research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 7| July 2015| Pages 840-843

Crystal structure of 5-amino-4H-1,2,4-triazol-1-ium pyrazine-2-carboxyl­ate: an unexpected salt arising from the deca­rboxylation of both precursors

CROSSMARK_Color_square_no_text.svg

aDepartment of Chemistry, CICECO – Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal, bREQUIMTE / LAQV & Departamento de Química e Bioquímica, Faculdade de Ciencias, Universidade do Porto, 4169-007 Porto, Portugal, cDepartment of Chemistry, QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal, and dDepartment of Organic and Macromolecular Chemistry, Ghent University, B-9000 Ghent, Belgium
*Correspondence e-mail: filipe.paz@ua.pt

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 13 June 2015; accepted 17 June 2015; online 24 June 2015)

Both the 3-amino-2H,4H-1,2,4-triazolium cation and the pyrazine-2-carboxyl­ate anion in the title salt, C2H5N4+·C5H3N2O2, were formed by an unexpected deca­rboxylation reaction, from 5-amino-1H-1,2,4-triazole-3-carb­oxy­lic acid and pyrazine-2,3-di­carb­oxy­lic acid, respectively. The dihedral angle between the pyrazine ring (r.m.s. deviation = 0.008 Å) and the carboxyl­ate group in the anion is 3.7 (3)°. The extended structure of the salt contains a supra­molecular zigzag tape in which cations and anions are engaged in strong and highly directional N—H⋯N,O hydrogen bonds, forming R22(8) and R22(9) graph-set motifs. The packing between the tapes is mediated by ππ stacking inter­actions between the triazole and pyrazine rings.

1. Chemical context

A remarkable feature of ionothermal synthesis is the fact that ionic liquids (ILs) can act simultaneously as sustainable solvents and structure-directing agents (also known as templates). This has been widely demonstrated by their potential in the discovery of unprecedented crystalline mat­erials (Xu et al., 2013[Xu, L., Kwon, Y. U., Castro, B. & Cunha-Silva, L. (2013). Cryst. Growth Des. 13, 1260-1266.]). Following our inter­est in the design and preparation of new types of metal-organic frameworks (MOFs), we have been exploring the use of 5-amino-1H-1,2,4-triazole-3-carb­oxy­lic acid (H2atrc) and pyrazine-2,3-di­carb­oxy­lic acid (H2Pzdc) as a double-ligand system in the presence of transition metal centers using ionothermal synthetic conditions. In the presence of AgNO3 the obtained product revealed, however, to be an unexpected organic salt (Bond, 2007[Bond, A. D. (2007). CrystEngComm, 9, 833-834.]) composed of the 3-amino-2H,4H(+)-1,2,4-triazolium cation and the pyrazine-2-carboxyl­ato anion.

[Scheme 1]

2. Structural commentary

The title compound is a product of decomposition of the H2atrc and H2Pzdc organic mol­ecules by way of decarb­oxyl­ation leading to, respectively, 3-amino-2H,4H-1,2,4-triazolium [(C2H5N4)+] and pyrazine-2-carboxyl­ate [(C5H3N2O2)]. The asymmetric unit is composed of one of each of these moieties, as depicted in both the chemical diagram and in Fig. 1[link].

[Figure 1]
Figure 1
The asymmetric unit of the title salt. Non-H atoms are represented as displacement ellipsoids drawn at the 50% probability level, while H atoms are depicted as small spheres with arbitrary radii. The atomic labelling scheme for all non-H atoms is provided. Hydrogen bonds are represented as dashed lines.

