Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The title compound, C4H5N3O2, possesses a planar triazole ring and contains two inter­molecular hydrogen bonds in the crystal structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805028102/ww6417sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805028102/ww6417Isup2.hkl
Contains datablock I

CCDC reference: 287755

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](C-C)= 0.002 Å
  • R factor = 0.037
  • wR factor = 0.111
  • Data-to-parameter ratio = 13.4

checkCIF/PLATON results

No syntax errors found


No errors found in this datablock

Comment top

Ribavirin (1-D-ribofuranosyl-1,2,4-triazole-3-carboxamide) (Vo et al., 2003) is a nucleoside analogue that has demonstrated efficacy in treating viral diseases both as monotherapy 14 (respiratory syncytial virus) and in combination therapy with interferon alpha (hepatitis C virus). Methyl 1H-1,2,4-triazole-3-carboxylate, (I) (Lin & Liu, 1984), has been used as starting materials for Ribavirin (Ramasamy et al., 2000). The structure of (I) (Fig. 1) displays two types of intermolecular hydrogen-bonding interactions, O1···H1—C1 and N1···H3—N3. The plane-to-plane distance of two molecules is 3.26 (2) Å.

Experimental top

5-Amino-1,2,4-triazole-3-carboxylic acid (100 g) and methanol (500 ml) were placed in a 2 l three-necked flask with mechanical stirring. The reaction mixture was slowly added with 98% sulfuric acid (250 g) under stirring and then heated under reflux for 16 h. The reaction mixture was cooled to 278 K for 10 h to afford a light-yellow wet solid. This solid was mixed with 98% surfuric acid (58 g) and water (350 ml), and the resulting mixture cooled to 273–2274 K. 30% aqueous sodium nitrite (150 g) was added slowly and the reaction allowed to continue for a further 2 h to give a grey solid. The grey solid and 350 ml me thanol was then placed in a 1 l flask with stirring and slowly heated to 313 K. When all the diazonium salt had been decomposed by methanol, the reaction solution was filtered and the filtrate was cooled to 283 K to afford the product, (I). Recrystallization from water and methanol gave 49 g of crystalline product of (I) (yield 49%).

