Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108022634/gd3225sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108022634/gd3225Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108022634/gd3225IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108022634/gd3225IIIsup4.hkl |
CCDC references: 703728; 703729; 703730
For related literature, see: Allen (2002); Chopra & Row (2008); Donnelly et al. (2008); Gelbrich et al. (2007); Kálmán et al. (1993); Noveron et al. (2002); Sheldrick (2008); Threlfall & Gelbrich (2007); Wardell et al. (2007, 2008).
For the preparation of (I)–(III) (Fink & Kurys, 1996), typically, the 2,3-, 2,4- and 2,5-difluorobenzoyl chlorides in dry CH2Cl2 (20–30 ml) were added dropwise (over a period of 2–3 min) to a cold (273 K) 20–30 ml solution of 4-aminopyridine containing Et3N (1.5 ml), and the reaction was stirred overnight at room temperature. Typical organic workup and washings furnished the products in reasonable yields of 40–90%. Crystals suitable for diffraction were grown from CHCl3 as colourless blocks over a period of 1–2 weeks. The three compounds gave clean 1H and 13C NMR spectra in δ6-DMSO and the infrared spectra (in CHCl3 solution, KBr disks) are as expected.
For (I), m.p. 385–387 K (uncorrected). IR (νC=O cm-1): 1684s, 1674m (CHCl3); 1667s (KBr). 1H NMR (400 MHz, DMSO): δ 10.98 (s, 1H, N—H), 8.51 (d, 2H, 4-pyr), 7.70 (d, 2H, 4-pyr), 7.67 (m [2 td], 1H, 2,3-Fbenz), 7.53 (m [tt], 1H, 2,3-Fbenz), 7.38 (m [2 t d], 1H, 2,3-Fbenz).
For (II), m.p. 391–393 K (uncorrected). IR (νC=O cm-1): 1662s (CHCl3); 1685s, 1674s (KBr). 1H NMR (400 MHz, DMSO): δ 10.85 (s, 1H, N—H), 8.50 (d, 2H, 4-pyr), 7.69 (d, 2H, 4-pyr), 7.80 (m, 1H, 2,4-Fbenz), 7.47 (m [td], 1H, 2,4-Fbenz), 7.26 (m [td], 1H, 2,4-Fbenz).
For (III), m.p. 433–435 K (uncorrected). IR (νC=O cm-1): 1684s (CHCl3); 1685s (KBr). 1H NMR (400 MHz, DMSO): δ 10.93 (s, 1H, N—H), 8.51 (d, 2H, 4-pyr), 7.70 (d, 2H, 4-pyr), 7.61 (m, 1H, 2,5-Fbenz), 7.48 (m, 2H, 2,5-Fbenz).
H atoms attached to C atoms were treated as riding using SHELXL97 (Sheldrick, 2008) defaults at 150 (1) K with [C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C); N-bound H atoms were refined freely with isotropic displacement parameters to bond lengths of 0.88 (2) Å in (I), 0.92 (4) Å in (II) and 0.89 (2) Å in (III).
For all compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and SORTX (McArdle, 1995); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PREP8 (Ferguson, 1998).
C12H8F2N2O | F(000) = 480 |
Mr = 234.20 | Dx = 1.536 Mg m−3 |
Monoclinic, P21/n | Melting point: 385 K |
Hall symbol: -p 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 12.5700 (6) Å | Cell parameters from 12328 reflections |
b = 5.1257 (2) Å | θ = 2.6–27.5° |
c = 16.5178 (8) Å | µ = 0.13 mm−1 |
β = 107.847 (2)° | T = 150 K |
V = 1013.03 (8) Å3 | Block, colourless |
Z = 4 | 0.38 × 0.36 × 0.30 mm |
Nonius KappaCCD diffractometer | 2292 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 1872 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ϕ, ω scans with κ offsets | θmax = 27.5°, θmin = 2.6° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −16→16 |
Tmin = 0.889, Tmax = 0.965 | k = −6→6 |
5827 measured reflections | l = −21→21 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0452P)2 + 0.3718P] where P = (Fo2 + 2Fc2)/3 |
2292 reflections | (Δ/σ)max < 0.001 |
158 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C12H8F2N2O | V = 1013.03 (8) Å3 |
Mr = 234.20 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.5700 (6) Å | µ = 0.13 mm−1 |
b = 5.1257 (2) Å | T = 150 K |
c = 16.5178 (8) Å | 0.38 × 0.36 × 0.30 mm |
β = 107.847 (2)° |
Nonius KappaCCD diffractometer | 2292 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1872 reflections with I > 2σ(I) |
Tmin = 0.889, Tmax = 0.965 | Rint = 0.033 |
5827 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.24 e Å−3 |
2292 reflections | Δρmin = −0.18 e Å−3 |
158 parameters |
x | y | z | Uiso*/Ueq | ||
F12 | 0.20330 (7) | 0.77680 (17) | 0.02099 (5) | 0.0309 (2) | |
F13 | 0.40168 (7) | 0.87823 (19) | 0.00503 (6) | 0.0377 (3) | |
O1 | 0.14765 (9) | 0.1291 (2) | 0.14635 (8) | 0.0360 (3) | |
C1 | 0.16668 (11) | 0.3556 (3) | 0.13137 (9) | 0.0251 (3) | |
N1 | 0.09370 (10) | 0.5544 (2) | 0.12683 (8) | 0.0254 (3) | |
C11 | 0.27630 (11) | 0.4290 (3) | 0.11850 (8) | 0.0239 (3) | |
C12 | 0.29056 (11) | 0.6304 (3) | 0.06672 (9) | 0.0245 (3) | |
C13 | 0.39432 (12) | 0.6836 (3) | 0.05801 (9) | 0.0279 (3) | |
C14 | 0.48711 (12) | 0.5420 (3) | 0.10112 (9) | 0.0308 (3) | |
C15 | 0.47431 (12) | 0.3376 (3) | 0.15251 (9) | 0.0320 (3) | |
C16 | 0.37000 (12) | 0.2807 (3) | 0.16037 (9) | 0.0288 (3) | |
C21 | −0.01346 (11) | 0.5355 (3) | 0.13734 (9) | 0.0240 (3) | |
C22 | −0.04349 (12) | 0.3409 (3) | 0.18500 (9) | 0.0270 (3) | |
C23 | −0.15038 (12) | 0.3501 (3) | 0.19325 (10) | 0.0300 (3) | |
N24 | −0.22677 (10) | 0.5331 (3) | 0.15855 (9) | 0.0327 (3) | |
C25 | −0.19528 (12) | 0.7184 (3) | 0.11343 (10) | 0.0326 (4) | |
C26 | −0.09093 (12) | 0.7281 (3) | 0.10129 (10) | 0.0285 (3) | |
H1 | 0.1150 (15) | 0.710 (4) | 0.1162 (12) | 0.038 (5)* | |
H14 | 0.5584 | 0.5830 | 0.0959 | 0.037* | |
H15 | 0.5373 | 0.2361 | 0.1825 | 0.038* | |
H16 | 0.3623 | 0.1382 | 0.1949 | 0.035* | |
H22 | 0.0074 | 0.2061 | 0.2110 | 0.032* | |
H23 | −0.1706 | 0.2171 | 0.2258 | 0.036* | |
H25 | −0.2476 | 0.8513 | 0.0882 | 0.039* | |
H26 | −0.0729 | 0.8644 | 0.0688 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F12 | 0.0274 (4) | 0.0300 (5) | 0.0369 (5) | 0.0041 (4) | 0.0121 (4) | 0.0083 (4) |
F13 | 0.0361 (5) | 0.0365 (5) | 0.0462 (5) | −0.0037 (4) | 0.0212 (4) | 0.0076 (4) |
O1 | 0.0373 (6) | 0.0210 (5) | 0.0572 (7) | 0.0001 (4) | 0.0254 (5) | 0.0019 (5) |
C1 | 0.0259 (7) | 0.0229 (7) | 0.0275 (7) | −0.0010 (6) | 0.0098 (5) | −0.0012 (6) |
N1 | 0.0238 (6) | 0.0205 (6) | 0.0340 (6) | −0.0008 (5) | 0.0121 (5) | 0.0023 (5) |
C11 | 0.0242 (7) | 0.0232 (7) | 0.0252 (7) | −0.0005 (6) | 0.0086 (5) | −0.0029 (5) |
C12 | 0.0231 (7) | 0.0242 (7) | 0.0257 (7) | 0.0024 (6) | 0.0068 (5) | −0.0009 (5) |
C13 | 0.0302 (7) | 0.0275 (7) | 0.0289 (7) | −0.0040 (6) | 0.0133 (6) | −0.0013 (6) |
C14 | 0.0234 (7) | 0.0377 (9) | 0.0330 (8) | −0.0034 (6) | 0.0110 (6) | −0.0081 (7) |
C15 | 0.0259 (7) | 0.0374 (9) | 0.0312 (7) | 0.0070 (6) | 0.0067 (6) | −0.0017 (7) |
C16 | 0.0299 (7) | 0.0294 (8) | 0.0277 (7) | 0.0034 (6) | 0.0097 (6) | 0.0010 (6) |
C21 | 0.0225 (6) | 0.0237 (7) | 0.0264 (7) | −0.0030 (6) | 0.0084 (5) | −0.0045 (6) |
C22 | 0.0261 (7) | 0.0248 (7) | 0.0307 (7) | −0.0010 (6) | 0.0097 (6) | 0.0003 (6) |
C23 | 0.0292 (7) | 0.0283 (8) | 0.0356 (8) | −0.0048 (6) | 0.0145 (6) | −0.0024 (6) |
N24 | 0.0256 (6) | 0.0322 (7) | 0.0414 (7) | −0.0017 (5) | 0.0118 (5) | −0.0053 (6) |
C25 | 0.0254 (7) | 0.0289 (8) | 0.0420 (9) | 0.0032 (6) | 0.0082 (6) | −0.0013 (7) |
C26 | 0.0279 (7) | 0.0242 (7) | 0.0333 (7) | −0.0006 (6) | 0.0095 (6) | 0.0011 (6) |
F12—C12 | 1.3523 (16) | C21—C22 | 1.393 (2) |
F13—C13 | 1.3487 (17) | C22—C23 | 1.392 (2) |
O1—C1 | 1.2259 (17) | C23—N24 | 1.339 (2) |
C1—N1 | 1.3574 (18) | N24—C25 | 1.340 (2) |
C1—C11 | 1.5048 (19) | C25—C26 | 1.387 (2) |
N1—C21 | 1.4133 (17) | N1—H1 | 0.88 (2) |
C11—C12 | 1.3872 (19) | C14—H14 | 0.9500 |
C11—C16 | 1.394 (2) | C15—H15 | 0.9500 |
C12—C13 | 1.3824 (19) | C16—H16 | 0.9500 |
C13—C14 | 1.373 (2) | C22—H22 | 0.9500 |
C14—C15 | 1.389 (2) | C23—H23 | 0.9500 |
C15—C16 | 1.388 (2) | C25—H25 | 0.9500 |
C21—C26 | 1.386 (2) | C26—H26 | 0.9500 |
O1—C1—N1 | 123.47 (13) | N24—C23—C22 | 124.67 (14) |
O1—C1—C11 | 120.58 (12) | C23—N24—C25 | 116.06 (12) |
N1—C1—C11 | 115.93 (12) | N24—C25—C26 | 124.02 (14) |
C1—N1—C21 | 126.54 (12) | C21—C26—C25 | 118.90 (14) |
C1—C11—C12 | 124.75 (12) | C1—N1—H1 | 116.9 (12) |
C1—C11—C16 | 117.70 (13) | C21—N1—H1 | 116.5 (12) |
C12—C11—C16 | 117.54 (13) | C13—C14—H14 | 120.8 |
F12—C12—C11 | 121.43 (12) | C15—C14—H14 | 120.8 |
F12—C12—C13 | 117.53 (13) | C16—C15—H15 | 119.8 |
C11—C12—C13 | 121.02 (13) | C14—C15—H15 | 119.8 |
F13—C13—C12 | 117.90 (13) | C15—C16—H16 | 119.4 |
F13—C13—C14 | 120.74 (13) | C11—C16—H16 | 119.4 |
C12—C13—C14 | 121.36 (14) | C23—C22—H22 | 121.1 |
C13—C14—C15 | 118.48 (13) | C21—C22—H22 | 121.1 |
C14—C15—C16 | 120.36 (13) | N24—C23—H23 | 117.7 |
C15—C16—C11 | 121.21 (14) | C22—C23—H23 | 117.7 |
C26—C21—C22 | 118.45 (13) | N24—C25—H25 | 118.0 |
C22—C21—N1 | 123.50 (13) | C26—C25—H25 | 118.0 |
C26—C21—N1 | 117.98 (13) | C21—C26—H26 | 120.6 |
C21—C22—C23 | 117.89 (13) | C25—C26—H26 | 120.6 |
O1—C1—N1—C21 | −0.6 (2) | F13—C13—C14—C15 | −177.70 (13) |
O1—C1—C11—C12 | 149.52 (15) | C12—C13—C14—C15 | 1.7 (2) |
C11—C1—N1—C21 | −179.45 (12) | C13—C14—C15—C16 | −0.6 (2) |
C1—N1—C21—C26 | −156.89 (14) | C14—C15—C16—C11 | −1.2 (2) |
N1—C1—C11—C12 | −31.6 (2) | C12—C11—C16—C15 | 1.9 (2) |
