Zwitterionic 6-methyl-2-oxo-3-[1-(ureido-iminio)eth-yl]-2H-pyran-4-olate monohydrate.

The title compound, C(9)H(11)N(3)O(4)·H(2)O, was prepared by the reaction of dehydro-acetic acid and semicarbazide hydro-chloride. It crystallizes in a zwitterionic form with cationic iminium and anionic enolate groups. In the crystal structure, the almost planar mol-ecules are held together by N-H⋯O, O-H⋯O and C-H⋯O hydrogen bonds, some of them involving the water molecules.

Related literature

For related literature, see: Tai et al. (2007 ▶); Zu-Pei Liang et al. (2007 ▶); Wojciechowski et al. (2003 ▶); Petek et al. (2006 ▶); Huang et al. (2006 ▶); Bernstein et al. (1995 ▶); Girija & Begum (2004a ▶); Girija et al. (2004b ▶); Gowda et al. (2007 ▶)..

Experimental

Crystal data

C9H11N3O4·H2O

M = 243.22

Monoclinic,

a = 7.1731 (4) Å

b = 12.6590 (10) Å

c = 12.3698 (3) Å

β = 104.603 (6)°

V = 1086.95 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.12 mm−1

T = 173 (2) K

0.35 × 0.05 × 0.02 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: none

11787 measured reflections

2485 independent reflections

1699 reflections with I > 2σ(I)

R int = 0.055

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.121

S = 1.03

2485 reflections

178 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.26 e Å−3

Data collection: COLLECT (Nonius, 1997 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); 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 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808026032/wk2091sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808026032/wk2091Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C9H11N3O4·H2O	F000 = 512
Mr = 243.22	Dx = 1.486 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2841 reflections
a = 7.1731 (4) Å	θ = 3.1–25.8º
b = 12.6590 (10) Å	µ = 0.12 mm−1
c = 12.3698 (3) Å	T = 173 (2) K
β = 104.603 (6)º	Prism, yellow
V = 1086.95 (11) Å3	0.35 × 0.05 × 0.02 mm
Z = 4

Nonius KappaCCD diffractometer	1699 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.055
Detector resolution: 9 pixels mm-1	θmax = 27.5º
T = 173(2) K	θmin = 2.9º
CCD scans	h = −9→9
Absorption correction: none	k = −16→15
11787 measured reflections	l = −15→16
2485 independent reflections

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)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.121	w = 1/[σ2(Fo2) + (0.0289P)2 + 0.445P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
2485 reflections	Δρmax = 0.33 e Å−3
178 parameters	Δρmin = −0.26 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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.

	x	y	z	Uiso*/Ueq
C1	0.5343 (3)	−0.25527 (15)	0.37044 (14)	0.0287 (4)
C2	0.7633 (2)	−0.06094 (14)	0.56842 (14)	0.0253 (4)
C3	0.8032 (4)	−0.11552 (17)	0.67854 (16)	0.0476 (6)
H3A	0.7151	−0.1734	0.6744	0.057*
H3B	0.7871	−0.0666	0.7348	0.057*
H3C	0.9329	−0.1418	0.6974	0.057*
C4	0.8087 (2)	0.04894 (13)	0.55327 (13)	0.0240 (4)
C5	0.9088 (3)	0.11044 (14)	0.64744 (15)	0.0292 (4)
C6	0.8929 (3)	0.26084 (15)	0.52451 (15)	0.0305 (4)
C7	0.8054 (3)	0.20520 (15)	0.43545 (15)	0.0316 (4)
H7	0.7733	0.2375	0.3657	0.038*
C8	0.7593 (2)	0.09564 (14)	0.44518 (14)	0.0269 (4)
C9	0.9441 (3)	0.37503 (16)	0.52619 (18)	0.0422 (5)
H9A	0.9024	0.4034	0.452	0.051*
H9B	1.0812	0.3829	0.5527	0.051*
H9C	0.8817	0.4123	0.5749	0.051*
N1	0.4877 (3)	−0.35801 (14)	0.36960 (16)	0.0397 (4)
N2	0.6282 (2)	−0.21693 (12)	0.47382 (13)	0.0336 (4)
N3	0.6811 (2)	−0.11234 (12)	0.47752 (12)	0.0272 (3)
O1	0.9689 (2)	0.08309 (11)	0.74427 (10)	0.0424 (4)
O3	0.6744 (2)	0.04451 (10)	0.35702 (10)	0.0369 (4)
O2	0.9464 (2)	0.21590 (10)	0.62831 (10)	0.0355 (3)
O4	0.4983 (2)	−0.19779 (11)	0.28793 (11)	0.0414 (4)
O1W	0.6521 (3)	−0.10956 (13)	0.12207 (12)	0.0470 (4)
H11W	0.597 (4)	−0.131 (2)	0.168 (2)	0.071*
H21W	0.763 (4)	−0.103 (2)	0.160 (2)	0.071*
H1A	0.440 (3)	−0.3872 (19)	0.308 (2)	0.048 (7)*
H1B	0.514 (3)	−0.3924 (17)	0.4326 (19)	0.037 (6)*
H2	0.650 (3)	−0.2591 (18)	0.5351 (19)	0.042 (6)*
H3	0.656 (4)	−0.069 (2)	0.410 (2)	0.075 (8)*

