Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113004204/wq3028sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113004204/wq3028Isup2.hkl | |
MDL mol file https://doi.org/10.1107/S0108270113004204/wq3028Isup4.mol | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113004204/wq3028IIsup3.hkl | |
MDL mol file https://doi.org/10.1107/S0108270113004204/wq3028IIsup5.mol | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113004204/wq3028Isup6.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113004204/wq3028IIsup7.cml |
CCDC references: 934577; 934578
(I) was prepared according to the literature procedure of Bretonniere et al. (2004). Recrystallization from ethanol yielded single crystals [m.p. 486–487 K, literature 485–487 K (Bretonniere et al., 2004)] suitable for X-ray crystallographic analysis.
For the synthesis of (II), (I) (120 mg, 0.5 mmol) was added to thionyl chloride (10 ml) and the solution was refluxed at 363 K for 3 h. Most of the thionyl chloride was evaporated under vacuum and the residue was poured into iced water (10 ml) and the pH was adjusted to neutral with sodium hydroxide. A yellow solid was obtained by suction filtration (yield: 90 mg, 70%). Recrystallization from ethyl acetate afforded good quality single crystals of (II) (m.p. 446–447 K). ESI–MS: m/z 258.51 [32%, M + H)+], 536.86 [100%, (2M + Na)+]. 1H NMR (CDCl3): δ 8.59 (dd, 2H, J = 4, 8 Hz, COCCH), 7.78 (td, 2H, J = 4, 8 Hz, COCCHCH), 7.51 (dd, 2H, J = 4, 8 Hz, NCCH), 7.34 (td, 2H, J = 4, 8 Hz, NCCHCH), 4.72 (t, 2H, J = 8 Hz, NCH2), 3.90 (t, 2H, J = 8 Hz, NCH2CH2).
H atoms attached to C atoms were positioned geometrically and allowed to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C). H atoms bound to O atoms were located from difference Fourier maps and treated in the riding-model approximation, with Uiso(H) = 1.5Ueq(O).
For both compounds, data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: APEX2 (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).
C15H13NO2 | F(000) = 504 |
Mr = 239.26 | Dx = 1.394 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1063 reflections |
a = 8.8247 (12) Å | θ = 2.4–22.7° |
b = 12.0858 (17) Å | µ = 0.09 mm−1 |
c = 10.9511 (15) Å | T = 298 K |
β = 102.510 (2)° | Block, yellow |
V = 1140.2 (3) Å3 | 0.20 × 0.13 × 0.12 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 2118 independent reflections |
Radiation source: fine-focus sealed tube | 1280 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
phi and ω scans | θmax = 25.5°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −10→10 |
Tmin = 0.986, Tmax = 0.989 | k = −14→12 |
5892 measured reflections | l = −8→13 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0404P)2 + 0.1684P] where P = (Fo2 + 2Fc2)/3 |
2118 reflections | (Δ/σ)max < 0.001 |
164 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C15H13NO2 | V = 1140.2 (3) Å3 |
Mr = 239.26 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.8247 (12) Å | µ = 0.09 mm−1 |
b = 12.0858 (17) Å | T = 298 K |
c = 10.9511 (15) Å | 0.20 × 0.13 × 0.12 mm |
β = 102.510 (2)° |
Bruker APEXII CCD area-detector diffractometer | 2118 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 1280 reflections with I > 2σ(I) |
Tmin = 0.986, Tmax = 0.989 | Rint = 0.042 |
5892 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.16 e Å−3 |
2118 reflections | Δρmin = −0.17 e Å−3 |
164 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 | ||
C1 | 0.5682 (2) | −0.05103 (16) | 0.24433 (19) | 0.0487 (6) | |
H1 | 0.4970 | −0.0982 | 0.2689 | 0.058* | |
C2 | 0.7233 (3) | −0.06954 (18) | 0.2874 (2) | 0.0561 (6) | |
H2 | 0.7578 | −0.1288 | 0.3403 | 0.067* | |
C3 | 0.8282 (3) | 0.00171 (17) | 0.2507 (2) | 0.0533 (6) | |
H3 | 0.9340 | −0.0102 | 0.2797 | 0.064* | |
C4 | 0.7798 (2) | 0.08916 (16) | 0.1727 (2) | 0.0482 (5) | |
H4 | 0.8530 | 0.1363 | 0.1510 | 0.058* | |
C5 | 0.6207 (2) | 0.10876 (15) | 0.12486 (18) | 0.0389 (5) | |
C6 | 0.5136 (2) | 0.03793 (15) | 0.16356 (18) | 0.0398 (5) | |
C7 | 0.3003 (2) | 0.14745 (15) | 0.03713 (18) | 0.0392 (5) | |
C8 | 0.4115 (2) | 0.21551 (14) | −0.00030 (18) | 0.0391 (5) | |
C9 | 0.3575 (2) | 0.30460 (16) | −0.08135 (19) | 0.0484 (5) | |
H9 | 0.4286 | 0.3520 | −0.1057 | 0.058* | |
C10 | 0.2023 (2) | 0.32211 (17) | −0.1244 (2) | 0.0531 (6) | |
H10 | 0.1694 | 0.3808 | −0.1787 | 0.064* | |
C11 | 0.0924 (2) | 0.25420 (18) | −0.0890 (2) | 0.0543 (6) | |
H11 | −0.0130 | 0.2670 | −0.1191 | 0.065* | |
C12 | 0.1414 (2) | 0.16846 (16) | −0.0093 (2) | 0.0485 (6) | |
H12 | 0.0683 | 0.1228 | 0.0149 | 0.058* | |
C13 | 0.3474 (2) | 0.05380 (15) | 0.11983 (18) | 0.0416 (5) | |
C14 | 0.6815 (2) | 0.25855 (16) | −0.0130 (2) | 0.0455 (5) | |
H14A | 0.6354 | 0.2746 | −0.0999 | 0.055* | |
H14B | 0.7729 | 0.2134 | −0.0112 | 0.055* | |
C15 | 0.7311 (3) | 0.36602 (16) | 0.0542 (2) | 0.0549 (6) | |
H15A | 0.7985 | 0.4064 | 0.0107 | 0.066* | |
H15B | 0.6406 | 0.4114 | 0.0548 | 0.066* | |
N1 | 0.56956 (17) | 0.19453 (12) | 0.04085 (15) | 0.0397 (4) | |
O1 | 0.24949 (16) | −0.00814 (11) | 0.15119 (14) | 0.0567 (4) | |
O2 | 0.8097 (2) | 0.34461 (13) | 0.17700 (16) | 0.0776 (5) | |
H2A | 0.7849 | 0.3908 | 0.2240 | 0.116* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0588 (15) | 0.0460 (12) | 0.0414 (13) | 0.0018 (10) | 0.0113 (11) | 0.0021 (10) |
C2 | 0.0671 (16) | 0.0500 (13) | 0.0475 (14) | 0.0109 (12) | 0.0046 (12) | 0.0066 (11) |
C3 | 0.0470 (13) | 0.0576 (14) | 0.0497 (14) | 0.0074 (11) | −0.0019 (11) | −0.0041 (11) |
C4 | 0.0457 (13) | 0.0468 (12) | 0.0505 (14) | −0.0005 (10) | 0.0067 (10) | −0.0018 (11) |
C5 | 0.0432 (12) | 0.0382 (11) | 0.0347 (11) | 0.0034 (9) | 0.0072 (9) | −0.0050 (9) |
C6 | 0.0484 (13) | 0.0375 (11) | 0.0337 (11) | 0.0012 (9) | 0.0093 (10) | −0.0035 (9) |
C7 | 0.0420 (12) | 0.0385 (11) | 0.0376 (12) | −0.0003 (9) | 0.0098 (9) | −0.0036 (9) |
C8 | 0.0434 (13) | 0.0389 (11) | 0.0346 (11) | 0.0018 (9) | 0.0077 (9) | −0.0037 (9) |
C9 | 0.0514 (14) | 0.0466 (12) | 0.0471 (13) | −0.0006 (10) | 0.0104 (11) | 0.0042 (11) |