O1—C1—C11—C16 | −29.2 (2) | C1—C11—C16—C15 | −179.31 (13) |
N1—C1—C11—C16 | 149.63 (13) | C1—N1—C21—C22 | 26.1 (2) |
C16—C11—C12—F12 | 177.19 (12) | C26—C21—C22—C23 | 0.4 (2) |
C1—C11—C12—F12 | −1.5 (2) | N1—C21—C22—C23 | 177.44 (13) |
C16—C11—C12—C13 | −0.8 (2) | C21—C22—C23—N24 | 0.0 (2) |
C1—C11—C12—C13 | −179.54 (13) | C22—C23—N24—C25 | −0.3 (2) |
F12—C12—C13—F13 | 0.4 (2) | C23—N24—C25—C26 | 0.2 (2) |
C11—C12—C13—F13 | 178.43 (12) | C22—C21—C26—C25 | −0.5 (2) |
F12—C12—C13—C14 | −179.05 (13) | N1—C21—C26—C25 | −177.72 (13) |
C11—C12—C13—C14 | −1.0 (2) | N24—C25—C26—C21 | 0.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.88 (2) | 2.21 (2) | 3.0181 (16) | 152.3 (16) |
N1—H1···F12 | 0.88 (2) | 2.212 (18) | 2.7803 (14) | 122.2 (15) |
C22—H22···O1 | 0.95 | 2.36 | 2.8807 (18) | 114 |
C14—H14···N24ii | 0.95 | 2.59 | 3.4273 (19) | 147 |
C15—H15···Cg1iii | 0.95 | 2.86 | 3.5941 (16) | 135 |
C25—H25···F13iv | 0.95 | 2.49 | 3.4240 (18) | 166 |
Symmetry codes: (i) x, y+1, z; (ii) x+1, y, z; (iii) −x+1/2, y−1/2, −z+1/2; (iv) −x, −y+2, −z. |
C12H8F2N2O | F(000) = 480 |
Mr = 234.20 | Dx = 1.559 Mg m−3 |
Monoclinic, P21/c | Melting point: 391 K |
Hall symbol: -p 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 8.3187 (6) Å | Cell parameters from 12237 reflections |
b = 5.5868 (6) Å | θ = 2.6–27.5° |
c = 21.715 (2) Å | µ = 0.13 mm−1 |
β = 98.517 (6)° | T = 150 K |
V = 998.07 (16) Å3 | Block, colourless |
Z = 4 | 0.24 × 0.16 × 0.03 mm |
Nonius KappaCCD diffractometer | 2248 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 1197 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.083 |
ϕ, ω scans with κ offsets | θmax = 27.5°, θmin = 2.6° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −10→10 |
Tmin = 0.969, Tmax = 0.996 | k = −6→7 |
6812 measured reflections | l = −27→28 |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.157 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0684P)2] where P = (Fo2 + 2Fc2)/3 |
2248 reflections | (Δ/σ)max < 0.001 |
158 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
C12H8F2N2O | V = 998.07 (16) Å3 |
Mr = 234.20 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.3187 (6) Å | µ = 0.13 mm−1 |
b = 5.5868 (6) Å | T = 150 K |
c = 21.715 (2) Å | 0.24 × 0.16 × 0.03 mm |
β = 98.517 (6)° |
Nonius KappaCCD diffractometer | 2248 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1197 reflections with I > 2σ(I) |
Tmin = 0.969, Tmax = 0.996 | Rint = 0.083 |
6812 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.157 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.22 e Å−3 |
2248 reflections | Δρmin = −0.27 e Å−3 |
158 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
F12 | 0.33130 (18) | 0.2730 (2) | 0.08087 (6) | 0.0475 (4) | |
F14 | 0.06367 (18) | −0.0413 (3) | 0.23708 (6) | 0.0528 (5) | |
O1 | 0.2144 (2) | −0.3342 (3) | −0.02686 (8) | 0.0520 (5) | |
C1 | 0.2306 (3) | −0.1351 (5) | −0.00339 (11) | 0.0371 (6) | |
N1 | 0.2865 (2) | 0.0569 (4) | −0.03263 (9) | 0.0390 (5) | |
C11 | 0.1865 (3) | −0.0936 (4) | 0.06019 (11) | 0.0362 (6) | |
C12 | 0.2364 (3) | 0.0969 (4) | 0.10006 (11) | 0.0383 (6) | |
C13 | 0.1983 (3) | 0.1188 (4) | 0.15936 (11) | 0.0420 (6) | |
C14 | 0.1035 (3) | −0.0589 (5) | 0.17904 (11) | 0.0403 (6) | |
C15 | 0.0484 (3) | −0.2528 (5) | 0.14245 (12) | 0.0417 (6) | |
C16 | 0.0914 (3) | −0.2671 (4) | 0.08382 (11) | 0.0398 (6) | |
C21 | 0.3302 (3) | 0.0663 (4) | −0.09274 (11) | 0.0353 (6) | |
C22 | 0.2967 (3) | −0.1138 (5) | −0.13730 (11) | 0.0391 (6) | |
C23 | 0.3446 (3) | −0.0780 (5) | −0.19485 (12) | 0.0430 (7) | |
N24 | 0.4182 (2) | 0.1182 (4) | −0.21226 (9) | 0.0427 (6) | |
C25 | 0.4485 (3) | 0.2890 (5) | −0.16867 (11) | 0.0419 (7) | |
C26 | 0.4088 (3) | 0.2708 (4) | −0.10933 (11) | 0.0404 (6) | |
H1 | 0.296 (4) | 0.200 (7) | −0.0118 (14) | 0.083 (11)* | |
H13 | 0.2358 | 0.2501 | 0.1854 | 0.050* | |
H15 | −0.0171 | −0.3727 | 0.1573 | 0.050* | |
H16 | 0.0550 | −0.4004 | 0.0584 | 0.048* | |
H22 | 0.2427 | −0.2567 | −0.1283 | 0.047* | |
H23 | 0.3235 | −0.2033 | −0.2245 | 0.052* | |
H25 | 0.5005 | 0.4314 | −0.1793 | 0.050* | |
H26 | 0.4349 | 0.3966 | −0.0801 | 0.048* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F12 | 0.0610 (10) | 0.0400 (9) | 0.0426 (9) | −0.0101 (7) | 0.0115 (7) | −0.0039 (7) |
F14 | 0.0730 (11) | 0.0510 (10) | 0.0385 (9) | 0.0092 (8) | 0.0218 (7) | 0.0011 (7) |
O1 | 0.0809 (14) | 0.0355 (11) | 0.0441 (11) | −0.0072 (9) | 0.0238 (9) | −0.0036 (9) |