	U11	U22	U33	U12	U13	U23
C1	0.0301 (9)	0.0304 (10)	0.0238 (8)	−0.0033 (7)	0.0036 (7)	−0.0023 (7)
C2	0.0258 (9)	0.0274 (9)	0.0222 (8)	0.0011 (7)	0.0049 (7)	0.0004 (7)
C3	0.0780 (16)	0.0371 (12)	0.0232 (10)	−0.0137 (11)	0.0043 (10)	0.0025 (8)
C4	0.0260 (9)	0.0241 (9)	0.0203 (8)	0.0006 (7)	0.0028 (7)	−0.0015 (6)
C5	0.0318 (10)	0.0288 (10)	0.0254 (9)	−0.0014 (8)	0.0042 (7)	−0.0023 (7)
C6	0.0341 (10)	0.0264 (9)	0.0306 (9)	−0.0012 (7)	0.0073 (8)	0.0002 (7)
C7	0.0379 (11)	0.0283 (10)	0.0256 (9)	0.0005 (8)	0.0023 (8)	0.0046 (7)
C8	0.0283 (9)	0.0260 (9)	0.0237 (9)	0.0027 (7)	0.0016 (7)	−0.0001 (7)
C9	0.0557 (13)	0.0270 (10)	0.0417 (12)	−0.0078 (9)	0.0082 (10)	−0.0023 (8)
N1	0.0568 (12)	0.0304 (9)	0.0295 (9)	−0.0110 (8)	0.0063 (8)	−0.0035 (8)
N2	0.0488 (10)	0.0240 (8)	0.0243 (8)	−0.0078 (7)	0.0023 (7)	0.0014 (6)
N3	0.0330 (8)	0.0230 (8)	0.0225 (7)	−0.0021 (6)	0.0016 (6)	0.0002 (6)
O1	0.0586 (9)	0.0412 (8)	0.0201 (6)	−0.0112 (7)	−0.0036 (6)	0.0005 (6)
O3	0.0539 (9)	0.0288 (7)	0.0204 (6)	−0.0043 (6)	−0.0046 (6)	0.0014 (5)
O2	0.0480 (8)	0.0284 (7)	0.0264 (7)	−0.0085 (6)	0.0024 (6)	−0.0033 (5)
O4	0.0562 (9)	0.0366 (8)	0.0248 (7)	−0.0108 (7)	−0.0018 (6)	0.0027 (6)
O1W	0.0593 (10)	0.0501 (10)	0.0294 (8)	−0.0083 (8)	0.0068 (7)	−0.0032 (7)

