Issue contents
Download PDF of article
Download CIF
3D view
Navigation
Highlighting
Dictionary of Crystallography reference
IUPAC Gold Book reference
more ...
Download citation
FormatBIBTeX
EndNote
RefMan
Refer
Medline
CIF
SGML
Plain Text
share
Previous article
Next article
Previous article
Issue contents
Download PDF of article
Download CIF
3D view
Navigation
Highlighting
Dictionary of Crystallography reference
IUPAC Gold Book reference
more ...
Download citation
FormatBIBTeX
EndNote
RefMan
Refer
Medline
CIF
SGML
Plain Text
share
Next article

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 67| Part 8| August 2011| Pages o2073-o2074
doi:10.1107/S160053681102811X

5-Amino-1H-1,2,4-triazol-4-ium-3-carboxyl­ate hemihydrate

José A. Fernandes,a Bing Liu,a,b João P. C. Tomé,c Luís Cunha-Silvab and Filipe A. Almeida Paza*

aDepartment of Chemistry, University of Aveiro, CICECO, 3810-193 Aveiro, Portugal, bREQUIMTE, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, 4169-007 Porto, Portugal, and cDepartment of Chemistry, University of Aveiro, QOPNA, 3810-193 Aveiro, Portugal
*Correspondence e-mail: filipe.paz@ua.pt

(Received 6 July 2011; accepted 13 July 2011; online 23 July 2011)

The asymmetric unit of the title compound, C3H4N4O2·0.5H2O, comprises two whole mol­ecules of 5-amino-1H-1,2,4-triazole-3-carb­oxy­lic acid in its zwitterionic form (proton transfer occurs from the carb­oxy­lic acid group to the N hetero­atom at position 1), plus one water mol­ecule of crystallization. The organic moieties are disposed into supra­molecular layers linked by N—H⋯O and N—H⋯N hydrogen bonds parallel to the bc plane. Additional O—H⋯O and N—H⋯O hydrogen bonds involving the water mol­ecules and the organic mol­ecules lead to the formation of double-deck supra­molecular arrangements which are inter­connected along the a axis via π–π stacking [centroid–centroid distance = 3.507 (3) Å].

Related literature

For related compounds with 5-amino-1H-1,2,4-triazole-3-carb­oxy­lic acid residues, see: Masiukiewicz et al. (2007[Masiukiewicz, E., Rzeszotarska, B., Wawrzycka-Gorczyca, I. & Kołodziejczyk, E. (2007). Synth. Commun. 37, 1917-1925.]); Ouakkaf et al. (2011[Ouakkaf, A., Berrah, F., Bouacida, S. & Roisnel, T. (2011). Acta Cryst. E67, o1171-o1172.]); Sun et al. (2011[Sun, Y.-G., Xiong, G., Guo, M.-Y., Ding, F., Wang, L., Gao, E.-J., Zhu, M.-C. & Verpoort, F. (2011). Z. Anorg. Allg. Chem. 637, 293-300.]); Wawrzycka-Gorczyca et al. (2003[Wawrzycka-Gorczyca, I., Rzeszotarska, B., Dżygiel, A., Masiukiewicz, E. & Kozioł, A. E. (2003). Z. Kristallogr. 218, 480-487.]). For previous work in crystal engineering, see: Amarante, Gonçalves et al. (2009[Amarante, T. R., Gonçalves, I. S. & Almeida Paz, F. A. (2009). Acta Cryst. E65, o1962-o1963.]); Amarante, Figueiredo et al. (2009[Amarante, T. R., Figueiredo, S., Lopes, A. D., Gonçalves, I. S. & Almeida Paz, F. A. (2009). Acta Cryst. E65, o2047.]); Shi et al. (2008[Shi, F.-N., Cunha-Silva, L., Sá Ferreira, R. A., Mafra, L., Trindade, T., Carlos, L. D., Paz, F. A. A. & Rocha, J. (2008). J. Am. Chem. Soc. 130, 150-167.]); Paz & Klinowski (2004[Paz, F. A. A. & Klinowski, J. (2004). J. Solid State Chem. 177, 3423-3432.], 2007[Paz, F. A. A. & Klinowski, J. (2007). Pure Appl. Chem. 79, 1097-1110.]); Paz et al. (2005[Paz, F. A. A., Rocha, J., Klinowski, J., Trindade , T., Shi, F.-N. & Mafra, L. (2005). Prog. Solid State Chem. 33, 113-125]). For graph-set notation, see: Grell et al. (1999[Grell, J., Bernstein, J. & Tinhofer, G. (1999). Acta Cryst. B55, 1030-1043.]). For a description of the Cambridge Structural Database, see: Allen (2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]).