C1 | 0.0426 (14) | 0.0324 (15) | 0.0365 (14) | −0.0010 (11) | 0.0067 (11) | 0.0007 (11) |
N1 | 0.0489 (13) | 0.0343 (13) | 0.0354 (12) | −0.0026 (10) | 0.0114 (9) | −0.0005 (10) |
C11 | 0.0408 (14) | 0.0333 (14) | 0.0351 (14) | 0.0031 (11) | 0.0079 (11) | −0.0016 (11) |
C12 | 0.0422 (14) | 0.0338 (15) | 0.0396 (15) | −0.0020 (11) | 0.0081 (11) | 0.0045 (11) |
C13 | 0.0521 (16) | 0.0353 (15) | 0.0383 (15) | 0.0044 (12) | 0.0055 (12) | −0.0038 (12) |
C14 | 0.0485 (15) | 0.0425 (16) | 0.0315 (14) | 0.0098 (12) | 0.0113 (11) | 0.0040 (12) |
C15 | 0.0471 (15) | 0.0388 (15) | 0.0412 (15) | 0.0004 (12) | 0.0130 (11) | 0.0049 (12) |
C16 | 0.0461 (15) | 0.0343 (15) | 0.0393 (15) | −0.0004 (11) | 0.0078 (12) | −0.0003 (11) |
C21 | 0.0388 (14) | 0.0301 (14) | 0.0378 (14) | 0.0024 (10) | 0.0081 (10) | 0.0029 (11) |
C22 | 0.0444 (14) | 0.0339 (15) | 0.0398 (15) | −0.0014 (11) | 0.0085 (11) | 0.0004 (11) |
C23 | 0.0538 (16) | 0.0335 (15) | 0.0414 (15) | 0.0005 (12) | 0.0064 (12) | −0.0035 (12) |
N24 | 0.0546 (13) | 0.0361 (13) | 0.0394 (13) | 0.0027 (10) | 0.0132 (10) | 0.0014 (10) |
C25 | 0.0514 (16) | 0.0332 (15) | 0.0431 (16) | 0.0014 (11) | 0.0141 (12) | 0.0020 (11) |
C26 | 0.0496 (15) | 0.0323 (15) | 0.0401 (15) | −0.0002 (11) | 0.0095 (11) | −0.0019 (11) |
F12—C12 | 1.365 (3) | C21—C22 | 1.395 (3) |
F14—C14 | 1.353 (3) | C22—C23 | 1.381 (3) |
O1—C1 | 1.222 (3) | C23—N24 | 1.337 (3) |
C1—N1 | 1.363 (3) | N24—C25 | 1.341 (3) |
C1—C11 | 1.498 (3) | C25—C26 | 1.381 (3) |
N1—C21 | 1.407 (3) | N1—H1 | 0.92 (4) |
C11—C12 | 1.396 (3) | C13—H13 | 0.9500 |
C11—C16 | 1.396 (3) | C15—H15 | 0.9500 |
C12—C13 | 1.376 (3) | C16—H16 | 0.9500 |
C13—C14 | 1.375 (4) | C22—H22 | 0.9500 |
C14—C15 | 1.381 (4) | C23—H23 | 0.9500 |
C15—C16 | 1.375 (3) | C25—H25 | 0.9500 |
C21—C26 | 1.390 (3) | C26—H26 | 0.9500 |
O1—C1—N1 | 123.1 (2) | N24—C23—C22 | 125.5 (2) |
O1—C1—C11 | 119.9 (2) | C23—N24—C25 | 115.4 (2) |
N1—C1—C11 | 117.0 (2) | N24—C25—C26 | 124.1 (2) |
C1—N1—C21 | 127.9 (2) | C25—C26—C21 | 119.3 (2) |
C12—C11—C16 | 115.7 (2) | C1—N1—H1 | 118 (2) |
C12—C11—C1 | 126.8 (2) | C21—N1—H1 | 114 (2) |
C16—C11—C1 | 117.4 (2) | C14—C13—H13 | 121.7 |
F12—C12—C13 | 116.4 (2) | C12—C13—H13 | 121.7 |
F12—C12—C11 | 119.5 (2) | C16—C15—H15 | 121.0 |
C13—C12—C11 | 124.0 (2) | C14—C15—H15 | 121.0 |
C14—C13—C12 | 116.7 (2) | C15—C16—H16 | 118.7 |
F14—C14—C13 | 117.9 (2) | C11—C16—H16 | 118.7 |
F14—C14—C15 | 119.1 (2) | C23—C22—H22 | 121.0 |
C13—C14—C15 | 123.0 (2) | C21—C22—H22 | 121.0 |
C16—C15—C14 | 117.9 (2) | C22—C23—H23 | 117.3 |
C15—C16—C11 | 122.7 (2) | N24—C23—H23 | 117.3 |
C26—C21—C22 | 117.8 (2) | N24—C25—H25 | 118.0 |
C26—C21—N1 | 117.9 (2) | C26—C25—H25 | 118.0 |
C22—C21—N1 | 124.4 (2) | C25—C26—H26 | 120.4 |
C23—C22—C21 | 117.9 (2) | C21—C26—H26 | 120.4 |
O1—C1—N1—C21 | 1.7 (4) | F14—C14—C15—C16 | −179.6 (2) |
O1—C1—C11—C12 | 161.5 (2) | C13—C14—C15—C16 | 0.1 (4) |
C11—C1—N1—C21 | −177.7 (2) | C14—C15—C16—C11 | −0.5 (4) |
C1—N1—C21—C26 | −169.8 (2) | C12—C11—C16—C15 | 0.2 (4) |
N1—C1—C11—C12 | −19.1 (4) | C1—C11—C16—C15 | 177.6 (2) |
O1—C1—C11—C16 | −15.6 (3) | C1—N1—C21—C22 | 11.7 (4) |
N1—C1—C11—C16 | 163.8 (2) | C26—C21—C22—C23 | 0.4 (3) |
C16—C11—C12—F12 | 179.25 (19) | N1—C21—C22—C23 | 178.9 (2) |
C1—C11—C12—F12 | 2.2 (4) | C21—C22—C23—N24 | −1.4 (4) |
C16—C11—C12—C13 | 0.5 (4) | C22—C23—N24—C25 | 1.2 (4) |
C1—C11—C12—C13 | −176.6 (2) | C23—N24—C25—C26 | 0.1 (4) |
F12—C12—C13—C14 | −179.6 (2) | N24—C25—C26—C21 | −1.1 (4) |
C11—C12—C13—C14 | −0.9 (4) | C22—C21—C26—C25 | 0.8 (3) |
C12—C13—C14—F14 | −179.7 (2) | N1—C21—C26—C25 | −177.9 (2) |
C12—C13—C14—C15 | 0.6 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···F12 | 0.92 (4) | 2.03 (3) | 2.720 (3) | 131 (3) |
C22—H22···O1 | 0.95 | 2.29 | 2.868 (3) | 118 |
C13—H13···N24i | 0.95 | 2.60 | 3.430 (3) | 146 |
Symmetry code: (i) x, −y+1/2, z+1/2. |
C12H8F2N2O | F(000) = 480 |
Mr = 234.20 | Dx = 1.537 Mg m−3 |
Monoclinic, P21/c | Melting point: 433 K |
Hall symbol: -p 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 6.2088 (4) Å | Cell parameters from 3173 reflections |
b = 11.0182 (5) Å | θ = 2.6–27.5° |
c = 14.8139 (9) Å | µ = 0.13 mm−1 |
β = 93.018 (3)° | T = 150 K |
V = 1012.01 (10) Å3 | Block, colourless |
Z = 4 | 0.22 × 0.16 × 0.10 mm |
Nonius KappaCCD diffractometer | 2295 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 1555 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