C1—O4	1.227 (2)	C6—C9	1.490 (3)
C1—N1	1.342 (2)	C7—C8	1.438 (3)
C1—N2	1.375 (2)	C7—H7	0.93
C2—N3	1.304 (2)	C8—O3	1.282 (2)
C2—C4	1.452 (2)	C9—H9A	0.96
C2—C3	1.489 (2)	C9—H9B	0.96
C3—H3A	0.96	C9—H9C	0.96
C3—H3B	0.96	N1—H1A	0.84 (3)
C3—H3C	0.96	N1—H1B	0.87 (2)
C4—C8	1.423 (2)	N2—N3	1.375 (2)
C4—C5	1.434 (2)	N2—H2	0.91 (2)
C5—O1	1.217 (2)	N3—H3	0.98 (3)
C5—O2	1.394 (2)	O1W—H11W	0.82 (3)
C6—C7	1.325 (3)	O1W—H21W	0.82 (3)
C6—O2	1.368 (2)
O4—C1—N1	124.65 (17)	C6—C7—H7	119.5
O4—C1—N2	121.02 (17)	C8—C7—H7	119.5
N1—C1—N2	114.33 (16)	O3—C8—C4	122.81 (16)
N3—C2—C4	115.73 (15)	O3—C8—C7	119.05 (15)
N3—C2—C3	119.87 (17)	C4—C8—C7	118.13 (15)
C4—C2—C3	124.41 (16)	C6—C9—H9A	109.5
C2—C3—H3A	109.5	C6—C9—H9B	109.5
C2—C3—H3B	109.5	H9A—C9—H9B	109.5
H3A—C3—H3B	109.5	C6—C9—H9C	109.5
C2—C3—H3C	109.5	H9A—C9—H9C	109.5
H3A—C3—H3C	109.5	H9B—C9—H9C	109.5
H3B—C3—H3C	109.5	C1—N1—H1A	118.7 (16)
C8—C4—C5	119.53 (16)	C1—N1—H1B	118.7 (14)
C8—C4—C2	120.58 (15)	H1A—N1—H1B	122 (2)
C5—C4—C2	119.87 (15)	N3—N2—C1	115.93 (15)
O1—C5—O2	113.83 (16)	N3—N2—H2	123.4 (14)
O1—C5—C4	128.74 (18)	C1—N2—H2	120.7 (14)
O2—C5—C4	117.43 (15)	C2—N3—N2	124.75 (15)
C7—C6—O2	121.43 (17)	C2—N3—H3	113.8 (17)
C7—C6—C9	126.21 (18)	N2—N3—H3	121.4 (17)
O2—C6—C9	112.36 (16)	C6—O2—C5	122.49 (14)
C6—C7—C8	120.93 (17)	H11W—O1W—H21W	102 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3i	0.84 (2)	2.18 (2)	3.015 (2)	176.3 (17)
N1—H1B···O1Wii	0.87 (2)	2.30 (2)	3.075 (2)	147.9 (19)
N2—H2···O1Wii	0.91 (2)	1.98 (2)	2.839 (2)	158 (2)
N3—H3···O3	0.98 (2)	1.60 (3)	2.476 (2)	147 (2)
O1W—H11W···O4	0.82 (3)	1.99 (3)	2.796 (2)	171 (3)
O1W—H21W···O1iii	0.82 (3)	2.00 (3)	2.823 (2)	178.0 (18)
C3—H3B···O1	0.96	2.29	2.812 (3)	114
C7—H7···O4iv	0.93	2.49	3.294 (2)	145

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3i	0.84 (2)	2.18 (2)	3.015 (2)	176.3 (17)
N1—H1B⋯O1Wii	0.87 (2)	2.30 (2)	3.075 (2)	147.9 (19)
N2—H2⋯O1Wii	0.91 (2)	1.98 (2)	2.839 (2)	158 (2)
N3—H3⋯O3	0.98 (2)	1.60 (3)	2.476 (2)	147 (2)
O1W—H11W⋯O4	0.82 (3)	1.99 (3)	2.796 (2)	171 (3)
O1W—H21W⋯O1iii	0.82 (3)	2.00 (3)	2.823 (2)	178.0 (18)
C3—H3B⋯O1	0.96	2.29	2.812 (3)	114
C7—H7⋯O4iv	0.93	2.49	3.294 (2)	145

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .