Ethyl 2-[(carbamoyl­amino)­imino]­propano­ate hemihydrate

Corrêa, C.C.; Graúdo, J.E.J.C.; Oliveira, L.F.C. de; Almeida, M.V. de; Diniz, R.

doi:10.1107/S160053681102530X

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o1882

doi:10.1107/S160053681102530X

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Ethyl 2-[(carbamoylamino)imino]propanoate hemihydrate

Charlane C. Corrêa,^a ^* José Eugênio J. C. Graúdo,^a Luiz Fernando C. de Oliveira,^a Mauro V. de Almeida ^b and Renata Diniz ^a

^aNúcleo de Espectroscopia e Estrutura Molecular (NEEM), Department of Chemistry - Federal University of Juiz de Fora - Minas Gerais, 36036-900, Brazil, and ^bDepartment of Chemistry - Federal University of Juiz de Fora - Minas Gerais, 36036-900, Brazil
^*Correspondence e-mail: charcorrea@gmail.com

(Received 7 June 2011; accepted 27 June 2011; online 2 July 2011)

The title compound, C₆H₁₁N₃O₃·0.5H₂O, has two independent molecules and one molecule of water in the asymmetric unit. The crystal packing is stabilized by intermolecular N—H⋯N, O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds. These interactions 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 N₁ = C(10)R₂²(10)R₂²(8) and N₂ = R₆⁴(20)R₂²(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_r = 182.19
Monoclinic, P 2₁ /n
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[F² > 2σ(F²)] = 0.059
wR(F²) = 0.137
S = 1.00
4228 reflections
255 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.18 e Å⁻³

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⋯O5^iv	0.88	2.01	2.826 (3)	153
C6—H6C⋯O4ⁱ	0.96	2.47	3.397 (3)	162
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681102530X/qm2011sup1.cif

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

Supporting information file. DOI: 10.1107/S160053681102530X/qm2011Isup3.cml

checkCIF report

Comment top

Semicarbazones have been important in the consistent advances in design of novel anticonvulsant agents through the work of Dimmock et al. (Dimmock,1993); the aryl semicarbazone 4-bromobenzaldehyde semicarbazone has been a standard anticonvulsant drug selected by the National Institutes of Health, USA. They can also be used as drugs for Chagas's disease (Cerecetto, 2000) as well as hypnotic, pesticide and herbicide uses (Armor, 1992). The synthesis of ethyl pyruvate semicarbazone (spe) (Scheme I) was reported more than 60 years (Kulka, 1946); but to date the structure determination has not been reported. This structure will permit further study of the metal coordination properties of these interesting ligands.

Figure 1 shows the ORTEP representation of the asymmetric unit of spe. There are two crystallographically independent molecules and one water of crystallization in the asymmetric unit. The main differences between these molecules are the distances involved in the hydrogen bonds between [O4···H1N1···N1 = 2.989 (3) Å; O1···H4N1···N4 = 3.030 (3) Å; O7···H1N2···N1 = 2.955 (3) Å and O7ⁱ···H4N2···N4 = 2.950 (3) Å] (symmetry code: i: x - 1/2, -y + 1/2, z + 1/2) and also by the torsion angles between the groups CH₃ and CH₂ [C10—O6—C9—O5 = 0.8 (4)° and C4—O3—C3—O2 =-1.3 (4)°; C10—O6—C9—C8 = -179.00 (2)° and C4—O3—C3—C2 = 179,60 (2)°; C12—C8—C9—O5 = -178.90 (3)° and C6—C2—C3—O2 = - 173.10 (3)°; C12—C8—C9—O6 = 1.0 (4)° and C6—C2—C3—O3 = 6.0 (3)°]. The water molecule of crystallization stabilizes the crystal lattice by the intermolecular hydrogen bonds N—H···N, O—H···O and O—H···N, with average distances between the electronegative atoms of: 2.656 (3), 2.818 (3), 2.963 (3) Å, respectively. The hydrogen bonding scheme is displayed in Figure 2 and using the graph-set notation the system can be best described as N₁=C(10)R₂²(10)R₂²(8) and N₂=R₆⁴(20)R₂²(8) (Etter, 1990).

There are two isomeric forms for compounds derived from ethyl pyruvate semicarbazone namely the E and Z isomers. The present structure is clearly the E form, Figures 1 and 2. The molecules of spe form a two-dimensional array in the ab plane with a zigzag motif which has an angle close to 35° between the zigzag planes.

Related literature top

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 top

For the preparation of ethyl pyruvate semicarbazone spe, 50 ml of an aqueous solution of semicarbazide chloride (1.019 g, 9.14 mmol) was added to a 50 ml of an ethanolic solution of ethylpyruvate (1.060 g, 9.14 mmol) and amonium acetate (0.744 g, 9.66 mmol), and the final mixture was heated at 80 °C for 6 h. Colorless crystals were formed. The compound decomposes at 175 °C. Elemental analysis gave the following results: Anal. Calcd. for C₆H₁₃O₄N₃: C,37,69; H,6,85; N,21,98%; Found: C,38,33; H,5,85; N,22,09%. Infrared spectra show absorption bands at 3506–3170 cm^-1 (νNH + νOH); 1698 cm^-1 (νCO); 1599 cm^-1 (νNH + νCN + νCC); 1480 cm^-1(νCOasym); 1357 cm^-1 (νCN); 1144 cm^-1 (νCOsym) and 1103 cm^-1 (νCOC).

Computing details top

Data collection: COLLECT (Hooft, 1999); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor 1997); 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).

Figures top

	Fig. 1. View ORTEP of crystal structure of compound spe.
	Fig. 2. Hydrogen bonds between molecules of ethyl pyruvate semicarbazone and the water molecule, elucidating the ring formed by hydrogen bonds.
	Fig. 3. Crystal packing of compound spe, viewed along the c axis.

Ethyl 2-[(carbamoylamino)imino]propanoate hydrate top

Crystal data top

C₆H₁₁N₃O₃·0.5H₂O	F(000) = 776
M_r = 182.19	D_x = 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

Data collection top

Nonius KappaCCD diffractometer	1816 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.109
Horizonally mounted graphite crystal monochromator	θ_max = 27.5°, θ_min = 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 top

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(F_o²) + (0.045P)² + 0.5582P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.137	(Δ/σ)_max < 0.001
S = 1.00	Δρ_max = 0.20 e Å⁻³
4228 reflections	Δρ_min = −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

Crystal data top

C₆H₁₁N₃O₃·0.5H₂O	V = 1856.8 (6) Å³
M_r = 182.19	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.173 (2) Å	µ = 0.11 mm⁻¹
b = 14.756 (3) Å	T = 293 K
c = 11.565 (2) Å	0.21 × 0.10 × 0.09 mm
β = 103.14 (3)°

Data collection top

Nonius KappaCCD diffractometer	1816 reflections with I > 2σ(I)
18093 measured reflections	R_int = 0.109
4228 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.20 e Å⁻³
4228 reflections	Δρ_min = −0.18 e Å⁻³
255 parameters	Absolute structure: no

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	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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···O7^iv	2.826 (3)
O1···C12ⁱ	3.388 (3)	O7···O5^v	2.826 (3)
O1···N4	3.030 (3)	O7···N6^v	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···N4^v	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)

Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+3, −y+1, −z+1; (iii) x−1/2, −y+1/2, z−1/2; (iv) x−1/2, −y+1/2, z+1/2; (v) x+1/2, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

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···O7^iv	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···O5^v	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

Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (iii) x−1/2, −y+1/2, z−1/2; (iv) x−1/2, −y+1/2, z+1/2; (v) x+1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₆H₁₁N₃O₃·0.5H₂O
M_r	182.19
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	11.173 (2), 14.756 (3), 11.565 (2)
β (°)	103.14 (3)
V (Å³)	1856.8 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.21 × 0.10 × 0.09

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	18093, 4228, 1816
R_int	0.109
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.137, 1.00
No. of reflections	4228
No. of parameters	255
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.18
Absolute structure	No

Computer programs: COLLECT (Hooft, 1999), SCALEPACK (Otwinowski & Minor, 1997), DENZO and SCALEPACK (Otwinowski & Minor 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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···O5^iv	0.88	2.01	2.826 (3)	153
C6—H6C···O4ⁱ	0.96	2.47	3.397 (3)	162

Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) x−1/2, −y+1/2, z+1/2; (iii) x−1/2, −y+1/2, z−1/2; (iv) x+1/2, −y+1/2, z−1/2.

Acknowledgements

The authors thank CNPq, CAPES, and FAPEMIG (Brazilian agencies) for financial support and also R. G. Bastos (LDRX-IF/UFF) for the X-ray diffraction facilities.

References

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