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Ethyl 1-ethyl-6-iodo-4-oxo-1,4-dihydroquinoline-3-carboxylate, C
14H
14INO
3, (I), and ethyl 1-cyclopropyl-6-iodo-4-oxo-1,4-dihydroquinoline-3-carboxylate, C
15H
14INO
3, (II), have isomorphous crystal structures, while ethyl 1-dimethylamino-6-iodo-4-oxo-1,4-dihydroquinoline-3-carboxylate, C
14H
15IN
2O
3, (III), possesses a different solid-state supramolecular architecture. In all three structures, O
I halogen-bonding interactions connect the quinolone molecules into infinite chains parallel to the unique crystallographic
b axis. In (I) and (II), these molecular chains are arranged in (101) layers,
via π–π stacking and C—H
π interactions, and these layers are then interlinked by C—H
O interactions. The structural fragments involved in the C—H
O interactions differ between (I) and (II), accounting for the observed difference in planarity of the quinolone moieties in the two isomorphous structures. In (III), C—H
O and C—H
π interactions form (100) molecular layers, which are crosslinked by O
I and C—H
I interactions.
Supporting information
CCDC references: 713832; 713833; 713834
The title compounds were prepared as described previously (Alihodžić et
al., 2007; Elder et al., 2007; Turner et al.,
2000).
Crystals of (I), (II) and (III) were grown by slow cooling of warm methanol,
methanol–dichloromethane (3:1 v/v) and dichloromethane
solutions, respectively.
Reflections 202 and 004 in the data set of (II) were omitted as outliers. H
atoms were constrained to ideal geometry using an appropriate riding model,
with C—H = 0.96 (methyl), 0.97 (methylene), 0.98 (methine) or 0.93 Å
(aromatic). Methyl H atoms were refined with Uiso(H) =
1.5Ueq(C); all other H atoms were refined with Uiso(H) =
1.2Ueq(C).
For all compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) integrated in WinGX (Farrugia, 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) integrated in WinGX (Farrugia, 1999); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2009).
(I) Ethyl 1-ethyl-6-iodo-4-oxo-1,4-dihydroquinoline-3-carboxylate
top
Crystal data top
C14H14INO3 | F(000) = 728 |
Mr = 371.05 | Dx = 1.786 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 12268 reflections |
a = 10.8169 (3) Å | θ = 4.0–31.9° |
b = 8.0588 (2) Å | µ = 2.32 mm−1 |
c = 15.8422 (4) Å | T = 295 K |
β = 91.326 (3)° | Prism, colourless |
V = 1380.61 (6) Å3 | 0.50 × 0.35 × 0.30 mm |
Z = 4 | |
Data collection top
Oxford Diffraction Xcalibur CCD diffractometer | 4010 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 3045 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
Detector resolution: 16.3426 pixels mm-1 | θmax = 30.0°, θmin = 4.1° |
ω and ϕ scans | h = −15→15 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | k = −11→11 |
Tmin = 0.396, Tmax = 0.498 | l = −22→22 |
21815 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.080 | w = 1/[σ2(Fo2) + (0.0502P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
4010 reflections | Δρmax = 0.74 e Å−3 |
175 parameters | Δρmin = −0.69 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: 0.0028 (5) |
Crystal data top
C14H14INO3 | V = 1380.61 (6) Å3 |
Mr = 371.05 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.8169 (3) Å | µ = 2.32 mm−1 |
b = 8.0588 (2) Å | T = 295 K |
c = 15.8422 (4) Å | 0.50 × 0.35 × 0.30 mm |
β = 91.326 (3)° | |
Data collection top
Oxford Diffraction Xcalibur CCD diffractometer | 4010 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | 3045 reflections with I > 2σ(I) |
Tmin = 0.396, Tmax = 0.498 | Rint = 0.015 |
21815 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.080 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.74 e Å−3 |
4010 reflections | Δρmin = −0.69 e Å−3 |
175 parameters | |
Special details top
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are
estimated using the full covariance matrix. The cell s.u.'s are taken into
account individually in the estimation of s.u.'s in distances, angles and
torsion angles; correlations between s.u.'s in cell parameters are only used
when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell s.u.'s is used for estimating s.u.'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 >
2σ(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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C2 | 0.52803 (18) | 0.2297 (2) | −0.07888 (11) | 0.0340 (4) | |
H2 | 0.5752 | 0.1920 | −0.1233 | 0.041* | |
C3 | 0.56926 (17) | 0.1942 (2) | 0.00146 (11) | 0.0322 (4) | |
C4 | 0.49926 (17) | 0.2478 (2) | 0.07310 (11) | 0.0354 (4) | |
C5 | 0.31198 (19) | 0.4005 (3) | 0.11492 (12) | 0.0374 (4) | |
H5 | 0.3353 | 0.3805 | 0.1709 | 0.045* | |
C6 | 0.20568 (19) | 0.4876 (3) | 0.09711 (13) | 0.0385 (4) | |
C7 | 0.17217 (19) | 0.5219 (3) | 0.01348 (14) | 0.0407 (4) | |