3. Supra­molecular features

The cation present in the title compound is rich in groups capable of forming strong N—H⋯N,O hydrogen-bonding inter­actions (see Table 1[link] for further geometrical details), many highly directional with the observed <(D—H⋯A) inter­action angles being above 165°. These supra­molecular contacts are the main driving force which mediate the crystal packing features of the title compound. Indeed, the donation of hydrogen atoms from the cation to the carboxyl­ate group of an adjacent anion (N6—H6B⋯O2 and N5—H5⋯O1) forms the known structurally robust R22(8) graph-set motif (dashed pink lines in Fig. 2[link]) (Grell et al., 1999[Grell, J., Bernstein, J. & Tinhofer, G. (1999). Acta Cryst. B55, 1030-1043.]). This graph-set motif has already been found in salts containing the title compound cation and carb­oxy­lic acids (see Database survey below). Two other inter­actions, N6—H6A⋯N1 (dashed aqua lines) and N4—H4A⋯O2, describe a second R22(9) hydrogen-bond motif. In contrast to the previous graph-set motif, the R22(9) ring has not been observed in structures containing the title-compound cation. The zigzag alternation of these two graph-set motifs leads to the formation of a highly coplanar supra­molecular tape running parallel to the [010] direction of the unit cell (Fig. 2[link]). Adjacent tapes inter­act by way of weak ππ stacking contacts between triazole and pyrazine rings, with the inter-centroid distance being 3.75 (3) Å (dashed orange lines in Fig. 2[link]).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N4—H4A⋯O2 0.90 (1) 1.77 (1) 2.655 (3) 166 (3)
N5—H5⋯O1i 0.90 (1) 1.73 (1) 2.632 (3) 176 (3)
N6—H6B⋯O2i 0.90 (1) 1.97 (1) 2.853 (3) 169 (3)
N6—H6A⋯N1 0.90 (1) 2.21 (1) 3.099 (3) 169 (3)
Symmetry code: (i) [-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}].
[Figure 2]
Figure 2
Supra­molecular tape running parallel to the [010] direction of the unit cell. N—H⋯N and N—H⋯N hydrogen bonds are depicted as dashed aqua and pink lines, respectively. Graph-set motifs present in the structure are highlighted. For geometric details of the represented supra­molecular contacts, see Table 1[link]. ππ stacking inter­actions between two adjacent supra­molecular tapes are shown as orange dashed lines.

4. Database survey

Triazole mol­ecules have been extensively used in the preparation of organic co-crystals (Kastelic et al., 2011[Kastelic, J., Lah, N., Kikelj, D. & Leban, I. (2011). Acta Cryst. C67, o370-o372.]; Remenar et al., 2003[Remenar, J. F., Morissette, S. L., Peterson, M. L., Moulton, B., MacPhee, J. M., Guzmán, H. R. & Almarsson, Ö. (2003). J. Am. Chem. Soc. 125, 8456-8457.]), and a survey of the Cambridge Structural Database (Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]) revealed the existence of about a dozen of crystallographic reports of co-crystals of the title compound cation (Byriel et al., 1992[Byriel, K. A., Kennard, C. H. L., Lynch, D. E., Smith, G. & Thompson, J. G. (1992). Aust. J. Chem. 45, 969.]; Essid et al., 2013[Essid, M., Marouani, H., Al-Deyab, S. S. & Rzaigui, M. (2013). Acta Cryst. E69, o1279.]; Joo et al., 2013[Joo, Y.-H., Chung, J. H., Cho, S. G. & Goh, E. M. (2013). New J. Chem. 37, 1180-1188.]; Luo et al., 2013[Luo, Y.-H., Xu, B. & Sun, B.-W. (2013). J. Cryst. Growth, 374, 88-98.]; Lynch et al., 1992[Lynch, D. E., Smith, G., Byriel, K. A. & Kennard, C. H. L. (1992). Acta Cryst. C48, 1265-1267.], 1998[Lynch, D. E., Latif, T., Smith, G., Byriel, K. A., Kennard, C. H. L. & Parsons, S. (1998). Aust. J. Chem. 51, 403-408.], 1999[Lynch, D. E., Dougall, T., Smith, G., Byriel, K. A. & Kennard, C. H. L. (1999). J. Chem. Crystallogr. 29, 67-73.]; Lynch, Smith, Byriel & Kennard, 1994[Lynch, D. E., Smith, G., Byriel, K. A. & Kennard, C. H. L. (1994). Acta Cryst. C50, 1291-1294.]; Lynch, Smith, Byriel, Kennard et al., 1994[Lynch, D. E., Smith, G., Byriel, K. A., Kennard, C. H. L. & Whittaker, A. K. (1994). Aust. J. Chem. 47, 309-319.]; Matulková et al., 2007[Matulková, I., Němec, I., Císařová, I., Němec, P. & Mička, Z. (2007). J. Mol. Struct. 834-836, 328-335.]; Smith et al., 1996[Smith, G., Lynch, D. E., Byriel, K. A. & Kennard, C. H. L. (1996). Acta Cryst. C52, 231-235.]). The only compounds known with both of the title compound entities present is a bimetallic complex also containing Cd2+ and NO3− ions (Chen et al., 2009[Chen, L.-F., Qin, Y.-Y., Li, Z.-J. & Yao, Y.-G. (2009). Chin. J. Struct. Chem. 28, 223-227.]).

5. Synthesis and crystallization

5-Amino-1H-1,2,4-triazole-3-carb­oxy­lic acid (H2atrc, 98% purity), pyrazine-2,3-di­carb­oxy­lic acid (H2Pzdc, 97% purity), 1-methyl­imidazole (99%+ purity), 1-bromo­butane (99% purity) and AgNO3 (99%+ purity) were purchased from Sigma–Aldrich and were used as received without further purification. 1-Butyl-3-methyl­imidazolium bromide ([BMI]Br) was prepared according to the literature method (Parnham & Morris, 2006[Parnham, E. R. & Morris, R. E. (2006). Chem. Mater. 18, 4882-4887.]) and was isolated as a pale-yellow oil (yield of ca 78%).

AgNO3 (0.0687 g; 0.400 mmol), H2atrc (0.0510 g; 0.400 mmol) and H2Pzdc (0.0607 g; 0.361 mmol) were mixed with 0.49 g of [BMI]Br and 0.3 mL of distilled water in a ca 25 mL Teflon-lined stainless-steel reaction vessel. The resulting mixture was heated to 383 K for 7 days. The vessel was then allowed to cool to ambient temperature at a rate of ca 1 K h−1. Small colourless crystals of the title compound were directly isolated from the vessel contents.

6. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. Hydrogen atoms bound to carbon were placed at idealized positions with C—H = 0.95 Å, and included in the final structural model in a riding-motion approximation with the isotropic thermal displacement parameters fixed at 1.2Ueq of the carbon atom to which they are attached. Hydrogen atoms associated with nitro­gen atoms were located directly from difference Fourier maps and were included in the model with the N—H and H⋯H (only for the –NH2 groups) distances restrained to 0.90 (1) and 1.55 (1) Å, respectively, in order to ensure a chemically reasonable environment for these groups. These hydrogen atoms were modelled with the isotropic thermal displacement parameters fixed at 1.5Ueq(N).

Table 2
Experimental details

Crystal data
Chemical formula C2H5N4+·C5H3N2O2
Mr 208.19
Crystal system, space group Monoclinic, P21/c
Temperature (K) 296
a, b, c (Å) 7.0599 (5), 12.1868 (8), 10.8385 (6)
β (°) 103.593 (4)
V3) 906.40 (10)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.12
Crystal size (mm) 0.09 × 0.04 × 0.03
 
Data collection
Diffractometer Bruker X8 Kappa CCD APEXII
Absorption correction Multi-scan (SADABS; Sheldrick, 1998[Sheldrick, G. M. (1998). SADABS. University of Göttingen, Germany.])
Tmin, Tmax 0.989, 0.997
No. of measured, independent and observed [I > 2σ(I)] reflections 12089, 1858, 1037
Rint 0.077
(sin θ/λ)max−1) 0.625
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.059, 0.133, 1.02
No. of reflections 1858
No. of parameters 148
No. of restraints 5
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.19, −0.20
Computer programs: APEX2 (Bruker, 2006[Bruker (2006). APEX2. Bruker AXS, Delft, The Netherlands.]), SAINT-Plus (Bruker, 2005[Bruker (2005). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 and SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]) and DIAMOND (Brandenburg, 2009[Brandenburg, K. (2009). DIAMOND. Crystal Impact GbR, Bonn, Germany.]).

Supporting information


Chemical context top

A remarkable feature of ionothermal synthesis is the fact that ionic liquids (ILs) can act simultaneously as sustainable solvents and structure-directing agents (also known as templates). This has been widely demonstrated by their potential in the discovery of unprecedented crystalline materials (Xu et al., 2013). Following our inter­est in the design and preparation of new types of metal-organic frameworks (MOFs), we have been exploring the use of 5-amino-1H-1,2,4-triazole-3-carb­oxy­lic acid (H2atrc) and pyrazine-2,3-di­carb­oxy­lic acid (H2Pzdc) as a double-ligand system in the presence of transition metal centers using ionothermal synthetic conditions. In the presence of AgNO3 the obtained product revealed, however, to be an unexpected organic salt (Bond, 2007) composed of the 3-amino-2H,4H(+)-1,2,4-triazolium cation and the pyrazine-2-carboxyl­ato anion.

Structural commentary top

The title compound is a product of decomposition of the H2atrc and H2Pzdc organic molecules by way of de­carboxyl­ation leading to, respectively, 3-amino-2H,4H-1,2,4-triazolium [(C2H5N4)+] and pyrazine-2-carboxyl­ate [(C5H3N2O2)-]. The asymmetric unit is composed of one of each of these moieties, as depicted in both the chemical diagram and in Fig. 1.

Supra­molecular features top

The cation present in the title compound is rich in groups capable of forming strong N—H···N,O hydrogen-bonding inter­actions (see Table 1 for further geometrical details), many highly directional with the observed <(D—H···A) inter­action angles being above 165°. These supra­molecular contacts are the main driving force which mediate the crystal packing features of the title compound. Indeed, the donation of hydrogen atoms from the cation to the carboxyl­ate group of an adjacent anion (N6—H6B···O2 and N5—H5···O1) forms the known structurally robust R22(8) graph-set motif (dashed pink lines in Fig. 2) (Grell et al., 1999). This graph-set motif has already been found in salts containing the title compound cation and carb­oxy­lic acids (see Database survey below). Two other inter­actions, N6—H6A···N1 (dashed aqua lines) and N4—H4A···O2, describe a second R22(9) hydrogen-bond motif. In contrast to the previous graph-set motif, the R22(9) ring has not been observed in structures containing the title-compound cation. The zigzag alternation of these two graph-set motifs leads to the formation of a highly coplanar supra­molecular tape running parallel to the [010] direction of the unit cell (Fig. 2). Adjacent tapes inter­act by way of weak ππ stacking contacts between triazole and pyrazine rings, with the inter-centroid distance being 3.75 (3) Å (dashed orange lines in Fig. 2).

Database survey top

Triazole molecules have been extensively used in the preparation of organic co-crystals (Kastelic et al., 2011; Remenar et al., 2003), and a survey of the Cambridge Structural Database (Groom & Allen, 2014) revealed the existence of about a dozen of crystallographic reports of co-crystals of the title compound cation (Byriel et al., 1992; Essid et al., 2013; Joo et al., 2013; Luo et al., 2013; Lynch et al., 1992, 1998, 1999; Lynch, Smith, Byriel & Kennard, 1994; Lynch, Smith, Byriel, Kennard et al., 1994; Matulková et al., 2007; Smith et al., 1996). The only compounds known with both of the title compound entities present is a bimetallic complex also containing Cd2+ and NO3- ions (Chen et al., 2009) .

Synthesis and crystallization top

5-Amino-1H-1,2,4-triazole-3-carb­oxy­lic acid (H2atrc, 98% purity), pyrazine-2,3-di­carb­oxy­lic acid (H2Pzdc, 97% purity), 1-methyl­imidazole (99%+ purity), 1-bromo­butane (99% purity) and AgNO3 (99%+ purity) were purchased from Sigma–Aldrich and were used as received without further purification. 1-Butyl-3-methyl­imidazolium bromide ([BMI]Br) was prepared according to the literature method (Parnham & Morris, 2006) and was isolated as a pale-yellow oil (yield of ca 78%).

