The title compound, C
19H
19NO
6, was synthesized by the reaction of 4-hydroxy-6-methylpyran-2-one and ethyl 4′-methoxy-2-cyanocinnamate in the presence of triethylbenzylammonium chloride in an aqueous medium. The pyranone ring is almost planar, while the fused pyran ring adopts a flattened boat conformation. The amino group is involved in both intra- and intermolecular N—H
O hydrogen bonds.
Supporting information
CCDC reference: 259592
Key indicators
- Single-crystal X-ray study
- T = 193 K
- Mean (C-C) = 0.003 Å
- H-atom completeness 74%
- R factor = 0.059
- wR factor = 0.163
- Data-to-parameter ratio = 15.5
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT432_ALERT_2_A Short Inter X...Y Contact C11B .. C11B .. 2.30 Ang.
Alert level C
CHEMW03_ALERT_2_C The ratio of given/expected molecular weight as
calculated from the _atom_site* data lies outside
the range 0.99 <> 1.01
From the CIF: _cell_formula_units_Z 4
From the CIF: _chemical_formula_weight 357.35
TEST: Calculate formula weight from _atom_site_*
atom mass num sum
C 12.01 19.00 228.21
H 1.01 14.00 14.11
N 14.01 1.00 14.01
O 16.00 6.00 95.99
Calculated formula weight 352.32
DIFMX01_ALERT_2_C The maximum difference density is > 0.1*ZMAX*0.75
_refine_diff_density_max given = 0.692
Test value = 0.600
DIFMX02_ALERT_1_C The minimum difference density is > 0.1*ZMAX*0.75
The relevant atom site should be identified.
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT043_ALERT_1_C Check Reported Molecular Weight ................ 357.35
PLAT044_ALERT_1_C Calculated and Reported Dx Differ .............. ?
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.75 mm
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.39
PLAT097_ALERT_2_C Maximum (Positive) Residual Density ............ 0.69 e/A 3
PLAT301_ALERT_3_C Main Residue Disorder ......................... 4.00 Perc.
Alert level G
FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the
_chemical_formula_sum and the formula from the _atom_site* data.
Atom count from _chemical_formula_sum:C19 H19 N1 O6
Atom count from the _atom_site data: C19 H14 N1 O6
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
From the CIF: _cell_formula_units_Z 4
From the CIF: _chemical_formula_sum C19 H19 N O6
TEST: Compare cell contents of formula and atom_site data
atom Z*formula cif sites diff
C 76.00 76.00 0.00
H 76.00 56.00 20.00
N 4.00 4.00 0.00
O 24.00 24.00 0.00
1 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
12 ALERT level C = Check and explain
3 ALERT level G = General alerts; check
8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
6 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Ethyl
2-amino-4-(4-methoxyphenyl)-7-methyl-5-oxopyrano[3,2-
c]pyran-3-carboxylate
top
Crystal data top
C19H19NO6 | F(000) = 752 |
Mr = 357.35 | Dx = 1.369 Mg m−3 |
Monoclinic, P21/c | Melting point = 445–447 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71070 Å |
a = 10.720 (4) Å | Cell parameters from 7929 reflections |
b = 8.934 (3) Å | θ = 3.1–27.5° |
c = 18.167 (6) Å | µ = 0.10 mm−1 |
β = 94.636 (7)° | T = 193 K |
V = 1734.2 (10) Å3 | Block, colorless |
Z = 4 | 0.75 × 0.65 × 0.45 mm |
Data collection top
Rigaku Mercury diffractometer | 3947 independent reflections |
Radiation source: fine-focus sealed tube | 3575 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
Detector resolution: 7.31 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω scans | h = −13→13 |
Absorption correction: multi-scan (Jacobson, 1998) | k = −10→11 |
Tmin = 0.914, Tmax = 0.955 | l = −23→23 |
18580 measured reflections | |
Refinement top
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.163 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0836P)2 + 0.9423P] where P = (Fo2 + 2Fc2)/3 |
3947 reflections | (Δ/σ)max < 0.001 |
255 parameters | Δρmax = 0.69 e Å−3 |
2 restraints | Δρmin = −0.29 e Å−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 | 1.05143 (13) | 0.37011 (14) | 0.17071 (8) | 0.0316 (3) | |
O2 | 1.02879 (14) | 0.89867 (15) | 0.14269 (9) | 0.0384 (4) | |
O3 | 1.16290 (12) | 0.79486 (14) | 0.22669 (8) | 0.0310 (3) | |
O4 | 0.79150 (16) | 0.27396 (18) | −0.00755 (9) | 0.0469 (4) | |
O5 | 0.76468 (14) | 0.52090 (18) | −0.02776 (8) | 0.0413 (4) | |
O6 | 0.45344 (14) | 0.85568 (19) | 0.17062 (9) | 0.0431 (4) | |
N1 | 0.9670 (2) | 0.19416 (19) | 0.09623 (12) | 0.0398 (4) | |
C1 | 0.96960 (18) | 0.3413 (2) | 0.11009 (11) | 0.0289 (4) | |
C2 | 0.90380 (17) | 0.4511 (2) | 0.07134 (10) | 0.0279 (4) | |
C3 | 0.91786 (16) | 0.61697 (19) | 0.09104 (10) | 0.0250 (4) | |
H3 | 0.9430 | 0.6713 | 0.0464 | 0.030* | |
C4 | 1.02227 (16) | 0.63387 (19) | 0.15156 (10) | 0.0247 (4) | |
C5 | 1.07889 (17) | 0.51683 (19) | 0.18778 (10) | 0.0266 (4) | |
C6 | 1.06648 (17) | 0.7822 (2) | 0.17081 (11) | 0.0281 (4) | |
C7 | 1.21540 (18) | 0.6730 (2) | 0.26323 (10) | 0.0298 (4) | |
C8 | 1.17603 (18) | 0.5343 (2) | 0.24587 (11) | 0.0303 (4) | |
H8 | 1.2116 | 0.4498 | 0.2714 | 0.036* | |
C9 | 0.81762 (18) | 0.4041 (2) | 0.01014 (11) | 0.0333 (4) | |
C10 | 0.6638 (2) | 0.4798 (4) | −0.08306 (14) | 0.0574 (7) | |
C11A | 0.6161 (4) | 0.6173 (4) | −0.1181 (2) | 0.0566 (10) | 0.72 |
C11B | 0.5482 (8) | 0.5342 (13) | −0.0517 (6) | 0.059 (3) | 0.28 |
C12 | 0.79546 (17) | 0.6860 (2) | 0.11309 (10) | 0.0252 (4) | |
C13 | 0.73489 (18) | 0.7965 (2) | 0.07003 (10) | 0.0301 (4) | |
H13 | 0.7728 | 0.8332 | 0.0281 | 0.036* | |
C14 | 0.61962 (18) | 0.8553 (2) | 0.08662 (10) | 0.0317 (4) | |
H14 | 0.5790 | 0.9294 | 0.0558 | 0.038* | |
C15 | 0.56546 (18) | 0.8044 (2) | 0.14825 (11) | 0.0302 (4) | |
C16 | 0.62577 (18) | 0.6950 (2) | 0.19298 (11) | 0.0322 (4) | |
H16 | 0.5887 | 0.6602 | 0.2356 | 0.039* | |
C17 | 0.73989 (18) | 0.6369 (2) | 0.17534 (10) | 0.0286 (4) | |
H17 | 0.7804 | 0.5627 | 0.2062 | 0.034* | |
C18 | 0.38029 (19) | 0.9528 (3) | 0.12169 (14) | 0.0422 (5) | |
H18A | 0.4272 | 1.0451 | 0.1144 | 0.063* | |
H18B | 0.3018 | 0.9772 | 0.1431 | 0.063* | |
H18C | 0.3618 | 0.9027 | 0.0741 | 0.063* | |
C19 | 1.3171 (2) | 0.7173 (2) | 0.31962 (12) | 0.0380 (5) | |
H19A | 1.3566 | 0.6274 | 0.3418 | 0.057* | |
H19B | 1.2819 | 0.7773 | 0.3581 | 0.057* | |
H19C | 1.3798 | 0.7764 | 0.2961 | 0.057* | |
H1A | 0.914 (3) | 0.169 (3) | 0.0590 (16) | 0.049 (7)* | |
H1B | 1.010 (3) | 0.132 (3) | 0.1260 (16) | 0.055 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0386 (7) | 0.0186 (6) | 0.0363 (7) | 0.0021 (5) | −0.0045 (6) | 0.0018 (5) |
O2 | 0.0410 (8) | 0.0195 (6) | 0.0530 (9) | 0.0043 (6) | −0.0061 (7) | 0.0038 (6) |
O3 | 0.0290 (7) | 0.0231 (6) | 0.0398 (8) | 0.0017 (5) | −0.0039 (6) | −0.0012 (5) |
O4 | 0.0494 (9) | 0.0363 (8) | 0.0532 (10) | −0.0015 (7) | −0.0067 (7) | −0.0157 (7) |
O5 | 0.0396 (8) | 0.0424 (9) | 0.0393 (8) | 0.0126 (7) | −0.0130 (6) | −0.0113 (7) |
O6 | 0.0315 (8) | 0.0492 (9) | 0.0494 (9) | 0.0122 (7) | 0.0089 (6) | 0.0016 (7) |
N1 | 0.0494 (11) | 0.0188 (8) | 0.0497 (11) | 0.0026 (7) | −0.0057 (9) | −0.0027 (7) |
C1 | 0.0308 (9) | 0.0226 (9) | 0.0334 (9) | 0.0001 (7) | 0.0029 (7) | −0.0020 (7) |
C2 | 0.0293 (9) | 0.0229 (8) | 0.0314 (9) | 0.0026 (7) | 0.0010 (7) | −0.0036 (7) |
C3 | 0.0270 (9) | 0.0206 (8) | 0.0272 (8) | 0.0037 (7) | 0.0009 (7) | 0.0007 (7) |
C4 | 0.0258 (8) | 0.0197 (8) | 0.0286 (9) | 0.0027 (6) | 0.0016 (7) | 0.0004 (7) |
C5 | 0.0297 (9) | 0.0193 (8) | 0.0307 (9) | 0.0008 (7) | 0.0026 (7) | 0.0013 (7) |
C6 | 0.0269 (9) | 0.0227 (9) | 0.0343 (10) | 0.0035 (7) | 0.0007 (7) | −0.0003 (7) |
C7 | 0.0291 (9) | 0.0294 (9) | 0.0308 (9) | 0.0042 (7) | 0.0010 (7) | 0.0011 (7) |
C8 | 0.0332 (9) | 0.0255 (9) | 0.0315 (9) | 0.0048 (7) | −0.0010 (7) | 0.0041 (7) |
C9 | 0.0312 (10) | 0.0326 (10) | 0.0360 (10) | 0.0055 (8) | 0.0011 (8) | −0.0080 (8) |
C10 | 0.0393 (12) | 0.082 (2) | 0.0471 (13) | 0.0092 (13) | −0.0191 (10) | −0.0154 (13) |
C11A | 0.062 (2) | 0.0421 (18) | 0.060 (2) | 0.0145 (16) | −0.0279 (18) | 0.0011 (16) |
C11B | 0.034 (4) | 0.078 (7) | 0.064 (6) | 0.002 (4) | −0.002 (4) | −0.023 (5) |
C12 | 0.0269 (8) | 0.0203 (8) | 0.0278 (9) | 0.0012 (7) | −0.0013 (7) | −0.0026 (7) |
C13 | 0.0341 (10) | 0.0279 (9) | 0.0283 (9) | 0.0058 (7) | 0.0024 (7) | 0.0031 (7) |
C14 | 0.0328 (10) | 0.0292 (9) | 0.0323 (9) | 0.0090 (8) | −0.0022 (7) | 0.0018 (8) |
C15 | 0.0262 (9) | 0.0285 (9) | 0.0357 (10) | 0.0024 (7) | 0.0008 (7) | −0.0062 (8) |
C16 | 0.0334 (10) | 0.0309 (10) | 0.0325 (10) | −0.0004 (8) | 0.0040 (8) | 0.0009 (8) |
C17 | 0.0330 (9) | 0.0218 (8) | 0.0304 (9) | 0.0017 (7) | −0.0009 (7) | 0.0024 (7) |
C18 | 0.0280 (10) | 0.0362 (11) | 0.0619 (14) | 0.0068 (8) | 0.0000 (9) | −0.0036 (10) |
C19 | 0.0332 (10) | 0.0376 (11) | 0.0416 (11) | 0.0005 (8) | −0.0063 (8) | −0.0015 (9) |
Geometric parameters (Å, º) top
O1—C5 | 1.373 (2) | C7—C8 | 1.339 (3) |
O1—C1 | 1.376 (2) | C7—C19 | 1.488 (3) |
O2—C6 | 1.214 (2) | C8—H8 | 0.9500 |
O3—C7 | 1.372 (2) | C10—C11A | 1.457 (4) |
O3—C6 | 1.394 (2) | C10—C11B | 1.487 (9) |
O4—C9 | 1.232 (3) | C12—C13 | 1.388 (3) |
O5—C9 | 1.350 (3) | C12—C17 | 1.391 (3) |
O5—C10 | 1.462 (3) | C13—C14 | 1.398 (3) |
O6—C15 | 1.377 (2) | C13—H13 | 0.9500 |
O6—C18 | 1.430 (3) | C14—C15 | 1.379 (3) |
N1—C1 | 1.339 (2) | C14—H14 | 0.9500 |
N1—H1A | 0.88 (3) | C15—C16 | 1.396 (3) |
N1—H1B | 0.88 (3) | C16—C17 | 1.390 (3) |
C1—C2 | 1.369 (3) | C16—H16 | 0.9500 |
C2—C9 | 1.449 (3) | C17—H17 | 0.9500 |
C2—C3 | 1.529 (2) | C18—H18A | 0.9800 |
C3—C4 | 1.512 (2) | C18—H18B | 0.9800 |
C3—C12 | 1.532 (2) | C18—H18C | 0.9800 |
C3—H3 | 1.0000 | C19—H19A | 0.9800 |
C4—C5 | 1.353 (2) | C19—H19B | 0.9800 |
C4—C6 | 1.441 (2) | C19—H19C | 0.9800 |
C5—C8 | 1.430 (3) | | |
| | | |
C5—O1—C1 | 118.05 (14) | O4—C9—C2 | 126.21 (19) |
C7—O3—C6 | 122.63 (15) | O5—C9—C2 | 112.52 (17) |
C9—O5—C10 | 114.43 (19) | C11A—C10—O5 | 107.6 (3) |
C15—O6—C18 | 117.77 (17) | C11A—C10—C11B | 67.6 (5) |
C1—N1—H1A | 113.4 (19) | O5—C10—C11B | 104.4 (4) |
C1—N1—H1B | 120.2 (19) | C13—C12—C17 | 118.11 (17) |
H1A—N1—H1B | 126 (3) | C13—C12—C3 | 120.71 (16) |
N1—C1—C2 | 127.21 (19) | C17—C12—C3 | 121.15 (16) |
N1—C1—O1 | 109.66 (17) | C12—C13—C14 | 121.81 (18) |
C2—C1—O1 | 123.13 (16) | C12—C13—H13 | 119.1 |
C1—C2—C9 | 117.19 (17) | C14—C13—H13 | 119.1 |
C1—C2—C3 | 122.47 (17) | C15—C14—C13 | 119.26 (17) |
C9—C2—C3 | 120.34 (16) | C15—C14—H14 | 120.4 |
C4—C3—C2 | 108.68 (14) | C13—C14—H14 | 120.4 |
C4—C3—C12 | 111.66 (14) | O6—C15—C14 | 124.35 (18) |
C2—C3—C12 | 112.41 (15) | O6—C15—C16 | 115.79 (18) |
C4—C3—H3 | 108.0 | C14—C15—C16 | 119.85 (17) |
C2—C3—H3 | 108.0 | C17—C16—C15 | 120.14 (18) |
C12—C3—H3 | 108.0 | C17—C16—H16 | 119.9 |
C5—C4—C6 | 117.84 (16) | C15—C16—H16 | 119.9 |