H7 | 0.1011 | 0.5832 | 0.0015 | 0.049* | |
C8 | 0.2426 (2) | 0.4663 (3) | −0.05113 (13) | 0.0387 (4) | |
H8 | 0.2190 | 0.4894 | −0.1067 | 0.046* | |
C9 | 0.35052 (17) | 0.3742 (2) | −0.03400 (11) | 0.0325 (4) | |
C10 | 0.38567 (16) | 0.3415 (2) | 0.05036 (11) | 0.0322 (4) | |
C11 | 0.68878 (19) | 0.1085 (3) | 0.01322 (12) | 0.0384 (4) | |
C12 | 0.8576 (2) | −0.0161 (4) | −0.05262 (16) | 0.0538 (6) | |
H12A | 0.8535 | −0.1166 | −0.0191 | 0.065* | |
H12B | 0.9144 | 0.0601 | −0.0245 | 0.065* | |
C13 | 0.9028 (3) | −0.0564 (3) | −0.13839 (18) | 0.0578 (6) | |
H13A | 0.8499 | −0.1384 | −0.1642 | 0.087* | |
H13B | 0.9856 | −0.0989 | −0.1338 | 0.087* | |
H13C | 0.9021 | 0.0422 | −0.1724 | 0.087* | |
C14 | 0.3902 (2) | 0.3422 (3) | −0.18834 (11) | 0.0443 (5) | |
H14A | 0.4630 | 0.3276 | −0.2222 | 0.053* | |
H14B | 0.3619 | 0.4556 | −0.1957 | 0.053* | |
C15 | 0.2900 (3) | 0.2247 (4) | −0.21974 (15) | 0.0618 (7) | |
H15B | 0.2174 | 0.2393 | −0.1868 | 0.093* | |
H15C | 0.3186 | 0.1124 | −0.2144 | 0.093* | |
H15A | 0.2704 | 0.2480 | −0.2780 | 0.093* | |
I1 | 0.094593 (14) | 0.568217 (19) | 0.196219 (9) | 0.04968 (8) | |
N1 | 0.42447 (14) | 0.3151 (2) | −0.09823 (9) | 0.0341 (3) | |
O1 | 0.52733 (14) | 0.2203 (2) | 0.14751 (9) | 0.0556 (4) | |
O2 | 0.7437 (2) | 0.0866 (3) | 0.08001 (11) | 0.0702 (6) | |
O3 | 0.73684 (14) | 0.05810 (18) | −0.05980 (10) | 0.0470 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C2 | 0.0322 (9) | 0.0391 (9) | 0.0308 (8) | −0.0001 (7) | 0.0023 (7) | −0.0003 (7) |
C3 | 0.0296 (9) | 0.0353 (9) | 0.0316 (8) | −0.0020 (7) | 0.0026 (7) | 0.0017 (7) |
C4 | 0.0306 (9) | 0.0452 (10) | 0.0305 (9) | −0.0008 (7) | 0.0011 (7) | 0.0026 (7) |
C5 | 0.0348 (10) | 0.0474 (11) | 0.0301 (9) | −0.0034 (8) | 0.0032 (7) | −0.0009 (7) |
C6 | 0.0344 (10) | 0.0401 (10) | 0.0415 (10) | −0.0011 (8) | 0.0076 (8) | −0.0043 (8) |
C7 | 0.0306 (10) | 0.0446 (10) | 0.0468 (11) | 0.0022 (8) | 0.0003 (8) | 0.0016 (9) |
C8 | 0.0345 (10) | 0.0476 (11) | 0.0337 (9) | 0.0012 (8) | −0.0033 (8) | 0.0026 (8) |
C9 | 0.0300 (9) | 0.0369 (9) | 0.0307 (8) | −0.0037 (7) | 0.0017 (7) | 0.0000 (7) |
C10 | 0.0291 (9) | 0.0391 (10) | 0.0283 (8) | −0.0029 (7) | 0.0018 (7) | 0.0008 (7) |
C11 | 0.0365 (10) | 0.0431 (10) | 0.0357 (10) | 0.0034 (8) | 0.0004 (8) | 0.0030 (8) |
C12 | 0.0390 (12) | 0.0677 (14) | 0.0547 (14) | 0.0170 (11) | −0.0001 (10) | −0.0056 (12) |
C13 | 0.0512 (14) | 0.0593 (15) | 0.0633 (15) | 0.0128 (11) | 0.0125 (12) | −0.0061 (11) |
C14 | 0.0450 (12) | 0.0619 (14) | 0.0261 (9) | 0.0070 (9) | −0.0003 (8) | 0.0071 (8) |
C15 | 0.0670 (17) | 0.0801 (17) | 0.0375 (11) | 0.0027 (14) | −0.0170 (11) | −0.0060 (12) |
I1 | 0.04642 (11) | 0.05494 (12) | 0.04832 (11) | 0.00447 (6) | 0.01515 (7) | −0.00530 (6) |
N1 | 0.0319 (8) | 0.0446 (9) | 0.0257 (7) | −0.0003 (6) | 0.0007 (6) | 0.0021 (6) |
O1 | 0.0430 (9) | 0.0954 (12) | 0.0285 (7) | 0.0151 (8) | 0.0018 (6) | 0.0091 (7) |
O2 | 0.0731 (13) | 0.1022 (15) | 0.0352 (8) | 0.0372 (11) | 0.0006 (8) | 0.0031 (8) |
O3 | 0.0350 (8) | 0.0657 (10) | 0.0403 (8) | 0.0146 (7) | −0.0001 (6) | −0.0070 (6) |
Geometric parameters (Å, º) top
C2—N1 | 1.344 (2) | C9—C10 | 1.406 (2) |
C2—C3 | 1.369 (2) | C11—O2 | 1.214 (3) |
C2—H2 | 0.9300 | C11—O3 | 1.342 (2) |
C3—C4 | 1.445 (2) | C12—O3 | 1.438 (3) |
C3—C11 | 1.474 (3) | C12—C13 | 1.491 (4) |
C4—O1 | 1.230 (2) | C12—H12A | 0.9700 |
C4—C10 | 1.479 (3) | C12—H12B | 0.9700 |
C5—C6 | 1.371 (3) | C13—H13A | 0.9600 |
C5—C10 | 1.395 (3) | C13—H13B | 0.9600 |
C5—H5 | 0.9300 | C13—H13C | 0.9600 |
C6—C7 | 1.393 (3) | C14—N1 | 1.483 (2) |
C6—I1 | 2.1019 (19) | C14—C15 | 1.515 (3) |
C7—C8 | 1.366 (3) | C14—H14A | 0.9700 |
C7—H7 | 0.9300 | C14—H14B | 0.9700 |
C8—C9 | 1.404 (3) | C15—H15B | 0.9600 |
C8—H8 | 0.9300 | C15—H15C | 0.9600 |
C9—N1 | 1.393 (2) | C15—H15A | 0.9600 |
| | | |
N1—C2—C3 | 124.82 (17) | O3—C11—C3 | 112.89 (16) |
N1—C2—H2 | 117.6 | O3—C12—C13 | 109.6 (2) |
C3—C2—H2 | 117.6 | O3—C12—H12A | 109.8 |
C2—C3—C4 | 120.14 (17) | C13—C12—H12A | 109.8 |
C2—C3—C11 | 118.78 (16) | O3—C12—H12B | 109.8 |
C4—C3—C11 | 121.00 (16) | C13—C12—H12B | 109.8 |
O1—C4—C3 | 125.20 (18) | H12A—C12—H12B | 108.2 |
O1—C4—C10 | 120.67 (17) | C12—C13—H13A | 109.5 |
C3—C4—C10 | 114.13 (15) | C12—C13—H13B | 109.5 |
C6—C5—C10 | 120.98 (18) | H13A—C13—H13B | 109.5 |
C6—C5—H5 | 119.5 | C12—C13—H13C | 109.5 |
C10—C5—H5 | 119.5 | H13A—C13—H13C | 109.5 |
C5—C6—C7 | 119.72 (18) | H13B—C13—H13C | 109.5 |
C5—C6—I1 | 119.72 (15) | N1—C14—C15 | 112.63 (18) |
C7—C6—I1 | 120.56 (15) | N1—C14—H14A | 109.1 |
C8—C7—C6 | 120.69 (19) | C15—C14—H14A | 109.1 |
C8—C7—H7 | 119.7 | N1—C14—H14B | 109.1 |
C6—C7—H7 | 119.7 | C15—C14—H14B | 109.1 |
C7—C8—C9 | 120.27 (18) | H14A—C14—H14B | 107.8 |
C7—C8—H8 | 119.9 | C14—C15—H15B | 109.5 |
C9—C8—H8 | 119.9 | C14—C15—H15C | 109.5 |
N1—C9—C8 | 121.90 (16) | H15B—C15—H15C | 109.5 |
N1—C9—C10 | 118.88 (16) | C14—C15—H15A | 109.5 |
C8—C9—C10 | 119.22 (17) | H15B—C15—H15A | 109.5 |
C5—C10—C9 | 119.10 (17) | H15C—C15—H15A | 109.5 |
C5—C10—C4 | 118.76 (16) | C2—N1—C9 | 119.89 (15) |
C9—C10—C4 | 122.14 (16) | C2—N1—C14 | 118.90 (16) |
O2—C11—O3 | 121.05 (19) | C9—N1—C14 | 121.21 (16) |
O2—C11—C3 | 126.02 (19) | C11—O3—C12 | 115.26 (17) |
| | | |
N1—C2—C3—C4 | 0.7 (3) | O1—C4—C10—C5 | 1.1 (3) |
N1—C2—C3—C11 | −176.15 (17) | C3—C4—C10—C5 | −179.32 (17) |
C2—C3—C4—O1 | 179.0 (2) | O1—C4—C10—C9 | −179.64 (19) |
C11—C3—C4—O1 | −4.2 (3) | C3—C4—C10—C9 | 0.0 (3) |
C2—C3—C4—C10 | −0.6 (3) | C2—C3—C11—O2 | 170.7 (2) |
C11—C3—C4—C10 | 176.15 (16) | C4—C3—C11—O2 | −6.1 (3) |
C10—C5—C6—C7 | −1.8 (3) | C2—C3—C11—O3 | −7.3 (3) |
C10—C5—C6—I1 | 178.18 (14) | C4—C3—C11—O3 | 175.87 (17) |
C5—C6—C7—C8 | 1.5 (3) | C3—C2—N1—C9 | 0.0 (3) |
I1—C6—C7—C8 | −178.43 (16) | C3—C2—N1—C14 | −179.13 (19) |
C6—C7—C8—C9 | −0.3 (3) | C8—C9—N1—C2 | 178.95 (18) |
C7—C8—C9—N1 | 179.83 (18) | C10—C9—N1—C2 | −0.6 (3) |
C7—C8—C9—C10 | −0.6 (3) | C8—C9—N1—C14 | −2.0 (3) |
C6—C5—C10—C9 | 0.8 (3) | C10—C9—N1—C14 | 178.44 (18) |
C6—C5—C10—C4 | −179.83 (18) | C15—C14—N1—C2 | 101.1 (2) |
N1—C9—C10—C5 | 179.94 (17) | C15—C14—N1—C9 | −78.0 (3) |
C8—C9—C10—C5 | 0.4 (3) | O2—C11—O3—C12 | −2.2 (3) |
N1—C9—C10—C4 | 0.6 (3) | C3—C11—O3—C12 | 175.88 (18) |
C8—C9—C10—C4 | −178.94 (18) | C13—C12—O3—C11 | −176.5 (2) |
(II) Ethyl 1-cyclopropyl-6-iodo-4-oxo-1,4-dihydroquinoline-3-carboxylate
top
Crystal data top
C15H14INO3 | F(000) = 752 |
Mr = 383.17 | Dx = 1.782 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 6715 reflections |
a = 10.8406 (2) Å | θ = 3.9–32.9° |
b = 8.2843 (2) Å | µ = 2.25 mm−1 |
c = 15.9269 (3) Å | T = 295 K |
β = 93.127 (2)° | Needle, colourless |
V = 1428.21 (5) Å3 | 0.60 × 0.35 × 0.20 mm |
Z = 4 | |
Data collection top
Oxford Diffraction Xcalibur CCD diffractometer | 4146 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 2708 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
Detector resolution: 16.3426 pixels mm-1 | θmax = 30.0°, θmin = 4.1° |
ω scans | h = −15→13 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | k = −10→11 |
Tmin = 0.313, Tmax = 0.638 | l = −22→22 |
13158 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.079 | w = 1/[σ2(Fo2) + (0.0441P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
4146 reflections | Δρmax = 0.82 e Å−3 |
183 parameters | Δρmin = −0.59 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: 0.0054 (6) |
Crystal data top
C15H14INO3 | V = 1428.21 (5) Å3 |
Mr = 383.17 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.8406 (2) Å | µ = 2.25 mm−1 |
b = 8.2843 (2) Å | T = 295 K |
c = 15.9269 (3) Å | 0.60 × 0.35 × 0.20 mm |
β = 93.127 (2)° | |
Data collection top
Oxford Diffraction Xcalibur CCD diffractometer | 4146 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | 2708 reflections with I > 2σ(I) |
Tmin = 0.313, Tmax = 0.638 | Rint = 0.017 |
13158 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.82 e Å−3 |
4146 reflections | Δρmin = −0.59 e Å−3 |
183 parameters | |
Special details top
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 >
2σ(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. Reflections 2 0 2 and 0 0 4 were omitted as outliers. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C2 | 0.51719 (17) | 0.2224 (2) | −0.07436 (13) | 0.0345 (4) | |
H2 | 0.5620 | 0.1800 | −0.1174 | 0.041* | |
C3 | 0.56069 (18) | 0.1968 (2) | 0.00669 (12) | 0.0325 (4) | |
C4 | 0.49446 (18) | 0.2587 (3) | 0.07631 (13) | 0.0371 (5) | |
C5 | 0.3188 (2) | 0.4317 (3) | 0.11251 (13) | 0.0376 (5) | |
H5 | 0.3452 | 0.4200 | 0.1687 | 0.045* | |
C6 | 0.2148 (2) | 0.5211 (3) | 0.09101 (14) | 0.0390 (5) | |
C7 | 0.1768 (2) | 0.5414 (3) | 0.00613 (15) | 0.0434 (5) | |
H7 | 0.1069 | 0.6025 | −0.0083 | 0.052* | |
C8 | 0.2413 (2) | 0.4727 (3) | −0.05525 (14) | 0.0400 (5) | |
H8 | 0.2155 | 0.4873 | −0.1114 | 0.048* | |
C9 | 0.34678 (19) | 0.3795 (2) | −0.03432 (13) | 0.0324 (4) | |
C10 | 0.38433 (18) | 0.3592 (2) | 0.05014 (13) | 0.0329 (4) | |
C11 | 0.6786 (2) | 0.1080 (2) | 0.02219 (14) | 0.0396 (5) | |
C12 | 0.8424 (2) | −0.0288 (3) | −0.03904 (18) | 0.0565 (7) | |
H12A | 0.8386 | −0.1202 | −0.0012 | 0.068* | |
H12B | 0.9029 | 0.0470 | −0.0153 | 0.068* | |
C13 | 0.8789 (3) | −0.0837 (3) | −0.1225 (2) | 0.0674 (8) | |
H13A | 0.8188 | −0.1591 | −0.1454 | 0.101* | |
H13B | 0.9583 | −0.1351 | −0.1167 | 0.101* | |
H13C | 0.8833 | 0.0075 | −0.1594 | 0.101* | |
C14 | 0.3732 (2) | 0.3237 (3) | −0.18489 (12) | 0.0405 (5) | |
H14 | 0.3904 | 0.4283 | −0.2105 | 0.049* | |
C15 | 0.2558 (2) | 0.2425 (3) | −0.21532 (14) | 0.0482 (6) | |
H15A | 0.2035 | 0.2978 | −0.2575 | 0.058* | |
