The title compound, C
15H
15NO
3, derived from the condensation of dehydroacetic acid and
p-toluidine, crystallizes in a zwitterionic form with cationic iminium and anionic enolate groups, which complete a six-membered pseudocycle
via an intramolecular N—H
O hydrogen bond. C—H
O interactions link the molecules into a two-dimensional network.
Supporting information
CCDC reference: 640420
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C)= 0.003 Å
- R factor = 0.040
- wR factor = 0.110
- Data-to-parameter ratio = 14.4
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Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
Please specify the role of each of the co-authors
for your paper.
| Author Response: This is the role of the six mauthors:
|
The first name: it's me, the synthesis and the text.
Second name: my professor.
Third name: resolution, figures and she helped me in the preparation of
the cif and the publication and the corrections.
Fourth: collecting data.
5 name and 6 name: we work in co-operation with them thus I have made
the synthesis in their laboratory. They provided discussions and input
of ideas.
1 ALERT level A = Data missing that is essential or data in wrong format
0 ALERT level G = General alerts. Data that may be required is missing
Data collection: COLLECT (Nonius, 1997); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999) and PARST (Nardelli, 1995).
(
E)-6-methyl-2-oxo-3-[1-(
p-tolyliminio)ethyl]-2
H-pyran-4-olate
top
Crystal data top
C15H15NO3 | F(000) = 544 |
Mr = 257.28 | Dx = 1.282 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2841 reflections |
a = 14.131 (2) Å | θ = 3.1–25.8° |
b = 7.8128 (6) Å | µ = 0.09 mm−1 |
c = 12.841 (2) Å | T = 173 K |
β = 109.92 (2)° | Prism, yellow |
V = 1332.9 (3) Å3 | 0.35 × 0.05 × 0.02 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD diffractometer | 1487 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.040 |
Detector resolution: 9 pixels mm-1 | θmax = 26.0°, θmin = 3.0° |
CCD scans | h = −16→17 |
10079 measured reflections | k = −9→9 |
2581 independent reflections | l = −15→15 |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.88 | w = 1/[σ2(Fo2) + (0.0634P)2] where P = (Fo2 + 2Fc2)/3 |
2581 reflections | (Δ/σ)max < 0.001 |
179 parameters | Δρmax = 0.11 e Å−3 |
0 restraints | Δρmin = −0.13 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.96325 (16) | 0.8363 (4) | 0.6561 (2) | 0.1078 (8) | |
H1A | 1 | 0.9416 | 0.6639 | 0.129* | |
H1B | 1.0013 | 0.7452 | 0.6393 | 0.129* | |
H1C | 0.9519 | 0.8111 | 0.7241 | 0.129* | |
C2 | 0.86497 (14) | 0.8531 (3) | 0.56502 (16) | 0.0724 (5) | |
C3 | 0.77491 (13) | 0.8298 (3) | 0.57339 (15) | 0.0695 (5) | |
H3 | 0.7704 | 0.7997 | 0.6416 | 0.084* | |
C4 | 0.68452 (13) | 0.8498 (2) | 0.48027 (14) | 0.0615 (4) | |
C5 | 0.69439 (12) | 0.8968 (2) | 0.37635 (13) | 0.0551 (4) | |
C6 | 0.79348 (13) | 0.9139 (3) | 0.36927 (15) | 0.0694 (5) | |
C7 | 0.60849 (12) | 0.9238 (2) | 0.28059 (13) | 0.0539 (4) | |
C8 | 0.61333 (14) | 0.9966 (2) | 0.17518 (14) | 0.0664 (5) | |
H8A | 0.6652 | 1.0821 | 0.1916 | 0.08* | |
H8B | 0.5497 | 1.0476 | 0.1341 | 0.08* | |
H8C | 0.6282 | 0.907 | 0.132 | 0.08* | |
C9 | 0.42279 (13) | 0.8904 (2) | 0.20279 (13) | 0.0574 (4) | |
C10 | 0.40667 (14) | 0.8122 (2) | 0.10152 (14) | 0.0658 (5) | |
H10 | 0.4602 | 0.7638 | 0.0853 | 0.079* | |
C11 | 0.31062 (15) | 0.8066 (3) | 0.02479 (16) | 0.0741 (5) | |
H11 | 0.3002 | 0.7546 | −0.0434 | 0.089* | |
C12 | 0.22964 (15) | 0.8761 (3) | 0.04661 (17) | 0.0767 (6) | |
C13 | 0.24728 (15) | 0.9513 (3) | 0.14907 (18) | 0.0815 (6) | |
H13 | 0.1936 | 0.9977 | 0.1659 | 0.098* | |
C14 | 0.34285 (14) | 0.9589 (3) | 0.22681 (15) | 0.0694 (5) | |
H14 | 0.3532 | 1.0102 | 0.2952 | 0.083* | |
C15 | 0.12531 (17) | 0.8683 (4) | −0.0396 (2) | 0.1129 (9) | |
H15A | 0.0827 | 0.9507 | −0.0219 | 0.136* | |
H15B | 0.0979 | 0.7557 | −0.0404 | 0.136* | |
H15C | 0.1292 | 0.8936 | −0.1112 | 0.136* | |
N1 | 0.51920 (10) | 0.88972 (19) | 0.28791 (12) | 0.0595 (4) | |
O1 | 0.81620 (10) | 0.9390 (3) | 0.28800 (11) | 0.1035 (6) | |
O2 | 0.60066 (9) | 0.8289 (2) | 0.49350 (10) | 0.0800 (4) | |
O3 | 0.87607 (9) | 0.8939 (2) | 0.46639 (11) | 0.0829 (4) | |
H1 | 0.5251 (14) | 0.860 (2) | 0.3600 (17) | 0.083 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0717 (14) | 0.136 (2) | 0.0970 (17) | −0.0151 (14) | 0.0053 (12) | −0.0027 (15) |
C2 | 0.0630 (11) | 0.0793 (14) | 0.0700 (11) | −0.0104 (9) | 0.0166 (9) | −0.0065 (9) |
C3 | 0.0620 (11) | 0.0862 (14) | 0.0578 (10) | −0.0068 (9) | 0.0170 (9) | 0.0068 (9) |
C4 | 0.0598 (10) | 0.0651 (11) | 0.0620 (10) | −0.0031 (8) | 0.0239 (8) | 0.0048 (8) |
C5 | 0.0584 (9) | 0.0560 (10) | 0.0559 (9) | −0.0067 (7) | 0.0259 (8) | −0.0064 (7) |
C6 | 0.0632 (11) | 0.0848 (14) | 0.0639 (10) | −0.0191 (9) | 0.0263 (9) | −0.0204 (9) |
C7 | 0.0640 (10) | 0.0476 (9) | 0.0566 (9) | −0.0060 (7) | 0.0289 (8) | −0.0036 (7) |
C8 | 0.0794 (12) | 0.0681 (12) | 0.0603 (10) | −0.0098 (9) | 0.0347 (9) | 0.0001 (8) |
C9 | 0.0605 (10) | 0.0592 (11) | 0.0530 (9) | −0.0006 (8) | 0.0202 (8) | 0.0114 (7) |
C10 | 0.0733 (11) | 0.0664 (12) | 0.0609 (10) | −0.0053 (9) | 0.0268 (9) | 0.0041 (8) |
C11 | 0.0843 (13) | 0.0740 (13) | 0.0589 (10) | −0.0159 (11) | 0.0178 (10) | 0.0090 (9) |
C12 | 0.0717 (12) | 0.0692 (13) | 0.0776 (13) | −0.0067 (10) | 0.0103 (10) | 0.0218 (10) |
C13 | 0.0647 (12) | 0.0807 (15) | 0.0971 (15) | 0.0095 (10) | 0.0248 (11) | 0.0100 (12) |
C14 | 0.0675 (11) | 0.0720 (13) | 0.0707 (11) | 0.0034 (9) | 0.0263 (9) | 0.0024 (9) |
C15 | 0.0803 (15) | 0.115 (2) | 0.1129 (18) | −0.0100 (14) | −0.0070 (13) | 0.0238 (15) |
N1 | 0.0600 (9) | 0.0686 (10) | 0.0529 (8) | −0.0009 (7) | 0.0229 (7) | 0.0087 (7) |
O1 | 0.0738 (9) | 0.1776 (17) | 0.0722 (8) | −0.0339 (10) | 0.0419 (7) | −0.0238 (9) |
O2 | 0.0598 (7) | 0.1195 (12) | 0.0647 (8) | −0.0002 (7) | 0.0263 (6) | 0.0259 (7) |
O3 | 0.0602 (7) | 0.1139 (12) | 0.0750 (9) | −0.0193 (7) | 0.0236 (7) | −0.0142 (8) |
Geometric parameters (Å, º) top
C1—C2 | 1.486 (3) | C8—H8C | 0.96 |
C1—H1A | 0.96 | C9—C14 | 1.377 (2) |
C1—H1B | 0.96 | C9—C10 | 1.383 (2) |
C1—H1C | 0.96 | C9—N1 | 1.427 (2) |
C2—C3 | 1.326 (2) | C10—C11 | 1.380 (3) |
C2—O3 | 1.366 (2) | C10—H10 | 0.93 |
C3—C4 | 1.430 (2) | C11—C12 | 1.379 (3) |
C3—H3 | 0.93 | C11—H11 | 0.93 |
C4—O2 | 1.2637 (19) | C12—C13 | 1.384 (3) |
C4—C5 | 1.436 (2) | C12—C15 | 1.513 (3) |
C5—C7 | 1.419 (2) | C13—C14 | 1.380 (3) |
C5—C6 | 1.440 (2) | C13—H13 | 0.93 |
C6—O1 | 1.208 (2) | C14—H14 | 0.93 |
C6—O3 | 1.396 (2) | C15—H15A | 0.96 |
C7—N1 | 1.324 (2) | C15—H15B | 0.96 |
C7—C8 | 1.491 (2) | C15—H15C | 0.96 |
C8—H8A | 0.96 | N1—H1 | 0.93 (2) |
C8—H8B | 0.96 | | |
| | | |
C2—C1—H1A | 109.5 | H8B—C8—H8C | 109.5 |
C2—C1—H1B | 109.5 | C14—C9—C10 | 119.82 (17) |
H1A—C1—H1B | 109.5 | C14—C9—N1 | 118.16 (15) |
C2—C1—H1C | 109.5 | C10—C9—N1 | 121.80 (16) |
H1A—C1—H1C | 109.5 | C11—C10—C9 | 119.49 (18) |
H1B—C1—H1C | 109.5 | C11—C10—H10 | 120.3 |
C3—C2—O3 | 121.59 (18) | C9—C10—H10 | 120.3 |
C3—C2—C1 | 126.1 (2) | C12—C11—C10 | 121.66 (19) |
O3—C2—C1 | 112.27 (18) | C12—C11—H11 | 119.2 |
C2—C3—C4 | 121.73 (17) | C10—C11—H11 | 119.2 |
C2—C3—H3 | 119.1 | C11—C12—C13 | 117.86 (18) |
C4—C3—H3 | 119.1 | C11—C12—C15 | 120.3 (2) |
O2—C4—C3 | 119.00 (15) | C13—C12—C15 | 121.8 (2) |
O2—C4—C5 | 123.40 (16) | C14—C13—C12 | 121.4 (2) |
C3—C4—C5 | 117.59 (15) | C14—C13—H13 | 119.3 |
C7—C5—C4 | 121.21 (14) | C12—C13—H13 | 119.3 |
C7—C5—C6 | 119.65 (15) | C9—C14—C13 | 119.77 (18) |
C4—C5—C6 | 119.13 (16) | C9—C14—H14 | 120.1 |
O1—C6—O3 | 113.73 (15) | C13—C14—H14 | 120.1 |
O1—C6—C5 | 128.32 (18) | C12—C15—H15A | 109.5 |
O3—C6—C5 | 117.91 (15) | C12—C15—H15B | 109.5 |
N1—C7—C5 | 117.59 (14) | H15A—C15—H15B | 109.5 |
N1—C7—C8 | 118.74 (16) | C12—C15—H15C | 109.5 |
C5—C7—C8 | 123.59 (15) | H15A—C15—H15C | 109.5 |
C7—C8—H8A | 109.5 | H15B—C15—H15C | 109.5 |
C7—C8—H8B | 109.5 | C7—N1—C9 | 128.99 (14) |
H8A—C8—H8B | 109.5 | C7—N1—H1 | 110.9 (12) |
C7—C8—H8C | 109.5 | C9—N1—H1 | 120.1 (12) |
H8A—C8—H8C | 109.5 | C2—O3—C6 | 121.95 (14) |
| | | |
C6—O3—C2—C3 | 0.2 (3) | C9—N1—C7—C8 | 9.5 (3) |
C6—O3—C2—C1 | 179.2 (2) | C4—C5—C7—N1 | −5.8 (2) |
O3—C2—C3—C4 | −1.4 (3) | C6—C5—C7—N1 | 173.21 (16) |
C1—C2—C3—C4 | 179.8 (2) | C4—C5—C7—C8 | 170.90 (16) |
C2—C3—C4—O2 | −178.80 (19) | C6—C5—C7—C8 | −10.1 (2) |
C2—C3—C4—C5 | −0.1 (3) | C7—N1—C9—C14 | −138.75 (18) |
O2—C4—C5—C7 | 0.4 (3) | C7—N1—C9—C10 | 46.6 (3) |
C3—C4—C5—C7 | −178.24 (17) | C14—C9—C10—C11 | 1.2 (3) |
O2—C4—C5—C6 | −178.66 (18) | N1—C9—C10—C11 | 175.70 (16) |
C3—C4—C5—C6 | 2.7 (3) | C9—C10—C11—C12 | −0.5 (3) |
C2—O3—C6—O1 | −175.50 (19) | C10—C11—C12—C13 | −0.5 (3) |
C2—O3—C6—C5 | 2.4 (3) | C10—C11—C12—C15 | 179.76 (19) |
C7—C5—C6—O1 | −5.3 (3) | C11—C12—C13—C14 | 0.8 (3) |
C4—C5—C6—O1 | 173.7 (2) | C15—C12—C13—C14 | −179.5 (2) |
C7—C5—C6—O3 | 177.14 (16) | C10—C9—C14—C13 | −0.9 (3) |
C4—C5—C6—O3 | −3.8 (3) | N1—C9—C14—C13 | −175.62 (17) |
C9—N1—C7—C5 | −173.64 (16) | C12—C13—C14—C9 | −0.1 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.93 (2) | 1.70 (2) | 2.5396 (19) | 148.4 (19) |
C3—H3···O1i | 0.93 | 2.57 | 3.354 (3) | 142 |
C8—H8A···O1 | 0.96 | 2.35 | 2.773 (3) | 106 |
C8—H8C···O2ii | 0.96 | 2.50 | 3.414 (2) | 160 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+3/2, z−1/2. |