ϕ, ω scans with κ offsets | θmax = 27.5°, θmin = 2.8° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −8→8 |
Tmin = 0.932, Tmax = 0.988 | k = −13→14 |
6136 measured reflections | l = −19→19 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.044 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.120 | w = 1/[σ2(Fo2) + (0.0625P)2 + 0.0245P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
2295 reflections | Δρmax = 0.21 e Å−3 |
159 parameters | Δρmin = −0.27 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.015 (4) |
C12H8F2N2O | V = 1012.01 (10) Å3 |
Mr = 234.20 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.2088 (4) Å | µ = 0.13 mm−1 |
b = 11.0182 (5) Å | T = 150 K |
c = 14.8139 (9) Å | 0.22 × 0.16 × 0.10 mm |
β = 93.018 (3)° |
Nonius KappaCCD diffractometer | 2295 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1555 reflections with I > 2σ(I) |
Tmin = 0.932, Tmax = 0.988 | Rint = 0.036 |
6136 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.120 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.21 e Å−3 |
2295 reflections | Δρmin = −0.27 e Å−3 |
159 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
F12 | 0.52432 (15) | 0.14293 (9) | 0.52228 (6) | 0.0348 (3) | |
F15 | 1.22204 (17) | 0.43599 (9) | 0.56952 (8) | 0.0430 (3) | |
O1 | 1.06883 (18) | 0.04700 (10) | 0.40055 (8) | 0.0290 (3) | |
C1 | 0.8934 (3) | 0.09249 (14) | 0.41366 (11) | 0.0231 (4) | |
N1 | 0.7049 (2) | 0.05987 (12) | 0.36865 (9) | 0.0251 (3) | |
C11 | 0.8758 (2) | 0.19442 (14) | 0.48050 (10) | 0.0223 (4) | |
C12 | 0.6988 (3) | 0.21626 (15) | 0.53140 (11) | 0.0265 (4) | |
C13 | 0.6938 (3) | 0.30864 (16) | 0.59425 (12) | 0.0328 (4) | |
C14 | 0.8705 (3) | 0.38450 (16) | 0.60598 (12) | 0.0345 (5) | |
C15 | 1.0471 (3) | 0.36289 (15) | 0.55668 (12) | 0.0306 (4) | |
C16 | 1.0556 (3) | 0.26969 (14) | 0.49455 (11) | 0.0255 (4) | |
C21 | 0.6718 (3) | −0.03641 (14) | 0.30797 (10) | 0.0230 (4) | |
C22 | 0.8243 (3) | −0.12549 (14) | 0.29181 (11) | 0.0246 (4) | |
C23 | 0.7666 (3) | −0.21728 (15) | 0.23112 (11) | 0.0272 (4) | |
N24 | 0.5755 (2) | −0.22661 (12) | 0.18534 (9) | 0.0286 (4) | |
C25 | 0.4321 (3) | −0.13938 (15) | 0.20199 (12) | 0.0301 (4) | |
C26 | 0.4708 (3) | −0.04471 (14) | 0.26199 (11) | 0.0274 (4) | |
H1 | 0.592 (3) | 0.1084 (19) | 0.3720 (13) | 0.042 (6)* | |
H13 | 0.5708 | 0.3199 | 0.6289 | 0.039* | |
H14 | 0.8695 | 0.4503 | 0.6474 | 0.041* | |
H16 | 1.1814 | 0.2570 | 0.4620 | 0.031* | |
H22 | 0.9637 | −0.1234 | 0.3215 | 0.030* | |
H23 | 0.8709 | −0.2783 | 0.2213 | 0.033* | |
H25 | 0.2950 | −0.1429 | 0.1705 | 0.036* | |
H26 | 0.3620 | 0.0138 | 0.2717 | 0.033* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F12 | 0.0312 (6) | 0.0413 (6) | 0.0324 (6) | −0.0037 (5) | 0.0076 (5) | −0.0018 (4) |
F15 | 0.0454 (7) | 0.0335 (6) | 0.0492 (8) | −0.0087 (5) | −0.0077 (5) | −0.0103 (5) |
O1 | 0.0279 (7) | 0.0273 (7) | 0.0320 (7) | 0.0012 (5) | 0.0041 (5) | −0.0041 (5) |
C1 | 0.0271 (9) | 0.0204 (8) | 0.0218 (9) | −0.0001 (7) | 0.0020 (7) | 0.0039 (6) |
N1 | 0.0265 (8) | 0.0217 (7) | 0.0271 (8) | 0.0043 (6) | −0.0003 (6) | −0.0037 (6) |
C11 | 0.0273 (9) | 0.0205 (8) | 0.0189 (8) | 0.0035 (7) | −0.0009 (7) | 0.0019 (6) |
C12 | 0.0266 (9) | 0.0274 (9) | 0.0255 (9) | 0.0007 (7) | 0.0000 (7) | 0.0022 (7) |
C13 | 0.0352 (10) | 0.0365 (10) | 0.0269 (10) | 0.0104 (9) | 0.0049 (8) | −0.0023 (8) |
C14 | 0.0468 (12) | 0.0284 (9) | 0.0277 (10) | 0.0087 (9) | −0.0032 (8) | −0.0064 (7) |
C15 | 0.0359 (10) | 0.0238 (9) | 0.0313 (10) | −0.0007 (8) | −0.0067 (8) | −0.0007 (7) |
C16 | 0.0303 (9) | 0.0238 (8) | 0.0223 (9) | 0.0038 (7) | −0.0003 (7) | 0.0012 (6) |
C21 | 0.0297 (9) | 0.0198 (8) | 0.0196 (9) | −0.0006 (7) | 0.0037 (7) | 0.0016 (6) |
C22 | 0.0265 (9) | 0.0242 (8) | 0.0231 (9) | 0.0014 (7) | 0.0013 (7) | 0.0020 (7) |
C23 | 0.0331 (9) | 0.0229 (9) | 0.0258 (9) | 0.0029 (7) | 0.0040 (7) | −0.0014 (7) |
N24 | 0.0345 (8) | 0.0247 (7) | 0.0266 (8) | 0.0005 (6) | 0.0008 (6) | −0.0022 (6) |
C25 | 0.0300 (10) | 0.0287 (9) | 0.0312 (10) | −0.0016 (8) | −0.0021 (7) | −0.0004 (7) |
C26 | 0.0295 (9) | 0.0228 (8) | 0.0297 (10) | 0.0031 (7) | 0.0009 (7) | 0.0000 (7) |
F12—C12 | 1.3527 (18) | C21—C26 | 1.393 (2) |
F15—C15 | 1.357 (2) | C22—C23 | 1.388 (2) |
O1—C1 | 1.2239 (19) | C23—N24 | 1.339 (2) |
C1—N1 | 1.364 (2) | N24—C25 | 1.342 (2) |
C1—C11 | 1.505 (2) | C25—C26 | 1.383 (2) |
N1—C21 | 1.399 (2) | N1—H1 | 0.89 (2) |