H15B | 0.2121 | 0.1792 | −0.1752 | 0.058* | |
C16 | 0.3786 (2) | 0.1815 (3) | −0.24061 (15) | 0.0505 (6) | |
H16A | 0.4087 | 0.0809 | −0.2160 | 0.061* | |
H16B | 0.4001 | 0.1994 | −0.2982 | 0.061* | |
I1 | 0.111620 (15) | 0.61988 (2) | 0.186353 (11) | 0.05525 (10) | |
N1 | 0.41297 (15) | 0.3055 (2) | −0.09567 (10) | 0.0336 (4) | |
O1 | 0.52079 (14) | 0.2335 (2) | 0.15105 (9) | 0.0570 (5) | |
O2 | 0.73195 (19) | 0.0919 (2) | 0.08887 (12) | 0.0680 (6) | |
O3 | 0.72183 (14) | 0.0486 (2) | −0.04857 (10) | 0.0488 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C2 | 0.0299 (10) | 0.0385 (11) | 0.0350 (10) | −0.0005 (8) | −0.0001 (8) | 0.0023 (9) |
C3 | 0.0275 (10) | 0.0341 (10) | 0.0354 (10) | −0.0008 (8) | −0.0029 (8) | 0.0070 (9) |
C4 | 0.0321 (11) | 0.0458 (12) | 0.0328 (11) | −0.0043 (9) | −0.0031 (9) | 0.0048 (9) |
C5 | 0.0386 (12) | 0.0452 (11) | 0.0290 (10) | −0.0053 (10) | 0.0016 (9) | −0.0004 (9) |
C6 | 0.0362 (11) | 0.0396 (11) | 0.0416 (11) | −0.0060 (9) | 0.0071 (9) | −0.0044 (10) |
C7 | 0.0374 (12) | 0.0418 (12) | 0.0509 (14) | 0.0044 (10) | 0.0030 (10) | −0.0018 (11) |
C8 | 0.0405 (12) | 0.0442 (12) | 0.0343 (11) | 0.0065 (10) | −0.0084 (9) | −0.0010 (10) |
C9 | 0.0311 (10) | 0.0346 (10) | 0.0311 (10) | 0.0000 (8) | −0.0024 (8) | −0.0016 (9) |
C10 | 0.0263 (10) | 0.0394 (11) | 0.0327 (10) | −0.0059 (8) | −0.0011 (8) | 0.0008 (9) |
C11 | 0.0382 (12) | 0.0411 (12) | 0.0393 (12) | −0.0020 (9) | −0.0019 (10) | 0.0048 (10) |
C12 | 0.0358 (13) | 0.0689 (17) | 0.0642 (17) | 0.0152 (12) | −0.0029 (12) | −0.0009 (14) |
C13 | 0.0596 (18) | 0.0614 (17) | 0.082 (2) | 0.0122 (13) | 0.0104 (16) | −0.0081 (16) |
C14 | 0.0473 (13) | 0.0468 (11) | 0.0266 (10) | 0.0061 (10) | −0.0044 (9) | 0.0047 (9) |
C15 | 0.0466 (13) | 0.0603 (14) | 0.0358 (12) | 0.0067 (12) | −0.0146 (10) | −0.0047 (11) |
C16 | 0.0526 (14) | 0.0650 (15) | 0.0332 (12) | 0.0112 (13) | −0.0042 (11) | −0.0066 (12) |
I1 | 0.05359 (13) | 0.05664 (13) | 0.05753 (13) | −0.00088 (7) | 0.02147 (9) | −0.00666 (8) |
N1 | 0.0313 (9) | 0.0411 (9) | 0.0277 (8) | 0.0018 (8) | −0.0053 (7) | 0.0002 (8) |
O1 | 0.0443 (9) | 0.0957 (14) | 0.0304 (8) | 0.0123 (9) | −0.0024 (7) | 0.0105 (9) |
O2 | 0.0630 (12) | 0.0958 (15) | 0.0434 (10) | 0.0378 (10) | −0.0128 (9) | 0.0041 (9) |
O3 | 0.0349 (8) | 0.0625 (10) | 0.0485 (9) | 0.0125 (8) | −0.0032 (7) | −0.0016 (8) |
Geometric parameters (Å, º) top
C2—N1 | 1.351 (2) | C11—O2 | 1.189 (3) |
C2—C3 | 1.367 (3) | C11—O3 | 1.338 (3) |
C2—H2 | 0.9300 | C12—O3 | 1.456 (3) |
C3—C4 | 1.447 (3) | C12—C13 | 1.479 (4) |
C3—C11 | 1.484 (3) | C12—H12A | 0.9700 |
C4—O1 | 1.227 (2) | C12—H12B | 0.9700 |
C4—C10 | 1.496 (3) | C13—H13A | 0.9600 |
C5—C6 | 1.376 (3) | C13—H13B | 0.9600 |
C5—C10 | 1.389 (3) | C13—H13C | 0.9600 |
C5—H5 | 0.9300 | C14—N1 | 1.470 (2) |
C6—C7 | 1.402 (3) | C14—C16 | 1.478 (3) |
C6—I1 | 2.100 (2) | C14—C15 | 1.496 (3) |
C7—C8 | 1.358 (3) | C14—H14 | 0.9800 |
C7—H7 | 0.9300 | C15—C16 | 1.499 (3) |
C8—C9 | 1.405 (3) | C15—H15A | 0.9700 |
C8—H8 | 0.9300 | C15—H15B | 0.9700 |
C9—N1 | 1.386 (3) | C16—H16A | 0.9700 |
C9—C10 | 1.394 (3) | C16—H16B | 0.9700 |
| | | |
N1—C2—C3 | 123.9 (2) | C13—C12—H12A | 109.9 |
N1—C2—H2 | 118.1 | O3—C12—H12B | 109.9 |
C3—C2—H2 | 118.1 | C13—C12—H12B | 109.9 |
C2—C3—C4 | 120.57 (18) | H12A—C12—H12B | 108.3 |
C2—C3—C11 | 118.94 (19) | C12—C13—H13A | 109.5 |
C4—C3—C11 | 120.47 (18) | C12—C13—H13B | 109.5 |
O1—C4—C3 | 125.74 (19) | H13A—C13—H13B | 109.5 |
O1—C4—C10 | 120.3 (2) | C12—C13—H13C | 109.5 |
C3—C4—C10 | 113.92 (17) | H13A—C13—H13C | 109.5 |
C6—C5—C10 | 119.9 (2) | H13B—C13—H13C | 109.5 |
C6—C5—H5 | 120.0 | N1—C14—C16 | 118.69 (19) |
C10—C5—H5 | 120.0 | N1—C14—C15 | 117.8 (2) |
C5—C6—C7 | 119.9 (2) | C16—C14—C15 | 60.54 (16) |
C5—C6—I1 | 119.40 (16) | N1—C14—H14 | 116.1 |
C7—C6—I1 | 120.70 (16) | C16—C14—H14 | 116.1 |
C8—C7—C6 | 120.6 (2) | C15—C14—H14 | 116.1 |
C8—C7—H7 | 119.7 | C14—C15—C16 | 59.12 (15) |
C6—C7—H7 | 119.7 | C14—C15—H15A | 117.9 |
C7—C8—C9 | 120.3 (2) | C16—C15—H15A | 117.9 |
C7—C8—H8 | 119.9 | C14—C15—H15B | 117.9 |
C9—C8—H8 | 119.9 | C16—C15—H15B | 117.9 |
N1—C9—C10 | 119.44 (18) | H15A—C15—H15B | 115.0 |
N1—C9—C8 | 121.44 (18) | C14—C16—C15 | 60.34 (16) |
C10—C9—C8 | 119.11 (19) | C14—C16—H16A | 117.7 |
C5—C10—C9 | 120.26 (19) | C15—C16—H16A | 117.7 |
C5—C10—C4 | 118.23 (18) | C14—C16—H16B | 117.7 |
C9—C10—C4 | 121.52 (19) | C15—C16—H16B | 117.7 |
O2—C11—O3 | 122.4 (2) | H16A—C16—H16B | 114.9 |
O2—C11—C3 | 125.2 (2) | C2—N1—C9 | 120.43 (17) |
O3—C11—C3 | 112.35 (18) | C2—N1—C14 | 119.49 (18) |
O3—C12—C13 | 108.9 (2) | C9—N1—C14 | 120.03 (16) |
O3—C12—H12A | 109.9 | C11—O3—C12 | 115.32 (18) |
| | | |
N1—C2—C3—C4 | 0.5 (3) | O1—C4—C10—C9 | −175.0 (2) |
N1—C2—C3—C11 | −178.00 (19) | C3—C4—C10—C9 | 4.1 (3) |
