Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807061326/hb2659sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807061326/hb2659Isup2.hkl |
CCDC reference: 673105
The title compound was prepared according to the method of Zhao & Huang (1993) and colourless blocks of (I) were recrystallized from ethyl acetate in 90% yield (m.p. 474–475 K). IR: ν= 3296 (NH), 1679 (lactam CO), 1627 (CO), 1599, 1521 cm-1. 1H-NMR:δ= 9.46 (s, 1H), 7.42 (d, 2H), 6.87 (d, 2H), 3.94 (t, 2H), 3.80 (t, 2H), 3.81 (s, 3H), 2.74 (t, 2H), 2.50 p.p.m. (t, 2H). 13C-NMR: δ= 190.1, 169.3, 160.5, 156.8, 133.5, 127.4, 128.9, 113.1, 85.2, 55.2, 42.6, 41.7, 32.5, 22.5 p.p.m.. MS: m/z = 272 (M+, 35), 271 (80), 244 (32), 229 (13), 215 (5), 163 (10), 135 (100) Anal. Calcd. for C15H16N2O3: C 66.16, H 5.92, N 10.29%; found: C 66.74, H 5.73, N 10.40%.
The H atoms were positioned geometrically (C—H = 0.93–0.97 Å, N—H = 0.86 Å) and refined as riding with Uiso(H) = 1.2Ueq(C, N) or 1.5Ueq(methyl C).
Data collection: RAPID-AUTO (Rigaku, 2001); cell refinement: RAPID-AUTO (Rigaku, 2001); data reduction: RAPID-AUTO (Rigaku, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
C15H16N2O3 | Z = 2 |
Mr = 272.30 | F(000) = 288 |
Triclinic, P1 | Dx = 1.391 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71069 Å |
a = 7.1455 (3) Å | Cell parameters from 5329 reflections |
b = 9.4356 (3) Å | θ = 2.3–27.5° |
c = 10.5282 (3) Å | µ = 0.10 mm−1 |
α = 80.565 (1)° | T = 296 K |
β = 79.468 (1)° | Block, colorless |
γ = 69.568 (1)° | 0.28 × 0.26 × 0.15 mm |
V = 650.10 (4) Å3 |
Rigaku R-AXIS RAPID IP area-detector diffractometer | 2958 independent reflections |
Radiation source: rotating anode | 2314 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω scans at fixed χ = 45° | θmax = 27.5°, θmin = 2.3° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −9→9 |
Tmin = 0.973, Tmax = 0.985 | k = −11→12 |
5329 measured reflections | l = −13→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)] = 0.067 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.15 | w = 1/[σ2(Fo2) + (0.0533P)2 + 0.282P] where P = (Fo2 + 2Fc2)/3 |
2958 reflections | (Δ/σ)max < 0.001 |
181 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C15H16N2O3 | γ = 69.568 (1)° |
Mr = 272.30 | V = 650.10 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.1455 (3) Å | Mo Kα radiation |
b = 9.4356 (3) Å | µ = 0.10 mm−1 |
c = 10.5282 (3) Å | T = 296 K |
α = 80.565 (1)° | 0.28 × 0.26 × 0.15 mm |
β = 79.468 (1)° |
Rigaku R-AXIS RAPID IP area-detector diffractometer | 2958 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2314 reflections with I > 2σ(I) |
Tmin = 0.973, Tmax = 0.985 | Rint = 0.025 |
5329 measured reflections |
R[F2 > 2σ(F2)] = 0.067 | 0 restraints |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.15 | Δρmax = 0.28 e Å−3 |
2958 reflections | Δρmin = −0.20 e Å−3 |
181 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 | 0.8836 (5) | 1.0184 (3) | 0.1877 (3) | 0.0592 (8) | |
H1A | 1.0187 | 0.9874 | 0.1403 | 0.071* | |
H1B | 0.8321 | 1.1285 | 0.1832 | 0.071* | |
C2 | 0.7469 (4) | 0.9591 (3) | 0.1340 (2) | 0.0501 (6) | |
H2A | 0.6389 | 1.0419 | 0.0977 | 0.060* | |
H2B | 0.8215 | 0.8928 | 0.0674 | 0.060* | |
C3 | 0.4947 (3) | 0.8389 (2) | 0.2575 (2) | 0.0383 (5) | |
C4 | 0.4227 (4) | 0.7760 (3) | 0.3901 (2) | 0.0457 (6) | |
H4A | 0.3499 | 0.7095 | 0.3810 | 0.055* | |
H4B | 0.3292 | 0.8594 | 0.4362 | 0.055* | |
C5 | 0.5916 (4) | 0.6877 (3) | 0.4709 (2) | 0.0430 (6) | |
H5A | 0.6686 | 0.5921 | 0.4358 | 0.052* | |
H5B | 0.5341 | 0.6649 | 0.5595 | 0.052* | |
C6 | 0.7309 (3) | 0.7784 (2) | 0.4708 (2) | 0.0350 (5) | |
C7 | 0.7621 (3) | 0.8663 (2) | 0.3560 (2) | 0.0345 (5) | |
C8 | 0.8298 (3) | 0.7768 (3) | 0.5773 (2) | 0.0366 (5) | |
C9 | 0.8096 (3) | 0.6717 (2) | 0.6990 (2) | 0.0344 (5) | |
C10 | 0.8432 (3) | 0.5168 (3) | 0.6992 (2) | 0.0374 (5) | |
H10 | 0.8755 | 0.4751 | 0.6207 | 0.045* | |
C11 | 0.8293 (3) | 0.4245 (3) | 0.8146 (2) | 0.0393 (5) | |
H11 | 0.8545 | 0.3211 | 0.8133 | 0.047* | |
C12 | 0.7775 (3) | 0.4859 (3) | 0.9326 (2) | 0.0367 (5) | |
C13 | 0.7434 (4) | 0.6399 (3) | 0.9343 (2) | 0.0412 (5) | |
H13 | 0.7079 | 0.6820 | 1.0127 | 0.049* | |
C14 | 0.7629 (4) | 0.7300 (3) | 0.8180 (2) | 0.0401 (5) | |
H14 | 0.7441 | 0.8324 | 0.8197 | 0.048* | |
C15 | 0.7128 (4) | 0.4473 (3) | 1.1643 (2) | 0.0548 (7) | |
H15A | 0.7077 | 0.3675 | 1.2329 | 0.082* | |
H15B | 0.5835 | 0.5257 | 1.1671 | 0.082* | |
H15C | 0.8128 | 0.4891 | 1.1751 | 0.082* | |
N1 | 0.8829 (3) | 0.9503 (2) | 0.32159 (18) | 0.0438 (5) | |
H1 | 0.9539 | 0.9629 | 0.3739 | 0.053* | |
N2 | 0.6675 (3) | 0.8741 (2) | 0.24873 (17) | 0.0378 (4) | |
O1 | 0.4075 (3) | 0.8629 (2) | 0.16296 (16) | 0.0515 (5) | |
O2 | 0.9317 (3) | 0.8615 (2) | 0.57509 (16) | 0.0530 (5) | |
O3 | 0.7638 (3) | 0.38697 (19) | 1.04175 (16) | 0.0501 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.082 (2) | 0.0592 (17) | 0.0498 (15) | −0.0444 (16) | −0.0190 (14) | 0.0165 (13) |
C2 | 0.0537 (15) | 0.0629 (17) | 0.0365 (13) | −0.0280 (13) | −0.0069 (11) | 0.0079 (11) |
C3 | 0.0376 (12) | 0.0355 (12) | 0.0425 (12) | −0.0105 (9) | −0.0103 (9) | −0.0046 (9) |
C4 | 0.0395 (13) | 0.0593 (16) | 0.0455 (13) | −0.0253 (12) | −0.0079 (10) | −0.0027 (11) |
C5 | 0.0494 (14) | 0.0503 (14) | 0.0373 (12) | −0.0292 (11) | −0.0080 (10) | 0.0045 (10) |
C6 | 0.0367 (11) | 0.0380 (12) | 0.0329 (11) | −0.0165 (9) | −0.0047 (9) | −0.0015 (9) |
C7 | 0.0327 (11) | 0.0362 (12) | 0.0361 (11) | −0.0117 (9) | −0.0058 (9) | −0.0060 (9) |
C8 | 0.0395 (12) | 0.0369 (12) | 0.0366 (11) | −0.0166 (10) | −0.0048 (9) | −0.0045 (9) |
C9 | 0.0340 (11) | 0.0367 (12) | 0.0355 (11) | −0.0138 (9) | −0.0099 (9) | −0.0016 (9) |
C10 | 0.0377 (12) | 0.0405 (13) | 0.0357 (11) | −0.0123 (10) | −0.0068 (9) | −0.0082 (9) |
C11 | 0.0411 (12) | 0.0301 (12) | 0.0473 (13) | −0.0105 (10) | −0.0098 (10) | −0.0040 (9) |
C12 | 0.0319 (11) | 0.0387 (12) | 0.0390 (12) | −0.0128 (9) | −0.0080 (9) | 0.0030 (9) |
C13 | 0.0495 (14) | 0.0421 (13) | 0.0338 (11) | −0.0165 (11) | −0.0050 (10) | −0.0066 (9) |
C14 | 0.0497 (14) | 0.0339 (12) | 0.0393 (12) | −0.0167 (10) | −0.0077 (10) | −0.0031 (9) |
C15 | 0.0595 (17) | 0.0629 (18) | 0.0367 (13) | −0.0204 (14) | −0.0013 (11) | 0.0043 (12) |
N1 | 0.0530 (12) | 0.0529 (12) | 0.0356 (10) | −0.0327 (10) | −0.0076 (9) | 0.0028 (9) |
N2 | 0.0418 (10) | 0.0428 (11) | 0.0312 (9) | −0.0187 (9) | −0.0077 (8) | 0.0030 (8) |
O1 | 0.0528 (10) | 0.0615 (12) | 0.0470 (10) | −0.0228 (9) | −0.0214 (8) | 0.0010 (8) |
O2 | 0.0710 (12) | 0.0630 (12) | 0.0447 (10) | −0.0466 (10) | −0.0173 (8) | 0.0050 (8) |
O3 | 0.0636 (11) | 0.0465 (10) | 0.0398 (9) | −0.0223 (9) | −0.0067 (8) | 0.0052 (7) |
C1—N1 | 1.450 (3) | C7—N2 | 1.398 (3) |
C1—C2 | 1.508 (4) | C8—O2 | 1.251 (3) |
C1—H1A | 0.9700 | C8—C9 | 1.504 (3) |
C1—H1B | 0.9700 | C9—C14 | 1.389 (3) |
C2—N2 | 1.474 (3) | C9—C10 | 1.395 (3) |
C2—H2A | 0.9700 | C10—C11 | 1.384 (3) |
C2—H2B | 0.9700 | C10—H10 | 0.9300 |
C3—O1 | 1.219 (3) | C11—C12 | 1.391 (3) |
C3—N2 | 1.371 (3) | C11—H11 | 0.9300 |
C3—C4 | 1.498 (3) | C12—O3 | 1.369 (3) |
C4—C5 | 1.521 (3) | C12—C13 | 1.389 (3) |
C4—H4A | 0.9700 | C13—C14 | 1.386 (3) |
C4—H4B | 0.9700 | C13—H13 | 0.9300 |
C5—C6 | 1.522 (3) | C14—H14 | 0.9300 |
C5—H5A | 0.9700 | C15—O3 | 1.430 (3) |
C5—H5B | 0.9700 | C15—H15A | 0.9600 |
C6—C7 | 1.379 (3) | C15—H15B | 0.9600 |
C6—C8 | 1.426 (3) | C15—H15C | 0.9600 |
C7—N1 | 1.332 (3) | N1—H1 | 0.8600 |
N1—C1—C2 | 104.15 (19) | O2—C8—C9 | 117.80 (19) |
N1—C1—H1A | 110.9 | C6—C8—C9 | 119.50 (18) |
C2—C1—H1A | 110.9 | C14—C9—C10 | 118.0 (2) |
N1—C1—H1B | 110.9 | C14—C9—C8 | 118.47 (19) |
C2—C1—H1B | 110.9 | C10—C9—C8 | 123.47 (19) |
H1A—C1—H1B | 108.9 | C11—C10—C9 | 120.9 (2) |
N2—C2—C1 | 103.22 (18) | C11—C10—H10 | 119.5 |
N2—C2—H2A | 111.1 | C9—C10—H10 | 119.5 |
C1—C2—H2A | 111.1 | C10—C11—C12 | 120.2 (2) |
N2—C2—H2B | 111.1 | C10—C11—H11 | 119.9 |
C1—C2—H2B | 111.1 | C12—C11—H11 | 119.9 |
H2A—C2—H2B | 109.1 | O3—C12—C13 | 124.0 (2) |
O1—C3—N2 | 120.5 (2) | O3—C12—C11 | 116.3 (2) |
O1—C3—C4 | 124.4 (2) | C13—C12—C11 | 119.7 (2) |
N2—C3—C4 | 115.00 (19) | C14—C13—C12 | 119.4 (2) |
C3—C4—C5 | 113.69 (19) | C14—C13—H13 | 120.3 |
C3—C4—H4A | 108.8 | C12—C13—H13 | 120.3 |
C5—C4—H4A | 108.8 | C13—C14—C9 | 121.8 (2) |
C3—C4—H4B | 108.8 | C13—C14—H14 | 119.1 |
C5—C4—H4B | 108.8 | C9—C14—H14 | 119.1 |
H4A—C4—H4B | 107.7 | O3—C15—H15A | 109.5 |
C4—C5—C6 | 111.05 (19) | O3—C15—H15B | 109.5 |
C4—C5—H5A | 109.4 | H15A—C15—H15B | 109.5 |
C6—C5—H5A | 109.4 | O3—C15—H15C | 109.5 |
C4—C5—H5B | 109.4 | H15A—C15—H15C | 109.5 |
C6—C5—H5B | 109.4 | H15B—C15—H15C | 109.5 |
H5A—C5—H5B | 108.0 | C7—N1—C1 | 113.64 (19) |
C7—C6—C8 | 119.26 (19) | C7—N1—H1 | 123.2 |
C7—C6—C5 | 115.36 (19) | C1—N1—H1 | 123.2 |
C8—C6—C5 | 125.37 (19) | C3—N2—C7 | 123.54 (18) |
N1—C7—C6 | 130.3 (2) | C3—N2—C2 | 123.97 (18) |
N1—C7—N2 | 107.69 (18) | C7—N2—C2 | 110.89 (18) |
C6—C7—N2 | 121.94 (19) | C12—O3—C15 | 117.26 (19) |
O2—C8—C6 | 122.7 (2) | ||
N1—C1—C2—N2 | 5.2 (3) | C10—C11—C12—C13 | −1.2 (3) |
O1—C3—C4—C5 | 152.2 (2) | O3—C12—C13—C14 | 179.5 (2) |
N2—C3—C4—C5 | −29.9 (3) | C11—C12—C13—C14 | −0.4 (3) |
C3—C4—C5—C6 | 49.7 (3) | C12—C13—C14—C9 | 2.0 (3) |
C4—C5—C6—C7 | −35.5 (3) | C10—C9—C14—C13 | −2.0 (3) |
C4—C5—C6—C8 | 145.3 (2) | C8—C9—C14—C13 | −179.5 (2) |
C8—C6—C7—N1 | 3.8 (4) | C6—C7—N1—C1 | 175.9 (3) |
C5—C6—C7—N1 | −175.4 (2) | N2—C7—N1—C1 | −1.4 (3) |
C8—C6—C7—N2 | −179.2 (2) | C2—C1—N1—C7 | −2.6 (3) |
C5—C6—C7—N2 | 1.6 (3) | O1—C3—N2—C7 | 172.3 (2) |
C7—C6—C8—O2 | 6.0 (4) | C4—C3—N2—C7 | −5.7 (3) |
C5—C6—C8—O2 | −174.9 (2) | O1—C3—N2—C2 | 8.0 (4) |
C7—C6—C8—C9 | −175.1 (2) | C4—C3—N2—C2 | −170.0 (2) |
C5—C6—C8—C9 | 4.0 (3) | N1—C7—N2—C3 | −161.0 (2) |
O2—C8—C9—C14 | 46.4 (3) | C6—C7—N2—C3 | 21.4 (3) |
C6—C8—C9—C14 | −132.5 (2) | N1—C7—N2—C2 | 5.1 (3) |
O2—C8—C9—C10 | −130.9 (2) | C6—C7—N2—C2 | −172.5 (2) |
C6—C8—C9—C10 | 50.1 (3) | C1—C2—N2—C3 | 159.5 (2) |
C14—C9—C10—C11 | 0.4 (3) | C1—C2—N2—C7 | −6.5 (3) |
C8—C9—C10—C11 | 177.7 (2) | C13—C12—O3—C15 | −0.5 (3) |
C9—C10—C11—C12 | 1.2 (3) | C11—C12—O3—C15 | 179.4 (2) |
C10—C11—C12—O3 | 178.94 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.86 | 2.18 | 2.711 (2) | 120 |
N1—H1···O2i | 0.86 | 2.26 | 2.982 (2) | 142 |
Symmetry code: (i) −x+2, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C15H16N2O3 |
Mr | 272.30 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 7.1455 (3), 9.4356 (3), 10.5282 (3) |
α, β, γ (°) | 80.565 (1), 79.468 (1), 69.568 (1) |
V (Å3) | 650.10 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.28 × 0.26 × 0.15 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID IP area-detector diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.973, 0.985 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5329, 2958, 2314 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.067, 0.153, 1.15 |
No. of reflections | 2958 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.20 |
Computer programs: RAPID-AUTO (Rigaku, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.86 | 2.18 | 2.711 (2) | 120 |
N1—H1···O2i | 0.86 | 2.26 | 2.982 (2) | 142 |
Symmetry code: (i) −x+2, −y+2, −z+1. |
Heterocyclic ketene aminals can react with wide variety of organic compounds to afford different kinds of heterocyclic or fused heterocyclic compounds, therefore, they may be used as versatile synthetic inter-mediates in heterocyclic synthesis (Zhao & Huang, 1993).
The title compound is a representative of such reagents. As shown in Figs. 1 and 2, the packing is consolidated by intermolecular and intermolecular N—H···O hydrogen bonds (Table 1).