C11—C12 | 1.386 (2) | C13—H13 | 0.9500 |
C11—C16 | 1.397 (2) | C14—H14 | 0.9500 |
C12—C13 | 1.381 (2) | C16—H16 | 0.9500 |
C13—C14 | 1.383 (3) | C22—H22 | 0.9500 |
C14—C15 | 1.370 (3) | C23—H23 | 0.9500 |
C15—C16 | 1.382 (2) | C25—H25 | 0.9500 |
C21—C22 | 1.393 (2) | C26—H26 | 0.9500 |
O1—C1—N1 | 124.22 (15) | N24—C23—C22 | 125.13 (16) |
O1—C1—C11 | 120.40 (15) | C23—N24—C25 | 115.51 (14) |
N1—C1—C11 | 115.35 (14) | N24—C25—C26 | 124.33 (16) |
C1—N1—C21 | 127.41 (14) | C25—C26—C21 | 118.99 (16) |
C1—C11—C12 | 125.07 (15) | C1—N1—H1 | 118.4 (13) |
C1—C11—C16 | 117.11 (14) | C21—N1—H1 | 113.8 (13) |
C12—C11—C16 | 117.76 (15) | C12—C13—H13 | 120.5 |
F12—C12—C11 | 119.72 (14) | C14—C13—H13 | 120.5 |
F12—C12—C13 | 117.45 (15) | C15—C14—H14 | 120.7 |
C11—C12—C13 | 122.80 (16) | C13—C14—H14 | 120.7 |
C12—C13—C14 | 118.95 (16) | C15—C16—H16 | 120.6 |
C13—C14—C15 | 118.69 (16) | C11—C16—H16 | 120.6 |
F15—C15—C14 | 118.63 (15) | C23—C22—H22 | 121.0 |
F15—C15—C16 | 118.44 (16) | C21—C22—H22 | 121.0 |
C14—C15—C16 | 122.94 (17) | N24—C23—H23 | 117.4 |
C11—C16—C15 | 118.83 (16) | C22—C23—H23 | 117.4 |
C22—C21—C26 | 117.98 (15) | N24—C25—H25 | 117.8 |
C26—C21—N1 | 117.51 (15) | C26—C25—H25 | 117.8 |
C22—C21—N1 | 124.50 (14) | C25—C26—H26 | 120.5 |
C21—C22—C23 | 118.06 (15) | C21—C26—H26 | 120.5 |
O1—C1—N1—C21 | 7.0 (3) | C13—C14—C15—C16 | 1.1 (3) |
O1—C1—C11—C12 | −148.88 (16) | F15—C15—C16—C11 | −179.62 (14) |
C11—C1—N1—C21 | −175.26 (14) | C14—C15—C16—C11 | 0.6 (3) |
C1—N1—C21—C26 | −172.89 (16) | C12—C11—C16—C15 | −1.2 (2) |
N1—C1—C11—C12 | 33.3 (2) | C1—C11—C16—C15 | −178.79 (14) |
O1—C1—C11—C16 | 28.5 (2) | C1—N1—C21—C22 | 8.4 (3) |
N1—C1—C11—C16 | −149.35 (14) | C26—C21—C22—C23 | −0.2 (2) |
C16—C11—C12—F12 | −177.66 (13) | N1—C21—C22—C23 | 178.52 (15) |
C1—C11—C12—F12 | −0.3 (2) | C21—C22—C23—N24 | 1.0 (3) |
C16—C11—C12—C13 | 0.3 (2) | C22—C23—N24—C25 | −0.7 (2) |
C1—C11—C12—C13 | 177.64 (15) | C23—N24—C25—C26 | −0.3 (2) |
F12—C12—C13—C14 | 179.32 (14) | N24—C25—C26—C21 | 1.0 (3) |
C11—C12—C13—C14 | 1.3 (3) | C22—C21—C26—C25 | −0.7 (2) |
C12—C13—C14—C15 | −2.0 (3) | N1—C21—C26—C25 | −179.51 (15) |
C13—C14—C15—F15 | −178.76 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N24i | 0.89 (2) | 2.24 (2) | 3.010 (2) | 145.3 (17) |
N1—H1···F12 | 0.89 (2) | 2.32 (2) | 2.7465 (17) | 109.7 (15) |
C22—H22···O1 | 0.95 | 2.29 | 2.873 (2) | 119 |
C22—H22···Cg1ii | 0.95 | 2.86 | 3.4966 (18) | 126 |
C14—H14···Cg2iii | 0.95 | 2.95 | 3.8012 (19) | 149 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+2, −y, −z+1; (iii) x, −y+1/2, z+1/2. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C12H8F2N2O | C12H8F2N2O | C12H8F2N2O |
Mr | 234.20 | 234.20 | 234.20 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 150 | 150 | 150 |
a, b, c (Å) | 12.5700 (6), 5.1257 (2), 16.5178 (8) | 8.3187 (6), 5.5868 (6), 21.715 (2) | 6.2088 (4), 11.0182 (5), 14.8139 (9) |
β (°) | 107.847 (2) | 98.517 (6) | 93.018 (3) |
V (Å3) | 1013.03 (8) | 998.07 (16) | 1012.01 (10) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.13 | 0.13 | 0.13 |
Crystal size (mm) | 0.38 × 0.36 × 0.30 | 0.24 × 0.16 × 0.03 | 0.22 × 0.16 × 0.10 |
Data collection | |||
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) | Multi-scan (SORTAV; Blessing, 1995) | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.889, 0.965 | 0.969, 0.996 | 0.932, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5827, 2292, 1872 | 6812, 2248, 1197 | 6136, 2295, 1555 |
Rint | 0.033 | 0.083 | 0.036 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 | 0.649 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.107, 1.05 | 0.055, 0.157, 1.01 | 0.044, 0.120, 1.04 |
No. of reflections | 2292 | 2248 | 2295 |
No. of parameters | 158 | 158 | 159 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.18 | 0.22, −0.27 | 0.21, −0.27 |
Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and SORTX (McArdle, 1995), PLATON (Spek, 2003), SHELXL97 (Sheldrick, 2008) and PREP8 (Ferguson, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.88 (2) | 2.21 (2) | 3.0181 (16) | 152.3 (16) |
N1—H1···F12 | 0.88 (2) | 2.212 (18) | 2.7803 (14) | 122.2 (15) |
C22—H22···O1 | 0.95 | 2.36 | 2.8807 (18) | 114 |
C14—H14···N24ii | 0.95 | 2.59 | 3.4273 (19) | 147 |
C15—H15···Cg1iii | 0.95 | 2.86 | 3.5941 (16) | 135 |
C25—H25···F13iv | 0.95 | 2.49 | 3.4240 (18) | 166 |
Symmetry codes: (i) x, y+1, z; (ii) x+1, y, z; (iii) −x+1/2, y−1/2, −z+1/2; (iv) −x, −y+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···F12 | 0.92 (4) | 2.03 (3) | 2.720 (3) | 131 (3) |
C22—H22···O1 | 0.95 | 2.29 | 2.868 (3) | 118 |
C13—H13···N24i | 0.95 | 2.60 | 3.430 (3) | 146 |
Symmetry code: (i) x, −y+1/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N24i | 0.89 (2) | 2.24 (2) | 3.010 (2) | 145.3 (17) |
N1—H1···F12 | 0.89 (2) | 2.32 (2) | 2.7465 (17) | 109.7 (15) |
C22—H22···O1 | 0.95 | 2.29 | 2.873 (2) | 119 |
C22—H22···Cg1ii | 0.95 | 2.86 | 3.4966 (18) | 126 |
C14—H14···Cg2iii | 0.95 | 2.95 | 3.8012 (19) | 149 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+2, −y, −z+1; (iii) x, −y+1/2, z+1/2. |
Torsion (°) | (I)a | (II)a | (III)a | (Fop)b |
O1—C1—N1—C21 | -0.6 (2) | 1.7 (4) | 7.0 (3) | 6.1 (2) |
O1—C1—C11—C12 | 149.52 (15) | 161.5 (2) | -148.88 (16) | -147.55 (14) |
C11—C1—N1—C21 | -179.45 (12) | -177.7 (2) | -175.26 (14) | -176.77 (12) |
C1—N1—C21—C26 | -156.89 (14) | -169.8 (2) | -172.89 (16) | 11.2 (2) |
C6/C5N | 10.02 (8) | 7.02 (8) | 42.39 (6) | 46.34 (5) |
Notes: (a) this work (C12H8F2N2O). (b) 2-fluoro-N'-(4-pyridyl)benzamide (C12H9FN2O) (Donnelly et al., 2008) |
X | MOHQOPb | (Fpp)c | (Fmp)c | (Fop)c | (III)d |
Formula | C12H10N2O | C12H9FN2O | C12H9FN2O | C12H9FN2O | C12H8F2N2O |
a | 5.6830 (2) | 5.6506 (3) | 5.7537 (3) | 5.9832 (3) | 6.2088 (3) |
b | 11.1380 (3) | 11.3882 (8) | 11.2421 (4) | 11.1508 (5) | 11.0182 (5) |
c | 15.2124 (16) | 15.4314 (8) | 15.1672 (7) | 14.8921 (7) | 14.8139 (9) |
β | 95.0784 (13) | 95.602 (3) | 94.188 (2) | 94.986 (3) | 93.018 (3) |
V (Å3) | 959.12 (6) | 988.27 (10) | 978.45 (8) | 989.80 (8) | 1012.01 (10) |
N···N (Å) | 3.01412 (16) | 3.022 (2) | 3.049 (2) | 3.0213 (17) | 3.010 (2) |
N···O (Å) | 3.4388 (13) | 3.438 (2) | 3.562 (2) | 3.7854 (16) | 4.005 (2) |
C6/C5N (°) | 45.95 (6) | 51.95 (6) | 48.75 (6) | 46.34 (5) | 42.39 (6) |
Notes: (a) Space group P21/c (No. 14) with Z=4. (b) MOHQOP = N'-(4-pyridyl)benzamide (Noveron et al., 2002). (c) (Donnelly et al., 2008) (Fpp/Fmp/Fop = 4-/3-/2-Fluoro-N'-(4-pyridyl)benzamides). (d) this research. |
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Our group has initiated a structural systematic study of fluoro-N'-(pyridyl)benzamide isomers (Donnelly et al., 2008) and are augmenting this research with the closely related difluoro-N-(pyridyl)benzamide series (see scheme) of which a total of 18 isomers are possible through condensation of the 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-difluorobenzoyl chlorides with the 4-/3-/2-aminopyridines. In contrast to the abundance of monosubstituted fluorobenzene FC6H4—X and pentafluorobenzene F5C6—Y derivatives in structural chemistry, there is a paucity of structural information on all six possible difluorobenzene derivatives F2C6H3—Z (X,Y,Z = remainder of molecule) from analysis of structural data in the Cambridge Structural Database (CSD, Version 5.29; Allen, 2002) (Fig. 1). In contrast to the 3531 (8) structures containing the pentafluorobenzene C6F5—Y group, the cumulative reported total of the six C6F2H3Z difluorobenzene moieties in compounds (at 438) is only < 13% of the C6F5 reported systems (see scheme).
Disorder in the orientation of the aromatic ring can arise and can influence the choice of a particular difluorobenzene fragment in crystal structures in order to minimize solid-state disorder effects. The potential for twofold rotational disorder is at a minimum in the more symmetrical 2,6-F2 and 3,5-F2 (no change on twofold rotation about the Cipso—Cpara axis) and at a maximum in the 2,3-F2, 2,5-F2 systems (two F atoms have to occupy different H-atom sites): the potential for disorder also exists for 2,4-F2 and 3,4-F2 substitution (where only one F atom has to swop sites with an H atom after twofold rotation). No disorder is present in either of the 2,3-, (I), 2,4-, (II) or 2,5-difluoro(4-pyridyl)benzamide systems (III).
Many structural studies have been reported to date on a variety of organic molecular classes and often with a particular emphasis on polymorphism, pseudopolymorphism and isomers (Gelbrich et al., 2007; Wardell et al., 2007; 2008; Chopra & Row, 2008). Augmenting our initial communication (Donnelly et al., 2008) we report here the molecular and crystal structures of the 2,3-difluoro-N-(4-pyridyl)benzamide, (I), 2,4-difluoro-N-(4-pyridyl)benzamide, (II), and 2,5-difluoro-N-(4-pyridyl)benzamide, (III), isomers.
The three isomers (I)–(III) are depicted in Figs. 2–4 and in the packing diagrams (Figs. 5–8). The geometric data (bond lengths and angles) are normal and are not discussed except for comparisons with related systems and their hydrogen bonding/packing (interactions in Tables 1–3 and torsion angles in Table 4). The defining feature of the molecular conformation is the benzene–pyridine dihedral angle, which is mutally oriented at 10.02 (8)° in (I), 7.02 (13)° in (II) and 42.39 (6)° in (III). In all three systems the ortho-F atom is positioned cisoid to the carbonyl O atom and as such there are two intramolecular contacts present involving C22···O1 and N1···F12 [both with S(6) motifs]. The C22···O1 distances vary from 2.868 (2) to 2.8807 (18) Å [C—H···O = 114–120°]; however, N1···F1 varies from 2.720 (3) (II) to 2.7803 (14) Å (I) and with angles 109.7 (15)° (III) to 131 (3)° (I) (as C1—N1—C21—C26 increases in angle, Table 4). The intramolecular contact data for (III) are similar to data for 2-fluoro-N'-(4-pyridyl)benzamide (Fop) (Donnelly et al., 2008). Moreover, (III) is isomorphous with all three 4-/3-/2-fluoro-N'-(4-pyridyl)benzamide isomers (Fpp/Fmp/Fop) and differs in composition with an extra F atom replacing a H atom on the benzene ring (see scheme) (Donnelly et al., 2008). For comparison, the unit-cell similarity indices Π of (III) with Fmp and Fop are 0.003 and 0.002, respectively, (Kálmán et al., 1993).
In (I), standard amide N—H···O═C hydrogen bonds (Table 1) form chains along [010], further linked by C—H14···N interactions to form sheets of R44(28) rings parallel to (001) (Fig. 5). Pairs of inversion-related sheets form short C—H···F contacts and these pairs of sheets form a three-dimensional network via C—H···π(pyridyl) interactions (Table 1).
In (II), a C—H···N hydrogen bond (Table 2) forms a zigzag C(10) chain along [001] (Fig. 6): there are no other interactions with an H···O/N/F distance < 2.5 Å. Conventional amide N—H···O═C interactions [as C(4) chains or R22(8) rings] are absent and the closest amide···amide contact for N1···O1i = 3.460 (3) Å: this is 0.45 Å longer than for (I) [symmetry code: (i) = x,y + 1,z]. The three closest intermolecular contacts with the carbonyl O1 atom range from 2.69 to 2.76 Å and with corresponding C—H···O1 angles of 126–141°. There are also two weak C15/23—H15/23···F14 contacts with C···F distances of 3.322 (3), 3.339 (3) Å. Though the interaction distances differ between (I) and (II), there is a broad similarity in overall packing.
In (III), the primary interaction is an N—H···N hydrogen bond (Table 3) which forms a zigzag C(96) chain along the [010] direction (Fig. 7). This interaction is augmented by longer C—H···π(arene) hydrogen bonds (Table 3), dipolar C=O···O═C interactions (Fig. 8) and weaker C—H···N/O/F contacts forming a three-dimensional network. The C=O···(O═C)i interactions link molecules about inversion centres in an antiparallel arrangement, with C1···O1i distances of 3.150 (2) Å [symmetry code: (i) = -x + 2,-y,-z + 1] (Fig. 8). The internal angles within the [C=O···(O═C)i] motif are 85.00 (10)° (for C1=O1···C1i) and 95.00 (10)° (for O1=C1···O1i) and close to the idealized antiparallel arrangement [90° angles – motif (II)] (Allen et al., 1998).
Data for (III) are similar to Fop (Donnelly et al., 2008) where the C1···O1i distance is 3.1919 (16) Å. The closest intermolecular amide···amide N1···O1ii distance is 4.005 (2) Å [with H1···O1ii 3.37 (2) Å] along the [100] axis, highlighting the lack of conventional intermolecular amide···amide hydrogen bonding in (III). This N1···O1ii distance [symmetry code: (ii) = x - 1,y,z] is longer than the corresponding N···O distances in the three isomers (Fpp), (Fmp) and (Fop) [3.438 (2)–3.7854 (16) Å] (Table 5) (these isomers have N—H···Npy as their primary interaction) (Donnelly et al., 2008). The trend of increasing amideN···Ocarbonyl distance correlates well with the increasing unit-cell 'a' dimension (amide···amide distance along [100]) and decreasing C6/C5N dihedral angle (preventing closer intermolecular N···O approach).
The primary interactions in (I)–(III) differ, although (I) and (II) are more closely matched in comparison to the hydrogen bonding in (III) (where N—H···Npy hydrogen bonding dominates) and they also differ in intermolecular N—H···O distance. The influence of π···π stacking interactions is small for (I)–(III) and with no substantial aromatic ring overlap: there are no parallel and overlapping aromatic planes within 3.5 Å of each other.
It is of interest that (III) crystallizes in the same space group, P21/c (No. 14), and with a similar unit cell as the (Fpp/Fmp/Fop) series (Donnelly et al., 2008) and also the parent N-(4-pyridyl)benzamide (IV) (Noveron et al., 2002) (Table 5). This isomorphous series of five compounds facilitates comparisons (where H is replaced by F) on progressing from the parent C12H10N2O (MOHQOP) (IV) to the isomorphous (Fpp/Fmp/Fop) C12H9FN2O series to C12H8F2N2O (III). The molecular conformations of (III) and the (Fpp/Fmp/Fop) series are similar as the spatial orientation of the 2,5-F2 atoms on the C6 benzene ring in (III) compares favourably with the ortho (2-substituted) F atom in (Fop) and the meta (3-substituted) F atom in (Fmp) (Table 5). The dominance and influence of the amideN—H···Npy hydrogen bonding in the packing for all five compounds is notable as it competes with potential N—H···O═C interactions and other weaker types of hydrogen bonding: there is a negligible influence of the isosteric replacement of H atoms by F atoms on packing. The molecular similarity in combination with the dominance of N—H···N hydrogen bonding influences the observed isomorphism in the five structures (IV), (Fpp/Fmp/Fop) and (III).
In expanding our structural systematic study of fluoro(pyridyl)benzamides, incorporating isomers, polymorphs and pseudopolymorphs, we will strive to group together examples with similar properties and behaviour as well as making comparisons with related published work so as 'not to impose a discontinuity on Nature's continuum' (Threlfall & Gelbrich, 2007). Work is in progress to expand these fluoro(pyridyl)benzamide series.