Ethyl 2-[(carbamoyl-amino)-imino]-propano-ate hemihydrate.

The title compound, C(6)H(11)N(3)O(3)·0.5H(2)O, has two independent mol-ecules and one mol-ecule of water in the asymmetric unit. The crystal packing is stabilized by inter-molecular N-H⋯N, O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds. These inter-actions form a two-dimensional array in the ab plane with a zigzag motif which has an angle close to 35° between the zigzag planes. The hydrogen bonding can be best described using the graph-set notation as N(1) = C(10)R(2) (2)(10)R(2) (2)(8) and N(2) = R(6) (4)(20)R(2) (2)(8).

Related literature

For the synthesis and applications of ethyl pyruvate semicarbazone, see: Kulka (1946 ▶); Dimmock et al. (1993 ▶); Cerecetto et al. (2000 ▶); Armor (1992 ▶). For hydrogen-bond motifs, see: Etter et al. (1990 ▶).

Experimental

Crystal data

C6H11N3O3·0.5H2O

M = 182.19

Monoclinic,

a = 11.173 (2) Å

b = 14.756 (3) Å

c = 11.565 (2) Å

β = 103.14 (3)°

V = 1856.8 (6) Å3

Z = 8

Mo Kα radiation

μ = 0.11 mm−1

T = 293 K

0.21 × 0.10 × 0.09 mm

Data collection

Nonius KappaCCD diffractometer

18093 measured reflections

4228 independent reflections

1816 reflections with I > 2σ(I)

R int = 0.109

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.137

S = 1.00

4228 reflections

255 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.20 e Å−3

Δρmin = −0.18 e Å−3

Data collection: COLLECT (Hooft, 1999 ▶); 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: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681102530X/qm2011sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681102530X/qm2011Isup2.hkl

Supplementary material file. DOI: 10.1107/S160053681102530X/qm2011Isup3.cml

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

C6H11N3O3·0.5H2O	F(000) = 776
Mr = 182.19	Dx = 1.303 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 33 reflections
a = 11.173 (2) Å	θ = 4.5–18.2°
b = 14.756 (3) Å	µ = 0.11 mm−1
c = 11.565 (2) Å	T = 293 K
β = 103.14 (3)°	Prism, colourless
V = 1856.8 (6) Å3	0.21 × 0.10 × 0.09 mm
Z = 8

Nonius KappaCCD diffractometer	1816 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.109
horizonally mounted graphite crystal	θmax = 27.5°, θmin = 5.2°
Detector resolution: 9 pixels mm-1	h = −13→14
CCD scans	k = −18→19
18093 measured reflections	l = −15→14
4228 independent reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.059	w = 1/[σ2(Fo2) + (0.045P)2 + 0.5582P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.137	(Δ/σ)max < 0.001
S = 1.00	Δρmax = 0.20 e Å−3
4228 reflections	Δρmin = −0.18 e Å−3
255 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.0059 (11)
Primary atom site location: structure-invariant direct methods	Absolute structure: no
Secondary atom site location: difference Fourier map

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.