C10 | 0.0553 (15) | 0.0533 (13) | 0.0481 (14) | 0.0100 (11) | 0.0055 (12) | 0.0066 (11) |
C11 | 0.0446 (13) | 0.0635 (14) | 0.0528 (15) | 0.0078 (11) | 0.0058 (11) | 0.0017 (12) |
C12 | 0.0435 (13) | 0.0537 (13) | 0.0498 (14) | −0.0005 (10) | 0.0135 (11) | −0.0010 (11) |
C13 | 0.0471 (13) | 0.0413 (11) | 0.0385 (12) | −0.0030 (9) | 0.0141 (10) | −0.0063 (10) |
C14 | 0.0459 (12) | 0.0479 (12) | 0.0448 (13) | −0.0039 (10) | 0.0148 (10) | 0.0006 (10) |
C15 | 0.0569 (14) | 0.0495 (13) | 0.0591 (15) | −0.0100 (11) | 0.0141 (12) | −0.0001 (12) |
N1 | 0.0399 (10) | 0.0383 (9) | 0.0408 (10) | −0.0017 (7) | 0.0083 (8) | 0.0014 (8) |
O1 | 0.0533 (9) | 0.0589 (9) | 0.0601 (11) | −0.0068 (7) | 0.0174 (8) | 0.0112 (8) |
O2 | 0.0831 (13) | 0.0644 (11) | 0.0728 (13) | 0.0145 (9) | −0.0104 (10) | −0.0198 (9) |
C1—C2 | 1.366 (3) | C9—C10 | 1.366 (3) |
C1—C6 | 1.409 (3) | C9—H9 | 0.9300 |
C1—H1 | 0.9300 | C10—C11 | 1.389 (3) |
C2—C3 | 1.386 (3) | C10—H10 | 0.9300 |
C2—H2 | 0.9300 | C11—C12 | 1.363 (3) |
C3—C4 | 1.368 (3) | C11—H11 | 0.9300 |
C3—H3 | 0.9300 | C12—H12 | 0.9300 |
C4—C5 | 1.408 (3) | C13—O1 | 1.246 (2) |
C4—H4 | 0.9300 | C14—N1 | 1.475 (2) |
C5—N1 | 1.395 (2) | C14—C15 | 1.510 (3) |
C5—C6 | 1.407 (2) | C14—H14A | 0.9700 |
C6—C13 | 1.454 (3) | C14—H14B | 0.9700 |
C7—C12 | 1.407 (3) | C15—O2 | 1.397 (3) |
C7—C8 | 1.408 (3) | C15—H15A | 0.9700 |
C7—C13 | 1.453 (3) | C15—H15B | 0.9700 |
C8—N1 | 1.393 (2) | O2—H2A | 0.8200 |
C8—C9 | 1.411 (3) | ||
C2—C1—C6 | 121.5 (2) | C9—C10—H10 | 119.3 |
C2—C1—H1 | 119.3 | C11—C10—H10 | 119.3 |
C6—C1—H1 | 119.3 | C12—C11—C10 | 118.9 (2) |
C1—C2—C3 | 118.7 (2) | C12—C11—H11 | 120.5 |
C1—C2—H2 | 120.6 | C10—C11—H11 | 120.5 |
C3—C2—H2 | 120.6 | C11—C12—C7 | 121.47 (19) |
C4—C3—C2 | 121.5 (2) | C11—C12—H12 | 119.3 |
C4—C3—H3 | 119.2 | C7—C12—H12 | 119.3 |
C2—C3—H3 | 119.2 | O1—C13—C7 | 121.19 (18) |
C3—C4—C5 | 120.91 (19) | O1—C13—C6 | 122.69 (18) |
C3—C4—H4 | 119.5 | C7—C13—C6 | 116.11 (17) |
C5—C4—H4 | 119.5 | N1—C14—C15 | 113.87 (16) |
N1—C5—C6 | 120.58 (17) | N1—C14—H14A | 108.8 |
N1—C5—C4 | 121.63 (17) | C15—C14—H14A | 108.8 |
C6—C5—C4 | 117.79 (18) | N1—C14—H14B | 108.8 |
C5—C6—C1 | 119.53 (18) | C15—C14—H14B | 108.8 |
C5—C6—C13 | 121.07 (18) | H14A—C14—H14B | 107.7 |
C1—C6—C13 | 119.39 (17) | O2—C15—C14 | 109.94 (17) |
C12—C7—C8 | 119.49 (18) | O2—C15—H15A | 109.7 |
C12—C7—C13 | 119.62 (18) | C14—C15—H15A | 109.7 |
C8—C7—C13 | 120.86 (18) | O2—C15—H15B | 109.7 |
N1—C8—C7 | 120.79 (17) | C14—C15—H15B | 109.7 |
N1—C8—C9 | 121.36 (17) | H15A—C15—H15B | 108.2 |
C7—C8—C9 | 117.84 (19) | C8—N1—C5 | 120.46 (15) |
C10—C9—C8 | 120.8 (2) | C8—N1—C14 | 119.05 (16) |
C10—C9—H9 | 119.6 | C5—N1—C14 | 120.32 (16) |
C8—C9—H9 | 119.6 | C15—O2—H2A | 109.5 |
C9—C10—C11 | 121.4 (2) | ||
C6—C1—C2—C3 | 0.3 (3) | C13—C7—C12—C11 | −178.76 (18) |
C1—C2—C3—C4 | −0.1 (3) | C12—C7—C13—O1 | −0.4 (3) |
C2—C3—C4—C5 | −1.2 (3) | C8—C7—C13—O1 | −178.46 (18) |
C3—C4—C5—N1 | −177.07 (18) | C12—C7—C13—C6 | 179.98 (17) |
