Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807057662/is2240sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807057662/is2240Isup2.hkl |
CCDC reference: 672959
To a solution of the ethyl 3-[(isopropylimino)methyleneamino]benzofuran-2-carboxylate (3 mmol) in dichloromethane (5 ml) was added morpholine (3 mmol). After stirring the reaction mixture for 4 h, the solvent was removed and anhydrous ethanol (10 ml) with several drops of EtONa in EtOH was added. The mixture was stirred for 4 h at room temperature. The solution was concentrated under reduced pressure and purification was accomplished by column chromatography on silica gel to give the title compound in a yield of 84%. Crystals suitable for single-crystal X-ray diffraction were obtained by vapour diffusion a mixed solvent of ethanol and dichloromethane (1:1 v/v) at room temperature.
All H-atoms were positioned geometrically (C—H = 0.93–0.98 Å) and refined using a riding model with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2001).
C17H19N3O3 | F(000) = 664 |
Mr = 313.35 | Dx = 1.331 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3120 reflections |
a = 14.6943 (8) Å | θ = 2.8–25.0° |
b = 8.7163 (6) Å | µ = 0.09 mm−1 |
c = 12.8126 (10) Å | T = 295 K |
β = 107.656 (1)° | Block, colourless |
V = 1563.73 (18) Å3 | 0.30 × 0.20 × 0.20 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 3056 independent reflections |
Radiation source: fine-focus sealed tube | 2351 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
ϕ and ω scans | θmax = 26.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −17→18 |
Tmin = 0.973, Tmax = 0.982 | k = −10→10 |
10348 measured reflections | l = −15→15 |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0749P)2] where P = (Fo2 + 2Fc2)/3 |
3056 reflections | (Δ/σ)max < 0.001 |
208 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C17H19N3O3 | V = 1563.73 (18) Å3 |
Mr = 313.35 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.6943 (8) Å | µ = 0.09 mm−1 |
b = 8.7163 (6) Å | T = 295 K |
c = 12.8126 (10) Å | 0.30 × 0.20 × 0.20 mm |
β = 107.656 (1)° |
Bruker SMART CCD area-detector diffractometer | 3056 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2351 reflections with I > 2σ(I) |
Tmin = 0.973, Tmax = 0.982 | Rint = 0.055 |
10348 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.19 e Å−3 |
3056 reflections | Δρmin = −0.20 e Å−3 |
208 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 | 0.16216 (18) | 0.5943 (2) | −0.03191 (15) | 0.0677 (6) | |
H1A | 0.1847 | 0.5485 | −0.0885 | 0.081* | |
H1B | 0.0999 | 0.5510 | −0.0382 | 0.081* | |
C2 | 0.22977 (15) | 0.5537 (2) | 0.07802 (14) | 0.0536 (5) | |
H2A | 0.2315 | 0.4433 | 0.0878 | 0.064* | |