[Scheme 1]

Experimental

Crystal data

  • C3H4N4O2·0.5H2O

  • Mr = 137.11

  • Triclinic, [P \overline 1]

  • a = 6.5440 (11) Å

  • b = 6.9490 (8) Å

  • c = 12.0723 (17) Å

  • α = 93.976 (7)°

  • β = 105.012 (9)°

  • γ = 99.703 (8)°

  • V = 518.96 (13) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.15 mm−1

  • T = 150 K

  • 0.10 × 0.07 × 0.04 mm
Data collection

  • Bruker X8 KappaCCD APEXII diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1997[Sheldrick, G. M. (1997). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.985, Tmax = 0.994

  • 4474 measured reflections

  • 1797 independent reflections

  • 1433 reflections with I > 2σ(I)

  • Rint = 0.032
Refinement

  • R[F2 > 2σ(F2)] = 0.066

  • wR(F2) = 0.202

  • S = 1.24

  • 1797 reflections

  • 202 parameters

  • 13 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.42 e Å−3

  • Δρmin = −0.46 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1⋯O1W 0.95 (1) 1.87 (2) 2.799 (5) 167 (5)
N3—H3⋯O1Wi 0.95 (1) 1.87 (3) 2.758 (5) 154 (5)
N4—H4A⋯O4 0.94 (1) 1.86 (2) 2.777 (5) 163 (4)
N4—H4B⋯N6i 0.94 (1) 2.29 (3) 3.125 (6) 146 (4)
N5—H5⋯O1ii 0.95 (1) 1.75 (1) 2.699 (5) 178 (5)
N7—H7⋯O3iii 0.95 (1) 1.66 (2) 2.579 (5) 161 (5)
N8—H8A⋯O2ii 0.94 (1) 2.10 (2) 2.989 (5) 155 (4)
N8—H8B⋯O1iv 0.94 (1) 2.17 (1) 3.117 (5) 178 (5)
O1W—H1X⋯O1v 0.95 (1) 1.94 (2) 2.839 (5) 159 (5)
O1W—H1Y⋯O4 0.95 (1) 1.70 (2) 2.634 (5) 170 (5)
Symmetry codes: (i) x, y-1, z; (ii) x, y, z-1; (iii) x, y+1, z; (iv) x, y+1, z-1; (v) -x, -y+1, -z+2.

Data collection: APEX2 (Bruker, 2006[Bruker (2006). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2005[Bruker (2005). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2009[Brandenburg, K. (2009). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681102811X/tk2764sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681102811X/tk2764Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681102811X/tk2764Isup3.cml

checkCIF report


Comment top

5-Amino-1H-1,2,4-triazole-3-carboxylic acid (H2Atrc) arises as a promising ligand which can be employed in the preparation of coordination compounds as a consequence of its multiple available sites to establish direct connections with metallic centres. However, surveying the Cambridge Structural Database (Allen, 2002) showed only a handful of crystalline compounds reported to date, namely organic derivatives (Masiukiewicz et al., 2007; Wawrzycka-Gorczyca et al., 2003), the sulfate salt (Ouakkaf et al., 2011) and a three-dimensional metal-organic framework (MOF) with Dy3+, very recently reported by Sun et al. (2011). Following our on-going interest on crystal engineering approaches of both organic crystals (Amarante, Gonçalves et al., 2009; Amarante, Figueiredo et al., 2009) and metal-organic frameworks (Shi et al., 2008; Paz & Klinowski, 2007; Paz et al., 2005; Paz & Klinowski, 2004), we are currently interested in exploring the coordination capabilities of H2Atrc and its residues. The title compound was isolated as a secondary minor product for which we wish to report its crystal structure at the low temperature of 150 K.

