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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 9| September 2012| Pages o2700-o2701

5-Amino-3-(4H-1,2,4-triazol-4-yl)-1H-1,2,4-triazole

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 25 July 2012; accepted 4 August 2012; online 11 August 2012)

The asymmetric unit of the title compound, C4H5N7, comprises two independent but virtually superimposable mol­ecules. Each mol­ecule is planar with the dihedral angles between the five-membered rings being 2.8 (3) and 2.1 (3)°. The crystal structure is formed by an extensive network of relatively strong N—H⋯N hydrogen-bond inter­actions. Individual mol­ecules are arranged into supra­molecular zigzag chains running parallel to [001] by way of the strongest N—H⋯N inter­actions. Adjacent chains are inter­connected by rather long (DA distances range from ca 3.00 to 3.03 Å) but highly directional (inter­action angles above ca 173°) hydrogen bonds forming a supra­molecular layer in the bc plane.

Related literature

For the synthesis of 1-butyl-3-methyl­imidazolium bromide and 1,2-diformyl­hydrazine, see: Liu et al. (2007[Liu, B., Zhang, X.-C. & Wang, Y.-F. (2007). Inorg. Chem. Commun. 10, 199-203.]); Parnham & Morris (2006[Parnham, E. R. & Morris, R. E. (2006). Chem. Mater. 18, 4882-4887.]). For the use of triazole mol­ecules, see: Wang et al. (2012[Wang, N., Feng, Y.-C., Shi, W., Zhao, B., Cheng, P., Liao, D.-Z. & Yan, S.-P. (2012). CrystEngComm, 14, 2769-2278.]); Zhang et al. (2009[Zhang, X.-C. & Liu, B. (2009). Inorg. Chem. Commun. 12, 808-810.]). For previous research studies on crystal engineering approaches, see: Fernandes et al. (2011[Fernandes, J. A., Liu, B., Tomé, J. C., Cunha-Silva, L. & Almeida Paz, F. A. (2011). Acta Cryst. E67, o2073-o2074.]); Silva et al. (2011[Silva, P., Vieira, F., Gomes, A. C., Ananias, D., Fernandes, J. A., Bruno, S. M., Soares, R., Valente, A. A., Rocha, J. & Paz, F. A. A. (2011). J. Am. Chem. Soc. 133, 15120-15138.]); Amarante et al. (2009[Amarante, T. R., Gonçalves, I. S. & Almeida Paz, F. A. (2009). Acta Cryst. E65, o1962-o1963.]); Paz & Klinowski (2007[Paz, F. A. A. & Klinowski, J. (2007). Pure Appl. Chem. 79, 1097-1110.]). 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
  • C4H5N7

  • Mr = 151.15

  • Monoclinic, P 21 /n

  • a = 13.765 (3) Å

  • b = 5.9378 (12) Å

  • c = 16.635 (4) Å

  • β = 112.914 (12)°

  • V = 1252.4 (5) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.12 mm−1

  • T = 293 K

  • 0.10 × 0.05 × 0.03 mm

Data collection
  • Bruker X8 Kappa CCD APEXII diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1998[Sheldrick, G. M. (1998). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.988, Tmax = 0.996

  • 8003 measured reflections

  • 2192 independent reflections

  • 975 reflections with I > 2σ(I)

  • Rint = 0.079

Refinement
  • R[F2 > 2σ(F2)] = 0.073

  • wR(F2) = 0.226

  • S = 0.96

  • 2192 reflections

  • 217 parameters

  • 8 restraints

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

  • Δρmax = 0.52 e Å−3

  • Δρmin = −0.36 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1A⋯N14i 0.90 (1) 2.43 (2) 3.239 (6) 150 (4)
N1—H1B⋯N4ii 0.90 (1) 2.11 (1) 3.002 (6) 173 (5)
N2—H2⋯N13i 0.90 (1) 1.93 (2) 2.772 (6) 155 (5)
N8—H8A⋯N7 0.90 (1) 2.43 (2) 3.264 (6) 154 (4)
N8—H8B⋯N11iii 0.90 (1) 2.14 (1) 3.034 (6) 176 (5)
N10—H10⋯N6 0.90 (1) 1.91 (2) 2.777 (6) 161 (5)
Symmetry codes: (i) x, y, z-1; (ii) x, y-1, z; (iii) x, y+1, z.