Refinement top

The vinyl and imine H atoms were restrained on their parent atoms, with C—H distances restrained to 0.93 Å and N—H restrained to 0.95 (3) Å. The methyl H atoms were positioned geometrically and refined using a riding model, with C—H = 0.96 Å and Uiso(H) = 1.2Ueq(C). In absence of significant anomalous dispersion effects, Friedel pair reflections were merged prior to refinement.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of the molecule of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The packing diagram of (I). Dotted lines represent intermolecular hydrogen-bonding interactions.
Methyl 1H-1,2,4-triazole-3-carboxylate top
Crystal data top
C4H5N3O2F(000) = 264
Mr = 127.11Dx = 1.464 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1220 reflections
a = 3.9737 (9) Åθ = 2.2–26.2°
b = 18.160 (4) ŵ = 0.12 mm1
c = 8.1865 (19) ÅT = 294 K
β = 102.596 (4)°Block, colourless
V = 576.5 (2) Å30.30 × 0.26 × 0.20 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
1168 independent reflections
Radiation source: fine-focus sealed tube846 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
ϕ and ω scansθmax = 26.4°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 24
Tmin = 0.960, Tmax = 0.976k = 2221
3192 measured reflectionsl = 1010
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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0566P)2 + 0.0868P]
where P = (Fo2 + 2Fc2)/3
1168 reflections(Δ/σ)max = 0.002
87 parametersΔρmax = 0.15 e Å3
0 restraintsΔρmin = 0.16 e Å3
Crystal data top
C4H5N3O2V = 576.5 (2) Å3
Mr = 127.11Z = 4
Monoclinic, P21/nMo Kα radiation
a = 3.9737 (9) ŵ = 0.12 mm1
b = 18.160 (4) ÅT = 294 K
c = 8.1865 (19) Å0.30 × 0.26 × 0.20 mm
β = 102.596 (4)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1168 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
846 reflections with I > 2σ(I)
Tmin = 0.960, Tmax = 0.976Rint = 0.023
3192 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.111H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.15 e Å3
1168 reflectionsΔρmin = 0.16 e Å3
87 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
O10.3505 (4)0.39535 (7)0.12670 (17)0.0685 (5)
O20.2107 (3)0.46242 (7)0.33138 (17)0.0597 (4)
N10.1973 (4)0.26613 (8)0.28949 (17)0.0487 (4)
N20.0297 (4)0.33867 (8)0.47971 (17)0.0486 (4)
N30.0137 (4)0.26701 (8)0.51244 (19)0.0485 (4)
C10.0859 (5)0.22506 (11)0.4003 (2)0.0517 (5)
H10.07880.17390.39930.062*
C20.1574 (4)0.33524 (9)0.34415 (19)0.0412 (4)
C30.2501 (4)0.40039 (9)0.2544 (2)0.0457 (4)
C40.3033 (6)0.52920 (11)0.2565 (3)0.0732 (6)
H4A0.54600.52890.25920.110*
H4B0.24870.57090.31800.110*
H4C0.17670.53230.14260.110*
H30.100 (6)0.2543 (14)0.608 (3)0.086 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.1045 (11)0.0556 (9)0.0588 (8)0.0018 (7)0.0469 (8)0.0036 (6)
O20.0812 (9)0.0453 (8)0.0596 (8)0.0005 (6)0.0309 (7)0.0028 (6)
N10.0631 (9)0.0461 (8)0.0430 (8)0.0002 (7)0.0250 (7)0.0001 (6)
N20.0572 (9)0.0508 (9)0.0431 (8)0.0033 (7)0.0223 (6)0.0002 (6)
N30.0556 (9)0.0545 (10)0.0411 (8)0.0012 (7)0.0227 (7)0.0038 (7)
C10.0640 (11)0.0470 (10)0.0492 (10)0.0008 (8)0.0231 (9)0.0016 (8)
C20.0438 (9)0.0469 (10)0.0355 (8)0.0032 (7)0.0146 (7)0.0003 (7)
C30.0513 (10)0.0463 (10)0.0427 (9)0.0037 (7)0.0174 (8)0.0002 (7)
C40.0970 (17)0.0455 (11)0.0835 (15)0.0051 (10)0.0334 (13)0.0017 (10)
Geometric parameters (Å, º) top
O1—C31.2008 (19)N3—C11.318 (2)
O2—C31.317 (2)N3—H30.95 (3)
O2—C41.442 (2)C1—H10.9300
N1—C11.323 (2)C2—C31.481 (2)
N1—C21.353 (2)C4—H4A0.9600
N2—C21.318 (2)C4—H4B0.9600
N2—N31.347 (2)C4—H4C0.9600
C3—O2—C4116.62 (15)N1—C2—C3121.13 (14)
C1—N1—C2102.43 (14)O1—C3—O2125.36 (16)
C2—N2—N3102.19 (13)O1—C3—C2122.46 (15)
C1—N3—N2110.42 (15)O2—C3—C2112.17 (14)
C1—N3—H3130.6 (15)O2—C4—H4A109.5
N2—N3—H3119.0 (15)O2—C4—H4B109.5
N3—C1—N1110.35 (17)H4A—C4—H4B109.5
N3—C1—H1124.8O2—C4—H4C109.5
N1—C1—H1124.8H4A—C4—H4C109.5
N2—C2—N1114.61 (14)H4B—C4—H4C109.5
N2—C2—C3124.26 (15)
C2—N2—N3—C10.12 (18)C4—O2—C3—O11.3 (3)
N2—N3—C1—N10.2 (2)C4—O2—C3—C2178.34 (15)
C2—N1—C1—N30.14 (19)N2—C2—C3—O1176.37 (16)
N3—N2—C2—N10.03 (18)N1—C2—C3—O13.1 (3)
N3—N2—C2—C3179.47 (15)N2—C2—C3—O23.9 (2)
C1—N1—C2—N20.06 (19)N1—C2—C3—O2176.59 (14)
C1—N1—C2—C3179.58 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···O1i0.932.573.138 (2)120
N3—H3···N1i0.95 (3)1.88 (3)2.822 (2)175 (2)
Symmetry code: (i) x1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC4H5N3O2
Mr127.11
Crystal system, space groupMonoclinic, P21/n
Temperature (K)294
a, b, c (Å)3.9737 (9), 18.160 (4), 8.1865 (19)
β (°) 102.596 (4)
V3)576.5 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.30 × 0.26 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.960, 0.976
No. of measured, independent and
observed [I > 2σ(I)] reflections
3192, 1168, 846
Rint0.023
(sin θ/λ)max1)0.626
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.111, 1.04
No. of reflections1168
No. of parameters87
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.15, 0.16

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

Selected geometric parameters (Å, º) top
O1—C31.2008 (19)N3—C11.318 (2)
N1—C11.323 (2)N3—H30.95 (3)
N1—C21.353 (2)C1—H10.9300
N2—C21.318 (2)C4—H4C0.9600
N2—N31.347 (2)
C1—N3—H3130.6 (15)N1—C1—H1124.8
N2—N3—H3119.0 (15)N1—C2—C3121.13 (14)
N3—C1—H1124.8O2—C4—H4A109.5
C2—N2—N3—C10.12 (18)C1—N1—C2—C3179.58 (15)
C2—N1—C1—N30.14 (19)N1—C2—C3—O13.1 (3)
N3—N2—C2—N10.03 (18)N1—C2—C3—O2176.59 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···O1i0.932.573.138 (2)120
N3—H3···N1i0.95 (3)1.88 (3)2.822 (2)175 (2)
Symmetry code: (i) x1/2, y+1/2, z+1/2.
 

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds