—C41 | −178.34 (13) |
O3—C3—C9—C4 | 79.72 (18) | C11—C21—C31—C41 | 1.1 (2) |
O3—C3—C9—C8 | −160.53 (14) | C21—C31—C41—C51 | 0.1 (2) |
N2—C3—C9—C4 | −97.54 (13) | C31—C41—C51—C61 | −1.0 (2) |
C5—C4—C9—C3 | 159.07 (12) | C41—C51—C61—C11 | 0.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C31—H31···O1i | 0.93 | 2.56 | 3.3589 (18) | 144 |
C51—H51···O3ii | 0.93 | 2.57 | 3.4064 (18) | 150 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x−1, y, z. |
C14H16FNO3 | F(000) = 560 |
Mr = 265.28 | Dx = 1.382 Mg m−3 |
Monoclinic, P21/c | Melting point: 423 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 11.3688 (8) Å | Cell parameters from 2473 reflections |
b = 8.7802 (6) Å | θ = 3.2–28.8° |
c = 12.7989 (10) Å | µ = 0.11 mm−1 |
β = 93.436 (7)° | T = 200 K |
V = 1275.29 (16) Å3 | Plate, colourless |
Z = 4 | 0.45 × 0.40 × 0.05 mm |
Oxford Gemini-S CCD area-detector diffractometer | 2499 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 1530 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
Detector resolution: 16.077 pixels mm-1 | θmax = 26.0°, θmin = 3.2° |
ω scans | h = −14→13 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | k = −10→10 |
Tmin = 0.881, Tmax = 0.980 | l = −15→15 |
8075 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.092 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.86 | w = 1/[σ2(Fo2) + (0.0463P)2] where P = (Fo2 + 2Fc2)/3 |
2499 reflections | (Δ/σ)max < 0.001 |
190 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C14H16FNO3 | V = 1275.29 (16) Å3 |
Mr = 265.28 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.3688 (8) Å | µ = 0.11 mm−1 |
b = 8.7802 (6) Å | T = 200 K |
c = 12.7989 (10) Å | 0.45 × 0.40 × 0.05 mm |
β = 93.436 (7)° |
Oxford Gemini-S CCD area-detector diffractometer | 2499 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 1530 reflections with I > 2σ(I) |
Tmin = 0.881, Tmax = 0.980 | Rint = 0.051 |
8075 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.092 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.86 | Δρmax = 0.18 e Å−3 |
2499 reflections | Δρmin = −0.16 e Å−3 |
190 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
F31 | 0.07190 (14) | 0.14561 (19) | 0.55050 (14) | 0.0578 (7) | 0.784 (4) |
O12 | 0.49018 (12) | 0.11533 (15) | 0.60592 (11) | 0.0405 (5) | |
O21 | 0.65771 (12) | 0.43023 (16) | 0.81044 (11) | 0.0363 (5) | |
O22 | 0.54066 (11) | 0.46189 (14) | 0.66584 (10) | 0.0322 (4) | |
N11 | 0.46302 (14) | 0.25094 (18) | 0.45646 (13) | 0.0271 (5) | |
C1 | 0.65784 (16) | 0.24514 (19) | 0.55040 (15) | 0.0250 (6) | |
C2 | 0.69525 (15) | 0.2733 (2) | 0.66620 (14) | 0.0249 (6) | |
C3 | 0.82771 (16) | 0.3025 (2) | 0.68136 (16) | 0.0333 (7) | |
C4 | 0.86591 (17) | 0.4320 (2) | 0.61238 (17) | 0.0378 (7) | |
C5 | 0.83022 (17) | 0.4007 (2) | 0.49798 (16) | 0.0373 (7) | |
C6 | 0.69886 (16) | 0.3734 (2) | 0.48017 (15) | 0.0284 (6) | |
C11 | 0.34466 (16) | 0.20884 (19) | 0.43100 (15) | 0.0265 (6) | |
C12 | 0.52953 (16) | 0.2008 (2) | 0.54022 (15) | 0.0259 (6) | |
C21 | 0.26381 (16) | 0.1982 (2) | 0.50736 (17) | 0.0319 (7) | |
