Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108012067/sk3227sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108012067/sk3227Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108012067/sk3227IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108012067/sk3227IIIsup4.hkl |
CCDC references: 692668; 692669; 692670
For related literature, see: Allen et al. (1998); Chopra & Row (2008); Day (2005); Dou et al. (1993); Gelbrich et al. (2007); Gilbert (2007); Gowda et al. (2008); Kálmán et al. (1993); Lu et al. (2003); Slovokhotov et al. (2004); Wardell et al. (2007, 2008).
Compound (I) has been synthesized previously both as (i) a labelled [carbonyl-11C]amide via a one-pot in situ reaction of the amine coupled with [11C]carboxymagnesium halides generated from Grignard reagents and cyclotron produced [11C]CO2 and (ii) an unlabelled amide via microwave-irradiated Grignard coupling reactions (Lu et al., 2003). N-(4-pyridiyl)benzamides have been patented as potential cardiotonics (Sakakibara et al., 1988).
For the preparation of (I)–(III), typically, 4-/3-/2-fluorobenzoyl chloride in dry CH2Cl2 (20–30 ml) was added dropwise (over a period of 2–3 min) to a 20–30 ml solution of para-aminopyridine containing 1.5 ml of Et3N, and the reaction mixtured was stirred overnight. Typical organic workup and washing furnished the products in reasonable yields of 20–40%. Crystals suitable for X-ray diffraction were grown from CHCl3 as colourless blocks over a period of 1–2 weeks.
For (I), m.p. 456–459 K (uncorrected). IR (ν C═O, cm-1): 1723 (s), 1682 (m) (CHCl3); 1677 (s) (KBr). 1H NMR (400 MHz, CDCl3): δ 8.47 (d, 2H, 4-pyr), 8.07 (br s, 1H, N—H), 7.84 (m, 2H, 4-Fbenz), 7.54 (d, 2H, 4-pyr), 7.12 (m, 2H, 4-Fbenz). For (II), m.p. 443–446 K (uncorrected). IR (ν C═O, cm-1): 1738 (w), 1710 (s) (CHCl3); 1683 (s) (KBr). 1H NMR (as above): δ 8.60 (d, 2H, 4-pyr), 7.93 (br s, 1H, N—H), 7.64 (m, 4H, 4-pyr and 3-Fbenz), 7.53 (m, 1H, 3-Fbenz), 7.35 (m, 1H, 3-Fbenz). For (III), m.p. 396–398 K (uncorrected). IR (ν C═O, cm-1): 1689 (s) (CHCl3); 1685 (s) (KBr). 1H NMR (as above): 8.66 (br d, 1H, N—H), 8.57 (d, 2H, 4-pyr), 8.17 (t, 1H, 2-FBenz), 7.64 (m, 2H, 4-pyr), 7.59 (m, 1H, 2-Fbenz), 7.36 (t, 1H, 2-Fbenz), 7.22 (t, 1H, 2-Fbenz).
H atoms attached to C atoms were treated as riding atoms using the SHELXL97 (Sheldrick, 2008) defaults at 150 (1) K [C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C)]; the N-bound H atoms were refined freely with isotropic displacement parameters to bond lengths of 0.84 (2) Å (I), 0.847 (19) Å (II) and 0.844 (19) Å (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).
C12H9FN2O | F(000) = 448 |
Mr = 216.21 | Dx = 1.453 Mg m−3 |
Monoclinic, P21/c | Melting point: 458 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 5.6506 (3) Å | Cell parameters from 3825 reflections |
b = 11.3882 (8) Å | θ = 2.6–27.5° |
c = 15.4314 (8) Å | µ = 0.11 mm−1 |
β = 95.602 (3)° | T = 150 K |
V = 988.27 (10) Å3 | Block, colourless |
Z = 4 | 0.26 × 0.14 × 0.12 mm |
Nonius KappaCCD diffractometer | 2246 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 1465 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
ϕ, ω scans with κ offsets | θmax = 27.5°, θmin = 2.7° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −7→7 |
Tmin = 0.893, Tmax = 0.988 | k = −13→14 |
7401 measured reflections | l = −19→19 |
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.147 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0836P)2] where P = (Fo2 + 2Fc2)/3 |
2246 reflections | (Δ/σ)max < 0.001 |
149 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C12H9FN2O | V = 988.27 (10) Å3 |
Mr = 216.21 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.6506 (3) Å | µ = 0.11 mm−1 |
b = 11.3882 (8) Å | T = 150 K |
c = 15.4314 (8) Å | 0.26 × 0.14 × 0.12 mm |
β = 95.602 (3)° |
Nonius KappaCCD diffractometer | 2246 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1465 reflections with I > 2σ(I) |
Tmin = 0.893, Tmax = 0.988 | Rint = 0.052 |
7401 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.147 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.28 e Å−3 |
2246 reflections | Δρmin = −0.31 e Å−3 |
149 parameters |
x | y | z | Uiso*/Ueq | ||