H2B | 0.2937 | 0.5884 | 0.0829 | 0.064* | |
C3 | 0.19492 (14) | 0.7938 (2) | 0.14628 (14) | 0.0486 (5) | |
H3A | 0.2579 | 0.8315 | 0.1500 | 0.058* | |
H3B | 0.1743 | 0.8448 | 0.2026 | 0.058* | |
C4 | 0.12570 (15) | 0.8262 (2) | 0.03509 (15) | 0.0557 (5) | |
H4A | 0.0627 | 0.7906 | 0.0333 | 0.067* | |
H4B | 0.1220 | 0.9362 | 0.0228 | 0.067* | |
C5 | 0.24703 (11) | 0.58098 (18) | 0.27059 (13) | 0.0346 (4) | |
C6 | 0.25432 (11) | 0.39190 (18) | 0.41491 (13) | 0.0380 (4) | |
C7 | 0.33065 (11) | 0.48739 (18) | 0.47503 (13) | 0.0367 (4) | |
C8 | 0.35964 (11) | 0.61393 (18) | 0.43272 (13) | 0.0352 (4) | |
C9 | 0.43885 (11) | 0.67559 (18) | 0.51855 (13) | 0.0388 (4) | |
C10 | 0.44830 (11) | 0.57894 (19) | 0.60791 (13) | 0.0392 (4) | |
C11 | 0.51631 (13) | 0.5987 (2) | 0.70796 (14) | 0.0489 (5) | |
H11 | 0.5211 | 0.5327 | 0.7664 | 0.059* | |
C12 | 0.57683 (13) | 0.7216 (2) | 0.71648 (16) | 0.0544 (5) | |
H12 | 0.6232 | 0.7403 | 0.7830 | 0.065* | |
C13 | 0.57051 (13) | 0.8188 (2) | 0.62820 (17) | 0.0554 (5) | |
H13 | 0.6134 | 0.8997 | 0.6368 | 0.066* | |
C14 | 0.50233 (13) | 0.7976 (2) | 0.52880 (16) | 0.0478 (5) | |
H14 | 0.4986 | 0.8626 | 0.4701 | 0.057* | |
C15 | 0.12556 (12) | 0.3688 (2) | 0.23733 (14) | 0.0427 (4) | |
H15 | 0.1030 | 0.4273 | 0.1690 | 0.051* | |
C16 | 0.04567 (13) | 0.3724 (3) | 0.28998 (17) | 0.0638 (6) | |
H16A | 0.0637 | 0.3120 | 0.3557 | 0.096* | |
H16B | −0.0116 | 0.3312 | 0.2399 | 0.096* | |
H16C | 0.0345 | 0.4764 | 0.3076 | 0.096* | |
C17 | 0.14822 (15) | 0.2078 (2) | 0.20649 (17) | 0.0598 (5) | |
H17A | 0.1975 | 0.2129 | 0.1716 | 0.090* | |
H17B | 0.0918 | 0.1630 | 0.1571 | 0.090* | |
H17C | 0.1696 | 0.1459 | 0.2713 | 0.090* | |
N1 | 0.19776 (9) | 0.62709 (15) | 0.16330 (11) | 0.0378 (3) | |
N2 | 0.21314 (9) | 0.44906 (14) | 0.30752 (10) | 0.0355 (3) | |
N3 | 0.31837 (9) | 0.66373 (15) | 0.32785 (11) | 0.0369 (3) | |
O1 | 0.15263 (10) | 0.75437 (16) | −0.04967 (10) | 0.0588 (4) | |
O2 | 0.22487 (9) | 0.27625 (14) | 0.44809 (10) | 0.0539 (4) | |
O3 | 0.38168 (8) | 0.46168 (14) | 0.58250 (9) | 0.0431 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.1010 (17) | 0.0613 (13) | 0.0350 (11) | 0.0039 (12) | 0.0117 (11) | −0.0025 (10) |
C2 | 0.0752 (13) | 0.0481 (11) | 0.0393 (11) | 0.0116 (9) | 0.0200 (10) | −0.0001 (8) |
C3 | 0.0659 (12) | 0.0399 (10) | 0.0391 (10) | 0.0046 (8) | 0.0146 (9) | 0.0044 (8) |
C4 | 0.0674 (13) | 0.0540 (11) | 0.0440 (11) | 0.0124 (9) | 0.0141 (10) | 0.0119 (9) |
C5 | 0.0393 (9) | 0.0324 (8) | 0.0332 (9) | 0.0022 (7) | 0.0126 (7) | 0.0010 (7) |
C6 | 0.0428 (9) | 0.0354 (9) | 0.0371 (9) | 0.0008 (7) | 0.0141 (8) | 0.0033 (7) |
C7 | 0.0419 (9) | 0.0385 (9) | 0.0291 (9) | 0.0040 (7) | 0.0097 (7) | 0.0032 (7) |