The asymmetric unit of title compound comprises two whole molecules of H2Atrc in its zwitterionic form (proton transference occurs from the carboxylic acid group to the N heteroatom at position 1) and a water molecule of crystallization as depicted in Fig. 1. The two individual molecular units are almost planar, with the observed deviations being smaller than 0.037 Å. The two organic moieties are also mutually located in the same average plane, with the average planes subtending an angle of ca 7.2 °. This planarity is extended throughout the entire crystal structure with the organic moieties being disposed in layers placed in the bc plane of the unit cell.

Due to the presence of a considerable number of proton donors and acceptors, the crystal structure is rich in hydrogen bonding interactions (see Table 1 for further details). In this context, the structural function of the two non-equivalent organic molecules composing the asymmetric unit is not the same since the hydrogen bonding interactions in which each moiety is involved differ considerably. While the moiety coined as A interacts with other symmetry-related moieties and also with B, the residue coined as B only interacts with A and with water molecules of crystallization. Given the coplanarity of the two non-equivalent H2Atrc molecules, mutual interactions occur solely along the aforementioned layers, forming several fused hydrogen-bonded rings (green dashed lines in Figs 2 and 3), best described by the graph set motifs R22(8), R33(9) and R32(11) (Grell et al., 1999). Because of the hydrogen bonds directly involving the crystallographically independent water molecule of crystallization (pink dashed lines in Fig. 3), individual moieties are arranged into double decker layers as depicted in Fig. 3. These supramolecular arrays interact between each other along the a-axis of the unit cell via weak interactions such as π-π stacking. The most structurally relevant of such interactions occurs between two symmetry-equivalent A moieties with an inter-centroid distance of 3.507 (3) Å (orange dashed lines in Figure 3).

Related literature top

For related compounds with 5-amino-1H-1,2,4-triazole-3-carboxylic acid residues, see: Masiukiewicz et al. (2007); Ouakkaf et al. (2011); Sun et al. (2011); Wawrzycka-Gorczyca et al. (2003). For previous work in crystal engineering approaches from our research group, see: Amarante, Gonçalves et al. (2009); Amarante, Figueiredo et al. (2009); Shi et al. (2008); Paz & Klinowski (2004, 2007); Paz et al. (2005). For graph-set notation, see: Grell et al. (1999). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

5-Amino-1H-1,2,4-triazole-3-carboxylic acid (H2Atrc) and MnSO4 were purchased from Sigma-Aldrich and they were used as received without purification.

H2Atrc (0.1 mmol, 12.8 mg) was dissolved in ca 15 ml of hot water (ca 358 K). The solution was then cooled to ambient temperature. A second aqueous solution of MnSO4 (0.1 mmol, 11.7 mg in ca 2 ml) was added drop wise to that containing the dissolved H2Atrc ligand. The resulting mixture solution was allowed to stand still over a period of one week and small colourless blocks were formed as a secondary product.

Refinement top

All hydrogen atoms bound to nitrogen (organic molecules) and to oxygen (water molecule of crystallization) were directly located from difference Fourier maps and included in the structural model with the O—H and N—H distances restrained to 0.95 (1) Å. The H···H distances in the water molecule and in the —NH2 groups were further restrained to 1.55 (1) Å in order to ensure a chemically reasonable geometry for these moieties. The Uiso of these hydrogen atoms were fixed at 1.5×Ueq of the parent nitrogen or oxygen atoms.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT-Plus (Bruker, 2005); data reduction: SAINT-Plus (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structures of the units composing the asymmetric unit of the title compound, showing the atomic labelling for all atoms. Non-hydrogen atoms are represented as displacement ellipsoids drawn at the 70% probability level. Hydrogen atoms are depicted as small spheres with arbitrary radii.
[Figure 2] Fig. 2. N—H···N and N—H···O interactions (dashed green lines) forming the supramolecular layer placed in the bc plane of the unit cell. The two distinct H2Atrc residues are depicted as molecules A and B. Supramolecular arrangements are described by their graph set notation following Grell et al. (1999). For geometric details on the represented supramolecular contacts see Table 1. Symmetry transformations used to generate equivalent atoms have been omitted for clarity.
[Figure 3] Fig. 3. Crystal packing of the title compound viewed in perspective along the [010] direction of the unit cell. Hydrogen bonding interactions between H2Atrc moieties are depicted as dashed green lines, while those involving the water molecules of crystallization are represented as dashed pink lines. π-π stacking interactions are represented as dashed orange lines.
5-Amino-1H-1,2,4-triazol-4-ium-3-carboxylate hemihydrate top
Crystal data top
C3H4N4O2·0.5H2OZ = 4
Mr = 137.11F(000) = 284
Triclinic, P1Dx = 1.755 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.5440 (11) ÅCell parameters from 2284 reflections
b = 6.9490 (8) Åθ = 3.0–26.5°
c = 12.0723 (17) ŵ = 0.15 mm−1
α = 93.976 (7)°T = 150 K
β = 105.012 (9)°Block, colourless
γ = 99.703 (8)°0.10 × 0.07 × 0.04 mm
V = 518.96 (13) Å3
Data collection top
Bruker X8 KappaCCD APEXII
diffractometer		1797 independent reflections
Radiation source: fine-focus sealed tube1433 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
ω and ϕ scansθmax = 25.3°, θmin = 3.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)		h = −7→7
Tmin = 0.985, Tmax = 0.994k = −8→8
4474 measured reflectionsl = −14→14
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.066Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.202H atoms treated by a mixture of independent and constrained refinement
S = 1.24 w = 1/[σ2(Fo2) + (0.053P)2 + 2.637P]
where P = (Fo2 + 2Fc2)/3
1797 reflections(Δ/σ)max < 0.001
202 parametersΔρmax = 0.42 e Å−3
13 restraintsΔρmin = −0.46 e Å−3
Crystal data top
C3H4N4O2·0.5H2Oγ = 99.703 (8)°
Mr = 137.11V = 518.96 (13) Å3
Triclinic, P1Z = 4
a = 6.5440 (11) ÅMo Kα radiation
b = 6.9490 (8) ŵ = 0.15 mm−1
c = 12.0723 (17) ÅT = 150 K
α = 93.976 (7)°0.10 × 0.07 × 0.04 mm
β = 105.012 (9)°
Data collection top
Bruker X8 KappaCCD APEXII
diffractometer		1797 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)		1433 reflections with I > 2σ(I)
Tmin = 0.985, Tmax = 0.994Rint = 0.032
4474 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.06613 restraints
wR(F2) = 0.202H atoms treated by a mixture of independent and constrained refinement
S = 1.24Δρmax = 0.42 e Å−3
1797 reflectionsΔρmin = −0.46 e Å−3
202 parameters
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
xyzUiso*/Ueq
O10.2627 (6)0.4287 (5)1.1942 (3)0.0210 (8)
O20.2494 (6)0.6539 (5)1.0686 (3)0.0204 (8)
C10.2566 (8)0.4869 (7)1.0970 (4)0.0181 (11)
C20.2597 (8)0.3319 (7)1.0033 (4)0.0145 (10)
C30.2551 (8)0.2009 (7)0.8332 (4)0.0151 (10)
N10.2483 (7)0.3692 (6)0.8926 (3)0.0156 (9)
H10.230 (9)0.492 (4)0.867 (5)0.023*
N20.2760 (7)0.1506 (6)1.0170 (3)0.0190 (10)
N30.2736 (7)0.0699 (6)0.9090 (3)0.0180 (9)
H30.262 (9)−0.066 (2)0.887 (5)0.027*
N40.2452 (7)0.1709 (6)0.7223 (3)0.0185 (10)
H4A0.234 (9)0.266 (5)0.670 (3)0.028*
H4B0.251 (9)0.049 (3)0.685 (3)0.028*
O30.2553 (6)0.3765 (5)0.4390 (3)0.0227 (9)
O40.2348 (6)0.5057 (5)0.6096 (3)0.0219 (9)
C40.2476 (8)0.5132 (7)0.5087 (4)0.0151 (10)
C50.2534 (8)0.7084 (7)0.4618 (4)0.0146 (10)
C60.2720 (8)0.9152 (7)0.3368 (4)0.0146 (10)
N50.2730 (7)0.7267 (6)0.3525 (3)0.0149 (9)
H50.272 (9)0.622 (5)0.298 (4)0.022*
N60.2409 (7)0.8740 (6)0.5147 (3)0.0167 (9)
N70.2527 (7)1.0044 (6)0.4344 (3)0.0157 (9)
H70.248 (9)1.139 (3)0.452 (5)0.024*
N80.2862 (8)0.9965 (6)0.2414 (4)0.0232 (10)
H8A0.274 (10)0.918 (6)0.172 (2)0.035*
H8B0.276 (10)1.127 (3)0.228 (4)0.035*
O1W0.1593 (6)0.7013 (5)0.7849 (3)0.0225 (9)
H1X0.009 (2)0.672 (8)0.775 (4)0.034*
H1Y0.194 (7)0.645 (8)0.720 (3)0.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.036 (2)0.0223 (19)0.0072 (17)0.0083 (16)0.0077 (15)0.0024 (14)
O20.030 (2)0.0150 (18)0.0164 (18)0.0058 (15)0.0074 (16)0.0005 (14)
C10.016 (3)0.018 (3)0.020 (3)0.004 (2)0.005 (2)−0.002 (2)
C20.018 (3)0.016 (2)0.010 (2)0.004 (2)0.0032 (19)0.0037 (19)
C30.016 (3)0.014 (2)0.014 (2)0.004 (2)0.002 (2)0.0019 (19)
N10.023 (2)0.0101 (19)0.015 (2)0.0050 (17)0.0064 (17)0.0020 (16)
N20.029 (2)0.019 (2)0.009 (2)0.0048 (19)0.0049 (18)0.0018 (17)
N30.030 (2)0.013 (2)0.012 (2)0.0046 (18)0.0065 (18)0.0002 (17)
N40.035 (3)0.015 (2)0.009 (2)0.0097 (19)0.0079 (19)0.0047 (17)
O30.040 (2)0.0126 (17)0.0193 (19)0.0071 (16)0.0121 (17)0.0045 (15)
O40.037 (2)0.0174 (18)0.0149 (19)0.0090 (16)0.0099 (16)0.0077 (14)
C40.022 (3)0.013 (2)0.011 (3)0.005 (2)0.005 (2)0.0067 (19)
C50.018 (3)0.014 (2)0.012 (2)0.004 (2)0.006 (2)0.0017 (19)
C60.018 (2)0.013 (2)0.014 (2)0.005 (2)0.004 (2)0.0044 (19)
N50.025 (2)0.011 (2)0.011 (2)0.0052 (17)0.0065 (17)0.0043 (16)
N60.023 (2)0.015 (2)0.013 (2)0.0035 (17)0.0045 (18)0.0066 (17)
N70.024 (2)0.0088 (19)0.015 (2)0.0058 (17)0.0059 (18)0.0024 (16)
N80.038 (3)0.018 (2)0.017 (2)0.009 (2)0.011 (2)0.0064 (18)
O1W0.033 (2)0.0174 (18)0.0194 (19)0.0064 (16)0.0098 (16)−0.0001 (15)
Geometric parameters (Å, º) top
O1—C11.260 (6)O4—C41.246 (6)
O2—C11.238 (6)C4—C51.504 (6)
C1—C21.513 (7)C5—N61.302 (6)
C2—N21.300 (6)C5—N51.370 (6)
C2—N11.364 (6)C6—N81.335 (6)
C3—N41.324 (6)C6—N51.337 (6)
C3—N31.332 (6)C6—N71.339 (6)
C3—N11.343 (6)N5—H50.947 (10)
N1—H10.946 (11)N6—N71.380 (5)
N2—N31.378 (6)N7—H70.948 (10)
N3—H30.947 (11)N8—H8A0.944 (10)
N4—H4A0.943 (10)N8—H8B0.944 (10)
N4—H4B0.944 (10)O1W—H1X0.946 (10)
O3—C41.241 (6)O1W—H1Y0.945 (10)
O2—C1—O1128.4 (4)O3—C4—C5114.0 (4)
O2—C1—C2116.0 (4)O4—C4—C5118.2 (4)
O1—C1—C2115.5 (4)N6—C5—N5112.4 (4)
N2—C2—N1111.7 (4)N6—C5—C4126.8 (4)
N2—C2—C1125.4 (4)N5—C5—C4120.8 (4)
N1—C2—C1122.9 (4)N8—C6—N5126.1 (4)
N4—C3—N3127.0 (5)N8—C6—N7127.1 (4)
N4—C3—N1127.2 (4)N5—C6—N7106.7 (4)
N3—C3—N1105.8 (4)C6—N5—C5106.3 (4)
C3—N1—C2107.2 (4)C6—N5—H5128 (3)
C3—N1—H1130 (3)C5—N5—H5126 (3)
C2—N1—H1123 (3)C5—N6—N7103.5 (4)
C2—N2—N3103.7 (4)C6—N7—N6111.1 (4)
C3—N3—N2111.6 (4)C6—N7—H7128 (3)
C3—N3—H3123 (3)N6—N7—H7121 (3)
N2—N3—H3125 (3)C6—N8—H8A121 (3)
C3—N4—H4A126 (3)C6—N8—H8B127 (3)
C3—N4—H4B123 (3)H8A—N8—H8B111 (4)
H4A—N4—H4B110.9 (16)H1X—O1W—H1Y111 (4)
O3—C4—O4127.8 (4)
O2—C1—C2—N2177.0 (5)O3—C4—C5—N6177.7 (5)
O1—C1—C2—N2−2.7 (7)O4—C4—C5—N6−1.9 (8)
O2—C1—C2—N1−2.0 (7)O3—C4—C5—N5−2.0 (7)
O1—C1—C2—N1178.2 (5)O4—C4—C5—N5178.3 (5)
N4—C3—N1—C2179.0 (5)N8—C6—N5—C5−179.5 (5)
N3—C3—N1—C2−1.0 (5)N7—C6—N5—C50.1 (5)
N2—C2—N1—C30.8 (6)N6—C5—N5—C6−0.1 (6)
C1—C2—N1—C3180.0 (4)C4—C5—N5—C6179.7 (4)
N1—C2—N2—N3−0.3 (6)N5—C5—N6—N70.1 (5)
C1—C2—N2—N3−179.5 (5)C4—C5—N6—N7−179.7 (5)
N4—C3—N3—N2−179.1 (5)N8—C6—N7—N6179.6 (5)
N1—C3—N3—N20.8 (6)N5—C6—N7—N60.0 (5)
C2—N2—N3—C3−0.3 (6)C5—N6—N7—C6−0.1 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1W0.95 (1)1.87 (2)2.799 (5)167 (5)
N3—H3···O1Wi0.95 (1)1.87 (3)2.758 (5)154 (5)
N4—H4A···O40.94 (1)1.86 (2)2.777 (5)163 (4)
N4—H4B···N6i0.94 (1)2.29 (3)3.125 (6)146 (4)
N5—H5···O1ii0.95 (1)1.75 (1)2.699 (5)178 (5)
N7—H7···O3iii0.95 (1)1.66 (2)2.579 (5)161 (5)
N8—H8A···O2ii0.94 (1)2.10 (2)2.989 (5)155 (4)
N8—H8B···O1iv0.94 (1)2.17 (1)3.117 (5)178 (5)
O1W—H1X···O1v0.95 (1)1.94 (2)2.839 (5)159 (5)
O1W—H1Y···O40.95 (1)1.70 (2)2.634 (5)170 (5)
Symmetry codes: (i) x, y−1, z; (ii) x, y, z−1; (iii) x, y+1, z; (iv) x, y+1, z−1; (v) −x, −y+1, −z+2.

Experimental details

Crystal data
Chemical formulaC3H4N4O2·0.5H2O
Mr137.11
Crystal system, space groupTriclinic, P1
Temperature (K)150
a, b, c (Å)6.5440 (11), 6.9490 (8), 12.0723 (17)
α, β, γ (°)93.976 (7), 105.012 (9), 99.703 (8)
V (Å3)518.96 (13)
Z4
Radiation typeMo Kα
µ (mm−1)0.15
Crystal size (mm)0.10 × 0.07 × 0.04
Data collection
DiffractometerBruker X8 KappaCCD APEXII
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1997)
Tmin, Tmax0.985, 0.994
No. of measured, independent and
observed [I > 2σ(I)] reflections		4474, 1797, 1433
Rint0.032
(sin θ/λ)max (Å−1)0.602
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.066, 0.202, 1.24
No. of reflections1797
No. of parameters202
No. of restraints13
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.42, −0.46

Computer programs: APEX2 (Bruker, 2006), SAINT-Plus (Bruker, 2005), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1W0.946 (11)1.868 (17)2.799 (5)167 (5)
N3—H3···O1Wi0.947 (11)1.87 (3)2.758 (5)154 (5)
N4—H4A···O40.943 (10)1.863 (16)2.777 (5)163 (4)
N4—H4B···N6i0.944 (10)2.29 (3)3.125 (6)146 (4)
N5—H5···O1ii0.947 (10)1.752 (12)2.699 (5)178 (5)
N7—H7···O3iii0.948 (10)1.66 (2)2.579 (5)161 (5)
N8—H8A···O2ii0.944 (10)2.10 (2)2.989 (5)155 (4)
N8—H8B···O1iv0.944 (10)2.173 (12)3.117 (5)178 (5)
O1W—H1X···O1v0.946 (10)1.94 (2)2.839 (5)159 (5)
O1W—H1Y···O40.945 (10)1.699 (16)2.634 (5)170 (5)
Symmetry codes: (i) x, y−1, z; (ii) x, y, z−1; (iii) x, y+1, z; (iv) x, y+1, z−1; (v) −x, −y+1, −z+2.
 

Acknowledgements

We are grateful to the Fundação para a Ciência e a Tecnologia (FCT, Portugal) for their general financial support under the R&D projects PTDC/QUI-QUI/098098/2008 and PTDC/CTM/100357/2008, and for the post-doctoral research grants, Nos. SFRH/BPD/63736/2009 (to JAF) and SFRH/BPD/47566/2008 (to BL). Thanks are also due to FCT for specific funding toward the purchase of the single-crystal diffractometer.

References

First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationAmarante, T. R., Figueiredo, S., Lopes, A. D., Gonçalves, I. S. & Almeida Paz, F. A. (2009). Acta Cryst. E65, o2047.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationAmarante, T. R., Gonçalves, I. S. & Almeida Paz, F. A. (2009). Acta Cryst. E65, o1962–o1963.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationBrandenburg, K. (2009). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
 First citationBruker (2005). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationBruker (2006). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationGrell, J., Bernstein, J. & Tinhofer, G. (1999). Acta Cryst. B55, 1030–1043.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationMasiukiewicz, E., Rzeszotarska, B., Wawrzycka-Gorczyca, I. & Kołodziejczyk, E. (2007). Synth. Commun. 37, 1917-1925.  Web of Science CSD CrossRef CAS Google Scholar
 First citationOuakkaf, A., Berrah, F., Bouacida, S. & Roisnel, T. (2011). Acta Cryst. E67, o1171–o1172.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationPaz, F. A. A. & Klinowski, J. (2004). J. Solid State Chem. 177, 3423–3432.  CAS Google Scholar
 First citationPaz, F. A. A. & Klinowski, J. (2007). Pure Appl. Chem. 79, 1097–1110.  Web of Science CrossRef CAS Google Scholar
 First citationPaz, F. A. A., Rocha, J., Klinowski, J., Trindade , T., Shi, F.-N. & Mafra, L. (2005). Prog. Solid State Chem. 33, 113–125  CrossRef CAS Google Scholar
 First citationSheldrick, G. M. (1997). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationShi, F.-N., Cunha-Silva, L., Sá Ferreira, R. A., Mafra, L., Trindade, T., Carlos, L. D., Paz, F. A. A. & Rocha, J. (2008). J. Am. Chem. Soc. 130, 150–167.  Web of Science CSD CrossRef PubMed CAS Google Scholar
 First citationSun, Y.-G., Xiong, G., Guo, M.-Y., Ding, F., Wang, L., Gao, E.-J., Zhu, M.-C. & Verpoort, F. (2011). Z. Anorg. Allg. Chem. 637, 293-300.  Web of Science CSD CrossRef CAS Google Scholar
 First citationWawrzycka-Gorczyca, I., Rzeszotarska, B., Dżygiel, A., Masiukiewicz, E. & Kozioł, A. E. (2003). Z. Kristallogr. 218, 480-487.  CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 67| Part 8| August 2011| Pages o2073-o2074
doi:10.1107/S160053681102811X
Follow Acta Cryst. E
Sign up for e-alerts
E-alerts
Follow Acta Cryst. on Twitter
Twitter
Follow us on facebook
Facebook
Sign up for RSS feeds
RSS