C22 | 0.62315 (16) | 0.39857 (19) | 0.71163 (15) | 0.0243 (6) | |
C31 | 0.15025 (18) | 0.1568 (2) | 0.47794 (19) | 0.0401 (8) | |
C41 | 0.11264 (19) | 0.1275 (2) | 0.3759 (2) | 0.0444 (8) | |
C51 | 0.1944 (2) | 0.1407 (2) | 0.3020 (2) | 0.0459 (8) | |
C61 | 0.30947 (18) | 0.1798 (2) | 0.32728 (17) | 0.0363 (7) | |
F51 | 0.1571 (6) | 0.1058 (9) | 0.2127 (5) | 0.077 (3) | 0.216 (4) |
H1 | 0.70130 | 0.15440 | 0.53040 | 0.0300* | |
H3A | 0.84760 | 0.32740 | 0.75410 | 0.0400* | |
H3B | 0.87010 | 0.21070 | 0.66460 | 0.0400* | |
H4A | 0.95080 | 0.44400 | 0.62090 | 0.0450* | |
H4B | 0.82980 | 0.52620 | 0.63380 | 0.0450* | |
H5A | 0.85260 | 0.48670 | 0.45600 | 0.0450* | |
H5B | 0.87240 | 0.31190 | 0.47500 | 0.0450* | |
H6A | 0.68080 | 0.34690 | 0.40740 | 0.0340* | |
H6B | 0.65670 | 0.46630 | 0.49490 | 0.0340* | |
H11 | 0.4966 (15) | 0.312 (2) | 0.4175 (14) | 0.021 (5)* | |
H21 | 0.28600 | 0.21870 | 0.57710 | 0.0380* | |
H22 | 0.608 (2) | 0.499 (3) | 0.840 (2) | 0.070 (8)* | |
H41 | 0.03510 | 0.09990 | 0.35780 | 0.0530* | |
H51 | 0.17190 | 0.12070 | 0.23260 | 0.0550* | 0.784 (4) |
H61 | 0.36320 | 0.18670 | 0.27550 | 0.0440* | |
H2 | 0.67870 | 0.17960 | 0.70430 | 0.0300* | |
H31 | 0.09610 | 0.14820 | 0.52930 | 0.0480* | 0.216 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
F31 | 0.0384 (10) | 0.0724 (13) | 0.0646 (13) | 0.0000 (8) | 0.0195 (9) | 0.0098 (9) |
O12 | 0.0400 (8) | 0.0417 (9) | 0.0391 (9) | −0.0110 (6) | −0.0022 (7) | 0.0182 (7) |
O21 | 0.0453 (9) | 0.0379 (8) | 0.0253 (8) | 0.0124 (7) | −0.0023 (7) | −0.0067 (7) |
O22 | 0.0333 (8) | 0.0353 (7) | 0.0279 (8) | 0.0102 (6) | 0.0004 (6) | 0.0027 (6) |
N11 | 0.0310 (9) | 0.0230 (9) | 0.0274 (10) | −0.0035 (7) | 0.0025 (8) | 0.0069 (8) |
C1 | 0.0301 (11) | 0.0211 (9) | 0.0239 (10) | 0.0037 (8) | 0.0023 (8) | −0.0018 (8) |
C2 | 0.0290 (10) | 0.0215 (9) | 0.0238 (11) | 0.0021 (8) | −0.0007 (8) | 0.0031 (8) |
C3 | 0.0326 (11) | 0.0341 (11) | 0.0326 (12) | 0.0069 (9) | −0.0024 (9) | −0.0046 (9) |
C4 | 0.0277 (11) | 0.0384 (12) | 0.0473 (13) | −0.0044 (9) | 0.0015 (10) | −0.0032 (11) |
C5 | 0.0365 (12) | 0.0360 (12) | 0.0404 (13) | −0.0016 (9) | 0.0110 (10) | 0.0039 (10) |
C6 | 0.0353 (11) | 0.0262 (10) | 0.0241 (11) | −0.0041 (8) | 0.0052 (8) | 0.0005 (9) |
C11 | 0.0279 (10) | 0.0171 (9) | 0.0342 (12) | 0.0009 (8) | −0.0006 (9) | 0.0036 (8) |
C12 | 0.0338 (11) | 0.0177 (9) | 0.0261 (11) | −0.0004 (8) | 0.0013 (9) | 0.0003 (9) |
C21 | 0.0335 (12) | 0.0265 (10) | 0.0356 (12) | 0.0022 (9) | 0.0025 (10) | 0.0040 (9) |
C22 | 0.0262 (10) | 0.0239 (10) | 0.0229 (11) | −0.0033 (8) | 0.0019 (8) | 0.0028 (8) |
C31 | 0.0306 (12) | 0.0349 (12) | 0.0553 (16) | 0.0017 (9) | 0.0062 (11) | 0.0091 (11) |
C41 | 0.0310 (12) | 0.0357 (12) | 0.0650 (17) | −0.0052 (9) | −0.0094 (12) | −0.0001 (12) |
C51 | 0.0422 (14) | 0.0441 (13) | 0.0496 (16) | −0.0021 (10) | −0.0118 (12) | −0.0067 (12) |
C61 | 0.0381 (12) | 0.0354 (12) | 0.0350 (13) | 0.0020 (9) | −0.0003 (10) | −0.0049 (10) |
F51 | 0.067 (5) | 0.116 (6) | 0.043 (4) | −0.013 (4) | −0.027 (4) | −0.019 (4) |
F31—C31 | 1.328 (3) | C21—C31 | 1.372 (3) |
F51—C51 | 1.234 (7) | C31—C41 | 1.374 (3) |
O12—C12 | 1.231 (2) | C41—C51 | 1.370 (3) |
O21—C22 | 1.331 (2) | C51—C61 | 1.372 (3) |
O22—C22 | 1.211 (2) | C1—H1 | 0.9800 |
O21—H22 | 0.92 (3) | C2—H2 | 0.9800 |
N11—C11 | 1.415 (2) | C3—H3A | 0.9700 |
N11—C12 | 1.348 (2) | C3—H3B | 0.9700 |
N11—H11 | 0.839 (18) | C4—H4A | 0.9700 |
C1—C12 | 1.508 (3) | C4—H4B | 0.9700 |
C1—C6 | 1.531 (3) | C5—H5A | 0.9700 |
C1—C2 | 1.537 (3) | C5—H5B | 0.9700 |
C2—C3 | 1.528 (3) | C6—H6A | 0.9700 |
C2—C22 | 1.509 (2) | C6—H6B | 0.9700 |
C3—C4 | 1.519 (3) | C21—H21 | 0.9300 |
C4—C5 | 1.521 (3) | C31—H31 | 0.9300 |
C5—C6 | 1.516 (3) | C41—H41 | 0.9300 |
C11—C61 | 1.387 (3) | C51—H51 | 0.9300 |
C11—C21 | 1.384 (3) | C61—H61 | 0.9300 |
C22—O21—H22 | 111.9 (15) | C12—C1—H1 | 106.00 |
C11—N11—C12 | 125.33 (16) | C1—C2—H2 | 107.00 |
C11—N11—H11 | 119.4 (12) | C3—C2—H2 | 107.00 |
C12—N11—H11 | 115.3 (12) | C22—C2—H2 | 107.00 |
C6—C1—C12 | 117.80 (15) | C2—C3—H3A | 109.00 |
C2—C1—C12 | 109.58 (15) | C2—C3—H3B | 109.00 |
C2—C1—C6 | 111.80 (14) | C4—C3—H3A | 109.00 |
C1—C2—C3 | 111.28 (15) | C4—C3—H3B | 109.00 |
C1—C2—C22 | 111.31 (15) | H3A—C3—H3B | 108.00 |
C3—C2—C22 | 112.50 (15) | C3—C4—H4A | 109.00 |
C2—C3—C4 | 111.45 (15) | C3—C4—H4B | 109.00 |
C3—C4—C5 | 110.81 (15) | C5—C4—H4A | 110.00 |
C4—C5—C6 | 112.14 (16) | C5—C4—H4B | 109.00 |
C1—C6—C5 | 111.10 (15) | H4A—C4—H4B | 108.00 |
N11—C11—C21 | 121.18 (17) | C4—C5—H5A | 109.00 |
N11—C11—C61 | 118.97 (17) | C4—C5—H5B | 109.00 |
C21—C11—C61 | 119.85 (18) | C6—C5—H5A | 109.00 |
N11—C12—C1 | 118.55 (16) | C6—C5—H5B | 109.00 |
O12—C12—N11 | 122.19 (17) | H5A—C5—H5B | 108.00 |
O12—C12—C1 | 119.19 (17) | C1—C6—H6A | 109.00 |
C11—C21—C31 | 118.5 (2) | C1—C6—H6B | 109.00 |
O21—C22—O22 | 122.68 (16) | C5—C6—H6A | 109.00 |
O21—C22—C2 | 112.47 (15) | C5—C6—H6B | 109.00 |
O22—C22—C2 | 124.82 (17) | H6A—C6—H6B | 108.00 |
F31—C31—C21 | 119.2 (2) | C11—C21—H21 | 121.00 |
F31—C31—C41 | 117.85 (19) | C31—C21—H21 | 121.00 |
C21—C31—C41 | 123.0 (2) | C21—C31—H31 | 119.00 |
C31—C41—C51 | 117.1 (2) | C41—C31—H31 | 118.00 |
C41—C51—C61 | 122.3 (2) | C31—C41—H41 | 121.00 |
F51—C51—C41 | 114.1 (4) | C51—C41—H41 | 121.00 |
F51—C51—C61 | 123.4 (4) | C41—C51—H51 | 119.00 |
C11—C61—C51 | 119.2 (2) | C61—C51—H51 | 119.00 |
C2—C1—H1 | 106.00 | C11—C61—H61 | 120.00 |
C6—C1—H1 | 106.00 | C51—C61—H61 | 120.00 |
C12—N11—C11—C21 | 42.1 (3) | C1—C2—C22—O22 | 5.0 (2) |
C12—N11—C11—C61 | −138.77 (19) | C3—C2—C22—O21 | −51.3 (2) |
C11—N11—C12—O12 | −2.7 (3) | C3—C2—C22—O22 | 130.70 (19) |
C11—N11—C12—C1 | 174.22 (16) | C2—C3—C4—C5 | −56.0 (2) |
C6—C1—C2—C3 | −53.38 (19) | C3—C4—C5—C6 | 56.5 (2) |
C6—C1—C2—C22 | 72.97 (18) | C4—C5—C6—C1 | −55.06 (19) |
C12—C1—C2—C3 | 174.14 (14) | N11—C11—C21—C31 | −179.98 (17) |
C12—C1—C2—C22 | −59.51 (18) | C61—C11—C21—C31 | 0.9 (3) |
C2—C1—C6—C5 | 53.4 (2) | N11—C11—C61—C51 | −179.22 (16) |
C12—C1—C6—C5 | −178.42 (16) | C21—C11—C61—C51 | 0.0 (3) |
C2—C1—C12—O12 | −39.7 (2) | C11—C21—C31—F31 | 179.75 (17) |
C2—C1—C12—N11 | 143.30 (16) | C11—C21—C31—C41 | −1.0 (3) |
C6—C1—C12—O12 | −168.95 (16) | F31—C31—C41—C51 | 179.52 (17) |
C6—C1—C12—N11 | 14.0 (2) | C21—C31—C41—C51 | 0.2 (3) |
C1—C2—C3—C4 | 54.8 (2) | C31—C41—C51—C61 | 0.7 (3) |
C22—C2—C3—C4 | −70.9 (2) | C41—C51—C61—C11 | −0.7 (3) |
C1—C2—C22—O21 | −176.93 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···O22i | 0.839 (18) | 2.281 (18) | 2.967 (2) | 139.1 (15) |
O21—H22···O12ii | 0.92 (3) | 1.69 (2) | 2.613 (2) | 176 (2) |
C3—H3A···O21 | 0.97 | 2.49 | 2.847 (2) | 102 |
C21—H21···O12 | 0.93 | 2.50 | 2.891 (2) | 106 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y+1/2, −z+3/2. |
C14H14FNO2 | F(000) = 520 |
Mr = 247.26 | Dx = 1.365 Mg m−3 |
Monoclinic, P21/n | Melting point: 432 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 10.7554 (3) Å | Cell parameters from 3937 reflections |
b = 6.6709 (2) Å | θ = 3.3–28.8° |
c = 16.8466 (4) Å | µ = 0.10 mm−1 |
β = 95.275 (3)° | T = 200 K |
V = 1203.59 (6) Å3 | Block, colourless |
Z = 4 | 0.45 × 0.40 × 0.35 mm |
Oxford Gemini-S CCD area-detector diffractometer | 2362 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 1826 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ω scans | θmax = 26.0°, θmin = 3.3° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | h = −13→12 |
Tmin = 0.960, Tmax = 0.990 | k = −8→8 |
7621 measured reflections | l = −15→20 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0535P)2] where P = (Fo2 + 2Fc2)/3 |
2362 reflections | (Δ/σ)max < 0.001 |
163 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C14H14FNO2 | V = 1203.59 (6) Å3 |
Mr = 247.26 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.7554 (3) Å | µ = 0.10 mm−1 |
b = 6.6709 (2) Å | T = 200 K |
c = 16.8466 (4) Å | 0.45 × 0.40 × 0.35 mm |
β = 95.275 (3)° |
Oxford Gemini-S CCD area-detector diffractometer | 2362 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 1826 reflections with I > 2σ(I) |
Tmin = 0.960, Tmax = 0.990 | Rint = 0.023 |
7621 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.20 e Å−3 |
2362 reflections | Δρmin = −0.21 e Å−3 |
163 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
F41 | 0.98589 (8) | 0.53072 (13) | 0.14464 (5) | 0.0484 (3) | |
O1 | 0.55788 (9) | −0.11575 (13) | 0.08309 (6) | 0.0369 (3) | |
O3 | 0.43405 (10) | 0.41618 (15) | 0.22711 (6) | 0.0416 (3) | |
N2 | 0.52616 (10) | 0.16853 (15) | 0.15684 (6) | 0.0259 (3) | |
C1 | 0.49326 (13) | −0.02013 (19) | 0.12431 (7) | 0.0267 (4) | |
C3 | 0.42763 (13) | 0.2562 (2) | 0.19302 (8) | 0.0300 (4) | |
C4 | 0.23234 (14) | 0.2201 (2) | 0.10688 (10) | 0.0394 (5) | |
C5 | 0.14036 (14) | 0.0722 (2) | 0.06559 (9) | 0.0393 (5) | |
C6 | 0.21097 (14) | −0.1016 (2) | 0.03281 (8) | 0.0387 (5) | |
C7 | 0.28566 (14) | −0.2128 (2) | 0.09896 (9) | 0.0371 (4) | |
C8 | 0.36912 (13) | −0.07747 (19) | 0.15378 (7) | 0.0297 (4) | |
C9 | 0.31420 (13) | 0.1243 (2) | 0.17605 (8) | 0.0312 (4) | |
C11 | 0.64598 (12) | 0.26057 (18) | 0.15225 (7) | 0.0235 (4) | |
C21 | 0.65288 (13) | 0.44927 (19) | 0.11827 (7) | 0.0278 (4) | |
C31 | 0.76764 (13) | 0.5408 (2) | 0.11575 (8) | 0.0308 (4) | |
C41 | 0.87280 (12) | 0.4400 (2) | 0.14655 (8) | 0.0300 (4) | |
