Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807027985/bi2189sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027985/bi2189Isup2.hkl |
CCDC reference: 655600
The title compound was prepared according to the procedure of Huang & Liu (1986) and recrystallized from ethyl acetate in 80% yield.
H atoms were placed geometrically with C—H = 0.93–0.97 Å or N—H = 0.86 Å and refined as riding with Uiso(H) = 1.2Ueq(C/N) or Uiso(H) = 1.5Ueq(methyl C).
Heterocyclic ketene aminals, also named cyclic 1,1-enediamines, are useful building blocks in organic synthesis, especially for the synthesis of heterocycles (Huang & Wang, 1994). The title compound (Fig. 1) was synthesized through consecutive nucleophilic addition and cyclocondensation reactions. The crystal structure was determined to provide unambiguous evidence for the molecular configuration.
The six-membered 1,3-diazoheterocyclic ring C1/C2/C3/N2/C4/N1 adopts a twisted conformation, in which the C1/C2/C3/N2 and N1/C1/C2/C3 torsion angles are -52.5 (2) and 54.2 (2)°, respectively. The phenyl ring C10–C15 forms a dihedral angle of 54.1 (1)° to the pyrimidinone ring.
The title compound is a heterocyclic ketene aminal; compounds of this type are useful building blocks in organic synthesis, especially for the synthesis of heterocycles. See: Huang & Liu (1986); Huang & Wang (1994).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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.
C16H16N2O3 | Z = 2 |
Mr = 284.12 | F(000) = 300 |
Triclinic, P1 | Dx = 1.393 Mg m−3 |
Hall symbol: -P 1 | Melting point = 437–439 K |
a = 7.9544 (18) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.3320 (19) Å | Cell parameters from 1694 reflections |
c = 11.063 (3) Å | θ = 2.5–26.4° |
α = 77.913 (3)° | µ = 0.10 mm−1 |
β = 73.384 (4)° | T = 294 K |
γ = 77.641 (4)° | Prism, colorless |
V = 677.7 (3) Å3 | 0.20 × 0.18 × 0.16 mm |
Bruker SMART CCD diffractometer | 1814 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.017 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
ω and φ scans | h = −9→4 |
3460 measured reflections | k = −9→9 |
2370 independent reflections | l = −13→12 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0568P)2 + 0.1309P] where P = (Fo2 + 2Fc2)/3 |
2370 reflections | (Δ/σ)max < 0.001 |
191 parameters | Δρmax = 0.12 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C16H16N2O3 | γ = 77.641 (4)° |
Mr = 284.12 | V = 677.7 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.9544 (18) Å | Mo Kα radiation |
b = 8.3320 (19) Å | µ = 0.10 mm−1 |
c = 11.063 (3) Å | T = 294 K |
α = 77.913 (3)° | 0.20 × 0.18 × 0.16 mm |
β = 73.384 (4)° |
Bruker SMART CCD diffractometer | 1814 reflections with I > 2σ(I) |
3460 measured reflections | Rint = 0.017 |
2370 independent reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.12 e Å−3 |
2370 reflections | Δρmin = −0.16 e Å−3 |
191 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 | ||