C3—C4—C5—C6 | 2.3 (3) | C8—C7—C13—C6 | 2.0 (3) |
N1—C5—C6—C1 | 177.30 (17) | C5—C6—C13—O1 | 179.19 (18) |
C4—C5—C6—C1 | −2.1 (3) | C1—C6—C13—O1 | 0.3 (3) |
N1—C5—C6—C13 | −1.6 (3) | C5—C6—C13—C7 | −1.2 (3) |
C4—C5—C6—C13 | 179.04 (17) | C1—C6—C13—C7 | 179.85 (17) |
C2—C1—C6—C5 | 0.8 (3) | N1—C14—C15—O2 | 63.4 (2) |
C2—C1—C6—C13 | 179.71 (18) | C7—C8—N1—C5 | −3.1 (3) |
C12—C7—C8—N1 | −177.87 (16) | C9—C8—N1—C5 | 177.43 (17) |
C13—C7—C8—N1 | 0.1 (3) | C7—C8—N1—C14 | 172.19 (17) |
C12—C7—C8—C9 | 1.6 (3) | C9—C8—N1—C14 | −7.3 (3) |
C13—C7—C8—C9 | 179.62 (17) | C6—C5—N1—C8 | 3.8 (3) |
N1—C8—C9—C10 | 177.77 (18) | C4—C5—N1—C8 | −176.83 (17) |
C7—C8—C9—C10 | −1.7 (3) | C6—C5—N1—C14 | −171.41 (17) |
C8—C9—C10—C11 | 0.9 (3) | C4—C5—N1—C14 | 7.9 (3) |
C9—C10—C11—C12 | 0.1 (3) | C15—C14—N1—C8 | 87.8 (2) |
C10—C11—C12—C7 | −0.1 (3) | C15—C14—N1—C5 | −96.9 (2) |
C8—C7—C12—C11 | −0.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···O1i | 0.82 | 1.91 | 2.722 (2) | 173 |
C3—H3···O2ii | 0.93 | 2.82 | 3.654 (3) | 150 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+2, y−1/2, −z+1/2. |
C15H12ClNO | F(000) = 536 |
Mr = 257.71 | Dx = 1.384 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2422 reflections |
a = 9.3632 (16) Å | θ = 2.5–26.9° |
b = 16.449 (3) Å | µ = 0.29 mm−1 |
c = 8.0359 (14) Å | T = 298 K |
β = 92.151 (2)° | Block, yellow |
V = 1236.8 (4) Å3 | 0.19 × 0.17 × 0.14 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 2291 independent reflections |
Radiation source: fine-focus sealed tube | 1787 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
phi and ω scans | θmax = 25.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −11→11 |
Tmin = 0.957, Tmax = 0.959 | k = −19→19 |
6398 measured reflections | l = −9→8 |
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)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.129 | w = 1/[σ2(Fo2) + (0.0565P)2 + 0.5138P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
2291 reflections | Δρmax = 0.43 e Å−3 |
164 parameters | Δρmin = −0.45 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.009 (2) |
C15H12ClNO | V = 1236.8 (4) Å3 |
Mr = 257.71 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.3632 (16) Å | µ = 0.29 mm−1 |
b = 16.449 (3) Å | T = 298 K |
c = 8.0359 (14) Å | 0.19 × 0.17 × 0.14 mm |
β = 92.151 (2)° |
Bruker APEXII CCD area-detector diffractometer | 2291 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 1787 reflections with I > 2σ(I) |
Tmin = 0.957, Tmax = 0.959 | Rint = 0.023 |
6398 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.43 e Å−3 |
2291 reflections | Δρmin = −0.45 e Å−3 |
164 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 | ||
C1 | 0.0205 (2) | 0.08043 (13) | 0.7814 (3) | 0.0488 (5) | |
H1 | −0.0168 | 0.0530 | 0.8712 | 0.059* | |
C2 | −0.0171 (3) | 0.15959 (14) | 0.7534 (3) | 0.0573 (6) | |
H2 | −0.0790 | 0.1859 | 0.8236 | 0.069* | |
C3 | 0.0379 (3) | 0.20009 (14) | 0.6197 (3) | 0.0618 (6) | |
H3 | 0.0123 | 0.2540 | 0.6003 | 0.074* | |
C4 | 0.1298 (3) | 0.16249 (14) | 0.5145 (3) | 0.0563 (6) | |
H4 | 0.1644 | 0.1910 | 0.4246 | 0.068* | |
C5 | 0.1719 (2) | 0.08091 (12) | 0.5421 (2) | 0.0433 (5) | |
C6 | 0.1141 (2) | 0.03964 (12) | 0.6778 (2) | 0.0405 (5) | |
C7 | 0.2452 (2) | −0.08379 (12) | 0.5968 (2) | 0.0407 (5) | |
C8 | 0.3009 (2) | −0.04030 (13) | 0.4635 (2) | 0.0430 (5) | |
C9 | 0.3915 (3) | −0.08196 (15) | 0.3559 (3) | 0.0563 (6) | |
H9 | 0.4311 | −0.0544 | 0.2678 | 0.068* | |
C10 | 0.4217 (3) | −0.16267 (16) | 0.3804 (3) | 0.0617 (6) | |
H10 | 0.4816 | −0.1890 | 0.3081 | 0.074* | |
C11 | 0.3649 (3) | −0.20603 (15) | 0.5104 (3) | 0.0581 (6) | |
H11 | 0.3850 | −0.2610 | 0.5244 | 0.070* | |
C12 | 0.2787 (2) | −0.16614 (13) | 0.6179 (3) | 0.0489 (5) | |
H12 | 0.2417 | −0.1944 | 0.7067 | 0.059* | |
C13 | 0.1518 (2) | −0.04469 (12) | 0.7143 (2) | 0.0440 (5) | |
C14 | 0.3403 (3) | 0.08770 (15) | 0.3099 (3) | 0.0551 (6) | |
H14A | 0.4369 | 0.0673 | 0.3009 | 0.066* | |
H14B | 0.3460 | 0.1446 | 0.3415 | 0.066* | |
C15 | 0.2605 (3) | 0.07982 (16) | 0.1430 (3) | 0.0585 (6) | |
H15A | 0.1650 | 0.1021 | 0.1495 | 0.070* | |
H15B | 0.2527 | 0.0230 | 0.1113 | 0.070* | |
N1 | 0.26716 (19) | 0.04160 (11) | 0.4393 (2) | 0.0468 (4) | |
O1 | 0.1067 (2) | −0.08161 (10) | 0.8371 (2) | 0.0683 (5) | |
Cl1 | 0.35873 (8) | 0.13471 (5) | −0.00726 (8) | 0.0890 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0485 (12) | 0.0582 (13) | 0.0397 (11) | 0.0000 (10) | 0.0019 (9) | −0.0059 (9) |
C2 | 0.0610 (14) | 0.0586 (14) | 0.0519 (13) | 0.0095 (11) | −0.0035 (11) | −0.0143 (11) |
C3 | 0.0748 (17) | 0.0455 (12) | 0.0639 (15) | 0.0084 (11) | −0.0132 (12) | −0.0089 (11) |
C4 | 0.0696 (15) | 0.0479 (12) | 0.0511 (13) | −0.0043 (11) | −0.0031 (11) | 0.0060 (10) |
C5 | 0.0462 (12) | 0.0458 (11) | 0.0376 (10) | −0.0050 (9) | −0.0022 (8) | −0.0026 (8) |
C6 | 0.0409 (11) | 0.0463 (11) | 0.0341 (10) | −0.0037 (8) | 0.0001 (8) | −0.0039 (8) |
C7 | 0.0392 (11) | 0.0451 (11) | 0.0376 (10) | −0.0041 (8) | −0.0002 (8) | −0.0008 (8) |
C8 | 0.0413 (11) | 0.0522 (12) | 0.0353 (10) | −0.0026 (9) | 0.0012 (8) | −0.0019 (8) |
C9 | 0.0571 (14) | 0.0713 (15) | 0.0411 (12) | 0.0030 (11) | 0.0107 (10) | −0.0003 (10) |
C10 | 0.0609 (15) | 0.0755 (17) | 0.0489 (13) | 0.0158 (12) | 0.0057 (11) | −0.0137 (11) |
C11 | 0.0629 (15) | 0.0508 (13) | 0.0600 (14) | 0.0084 (11) | −0.0037 (11) | −0.0075 (11) |
C12 | 0.0501 (12) | 0.0474 (12) | 0.0490 (12) | −0.0025 (9) | 0.0013 (9) | 0.0022 (9) |
C13 | 0.0465 (11) | 0.0486 (12) | 0.0372 (10) | −0.0039 (9) | 0.0058 (8) | 0.0013 (9) |
C14 | 0.0517 (13) | 0.0647 (14) | 0.0491 (12) | −0.0135 (11) | 0.0036 (10) | 0.0082 (10) |
C15 | 0.0533 (14) | 0.0758 (16) | 0.0466 (12) | −0.0135 (11) | 0.0055 (10) | 0.0106 (11) |
N1 | 0.0516 (10) | 0.0506 (10) | 0.0387 (9) | −0.0052 (8) | 0.0081 (7) | 0.0054 (7) |
O1 | 0.0856 (13) | 0.0643 (10) | 0.0575 (10) | 0.0044 (9) | 0.0365 (9) | 0.0130 (8) |
Cl1 | 0.0844 (5) | 0.1281 (7) | 0.0552 (4) | −0.0349 (4) | 0.0126 (3) | 0.0287 (4) |