C2—C3—C4—O1 | 174.8 (2) | C2—C3—C11—O2 | 172.3 (2) |
C11—C3—C4—O1 | −6.7 (3) | C4—C3—C11—O2 | −6.2 (3) |
C2—C3—C4—C10 | −4.2 (3) | C2—C3—C11—O3 | −6.6 (3) |
C11—C3—C4—C10 | 174.19 (17) | C4—C3—C11—O3 | 174.98 (19) |
C10—C5—C6—C7 | −1.4 (3) | N1—C14—C15—C16 | −109.0 (2) |
C10—C5—C6—I1 | 176.84 (16) | N1—C14—C16—C15 | 107.6 (2) |
C5—C6—C7—C8 | 0.5 (3) | C3—C2—N1—C9 | 3.9 (3) |
I1—C6—C7—C8 | −177.69 (17) | C3—C2—N1—C14 | −178.9 (2) |
C6—C7—C8—C9 | 0.3 (3) | C10—C9—N1—C2 | −3.9 (3) |
C7—C8—C9—N1 | 178.8 (2) | C8—C9—N1—C2 | 177.11 (19) |
C7—C8—C9—C10 | −0.2 (3) | C10—C9—N1—C14 | 178.95 (19) |
C6—C5—C10—C9 | 1.5 (3) | C8—C9—N1—C14 | 0.0 (3) |
C6—C5—C10—C4 | −178.04 (18) | C16—C14—N1—C2 | 43.7 (3) |
N1—C9—C10—C5 | −179.70 (19) | C15—C14—N1—C2 | 113.5 (2) |
C8—C9—C10—C5 | −0.7 (3) | C16—C14—N1—C9 | −139.1 (2) |
N1—C9—C10—C4 | −0.2 (3) | C15—C14—N1—C9 | −69.3 (3) |
C8—C9—C10—C4 | 178.80 (19) | O2—C11—O3—C12 | −3.6 (3) |
O1—C4—C10—C5 | 4.5 (3) | C3—C11—O3—C12 | 175.24 (19) |
C3—C4—C10—C5 | −176.37 (19) | C13—C12—O3—C11 | −178.4 (2) |
(III) Ethyl 1-(dimethylamino)-6-iodo-4-oxo-1,4-dihydroquinoline-3-carboxylate
top
Crystal data top
C14H15IN2O3 | F(000) = 760 |
Mr = 386.18 | Dx = 1.732 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 8549 reflections |
a = 10.8437 (3) Å | θ = 4.0–32.7° |
b = 9.9660 (2) Å | µ = 2.17 mm−1 |
c = 14.4482 (4) Å | T = 295 K |
β = 108.436 (3)° | Plate, colourless |
V = 1481.26 (7) Å3 | 0.60 × 0.50 × 0.15 mm |
Z = 4 | |
Data collection top
Oxford Diffraction Xcalibur CCD diffractometer | 4265 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 3414 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
Detector resolution: 16.3426 pixels mm-1 | θmax = 30.0°, θmin = 4.0° |
ω scans | h = −15→14 |
Absorption correction: multi-scan CrysAlis RED (Oxford Diffraction, 2007) | k = −14→14 |
Tmin = 0.296, Tmax = 0.722 | l = −20→20 |
13165 measured reflections | |
Refinement top
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)] = 0.030 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0368P)2 + 0.8397P] where P = (Fo2 + 2Fc2)/3 |
4265 reflections | (Δ/σ)max < 0.001 |
184 parameters | Δρmax = 1.08 e Å−3 |
0 restraints | Δρmin = −0.85 e Å−3 |
Crystal data top
C14H15IN2O3 | V = 1481.26 (7) Å3 |
Mr = 386.18 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.8437 (3) Å | µ = 2.17 mm−1 |
b = 9.9660 (2) Å | T = 295 K |
c = 14.4482 (4) Å | 0.60 × 0.50 × 0.15 mm |
β = 108.436 (3)° | |
Data collection top
Oxford Diffraction Xcalibur CCD diffractometer | 4265 independent reflections |
Absorption correction: multi-scan CrysAlis RED (Oxford Diffraction, 2007) | 3414 reflections with I > 2σ(I) |
Tmin = 0.296, Tmax = 0.722 | Rint = 0.015 |
13165 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.09 | Δρmax = 1.08 e Å−3 |
4265 reflections | Δρmin = −0.85 e Å−3 |
184 parameters | |
Special details top
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are
estimated using the full covariance matrix. The cell s.u.'s are taken into
account individually in the estimation of s.u.'s in distances, angles and
torsion angles; correlations between s.u.'s in cell parameters are only used
when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell s.u.'s is used for estimating s.u.'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 >
2σ(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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C2 | 1.1119 (2) | 0.0898 (2) | 0.40704 (16) | 0.0307 (4) | |
H2 | 1.1969 | 0.0582 | 0.4285 | 0.037* | |
C3 | 1.0132 (2) | −0.0029 (2) | 0.38503 (15) | 0.0295 (4) | |
C4 | 0.8792 (2) | 0.0423 (2) | 0.35534 (16) | 0.0305 (4) | |
C5 | 0.7382 (2) | 0.2417 (2) | 0.30366 (16) | 0.0331 (4) | |
H5 | 0.6668 | 0.1845 | 0.2883 | 0.040* | |
C6 | 0.7196 (2) | 0.3776 (2) | 0.28923 (17) | 0.0345 (5) | |
C7 | 0.8258 (2) | 0.4644 (2) | 0.31387 (18) | 0.0365 (5) | |
H7 | 0.8124 | 0.5563 | 0.3050 | 0.044* | |
C8 | 0.9498 (2) | 0.4153 (2) | 0.35117 (18) | 0.0361 (5) | |
H8 | 1.0204 | 0.4736 | 0.3678 | 0.043* | |
C9 | 0.9694 (2) | 0.2768 (2) | 0.36405 (15) | 0.0295 (4) | |
C10 | 0.8634 (2) | 0.1891 (2) | 0.34122 (15) | 0.0282 (4) | |
C11 | 1.0467 (2) | −0.1473 (2) | 0.39283 (16) | 0.0329 (4) | |
C12 | 1.2203 (2) | −0.3041 (2) | 0.43850 (19) | 0.0402 (5) | |
H12A | 1.1907 | −0.3495 | 0.3760 | 0.048* | |
H12B | 1.1870 | −0.3518 | 0.4841 | 0.048* | |
C13 | 1.3662 (3) | −0.2995 (3) | 0.4757 (3) | 0.0575 (7) | |
H13A | 1.3978 | −0.2522 | 0.4299 | 0.086* | |
H13B | 1.4000 | −0.3893 | 0.4835 | 0.086* | |
H13C | 1.3941 | −0.2542 | 0.5375 | 0.086* | |
C14 | 1.2791 (3) | 0.2989 (3) | 0.3616 (2) | 0.0544 (7) | |
H14A | 1.3184 | 0.2116 | 0.3702 | 0.082* | |
H14B | 1.3457 | 0.3663 | 0.3767 | 0.082* | |
H14C | 1.2248 | 0.3092 | 0.2951 | 0.082* | |