AgNO3 (0.0687 g; 0.400 mmol), H2atrc (0.0510 g; 0.400 mmol) and H2Pzdc (0.0607 g; 0.361 mmol) were mixed with 0.49 g of [BMI]Br and 0.3 mL of distilled water in a ca 25 mL Teflon-lined stainless-steel reaction vessel. The resulting mixture was heated to 383 K for 7 days. The vessel was then allowed to cool to ambient temperature at a rate of ca 1 K h-1. Small colourless crystals of the title compound were directly isolated from the vessel contents.

Refinement details top

Hydrogen atoms bound to carbon were placed at idealized positions with C—H = 0.95 Å, and included in the final structural model in a riding-motion approximation with the isotropic thermal displacement parameters fixed at 1.2Ueq of the carbon atom to which they are attached. Hydrogen atoms associated with nitro­gen atoms were located directly from difference Fourier maps and were included in the model with the N—H and H···H (only for the –NH2 groups) distances restrained to 0.90 (1) and 1.55 (1) Å, respectively, in order to ensure a chemically reasonable environment for these groups. These hydrogen atoms were modelled with the isotropic thermal displacement parameters fixed at 1.5Ueq(N).

Related literature top

For related literature, see: Allen (2002); Bond (2007); Byriel et al. (1992); Chen et al. (2009); Essid et al. (2013); Grell et al. (1999); Joo et al. (2013); Kastelic et al. (2011); Luo et al. (2013); Lynch et al. (1992, 1998, 1999); Lynch, Smith, Byriel & Kennard (1994); Lynch, Smith, Byriel, Kennard & Whittaker (1994); Matulková et al. (2007); Parnham & Morris (2006); Remenar et al. (2003); Smith et al. (1996).

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: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title salt. Non-H atoms are represented as displacement ellipsoids drawn at the 50% probability level, while H atoms are depicted as small spheres with arbitrary radii. The atomic labelling scheme for all non-H atoms is provided. Hydrogen bonds are represented as dashed lines.
[Figure 2] Fig. 2. Supramolecular tape running parallel to the [010] direction of the unit cell. N—H···N and N—H···N hydrogen bonds are depicted as dashed aqua and pink lines, respectively. Graph-set motifs present in the structure are highlighted. For geometric details of the represented supramolecular contacts, see Table 1. ππ stacking interactions between two adjacent supramolecular tapes are shown as orange dashed lines.
5-Amino-4H-1,2,4-triazol-1-ium pyrazine-2-carboxylate top
Crystal data top
C2H5N4+·C5H3N2O2F(000) = 432
Mr = 208.19Dx = 1.526 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.0599 (5) ÅCell parameters from 1298 reflections
b = 12.1868 (8) Åθ = 2.6–19.7°
c = 10.8385 (6) ŵ = 0.12 mm1
β = 103.593 (4)°T = 296 K
V = 906.40 (10) Å3Block, colourless
Z = 40.09 × 0.04 × 0.03 mm
Data collection top
Bruker X8 Kappa CCD APEXII
diffractometer
1037 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.077
ω / ϕ scansθmax = 26.4°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1998)
h = 88
Tmin = 0.989, Tmax = 0.997k = 1515
12089 measured reflectionsl = 1313
1858 independent reflections
Refinement top
Refinement on F25 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.059H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.133 w = 1/[σ2(Fo2) + (0.0599P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
1858 reflectionsΔρmax = 0.19 e Å3
148 parametersΔρmin = 0.20 e Å3
Crystal data top
C2H5N4+·C5H3N2O2V = 906.40 (10) Å3
Mr = 208.19Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.0599 (5) ŵ = 0.12 mm1
b = 12.1868 (8) ÅT = 296 K
c = 10.8385 (6) Å0.09 × 0.04 × 0.03 mm
β = 103.593 (4)°
Data collection top
Bruker X8 Kappa CCD APEXII
diffractometer
1858 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1998)
1037 reflections with I > 2σ(I)
Tmin = 0.989, Tmax = 0.997Rint = 0.077
12089 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0595 restraints
wR(F2) = 0.133H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.19 e Å3
1858 reflectionsΔρmin = 0.20 e Å3
148 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.2890 (3)0.79063 (17)0.49872 (19)0.0389 (6)
N20.0664 (3)0.79145 (18)0.2472 (2)0.0468 (6)
C10.2177 (4)0.8840 (2)0.4404 (2)0.0334 (6)
C20.1066 (4)0.8815 (2)0.3165 (2)0.0412 (7)
H20.05710.94760.27970.049*
C30.1381 (4)0.6995 (2)0.3059 (2)0.0448 (7)
H30.11470.63340.26230.054*
C40.2461 (4)0.6993 (2)0.4297 (3)0.0442 (7)
H40.29120.63260.46680.053*
C50.2560 (4)0.9921 (2)0.5101 (2)0.0378 (7)
O10.1745 (3)1.07442 (14)0.45075 (15)0.0481 (6)
O20.3628 (3)0.99415 (14)0.61986 (16)0.0543 (6)
N30.7128 (4)0.94320 (19)0.8957 (2)0.0622 (8)
N40.6167 (4)0.88117 (19)0.7929 (2)0.0476 (6)
H4A0.535 (3)0.912 (2)0.7253 (18)0.071*
N50.7480 (3)0.76575 (18)0.93596 (19)0.0417 (6)
H50.778 (4)0.6996 (13)0.972 (2)0.063*
N60.5628 (4)0.6942 (2)0.7405 (2)0.0540 (7)
H6A0.473 (3)0.714 (2)0.6709 (19)0.081*
H6B0.585 (5)0.6271 (13)0.775 (3)0.081*
C60.6369 (4)0.7751 (2)0.8181 (2)0.0365 (7)
C70.7892 (5)0.8695 (2)0.9782 (3)0.0553 (8)
H70.86490.88611.05840.066*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0450 (14)0.0290 (13)0.0400 (12)0.0006 (11)0.0049 (10)0.0005 (10)
N20.0557 (16)0.0387 (14)0.0406 (12)0.0008 (12)0.0005 (11)0.0086 (12)
C10.0331 (15)0.0309 (15)0.0355 (13)0.0004 (13)0.0067 (11)0.0022 (12)
C20.0495 (18)0.0320 (16)0.0367 (14)0.0061 (14)0.0007 (13)0.0020 (12)
C30.0487 (19)0.0352 (17)0.0478 (16)0.0016 (15)0.0059 (14)0.0099 (13)
C40.0499 (18)0.0299 (16)0.0497 (16)0.0036 (14)0.0056 (14)0.0028 (13)
C50.0420 (17)0.0344 (16)0.0330 (13)0.0001 (14)0.0006 (12)0.0036 (12)
O10.0625 (14)0.0319 (11)0.0402 (10)0.0058 (9)0.0074 (9)0.0021 (8)
O20.0708 (14)0.0375 (12)0.0399 (10)0.0067 (10)0.0165 (10)0.0025 (9)
N30.089 (2)0.0419 (15)0.0461 (14)0.0029 (15)0.0032 (13)0.0024 (12)
N40.0625 (18)0.0367 (15)0.0386 (13)0.0037 (13)0.0019 (12)0.0061 (11)
N50.0480 (14)0.0362 (15)0.0359 (12)0.0025 (12)0.0004 (11)0.0083 (11)
N60.0607 (18)0.0440 (16)0.0491 (15)0.0005 (15)0.0038 (13)0.0030 (13)
C60.0391 (17)0.0349 (18)0.0348 (13)0.0044 (13)0.0068 (12)0.0057 (12)
C70.074 (2)0.046 (2)0.0383 (15)0.0020 (17)0.0026 (15)0.0012 (14)
Geometric parameters (Å, º) top
N1—C41.335 (3)N3—C71.293 (3)
N1—C11.341 (3)N3—N41.384 (3)
N2—C21.323 (3)N4—C61.322 (3)
N2—C31.328 (3)N4—H4A0.902 (10)
C1—C21.387 (3)N5—C61.338 (3)
C1—C51.512 (3)N5—C71.353 (3)
C2—H20.9300N5—H50.901 (10)
C3—C41.379 (4)N6—C61.321 (3)
C3—H30.9300N6—H6A0.899 (10)
C4—H40.9300N6—H6B0.896 (10)
C5—O21.250 (2)C7—H70.9300
C5—O11.256 (3)
C4—N1—C1115.6 (2)C7—N3—N4102.9 (2)
C2—N2—C3114.9 (2)C6—N4—N3111.1 (2)
N1—C1—C2120.2 (2)C6—N4—H4A126 (2)
N1—C1—C5120.1 (2)N3—N4—H4A121.7 (19)
C2—C1—C5119.8 (2)C6—N5—C7105.9 (2)
N2—C2—C1124.4 (2)C6—N5—H5121.3 (18)
N2—C2—H2117.8C7—N5—H5132.7 (18)
C1—C2—H2117.8C6—N6—H6A115 (2)
N2—C3—C4122.0 (2)C6—N6—H6B115 (2)
N2—C3—H3119.0H6A—N6—H6B128 (3)
C4—C3—H3119.0N6—C6—N4126.2 (2)
N1—C4—C3123.0 (2)N6—C6—N5126.9 (2)
N1—C4—H4118.5N4—C6—N5106.9 (2)
C3—C4—H4118.5N3—C7—N5113.2 (2)
O2—C5—O1125.0 (2)N3—C7—H7123.4
O2—C5—C1119.3 (2)N5—C7—H7123.4
O1—C5—C1115.7 (2)
C4—N1—C1—C20.3 (4)N1—C1—C5—O1176.1 (2)
C4—N1—C1—C5179.5 (2)C2—C1—C5—O13.1 (4)
C3—N2—C2—C11.2 (4)C7—N3—N4—C60.8 (3)
N1—C1—C2—N21.4 (4)N3—N4—C6—N6179.8 (3)
C5—C1—C2—N2179.4 (2)N3—N4—C6—N50.9 (3)
C2—N2—C3—C40.1 (4)C7—N5—C6—N6179.9 (3)
C1—N1—C4—C30.8 (4)C7—N5—C6—N40.6 (3)
N2—C3—C4—N11.0 (4)N4—N3—C7—N50.4 (4)
N1—C1—C5—O23.7 (4)C6—N5—C7—N30.1 (4)
C2—C1—C5—O2177.1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···O20.90 (1)1.77 (1)2.655 (3)166 (3)
N5—H5···O1i0.90 (1)1.73 (1)2.632 (3)176 (3)
N6—H6B···O2i0.90 (1)1.97 (1)2.853 (3)169 (3)
N6—H6A···N10.90 (1)2.21 (1)3.099 (3)169 (3)
Symmetry code: (i) x+1, y1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···O20.902 (10)1.769 (12)2.655 (3)166 (3)
N5—H5···O1i0.901 (10)1.733 (11)2.632 (3)176 (3)
N6—H6B···O2i0.896 (10)1.968 (12)2.853 (3)169 (3)
N6—H6A···N10.899 (10)2.212 (12)3.099 (3)169 (3)
Symmetry code: (i) x+1, y1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC2H5N4+·C5H3N2O2
Mr208.19
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)7.0599 (5), 12.1868 (8), 10.8385 (6)
β (°) 103.593 (4)
V3)906.40 (10)
Z4
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.09 × 0.04 × 0.03
Data collection
DiffractometerBruker X8 Kappa CCD APEXII
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1998)
Tmin, Tmax0.989, 0.997
No. of measured, independent and
observed [I > 2σ(I)] reflections
12089, 1858, 1037
Rint0.077
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.059, 0.133, 1.01
No. of reflections1858
No. of parameters148
No. of restraints5
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.19, 0.20

Computer programs: APEX2 (Bruker, 2006), SAINT-Plus (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), DIAMOND (Brandenburg, 2009), SHELXTL (Sheldrick, 2008).

 

Acknowledgements

Funding Sources and Entities: The Fundação para a Ciência e a Tecnologia (FCT, Portugal), the European Union, QREN, FEDER through Programa Operacional Factores de Comp­et­i­tividade (COMPETE), CICECO-Aveiro Institute of Materials (Ref. FCT UID/CTM/50011/2013), REQUIMTE/LAQV (Ref. FCT UID/QUI/50006/2013) financed by national funds through the FCT/MEC and when applicable co-financed by FEDER under the PT2020 Partnership Agreement.Projects and Individual grants: We wish to thank the FCT for funding the R&D projects FCOMP-01–0124-FEDER-041282 (Ref. FCT EXPL/CTM-NAN/0013/2013) and FCOMP-01–0124-FEDER-041445 (Ref. FCT EXPL/QEQ-QUI/0199/2013), and also CICECO for specific funding towards the purchase of the single-crystal diffractometer. The FCT is gratefully acknowledged for the post-doctoral research grants Nos. SFRH/BPD/63736/2009 and SFRH/BPD/47566/2008 (to JAF and BL, respectively).

References

First citationBond, A. D. (2007). CrystEngComm, 9, 833–834.  Web of Science CrossRef CAS 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, Delft, The Netherlands.  Google Scholar
First citationByriel, K. A., Kennard, C. H. L., Lynch, D. E., Smith, G. & Thompson, J. G. (1992). Aust. J. Chem. 45, 969.  CSD CrossRef Google Scholar
First citationChen, L.-F., Qin, Y.-Y., Li, Z.-J. & Yao, Y.-G. (2009). Chin. J. Struct. Chem. 28, 223–227.  CAS Google Scholar
First citationEssid, M., Marouani, H., Al-Deyab, S. S. & Rzaigui, M. (2013). Acta Cryst. E69, o1279.  CSD CrossRef IUCr Journals 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 citationGroom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671.  Web of Science CrossRef CAS Google Scholar
First citationJoo, Y.-H., Chung, J. H., Cho, S. G. & Goh, E. M. (2013). New J. Chem. 37, 1180–1188.  CSD CrossRef CAS Google Scholar
First citationKastelic, J., Lah, N., Kikelj, D. & Leban, I. (2011). Acta Cryst. C67, o370–o372.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationLuo, Y.-H., Xu, B. & Sun, B.-W. (2013). J. Cryst. Growth, 374, 88–98.  CSD CrossRef CAS Google Scholar
First citationLynch, D. E., Dougall, T., Smith, G., Byriel, K. A. & Kennard, C. H. L. (1999). J. Chem. Crystallogr. 29, 67–73.  Web of Science CSD CrossRef CAS Google Scholar
First citationLynch, D. E., Latif, T., Smith, G., Byriel, K. A., Kennard, C. H. L. & Parsons, S. (1998). Aust. J. Chem. 51, 403–408.  Web of Science CSD CrossRef CAS Google Scholar
First citationLynch, D. E., Smith, G., Byriel, K. A. & Kennard, C. H. L. (1992). Acta Cryst. C48, 1265–1267.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationLynch, D. E., Smith, G., Byriel, K. A. & Kennard, C. H. L. (1994). Acta Cryst. C50, 1291–1294.  CSD CrossRef CAS IUCr Journals Google Scholar
First citationLynch, D. E., Smith, G., Byriel, K. A., Kennard, C. H. L. & Whittaker, A. K. (1994). Aust. J. Chem. 47, 309–319.  CSD CrossRef CAS Google Scholar
First citationMatulková, I., Němec, I., Císařová, I., Němec, P. & Mička, Z. (2007). J. Mol. Struct. 834–836, 328–335.  Google Scholar
First citationParnham, E. R. & Morris, R. E. (2006). Chem. Mater. 18, 4882–4887.  Web of Science CSD CrossRef CAS Google Scholar
First citationRemenar, J. F., Morissette, S. L., Peterson, M. L., Moulton, B., MacPhee, J. M., Guzmán, H. R. & Almarsson, Ö. (2003). J. Am. Chem. Soc. 125, 8456–8457.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationSheldrick, G. M. (1998). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationSmith, G., Lynch, D. E., Byriel, K. A. & Kennard, C. H. L. (1996). Acta Cryst. C52, 231–235.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationXu, L., Kwon, Y. U., Castro, B. & Cunha-Silva, L. (2013). Cryst. Growth Des. 13, 1260–1266.  CSD CrossRef CAS Google Scholar

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Volume 71| Part 7| July 2015| Pages 840-843
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