F14 | 0.8735 (2) | 0.46409 (10) | 0.64546 (7) | 0.0433 (4) | |
O1 | 1.0970 (2) | 0.04686 (11) | 0.40121 (8) | 0.0315 (4) | |
C1 | 0.9026 (3) | 0.08923 (17) | 0.41224 (11) | 0.0251 (4) | |
N1 | 0.6915 (3) | 0.05045 (15) | 0.37056 (10) | 0.0278 (4) | |
C11 | 0.8830 (3) | 0.18991 (17) | 0.47289 (11) | 0.0238 (4) | |
C12 | 1.0694 (3) | 0.27022 (17) | 0.48160 (11) | 0.0254 (4) | |
C13 | 1.0653 (3) | 0.36349 (17) | 0.53916 (11) | 0.0289 (5) | |
C14 | 0.8749 (3) | 0.37344 (18) | 0.58769 (11) | 0.0299 (5) | |
C15 | 0.6878 (3) | 0.29550 (18) | 0.58138 (11) | 0.0294 (5) | |
C16 | 0.6910 (3) | 0.20322 (17) | 0.52267 (11) | 0.0273 (5) | |
C21 | 0.6586 (3) | −0.04340 (17) | 0.31258 (11) | 0.0245 (4) | |
C22 | 0.4437 (3) | −0.05136 (17) | 0.26019 (12) | 0.0284 (5) | |
C23 | 0.4087 (3) | −0.14270 (18) | 0.20207 (12) | 0.0306 (5) | |
N24 | 0.5668 (3) | −0.22853 (15) | 0.19251 (9) | 0.0298 (4) | |
C25 | 0.7701 (3) | −0.22039 (17) | 0.24471 (11) | 0.0275 (5) | |
C26 | 0.8244 (3) | −0.13173 (17) | 0.30464 (11) | 0.0261 (5) | |
H1 | 0.581 (4) | 0.100 (2) | 0.3688 (13) | 0.045 (7)* | |
H12 | 1.2003 | 0.2611 | 0.4479 | 0.031* | |
H13 | 1.1911 | 0.4192 | 0.5449 | 0.035* | |
H15 | 0.5596 | 0.3046 | 0.6163 | 0.035* | |
H16 | 0.5626 | 0.1491 | 0.5163 | 0.033* | |
H22 | 0.3228 | 0.0057 | 0.2646 | 0.034* | |
H23 | 0.2623 | −0.1452 | 0.1662 | 0.037* | |
H25 | 0.8858 | −0.2801 | 0.2402 | 0.033* | |
H26 | 0.9723 | −0.1313 | 0.3397 | 0.031* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F14 | 0.0488 (7) | 0.0369 (8) | 0.0442 (7) | 0.0033 (6) | 0.0048 (6) | −0.0195 (6) |
O1 | 0.0278 (7) | 0.0295 (9) | 0.0376 (8) | 0.0023 (6) | 0.0047 (6) | −0.0049 (6) |
C1 | 0.0285 (10) | 0.0254 (11) | 0.0212 (9) | 0.0021 (8) | 0.0013 (7) | 0.0024 (8) |
N1 | 0.0270 (8) | 0.0271 (10) | 0.0284 (9) | 0.0044 (8) | −0.0029 (7) | −0.0055 (7) |
C11 | 0.0257 (9) | 0.0236 (11) | 0.0213 (9) | 0.0050 (8) | −0.0021 (7) | 0.0026 (8) |
C12 | 0.0248 (9) | 0.0260 (11) | 0.0253 (9) | 0.0034 (8) | 0.0015 (7) | 0.0013 (8) |
C13 | 0.0287 (9) | 0.0248 (11) | 0.0318 (10) | 0.0008 (8) | −0.0033 (8) | −0.0003 (9) |
C14 | 0.0370 (10) | 0.0255 (11) | 0.0259 (10) | 0.0078 (9) | −0.0041 (8) | −0.0072 (8) |
C15 | 0.0264 (9) | 0.0353 (13) | 0.0267 (10) | 0.0072 (8) | 0.0036 (8) | −0.0010 (9) |
C16 | 0.0258 (9) | 0.0290 (12) | 0.0261 (9) | 0.0022 (8) | −0.0024 (8) | −0.0004 (8) |
C21 | 0.0276 (9) | 0.0244 (11) | 0.0216 (9) | −0.0011 (8) | 0.0034 (7) | 0.0001 (8) |
C22 | 0.0243 (9) | 0.0302 (12) | 0.0302 (10) | 0.0016 (8) | 0.0011 (8) | −0.0017 (9) |
C23 | 0.0249 (9) | 0.0350 (13) | 0.0316 (10) | −0.0004 (9) | 0.0005 (8) | −0.0017 (9) |
N24 | 0.0291 (8) | 0.0314 (10) | 0.0288 (9) | −0.0022 (7) | 0.0023 (7) | −0.0061 (7) |
C25 | 0.0300 (10) | 0.0248 (11) | 0.0278 (10) | 0.0006 (8) | 0.0026 (8) | 0.0011 (9) |
C26 | 0.0271 (9) | 0.0271 (11) | 0.0235 (9) | 0.0009 (8) | −0.0009 (7) | 0.0029 (8) |
F14—C14 | 1.365 (2) | C22—C23 | 1.375 (3) |
O1—C1 | 1.227 (2) | N24—C23 | 1.342 (2) |
N1—C1 | 1.372 (2) | N24—C25 | 1.340 (2) |
N1—C21 | 1.395 (2) | C25—C26 | 1.383 (2) |
C1—C11 | 1.491 (3) | N1—H1 | 0.84 (2) |
C11—C12 | 1.392 (3) | C12—H12 | 0.9500 |
C11—C16 | 1.397 (2) | C13—H13 | 0.9500 |
C12—C13 | 1.386 (2) | C15—H15 | 0.9500 |
C13—C14 | 1.374 (3) | C16—H16 | 0.9500 |
C14—C15 | 1.377 (3) | C22—H22 | 0.9500 |
C15—C16 | 1.389 (3) | C23—H23 | 0.9500 |
C21—C26 | 1.388 (3) | C25—H25 | 0.9500 |
C21—C22 | 1.395 (2) | C26—H26 | 0.9500 |
C1—N1—C21 | 127.07 (16) | N24—C25—C26 | 124.99 (18) |
O1—C1—N1 | 123.90 (18) | C25—C26—C21 | 118.71 (16) |
O1—C1—C11 | 120.78 (16) | C1—N1—H1 | 113.8 (15) |
N1—C1—C11 | 115.31 (16) | C21—N1—H1 | 116.5 (15) |
C12—C11—C1 | 117.66 (16) | C13—C12—H12 | 119.8 |
C16—C11—C1 | 122.52 (17) | C11—C12—H12 | 119.8 |
C12—C11—C16 | 119.77 (17) | C14—C13—H13 | 120.8 |
C13—C12—C11 | 120.37 (17) | C12—C13—H13 | 120.8 |
C14—C13—C12 | 118.38 (18) | C14—C15—H15 | 120.8 |
F14—C14—C13 | 118.23 (17) | C16—C15—H15 | 120.8 |
F14—C14—C15 | 118.73 (17) | C15—C16—H16 | 120.0 |
C13—C14—C15 | 123.03 (18) | C11—C16—H16 | 120.0 |
C14—C15—C16 | 118.37 (17) | C23—C22—H22 | 120.4 |
C15—C16—C11 | 120.07 (17) | C21—C22—H22 | 120.4 |
C26—C21—N1 | 124.28 (16) | N24—C23—H23 | 117.7 |
C26—C21—C22 | 117.31 (17) | C22—C23—H23 | 117.7 |
N1—C21—C22 | 118.39 (16) | N24—C25—H25 | 117.5 |
C23—C22—C21 | 119.26 (17) | C26—C25—H25 | 117.5 |
N24—C23—C22 | 124.60 (16) | C25—C26—H26 | 120.6 |
C25—N24—C23 | 115.11 (16) | C21—C26—H26 | 120.6 |
O1—C1—N1—C21 | 2.5 (3) | C13—C14—C15—C16 | −0.6 (3) |
O1—C1—C11—C12 | 32.0 (2) | C14—C15—C16—C11 | 1.1 (3) |
C11—C1—N1—C21 | −178.28 (16) | C12—C11—C16—C15 | −0.8 (3) |
C1—N1—C21—C26 | 17.7 (3) | C1—C11—C16—C15 | 176.75 (16) |
N1—C1—C11—C12 | −147.30 (17) | C1—N1—C21—C22 | −163.85 (17) |
O1—C1—C11—C16 | −145.58 (18) | C26—C21—C22—C23 | −2.0 (3) |
N1—C1—C11—C16 | 35.1 (2) | N1—C21—C22—C23 | 179.44 (17) |
C16—C11—C12—C13 | −0.2 (3) | C25—N24—C23—C22 | −0.1 (3) |
C1—C11—C12—C13 | −177.84 (15) | C21—C22—C23—N24 | 1.4 (3) |
C11—C12—C13—C14 | 0.8 (3) | C23—N24—C25—C26 | −0.6 (3) |
C12—C13—C14—F14 | 178.80 (15) | N24—C25—C26—C21 | 0.0 (3) |
C12—C13—C14—C15 | −0.4 (3) | N1—C21—C26—C25 | 179.81 (16) |
F14—C14—C15—C16 | −179.75 (15) | C22—C21—C26—C25 | 1.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N24i | 0.84 (2) | 2.29 (2) | 3.022 (2) | 146 (2) |
C26—H26···O1 | 0.95 | 2.32 | 2.878 (2) | 117 |
C26—H26···Cg1ii | 0.95 | 2.71 | 3.373 (2) | 128 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+2, −y, −z+1. |
C12H9FN2O | F(000) = 448 |
Mr = 216.21 | Dx = 1.468 Mg m−3 |
Monoclinic, P21/c | Melting point: 443 K |
Hall symbol: -p 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 5.7537 (3) Å | Cell parameters from 3355 reflections |
b = 11.2421 (4) Å | θ = 2.6–27.5° |
c = 15.1672 (7) Å | µ = 0.11 mm−1 |
β = 94.188 (2)° | T = 150 K |
V = 978.45 (8) Å3 | Block, colourless |
Z = 4 | 0.32 × 0.20 × 0.12 mm |
Nonius KappaCCD diffractometer | 2236 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 1474 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
ϕ, ω scans with κ offsets | θmax = 27.5°, θmin = 2.3° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −7→7 |
Tmin = 0.801, Tmax = 0.989 | k = −11→14 |
8753 measured reflections | l = −15→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)] = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.132 | w = 1/[σ2(Fo2) + (0.0665P)2 + 0.118P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
2236 reflections | Δρmax = 0.26 e Å−3 |
150 parameters | Δρmin = −0.28 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: 0.013 (3) |
C12H9FN2O | V = 978.45 (8) Å3 |
Mr = 216.21 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.7537 (3) Å | µ = 0.11 mm−1 |
b = 11.2421 (4) Å | T = 150 K |
c = 15.1672 (7) Å | 0.32 × 0.20 × 0.12 mm |
β = 94.188 (2)° |
Nonius KappaCCD diffractometer | 2236 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1474 reflections with I > 2σ(I) |
Tmin = 0.801, Tmax = 0.989 | Rint = 0.054 |
8753 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.132 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.26 e Å−3 |
2236 reflections | Δρmin = −0.28 e Å−3 |
150 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | ||
F13 | 1.1776 (2) | 0.44628 (9) | 0.57174 (8) | 0.0407 (4) | |
O1 | 1.0899 (2) | 0.05614 (10) | 0.40398 (8) | 0.0279 (3) | |
C1 | 0.8963 (3) | 0.09551 (15) | 0.41512 (11) | 0.0229 (4) | |
N1 | 0.6955 (3) | 0.05768 (13) | 0.36911 (10) | 0.0252 (4) | |
C11 | 0.8604 (3) | 0.19234 (14) | 0.48091 (11) | 0.0228 (4) | |
C12 | 1.0381 (3) | 0.27533 (14) | 0.49562 (11) | 0.0250 (4) | |
C13 | 1.0080 (3) | 0.36367 (15) | 0.55715 (12) | 0.0292 (4) | |
C14 | 0.8134 (3) | 0.37190 (17) | 0.60440 (12) | 0.0328 (5) | |
C15 | 0.6405 (3) | 0.28725 (17) | 0.58981 (12) | 0.0311 (5) | |
C16 | 0.6617 (3) | 0.19786 (15) | 0.52751 (12) | 0.0266 (4) | |
C21 | 0.6721 (3) | −0.03611 (14) | 0.30820 (11) | 0.0228 (4) | |
C22 | 0.4626 (3) | −0.04577 (15) | 0.25645 (12) | 0.0253 (4) | |
C23 | 0.4323 (3) | −0.13842 (16) | 0.19713 (12) | 0.0274 (4) | |
N24 | 0.5922 (3) | −0.22350 (13) | 0.18647 (10) | 0.0270 (4) | |
C25 | 0.7921 (3) | −0.21215 (15) | 0.23682 (12) | 0.0262 (4) | |
C26 | 0.8418 (3) | −0.12211 (15) | 0.29768 (11) | 0.0241 (4) | |
H1 | 0.580 (3) | 0.1045 (17) | 0.3684 (12) | 0.024 (5)* | |
H12 | 1.1753 | 0.2715 | 0.4645 | 0.030* | |
H14 | 0.7982 | 0.4341 | 0.6460 | 0.039* | |
H15 | 0.5062 | 0.2902 | 0.6226 | 0.037* | |
H16 | 0.5409 | 0.1409 | 0.5169 | 0.032* | |
