Zwitterionic (E)-6-methyl-2-oxo-3-[1-(p-tolyl­iminio)eth­yl]-2H-pyran-4-olate

The title compound, C₁₅H₁₅NO₃, 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.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C)= 0.003 Å
• R factor = 0.040
• wR factor = 0.110
• Data-to-parameter ratio = 14.4

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Computing details

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]-2H-pyran-4-olate

Crystal data

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) Å^3	0.35 × 0.05 × 0.02 mm
Z = 4

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 0.88	w = 1/[σ^2(Fo^2) + (0.0634P)^2] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

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···O1^i	0.93	2.57	3.354 (3)	142
C8—H8A···O1	0.96	2.35	2.773 (3)	106
C8—H8C···O2^ii	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.