The title compound, C
16H
16N
2O
3, was synthesized by the reaction of phenylmethylidenemalononitrile and ethyl acetoacetate in the presence of triethylbenzylammonium chloride in an aqueous medium. The pyran ring adopts a boat conformation. The phenyl ring and the basal plane of the pyran ring make a dihedral angle of 94.5 (2)°. Intermolecular N—H
O and N—H
N hydrogen bonds link the molecules into ribbons along the
a axis.
Supporting information
CCDC reference: 270287
Key indicators
- Single-crystal X-ray study
- T = 289 K
- Mean (C-C) = 0.003 Å
- R factor = 0.044
- wR factor = 0.110
- Data-to-parameter ratio = 11.9
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT031_ALERT_4_C Refined Extinction Parameter within Range ...... 3.00 Sigma
PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.74 Ratio
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C15'
PLAT301_ALERT_3_C Main Residue Disorder ......................... 9.00 Perc.
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 33
C1 -C2 -C13 -N2 -154.00 4.00 1.555 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 34
C3 -C2 -C13 -N2 31.00 4.00 1.555 1.555 1.555 1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 22.20 Deg.
C15 -O2 -C15' 1.555 1.555 1.555
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
7 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
3 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
3 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 1997); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Ethyl 6-amino-5-cyano-2-methyl-4-phenyl-4
H-pyran-3-carboxylate
top
Crystal data top
C16H16N2O3 | Z = 2 |
Mr = 284.31 | F(000) = 300 |
Triclinic, P1 | Dx = 1.282 Mg m−3 |
Hall symbol: -P 1 | Melting point = 465–467 K |
a = 8.1402 (16) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.3393 (19) Å | Cell parameters from 28 reflections |
c = 11.206 (2) Å | θ = 3.5–27.7° |
α = 107.047 (3)° | µ = 0.09 mm−1 |
β = 103.066 (4)° | T = 289 K |
γ = 106.257 (3)° | Block, colorless |
V = 736.5 (2) Å3 | 0.44 × 0.24 × 0.18 mm |
Data collection top
Bruker P4 diffractometer | Rint = 0.035 |
Radiation source: normal-focus sealed tube | θmax = 25.0°, θmin = 2.5° |
Graphite monochromator | h = −9→9 |
ω scans | k = −11→10 |
3837 measured reflections | l = −7→13 |
2555 independent reflections | 3 standard reflections every 97 reflections |
1859 reflections with I > 2σ(I) | intensity decay: 2.8% |
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)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.110 | w = 1/[σ2(Fo2) + (0.056P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max < 0.001 |
2555 reflections | Δρmax = 0.15 e Å−3 |
215 parameters | Δρmin = −0.15 e Å−3 |
6 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.009 (3) |
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 >
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