H22 | 0.3419 | 0.0109 | 0.2620 | 0.030* | |
H23 | 0.2896 | −0.1424 | 0.1616 | 0.033* | |
H25 | 0.9090 | −0.2705 | 0.2303 | 0.031* | |
H26 | 0.9877 | −0.1192 | 0.3313 | 0.029* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F13 | 0.0416 (7) | 0.0300 (6) | 0.0487 (8) | −0.0060 (5) | −0.0072 (6) | −0.0098 (5) |
O1 | 0.0249 (7) | 0.0266 (7) | 0.0322 (8) | 0.0010 (5) | 0.0016 (6) | −0.0025 (5) |
C1 | 0.0264 (10) | 0.0217 (8) | 0.0205 (9) | −0.0005 (8) | 0.0010 (8) | 0.0030 (7) |
N1 | 0.0240 (8) | 0.0244 (8) | 0.0264 (9) | 0.0049 (7) | −0.0036 (7) | −0.0051 (6) |
C11 | 0.0259 (9) | 0.0227 (9) | 0.0191 (10) | 0.0040 (7) | −0.0032 (7) | 0.0020 (7) |
C12 | 0.0259 (9) | 0.0261 (10) | 0.0227 (10) | 0.0037 (8) | −0.0013 (8) | 0.0019 (7) |
C13 | 0.0320 (10) | 0.0240 (9) | 0.0298 (11) | 0.0000 (8) | −0.0104 (8) | −0.0006 (8) |
C14 | 0.0392 (11) | 0.0316 (10) | 0.0267 (11) | 0.0111 (9) | −0.0041 (9) | −0.0047 (8) |
C15 | 0.0302 (10) | 0.0376 (11) | 0.0256 (10) | 0.0083 (9) | 0.0018 (8) | 0.0004 (8) |
C16 | 0.0269 (10) | 0.0286 (10) | 0.0238 (10) | 0.0033 (8) | −0.0016 (8) | 0.0009 (7) |
C21 | 0.0273 (10) | 0.0223 (9) | 0.0188 (9) | −0.0032 (7) | 0.0027 (8) | 0.0021 (7) |
C22 | 0.0231 (10) | 0.0274 (9) | 0.0251 (10) | 0.0020 (7) | −0.0005 (8) | −0.0001 (7) |
C23 | 0.0249 (9) | 0.0290 (10) | 0.0277 (10) | −0.0004 (8) | −0.0024 (8) | 0.0003 (8) |
N24 | 0.0281 (9) | 0.0275 (8) | 0.0252 (8) | −0.0011 (7) | 0.0007 (7) | −0.0018 (6) |
C25 | 0.0257 (10) | 0.0251 (9) | 0.0280 (10) | 0.0028 (8) | 0.0020 (8) | −0.0017 (8) |
C26 | 0.0233 (9) | 0.0254 (9) | 0.0234 (10) | 0.0011 (7) | −0.0003 (7) | 0.0011 (7) |
F13—C13 | 1.354 (2) | C22—C23 | 1.379 (2) |
O1—C1 | 1.222 (2) | N24—C23 | 1.345 (2) |
C1—C11 | 1.501 (2) | N24—C25 | 1.339 (2) |
N1—C1 | 1.373 (2) | C25—C26 | 1.386 (2) |
N1—C21 | 1.402 (2) | N1—H1 | 0.847 (19) |
C11—C16 | 1.389 (2) | C12—H12 | 0.9500 |
C11—C12 | 1.390 (2) | C14—H14 | 0.9500 |
C12—C13 | 1.382 (2) | C15—H15 | 0.9500 |
C13—C14 | 1.376 (3) | C16—H16 | 0.9500 |
C14—C15 | 1.383 (3) | C22—H22 | 0.9500 |
C15—C16 | 1.391 (3) | C23—H23 | 0.9500 |
C21—C26 | 1.392 (2) | C25—H25 | 0.9500 |
C21—C22 | 1.394 (2) | C26—H26 | 0.9500 |
C1—N1—C21 | 127.20 (15) | N24—C25—C26 | 125.21 (16) |
O1—C1—N1 | 124.02 (16) | C25—C26—C21 | 118.12 (16) |
O1—C1—C11 | 121.70 (16) | C1—N1—H1 | 116.4 (12) |
N1—C1—C11 | 114.28 (15) | C21—N1—H1 | 114.9 (13) |
C12—C11—C1 | 117.28 (16) | C13—C12—H12 | 121.2 |
C16—C11—C1 | 121.93 (16) | C11—C12—H12 | 121.2 |
C16—C11—C12 | 120.76 (16) | C13—C14—H14 | 120.9 |
C13—C12—C11 | 117.63 (17) | C15—C14—H14 | 120.9 |
F13—C13—C14 | 118.24 (16) | C14—C15—H15 | 119.7 |
F13—C13—C12 | 118.62 (17) | C16—C15—H15 | 119.7 |
C14—C13—C12 | 123.14 (17) | C11—C16—H16 | 120.2 |
C13—C14—C15 | 118.28 (17) | C15—C16—H16 | 120.2 |
C14—C15—C16 | 120.56 (18) | C23—C22—H22 | 120.4 |
C11—C16—C15 | 119.62 (17) | C21—C22—H22 | 120.4 |
C26—C21—C22 | 117.81 (16) | N24—C23—H23 | 117.9 |
C26—C21—N1 | 124.32 (16) | C22—C23—H23 | 117.9 |
C22—C21—N1 | 117.85 (15) | N24—C25—H25 | 117.4 |
C23—C22—C21 | 119.27 (16) | C26—C25—H25 | 117.4 |
N24—C23—C22 | 124.11 (17) | C25—C26—H26 | 120.9 |
C25—N24—C23 | 115.47 (15) | C21—C26—H26 | 120.9 |
O1—C1—N1—C21 | 5.4 (3) | C13—C14—C15—C16 | −1.4 (3) |
O1—C1—C11—C12 | 31.8 (2) | C12—C11—C16—C15 | −0.2 (3) |
C21—N1—C1—C11 | −175.38 (15) | C1—C11—C16—C15 | 177.92 (16) |
C1—N1—C21—C26 | 13.8 (3) | C14—C15—C16—C11 | 1.3 (3) |
O1—C1—C11—C16 | −146.41 (17) | C1—N1—C21—C22 | −168.05 (16) |
N1—C1—C11—C16 | 34.4 (2) | C26—C21—C22—C23 | −0.5 (3) |
N1—C1—C11—C12 | −147.44 (15) | N1—C21—C22—C23 | −178.73 (15) |
C16—C11—C12—C13 | −0.8 (2) | C25—N24—C23—C22 | −1.4 (3) |
C1—C11—C12—C13 | −179.00 (15) | C21—C22—C23—N24 | 1.4 (3) |
C11—C12—C13—F13 | −179.21 (15) | C23—N24—C25—C26 | 0.6 (3) |
C11—C12—C13—C14 | 0.7 (3) | N24—C25—C26—C21 | 0.2 (3) |
F13—C13—C14—C15 | −179.72 (16) | C22—C21—C26—C25 | −0.2 (2) |
C12—C13—C14—C15 | 0.3 (3) | N1—C21—C26—C25 | 177.91 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N24i | 0.847 (19) | 2.30 (2) | 3.049 (2) | 147.6 (16) |
C26—H26···O1 | 0.95 | 2.31 | 2.884 (2) | 118 |
C26—H26···Cg1ii | 0.95 | 2.78 | 3.4407 (18) | 128 |
C14—H14···Cg2iii | 0.95 | 2.88 | 3.808 (2) | 165 |
C15—H15···Cg2iv | 0.95 | 2.83 | 3.505 (2) | 129 |
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; (iv) −x+1, −y, −z+1. |
C12H9FN2O | F(000) = 448 |
Mr = 216.21 | Dx = 1.451 Mg m−3 |
Monoclinic, P21/c | Melting point: 396 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 5.9832 (3) Å | Cell parameters from 2924 reflections |
b = 11.1508 (5) Å | θ = 2.8–27.5° |
c = 14.8921 (7) Å | µ = 0.11 mm−1 |
β = 94.986 (3)° | T = 150 K |
V = 989.80 (8) Å3 | Block, colourless |
Z = 4 | 0.35 × 0.30 × 0.18 mm |
Nonius KappaCCD diffractometer | 2252 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 1744 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ϕ, ω scans with κ offsets | θmax = 27.5°, θmin = 2.8° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −7→7 |
Tmin = 0.911, Tmax = 0.982 | k = −13→14 |
6092 measured reflections | l = −19→19 |
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) = 0.121 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0667P)2 + 0.1717P] where P = (Fo2 + 2Fc2)/3 |
2252 reflections | (Δ/σ)max = 0.001 |
149 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C12H9FN2O | V = 989.80 (8) Å3 |
Mr = 216.21 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.9832 (3) Å | µ = 0.11 mm−1 |
b = 11.1508 (5) Å | T = 150 K |
c = 14.8921 (7) Å | 0.35 × 0.30 × 0.18 mm |
β = 94.986 (3)° |
Nonius KappaCCD diffractometer | 2252 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1744 reflections with I > 2σ(I) |
Tmin = 0.911, Tmax = 0.982 | Rint = 0.031 |
6092 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.121 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.18 e Å−3 |
2252 reflections | Δρmin = −0.24 e Å−3 |
149 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 | 0.52935 (14) | 0.13712 (8) | 0.52681 (5) | 0.0336 (3) | |
O1 | 1.08051 (17) | 0.05396 (9) | 0.40178 (7) | 0.0302 (3) | |
C1 | 0.8988 (2) | 0.09687 (12) | 0.41552 (9) | 0.0224 (3) | |
N1 | 0.7012 (2) | 0.06364 (11) | 0.37018 (8) | 0.0262 (3) | |
C11 | 0.8830 (2) | 0.19650 (12) | 0.48261 (9) | 0.0226 (3) | |
C12 | 0.7042 (2) | 0.21337 (13) | 0.53489 (9) | 0.0254 (3) | |
C13 | 0.6992 (3) | 0.30509 (14) | 0.59716 (10) | 0.0334 (4) | |
C14 | 0.8783 (3) | 0.38375 (14) | 0.60715 (10) | 0.0355 (4) | |
C15 | 1.0606 (3) | 0.36933 (13) | 0.55681 (10) | 0.0319 (4) | |
C16 | 1.0637 (3) | 0.27587 (13) | 0.49565 (9) | 0.0266 (3) | |
C21 | 0.6653 (2) | −0.02922 (12) | 0.30769 (9) | 0.0228 (3) | |
C22 | 0.4561 (2) | −0.03615 (13) | 0.25859 (10) | 0.0277 (3) | |
C23 | 0.4166 (3) | −0.12762 (14) | 0.19667 (10) | 0.0302 (3) | |
N24 | 0.5662 (2) | −0.21282 (11) | 0.18027 (8) | 0.0287 (3) | |
C25 | 0.7647 (3) | −0.20485 (13) | 0.22909 (9) | 0.0270 (3) | |
C26 | 0.8236 (2) | −0.11715 (12) | 0.29229 (9) | 0.0239 (3) | |
H1 | 0.587 (3) | 0.1064 (16) | 0.3749 (11) | 0.034 (5)* | |
H13 | 0.5752 | 0.3139 | 0.6324 | 0.040* | |
H14 | 0.8764 | 0.4482 | 0.6488 | 0.043* | |
H15 | 1.1834 | 0.4235 | 0.5642 | 0.038* | |
H16 | 1.1904 | 0.2656 | 0.4621 | 0.032* | |
H22 | 0.3427 | 0.0211 | 0.2676 | 0.033* | |
H23 | 0.2738 | −0.1304 | 0.1634 | 0.036* | |
H25 | 0.8737 | −0.2643 | 0.2195 | 0.032* | |
H26 | 0.9680 | −0.1167 | 0.3244 | 0.029* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F12 | 0.0297 (5) | 0.0385 (5) | 0.0334 (5) | −0.0044 (4) | 0.0074 (4) | −0.0025 (4) |
O1 | 0.0265 (6) | 0.0298 (6) | 0.0349 (6) | 0.0012 (4) | 0.0062 (4) | −0.0058 (4) |
C1 | 0.0262 (7) | 0.0208 (7) | 0.0206 (6) | 0.0004 (5) | 0.0035 (5) | 0.0031 (5) |
N1 | 0.0256 (7) | 0.0257 (6) | 0.0269 (6) | 0.0054 (5) | 0.0002 (5) | −0.0055 (5) |
C11 | 0.0277 (7) | 0.0216 (7) | 0.0182 (6) | 0.0033 (5) | 0.0008 (5) | 0.0022 (5) |
C12 | 0.0264 (7) | 0.0267 (7) | 0.0229 (7) | 0.0027 (6) | 0.0008 (5) | 0.0015 (6) |
C13 | 0.0368 (9) | 0.0361 (9) | 0.0278 (8) | 0.0092 (7) | 0.0066 (6) | −0.0022 (6) |
C14 | 0.0493 (10) | 0.0278 (8) | 0.0289 (8) | 0.0058 (7) | 0.0001 (7) | −0.0079 (6) |
C15 | 0.0381 (9) | 0.0248 (8) | 0.0318 (8) | −0.0021 (6) | −0.0020 (6) | −0.0017 (6) |
C16 | 0.0305 (8) | 0.0263 (7) | 0.0230 (7) | 0.0011 (6) | 0.0021 (6) | 0.0024 (6) |
C21 | 0.0276 (7) | 0.0217 (7) | 0.0196 (6) | −0.0012 (5) | 0.0046 (5) | 0.0006 (5) |
C22 | 0.0253 (8) | 0.0277 (7) | 0.0301 (7) | 0.0021 (6) | 0.0033 (6) | −0.0016 (6) |