C51 | 0.86864 (13) | 0.2524 (2) | 0.17993 (8) | 0.0299 (4) | |
C61 | 0.75336 (13) | 0.16258 (19) | 0.18286 (7) | 0.0268 (4) | |
H4A | 0.18650 | 0.33150 | 0.12700 | 0.0470* | |
H4B | 0.28550 | 0.27280 | 0.06830 | 0.0470* | |
H5A | 0.08460 | 0.02270 | 0.10320 | 0.0470* | |
H5B | 0.09050 | 0.13870 | 0.02250 | 0.0470* | |
H6A | 0.15220 | −0.19280 | 0.00450 | 0.0460* | |
H6B | 0.26670 | −0.05140 | −0.00470 | 0.0460* | |
H7A | 0.33720 | −0.31210 | 0.07570 | 0.0440* | |
H7B | 0.22860 | −0.28340 | 0.13050 | 0.0440* | |
H8 | 0.38820 | −0.15140 | 0.20370 | 0.0360* | |
H9 | 0.26820 | 0.11140 | 0.22340 | 0.0370* | |
H21 | 0.58060 | 0.51380 | 0.09730 | 0.0330* | |
H31 | 0.77370 | 0.66780 | 0.09370 | 0.0370* | |
H51 | 0.94140 | 0.18770 | 0.20000 | 0.0360* | |
H61 | 0.74790 | 0.03600 | 0.20540 | 0.0320* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F41 | 0.0260 (5) | 0.0518 (6) | 0.0683 (6) | −0.0098 (4) | 0.0099 (4) | −0.0038 (4) |
O1 | 0.0337 (6) | 0.0256 (5) | 0.0518 (6) | 0.0048 (5) | 0.0068 (5) | −0.0063 (4) |
O3 | 0.0325 (6) | 0.0417 (6) | 0.0517 (6) | −0.0059 (5) | 0.0094 (5) | −0.0228 (5) |
N2 | 0.0222 (6) | 0.0252 (6) | 0.0302 (6) | −0.0006 (5) | 0.0017 (5) | −0.0027 (4) |
C1 | 0.0279 (8) | 0.0202 (7) | 0.0310 (7) | 0.0031 (6) | −0.0022 (6) | 0.0028 (5) |
C3 | 0.0255 (8) | 0.0341 (8) | 0.0303 (7) | −0.0019 (6) | 0.0029 (6) | −0.0062 (6) |
C4 | 0.0229 (8) | 0.0339 (8) | 0.0604 (9) | 0.0041 (6) | −0.0017 (7) | −0.0067 (7) |
C5 | 0.0245 (8) | 0.0433 (8) | 0.0487 (8) | 0.0001 (7) | −0.0049 (7) | −0.0056 (7) |
C6 | 0.0318 (8) | 0.0491 (9) | 0.0348 (7) | −0.0072 (7) | 0.0013 (7) | −0.0116 (6) |
C7 | 0.0338 (8) | 0.0275 (7) | 0.0496 (8) | −0.0064 (7) | 0.0022 (7) | −0.0053 (6) |
C8 | 0.0301 (8) | 0.0287 (7) | 0.0299 (7) | −0.0042 (6) | −0.0001 (6) | 0.0055 (5) |
C9 | 0.0267 (7) | 0.0364 (7) | 0.0317 (7) | −0.0056 (6) | 0.0088 (6) | −0.0095 (6) |
C11 | 0.0221 (7) | 0.0243 (6) | 0.0238 (6) | −0.0007 (5) | 0.0011 (5) | −0.0031 (5) |
C21 | 0.0243 (7) | 0.0276 (7) | 0.0309 (7) | 0.0037 (6) | −0.0007 (6) | 0.0004 (5) |
C31 | 0.0331 (8) | 0.0263 (7) | 0.0334 (7) | −0.0004 (6) | 0.0056 (6) | 0.0023 (6) |
C41 | 0.0207 (7) | 0.0361 (8) | 0.0338 (7) | −0.0045 (6) | 0.0060 (6) | −0.0064 (6) |
C51 | 0.0224 (7) | 0.0368 (8) | 0.0298 (7) | 0.0069 (6) | −0.0013 (6) | −0.0027 (6) |
C61 | 0.0291 (7) | 0.0268 (7) | 0.0244 (6) | 0.0039 (6) | 0.0016 (6) | 0.0012 (5) |
F41—C41 | 1.3616 (16) | C31—C41 | 1.3758 (19) |
O1—C1 | 1.2087 (16) | C41—C51 | 1.3744 (19) |
O3—C3 | 1.2109 (17) | C51—C61 | 1.382 (2) |
N2—C1 | 1.4049 (16) | C4—H4A | 0.9700 |
N2—C3 | 1.3983 (17) | C4—H4B | 0.9700 |
N2—C11 | 1.4360 (17) | C5—H5A | 0.9700 |
C1—C8 | 1.5157 (19) | C5—H5B | 0.9700 |
C3—C9 | 1.510 (2) | C6—H6A | 0.9700 |
C4—C5 | 1.520 (2) | C6—H6B | 0.9700 |
C4—C9 | 1.534 (2) | C7—H7A | 0.9700 |
C5—C6 | 1.518 (2) | C7—H7B | 0.9700 |
C6—C7 | 1.508 (2) | C8—H8 | 0.9800 |
C7—C8 | 1.5236 (19) | C9—H9 | 0.9800 |
C8—C9 | 1.5304 (19) | C21—H21 | 0.9300 |
C11—C21 | 1.3877 (17) | C31—H31 | 0.9300 |
C11—C61 | 1.3848 (18) | C51—H51 | 0.9300 |