O1 | 0.58919 (16) | 0.28590 (17) | 0.11492 (13) | 0.0664 (4) | |
O2 | −0.22334 (15) | 0.58455 (15) | 0.22135 (13) | 0.0572 (4) | |
O3 | −0.29821 (17) | 1.13578 (14) | 0.55187 (12) | 0.0580 (4) | |
N1 | 0.29385 (17) | 0.30686 (16) | 0.13068 (13) | 0.0438 (3) | |
N2 | −0.00321 (18) | 0.32891 (16) | 0.13146 (13) | 0.0470 (4) | |
H2 | −0.1095 | 0.3840 | 0.1478 | 0.056* | |
C1 | 0.3389 (3) | 0.1542 (2) | 0.0723 (2) | 0.0635 (5) | |
H1A | 0.4377 | 0.0815 | 0.1006 | 0.076* | |
H1B | 0.3757 | 0.1833 | −0.0199 | 0.076* | |
C2 | 0.1820 (3) | 0.0633 (2) | 0.10810 (19) | 0.0610 (5) | |
H2A | 0.2112 | −0.0306 | 0.0625 | 0.073* | |
H2B | 0.1541 | 0.0213 | 0.1990 | 0.073* | |
C3 | 0.0250 (2) | 0.1795 (2) | 0.07471 (17) | 0.0510 (4) | |
H3A | 0.0460 | 0.2086 | −0.0174 | 0.061* | |
H3B | −0.0798 | 0.1262 | 0.1069 | 0.061* | |
C4 | 0.1214 (2) | 0.38749 (18) | 0.16018 (14) | 0.0385 (4) | |
C5 | 0.0801 (2) | 0.53028 (18) | 0.22182 (14) | 0.0382 (4) | |
C6 | 0.2259 (2) | 0.5872 (2) | 0.23969 (16) | 0.0452 (4) | |
H6 | 0.2029 | 0.6824 | 0.2771 | 0.054* | |
C7 | 0.3953 (2) | 0.5109 (2) | 0.20547 (16) | 0.0499 (4) | |
H7 | 0.4854 | 0.5546 | 0.2190 | 0.060* | |
C8 | 0.4387 (2) | 0.3644 (2) | 0.14882 (15) | 0.0477 (4) | |
C9 | −0.0996 (2) | 0.61628 (19) | 0.25642 (16) | 0.0416 (4) | |
C10 | −0.1457 (2) | 0.75394 (18) | 0.33420 (15) | 0.0400 (4) | |
C11 | −0.2538 (2) | 0.8991 (2) | 0.29682 (15) | 0.0438 (4) | |
H11 | −0.2930 | 0.9084 | 0.2237 | 0.053* | |
C12 | −0.3050 (2) | 1.03035 (19) | 0.36520 (16) | 0.0459 (4) | |
H12 | −0.3734 | 1.1283 | 0.3362 | 0.055* | |
C13 | −0.2537 (2) | 1.01488 (19) | 0.47683 (15) | 0.0434 (4) | |
C14 | −0.1506 (2) | 0.8687 (2) | 0.51784 (16) | 0.0509 (4) | |
H14 | −0.1187 | 0.8564 | 0.5943 | 0.061* | |
C15 | −0.0949 (2) | 0.7414 (2) | 0.44651 (16) | 0.0482 (4) | |
H15 | −0.0221 | 0.6456 | 0.4738 | 0.058* | |
C16 | −0.3885 (3) | 1.2929 (2) | 0.5050 (2) | 0.0648 (5) | |
H16A | −0.3154 | 1.3387 | 0.4253 | 0.097* | |
H16B | −0.4122 | 1.3671 | 0.5658 | 0.097* | |
H16C | −0.4986 | 1.2790 | 0.4923 | 0.097* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0416 (7) | 0.0836 (10) | 0.0730 (9) | 0.0115 (6) | −0.0199 (6) | −0.0244 (7) |
O2 | 0.0383 (6) | 0.0571 (7) | 0.0841 (9) | −0.0064 (5) | −0.0148 (6) | −0.0305 (7) |
O3 | 0.0664 (8) | 0.0503 (7) | 0.0611 (8) | 0.0042 (6) | −0.0215 (6) | −0.0239 (6) |
N1 | 0.0419 (8) | 0.0427 (7) | 0.0465 (8) | 0.0027 (6) | −0.0141 (6) | −0.0123 (6) |
N2 | 0.0410 (8) | 0.0434 (8) | 0.0598 (9) | −0.0053 (6) | −0.0114 (6) | −0.0184 (6) |
C1 | 0.0541 (11) | 0.0619 (12) | 0.0782 (13) | 0.0136 (9) | −0.0207 (10) | −0.0369 (10) |
C2 | 0.0821 (14) | 0.0440 (10) | 0.0607 (11) | −0.0035 (9) | −0.0211 (10) | −0.0192 (8) |
C3 | 0.0549 (11) | 0.0496 (10) | 0.0513 (10) | −0.0113 (8) | −0.0082 (8) | −0.0185 (8) |
C4 | 0.0397 (9) | 0.0363 (8) | 0.0384 (8) | −0.0061 (6) | −0.0104 (7) | −0.0027 (6) |
C5 | 0.0383 (8) | 0.0343 (8) | 0.0427 (9) | −0.0063 (6) | −0.0114 (7) | −0.0055 (6) |