C23 | 0.0266 (8) | 0.0324 (8) | 0.0313 (7) | −0.0022 (6) | 0.0011 (6) | −0.0033 (6) |
N24 | 0.0311 (7) | 0.0270 (7) | 0.0281 (6) | −0.0019 (5) | 0.0033 (5) | −0.0036 (5) |
C25 | 0.0316 (8) | 0.0230 (7) | 0.0272 (7) | 0.0019 (6) | 0.0057 (6) | 0.0005 (6) |
C26 | 0.0266 (7) | 0.0235 (7) | 0.0213 (6) | 0.0015 (6) | 0.0011 (5) | 0.0009 (5) |
F12—C12 | 1.3451 (16) | C22—C23 | 1.382 (2) |
O1—C1 | 1.2212 (17) | C23—N24 | 1.3421 (19) |
C1—N1 | 1.3610 (18) | N24—C25 | 1.3404 (19) |
C1—C11 | 1.5026 (19) | C25—C26 | 1.382 (2) |
N1—C21 | 1.3962 (18) | N1—H1 | 0.844 (19) |
C11—C12 | 1.3900 (19) | C13—H13 | 0.9500 |
C11—C16 | 1.398 (2) | C14—H14 | 0.9500 |
C12—C13 | 1.383 (2) | C15—H15 | 0.9500 |
C13—C14 | 1.383 (2) | C16—H16 | 0.9500 |
C14—C15 | 1.386 (2) | C22—H22 | 0.9500 |
C15—C16 | 1.385 (2) | C23—H23 | 0.9500 |
C21—C22 | 1.396 (2) | C25—H25 | 0.9500 |
C21—C26 | 1.3960 (19) | C26—H26 | 0.9500 |
O1—C1—N1 | 123.90 (13) | N24—C25—C26 | 125.32 (13) |
O1—C1—C11 | 120.62 (13) | C25—C26—C21 | 118.19 (13) |
N1—C1—C11 | 115.41 (12) | C1—N1—H1 | 118.8 (12) |
C1—N1—C21 | 127.53 (12) | C21—N1—H1 | 113.4 (12) |
C12—C11—C16 | 117.43 (13) | C12—C13—H13 | 120.7 |
C12—C11—C1 | 124.64 (13) | C14—C13—H13 | 120.7 |
C16—C11—C1 | 117.91 (12) | C13—C14—H14 | 119.8 |
F12—C12—C13 | 117.75 (12) | C15—C14—H14 | 119.8 |
F12—C12—C11 | 119.67 (12) | C16—C15—H15 | 120.0 |
C13—C12—C11 | 122.57 (14) | C14—C15—H15 | 120.0 |
C12—C13—C14 | 118.65 (14) | C15—C16—H16 | 119.6 |
C13—C14—C15 | 120.50 (14) | C11—C16—H16 | 119.6 |
C16—C15—C14 | 119.95 (15) | C23—C22—H22 | 120.5 |
C15—C16—C11 | 120.88 (14) | C21—C22—H22 | 120.5 |
C22—C21—C26 | 117.74 (13) | N24—C23—H23 | 117.8 |
C22—C21—N1 | 117.98 (12) | C22—C23—H23 | 117.8 |
C26—C21—N1 | 124.28 (13) | N24—C25—H25 | 117.3 |
C23—C22—C21 | 118.95 (13) | C26—C25—H25 | 117.3 |
N24—C23—C22 | 124.47 (14) | C25—C26—H26 | 120.9 |
C25—N24—C23 | 115.32 (12) | C21—C26—H26 | 120.9 |
O1—C1—N1—C21 | 6.1 (2) | C13—C14—C15—C16 | 0.3 (2) |
O1—C1—C11—C12 | −147.55 (14) | C14—C15—C16—C11 | 1.1 (2) |
C11—C1—N1—C21 | −176.77 (12) | C12—C11—C16—C15 | −1.6 (2) |
C1—N1—C21—C26 | 11.2 (2) | C1—C11—C16—C15 | −179.67 (12) |
N1—C1—C11—C12 | 35.21 (19) | C1—N1—C21—C22 | −170.14 (13) |
O1—C1—C11—C16 | 30.35 (19) | C26—C21—C22—C23 | −1.0 (2) |
N1—C1—C11—C16 | −146.89 (13) | N1—C21—C22—C23 | −179.73 (13) |
C16—C11—C12—F12 | −177.97 (12) | C21—C22—C23—N24 | 0.7 (2) |
C1—C11—C12—F12 | −0.1 (2) | C22—C23—N24—C25 | 0.1 (2) |
C16—C11—C12—C13 | 0.7 (2) | C23—N24—C25—C26 | −0.6 (2) |
C1—C11—C12—C13 | 178.64 (13) | N24—C25—C26—C21 | 0.3 (2) |
F12—C12—C13—C14 | 179.36 (13) | C22—C21—C26—C25 | 0.52 (19) |
C11—C12—C13—C14 | 0.6 (2) | N1—C21—C26—C25 | 179.21 (13) |
C12—C13—C14—C15 | −1.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N24i | 0.844 (19) | 2.333 (18) | 3.0213 (17) | 139.1 (15) |
N1—H1···F12 | 0.844 (19) | 2.342 (17) | 2.7544 (15) | 110.6 (14) |
C26—H26···O1 | 0.95 | 2.30 | 2.8681 (17) | 118 |
C26—H26···Cg1ii | 0.95 | 2.83 | 3.4549 (13) | 124 |
C14—H14···Cg2iii | 0.95 | 2.93 | 3.7693 (17) | 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 | C12H9FN2O | C12H9FN2O | C12H9FN2O |
Mr | 216.21 | 216.21 | 216.21 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 150 | 150 | 150 |
a, b, c (Å) | 5.6506 (3), 11.3882 (8), 15.4314 (8) | 5.7537 (3), 11.2421 (4), 15.1672 (7) | 5.9832 (3), 11.1508 (5), 14.8921 (7) |
β (°) | 95.602 (3) | 94.188 (2) | 94.986 (3) |
V (Å3) | 988.27 (10) | 978.45 (8) | 989.80 (8) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.11 | 0.11 | 0.11 |
Crystal size (mm) | 0.26 × 0.14 × 0.12 | 0.32 × 0.20 × 0.12 | 0.35 × 0.30 × 0.18 |
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 | 0.893, 0.988 | 0.801, 0.989 | 0.911, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7401, 2246, 1465 | 8753, 2236, 1474 | 6092, 2252, 1744 |
Rint | 0.052 | 0.054 | 0.031 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 | 0.649 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.147, 1.03 | 0.048, 0.132, 1.06 | 0.044, 0.121, 1.04 |
No. of reflections | 2246 | 2236 | 2252 |
No. of parameters | 149 | 150 | 149 |
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) | 0.28, −0.31 | 0.26, −0.28 | 0.18, −0.24 |
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).
O1—C1—N1—C21 | 2.5 (3) | C11—C1—N1—C21 | −178.28 (16) |
O1—C1—C11—C12 | 32.0 (2) | C1—N1—C21—C26 | 17.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N24i | 0.84 (2) | 2.29 (2) | 3.022 (2) | 146 (2) |
C26—H26···O1 | 0.95 | 2.32 | 2.878 (2) | 117 |
C26—H26···Cg1ii | 0.95 | 2.71 | 3.373 (2) | 128 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+2, −y, −z+1. |
O1—C1—N1—C21 | 5.4 (3) | C21—N1—C1—C11 | −175.38 (15) |
O1—C1—C11—C12 | 31.8 (2) | C1—N1—C21—C26 | 13.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N24i | 0.847 (19) | 2.30 (2) | 3.049 (2) | 147.6 (16) |
C26—H26···O1 | 0.95 | 2.31 | 2.884 (2) | 118 |
C26—H26···Cg1ii | 0.95 | 2.78 | 3.4407 (18) | 128 |
C14—H14···Cg2iii | 0.95 | 2.88 | 3.808 (2) | 165 |
C15—H15···Cg2iv | 0.95 | 2.83 | 3.505 (2) | 129 |
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; (iv) −x+1, −y, −z+1. |
O1—C1—N1—C21 | 6.1 (2) | C11—C1—N1—C21 | −176.77 (12) |
O1—C1—C11—C12 | −147.55 (14) | C1—N1—C21—C26 | 11.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N24i | 0.844 (19) | 2.333 (18) | 3.0213 (17) | 139.1 (15) |
N1—H1···F12 | 0.844 (19) | 2.342 (17) | 2.7544 (15) | 110.6 (14) |
C26—H26···O1 | 0.95 | 2.30 | 2.8681 (17) | 118 |
C26—H26···Cg1ii | 0.95 | 2.83 | 3.4549 (13) | 124 |
C14—H14···Cg2iii | 0.95 | 2.93 | 3.7693 (17) | 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. |
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Structural systematics of small molecules has undergone an enormous change in the past decade with technical advances in the ability to collect and analyse many crystal structures within a short timeframe. Of interest in this research are studies on polymorphism, pseudopolymorphism and isomers and their impact on the development of new materials (Gelbrich et al., 2007; Wardell et al., 2007, 2008). As progress in predicting crystal structures continues to greatly expand knowledge from first principles, it is the drive amongst synthetic chemists and chemical crystallographers to assemble comprehensive sets of crystal structure data that will provide a continual challenge to but also aid in the on-going development of this predictive science (Day et al., 2005). A relatively facile method of obtaining extensive and related crystal structure data sets is the assembly of isomer grids and subsequent grid expansion (with polymorphs of individual compounds), using variable solvent content and cocrystallizations to generate pseudopolymorphs, and using variable temperature studies to analyse for potential phase changes. We report here the molecular and crystal structures of the 4-, 3- and 2-fluoro-N'-(4-pyridyl)benzamide isomers, (I)–(III) (Figs. 1–3), obtained from the reaction of 4-, 3- and 2-fluorobenzoyl chloride and para-aminopyridine. This is the first in a series of studies of isomer and model compounds for the assembly of an isomer grid.
The geometric data (bond lengths and angles) in (I) to (III) are normal and are not discussed except for some comparisons and with reference to the hydrogen bonding. It is of note that the C—F bond lengths differ markedly [1.365 (2) Å in (I), 1.354 (2) Å (II) and 1.3451 (16) Å (III)], probably as a result of the secondary hydrogen bonding (see below). The F atom is located cisoid to the C═O group in (II) but transoid in (III). No noticeable trends are evident from analysis of the bond-angle data. The defining feature of the molecular conformation is the C6/C5N dihedral angle, which is mutually oriented at 51.95 (6)° in (I), 48.75 (6)° in (II) and 46.34 (5)° (III) (see the torsion angles in Tables 1, 3 and 5); pyramidalization is not discernible at the amide N1 atom, with angles summing to within 3° of 360°.
For molecular comparisons, the asymmetric units have been chosen to be closest to the origin and with the molecular axis aligned in similar orientations. A key feature in all three isomers is the intramolecular interaction between atoms C26 and O1 [with an S(6) motif], with C26···O1 in the narrow range of 2.87 (1) Å. In (III) there is an additional intramolecular N—H···F interaction [N···F = 2.7544 (15) Å] between the ortho-F and amide NH atoms (see Tables 2, 4 and 6).
The defining and primary intermolecular interaction in all three systems is the amideN—H···Npyr hydrogen bond that links molecules into one-dimensional zigzag chains [graph set C(6)] along the [010] direction [with N···N distances of 3.022 (2), 3.049 (2), 3.0213 (17) Å].