C5—C4—C3 | 123.59 (16) | C16—C17—C12 | 120.81 (17) |
C6—C4—C3 | 118.56 (15) | C16—C17—H17 | 119.6 |
C4—C5—O1 | 123.25 (17) | C12—C17—H17 | 119.6 |
C4—C5—C8 | 123.09 (17) | O6—C18—H18A | 109.5 |
O1—C5—C8 | 113.62 (15) | O6—C18—H18B | 109.5 |
O2—C6—O3 | 116.05 (16) | H18A—C18—H18B | 109.5 |
O2—C6—C4 | 126.47 (17) | O6—C18—H18C | 109.5 |
O3—C6—C4 | 117.48 (15) | H18A—C18—H18C | 109.5 |
C8—C7—O3 | 120.76 (17) | H18B—C18—H18C | 109.5 |
C8—C7—C19 | 127.43 (18) | C7—C19—H19A | 109.5 |
O3—C7—C19 | 111.80 (17) | C7—C19—H19B | 109.5 |
C7—C8—C5 | 118.14 (17) | H19A—C19—H19B | 109.5 |
C7—C8—H8 | 120.9 | C7—C19—H19C | 109.5 |
C5—C8—H8 | 120.9 | H19A—C19—H19C | 109.5 |
O4—C9—O5 | 121.27 (19) | H19B—C19—H19C | 109.5 |
| | | |
C5—O1—C1—N1 | 171.80 (17) | O3—C7—C8—C5 | 0.7 (3) |
C5—O1—C1—C2 | −7.7 (3) | C19—C7—C8—C5 | −177.95 (18) |
N1—C1—C2—C9 | 2.7 (3) | C4—C5—C8—C7 | −2.4 (3) |
O1—C1—C2—C9 | −177.93 (17) | O1—C5—C8—C7 | 175.62 (17) |
N1—C1—C2—C3 | −177.92 (19) | C10—O5—C9—O4 | 8.1 (3) |
O1—C1—C2—C3 | 1.5 (3) | C10—O5—C9—C2 | −171.49 (17) |
C1—C2—C3—C4 | 6.1 (2) | C1—C2—C9—O4 | 5.1 (3) |
C9—C2—C3—C4 | −174.46 (16) | C3—C2—C9—O4 | −174.31 (19) |
C1—C2—C3—C12 | −117.98 (19) | C1—C2—C9—O5 | −175.30 (17) |
C9—C2—C3—C12 | 61.4 (2) | C3—C2—C9—O5 | 5.3 (3) |
C2—C3—C4—C5 | −8.5 (2) | C9—O5—C10—C11A | 179.4 (2) |
C12—C3—C4—C5 | 116.05 (19) | C9—O5—C10—C11B | 108.8 (5) |
C2—C3—C4—C6 | 169.94 (15) | C4—C3—C12—C13 | 123.04 (18) |
C12—C3—C4—C6 | −65.5 (2) | C2—C3—C12—C13 | −114.52 (19) |
C6—C4—C5—O1 | −175.11 (17) | C4—C3—C12—C17 | −59.0 (2) |
C3—C4—C5—O1 | 3.3 (3) | C2—C3—C12—C17 | 63.5 (2) |
C6—C4—C5—C8 | 2.7 (3) | C17—C12—C13—C14 | −1.7 (3) |
C3—C4—C5—C8 | −178.82 (17) | C3—C12—C13—C14 | 176.32 (17) |
C1—O1—C5—C4 | 5.3 (3) | C12—C13—C14—C15 | 1.3 (3) |
C1—O1—C5—C8 | −172.70 (15) | C18—O6—C15—C14 | 8.9 (3) |
C7—O3—C6—O2 | −179.64 (17) | C18—O6—C15—C16 | −171.93 (18) |
C7—O3—C6—C4 | −0.2 (3) | C13—C14—C15—O6 | 178.94 (18) |
C5—C4—C6—O2 | 177.95 (19) | C13—C14—C15—C16 | −0.2 (3) |
C3—C4—C6—O2 | −0.6 (3) | O6—C15—C16—C17 | −179.54 (17) |
C5—C4—C6—O3 | −1.4 (3) | C14—C15—C16—C17 | −0.3 (3) |
C3—C4—C6—O3 | −179.92 (15) | C15—C16—C17—C12 | −0.2 (3) |
C6—O3—C7—C8 | 0.6 (3) | C13—C12—C17—C16 | 1.2 (3) |
C6—O3—C7—C19 | 179.39 (16) | C3—C12—C17—C16 | −176.86 (17) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18C···O4i | 0.98 | 2.52 | 3.344 (3) | 142 |
C19—H19C···O6ii | 0.98 | 2.57 | 3.410 (3) | 144 |
N1—H1A···O4 | 0.88 (3) | 1.95 (3) | 2.651 (3) | 136 (3) |
N1—H1B···O2iii | 0.88 (3) | 2.11 (3) | 2.834 (2) | 139 (2) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x+1, y, z; (iii) x, y−1, z. |