C15 | 1.2772 (3) | 0.2952 (3) | 0.5288 (2) | 0.0557 (7) | |
H15A | 1.2202 | 0.2859 | 0.5674 | 0.084* | |
H15B | 1.3325 | 0.3717 | 0.5509 | 0.084* | |
H15C | 1.3296 | 0.2159 | 0.5352 | 0.084* | |
I1 | 0.528239 (16) | 0.448973 (19) | 0.232078 (13) | 0.04868 (7) | |
N1 | 1.09375 (17) | 0.22254 (19) | 0.39966 (14) | 0.0320 (4) | |
N2 | 1.20033 (18) | 0.3137 (2) | 0.42655 (15) | 0.0370 (4) | |
O1 | 0.78397 (17) | −0.03142 (17) | 0.34317 (16) | 0.0456 (4) | |
O2 | 0.97176 (18) | −0.23885 (18) | 0.36945 (17) | 0.0563 (5) | |
O3 | 1.17598 (16) | −0.16656 (17) | 0.42855 (14) | 0.0424 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C2 | 0.0228 (9) | 0.0320 (10) | 0.0359 (11) | −0.0017 (8) | 0.0072 (8) | 0.0015 (8) |
C3 | 0.0271 (10) | 0.0270 (9) | 0.0331 (10) | −0.0021 (8) | 0.0077 (8) | 0.0000 (8) |
C4 | 0.0275 (10) | 0.0294 (10) | 0.0334 (10) | −0.0035 (8) | 0.0080 (8) | −0.0038 (8) |
C5 | 0.0256 (10) | 0.0350 (11) | 0.0374 (11) | −0.0035 (8) | 0.0080 (8) | −0.0032 (9) |
C6 | 0.0279 (10) | 0.0355 (11) | 0.0378 (11) | 0.0028 (9) | 0.0074 (9) | 0.0000 (9) |
C7 | 0.0334 (11) | 0.0316 (11) | 0.0439 (12) | 0.0013 (9) | 0.0114 (10) | 0.0019 (9) |
C8 | 0.0302 (11) | 0.0303 (10) | 0.0459 (12) | −0.0048 (8) | 0.0094 (10) | 0.0009 (9) |
C9 | 0.0247 (9) | 0.0309 (10) | 0.0326 (10) | −0.0022 (8) | 0.0087 (8) | 0.0000 (8) |
C10 | 0.0253 (9) | 0.0283 (9) | 0.0307 (9) | −0.0026 (8) | 0.0084 (8) | −0.0011 (8) |
C11 | 0.0316 (11) | 0.0310 (10) | 0.0357 (11) | −0.0021 (9) | 0.0102 (9) | 0.0013 (9) |
C12 | 0.0393 (12) | 0.0324 (11) | 0.0491 (13) | 0.0062 (9) | 0.0142 (11) | 0.0067 (10) |
C13 | 0.0382 (14) | 0.0560 (17) | 0.077 (2) | 0.0130 (13) | 0.0162 (14) | 0.0142 (15) |
C14 | 0.0432 (14) | 0.0696 (19) | 0.0528 (15) | −0.0188 (14) | 0.0187 (13) | 0.0054 (14) |
C15 | 0.0477 (15) | 0.074 (2) | 0.0442 (14) | −0.0267 (15) | 0.0120 (12) | −0.0126 (13) |
I1 | 0.03235 (9) | 0.04715 (11) | 0.06022 (12) | 0.01026 (7) | 0.00564 (7) | 0.00032 (8) |
N1 | 0.0227 (8) | 0.0298 (9) | 0.0420 (10) | −0.0054 (7) | 0.0079 (7) | −0.0005 (7) |
N2 | 0.0228 (8) | 0.0344 (10) | 0.0510 (11) | −0.0079 (7) | 0.0077 (8) | −0.0011 (8) |
O1 | 0.0257 (8) | 0.0353 (9) | 0.0721 (12) | −0.0072 (7) | 0.0101 (8) | −0.0016 (8) |
O2 | 0.0355 (9) | 0.0306 (9) | 0.0947 (15) | −0.0049 (7) | 0.0088 (10) | −0.0007 (9) |
O3 | 0.0308 (8) | 0.0300 (8) | 0.0610 (10) | 0.0014 (7) | 0.0067 (8) | 0.0031 (7) |
Geometric parameters (Å, º) top
C2—N1 | 1.337 (3) | C11—O2 | 1.197 (3) |
C2—C3 | 1.372 (3) | C11—O3 | 1.346 (3) |
C2—H2 | 0.9300 | C12—O3 | 1.444 (3) |
C3—C4 | 1.451 (3) | C12—C13 | 1.502 (4) |
C3—C11 | 1.480 (3) | C12—H12A | 0.9700 |
C4—O1 | 1.233 (3) | C12—H12B | 0.9700 |
C4—C10 | 1.480 (3) | C13—H13A | 0.9600 |
C5—C6 | 1.376 (3) | C13—H13B | 0.9600 |
C5—C10 | 1.395 (3) | C13—H13C | 0.9600 |
C5—H5 | 0.9300 | C14—N2 | 1.463 (3) |
C6—C7 | 1.394 (3) | C14—H14A | 0.9600 |
C6—I1 | 2.100 (2) | C14—H14B | 0.9600 |
C7—C8 | 1.372 (3) | C14—H14C | 0.9600 |
C7—H7 | 0.9300 | C15—N2 | 1.460 (3) |
C8—C9 | 1.400 (3) | C15—H15A | 0.9600 |
C8—H8 | 0.9300 | C15—H15B | 0.9600 |
C9—N1 | 1.391 (3) | C15—H15C | 0.9600 |
C9—C10 | 1.398 (3) | N1—N2 | 1.424 (2) |
| | | |
N1—C2—C3 | 124.3 (2) | O3—C12—H12A | 110.4 |
N1—C2—H2 | 117.8 | C13—C12—H12A | 110.4 |
C3—C2—H2 | 117.8 | O3—C12—H12B | 110.4 |
C2—C3—C4 | 119.6 (2) | C13—C12—H12B | 110.4 |
C2—C3—C11 | 118.9 (2) | H12A—C12—H12B | 108.6 |
C4—C3—C11 | 121.53 (19) | C12—C13—H13A | 109.5 |
O1—C4—C3 | 124.9 (2) | C12—C13—H13B | 109.5 |
O1—C4—C10 | 120.9 (2) | H13A—C13—H13B | 109.5 |
C3—C4—C10 | 114.13 (18) | C12—C13—H13C | 109.5 |
C6—C5—C10 | 120.5 (2) | H13A—C13—H13C | 109.5 |
C6—C5—H5 | 119.7 | H13B—C13—H13C | 109.5 |
C10—C5—H5 | 119.7 | N2—C14—H14A | 109.5 |
C5—C6—C7 | 120.2 (2) | N2—C14—H14B | 109.5 |
C5—C6—I1 | 118.21 (17) | H14A—C14—H14B | 109.5 |
C7—C6—I1 | 121.62 (17) | N2—C14—H14C | 109.5 |
C8—C7—C6 | 120.5 (2) | H14A—C14—H14C | 109.5 |
C8—C7—H7 | 119.8 | H14B—C14—H14C | 109.5 |
C6—C7—H7 | 119.8 | N2—C15—H15A | 109.5 |
C7—C8—C9 | 119.5 (2) | N2—C15—H15B | 109.5 |
C7—C8—H8 | 120.2 | H15A—C15—H15B | 109.5 |
C9—C8—H8 | 120.2 | N2—C15—H15C | 109.5 |
N1—C9—C10 | 118.22 (19) | H15A—C15—H15C | 109.5 |
N1—C9—C8 | 121.36 (19) | H15B—C15—H15C | 109.5 |
C10—C9—C8 | 120.4 (2) | C2—N1—C9 | 120.96 (18) |
C5—C10—C9 | 118.88 (19) | C2—N1—N2 | 121.57 (18) |
C5—C10—C4 | 118.77 (19) | C9—N1—N2 | 117.46 (17) |
C9—C10—C4 | 122.36 (19) | N1—N2—C15 | 110.49 (19) |
O2—C11—O3 | 122.1 (2) | N1—N2—C14 | 110.4 (2) |
O2—C11—C3 | 126.2 (2) | C15—N2—C14 | 112.0 (2) |
O3—C11—C3 | 111.61 (19) | C11—O3—C12 | 116.54 (18) |
O3—C12—C13 | 106.7 (2) | | |
| | | |
N1—C2—C3—C4 | −2.6 (3) | C3—C4—C10—C5 | 173.91 (19) |
N1—C2—C3—C11 | 177.7 (2) | O1—C4—C10—C9 | 173.2 (2) |
C2—C3—C4—O1 | −172.6 (2) | C3—C4—C10—C9 | −6.0 (3) |
C11—C3—C4—O1 | 7.1 (3) | C2—C3—C11—O2 | −174.3 (2) |
C2—C3—C4—C10 | 6.6 (3) | C4—C3—C11—O2 | 6.1 (4) |
C11—C3—C4—C10 | −173.73 (19) | C2—C3—C11—O3 | 4.4 (3) |
C10—C5—C6—C7 | −1.2 (3) | C4—C3—C11—O3 | −175.26 (19) |
C10—C5—C6—I1 | 179.83 (15) | C3—C2—N1—C9 | −2.8 (3) |
C5—C6—C7—C8 | 1.1 (4) | C3—C2—N1—N2 | 178.0 (2) |
I1—C6—C7—C8 | 179.95 (18) | C10—C9—N1—C2 | 3.5 (3) |
C6—C7—C8—C9 | 0.3 (4) | C8—C9—N1—C2 | −176.5 (2) |
C7—C8—C9—N1 | 178.6 (2) | C10—C9—N1—N2 | −177.33 (18) |
C7—C8—C9—C10 | −1.4 (3) | C8—C9—N1—N2 | 2.7 (3) |
C6—C5—C10—C9 | 0.1 (3) | C2—N1—N2—C15 | −59.0 (3) |
C6—C5—C10—C4 | −179.8 (2) | C9—N1—N2—C15 | 121.8 (2) |
N1—C9—C10—C5 | −178.77 (19) | C2—N1—N2—C14 | 65.4 (3) |
C8—C9—C10—C5 | 1.2 (3) | C9—N1—N2—C14 | −113.8 (2) |
N1—C9—C10—C4 | 1.2 (3) | O2—C11—O3—C12 | −0.7 (3) |
C8—C9—C10—C4 | −178.8 (2) | C3—C11—O3—C12 | −179.40 (19) |
O1—C4—C10—C5 | −6.9 (3) | C13—C12—O3—C11 | 177.9 (2) |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C14H14INO3 | C15H14INO3 | C14H15IN2O3 |
Mr | 371.05 | 383.17 | 386.18 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n | Monoclinic, P21/c |
Temperature (K) | 295 | 295 | 295 |
a, b, c (Å) | 10.8169 (3), 8.0588 (2), 15.8422 (4) | 10.8406 (2), 8.2843 (2), 15.9269 (3) | 10.8437 (3), 9.9660 (2), 14.4482 (4) |
β (°) | 91.326 (3) | 93.127 (2) | 108.436 (3) |
V (Å3) | 1380.61 (6) | 1428.21 (5) | 1481.26 (7) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 2.32 | 2.25 | 2.17 |
Crystal size (mm) | 0.50 × 0.35 × 0.30 | 0.60 × 0.35 × 0.20 | 0.60 × 0.50 × 0.15 |
|
Data collection |
Diffractometer | Oxford Diffraction Xcalibur CCD diffractometer | Oxford Diffraction Xcalibur CCD diffractometer | Oxford Diffraction Xcalibur CCD diffractometer |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | Multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | Multi-scan CrysAlis RED (Oxford Diffraction, 2007) |
Tmin, Tmax | 0.396, 0.498 | 0.313, 0.638 | 0.296, 0.722 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21815, 4010, 3045 | 13158, 4146, 2708 | 13165, 4265, 3414 |
Rint | 0.015 | 0.017 | 0.015 |
(sin θ/λ)max (Å−1) | 0.703 | 0.703 | 0.703 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.080, 1.07 | 0.029, 0.079, 1.01 | 0.030, 0.079, 1.09 |
No. of reflections | 4010 | 4146 | 4265 |
No. of parameters | 175 | 183 | 184 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.74, −0.69 | 0.82, −0.59 | 1.08, −0.85 |
Halogen-bond geometry (Å, °) in (I), (II), and (III) top | O1···Ii | θ1(O1···Ii—C6i) | θ2(C4═O1···Ii) |
(I) | 3.0857 (15) | 169.86 (7) | 137.69 (13) |
(II) | 3.1715 (15) | 171.31 (7) | 138.69 (13) |
(III) | 3.218 (2) | 163.07 (6) | 145.90 (15) |
Symmetry code: (i) 1/2 - x, y - 1/2, 1/2 - z for (I) and
(II); 1 - x, y - 1/2, 1/2 - z for (III). |
C—H···A interactions (Å, °) in (I), (II), and (III) topCg2 is the centroid of the benzene ring C5–C10. |
| D—H···A | D—H | H···A | D···A | D—H···A |
(I) | C15—H15A···O2ii | 0.96 | 2.62 | 3.543 (4) | 160 |
| C12—H12A···Cg2iii | 0.97 | 2.92 | 3.677 (3) | 136 |
(II) | C15—H15A···O1ii | 0.97 | 2.41 | 3.236 (3) | 143 |
| C12—H12A···Cg2iii | 0.97 | 3.05 | 3.749 (3) | 130 |
(III) | C14—H14C···O1iv | 0.96 | 2.53 | 3.286 (3) | 136 |
| C15—H15A···O2v | 0.96 | 2.57 | 3.504 (4) | 166 |
| C5—H5···Ii | 0.93 | 3.11 | 4.023 (2) | 167 |
| C12—H12B···Cg2v | 0.97 | 2.86 | 3.675 (3) | 142 |
Symmetry codes: (i) 1 - x, y - 1/2, 1/2 - z;
(ii) x - 1/2, 1/2 - y, z - 1/2; (iii)
1 - x, -y, -z; (iv) 2 - x, 1/2 + y,
1/2 - z; (v) 2 - x, -y, 1 - z. |
π–π interactions in (I) and (II) topCg1 and Cg2 are the centroids of the heterocyclic ring
N1/C2–C4/C9–C10 (Ring 1) and the benzene ring C5–C10 (Ring 2),
respectively. α is the dihedral angle between the mean planes of the two
interacting rings. |
| Ring m···Ring nvi | Cgm···Cgnvi (Å) | α (°) | Mean plane of Ring m···Cgnvi (Å) | Ring offset (Å) |
(I) | Ring 1···Ring 1vi | 3.6198 (9) | 0 | 3.4380 (7) | ca 1.13 |
| Ring 1···Ring 2vi | 3.6625 (11) | 0.63 (9) | 3.4269 (9) | |
(II) | Ring 1···Ring 1vi | 3.6883 (11) | 0 | 3.4703 (8) | ca 1.25 |
| Ring 1···Ring 2vi | 3.6373 (12) | 0.94 (10) | 3.4341 (9) | |
Symmetry code: (vi) 1 - x, 1 - y, -z. |
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Halogen bonding is an interaction between halogen atoms (I, Br and Cl) acting as Lewis acids and neutral or anionic Lewis bases (Karpfen, 2008). The interaction has received a great deal of attention recently as it has frequently been observed in solids (Metrangolo et al., 2008), liquids (Wash et al., 1999) and gases (Legon, 2008). It has also been found in liquid crystals (Nguyen et al., 2004), as well as in biologically important molecules (Metrangolo et al., 2005). For this reason, halogen bonding is considered to be just as important as the analogous hydrogen bonding (Corradi et al., 2000; Aakeröy et al., 2007).