In (I), weaker C—H···π(arene) and C—F···π(arene) contacts (about inversion centres) link alternating chains into a two-dimensional sheet (Table 2 [would it be useful to include details of the F···π interactions?), with each chain dovetailing into its two nearest neighbouring chains aligned in the opposite direction along [010] (Figs. 4 and 5). There are no C—H···F—C or C—F···F—C interactions.
In (II), the primary interaction is augmented by three weaker C—H···π(arene) contacts per molecule, linking the alternating chains into a two-dimensional sheet (Table 4); each chain dovetails as in (I) (Figs. 6 and 7). Instead of C—F···π(arene) facial contacts as for (I), the location of the F atom provides alternative interaction sites. The most notable is the C13—F13···(F13–C13)v contact about an inversion centre [F13···C13v = 3.037 (2) Å and F13···F13v = 3.1180 (17) Å; symmetry code: (v) -x, -y, -z], with an offset C6 interplanar separation of 3.01 Å. Two weak C—H···F contacts are also present (H···F = 2.65 Å, and C—H···F = 115 and 117°).
In (III), the one-dimensional chains are further linked by C—H···π(arene) contacts into two-dimensional sheets (Figs. 8 and 9, and Table 6). Molecules are also linked via antiparallel C═O···O═Cii interactions (Allen et al., 1998) aligned about inversion centres, with C1···O1ii distances of 3.1919 (16) Å [symmetry code: (ii) - x + 2, -y, -z + 1).
Usually benzamides form intermolecular N—H···O═C interactions [with a C(4) graph set] as their primary interaction in the absence of other competing strong donors/acceptors (Gowda et al., 2008). In (I)–(III), the amide NH group and pyridinyl N acceptor form amidoN—H···Npyr chains [graph set C(6)] as the primary interaction, thus preventing the formation of standard C(4) chains. In (I), the closest intermolecular N···O contact {N1···O1iii = 3.438 (2) Å along [100]; N—H···O = 125°; symmetry code: (iii) x - 1, y, z} is 0.4 Å longer and ~20° smaller in angle than the amidoN—H···Npyr interaction. For (II), the closest intermolecular N···O contact [N1···O1vi = 3.562 (2) Å along [100]; N—H···Ovi = 130°; symmetry code: (vi) x + 1, y, z) is 0.5 Å longer and ca 18° smaller in angle than the amidoN—H···Npyr interaction,while in (III) [N1···O1iv = 3.7854 (16) Å along [100]; N—H···Oiv = 135°; symmetry code: (iv) x + 1, y, z] it is ~0.75 Å longer and ca 4° smaller in angle than the amidoN—H···Npyr interaction.
All three isomers have similar unit-cell parameters in the monoclinic space group P21/c (No. 14), and have similar packing and hydrogen bond motifs (similar at the primary level, but different at the secondary interaction levels), and they are isomorphous (in the strict interpretation of the definition as the atom site coordinates coincide) in the solid state [apart from H→F/F→H peripheral atom changes when comparing the para (I), meta (II) and ortho (III) substitution]. The close similarity in the packing of all three structures is relatively easy to visualize (Figs. 4,6 and 8 display three zigzag chains with the unit cell axes). For comparison, the unit cell similarity index, Π, is less than 0.015 for the (I)/(II)/(III) pairs (Kálmán et al., 1993): homeostructural crystal pairs and packing 'similarities' generated by substituent migration in dichloroanilines have also been discussed by Dou et al. (1993) and Kálmán et al. (1993).
The replacement of an F atom on the C6 ring involves isosteric replacement of an H atom. The change of the F atom site from para to meta to ortho only (as can be reasoned) generates different secondary interactions, as primary amidoN—H···Npyr interactions define the principal aggregation mode. Chopra & Row (2008) have recently reported a comprehensive study on a series of mono- and difluorobenzanilides [(DC3)–(DC1), hereafter denoted DC(3–1); see scheme below]. The DC(3–1) structures correspond to (I)–(III) by replacement of the pyridinyl N atom by a CH group. The DC(3–1) packing is dominated by standard N—H···O═C hydrogen bonds [3.165 (4)–3.254 (4) Å], the intramolecular C6/C6 plane angles range from 23.0 (3) to 32.9 (1)°, and the N···O distances are at least 0.2 Å shorter than the corresponding data in (I)–(III) (Chopra & Row, 2008). In these fluorobenzanilides, alteration of the packing modes is observed in the F-atom position change through para to meta to ortho. In related work, Gowda et al. (2008) have also reported a series of similar substituted alkyl and chlorophenylbenzamides. Wardell et al. (2008) have also recently reported an extensive series of N-arylpyrazinecarboxamides; however, the authors state that isomeric compounds in this series `show little resemblance in the supramolecular behaviour beyond crystallization in the same space group'. Clearly, more expanded isomer series are needed for detailed structural and computational comparisons.
Melting-point analysis and correlations with structural properties have been reviewed for organic compounds by several groups recently (Slovokhotov et al., 2004; Gilbert, 2007). Researchers have noted that more symmetrical structural isomers almost always possess higher melting points than their less symmetric analogues (Gilbert, 2007). Compounds (I)–(III) can only possess mirror symmetry (Cs) as the highest possible molecular symmetry in the appropriate conformation (solution/gas phase), but for (III) this is unlikely on steric grounds (N—H···F steric hindrance). There is a distinct trend from (I) (456–459 K) to (II) (443–446 K) to (III) (396–398 K). The overall packing is very similar at the primary N—H···Npyr level and reasonably comparable (in terms of the number and type of weak interactions) at the secondary level.
An explanation for this melting point trend may be the distinct N—H···O=C distance differences of 3.438 (2) Å, 3.562 (2) Å, 3.7854 (16) Å in (I)-(III), resulting from molecular packing; the packing may be such as to prevent the potential (though temporary) formation of amideN—H···O=C interactions as the N—H···Npyr interactions weaken on heating. In (I), without the steric demand of an ortho-F atom, the weakening of the N—H···Npyr hydrogen bond may be compensated for and offset by some increasing but temporary N—H···O=C interaction, resulting in the observed melting point trend.
The present series is unusual as the three isomers are isomorphous (have similar unit-cell parameters, packing and alignment) but differ in F/H peripheral atom site position and in their interactions/contacts at the secondary level.