C1—C2 | 1.365 (3) | C8—C9 | 1.411 (3) |
C1—C6 | 1.402 (3) | C9—C10 | 1.370 (3) |
C1—H1 | 0.9300 | C9—H9 | 0.9300 |
C2—C3 | 1.381 (3) | C10—C11 | 1.387 (3) |
C2—H2 | 0.9300 | C10—H10 | 0.9300 |
C3—C4 | 1.375 (3) | C11—C12 | 1.371 (3) |
C3—H3 | 0.9300 | C11—H11 | 0.9300 |
C4—C5 | 1.414 (3) | C12—H12 | 0.9300 |
C4—H4 | 0.9300 | C13—O1 | 1.246 (2) |
C5—N1 | 1.397 (3) | C14—N1 | 1.476 (3) |
C5—C6 | 1.410 (3) | C14—C15 | 1.516 (3) |
C6—C13 | 1.458 (3) | C14—H14A | 0.9700 |
C7—C12 | 1.399 (3) | C14—H14B | 0.9700 |
C7—C8 | 1.405 (3) | C15—Cl1 | 1.789 (2) |
C7—C13 | 1.460 (3) | C15—H15A | 0.9700 |
C8—N1 | 1.396 (3) | C15—H15B | 0.9700 |
C2—C1—C6 | 121.4 (2) | C9—C10—C11 | 121.6 (2) |
C2—C1—H1 | 119.3 | C9—C10—H10 | 119.2 |
C6—C1—H1 | 119.3 | C11—C10—H10 | 119.2 |
C1—C2—C3 | 119.1 (2) | C12—C11—C10 | 118.7 (2) |
C1—C2—H2 | 120.4 | C12—C11—H11 | 120.7 |
C3—C2—H2 | 120.4 | C10—C11—H11 | 120.7 |
C4—C3—C2 | 121.4 (2) | C11—C12—C7 | 121.4 (2) |
C4—C3—H3 | 119.3 | C11—C12—H12 | 119.3 |
C2—C3—H3 | 119.3 | C7—C12—H12 | 119.3 |
C3—C4—C5 | 120.5 (2) | O1—C13—C6 | 122.42 (18) |
C3—C4—H4 | 119.7 | O1—C13—C7 | 121.77 (19) |
C5—C4—H4 | 119.7 | C6—C13—C7 | 115.80 (17) |
N1—C5—C6 | 120.45 (18) | N1—C14—C15 | 110.68 (17) |
N1—C5—C4 | 121.83 (18) | N1—C14—H14A | 109.5 |
C6—C5—C4 | 117.72 (19) | C15—C14—H14A | 109.5 |
C1—C6—C5 | 119.71 (19) | N1—C14—H14B | 109.5 |
C1—C6—C13 | 119.18 (18) | C15—C14—H14B | 109.5 |
C5—C6—C13 | 121.10 (17) | H14A—C14—H14B | 108.1 |
C12—C7—C8 | 119.82 (18) | C14—C15—Cl1 | 107.78 (15) |
C12—C7—C13 | 119.02 (18) | C14—C15—H15A | 110.2 |
C8—C7—C13 | 121.16 (18) | Cl1—C15—H15A | 110.2 |
N1—C8—C7 | 120.60 (17) | C14—C15—H15B | 110.2 |
N1—C8—C9 | 121.45 (18) | Cl1—C15—H15B | 110.2 |
C7—C8—C9 | 118.0 (2) | H15A—C15—H15B | 108.5 |
C10—C9—C8 | 120.6 (2) | C8—N1—C5 | 120.71 (16) |
C10—C9—H9 | 119.7 | C8—N1—C14 | 119.04 (17) |
C8—C9—H9 | 119.7 | C5—N1—C14 | 120.15 (18) |
C6—C1—C2—C3 | 0.3 (3) | C13—C7—C12—C11 | 179.47 (19) |
C1—C2—C3—C4 | −0.1 (4) | C1—C6—C13—O1 | −1.8 (3) |
C2—C3—C4—C5 | −0.7 (4) | C5—C6—C13—O1 | 177.2 (2) |
C3—C4—C5—N1 | −178.8 (2) | C1—C6—C13—C7 | 177.64 (18) |
C3—C4—C5—C6 | 1.4 (3) | C5—C6—C13—C7 | −3.4 (3) |
C2—C1—C6—C5 | 0.4 (3) | C12—C7—C13—O1 | 3.4 (3) |
C2—C1—C6—C13 | 179.4 (2) | C8—C7—C13—O1 | −176.9 (2) |
N1—C5—C6—C1 | 178.93 (18) | C12—C7—C13—C6 | −176.02 (18) |
C4—C5—C6—C1 | −1.2 (3) | C8—C7—C13—C6 | 3.6 (3) |
N1—C5—C6—C13 | −0.1 (3) | N1—C14—C15—Cl1 | −178.30 (16) |
C4—C5—C6—C13 | 179.81 (19) | C7—C8—N1—C5 | −3.2 (3) |
C12—C7—C8—N1 | 179.16 (18) | C9—C8—N1—C5 | 176.92 (19) |
C13—C7—C8—N1 | −0.5 (3) | C7—C8—N1—C14 | 173.09 (18) |
C12—C7—C8—C9 | −0.9 (3) | C9—C8—N1—C14 | −6.8 (3) |
C13—C7—C8—C9 | 179.39 (19) | C6—C5—N1—C8 | 3.5 (3) |
N1—C8—C9—C10 | −179.0 (2) | C4—C5—N1—C8 | −176.41 (19) |
C7—C8—C9—C10 | 1.1 (3) | C6—C5—N1—C14 | −172.76 (18) |
C8—C9—C10—C11 | −0.1 (4) | C4—C5—N1—C14 | 7.4 (3) |
C9—C10—C11—C12 | −1.1 (4) | C15—C14—N1—C8 | 88.0 (2) |
C10—C11—C12—C7 | 1.2 (3) | C15—C14—N1—C5 | −95.8 (2) |
