Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110034128/dn3145sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110034128/dn3145Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110034128/dn3145IIsup3.hkl |
CCDC references: 798598; 798599
7-Amino-2-(methylthio)[1,2,4]triazolo[1,5-a]pyrimidine-6-carboxylic acid was a Maybridge (UK) product commercialized by C. Erba. Crystals of (I) were obtained by slow evaporation of a DMF/HCOOH 1:1 solution at 277 K, while crystals of (II) were grown by the liquid–liquid diffusion method in dimethylsulfoxide/water at room temperature. In both cases, the crystals were colourless [(II) given as white in CIF tables - please clarify], exhibiting prismatic shapes [Both given as block in CIF tables - please clarify]. Good crystal quality specimens of dimensions 0.25 × 0.25 × 0.10 mm [(I)] and 0.28 × 0.16 × 0.05 mm [(II)] were used for the X-ray diffraction experiments.
IR spectra (Nujol mulls, CsI windows) were recorded with a Perkin–Elmer Spectrum One FT–IR spectrometer. 1H and 13C NMR spectra, in DMSO-d6, were recorded with a Bruker AC 300 Avance instrument operating at 300 and 75 MHz, respectively. On the basis of spectroscopic studies on anthranilic acid (Samsonowicz et al., 2005), we report the following IR assignments (ν, cm-1): 3498 [s, νas(NH2)], 3333 [s, νsy(NH2)], 1698 [vs, ν(CO)], 1336 [vs, ν(C—NH2)], 1256 [vs, ν(C—OH)]. NMR assignments were tried by COSY, HMBC, HSCQ and DEPT two-dimensional spectra. 1H NMR (ligand skeleton, DMSO-d6, δ, p.p.m.): 8.65, 8.96 (d, 2H, –NH2), 8.81 (s, 1H, arom. CH), 2.73 (s, 3H, S—CH3); 13C NMR (ligand skeleton, DMSO-d6, δ, p.p.m.): 168.27 (COOH), 168.03 (C2), 94.67 (C3a), 156.75 (C5), 157.63 (C6), 149.71 (C7).
H atoms were located from Fourier difference syntheses and placed in calculated positions using a riding model, with C—H = 0.93–0.96 Å, N—H = 0.87 Å and O—H = 0.91 Å, and with Uiso(H) = kUeq(parent atom), where k = 1.5 for Csp3—H and O—H bonds, and 1.2 for the rest. [Please check added details]
Data collection: COLLECT (Nonius, 1998) for (I); CrysAlis CCD (Oxford Diffraction, 2004) for (II). Cell refinement: COLLECT (Nonius, 1998) for (I); CrysAlis RED (Oxford Diffraction, 2004) for (II). Data reduction: HKL (Otwinowski & Minor, 1997) for (I); CrysAlis RED (Oxford Diffraction, 2004) for (II). Program(s) used to solve structure: SIR92 (Altomare et al., 1993) for (I); SIR2004 (Burla et al., 2005) for (II). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008). Molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009) for (I); ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997) for (II). For both compounds, software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C7H7N5O2S·C3H7NO | F(000) = 624 |
Mr = 298.33 | Dx = 1.483 Mg m−3 |
Monoclinic, P21/c | Melting point: 300 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 12.1365 (6) Å | Cell parameters from 3215 reflections |