	x	y	z	Uiso*/Ueq
N6	0.63805 (17)	0.15088 (15)	0.54625 (17)	0.0361 (5)
O4	0.88839 (14)	0.22111 (13)	0.43482 (14)	0.0462 (5)
O1	1.12914 (15)	0.27042 (14)	0.71551 (14)	0.0482 (5)
N5	0.70387 (18)	0.17912 (16)	0.4671 (2)	0.0387 (6)
N2	1.31214 (18)	0.31483 (16)	0.6804 (2)	0.0394 (6)
N3	1.37693 (17)	0.34035 (15)	0.59917 (16)	0.0347 (5)
O6	0.34452 (15)	0.08529 (13)	0.56959 (15)	0.0493 (5)
O3	1.66804 (14)	0.40150 (13)	0.56711 (15)	0.0451 (5)
O7	1.25278 (16)	0.33845 (15)	0.32243 (15)	0.0577 (6)
H7A	1.3224	0.3672	0.3643	0.087*
H7B	1.1933	0.3754	0.2876	0.087*
C8	0.5218 (2)	0.13447 (18)	0.5091 (2)	0.0339 (6)
N1	1.1427 (2)	0.29295 (18)	0.52453 (19)	0.0458 (7)
C1	1.1895 (2)	0.29159 (18)	0.6407 (2)	0.0337 (6)
C2	1.4919 (2)	0.36056 (17)	0.6338 (2)	0.0333 (6)
C7	0.8274 (2)	0.19917 (18)	0.5083 (2)	0.0370 (7)
O5	0.51752 (17)	0.09562 (17)	0.71042 (17)	0.0733 (7)
O2	1.49015 (16)	0.39939 (15)	0.42999 (16)	0.0612 (6)
N4	0.8733 (2)	0.19408 (19)	0.6242 (2)	0.0503 (7)
C9	0.4642 (2)	0.10351 (19)	0.6078 (2)	0.0420 (7)
C3	1.5468 (2)	0.38847 (19)	0.5318 (2)	0.0397 (7)
C10	0.2801 (2)	0.0561 (2)	0.6597 (3)	0.0576 (9)
H10A	0.2850	0.1026	0.7199	0.069*
H10B	0.3167	0.0010	0.6978	0.069*
C12	0.4459 (2)	0.1434 (2)	0.3850 (2)	0.0542 (8)
H12A	0.4931	0.1239	0.3298	0.081*
H12B	0.4223	0.2056	0.3696	0.081*
H12C	0.3736	0.1065	0.3759	0.081*
C11	0.1485 (3)	0.0396 (2)	0.5977 (3)	0.0725 (10)
H11A	0.1141	0.0941	0.5584	0.109*
H11B	0.1026	0.0221	0.6549	0.109*
H11C	0.1446	−0.0079	0.5403	0.109*
C5	1.8633 (3)	0.4440 (2)	0.5311 (3)	0.0700 (10)
H5A	1.8705	0.4941	0.5852	0.105*
H5B	1.9075	0.4575	0.4709	0.105*
H5C	1.8971	0.3906	0.5735	0.105*
C4	1.7302 (2)	0.4283 (2)	0.4739 (3)	0.0533 (8)
H4A	1.6936	0.4833	0.4354	0.064*
H4B	1.7223	0.3809	0.4145	0.064*
C6	1.5688 (2)	0.3594 (2)	0.7578 (2)	0.0595 (9)
H6A	1.6120	0.4159	0.7742	0.089*
H6B	1.6270	0.3106	0.7661	0.089*
H6C	1.5169	0.3509	0.8126	0.089*
H2N	1.344 (2)	0.3065 (15)	0.753 (2)	0.026 (7)*
H4N1	0.949 (3)	0.2061 (19)	0.653 (2)	0.061 (9)*
H1N1	1.066 (3)	0.2794 (19)	0.501 (2)	0.055 (9)*
H5N	0.672 (2)	0.1881 (19)	0.395 (2)	0.056 (9)*
H4N2	0.826 (3)	0.1839 (18)	0.678 (2)	0.051 (8)*
H1N2	1.190 (3)	0.3057 (18)	0.475 (2)	0.048 (8)*

	U11	U22	U33	U12	U13	U23
N6	0.0261 (11)	0.0499 (15)	0.0330 (12)	−0.0012 (10)	0.0084 (9)	0.0002 (10)
O4	0.0291 (9)	0.0795 (15)	0.0315 (10)	−0.0106 (10)	0.0100 (8)	−0.0059 (10)
O1	0.0293 (9)	0.0856 (16)	0.0318 (10)	−0.0126 (10)	0.0115 (8)	−0.0038 (10)
N5	0.0262 (11)	0.0616 (17)	0.0279 (12)	−0.0037 (11)	0.0054 (10)	−0.0026 (12)
N2	0.0243 (11)	0.0687 (18)	0.0248 (12)	−0.0053 (11)	0.0048 (9)	0.0055 (12)
N3	0.0262 (11)	0.0472 (15)	0.0316 (12)	−0.0042 (10)	0.0082 (9)	0.0021 (10)
O6	0.0295 (9)	0.0687 (14)	0.0507 (11)	−0.0117 (10)	0.0113 (8)	0.0018 (10)
O3	0.0249 (9)	0.0636 (14)	0.0499 (11)	−0.0033 (9)	0.0150 (8)	0.0059 (10)
O7	0.0378 (10)	0.0966 (16)	0.0365 (9)	0.0016 (11)	0.0036 (8)	−0.0013 (11)
C8	0.0269 (13)	0.0424 (17)	0.0326 (14)	0.0004 (12)	0.0071 (11)	0.0002 (12)
N1	0.0259 (12)	0.081 (2)	0.0305 (13)	−0.0111 (13)	0.0063 (11)	−0.0008 (12)
C1	0.0244 (13)	0.0485 (18)	0.0287 (14)	−0.0020 (12)	0.0071 (11)	−0.0032 (12)
C2	0.0227 (12)	0.0410 (17)	0.0366 (14)	0.0009 (12)	0.0073 (10)	0.0007 (12)
C7	0.0266 (13)	0.0505 (19)	0.0336 (15)	−0.0015 (13)	0.0062 (12)	−0.0056 (13)
O5	0.0409 (11)	0.132 (2)	0.0447 (12)	−0.0193 (13)	0.0040 (10)	0.0239 (13)
O2	0.0401 (11)	0.1044 (18)	0.0385 (11)	−0.0128 (12)	0.0076 (9)	0.0136 (11)
N4	0.0290 (13)	0.093 (2)	0.0281 (13)	−0.0114 (13)	0.0049 (11)	−0.0015 (13)
C9	0.0288 (14)	0.052 (2)	0.0444 (17)	−0.0046 (13)	0.0061 (12)	0.0043 (14)
C3	0.0295 (14)	0.0485 (19)	0.0423 (16)	−0.0007 (13)	0.0107 (12)	0.0012 (14)
C10	0.0437 (17)	0.071 (2)	0.065 (2)	−0.0103 (16)	0.0258 (15)	0.0107 (17)
C12	0.0320 (15)	0.084 (2)	0.0445 (17)	−0.0064 (15)	0.0040 (13)	0.0101 (16)
C11	0.0404 (17)	0.077 (3)	0.106 (3)	−0.0113 (17)	0.0272 (18)	0.005 (2)
C5	0.0455 (17)	0.081 (3)	0.093 (2)	−0.0205 (17)	0.0336 (17)	−0.013 (2)
C4	0.0407 (16)	0.061 (2)	0.066 (2)	−0.0024 (15)	0.0293 (15)	0.0131 (16)
C6	0.0288 (14)	0.104 (3)	0.0435 (17)	−0.0072 (16)	0.0042 (13)	0.0098 (17)

N6—C8	1.295 (3)	O7—H7B	0.8700
N6—N5	1.363 (3)	N1—H1N1	0.86 (3)
O4—C7	1.246 (3)	N1—H1N2	0.88 (3)
O1—C1	1.252 (3)	N2—H2N	0.84 (2)
N5—C7	1.386 (3)	N5—H5N	0.84 (2)
N2—N3	1.363 (3)	N4—H4N1	0.85 (3)
N2—C1	1.386 (3)	N4—H4N2	0.92 (3)
N3—C2	1.291 (3)	C5—H5C	0.9600
O6—C9	1.337 (3)	C5—H5A	0.9600
O6—C10	1.460 (3)	C5—H5B	0.9600
O3—C3	1.337 (3)	C4—H4A	0.9700
O3—C4	1.463 (3)	C4—H4B	0.9700
C8—C12	1.498 (3)	C6—H6C	0.9600
C8—C9	1.503 (3)	C6—H6A	0.9600
N1—C1	1.326 (3)	C6—H6B	0.9600
C2—C6	1.495 (3)	C11—H11A	0.9600
C2—C3	1.505 (3)	C11—H11B	0.9600
C7—N4	1.324 (3)	C11—H11C	0.9600
O5—C9	1.207 (3)	C10—H10A	0.9700
O2—C3	1.215 (3)	C10—H10B	0.9700
C10—C11	1.502 (4)	C12—H12A	0.9600
C5—C4	1.502 (4)	C12—H12B	0.9600
O7—H7A	0.9100	C12—H12C	0.9600
O1···N5i	2.935 (3)	O5···O7iv	2.826 (3)
O1···C12i	3.388 (3)	O7···O5v	2.826 (3)
O1···N4	3.030 (3)	O7···N6v	3.164 (3)
O2···C3ii	3.201 (4)	O7···O2	2.809 (3)
O2···O7	2.809 (3)	O7···N1	2.955 (3)
O2···N3	2.704 (3)	O7···N3	3.186 (3)
O4···N1	2.989 (3)	O7···N4v	2.950 (3)
O4···C6iii	3.397 (3)	N1···N3	2.656 (3)
O4···N2iii	2.920 (3)	N4···N6	2.655 (3)
O5···N6	2.692 (3)
C8—N6—N5	119.2 (2)	C7—N4—H4N1	120.3 (16)
N6—N5—C7	118.8 (2)	C7—N4—H4N2	123.1 (16)
N3—N2—C1	118.7 (2)	H5A—C5—H5B	109.00
C2—N3—N2	119.8 (2)	H5B—C5—H5C	109.00
C9—O6—C10	116.3 (2)	H5A—C5—H5C	110.00
C3—O3—C4	115.6 (2)	C4—C5—H5C	109.00
N6—C8—C12	127.4 (2)	C4—C5—H5B	109.00
N6—C8—C9	112.1 (2)	O3—C4—H4A	110.00
C12—C8—C9	120.5 (2)	O3—C4—H4B	110.00
O1—C1—N1	123.6 (2)	H4A—C4—H4B	109.00
O1—C1—N2	118.7 (2)	C5—C4—H4A	110.00
N1—C1—N2	117.7 (2)	C5—C4—H4B	110.00
N3—C2—C6	127.6 (2)	C2—C6—H6C	109.00
N3—C2—C3	112.0 (2)	H6B—C6—H6A	109.00
C6—C2—C3	120.4 (2)	C2—C6—H6B	109.00
O4—C7—N4	124.0 (2)	H6B—C6—H6C	110.00
O4—C7—N5	118.5 (2)	H6A—C6—H6C	109.00
N4—C7—N5	117.5 (2)	C2—C6—H6A	109.00
O5—C9—O6	122.6 (2)	C10—C11—H11A	109.00
O5—C9—C8	125.1 (2)	C10—C11—H11B	109.00
O6—C9—C8	112.3 (2)	H11A—C11—H11B	109.00
O2—C3—O3	123.1 (2)	H11A—C11—H11C	109.00
O2—C3—C2	125.5 (2)	H11B—C11—H11C	109.00
O3—C3—C2	111.4 (2)	C10—C11—H11C	110.00
O6—C10—C11	107.2 (2)	O6—C10—H10A	110.00
O3—C4—C5	107.8 (2)	C11—C10—H10A	110.00
H7A—O7—H7B	114.00	C11—C10—H10B	110.00
C1—N1—H1N2	120.3 (18)	O6—C10—H10B	110.00
H1N1—N1—H1N2	123 (2)	C8—C12—H12B	109.00
C1—N1—H1N1	116.8 (16)	C8—C12—H12C	109.00
C1—N2—H2N	117.1 (16)	C8—C12—H12A	109.00
N3—N2—H2N	123.8 (16)	H12A—C12—H12C	109.00
C7—N5—H5N	118.2 (16)	H12B—C12—H12C	109.00
N6—N5—H5N	122.9 (16)	H12A—C12—H12B	110.00
C4—O3—C3—O2	−1.3 (4)	N6—N5—C7—O4	176.9 (2)
C4—O3—C3—C2	179.6 (2)	N6—N5—C7—N4	−3.4 (4)
C3—O3—C4—C5	177.3 (2)	N5—N6—C8—C9	179.6 (2)
C10—O6—C9—C8	−179.0 (2)	N5—N6—C8—C12	−0.5 (4)
C9—O6—C10—C11	180.0 (3)	N3—C2—C3—O2	6.4 (4)
C10—O6—C9—O5	0.8 (4)	C6—C2—C3—O2	−173.1 (3)
C1—N2—N3—C2	−178.6 (2)	C6—C2—C3—O3	6.0 (3)
N3—N2—C1—O1	−178.2 (2)	N3—C2—C3—O3	−174.5 (2)
N3—N2—C1—N1	2.0 (4)	N6—C8—C9—O5	1.0 (4)
N2—N3—C2—C6	0.4 (4)	N6—C8—C9—O6	−179.1 (2)
N2—N3—C2—C3	−179.1 (2)	C12—C8—C9—O5	−178.9 (3)
C7—N5—N6—C8	178.1 (2)	C12—C8—C9—O6	1.0 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4N1···O1	0.85 (3)	2.19 (3)	3.030 (3)	166 (3)
N1—H1N1···O4	0.86 (3)	2.14 (3)	2.989 (3)	169 (3)
N2—H2N···O4i	0.84 (2)	2.09 (2)	2.920 (3)	169 (2)
N4—H4N2···O7iv	0.92 (3)	2.05 (3)	2.950 (3)	169 (3)
N1—H1N2···N3	0.88 (3)	2.31 (3)	2.656 (3)	103.5 (18)
N1—H1N2···O7	0.88 (3)	2.10 (3)	2.955 (3)	163 (3)
N5—H5N···O1iii	0.84 (2)	2.11 (2)	2.935 (3)	167 (2)
O7—H7A···O2	0.92	1.92	2.809 (3)	163
O7—H7B···O5v	0.88	2.01	2.826 (3)	153
C6—H6C···O4i	0.96	2.47	3.397 (3)	162
C6—H6C···N2	0.96	2.50	2.879 (3)	103
C12—H12C···O6	0.96	2.36	2.770 (3)	105

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4N1⋯O1	0.85 (3)	2.19 (3)	3.030 (3)	166 (3)
N1—H1N1⋯O4	0.86 (3)	2.14 (3)	2.989 (3)	169 (3)
N2—H2N⋯O4i	0.84 (2)	2.09 (2)	2.920 (3)	169 (2)
N4—H4N2⋯O7ii	0.92 (3)	2.05 (3)	2.950 (3)	169 (3)
N1—H1N2⋯N3	0.88 (3)	2.31 (3)	2.656 (3)	103.5 (18)
N1—H1N2⋯O7	0.88 (3)	2.10 (3)	2.955 (3)	163 (3)
N5—H5N⋯O1iii	0.84 (2)	2.11 (2)	2.935 (3)	167 (2)
O7—H7A⋯O2	0.92	1.92	2.809 (3)	163
O7—H7B⋯O5iv	0.88	2.01	2.826 (3)	153
C6—H6C⋯O4i	0.96	2.47	3.397 (3)	162

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