C8—C7—C12—C11 | −0.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O1i | 0.93 | 2.56 | 3.330 (3) | 140 |
C15—H15A···O1ii | 0.97 | 2.57 | 3.448 (3) | 150 |
C10—H10···Cl1iii | 0.93 | 3.02 | 3.727 (3) | 134 |
C11—H11···Cl1iv | 0.93 | 2.96 | 3.683 (2) | 136 |
Symmetry codes: (i) −x, −y, −z+2; (ii) −x, −y, −z+1; (iii) −x+1, −y, −z; (iv) −x+1, y−1/2, −z+1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C15H13NO2 | C15H12ClNO |
Mr | 239.26 | 257.71 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 8.8247 (12), 12.0858 (17), 10.9511 (15) | 9.3632 (16), 16.449 (3), 8.0359 (14) |
β (°) | 102.510 (2) | 92.151 (2) |
V (Å3) | 1140.2 (3) | 1236.8 (4) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.29 |
Crystal size (mm) | 0.20 × 0.13 × 0.12 | 0.19 × 0.17 × 0.14 |
Data collection | ||
Diffractometer | Bruker APEXII CCD area-detector diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.986, 0.989 | 0.957, 0.959 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5892, 2118, 1280 | 6398, 2291, 1787 |
Rint | 0.042 | 0.023 |
(sin θ/λ)max (Å−1) | 0.606 | 0.606 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.108, 1.00 | 0.046, 0.129, 1.06 |
No. of reflections | 2118 | 2291 |
No. of parameters | 164 | 164 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.17 | 0.43, −0.45 |
Computer programs: APEX2 (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···O1i | 0.82 | 1.91 | 2.722 (2) | 172.6 |
C3—H3···O2ii | 0.93 | 2.82 | 3.654 (3) | 149.7 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+2, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O1i | 0.93 | 2.56 | 3.330 (3) | 139.9 |
C15—H15A···O1ii | 0.97 | 2.57 | 3.448 (3) | 150.3 |
C10—H10···Cl1iii | 0.93 | 3.02 | 3.727 (3) | 133.6 |
C11—H11···Cl1iv | 0.93 | 2.96 | 3.683 (2) | 136.0 |
Symmetry codes: (i) −x, −y, −z+2; (ii) −x, −y, −z+1; (iii) −x+1, −y, −z; (iv) −x+1, y−1/2, −z+1/2. |
Acridone is an important molecular scaffold and its numerous derivatives have displayed useful pharmacological properties and light absorption/emission related applications (Kumar & Kumari, 2011; Kelly et al., 2009; Hernandez-Olmos et al., 2012; Borisov & Klimant, 2012). The acridone derivative 10-(2-hydroxyethyl)acridin-9(10H)-one, (I), can be readily modified at the hydroxy group to obtain useful photosensitive materials (Zhang et al., 2006; Agiamarnioti et al., 2006; Sugiyama et al., 2005; Arioka & Sugiyama, 2005; Bretonniere et al., 2004; Zhang et al., 2002; You et al., 2002; Du & Li, 1992, 1996), but the detailed structure of (I) has not yet been determined. With (I), we synthesized a new the new compound 10-(2-chloroethyl)acridin-9(10H)-one, (II), which is anticipated to be a useful intermediate for the synthesis of further acridone derivatives using alkylation chemistry. Although (I) and (II) have a similar skeleton, the X-ray crystallographic studies reported here show that their molecular and crystal structures differ markedly, owing to their diverse supramolecular interactions.
The molecule of (I) (Fig. 1) is asymmetric in the crystal. The acridone moiety is essentially flat, with the r.m.s. deviation from the best plane being 0.017 (2) Å and the largest deviation from the mean plane being 0.043 (2) Å for the N atom. The attached methylene C atom deviates slightly from this plane [0.236 (2) Å] to minimize nonbonded interactions between the methylene H atoms and the nearby acridone H atoms. Terminal atom O2 deviates significantly from the least-squares plane through atoms N1, C14 and C15 by 1.175 (2) Å; the conformation of the hydroxyethyl substituent is represented by the torsion angles C5—N1—C14—C15 and N1—C14—C15—O2 of 96.9 (2) and 63.4 (2)°, respectively. Two inversion-related antiparallel molecules of (I) form an offset π–π stacked dimer, having atoms C7, C6 and C2 of one molecule lying above the centroids of the three fused rings of the second acridone molecule at distances of 3.402 (2), 3.381 (2) and 3.377 (2) Å, respectively. The distance between the planes of the aromatic π systems in this dimer is 3.377 (2) Å, while the offset is 1.461 (2) Å. Such π-stacking interactions seem to be a common feature for acridone-containing organic or coordination compounds according to a search of the Cambridge Structural Database (CSD; Version 5.34; Allen, 2002) (Miernik & Lis, 1996; Miernik et al., 1993; Fan et al., 2009; Baudouin et al., 1985; Orda-Zgadzaj & Abraham, 2008; Pho et al., 2010; Wong et al., 2000; Yu et al., 2010). Here we regard this closely contacted pair of molecules as a dimer. As illustrated in Fig. 2, each dimer of (I) is roughly perpendicularly connected to four other neighbouring dimers through O—H···O hydrogen bonds between the hydroxy group and the carbonyl O atom (Table 1), as well as two kinds of C—H···π interactions [C2—H2···Cg1i, with C2···Cg1i = 3.641 (2) Å and angle = 153.0°; C9—H9···Cg2vi, with C9···Cg2vii = 4.514 (2) Å and angle = 160.9°; symmetry codes: (vi) -x+1, y-1/2, -z+1/2; (vii) x, -y+1/2, z-1/2; Cg1 and Cg2 are the centroids of the C7–C12 and C1–C6 rings, respectively]. Although the latter C—H···Cg interaction is quite weak compared to the former, the location of the relative atoms is suitable for the C—H···π interaction (Nishio et al., 2009; Takahashi et al., 2010; Nishio, 2011). The dimers are connected into a two-dimensional layer perpendicular to the a axis (Fig. 2). Among the layers are only weak nonconventional C—H···O hydrogen bonds (Table 1 and Fig. 3), leading to a three-dimensional supramolecular network.
The reaction of (I) with thionyl chloride results in replacement of the hydroxy group with a chlorine substituent. The resulting compound, 10-(2-chloroethyl)acridin-9(10H)-one, (II) (Fig. 4), to the best of our knowledge, has not been reported previously. The acridone moiety in (II) is slightly less planar than that in (I), with the r.m.s. deviation from the best plane being 0.043 (2) Å and the largest deviation from the mean plane being 0.060 (2) Å for the N atom. The attached methylene C atom deviates from the plane by 0.219 (3) Å, a smaller deviation than that in (I). The molecules of (II) form a similar inversion-related π-stacked dimer to (I), however, the π-stacking interactions are significantly weaker than those in (I). The distance between the planes of the aromatic π-systems in this dimer is 3.540 (2) Å, while the offset distance is 1.806 (2) Å. Atoms C7, C6 and C2 lie above the centroids of the three fused rings of the second acridone molecule at distances of 3.585 (2), 3.621 (2) and 3.530 (3) Å, respectively. The conformation of the chloroethyl side chain in (II), which is antiperiplanar, differs significantly to the hydroxyethyl side chain in (I), which adopts a gauche conformation. The N1—C14—C15—Cl1 torsion angle is -178.3 (2)°, meaning that the four atoms actually form a plane which essentially bisects the whole molecule of (II). Lacking a hydroxy group, there are no classic hydrogen bonds present in (II), instead nonconventional secondary interactions play key roles in the crystal packing. Cl···π halogen bonding (Parisini et al., 2011; Rahman et al., 2003; El-Sheshtawy et al., 2012; Bauzá et al., 2012) between the Cl1 atom and the C1–C6 benzene ring [Cl1···Cg2viii = 3.764 (1) Å; symmetry code: (viii) x, y, z-1], as well as two kinds of C—H···O hydrogen bonds (Table 2), connect the dimers into a one-dimensional chain along the c direction (Fig. 5). C—H···π interactions between the C14—H14A group and the C7—C12 benzene ring [C14···Cg1ix = 3.454 (2) Å and angle = 160.9°; symmetry code: (ix) -x+1, -y, -z+1] further link the one-dimensional chains into a two-dimensional layer lying in the bc plane (Fig. 5). Neighbouring layers are connected together via two kinds of C—H···Cl hydrogen bonds (Table 2 and Fig. 6), leading to a three-dimensional supramolecular network.
As discussed above, exchange of the substituent (OH or Cl) induces an interesting effect on the crystal packing. In both (I) and (II), the dimeric unit formed by π–π contacts is the essential subunit for the construction of the supramolecular networks. The π–π contacts in (I) are markedly stronger and interlocked with O—H···O and C—H···O hydrogen bonds, whereas in (II) classic hydrogen bonds are absent and a weakly bound layered structure is observed. Such differences in intermolecular interactions results in a higher melting point for (I) (446–447 K) over (II) (486–487 K) despite their similar skeletons and a larger molecular weight for (II).