C8 | 0.0374 (8) | 0.0330 (8) | 0.0345 (9) | 0.0033 (7) | 0.0102 (7) | −0.0011 (7) |
C9 | 0.0419 (9) | 0.0350 (9) | 0.0388 (10) | 0.0045 (7) | 0.0110 (8) | −0.0058 (7) |
C10 | 0.0407 (9) | 0.0417 (9) | 0.0358 (9) | 0.0055 (7) | 0.0124 (8) | −0.0043 (7) |
C11 | 0.0499 (10) | 0.0587 (12) | 0.0363 (10) | 0.0064 (9) | 0.0105 (8) | −0.0050 (9) |
C12 | 0.0487 (11) | 0.0624 (13) | 0.0439 (11) | 0.0080 (9) | 0.0017 (9) | −0.0188 (10) |
C13 | 0.0490 (11) | 0.0461 (11) | 0.0650 (14) | −0.0027 (8) | 0.0081 (10) | −0.0155 (10) |
C14 | 0.0472 (10) | 0.0409 (10) | 0.0522 (12) | 0.0001 (8) | 0.0104 (9) | −0.0052 (8) |
C15 | 0.0439 (10) | 0.0461 (10) | 0.0343 (9) | −0.0095 (7) | 0.0062 (8) | 0.0005 (8) |
C16 | 0.0426 (11) | 0.0864 (15) | 0.0617 (13) | −0.0057 (10) | 0.0150 (10) | −0.0009 (12) |
C17 | 0.0696 (13) | 0.0501 (11) | 0.0589 (13) | −0.0179 (10) | 0.0181 (11) | −0.0119 (10) |
N1 | 0.0454 (8) | 0.0365 (8) | 0.0308 (7) | −0.0003 (6) | 0.0107 (6) | 0.0026 (6) |
N2 | 0.0386 (7) | 0.0332 (7) | 0.0347 (8) | −0.0017 (6) | 0.0112 (6) | 0.0009 (6) |
N3 | 0.0404 (8) | 0.0348 (7) | 0.0349 (8) | −0.0021 (6) | 0.0105 (6) | 0.0019 (6) |
O1 | 0.0795 (9) | 0.0604 (9) | 0.0360 (7) | 0.0025 (7) | 0.0170 (7) | 0.0114 (6) |
O2 | 0.0622 (8) | 0.0488 (7) | 0.0486 (8) | −0.0137 (6) | 0.0135 (7) | 0.0134 (6) |
O3 | 0.0480 (7) | 0.0470 (7) | 0.0316 (7) | −0.0015 (5) | 0.0079 (5) | 0.0041 (5) |
C1—O1 | 1.414 (2) | C8—C9 | 1.441 (2) |
C1—C2 | 1.499 (3) | C9—C14 | 1.394 (2) |
C1—H1A | 0.9700 | C9—C10 | 1.394 (2) |
C1—H1B | 0.9700 | C10—C11 | 1.376 (2) |
C2—N1 | 1.461 (2) | C10—O3 | 1.384 (2) |
C2—H2A | 0.9700 | C11—C12 | 1.375 (3) |
C2—H2B | 0.9700 | C11—H11 | 0.9300 |
C3—N1 | 1.468 (2) | C12—C13 | 1.394 (3) |
C3—C4 | 1.505 (2) | C12—H12 | 0.9300 |
C3—H3A | 0.9700 | C13—C14 | 1.373 (3) |
C3—H3B | 0.9700 | C13—H13 | 0.9300 |
C4—O1 | 1.410 (2) | C14—H14 | 0.9300 |
C4—H4A | 0.9700 | C15—N2 | 1.5007 (19) |
C4—H4B | 0.9700 | C15—C16 | 1.521 (3) |
C5—N3 | 1.300 (2) | C15—C17 | 1.522 (3) |
C5—N2 | 1.392 (2) | C15—H15 | 0.9800 |
C5—N1 | 1.404 (2) | C16—H16A | 0.9600 |
C6—O2 | 1.2230 (19) | C16—H16B | 0.9600 |
C6—N2 | 1.415 (2) | C16—H16C | 0.9600 |
C6—C7 | 1.421 (2) | C17—H17A | 0.9600 |
C7—C8 | 1.353 (2) | C17—H17B | 0.9600 |
C7—O3 | 1.3719 (18) | C17—H17C | 0.9600 |
C8—N3 | 1.3664 (19) | ||
O1—C1—C2 | 112.91 (16) | O3—C10—C9 | 111.46 (14) |
O1—C1—H1A | 109.0 | C12—C11—C10 | 116.14 (18) |
C2—C1—H1A | 109.0 | C12—C11—H11 | 121.9 |
O1—C1—H1B | 109.0 | C10—C11—H11 | 121.9 |
C2—C1—H1B | 109.0 | C11—C12—C13 | 121.79 (18) |
H1A—C1—H1B | 107.8 | C11—C12—H12 | 119.1 |
N1—C2—C1 | 109.10 (16) | C13—C12—H12 | 119.1 |
N1—C2—H2A | 109.9 | C14—C13—C12 | 121.41 (18) |
C1—C2—H2A | 109.9 | C14—C13—H13 | 119.3 |
N1—C2—H2B | 109.9 | C12—C13—H13 | 119.3 |
C1—C2—H2B | 109.9 | C13—C14—C9 | 117.98 (18) |
H2A—C2—H2B | 108.3 | C13—C14—H14 | 121.0 |
N1—C3—C4 | 107.88 (14) | C9—C14—H14 | 121.0 |
N1—C3—H3A | 110.1 | N2—C15—C16 | 111.19 (14) |
C4—C3—H3A | 110.1 | N2—C15—C17 | 111.71 (14) |
N1—C3—H3B | 110.1 | C16—C15—C17 | 113.16 (16) |
C4—C3—H3B | 110.1 | N2—C15—H15 | 106.8 |
H3A—C3—H3B | 108.4 | C16—C15—H15 | 106.8 |
O1—C4—C3 | 112.25 (15) | C17—C15—H15 | 106.8 |
O1—C4—H4A | 109.2 | C15—C16—H16A | 109.5 |
C3—C4—H4A | 109.2 | C15—C16—H16B | 109.5 |
O1—C4—H4B | 109.2 | H16A—C16—H16B | 109.5 |
C3—C4—H4B | 109.2 | C15—C16—H16C | 109.5 |
H4A—C4—H4B | 107.9 | H16A—C16—H16C | 109.5 |
N3—C5—N2 | 125.23 (14) | H16B—C16—H16C | 109.5 |
N3—C5—N1 | 118.79 (14) | C15—C17—H17A | 109.5 |
N2—C5—N1 | 115.97 (13) | C15—C17—H17B | 109.5 |
O2—C6—N2 | 122.42 (14) | H17A—C17—H17B | 109.5 |
O2—C6—C7 | 126.76 (15) | C15—C17—H17C | 109.5 |
N2—C6—C7 | 110.81 (14) | H17A—C17—H17C | 109.5 |
C8—C7—O3 | 113.12 (14) | H17B—C17—H17C | 109.5 |
C8—C7—C6 | 123.54 (15) | C5—N1—C2 | 114.79 (13) |
O3—C7—C6 | 123.34 (14) | C5—N1—C3 | 114.31 (13) |
C7—C8—N3 | 123.58 (14) | C2—N1—C3 | 108.86 (14) |
C7—C8—C9 | 106.12 (14) | C5—N2—C6 | 121.99 (13) |
N3—C8—C9 | 130.30 (15) | C5—N2—C15 | 120.77 (13) |
C14—C9—C10 | 119.10 (16) | C6—N2—C15 | 117.04 (13) |
C14—C9—C8 | 135.96 (16) | C5—N3—C8 | 114.83 (14) |
C10—C9—C8 | 104.93 (15) | C4—O1—C1 | 110.59 (15) |
C11—C10—O3 | 124.98 (16) | C7—O3—C10 | 104.34 (12) |
C11—C10—C9 | 123.56 (17) | ||
O1—C1—C2—N1 | 56.7 (2) | N2—C5—N1—C3 | 147.50 (15) |
N1—C3—C4—O1 | −59.8 (2) | C1—C2—N1—C5 | 171.39 (15) |
O2—C6—C7—C8 | 179.81 (16) | C1—C2—N1—C3 | −59.0 (2) |
N2—C6—C7—C8 | −1.0 (2) | C4—C3—N1—C5 | −169.89 (14) |
O2—C6—C7—O3 | −1.1 (3) | C4—C3—N1—C2 | 60.28 (19) |
N2—C6—C7—O3 | 178.09 (13) | N3—C5—N2—C6 | 0.6 (2) |
O3—C7—C8—N3 | −178.91 (13) | N1—C5—N2—C6 | −178.25 (13) |
C6—C7—C8—N3 | 0.3 (3) | N3—C5—N2—C15 | 175.37 (15) |
O3—C7—C8—C9 | 1.80 (18) | N1—C5—N2—C15 | −3.4 (2) |
C6—C7—C8—C9 | −179.00 (15) | O2—C6—N2—C5 | 179.85 (15) |
C7—C8—C9—C14 | 177.12 (19) | C7—C6—N2—C5 | 0.6 (2) |
N3—C8—C9—C14 | −2.1 (3) | O2—C6—N2—C15 | 4.9 (2) |
C7—C8—C9—C10 | −1.57 (17) | C7—C6—N2—C15 | −174.36 (13) |
N3—C8—C9—C10 | 179.21 (16) | C16—C15—N2—C5 | −116.10 (17) |
C14—C9—C10—C11 | 1.4 (2) | C17—C15—N2—C5 | 116.43 (16) |
C8—C9—C10—C11 | −179.65 (15) | C16—C15—N2—C6 | 58.96 (19) |
C14—C9—C10—O3 | −178.08 (14) | C17—C15—N2—C6 | −68.51 (18) |
C8—C9—C10—O3 | 0.88 (17) | N2—C5—N3—C8 | −1.3 (2) |
O3—C10—C11—C12 | 179.25 (15) | N1—C5—N3—C8 | 177.44 (13) |
C9—C10—C11—C12 | −0.2 (2) | C7—C8—N3—C5 | 0.9 (2) |
C10—C11—C12—C13 | −1.1 (3) | C9—C8—N3—C5 | −179.98 (15) |
C11—C12—C13—C14 | 1.1 (3) | C3—C4—O1—C1 | 56.7 (2) |
C12—C13—C14—C9 | 0.2 (3) | C2—C1—O1—C4 | −55.0 (2) |
C10—C9—C14—C13 | −1.4 (2) | C8—C7—O3—C10 | −1.25 (17) |
C8—C9—C14—C13 | −179.94 (17) | C6—C7—O3—C10 | 179.55 (15) |
N3—C5—N1—C2 | 95.44 (18) | C11—C10—O3—C7 | −179.31 (15) |
N2—C5—N1—C2 | −85.67 (18) | C9—C10—O3—C7 | 0.16 (17) |
N3—C5—N1—C3 | −31.4 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C17—H17C···O2 | 0.96 | 2.44 | 3.015 (2) | 118 |
C16—H16A···O2 | 0.96 | 2.33 | 2.916 (2) | 119 |
C15—H15···N1 | 0.98 | 2.24 | 2.776 (2) | 113 |
Experimental details
Crystal data | |
Chemical formula | C17H19N3O3 |
Mr | 313.35 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 14.6943 (8), 8.7163 (6), 12.8126 (10) |
β (°) | 107.656 (1) |
V (Å3) | 1563.73 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.973, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10348, 3056, 2351 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.132, 1.02 |
No. of reflections | 3056 |
No. of parameters | 208 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.20 |
Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXTL (Sheldrick, 2001).
D—H···A | D—H | H···A | D···A | D—H···A |
C17—H17C···O2 | 0.96 | 2.44 | 3.015 (2) | 118 |
C16—H16A···O2 | 0.96 | 2.33 | 2.916 (2) | 119 |
C15—H15···N1 | 0.98 | 2.24 | 2.776 (2) | 113 |
Pyrimidine derivatives are attracting increasing attention in the synthetic chemistry community because of the important role played by such systems in many natural products, antibiotics and drugs (Hayakawa et al., 2007; Aly, 2005). In recent years, we have been engaged in the preparation of derivatives of heterocycles using the aza-Wittig reaction (Ding et al., 2004). Some X-ray crystal structures of fused pyrimidinone derivatives have been reported (Hu et al., 2005, 2006, 2007). In this paper, we present X-ray crystallographic analysis of the compound, (I), which may be used as a new precursor for obtaining bioactive molecules.
In the molecule, the bond lengths and angles are unexceptional. All ring atoms in the benzofuro[3,2-d]pyrimidine system are essentially coplanar (Fig. 1). The morpholino ring shows a distorted chair conformation [ϕ = 203 (2)° and θ = 5.75 (2)°, puckering amplitude = 0.574 (2) Å]. Intramolecular C—H···O and C—H···N hydrogen bonds stabilize the conformation of the molecule (Table 1). Further stability of the crystal structure is provided by offset π–π stacking interactions (Janiak, 2000) involving the fused benzofuro[3,2-d]pyrimidine system (Fig. 2). The interplanar distance is 3.355 (1)–3.376 (1) Å, with distances of 3.497 (1)–3.584 (1) Å between adjacent ring centroids (symmetry code relating the adjacent ring: 1 - x, 1 - y, 1 - z).