The title compound, C
17H
13NO
4, exists as a planar molecule; adjacent molecules are linked by electrostatic C-H

O [C

O = 3.318 (4) and 3.455 (4) Å] interactions into a linear chain.
Supporting information
CCDC reference: 150392
7-Methoxy-3-aminocoumarin (Khoo, 1999) was condensed with salicylaldehyde in chloroform to yield the Schiff base (m.p. 410–411 K) in 60% yield. CNH elemental analysis: found (calculated) for C17H13NO4: C 68.50 (69.15), H 3.56 (4.41), N 4.87% (4.75%). Yellow–orange plates were obtained upon recrystallization with benzene.
Data collection: XSCANS (Siemens, 1998); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.
7-Methoxy-3-(salicylideneamino)coumarin
top
Crystal data top
C17H13NO4 | F(000) = 616 |
Mr = 295.28 | Dx = 1.425 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 6.660 (1) Å | Cell parameters from 24 reflections |
b = 31.984 (8) Å | θ = 3.5–12.5° |
c = 7.123 (2) Å | µ = 0.10 mm−1 |
β = 114.93 (2)° | T = 298 K |
V = 1375.9 (6) Å3 | Plate, yellow |
Z = 4 | 0.60 × 0.40 × 0.14 mm |
Data collection top
Siemens P4 four-circle diffractometer | 1449 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.027 |
Graphite monochromator | θmax = 25.0°, θmin = 2.6° |
ω scans | h = −1→7 |
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968) | k = −1→38 |
Tmin = 0.875, Tmax = 0.966 | l = −8→8 |
3194 measured reflections | 3 standard reflections every 97 reflections |
2416 independent reflections | intensity decay: none |
Refinement top
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)] = 0.056 | H-atom parameters constrained |
wR(F2) = 0.172 | w = 1/[σ2(Fo2) + (0.0731P)2 + 0.6431P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2416 reflections | Δρmax = 0.24 e Å−3 |
202 parameters | Δρmin = −0.24 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: 0.002 (1) |
Crystal data top
C17H13NO4 | V = 1375.9 (6) Å3 |
Mr = 295.28 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.660 (1) Å | µ = 0.10 mm−1 |
b = 31.984 (8) Å | T = 298 K |
c = 7.123 (2) Å | 0.60 × 0.40 × 0.14 mm |
β = 114.93 (2)° | |
Data collection top
Siemens P4 four-circle diffractometer | 1449 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968) | Rint = 0.027 |
Tmin = 0.875, Tmax = 0.966 | 3 standard reflections every 97 reflections |
3194 measured reflections | intensity decay: none |
2416 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.172 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.24 e Å−3 |
2416 reflections | Δρmin = −0.24 e Å−3 |
202 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 1.1196 (3) | 0.2142 (1) | 0.7412 (4) | 0.042 (1) | |