C21—C31 | 1.381 (2) | C61—H61 | 0.9300 |
C1—N2—C3 | 111.77 (11) | C9—C4—H4B | 109.00 |
C1—N2—C11 | 123.86 (10) | H4A—C4—H4B | 108.00 |
C3—N2—C11 | 124.37 (10) | C4—C5—H5A | 110.00 |
O1—C1—N2 | 124.01 (12) | C4—C5—H5B | 110.00 |
O1—C1—C8 | 128.71 (12) | C6—C5—H5A | 110.00 |
N2—C1—C8 | 107.23 (10) | C6—C5—H5B | 110.00 |
O3—C3—N2 | 124.26 (13) | H5A—C5—H5B | 108.00 |
O3—C3—C9 | 127.82 (13) | C5—C6—H6A | 109.00 |
N2—C3—C9 | 107.77 (11) | C5—C6—H6B | 109.00 |
C5—C4—C9 | 112.41 (11) | C7—C6—H6A | 109.00 |
C4—C5—C6 | 109.64 (12) | C7—C6—H6B | 109.00 |
C5—C6—C7 | 110.94 (12) | H6A—C6—H6B | 108.00 |
C6—C7—C8 | 113.62 (11) | C6—C7—H7A | 109.00 |
C1—C8—C7 | 116.02 (11) | C6—C7—H7B | 109.00 |
C1—C8—C9 | 103.29 (10) | C8—C7—H7A | 109.00 |
C7—C8—C9 | 116.78 (11) | C8—C7—H7B | 109.00 |
C3—C9—C4 | 107.36 (11) | H7A—C7—H7B | 108.00 |
C3—C9—C8 | 103.63 (11) | C1—C8—H8 | 107.00 |
C4—C9—C8 | 112.81 (11) | C7—C8—H8 | 107.00 |
N2—C11—C21 | 119.50 (11) | C9—C8—H8 | 107.00 |
N2—C11—C61 | 120.00 (11) | C3—C9—H9 | 111.00 |
C21—C11—C61 | 120.49 (12) | C4—C9—H9 | 111.00 |
C11—C21—C31 | 119.71 (12) | C8—C9—H9 | 111.00 |
C21—C31—C41 | 118.58 (12) | C11—C21—H21 | 120.00 |
F41—C41—C31 | 118.62 (12) | C31—C21—H21 | 120.00 |
F41—C41—C51 | 118.50 (12) | C21—C31—H31 | 121.00 |
C31—C41—C51 | 122.87 (13) | C41—C31—H31 | 121.00 |
C41—C51—C61 | 118.19 (12) | C41—C51—H51 | 121.00 |
C11—C61—C51 | 120.15 (12) | C61—C51—H51 | 121.00 |
C5—C4—H4A | 109.00 | C11—C61—H61 | 120.00 |
C5—C4—H4B | 109.00 | C51—C61—H61 | 120.00 |
C9—C4—H4A | 109.00 | ||
C3—N2—C1—O1 | 172.13 (12) | C5—C4—C9—C3 | 160.52 (12) |
C3—N2—C1—C8 | −10.28 (14) | C5—C4—C9—C8 | 46.98 (16) |
C11—N2—C1—O1 | −7.02 (19) | C4—C5—C6—C7 | 61.54 (15) |
C11—N2—C1—C8 | 170.58 (10) | C5—C6—C7—C8 | −51.74 (16) |
C1—N2—C3—O3 | 177.95 (13) | C6—C7—C8—C1 | −81.87 (15) |
C1—N2—C3—C9 | −6.20 (14) | C6—C7—C8—C9 | 40.33 (17) |
C11—N2—C3—O3 | −2.9 (2) | C1—C8—C9—C3 | −24.62 (12) |
C11—N2—C3—C9 | 172.94 (11) | C1—C8—C9—C4 | 91.17 (13) |
C1—N2—C11—C21 | 123.46 (13) | C7—C8—C9—C3 | −153.23 (11) |
C1—N2—C11—C61 | −57.67 (16) | C7—C8—C9—C4 | −37.44 (16) |
C3—N2—C11—C21 | −55.58 (16) | N2—C11—C21—C31 | 178.18 (11) |
C3—N2—C11—C61 | 123.29 (13) | C61—C11—C21—C31 | −0.69 (18) |
O1—C1—C8—C7 | −31.58 (19) | N2—C11—C61—C51 | −178.75 (11) |
O1—C1—C8—C9 | −160.66 (13) | C21—C11—C61—C51 | 0.12 (18) |
N2—C1—C8—C7 | 150.98 (11) | C11—C21—C31—C41 | 0.72 (19) |
N2—C1—C8—C9 | 21.90 (12) | C21—C31—C41—F41 | −179.51 (11) |
O3—C3—C9—C4 | 75.71 (17) | C21—C31—C41—C51 | −0.2 (2) |
O3—C3—C9—C8 | −164.71 (13) | F41—C41—C51—C61 | 178.95 (11) |
N2—C3—C9—C4 | −99.95 (12) | C31—C41—C51—C61 | −0.4 (2) |
N2—C3—C9—C8 | 19.63 (13) | C41—C51—C61—C11 | 0.40 (19) |
C9—C4—C5—C6 | −59.53 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C21—H21···O1i | 0.93 | 2.49 | 3.1151 (16) | 125 |
C51—H51···O3ii | 0.93 | 2.51 | 3.3728 (17) | 155 |
Symmetry codes: (i) x, y+1, z; (ii) −x+3/2, y−1/2, −z+1/2. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C14H14FNO2 | C14H16FNO3 | C14H14FNO2 |
Mr | 247.26 | 265.28 | 247.26 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c | Monoclinic, P21/n |
Temperature (K) | 200 | 200 | 200 |
a, b, c (Å) | 8.0316 (4), 8.1702 (4), 9.2085 (5) | 11.3688 (8), 8.7802 (6), 12.7989 (10) | 10.7554 (3), 6.6709 (2), 16.8466 (4) |
α, β, γ (°) | 98.595 (4), 93.324 (4), 97.260 (4) | 90, 93.436 (7), 90 | 90, 95.275 (3), 90 |
V (Å3) | 590.86 (5) | 1275.29 (16) | 1203.59 (6) |
Z | 2 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.11 | 0.10 |
Crystal size (mm) | 0.40 × 0.30 × 0.25 | 0.45 × 0.40 × 0.05 | 0.45 × 0.40 × 0.35 |
Data collection | |||
Diffractometer | Oxford Gemini-S CCD area-detector diffractometer | Oxford Gemini-S CCD area-detector diffractometer | Oxford Gemini-S CCD area-detector diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) |
Tmin, Tmax | 0.969, 0.989 | 0.881, 0.980 | 0.960, 0.990 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7051, 2305, 1783 | 8075, 2499, 1530 | 7621, 2362, 1826 |
Rint | 0.022 | 0.051 | 0.023 |
(sin θ/λ)max (Å−1) | 0.617 | 0.617 | 0.617 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.098, 1.08 | 0.044, 0.092, 0.86 | 0.035, 0.091, 1.03 |
No. of reflections | 2305 | 2499 | 2362 |
No. of parameters | 163 | 190 | 163 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.20 | 0.18, −0.16 | 0.20, −0.21 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
C31—H31···O1i | 0.93 | 2.56 | 3.3589 (18) | 144 |
C51—H51···O3ii | 0.93 | 2.57 | 3.4064 (18) | 150 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···O22i | 0.839 (18) | 2.281 (18) | 2.967 (2) | 139.1 (15) |
O21—H22···O12ii | 0.92 (3) | 1.69 (2) | 2.613 (2) | 176 (2) |
C3—H3A···O21 | 0.97 | 2.49 | 2.847 (2) | 102 |
C21—H21···O12 | 0.93 | 2.50 | 2.891 (2) | 106 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y+1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C21—H21···O1i | 0.93 | 2.49 | 3.1151 (16) | 125 |
C51—H51···O3ii | 0.93 | 2.51 | 3.3728 (17) | 155 |
Symmetry codes: (i) x, y+1, z; (ii) −x+3/2, y−1/2, −z+1/2. |
cis-Cyclohexane-1,2-dicarboxylic acid (cis-CHDC) is of interest because, unlike the trans isomer which forms separable dl pairs, it exists as an unresolvable racemic mixture of (1R,2S) and (1S,2R) enantiomeric components (Eliel, 1962). This situation arises because of the low interconversion potential between these components, resulting in racemization. The 1:1 stoichiometric reaction of cyclohexane-1,2-dicarboxylic anhydride (cis-CHDC anhydride, which has the cis configuration) with Lewis bases usually gives the hydrogen cis-CHDC proton-transfer salts, and the structures of a limited number of these have been determined: the racemic ammonium salt (a dihydrate) (Smith & Wermuth, 2011a), the isomeric racemic anhydrous 2-aminopyridinium (Smith & Wermuth, 2011b) and 4-aminopyridinium salts (Smith & Wermuth, 2011d), and the chiral brucinium salt [a dihydrate in which the (1R)-carboxylate (2S)-carboxy cis-CHDC species has been captured] (Smith et al., 2012). The structure of the 1:1 adducts of cis-CHDC with 4,4'-bipyridine (Bhogala et al., 2005) and with isoquinoline (Smith & Wermuth, 2011c) are also known.