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


Comment top

In the context of our interest in Crystal Engineering approaches (Wang et al. 2012; Fernandes et al.; 2011; Silva et al., 2011; Amarante, Gonçalves et al., 2009; Amarante et al., 2009; Paz & Klinowski, 2007), we are currently designing new triazole molecules which could be simultaneously employed in the construction of novel Metal-Organic Frameworks (MOFs) or organic crystals. We note that this type of molecule has received considerable interest in the synthesis of polynuclear complexes and in the preparation of MOFs (Zhang et al., 2009). A survey in the Cambridge structural Database (Allen, 2002) and in the literature revealed that the use of the asymmetrical bridging bitriazole molecule 5-amino-3-(1,2,4-triazol-4-yl)-1H-1,2,4-triazole (HAtrtr) has not been reported to date, either in MOFs nor in organic crystals. Furthermore, to the best of our knowledge, its crystal structure has not been reported. Following our recent efforts we were able to isolate good-quality single-crystals of the title compound as a minor secondary phase and here we wish to report its crystal structure at ambient temperature.

The asymmetric unit of the title compound (I) comprises two whole molecules (i.e., Z'=2) of HAtrtr as depicted in Fig. 1. We note that these two individual moieties are almost perfectly overlaid by assuming a combination of both inversion and molecular flexibility (maximum distance of ca 0.021 Å with RMS of ca 0.014 Å). Nevertheless, this feature is not described by crystal symmetry as the "head-to-tail" orientation of the molecules can not be described by the screw-axis parallel to the b-axis of the unit cell. Both molecules are almost planar with the dihedral angles between the 1,2,4-triazole rings being only of ca 2.8 and 2.1°. In addition, the medium planes of all non-hydrogen atoms of each molecule subtend an angle of just ca 7.1°, indicating that the molecules can also be envisaged as coplanar.

HAtrtr is rich in groups capable of forming strong N—H···N hydrogen bonding interactions (see Table 1 for further geometrical details), which direct the crystal packing features of the title compound. The most striking intermolecular interactions concern the double donation of hydrogen atoms from each 5-amino-3-(1,2,4-triazole moiety to the 1,2,4-triazole group of an adjacent molecule (N1—H1A···N14, N2—H2···N13, N8—H8A···N7 and N10—H10···N6), forming a R22(7) graph set motif (dashed yellow lines in Fig. 2) (Grell et al., 1999). This supramolecular motif constitutes the basis of the formation of a supramolecular zigzag tape parallel to the c axis, for which the repeating motif are the two molecules composing the asymmetric unit. Tapes are interconnected by additional N—H···N interactions (N1—H1B···N4 and N8—H8B···N11) which, despite being slightly long (dD···A ranging from 3.002 (6) to 3.034 (6) Å), are nevertheless highly directional with the interaction angles approaching linearity (of ca 173 and 176°). Noteworthy, these inter-chain connections are further strengthened by the presence of two weak C—H···N interactions (not represented): C3—H3···N3i with dC···N=3.389 (6) Å and <(CHN)=174°; C8—H8···N9ii with dC···N=3.435 (6) Å and <(CHN)=167° (symmetry codes: (i) x, 1 + y, z; (ii) x, -1 + y, z). The combination of these N—H···N and C—H···N contacts can be described by the R22(8) graph set motif.

The hydrogen bonding interactions connecting adjacent molecular units and summarized in the previous paragraph lead to the formation of a two-dimensional supramolecular layer placed in the bc plane as shown in Fig. 2. Individual layers close pack parallel to the a-axis of the unit cell mediated by offset π-π contacts between HAtrtr molecules (Fig. 3 and Table 2 for intercentroid distances). Noteworthy, the inter-layer distance along the a axis alternates: layers are disposed into pairs so to promote the aforementioned strong offset π-π contacts within one pair; connections between adjacent pairs of supramolecular layers are weaker (i.e. longer inter-centroid distances - not shown).

Related literature top

For the synthesis of 1-butyl-3-methylimidazolium bromide and 1,2-diformylhydrazine, see: Liu et al. (2007); Parnham & Morris (2006). For the use of triazole molecules, see: Wang et al. (2012); Zhang et al. (2009). For previous research studies on crystal engineering approaches, see: Fernandes et al. (2011); Silva et al. (2011); Amarante et al. (2009); Paz & Klinowski (2007). For graph-set notation, see: Grell et al. (1999). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

3,5-Di(amino)-1,2,4-triazole (98% purity) and Mn(OAc)2.4H2O (99%+ purity) were purchased from Sigma-Aldrich and were used as received without further purification. 5-Amino-3-(1,2,4-triazol-4-yl)-1H-1,2,4-triazole and 1,2-diformylhydrazine were prepared by methods reported in the literature (Liu et al., 2007). 1-Butyl-3-methylimidazolium bromide ([BMI]Br) was also prepared according to literature procedures (Parnham & Morris, 2006) (pale-yellow oil; yield: 78°).

1,2-Diformylhydrazine (0.1 mol; 8.8095 g) and 3,5-di(amino)-1,2,4-triazole (0.05 mol; 4.9564 g) were mixed in a 25 mL Teflon-lined stainless-steel reaction vessel and heated at 170 °C for 3 days in a furnace. After this time, the vessel was allowed to cool slowly to ambient temperature yielding 5-amino-3-(1,2,4-triazol-4-yl)-1H-1,2,4-triazole (HAtrtr) as a white microcrystalline powder. The solid was then washed with copious amounts of water and ethanol and dried at ca 60 °C for 24 h. Yield: 6.85 g, 67.4%.

HAtrtr (0.2 mmol, 0.0407 g) and Mn(OAc)2.4H2O (1.0 mmol, 0.2451 g) were mixed with ca 0.50 g of [BMI]Br in a 25 mL teflon-lined stainless-steel reaction vessel. The resulting mixture was heated to 110 °C for 7 days. The vessel was then allowed to cool to ambient temperature at a rate of ca 1 °C/h. Small colourless platelets of HAtrtr were formed as a minor secondary product, whose crystal structure is reported in this manuscript.

Refinement top

Hydrogen atoms bound to carbon were placed at their idealized positions with C—H = 0.93 Å and included in the final structural model in the riding-motion approximation with isotropic displacement parameters fixed at 1.2×Ueq(C).

Hydrogen atoms associated with nitrogen have been directly located from difference Fourier maps and were included in the structural model with the N—H and H···H (only for the –NH2 moieties) distances restrained to 0.900 (5) and 1.560 (5) Å, respectively, in order to ensure a chemically reasonable environment. These hydrogen atoms were refined using a riding-motion approximation with isotropic displacement parameters fixed at 1.5×Ueq(N).

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. Asymmetric unit of the title compound showing all non-hydrogen atoms represented as anisotropic displacement ellipsoids drawn at the 50% probability level and hydrogen atoms as small spheres with arbitrary radius. The labeling scheme for all non-hydrogen atoms is also provided.
[Figure 2] Fig. 2. Two-dimensional supramolecular network placed in the bc plane formed by the N—H···N hydrogen bonding interactions between adjacent molecular units. Zigzag supramolecular tapes running parallel to the c axis of the unit cell are based on R22(7) graph set motifs (yellow dashed lines) formed between the 5-amino-3-(1,2,4-triazole) moiety of one molecule and the 1,2,4-triazole group from the adjacent one. Connections between adjacent tapes (dashed green lines) are ensured by additional N—H···N interactions along [010]. For geometrical details on the represented hydrogen bonding interactions see Table 1.
[Figure 3] Fig. 3. (a) Schematic representation of the supramolecular π-π interactions between HAtrtr molecules belonging to adjacent supramolecular layers. For clarity one layer is represented as pink bonds and all hydrogen atoms have omitted. For inter-centroid distances see Table 2. (b) Crystal packing of the title compound viewed along [001] direction, clearly showing the planar nature of the two-dimensional supramolecular layer.
5-Amino-3-(4H-1,2,4-triazol-4-yl)-1H-1,2,4-triazole top
Crystal data top
C4H5N7F(000) = 624
Mr = 151.15Dx = 1.603 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 823 reflections
a = 13.765 (3) Åθ = 2.7–21.7°
b = 5.9378 (12) ŵ = 0.12 mm1
c = 16.635 (4) ÅT = 293 K
β = 112.914 (12)°Prism, yellow
V = 1252.4 (5) Å30.10 × 0.05 × 0.03 mm
Z = 8
Data collection top
Bruker X8 Kappa CCD APEXII
diffractometer
2192 independent reflections
Radiation source: fine-focus sealed tube975 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.079
ω / ϕ scansθmax = 25.0°, θmin = 3.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1998)
h = 1616
Tmin = 0.988, Tmax = 0.996k = 75
8003 measured reflectionsl = 1919
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)] = 0.073Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.226H atoms treated by a mixture of independent and constrained refinement
S = 0.96 w = 1/[σ2(Fo2) + (0.1189P)2]
where P = (Fo2 + 2Fc2)/3
2192 reflections(Δ/σ)max < 0.001
217 parametersΔρmax = 0.52 e Å3
8 restraintsΔρmin = 0.36 e Å3
Crystal data top
C4H5N7V = 1252.4 (5) Å3
Mr = 151.15Z = 8
Monoclinic, P21/nMo Kα radiation
a = 13.765 (3) ŵ = 0.12 mm1
b = 5.9378 (12) ÅT = 293 K
c = 16.635 (4) Å0.10 × 0.05 × 0.03 mm
β = 112.914 (12)°
Data collection top
Bruker X8 Kappa CCD APEXII
diffractometer
2192 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1998)
975 reflections with I > 2σ(I)
Tmin = 0.988, Tmax = 0.996Rint = 0.079
8003 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0738 restraints
wR(F2) = 0.226H atoms treated by a mixture of independent and constrained refinement
S = 0.96Δρmax = 0.52 e Å3
2192 reflectionsΔρmin = 0.36 e Å3
217 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
N10.6176 (4)0.3457 (6)0.1686 (3)0.0465 (13)
H1B0.625 (4)0.477 (4)0.140 (3)0.070*
H1A0.625 (4)0.341 (7)0.2198 (16)0.070*
N20.6244 (3)0.0473 (7)0.1487 (3)0.0431 (12)
H20.624 (4)0.106 (9)0.1987 (18)0.065*
N40.6274 (3)0.2015 (6)0.0855 (3)0.0443 (12)
C20.6268 (4)0.0647 (8)0.0238 (3)0.0346 (12)
N30.6228 (3)0.1582 (6)0.0393 (2)0.0326 (10)
C10.6217 (4)0.1618 (8)0.1201 (3)0.0368 (12)
N60.6346 (3)0.1685 (7)0.1884 (3)0.0477 (12)
N70.6317 (3)0.3877 (7)0.1576 (3)0.0493 (12)
C30.6290 (4)0.3720 (8)0.0783 (3)0.0449 (14)
H30.62720.49360.04260.054*
N50.6292 (3)0.1502 (6)0.0556 (2)0.0339 (10)
C40.6328 (4)0.0325 (9)0.1264 (3)0.0420 (13)
H40.63380.12380.13020.050*
N100.6263 (3)0.2101 (6)0.3519 (3)0.0417 (12)
H100.636 (4)0.166 (9)0.3037 (19)0.063*
N110.6323 (3)0.0579 (6)0.4167 (3)0.0383 (11)
C60.6227 (3)0.1927 (7)0.4747 (3)0.0312 (11)
N90.6124 (3)0.4162 (6)0.4575 (3)0.0350 (10)
C50.6144 (4)0.4198 (8)0.3774 (3)0.0341 (12)
N140.6344 (3)0.1263 (7)0.6590 (3)0.0441 (11)
N130.6262 (3)0.0938 (7)0.6861 (3)0.0487 (12)
C70.6202 (4)0.2269 (8)0.6221 (3)0.0440 (14)
H70.61360.38270.62290.053*
N120.6250 (3)0.1088 (6)0.5547 (2)0.0342 (10)
C80.6339 (4)0.1094 (8)0.5814 (3)0.0411 (13)
H80.63900.23110.54800.049*
N80.6036 (4)0.6025 (7)0.3278 (3)0.0509 (13)
H8A0.605 (4)0.589 (7)0.2746 (15)0.076*
H8B0.615 (4)0.737 (4)0.355 (3)0.076*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.083 (3)0.031 (2)0.035 (3)0.001 (2)0.033 (3)0.005 (2)
N20.084 (3)0.030 (2)0.026 (3)0.003 (2)0.032 (3)0.001 (2)
N40.083 (3)0.033 (2)0.028 (3)0.001 (2)0.033 (2)0.000 (2)
C20.045 (3)0.036 (3)0.026 (3)0.004 (2)0.017 (3)0.002 (2)
N30.051 (3)0.030 (2)0.022 (2)0.0005 (17)0.020 (2)0.0000 (17)
C10.050 (3)0.036 (3)0.030 (3)0.001 (2)0.022 (3)0.001 (2)
N60.075 (3)0.051 (3)0.025 (3)0.007 (2)0.028 (2)0.002 (2)
N70.066 (3)0.044 (3)0.044 (3)0.008 (2)0.028 (3)0.008 (2)
C30.067 (4)0.042 (3)0.030 (3)0.005 (3)0.022 (3)0.011 (2)
N50.052 (3)0.035 (2)0.021 (3)0.0012 (19)0.022 (2)0.0004 (18)
C40.059 (4)0.045 (3)0.027 (3)0.005 (2)0.022 (3)0.003 (3)
N100.073 (3)0.032 (3)0.029 (3)0.004 (2)0.029 (3)0.004 (2)
N110.067 (3)0.031 (2)0.023 (2)0.0016 (19)0.024 (2)0.0013 (19)
C60.043 (3)0.033 (3)0.022 (3)0.000 (2)0.017 (2)0.002 (2)
N90.055 (3)0.029 (2)0.026 (2)0.0003 (18)0.021 (2)0.0082 (18)
C50.050 (3)0.028 (3)0.028 (3)0.001 (2)0.020 (3)0.000 (2)
N140.061 (3)0.045 (3)0.030 (3)0.002 (2)0.022 (2)0.006 (2)
N130.073 (3)0.048 (3)0.029 (3)0.002 (2)0.024 (2)0.003 (2)
C70.069 (4)0.038 (3)0.033 (3)0.001 (2)0.029 (3)0.000 (3)
N120.052 (3)0.030 (2)0.024 (3)0.0001 (18)0.020 (2)0.0002 (18)
C80.059 (4)0.039 (3)0.032 (3)0.003 (2)0.026 (3)0.004 (2)
N80.097 (4)0.030 (2)0.036 (3)0.001 (2)0.037 (3)0.002 (2)
Geometric parameters (Å, º) top
N1—C11.345 (6)N10—C51.346 (6)
N1—H1B0.900 (5)N10—N111.385 (5)
N1—H1A0.899 (5)N10—H100.901 (5)
N2—C11.335 (6)N11—C61.299 (5)
N2—N41.382 (5)C6—N91.353 (5)
N2—H20.899 (5)C6—N121.410 (5)
N4—C21.312 (6)N9—C51.344 (6)
C2—N31.346 (5)C5—N81.336 (6)
C2—N51.403 (5)N14—C81.293 (6)
N3—C11.337 (6)N14—N131.401 (5)
N6—C41.303 (6)N13—C71.302 (6)
N6—N71.394 (6)C7—N121.346 (6)
N7—C31.307 (6)C7—H70.9300
C3—N51.370 (6)N12—C81.360 (6)
C3—H30.9300C8—H80.9300
N5—C41.353 (6)N8—H8A0.899 (5)
C4—H40.9300N8—H8B0.900 (5)
C1—N1—H1B114 (3)C5—N10—N11109.6 (4)
C1—N1—H1A123 (3)C5—N10—H10129 (4)
H1B—N1—H1A120 (4)N11—N10—H10121 (4)
C1—N2—N4110.0 (4)C6—N11—N10100.6 (4)
C1—N2—H2134 (4)N11—C6—N9118.7 (4)
N4—N2—H2116 (4)N11—C6—N12120.8 (4)
C2—N4—N2100.2 (4)N9—C6—N12120.5 (4)
N4—C2—N3118.1 (4)C5—N9—C6100.6 (4)
N4—C2—N5120.5 (4)N8—C5—N9125.8 (4)
N3—C2—N5121.4 (4)N8—C5—N10123.7 (4)
C1—N3—C2101.1 (4)N9—C5—N10110.5 (4)
N2—C1—N3110.6 (4)C8—N14—N13106.2 (4)
N2—C1—N1122.8 (5)C7—N13—N14106.9 (4)
N3—C1—N1126.6 (5)N13—C7—N12110.9 (4)
C4—N6—N7107.4 (4)N13—C7—H7124.5
C3—N7—N6106.8 (4)N12—C7—H7124.5
N7—C3—N5110.1 (5)C7—N12—C8104.6 (4)
N7—C3—H3124.9C7—N12—C6127.8 (4)
N5—C3—H3124.9C8—N12—C6127.6 (4)
C4—N5—C3105.1 (4)N14—C8—N12111.4 (4)
C4—N5—C2127.7 (4)N14—C8—H8124.3
C3—N5—C2127.2 (4)N12—C8—H8124.3
N6—C4—N5110.6 (4)C5—N8—H8A120 (3)
N6—C4—H4124.7C5—N8—H8B117 (3)
N5—C4—H4124.7H8A—N8—H8B120 (4)
C1—N2—N4—C20.4 (5)C5—N10—N11—C60.3 (5)
N2—N4—C2—N30.7 (6)N10—N11—C6—N90.9 (6)
N2—N4—C2—N5179.9 (4)N10—N11—C6—N12179.6 (4)
N4—C2—N3—C10.7 (6)N11—C6—N9—C51.0 (6)
N5—C2—N3—C1180.0 (4)N12—C6—N9—C5179.8 (4)
N4—N2—C1—N30.0 (6)C6—N9—C5—N8177.7 (5)
N4—N2—C1—N1179.4 (4)C6—N9—C5—N100.7 (5)
C2—N3—C1—N20.4 (5)N11—N10—C5—N8178.2 (5)
C2—N3—C1—N1179.8 (5)N11—N10—C5—N90.3 (5)
C4—N6—N7—C30.4 (5)C8—N14—N13—C70.7 (5)
N6—N7—C3—N50.4 (6)N14—N13—C7—N120.6 (6)
N7—C3—N5—C40.3 (5)N13—C7—N12—C80.3 (6)
N7—C3—N5—C2180.0 (4)N13—C7—N12—C6178.9 (4)
N4—C2—N5—C4177.5 (5)N11—C6—N12—C7177.2 (4)
N3—C2—N5—C43.3 (7)N9—C6—N12—C71.5 (7)
N4—C2—N5—C32.1 (7)N11—C6—N12—C81.8 (7)
N3—C2—N5—C3177.1 (4)N9—C6—N12—C8179.4 (4)
N7—N6—C4—N50.2 (5)N13—N14—C8—N120.5 (5)
C3—N5—C4—N60.0 (5)C7—N12—C8—N140.2 (5)
C2—N5—C4—N6179.7 (4)C6—N12—C8—N14179.4 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N14i0.90 (1)2.43 (2)3.239 (6)150 (4)
N1—H1B···N4ii0.90 (1)2.11 (1)3.002 (6)173 (5)
N2—H2···N13i0.90 (1)1.93 (2)2.772 (6)155 (5)
N8—H8A···N70.90 (1)2.43 (2)3.264 (6)154 (4)
N8—H8B···N11iii0.90 (1)2.14 (1)3.034 (6)176 (5)
N10—H10···N60.90 (1)1.91 (2)2.777 (6)161 (5)
Symmetry codes: (i) x, y, z1; (ii) x, y1, z; (iii) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC4H5N7
Mr151.15
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)13.765 (3), 5.9378 (12), 16.635 (4)
β (°) 112.914 (12)
V3)1252.4 (5)
Z8
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.10 × 0.05 × 0.03
Data collection
DiffractometerBruker X8 Kappa CCD APEXII
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1998)
Tmin, Tmax0.988, 0.996
No. of measured, independent and
observed [I > 2σ(I)] reflections
8003, 2192, 975
Rint0.079
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.073, 0.226, 0.96
No. of reflections2192
No. of parameters217
No. of restraints8
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.52, 0.36

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—H1A···N14i0.899 (5)2.43 (2)3.239 (6)150 (4)
N1—H1B···N4ii0.900 (5)2.107 (11)3.002 (6)173 (5)
N2—H2···N13i0.899 (5)1.93 (2)2.772 (6)155 (5)
N8—H8A···N70.899 (5)2.43 (2)3.264 (6)154 (4)
N8—H8B···N11iii0.900 (5)2.135 (8)3.034 (6)176 (5)
N10—H10···N60.901 (5)1.912 (19)2.777 (6)161 (5)
Symmetry codes: (i) x, y, z1; (ii) x, y1, z; (iii) x, y+1, z.
Selected π-π contacts top
π-π interactiond(Cg···Cg)
Cg(1)···Cg(2)i3.580 (3)
Cg(3)···Cg(4)ii3.700 (3)
Symmetry codes: (i) 1-x, -y, -z; (ii) 1-x, -y, 1-z; Cg(1): centroid of the ring formed by N2, N3, N4, C1 and C2; Cg(2): centroid of the ring formed by N5, N6, N7, C3 and C4; Cg(3): centroid of the ring formed by N9, N10, N11, C5 and C6; Cg(4): centroid of the ring formed by N12, N13, N14, C7 and C8.
 

Acknowledgements

The authors gratefully acknowledge the Fundação para a Ciência e a Tecnologia (FCT, MEC, Portugal), the European Union, QREN, FEDER, COMPETE for financial support by the strategic projects PEst-C/CTM/LA0011/2011 (to CICECO) and Pest-C/EQB/LA0006/2011 (to REQUIMTE), the R&D projects PTDC/CTM/100357/2008 and PTDC/QUI-QUI/098098/2008 (FCOMP-01–0124-FEDER-010785), as well as the post-doctoral research grant SFRH/BPD/47566/2008 (to BL). They also wish to thank FCT for the specific funding towards the purchase of the single-crystal X-ray diffractometer.

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Volume 68| Part 9| September 2012| Pages o2700-o2701
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