b = 11.2180 (7) Å | θ = 1.8–28.2° |
c = 10.3559 (5) Å | µ = 0.26 mm−1 |
β = 108.570 (3)° | T = 293 K |
V = 1336.52 (12) Å3 | Block, colourless |
Z = 4 | 0.25 × 0.25 × 0.10 mm |
Nonius Kappa CCD area-detector diffractometer | 2605 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 28.2°, θmin = 1.8° |
ω scans | h = −15→15 |
3215 measured reflections | k = −14→0 |
3215 independent reflections | l = −13→0 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.16 | w = 1/[σ2(Fo2) + (0.0346P)2 + 1.4222P] where P = (Fo2 + 2Fc2)/3 |
3214 reflections | (Δ/σ)max = 0.001 |
184 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C7H7N5O2S·C3H7NO | V = 1336.52 (12) Å3 |
Mr = 298.33 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.1365 (6) Å | µ = 0.26 mm−1 |
b = 11.2180 (7) Å | T = 293 K |
c = 10.3559 (5) Å | 0.25 × 0.25 × 0.10 mm |
β = 108.570 (3)° |
Nonius Kappa CCD area-detector diffractometer | 2605 reflections with I > 2σ(I) |
3215 measured reflections | Rint = 0.000 |
3215 independent reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.16 | Δρmax = 0.31 e Å−3 |
3214 reflections | Δρmin = −0.31 e Å−3 |
184 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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. |
x | y | z | Uiso*/Ueq | ||
S2 | 0.09115 (5) | 0.76074 (5) | 0.65910 (6) | 0.02886 (15) | |
O6A | 0.52951 (15) | 0.94673 (14) | 0.20689 (17) | 0.0310 (4) | |
H6A | 0.5790 | 0.9231 | 0.1620 | 0.046* | |
O6B | 0.51541 (13) | 0.74917 (14) | 0.22558 (16) | 0.0274 (3) | |
N1 | 0.24116 (15) | 0.73836 (16) | 0.52151 (19) | 0.0245 (4) | |
N3 | 0.19432 (16) | 0.93305 (16) | 0.5478 (2) | 0.0265 (4) | |
N4 | 0.31502 (17) | 1.02405 (17) | 0.4288 (2) | 0.0270 (4) | |
N7 | 0.38610 (16) | 0.66547 (16) | 0.3774 (2) | 0.0270 (4) | |
H7A | 0.3540 | 0.6110 | 0.4150 | 0.032* | |
H7B | 0.4260 | 0.6470 | 0.3250 | 0.032* | |
N8 | 0.29896 (15) | 0.81479 (16) | 0.46233 (18) | 0.0230 (4) | |
C2 | 0.18119 (19) | 0.8155 (2) | 0.5703 (2) | 0.0242 (4) | |
C3a | 0.27024 (19) | 0.93125 (19) | 0.4785 (2) | 0.0238 (4) | |
C5 | 0.38584 (19) | 0.9927 (2) | 0.3592 (2) | 0.0258 (5) | |
H5 | 0.4189 | 1.0541 | 0.3236 | 0.031* | |
C6 | 0.41514 (19) | 0.87576 (19) | 0.3345 (2) | 0.0234 (4) | |
C7 | 0.36913 (18) | 0.78044 (19) | 0.3896 (2) | 0.0226 (4) | |
C21 | 0.0395 (2) | 0.8986 (2) | 0.7080 (3) | 0.0403 (6) | |
H21A | −0.0045 | 0.8822 | 0.7683 | 0.060* | |
H21B | −0.0091 | 0.9387 | 0.6283 | 0.060* | |
H21C | 0.1045 | 0.9485 | 0.7536 | 0.060* | |
C61 | 0.49027 (19) | 0.85038 (19) | 0.2514 (2) | 0.0244 (4) | |
O11 | 0.67548 (14) | 0.92678 (14) | 0.07291 (17) | 0.0294 (4) | |
N9 | 0.77504 (16) | 0.84076 (16) | −0.05435 (19) | 0.0255 (4) | |
C9 | 0.8397 (2) | 0.9484 (2) | −0.0624 (3) | 0.0295 (5) | |
H9A | 0.9202 | 0.9375 | −0.0107 | 0.044* | |
H9B | 0.8089 | 1.0145 | −0.0260 | 0.044* | |
H9C | 0.8327 | 0.9641 | −0.1558 | 0.044* | |