Quinolones have been thoroughly investigated since the early 1960s as potent antibacterial agents (Andriole, 1998). Many quinolonic structures have been characterized and quinolone chemistry has been well explored (Grohe, 1998). A search of the Cambridge Structural Database (CSD; Version 5.30 with May 2009 updates; Allen, 2002) revealed 267 solid-state structures containing the quinolone moiety, 201 of which are halogenated. 61 of these contain Cl, 5 contain Br and only one contains I (CSD refcode BARTIX; Keller et al., 1981). To the best of our knowledge, there has been no report on O···I halogen bonding for this class of compounds. We have observed O···I halogen bonding in the crystal structures of ethyl 1-ethyl-, 1-cyclopropyl- and 1-(dimethylamino)-6-iodo-4-oxo-1,4-dihydroquinoline-3-carboxylate, (I), (II) and (III), respectively. The solid-state structures of (I) and (II) are isomorphous by substitution of the N-substituent.
The non-substituted 4-quinolone molecule (CSD refcode NICJOZ; Nasiri et al., 2006) is planar. Depending on the number, position and type of substituents, as well as the mode of crystal packing, the quinolone moiety (atoms N1/C2–C10/O1 for the structures presented herein; Fig. 1) can significantly deviate from planarity (by up to 0.23 Å in some quinolones; e.g. Polborn et al., 1992; Gulyakevich et al., 1999; Hashimoto et al., 2007). The quinolone moiety in (I) is almost planar [the largest deviation from the mean plane is 0.012 (2) Å for atom C3], whereas the quinolone moieties in (II) and (III) are more distorted from planarity, the largest displacement from the mean plane being that of keto atom O1 [0.072 (2) Å in (II) and 0.102 (2) Å in (III)]. The observed difference in the quinolone (non)planarity between isomorphous structures (I) and (II) could be attributed to slightly different intermolecular interactions (see below). In all three studied structures, the non-H atoms in the ester moiety (C11–C13/O2/O3) are nearly coplanar. The angles between the mean planes of the quinolone and ester moieties are 9.54 (12), 9.88 (11) and 7.72 (13)° for (I), (II) and (III), respectively. The 3-carboxy and quinolone carbonyl groups are mutually in a syn conformation, as also observed for the crystal structures of several other 4-quinolone-3-carboxylic acid ethyl esters (Barrett et al., 1995, 1996; Al-Hiari et al., 2006; Ukrainets et al., 2007; Abu-Sheaib et al., 2008; Pan et al., 2008). The N-ethyl group in (I) is out of the quinolone plane, with a C9—N1—C14—C15 torsion angle of -78.0 (3)°. The angle between the planes through the N-cyclopropyl group (C14–C16) and the quinolone moiety in (II) is 59.92 (18)°, while the plane of the N-(dimethylamino) group (N2/C14/C15) is inclined to the mean plane of the quinolone moiety at 83.9 (2)° in (III).
Intermolecular halogen O···I bonds involving the quinolone keto groups (Table 1) play an important role in the solid-state supramolecular architectures of all three title quinolone esters. In all of these structures, molecules connected by O···I bonds form infinite zigzag chains parallel to the crystallographic b axis (Figs. 2 and 3). The mean quinolone planes of the two halogen-bonded molecules in (III) make an angle of 10.93 (5)°, while this angle is much larger in the structures of (I) and (II) [63.39 (5) and 70.37 (5)°, respectively]. As found by a search of the CSD, refcodes EVINIG (Song et al., 2004) and BAKSUC (Mphahlele et al., 2002) are the only two other quinolone structures with halogen bonds involving the quinolone keto group. In EVINIG (7-chloro-1-ethyl-6-fluoro-4-quinolone-3-carboxylic acid), O···Cl interactions connect the molecules into infinite chains. Contrary to the zigzag chains in (I), (II) and (III), the molecular chains formed by halogen bonding in EVINIG are straight, the quinolone moieties of the linked molecules being coplanar. In BAKSUC [3-bromo-2-(4'-fluorophenyl)-4-quinolone], six quinolone molecules are joined via O···Br bonds into a ring with R66(24) topology (Etter et al., 1990; Bernstein et al., 1995) and crystallographic 3 symmetry. There is only one example of iodine halogen bonding for the quinolone compounds (CSD refcode BARTIX; Keller et al., 1981), where a 6-iodo-4-quinolonium cation makes a discrete N···I interaction with a 7,7,8,8-tetracyanoquinodimethane molecule.
In the isomorphous structures of (I) and (II), each quinolone molecule is stacked between two neighbouring molecules, both belonging to the same molecular chain formed by halogen bonding (Fig. 2). Molecules from different chains are connected into centrosymmetric dimers by C—H···π interactions (Table 2), and packing along the crystallographic b axis is achieved by π–π interactions (Desiraju & Gavezzotti, 1989) between adjacent molecular dimers (Table 3). Therefore, each molecular chain forms zipper-like motifs with two adjacent chains, resulting in (101) molecular layers (Fig. 2). These layers are crosslinked by C—H···O interactions, but these are different in the two isomorphous structures (illustrated in Fig. 4 and Table 2). In the structure of (I), C—H···O interactions engage the N-ethyl and ester carbonyl groups. By contrast, molecules of (II) are linked by C—H···O interactions between the N-cyclopropyl and quinolone keto groups, thus accounting for the considerable displacement of keto atom O1 from the quinolone mean plane in (II) noted above. The molecular chains formed via the C—H···O interactions run in the [101] direction, and for both isomorphs can be described by graph-set motif C(8) (Fig. 4).
Molecules in (III) are arranged into (100) layers via C—H···π and C—H···O interactions (Table 2 and Fig. 5). C12—H12B···Cg2v and C15—H15A···O2v interactions form centrosymmetric dimers, similar to those observed in the structures of (I) and (II), which are then linked by C14—H14C···O1iv interactions (symmetry codes as in Table 2). If each molecular dimer is represented by a node, then the pattern created by the C14—H14C···O1iv interactions can be described as a two-dimensional network with (4,4) topology (Wells, 1977; Batten & Robson 1998; Fig. 5). As found in (II), the C14—H14C···O1iv interaction affects the planarity of the quinolone moiety by displacing keto atom O1 significantly from the mean quinolone plane. The (100) molecular layers are crosslinked by O···I and C—H···I interactions (Table 2).