O2 | 1.2663 (4) | 0.2757 (1) | 0.7495 (5) | 0.057 (1) | |
O3 | 0.8488 (4) | 0.0768 (1) | 0.7442 (4) | 0.055 (1) | |
O4 | 0.6349 (5) | 0.3785 (1) | 0.8008 (5) | 0.062 (1) | |
N1 | 0.8780 (4) | 0.3180 (1) | 0.7586 (4) | 0.037 (1) | |
C1 | 0.9576 (5) | 0.3900 (1) | 0.7389 (5) | 0.040 (1) | |
C2 | 0.7764 (6) | 0.4049 (1) | 0.7712 (5) | 0.046 (1) | |
C3 | 0.7418 (7) | 0.4473 (1) | 0.7733 (6) | 0.059 (1) | |
C4 | 0.8810 (7) | 0.4753 (1) | 0.7440 (6) | 0.059 (1) | |
C5 | 1.0596 (6) | 0.4615 (1) | 0.7103 (6) | 0.056 (1) | |
C6 | 1.0964 (6) | 0.4193 (1) | 0.7081 (5) | 0.049 (1) | |
C7 | 1.0050 (5) | 0.3462 (1) | 0.7364 (5) | 0.041 (1) | |
C8 | 1.1100 (5) | 0.2570 (1) | 0.7495 (5) | 0.039 (1) | |
C9 | 0.9126 (5) | 0.2751 (1) | 0.7584 (4) | 0.035 (1) | |
C10 | 0.7575 (5) | 0.2494 (1) | 0.7712 (5) | 0.037 (1) | |
C11 | 0.7766 (5) | 0.2050 (1) | 0.7683 (5) | 0.036 (1) | |
C12 | 0.9594 (5) | 0.1882 (1) | 0.7502 (5) | 0.036 (1) | |
C13 | 0.9919 (5) | 0.1461 (1) | 0.7396 (5) | 0.042 (1) | |
C14 | 0.8375 (5) | 0.1190 (1) | 0.7512 (5) | 0.041 (1) | |
C15 | 0.6499 (6) | 0.1347 (1) | 0.7704 (5) | 0.045 (1) | |
C16 | 0.6213 (5) | 0.1766 (1) | 0.7782 (5) | 0.042 (1) | |
C17 | 1.0282 (6) | 0.0597 (1) | 0.7112 (7) | 0.060 (1) | |
H3 | 0.6217 | 0.4570 | 0.7950 | 0.088* | |
H4 | 0.6690 | 0.3543 | 0.7891 | 0.093* | |
H4a | 0.8552 | 0.5038 | 0.7468 | 0.089* | |
H5 | 1.1537 | 0.4806 | 0.6893 | 0.084* | |
H6 | 1.2167 | 0.4099 | 0.6856 | 0.074* | |
H7 | 1.1297 | 0.3380 | 0.7184 | 0.061* | |
H10 | 0.6349 | 0.2609 | 0.7823 | 0.055* | |
H13 | 1.1156 | 0.1360 | 0.7248 | 0.063* | |
H15 | 0.5451 | 0.1164 | 0.7777 | 0.068* | |
H16 | 0.4961 | 0.1866 | 0.7903 | 0.064* | |
H17a | 1.0332 | 0.0724 | 0.5911 | 0.090* | |
H17b | 1.0081 | 0.0301 | 0.6904 | 0.090* | |
H17c | 1.1644 | 0.0652 | 0.8299 | 0.090* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.029 (1) | 0.044 (1) | 0.057 (1) | 0.005 (1) | 0.022 (1) | −0.001 (1) |
O2 | 0.036 (1) | 0.055 (2) | 0.088 (2) | 0.002 (1) | 0.035 (1) | 0.005 (1) |
O3 | 0.053 (2) | 0.043 (1) | 0.070 (2) | 0.002 (1) | 0.026 (1) | 0.002 (1) |
O4 | 0.060 (2) | 0.050 (2) | 0.094 (2) | 0.008 (1) | 0.051 (2) | 0.008 (2) |
N1 | 0.033 (1) | 0.042 (2) | 0.037 (2) | 0.006 (1) | 0.014 (1) | 0.000 (1) |
C1 | 0.038 (2) | 0.046 (2) | 0.032 (2) | 0.001 (1) | 0.011 (1) | −0.001 (1) |
C2 | 0.048 (2) | 0.045 (2) | 0.049 (2) | 0.001 (2) | 0.025 (2) | 0.001 (2) |
C3 | 0.067 (3) | 0.050 (2) | 0.070 (3) | 0.011 (2) | 0.039 (2) | 0.001 (2) |
C4 | 0.071 (3) | 0.037 (2) | 0.068 (3) | 0.003 (2) | 0.028 (2) | −0.002 (2) |
C5 | 0.053 (2) | 0.048 (2) | 0.056 (2) | −0.011 (2) | 0.014 (2) | 0.003 (2) |
C6 | 0.041 (2) | 0.053 (2) | 0.049 (2) | −0.003 (2) | 0.014 (2) | 0.000 (2) |
C7 | 0.031 (2) | 0.051 (2) | 0.040 (2) | 0.008 (2) | 0.014 (1) | 0.002 (1) |
C8 | 0.028 (2) | 0.048 (2) | 0.038 (2) | 0.004 (1) | 0.013 (1) | 0.000 (1) |
C9 | 0.029 (2) | 0.044 (2) | 0.028 (2) | 0.008 (1) | 0.009 (1) | 0.001 (1) |
C10 | 0.030 (2) | 0.046 (2) | 0.036 (2) | 0.005 (1) | 0.016 (1) | −0.003 (1) |
C11 | 0.026 (1) | 0.051 (2) | 0.031 (2) | 0.005 (1) | 0.012 (1) | 0.003 (1) |
C12 | 0.025 (1) | 0.048 (2) | 0.034 (2) | 0.001 (1) | 0.011 (1) | 0.000 (1) |
C13 | 0.032 (2) | 0.049 (2) | 0.045 (2) | 0.009 (2) | 0.016 (1) | 0.001 (2) |
C14 | 0.039 (2) | 0.046 (2) | 0.035 (2) | 0.002 (2) | 0.011 (1) | 0.003 (1) |
C15 | 0.038 (2) | 0.054 (2) | 0.045 (2) | −0.004 (2) | 0.019 (2) | 0.004 (2) |
C16 | 0.032 (2) | 0.054 (2) | 0.045 (2) | 0.002 (2) | 0.020 (1) | 0.004 (2) |
C17 | 0.053 (2) | 0.048 (2) | 0.075 (3) | 0.009 (2) | 0.022 (2) | −0.010 (2) |
Geometric parameters (Å, º) top
O1—C12 | 1.375 (4) | C11—C16 | 1.401 (4) |
O1—C8 | 1.374 (4) | C12—C13 | 1.373 (5) |
O2—C8 | 1.201 (4) | C13—C14 | 1.373 (5) |
O3—C14 | 1.354 (4) | C14—C15 | 1.406 (5) |
O3—C17 | 1.420 (4) | C15—C16 | 1.357 (5) |
O4—C2 | 1.348 (4) | O4—H4 | 0.8200 |
N1—C7 | 1.292 (4) | C3—H3 | 0.9300 |
N1—C9 | 1.390 (4) | C4—H4a | 0.9300 |
C1—C6 | 1.395 (5) | C5—H5 | 0.9300 |
C1—C2 | 1.403 (5) | C6—H6 | 0.9300 |
C1—C7 | 1.438 (5) | C7—H7 | 0.9300 |
C2—C3 | 1.375 (5) | C10—H10 | 0.9300 |
C3—C4 | 1.368 (6) | C13—H13 | 0.9300 |
C4—C5 | 1.381 (6) | C15—H15 | 0.9300 |
C5—C6 | 1.375 (5) | C16—H16 | 0.9300 |
C8—C9 | 1.462 (4) | C17—H17a | 0.9600 |
C9—C10 | 1.355 (4) | C17—H17b | 0.9600 |
C10—C11 | 1.426 (4) | C17—H17c | 0.9600 |
C11—C12 | 1.385 (4) | | |
| | | |
C12—O1—C8 | 123.3 (2) | O3—C14—C15 | 115.2 (3) |
C14—O3—C17 | 117.0 (3) | C13—C14—C15 | 120.0 (3) |
C7—N1—C9 | 124.9 (3) | C16—C15—C14 | 120.2 (3) |
C6—C1—C2 | 118.1 (3) | C15—C16—C11 | 121.2 (3) |
C6—C1—C7 | 119.2 (3) | C2—O4—H4 | 109.5 |
C2—C1—C7 | 122.7 (3) | C4—C3—H3 | 119.4 |
O4—C2—C3 | 119.0 (3) | C2—C3—H3 | 119.4 |
O4—C2—C1 | 121.3 (3) | C3—C4—H4a | 119.8 |
C3—C2—C1 | 119.7 (3) | C5—C4—H4a | 119.8 |
C4—C3—C2 | 121.1 (4) | C6—C5—H5 | 120.4 |
C3—C4—C5 | 120.4 (4) | C4—C5—H5 | 120.4 |
C6—C5—C4 | 119.1 (4) | C5—C6—H6 | 119.2 |
C5—C6—C1 | 121.6 (4) | C1—C6—H6 | 119.2 |
N1—C7—C1 | 121.4 (3) | N1—C7—H7 | 119.3 |
O2—C8—O1 | 116.1 (3) | C1—C7—H7 | 119.3 |
O2—C8—C9 | 126.7 (3) | C9—C10—H10 | 119.0 |
O1—C8—C9 | 117.1 (3) | C11—C10—H10 | 119.0 |
C10—C9—N1 | 118.0 (3) | C12—C13—H13 | 120.8 |