However, with certain bases, particularly the anilines, but including urea, formation of amide carboxylates or cyclic imides may occur, analogous to those formed with phthalic anhydride, the phthalimides and the phthalanilic acids. The mechanism for the formation of the cyclic imide from the amide carboxylic acid via the loss of a mole of water has been proposed and found to proceed efficiently in the presence of acetic acid (Perry & Parveen, 2001). Commonly, the N-substituted hexahydroisoindoline-1,3-diones were prepared from the reaction of the primary amine with cis-CHDC anhydride using a condensation reaction promoted by hexamethyldisilazine (HMDS) (Reddy et al., 1997). However, occasionally the reaction may proceed in a facile manner, e.g. in the case of phthalic anhydride with certain anilines (giving either a phthalanilic acid or the cyclic phthalimide), or cis-CHDC anhydride with the aniline or urea. The structures of the cis-CHDC cyclic imides with 5-benzyloxy-2,4-dichloroaniline (Wang et al., 2005) or with urea (Wang et al., 2007) represent the only reported examples and in these the configuration is naturally racemic cis (R,S) or (S,R). With the cis-CHDC amide acids, there is only one example in the crystallographic literature, an unusual diastereoisomeric amide formed with phenylethylamine (Takahashi et al., 2003). Another unusual structure is the asymmetric imide carboxylic acid cis-2-(3-oxo-1,3,4,5,6,7-hexahydroisobenzofuran-1-yl)cyclohexane-1-carboxylic acid monohydrate, formed in the self-condensation of cis-CHDC anhydride with triethylamine (Newman et al., 2000).
Our 1:1 reaction of a series of substituted anilines with cis-CHDC anhydride under mild reaction conditions in a 50% ethanol–water solution yielded, in some cases, both cyclic imides and amide acids, and those formed with the isomeric monofluoroanilines are reported here. With the 2- and 4-fluoroanilines, the isomeric cyclic imides cis-2-(2-fluorophenyl)-3a,4,5,6,7,7a-hexahydroisoindole-1,3-dione, (I), and cis-2-(4-fluorophenyl)-3a,4,5,6,7,7a-hexahydroisoindole-1,3-dione, (III), respectively, were formed, while with 3-fluoroaniline, rac-cis-[2-(3-fluorophenyl)carbamoyl]cyclohexane-1-carboxylic acid, (II), was obtained. The structures of compounds (I)–(III) are shown in Figs. 1–3.
The two racemic cyclic imides, (I) and (III) (Figs. 1 and 3), from the 2- and 4-fluoroanilines, show many structural similarities. Both are conformationally similar with the five-membered isoindolyl ring system being distorted, with maximum deviations from planarity for either atom C8 or C9 of 0.152 (1) Å in (I) and 0.149 (1) Å in (III). There are also comparable benzene-ring rotations about the imide N—Caromatic bond, as indicated by the dihedral angles of 55.40 (8)° in (I) and 51.83 (7)° in (III) between the benzene and isoindole rings. Another feature common to both molecules is the strain within the cyclohexane ring system, which is indicated by the larger displacement parameters observed for the constituent C atoms. This has also been observed in other examples of cyclic imides of this series and is at its most extreme in the 4-bromo derivative (Smith & Wermuth, 2012), in which two independent and conformationally different molecules constitute the asymmetric unit contents, one with the cyclohexane ring ordered and the other disordered, having partial replacement of the (1R,2S)-substituted cyclohexane enantiomer by the (1S,2R) component. In the crystal packing of the two title imides, only weak aromatic C—H···O hydrogen-bonding interactions are found (Tables 1 and 3).
With the cis-amide carboxylic acid, (II) (Fig. 2), the benzene ring is rotationally disordered, with atom F31 at C31 [site-occupancy factor of 0.782 (4)] related to the minor component F51 at C51 [site-occupancy factor of 0.216 (4)]. The aminocarbonyl group defined by atoms C1/C12/O12/N11 is rotated out of the benzene plane [torsion angle C21—C11—N11—C12 = 42.1 (3)°], corresponding to a dihedral angle of 19.15 (10)° between these planes. The axially located carboxylic acid group is close to being coplanar with the C1—C2 bond of the cyclohexane ring [torsion angle C1—C2—C22—O21 = -176.91 (15)°]. In the crystal structure of (II), the molecules lie along the approximate a cell direction and form stacks down b through centrosymmetrically alternating molecular associations, and are linked by intermolecular amide–carboxyl N—H···O hydrogen bonds (Table 1). Lateral carboxyl–amide O—H···O hydrogen bonds link the stacks across c, giving a two-dimensional sheet structure extending along the (011) planes in the unit cell (Fig. 4).
The structures reported herein represent examples of two possible products, either amide carboxylic acids or cyclic imides, from the facile 1:1 stoichiometric reaction of cis-cyclohexane-1,2-dicarboxylic anhydride with substituted anilines, and have few analogues reported in the crystallographic literature.