O1 | 0.13498 (15) | 0.40090 (13) | 0.82664 (11) | 0.0524 (3) | |
O2 | 0.61798 (16) | 0.57641 (16) | 0.74546 (13) | 0.0703 (4) | |
O3 | 0.72773 (17) | 0.43183 (15) | 0.84284 (14) | 0.0697 (4) | |
N1 | −0.0462 (2) | 0.2452 (2) | 0.89645 (16) | 0.0554 (4) | |
N2 | 0.1987 (2) | −0.0067 (2) | 0.98632 (17) | 0.0712 (5) | |
C1 | 0.1105 (2) | 0.27912 (19) | 0.87218 (15) | 0.0434 (4) | |
C2 | 0.2348 (2) | 0.20971 (18) | 0.88705 (15) | 0.0423 (4) | |
C3 | 0.3921 (2) | 0.24600 (18) | 0.83584 (15) | 0.0427 (4) | |
H3 | 0.5011 | 0.2584 | 0.9034 | 0.051* | |
C4 | 0.4240 (2) | 0.40389 (18) | 0.81725 (15) | 0.0427 (4) | |
C5 | 0.3009 (2) | 0.47198 (19) | 0.81313 (15) | 0.0452 (4) | |
C6 | 0.3602 (2) | 0.10740 (18) | 0.70930 (16) | 0.0453 (4) | |
C7 | 0.4325 (3) | −0.0085 (2) | 0.7129 (2) | 0.0621 (5) | |
H7 | 0.5069 | −0.0002 | 0.7929 | 0.075* | |
C8 | 0.3947 (3) | −0.1382 (2) | 0.5970 (3) | 0.0783 (7) | |
H8 | 0.4433 | −0.2165 | 0.6001 | 0.094* | |
C9 | 0.2863 (3) | −0.1512 (2) | 0.4781 (2) | 0.0785 (7) | |
H9 | 0.2620 | −0.2378 | 0.4009 | 0.094* | |
C10 | 0.2146 (3) | −0.0372 (2) | 0.4738 (2) | 0.0750 (6) | |
H10 | 0.1411 | −0.0457 | 0.3933 | 0.090* | |
C11 | 0.2506 (3) | 0.0917 (2) | 0.58876 (18) | 0.0602 (5) | |
H11 | 0.2002 | 0.1688 | 0.5848 | 0.072* | |
C12 | 0.3033 (3) | 0.6245 (2) | 0.7961 (2) | 0.0651 (5) | |
H12A | 0.4256 | 0.6905 | 0.8106 | 0.078* | |
H12B | 0.2579 | 0.6813 | 0.8588 | 0.078* | |
H12C | 0.2281 | 0.6001 | 0.7078 | 0.078* | |
C13 | 0.2111 (2) | 0.0898 (2) | 0.94084 (16) | 0.0490 (5) | |
C14 | 0.6038 (2) | 0.47212 (19) | 0.80435 (16) | 0.0482 (4) | |
C15 | 0.7911 (6) | 0.6809 (6) | 0.7451 (6) | 0.0668 (17) | 0.509 (6) |
H15A | 0.8935 | 0.6780 | 0.8072 | 0.080* | 0.509 (6) |
H15B | 0.7983 | 0.7916 | 0.7687 | 0.080* | 0.509 (6) |
C16 | 0.7893 (8) | 0.6121 (7) | 0.6054 (5) | 0.0823 (17) | 0.509 (6) |
H16A | 0.7875 | 0.5043 | 0.5854 | 0.099* | 0.509 (6) |
H16B | 0.8960 | 0.6780 | 0.5962 | 0.099* | 0.509 (6) |
H16C | 0.6831 | 0.6101 | 0.5452 | 0.099* | 0.509 (6) |
C15' | 0.7991 (6) | 0.6204 (7) | 0.7311 (8) | 0.0668 (17) | 0.491 (6) |
H15C | 0.8201 | 0.5246 | 0.6866 | 0.080* | 0.491 (6) |
H15D | 0.8934 | 0.6806 | 0.8172 | 0.080* | 0.491 (6) |
C16' | 0.7974 (9) | 0.7225 (11) | 0.6497 (8) | 0.116 (3) | 0.491 (6) |
H16D | 0.7072 | 0.6594 | 0.5636 | 0.139* | 0.491 (6) |
H16E | 0.9147 | 0.7601 | 0.6406 | 0.139* | 0.491 (6) |
H16F | 0.7694 | 0.8132 | 0.6928 | 0.139* | 0.491 (6) |
H1A | −0.082 | 0.1677 | 0.9240 | 0.060* | |
H1B | −0.110 | 0.3031 | 0.8846 | 0.066* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0509 (7) | 0.0588 (7) | 0.0675 (8) | 0.0272 (6) | 0.0288 (6) | 0.0383 (6) |
O2 | 0.0559 (8) | 0.0828 (9) | 0.0798 (9) | 0.0127 (7) | 0.0297 (7) | 0.0484 (8) |
O3 | 0.0515 (8) | 0.0627 (8) | 0.0999 (11) | 0.0245 (7) | 0.0311 (8) | 0.0302 (8) |
N1 | 0.0530 (10) | 0.0606 (10) | 0.0755 (11) | 0.0279 (8) | 0.0349 (9) | 0.0406 (9) |