C6 | 0.0453 (9) | 0.0415 (9) | 0.0518 (10) | −0.0076 (7) | −0.0158 (8) | −0.0087 (7) |
C7 | 0.0395 (9) | 0.0584 (10) | 0.0567 (10) | −0.0091 (8) | −0.0174 (8) | −0.0113 (8) |
C8 | 0.0406 (9) | 0.0562 (10) | 0.0434 (9) | 0.0022 (8) | −0.0156 (7) | −0.0054 (8) |
C9 | 0.0392 (9) | 0.0365 (8) | 0.0497 (9) | −0.0101 (7) | −0.0093 (7) | −0.0067 (7) |
C10 | 0.0365 (8) | 0.0360 (8) | 0.0459 (9) | −0.0074 (6) | −0.0069 (7) | −0.0063 (7) |
C11 | 0.0425 (9) | 0.0463 (9) | 0.0434 (9) | −0.0036 (7) | −0.0129 (7) | −0.0095 (7) |
C12 | 0.0454 (9) | 0.0385 (9) | 0.0507 (10) | 0.0021 (7) | −0.0139 (8) | −0.0072 (7) |
C13 | 0.0433 (9) | 0.0395 (9) | 0.0461 (9) | −0.0057 (7) | −0.0068 (7) | −0.0114 (7) |
C14 | 0.0613 (11) | 0.0482 (10) | 0.0441 (9) | −0.0032 (8) | −0.0191 (8) | −0.0072 (8) |
C15 | 0.0549 (10) | 0.0357 (8) | 0.0511 (10) | −0.0006 (7) | −0.0169 (8) | −0.0024 (7) |
C16 | 0.0742 (13) | 0.0444 (10) | 0.0762 (13) | 0.0039 (9) | −0.0202 (11) | −0.0230 (9) |
O1—C8 | 1.2298 (19) | C5—C9 | 1.438 (2) |
O2—C9 | 1.2495 (19) | C6—C7 | 1.344 (2) |
O3—C13 | 1.3633 (18) | C6—H6 | 0.930 |
O3—C16 | 1.423 (2) | C7—C8 | 1.421 (2) |
N1—C4 | 1.3714 (19) | C7—H7 | 0.930 |
N1—C8 | 1.416 (2) | C9—C10 | 1.498 (2) |
N1—C1 | 1.476 (2) | C10—C11 | 1.386 (2) |
N2—C4 | 1.332 (2) | C10—C15 | 1.390 (2) |
N2—C3 | 1.457 (2) | C11—C12 | 1.384 (2) |
N2—H2 | 0.860 | C11—H11 | 0.930 |
C1—C2 | 1.512 (3) | C12—C13 | 1.381 (2) |
C1—H1A | 0.970 | C12—H12 | 0.930 |
C1—H1B | 0.970 | C13—C14 | 1.384 (2) |
C2—C3 | 1.493 (3) | C14—C15 | 1.376 (2) |
C2—H2A | 0.970 | C14—H14 | 0.930 |
C2—H2B | 0.970 | C15—H15 | 0.930 |
C3—H3A | 0.970 | C16—H16A | 0.960 |
C3—H3B | 0.970 | C16—H16B | 0.960 |
C4—C5 | 1.426 (2) | C16—H16C | 0.960 |
C5—C6 | 1.420 (2) | ||
C13—O3—C16 | 117.28 (14) | C6—C7—C8 | 120.88 (16) |
C4—N1—C8 | 123.72 (13) | C6—C7—H7 | 119.6 |
C4—N1—C1 | 120.34 (14) | C8—C7—H7 | 119.6 |
C8—N1—C1 | 115.91 (13) | O1—C8—N1 | 118.55 (16) |
C4—N2—C3 | 125.61 (14) | O1—C8—C7 | 125.50 (16) |
C4—N2—H2 | 117.2 | N1—C8—C7 | 115.94 (14) |
C3—N2—H2 | 117.2 | O2—C9—C5 | 122.69 (14) |
N1—C1—C2 | 111.30 (15) | O2—C9—C10 | 116.66 (14) |
N1—C1—H1A | 109.4 | C5—C9—C10 | 120.62 (14) |
C2—C1—H1A | 109.4 | C11—C10—C15 | 117.62 (14) |
N1—C1—H1B | 109.4 | C11—C10—C9 | 118.49 (14) |
C2—C1—H1B | 109.4 | C15—C10—C9 | 123.77 (14) |
H1A—C1—H1B | 108.0 | C12—C11—C10 | 121.86 (15) |
C3—C2—C1 | 109.44 (16) | C12—C11—H11 | 119.1 |
C3—C2—H2A | 109.8 | C10—C11—H11 | 119.1 |
C1—C2—H2A | 109.8 | C13—C12—C11 | 119.49 (14) |
C3—C2—H2B | 109.8 | C13—C12—H12 | 120.3 |
C1—C2—H2B | 109.8 | C11—C12—H12 | 120.3 |
H2A—C2—H2B | 108.2 | O3—C13—C12 | 124.20 (14) |
N2—C3—C2 | 108.93 (14) | O3—C13—C14 | 116.40 (15) |
N2—C3—H3A | 109.9 | C12—C13—C14 | 119.40 (15) |
C2—C3—H3A | 109.9 | C15—C14—C13 | 120.56 (16) |
N2—C3—H3B | 109.9 | C15—C14—H14 | 119.7 |
C2—C3—H3B | 109.9 | C13—C14—H14 | 119.7 |
H3A—C3—H3B | 108.3 | C14—C15—C10 | 120.98 (15) |
N2—C4—N1 | 118.91 (14) | C14—C15—H15 | 119.5 |
N2—C4—C5 | 121.85 (14) | C10—C15—H15 | 119.5 |
N1—C4—C5 | 119.23 (13) | O3—C16—H16A | 109.5 |
C6—C5—C4 | 116.56 (13) | O3—C16—H16B | 109.5 |
C6—C5—C9 | 122.47 (14) | H16A—C16—H16B | 109.5 |
C4—C5—C9 | 120.86 (13) | O3—C16—H16C | 109.5 |
C7—C6—C5 | 123.47 (15) | H16A—C16—H16C | 109.5 |
C7—C6—H6 | 118.3 | H16B—C16—H16C | 109.5 |
C5—C6—H6 | 118.3 | ||
C4—N1—C1—C2 | −26.8 (2) | C6—C7—C8—O1 | −179.74 (17) |
C8—N1—C1—C2 | 155.27 (15) | C6—C7—C8—N1 | 0.5 (2) |
N1—C1—C2—C3 | 54.2 (2) | C6—C5—C9—O2 | 167.23 (15) |
C4—N2—C3—C2 | 26.0 (2) | C4—C5—C9—O2 | −8.9 (2) |
C1—C2—C3—N2 | −52.5 (2) | C6—C5—C9—C10 | −10.8 (2) |
C3—N2—C4—N1 | 2.6 (2) | C4—C5—C9—C10 | 173.00 (14) |
C3—N2—C4—C5 | −176.66 (15) | O2—C9—C10—C11 | −43.4 (2) |
C8—N1—C4—N2 | 175.55 (14) | C5—C9—C10—C11 | 134.74 (16) |
C1—N1—C4—N2 | −2.2 (2) | O2—C9—C10—C15 | 132.67 (17) |
C8—N1—C4—C5 | −5.1 (2) | C5—C9—C10—C15 | −49.2 (2) |
C1—N1—C4—C5 | 177.15 (15) | C15—C10—C11—C12 | 2.4 (2) |
N2—C4—C5—C6 | −175.92 (14) | C9—C10—C11—C12 | 178.70 (14) |
N1—C4—C5—C6 | 4.8 (2) | C10—C11—C12—C13 | −2.7 (2) |
N2—C4—C5—C9 | 0.5 (2) | C16—O3—C13—C12 | −6.4 (2) |
N1—C4—C5—C9 | −178.82 (14) | C16—O3—C13—C14 | 173.73 (16) |
C4—C5—C6—C7 | −2.1 (2) | C11—C12—C13—O3 | −179.36 (15) |
C9—C5—C6—C7 | −178.48 (15) | C11—C12—C13—C14 | 0.5 (2) |
C5—C6—C7—C8 | −0.5 (3) | O3—C13—C14—C15 | −178.17 (15) |
C4—N1—C8—O1 | −177.41 (14) | C12—C13—C14—C15 | 1.9 (3) |
C1—N1—C8—O1 | 0.4 (2) | C13—C14—C15—C10 | −2.3 (3) |
C4—N1—C8—C7 | 2.4 (2) | C11—C10—C15—C14 | 0.2 (2) |
C1—N1—C8—C7 | −179.77 (15) | C9—C10—C15—C14 | −175.97 (15) |
Experimental details
Crystal data | |
Chemical formula | C16H16N2O3 |
Mr | 284.12 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 294 |
a, b, c (Å) | 7.9544 (18), 8.3320 (19), 11.063 (3) |
α, β, γ (°) | 77.913 (3), 73.384 (4), 77.641 (4) |
V (Å3) | 677.7 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.20 × 0.18 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3460, 2370, 1814 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.111, 1.00 |
No. of reflections | 2370 |
No. of parameters | 191 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.12, −0.16 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
Heterocyclic ketene aminals, also named cyclic 1,1-enediamines, are useful building blocks in organic synthesis, especially for the synthesis of heterocycles (Huang & Wang, 1994). The title compound (Fig. 1) was synthesized through consecutive nucleophilic addition and cyclocondensation reactions. The crystal structure was determined to provide unambiguous evidence for the molecular configuration.
The six-membered 1,3-diazoheterocyclic ring C1/C2/C3/N2/C4/N1 adopts a twisted conformation, in which the C1/C2/C3/N2 and N1/C1/C2/C3 torsion angles are -52.5 (2) and 54.2 (2)°, respectively. The phenyl ring C10–C15 forms a dihedral angle of 54.1 (1)° to the pyrimidinone ring.