C10—C9—C8 | 119.1 (3) | C14—C13—H13 | 120.8 |
N1—C9—C8 | 122.9 (3) | C16—C15—H15 | 119.9 |
C9—C10—C11 | 122.0 (3) | C14—C15—H15 | 119.9 |
C12—C11—C16 | 116.8 (3) | C15—C16—H16 | 119.4 |
C12—C11—C10 | 118.3 (3) | C11—C16—H16 | 119.4 |
C16—C11—C10 | 124.9 (3) | O3—C17—H17a | 109.5 |
C13—C12—O1 | 116.6 (3) | O3—C17—H17b | 109.5 |
C13—C12—C11 | 123.4 (3) | H17a—C17—H17b | 109.5 |
O1—C12—C11 | 120.0 (3) | O3—C17—H17b | 109.5 |
C12—C13—C14 | 118.4 (3) | H17a—C17—H17c | 109.5 |
O3—C14—C13 | 124.8 (3) | H17b—C17—H17c | 109.5 |
| | | |
C6—C1—C2—O4 | 179.6 (3) | N1—C9—C10—C11 | 178.8 (3) |
C7—C1—C2—O4 | −0.3 (5) | C8—C9—C10—C11 | −2.5 (4) |
C6—C1—C2—C3 | −0.5 (5) | C9—C10—C11—C12 | −0.5 (4) |
C7—C1—C2—C3 | 179.5 (3) | C9—C10—C11—C16 | −179.1 (3) |
O4—C2—C3—C4 | 180.0 (4) | C8—O1—C12—C13 | 179.8 (3) |
C1—C2—C3—C4 | 0.1 (6) | C8—O1—C12—C11 | 0.1 (4) |
C2—C3—C4—C5 | 0.4 (7) | C16—C11—C12—C13 | 0.7 (5) |
C3—C4—C5—C6 | −0.5 (6) | C10—C11—C12—C13 | −178.0 (3) |
C4—C5—C6—C1 | 0.1 (6) | C16—C11—C12—O1 | −179.5 (3) |
C2—C1—C6—C5 | 0.4 (5) | C10—C11—C12—O1 | 1.8 (4) |
C7—C1—C6—C5 | −179.6 (3) | O1—C12—C13—C14 | 179.0 (3) |
C9—N1—C7—C1 | −179.9 (3) | C11—C12—C13—C14 | −1.2 (5) |
C6—C1—C7—N1 | −178.1 (3) | C17—O3—C14—C13 | −3.5 (5) |
C2—C1—C7—N1 | 1.9 (5) | C17—O3—C14—C15 | 176.0 (3) |
C12—O1—C8—O2 | 176.7 (3) | C12—C13—C14—O3 | −179.6 (3) |
C12—O1—C8—C9 | −3.0 (4) | C12—C13—C14—C15 | 0.9 (5) |
C7—N1—C9—C10 | −176.2 (3) | O3—C14—C15—C16 | −179.8 (3) |
C7—N1—C9—C8 | 5.2 (5) | C13—C14—C15—C16 | −0.2 (5) |
O2—C8—C9—C10 | −175.5 (3) | C14—C15—C16—C11 | −0.3 (5) |
O1—C8—C9—C10 | 4.1 (4) | C12—C11—C16—C15 | 0.1 (5) |
O2—C8—C9—N1 | 3.1 (5) | C10—C11—C16—C15 | 178.7 (3) |
O1—C8—C9—N1 | −177.3 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···N1 | 0.82 | 1.89 | 2.620 (3) | 147 |
C16—H16···O1i | 0.93 | 2.54 | 3.455 (4) | 168 |
C10—H10···O2i | 0.93 | 2.41 | 3.318 (4) | 165 |
Symmetry code: (i) x−1, y, z. |
Experimental details
Crystal data |
Chemical formula | C17H13NO4 |
Mr | 295.28 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 6.660 (1), 31.984 (8), 7.123 (2) |
β (°) | 114.93 (2) |
V (Å3) | 1375.9 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.60 × 0.40 × 0.14 |
|
Data collection |
Diffractometer | Siemens P4 four-circle diffractometer |
Absorption correction | Empirical (using intensity measurements) via ψ scan (North et al., 1968) |
Tmin, Tmax | 0.875, 0.966 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3194, 2416, 1449 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.594 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.172, 1.05 |
No. of reflections | 2416 |
No. of parameters | 202 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.24 |
Selected geometric parameters (Å, º) topO1—C12 | 1.375 (4) | C3—C4 | 1.368 (6) |
O1—C8 | 1.374 (4) | C4—C5 | 1.381 (6) |
O2—C8 | 1.201 (4) | C5—C6 | 1.375 (5) |
O3—C14 | 1.354 (4) | C8—C9 | 1.462 (4) |
O3—C17 | 1.420 (4) | C9—C10 | 1.355 (4) |
O4—C2 | 1.348 (4) | C10—C11 | 1.426 (4) |
N1—C7 | 1.292 (4) | C11—C12 | 1.385 (4) |
N1—C9 | 1.390 (4) | C11—C16 | 1.401 (4) |
C1—C6 | 1.395 (5) | C12—C13 | 1.373 (5) |
C1—C2 | 1.403 (5) | C13—C14 | 1.373 (5) |
C1—C7 | 1.438 (5) | C14—C15 | 1.406 (5) |
C2—C3 | 1.375 (5) | C15—C16 | 1.357 (5) |
| | | |
C12—O1—C8 | 123.3 (2) | C10—C9—N1 | 118.0 (3) |
C14—O3—C17 | 117.0 (3) | C10—C9—C8 | 119.1 (3) |
C7—N1—C9 | 124.9 (3) | N1—C9—C8 | 122.9 (3) |
C6—C1—C2 | 118.1 (3) | C9—C10—C11 | 122.0 (3) |
C6—C1—C7 | 119.2 (3) | C12—C11—C16 | 116.8 (3) |
C2—C1—C7 | 122.7 (3) | C12—C11—C10 | 118.3 (3) |
O4—C2—C3 | 119.0 (3) | C16—C11—C10 | 124.9 (3) |
O4—C2—C1 | 121.3 (3) | C13—C12—O1 | 116.6 (3) |
C3—C2—C1 | 119.7 (3) | C13—C12—C11 | 123.4 (3) |
C4—C3—C2 | 121.1 (4) | O1—C12—C11 | 120.0 (3) |
C3—C4—C5 | 120.4 (4) | C12—C13—C14 | 118.4 (3) |
C6—C5—C4 | 119.1 (4) | O3—C14—C13 | 124.8 (3) |
C5—C6—C1 | 121.6 (4) | O3—C14—C15 | 115.2 (3) |
N1—C7—C1 | 121.4 (3) | C13—C14—C15 | 120.0 (3) |
O2—C8—O1 | 116.1 (3) | C16—C15—C14 | 120.2 (3) |
O2—C8—C9 | 126.7 (3) | C15—C16—C11 | 121.2 (3) |
O1—C8—C9 | 117.1 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···N1 | 0.82 | 1.89 | 2.620 (3) | 147.0 |
C16—H16···O1i | 0.93 | 2.54 | 3.455 (4) | 168.0 |
C10—H10···O2i | 0.93 | 2.41 | 3.318 (4) | 164.6 |
Symmetry code: (i) x−1, y, z. |
Our observation that the fluorescence quantum yield (relative to quinine sulfate) of 7-methoxy-3-(salicylideneamino)coumarin, (I), in methanol is twice that of unsubstituted 3-(salicylideneamino)coumarin in methanol prompted us to carry out an X-ray analysis of (I). Compound (I) exists as discrete molecules; however, adjacent molecules are linked by a pair of C—H···O interactions into chains. These interactions are not van der Waals contacts; these are electrostatic attractions, as the distances and angles compare well with values accepted for conventional C—H···X hydrogen bonding (Iyere et al., 1998; Ng, 1999). Such interactions are not present in, for example, coumarin-3-carboxylic acid (Dobson & Gerkin, 1996) and 3-(2-benzothiazolyl)-7-(diethylamino)coumarin (Jasinski & Paight, 1995); in these two compounds, the 4- and 5-positions of the coumarin unit are not substituted.