N2 | 0.0739 (12) | 0.0739 (11) | 0.1008 (14) | 0.0371 (9) | 0.0479 (11) | 0.0576 (11) |
C1 | 0.0486 (10) | 0.0439 (9) | 0.0418 (10) | 0.0165 (8) | 0.0189 (8) | 0.0198 (8) |
C2 | 0.0489 (10) | 0.0411 (9) | 0.0426 (9) | 0.0187 (8) | 0.0196 (8) | 0.0185 (7) |
C3 | 0.0430 (10) | 0.0457 (9) | 0.0422 (9) | 0.0183 (7) | 0.0150 (8) | 0.0185 (8) |
C4 | 0.0451 (10) | 0.0424 (9) | 0.0390 (9) | 0.0143 (7) | 0.0158 (8) | 0.0139 (7) |
C5 | 0.0461 (10) | 0.0466 (9) | 0.0462 (10) | 0.0150 (8) | 0.0188 (8) | 0.0217 (8) |
C6 | 0.0472 (10) | 0.0433 (9) | 0.0527 (11) | 0.0177 (8) | 0.0265 (9) | 0.0203 (8) |
C7 | 0.0743 (13) | 0.0550 (11) | 0.0727 (14) | 0.0310 (10) | 0.0367 (11) | 0.0300 (10) |
C8 | 0.1048 (18) | 0.0520 (12) | 0.1037 (19) | 0.0414 (12) | 0.0626 (16) | 0.0318 (13) |
C9 | 0.1038 (18) | 0.0530 (13) | 0.0736 (16) | 0.0199 (12) | 0.0512 (14) | 0.0099 (12) |
C10 | 0.0850 (16) | 0.0692 (14) | 0.0571 (13) | 0.0215 (12) | 0.0261 (11) | 0.0104 (11) |
C11 | 0.0687 (13) | 0.0598 (12) | 0.0521 (12) | 0.0283 (10) | 0.0224 (10) | 0.0157 (10) |
C12 | 0.0689 (13) | 0.0614 (11) | 0.0839 (15) | 0.0308 (10) | 0.0339 (11) | 0.0410 (11) |
C13 | 0.0503 (11) | 0.0516 (10) | 0.0551 (11) | 0.0229 (8) | 0.0260 (9) | 0.0240 (9) |
C14 | 0.0491 (11) | 0.0417 (10) | 0.0457 (10) | 0.0120 (8) | 0.0168 (9) | 0.0098 (8) |
C15 | 0.0599 (16) | 0.049 (3) | 0.083 (2) | 0.0015 (19) | 0.0304 (13) | 0.027 (3) |
C16 | 0.092 (4) | 0.075 (4) | 0.098 (4) | 0.029 (3) | 0.056 (3) | 0.040 (3) |
C15' | 0.0599 (16) | 0.049 (3) | 0.083 (2) | 0.0015 (19) | 0.0304 (13) | 0.027 (3) |
C16' | 0.093 (4) | 0.149 (7) | 0.158 (7) | 0.038 (5) | 0.068 (5) | 0.116 (7) |
Geometric parameters (Å, º) top
O1—C1 | 1.3612 (18) | C8—C9 | 1.371 (3) |
O1—C5 | 1.3915 (18) | C8—H8 | 0.9300 |
O2—C14 | 1.321 (2) | C9—C10 | 1.358 (3) |
O2—C15 | 1.474 (3) | C9—H9 | 0.9300 |
O2—C15' | 1.475 (3) | C10—C11 | 1.385 (2) |
O3—C14 | 1.207 (2) | C10—H10 | 0.9300 |
N1—C1 | 1.335 (2) | C11—H11 | 0.9300 |
N1—H1A | 0.87 | C12—H12A | 0.9600 |
N1—H1B | 0.87 | C12—H12B | 0.9600 |
N2—C13 | 1.150 (2) | C12—H12C | 0.9600 |
C1—C2 | 1.352 (2) | C15—C16 | 1.503 (3) |
C2—C13 | 1.408 (2) | C15—H15A | 0.9700 |
C2—C3 | 1.513 (2) | C15—H15B | 0.9700 |
C3—C4 | 1.508 (2) | C16—H16A | 0.9600 |
C3—C6 | 1.524 (2) | C16—H16B | 0.9600 |
C3—H3 | 0.9800 | C16—H16C | 0.9600 |
C4—C5 | 1.328 (2) | C15'—C16' | 1.502 (3) |
C4—C14 | 1.482 (2) | C15'—H15C | 0.9700 |
C5—C12 | 1.487 (2) | C15'—H15D | 0.9700 |
C6—C7 | 1.375 (2) | C16'—H16D | 0.9600 |
C6—C11 | 1.381 (2) | C16'—H16E | 0.9600 |
C7—C8 | 1.392 (3) | C16'—H16F | 0.9600 |
C7—H7 | 0.9300 | | |
| | | |
C1—O1—C5 | 120.00 (13) | C8—C9—H9 | 120.2 |
C14—O2—C15 | 124.4 (3) | C9—C10—C11 | 120.2 (2) |
C14—O2—C15' | 108.3 (3) | C9—C10—H10 | 119.9 |
C15—O2—C15' | 22.2 (3) | C11—C10—H10 | 119.9 |
C1—N1—H1A | 121 | C6—C11—C10 | 121.0 (2) |
C1—N1—H1B | 118 | C6—C11—H11 | 119.5 |
H1A—N1—H1B | 121 | C10—C11—H11 | 119.5 |
N1—C1—C2 | 128.72 (16) | C5—C12—H12A | 109.5 |
N1—C1—O1 | 110.20 (15) | C5—C12—H12B | 109.5 |
C2—C1—O1 | 121.08 (14) | H12A—C12—H12B | 109.5 |
C1—C2—C13 | 120.04 (15) | C5—C12—H12C | 109.5 |
C1—C2—C3 | 121.71 (14) | H12A—C12—H12C | 109.5 |
C13—C2—C3 | 118.01 (14) | H12B—C12—H12C | 109.5 |
C4—C3—C2 | 109.47 (13) | N2—C13—C2 | 177.45 (19) |
C4—C3—C6 | 112.36 (13) | O3—C14—O2 | 122.38 (16) |
C2—C3—C6 | 111.12 (12) | O3—C14—C4 | 121.80 (17) |
C4—C3—H3 | 107.9 | O2—C14—C4 | 115.80 (16) |
C2—C3—H3 | 107.9 | O2—C15—C16 | 104.7 (4) |
C6—C3—H3 | 107.9 | O2—C15—H15A | 110.8 |
C5—C4—C14 | 124.63 (16) | C16—C15—H15A | 110.8 |
C5—C4—C3 | 122.26 (14) | O2—C15—H15B | 110.8 |
C14—C4—C3 | 113.11 (14) | C16—C15—H15B | 110.8 |
C4—C5—O1 | 121.34 (15) | H15A—C15—H15B | 108.9 |
C4—C5—C12 | 131.25 (15) | O2—C15'—C16' | 105.3 (4) |
O1—C5—C12 | 107.41 (14) | O2—C15'—H15C | 110.7 |
C7—C6—C11 | 118.47 (16) | C16'—C15'—H15C | 110.7 |
C7—C6—C3 | 121.08 (16) | O2—C15'—H15D | 110.7 |
C11—C6—C3 | 120.38 (15) | C16'—C15'—H15D | 110.7 |
C6—C7—C8 | 120.2 (2) | H15C—C15'—H15D | 108.8 |
C6—C7—H7 | 119.9 | C15'—C16'—H16D | 109.5 |
C8—C7—H7 | 119.9 | C15'—C16'—H16E | 109.5 |
C9—C8—C7 | 120.5 (2) | H16D—C16'—H16E | 109.5 |
C9—C8—H8 | 119.7 | C15'—C16'—H16F | 109.5 |
C7—C8—H8 | 119.7 | H16D—C16'—H16F | 109.5 |
C10—C9—C8 | 119.68 (19) | H16E—C16'—H16F | 109.5 |
C10—C9—H9 | 120.2 | | |
| | | |
C5—O1—C1—N1 | 170.67 (13) | C2—C3—C6—C11 | 80.55 (19) |
C5—O1—C1—C2 | −9.5 (2) | C11—C6—C7—C8 | −0.1 (3) |
N1—C1—C2—C13 | −3.5 (3) | C3—C6—C7—C8 | 176.99 (15) |
O1—C1—C2—C13 | 176.68 (14) | C6—C7—C8—C9 | 0.5 (3) |
N1—C1—C2—C3 | 170.80 (16) | C7—C8—C9—C10 | −0.4 (3) |
O1—C1—C2—C3 | −9.0 (2) | C8—C9—C10—C11 | 0.0 (3) |
C1—C2—C3—C4 | 20.6 (2) | C7—C6—C11—C10 | −0.3 (3) |
C13—C2—C3—C4 | −164.94 (14) | C3—C6—C11—C10 | −177.42 (16) |
C1—C2—C3—C6 | −104.05 (17) | C9—C10—C11—C6 | 0.4 (3) |
C13—C2—C3—C6 | 70.37 (19) | C1—C2—C13—N2 | −154 (4) |
C2—C3—C4—C5 | −16.3 (2) | C3—C2—C13—N2 | 31 (4) |
C6—C3—C4—C5 | 107.65 (17) | C15—O2—C14—O3 | −13.8 (3) |
C2—C3—C4—C14 | 163.73 (13) | C15'—O2—C14—O3 | 3.3 (4) |
C6—C3—C4—C14 | −72.29 (17) | C15—O2—C14—C4 | 167.7 (3) |
C14—C4—C5—O1 | −179.69 (13) | C15'—O2—C14—C4 | −175.2 (3) |
C3—C4—C5—O1 | 0.4 (2) | C5—C4—C14—O3 | 159.91 (17) |
C14—C4—C5—C12 | −0.1 (3) | C3—C4—C14—O3 | −20.1 (2) |
C3—C4—C5—C12 | 179.96 (16) | C5—C4—C14—O2 | −21.6 (2) |
C1—O1—C5—C4 | 14.0 (2) | C3—C4—C14—O2 | 158.32 (13) |
C1—O1—C5—C12 | −165.66 (14) | C14—O2—C15—C16 | 108.7 (5) |
C4—C3—C6—C7 | 140.45 (16) | C15'—O2—C15—C16 | 61.1 (12) |
C2—C3—C6—C7 | −96.50 (18) | C14—O2—C15'—C16' | 173.4 (6) |
C4—C3—C6—C11 | −42.5 (2) | C15—O2—C15'—C16' | −46.5 (11) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O3i | 0.87 | 2.08 | 2.949 (2) | 176 |
N1—H1A···N2ii | 0.87 | 2.17 | 3.022 (2) | 168 |
Symmetry codes: (i) x−1, y, z; (ii) −x, −y, −z+2. |