C10 | 0.7977 (2) | 0.7360 (2) | −0.1246 (3) | 0.0318 (5) | |
H10A | 0.7735 | 0.7511 | −0.2208 | 0.048* | |
H10B | 0.7551 | 0.6694 | −0.1066 | 0.048* | |
H10C | 0.8793 | 0.7184 | −0.0927 | 0.048* | |
C11 | 0.6988 (2) | 0.8390 (2) | 0.0124 (2) | 0.0266 (5) | |
H11 | 0.6601 | 0.7678 | 0.0144 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S2 | 0.0290 (3) | 0.0298 (3) | 0.0309 (3) | −0.0016 (2) | 0.0140 (2) | 0.0007 (2) |
O6A | 0.0404 (9) | 0.0215 (8) | 0.0394 (10) | 0.0012 (7) | 0.0244 (8) | 0.0016 (7) |
O6B | 0.0319 (8) | 0.0218 (8) | 0.0319 (9) | 0.0019 (6) | 0.0148 (7) | −0.0005 (7) |
N1 | 0.0269 (9) | 0.0225 (9) | 0.0261 (9) | −0.0029 (7) | 0.0114 (7) | 0.0006 (7) |
N3 | 0.0302 (10) | 0.0224 (9) | 0.0296 (10) | 0.0004 (7) | 0.0135 (8) | −0.0007 (8) |
N4 | 0.0328 (10) | 0.0206 (9) | 0.0303 (10) | 0.0006 (8) | 0.0137 (8) | 0.0002 (8) |
N7 | 0.0332 (10) | 0.0191 (9) | 0.0340 (11) | 0.0007 (8) | 0.0184 (9) | 0.0017 (8) |
N8 | 0.0258 (9) | 0.0195 (9) | 0.0247 (9) | −0.0002 (7) | 0.0095 (7) | 0.0013 (7) |
C2 | 0.0250 (10) | 0.0261 (11) | 0.0217 (10) | −0.0012 (9) | 0.0080 (8) | −0.0006 (9) |
C3a | 0.0268 (10) | 0.0198 (10) | 0.0255 (11) | 0.0010 (8) | 0.0094 (9) | −0.0024 (8) |
C5 | 0.0303 (11) | 0.0202 (10) | 0.0281 (11) | 0.0004 (9) | 0.0110 (9) | 0.0028 (9) |
C6 | 0.0262 (10) | 0.0207 (10) | 0.0237 (11) | 0.0004 (8) | 0.0085 (9) | −0.0001 (8) |
C7 | 0.0234 (10) | 0.0207 (10) | 0.0236 (10) | 0.0005 (8) | 0.0076 (8) | −0.0006 (8) |
C21 | 0.0471 (15) | 0.0378 (15) | 0.0469 (16) | 0.0031 (12) | 0.0303 (13) | −0.0007 (12) |
C61 | 0.0266 (10) | 0.0222 (11) | 0.0244 (11) | −0.0003 (8) | 0.0081 (9) | 0.0012 (8) |
O11 | 0.0364 (9) | 0.0232 (8) | 0.0344 (9) | 0.0007 (7) | 0.0194 (7) | 0.0002 (7) |
N9 | 0.0295 (9) | 0.0203 (9) | 0.0275 (10) | 0.0002 (7) | 0.0104 (8) | −0.0011 (7) |
C9 | 0.0331 (12) | 0.0236 (11) | 0.0349 (13) | −0.0010 (9) | 0.0151 (10) | 0.0013 (9) |
C10 | 0.0344 (12) | 0.0280 (12) | 0.0340 (13) | 0.0007 (10) | 0.0125 (10) | −0.0077 (10) |
C11 | 0.0308 (11) | 0.0217 (11) | 0.0270 (11) | 0.0005 (9) | 0.0088 (9) | 0.0018 (9) |
N1—C2 | 1.330 (3) | N7—H7B | 0.8598 |
N1—N8 | 1.370 (2) | C5—H5 | 0.9300 |
N3—C3a | 1.337 (3) | C6—C61 | 1.468 (3) |
N3—C2 | 1.357 (3) | C21—H21A | 0.9600 |
N4—C5 | 1.333 (3) | C21—H21B | 0.9600 |
N4—C3a | 1.350 (3) | C21—H21C | 0.9600 |
N8—C7 | 1.360 (3) | O11—C11 | 1.248 (3) |
N8—C3a | 1.376 (3) | N9—C11 | 1.319 (3) |
C5—C6 | 1.404 (3) | N9—C10 | 1.454 (3) |
C6—C7 | 1.408 (3) | N9—C9 | 1.457 (3) |
S2—C2 | 1.748 (2) | C9—H9A | 0.9600 |
S2—C21 | 1.801 (3) | C9—H9B | 0.9600 |
O6A—C61 | 1.322 (3) | C9—H9C | 0.9600 |
O6A—H6A | 0.9086 | C10—H10A | 0.9600 |
O6B—C61 | 1.227 (3) | C10—H10B | 0.9600 |
N7—C7 | 1.318 (3) | C10—H10C | 0.9600 |
N7—H7A | 0.8793 | C11—H11 | 0.9300 |
C2—S2—C21 | 100.26 (11) | S2—C21—H21B | 109.5 |
C61—O6A—H6A | 108.1 | H21A—C21—H21B | 109.5 |
C2—N1—N8 | 100.53 (17) | S2—C21—H21C | 109.5 |
C3a—N3—C2 | 102.49 (18) | H21A—C21—H21C | 109.5 |
C5—N4—C3a | 114.20 (19) | H21B—C21—H21C | 109.5 |
C7—N7—H7A | 122.2 | O6B—C61—O6A | 122.6 (2) |
C7—N7—H7B | 115.6 | O6B—C61—C6 | 123.5 (2) |
H7A—N7—H7B | 122.0 | O6A—C61—C6 | 113.96 (18) |
C7—N8—N1 | 124.79 (18) | C11—N9—C10 | 121.71 (19) |
C7—N8—C3a | 124.32 (18) | C11—N9—C9 | 121.54 (19) |
N1—N8—C3a | 110.76 (17) | C10—N9—C9 | 116.75 (18) |
N1—C2—N3 | 117.3 (2) | N9—C9—H9A | 109.5 |
N1—C2—S2 | 118.72 (17) | N9—C9—H9B | 109.5 |
N3—C2—S2 | 123.98 (17) | H9A—C9—H9B | 109.5 |
N3—C3a—N4 | 128.5 (2) | N9—C9—H9C | 109.5 |
N3—C3a—N8 | 108.91 (18) | H9A—C9—H9C | 109.5 |
N4—C3a—N8 | 122.55 (19) | H9B—C9—H9C | 109.5 |
N4—C5—C6 | 126.1 (2) | N9—C10—H10A | 109.5 |
N4—C5—H5 | 117.0 | N9—C10—H10B | 109.5 |
C6—C5—H5 | 117.0 | H10A—C10—H10B | 109.5 |
C5—C6—C7 | 118.7 (2) | N9—C10—H10C | 109.5 |
C5—C6—C61 | 121.90 (19) | H10A—C10—H10C | 109.5 |
C7—C6—C61 | 119.40 (19) | H10B—C10—H10C | 109.5 |
N7—C7—N8 | 118.35 (19) | O11—C11—N9 | 124.1 (2) |
N7—C7—C6 | 127.6 (2) | O11—C11—H11 | 118.0 |
N8—C7—C6 | 114.09 (19) | N9—C11—H11 | 118.0 |
S2—C21—H21A | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
O6A—H6A···O11 | 0.91 | 1.71 | 2.584 (2) | 162 |
N7—H7A···O11i | 0.88 | 2.11 | 2.870 (2) | 145 |
N7—H7B···O6B | 0.86 | 2.06 | 2.718 (2) | 132 |
N7—H7B···O6Ai | 0.86 | 2.36 | 2.899 (2) | 121 |
C5—H5···O6Bii | 0.93 | 2.44 | 3.340 (3) | 163 |
C9—H9B···N1ii | 0.96 | 2.59 | 3.462 (3) | 152 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2. |
C7H7N5O2S·H2O | F(000) = 504 |
Mr = 243.26 | Dx = 1.632 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6449 reflections |
a = 4.0134 (3) Å | θ = 3.4–27.5° |
b = 20.3287 (12) Å | µ = 0.33 mm−1 |
c = 12.6897 (7) Å | T = 293 K |
β = 107.039 (6)° | Block, colourless |
V = 989.87 (11) Å3 | 0.28 × 0.16 × 0.05 mm |
Z = 4 |
Oxford Supernova CCD area-detector diffractometer | 1816 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.026 |
Graphite monochromator | θmax = 27.5°, θmin = 3.4° |
ω scans | h = −4→5 |
6449 measured reflections | k = −26→20 |
2242 independent reflections | l = −15→15 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0647P)2 + 0.0359P] where P = (Fo2 + 2Fc2)/3 |
2242 reflections | (Δ/σ)max = 0.001 |
146 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
C7H7N5O2S·H2O | V = 989.87 (11) Å3 |
Mr = 243.26 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 4.0134 (3) Å | µ = 0.33 mm−1 |
b = 20.3287 (12) Å | T = 293 K |
c = 12.6897 (7) Å | 0.28 × 0.16 × 0.05 mm |
β = 107.039 (6)° |
Oxford Supernova CCD area-detector diffractometer | 1816 reflections with I > 2σ(I) |
6449 measured reflections | Rint = 0.026 |
2242 independent reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.39 e Å−3 |
2242 reflections | Δρmin = −0.34 e Å−3 |
146 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2σ(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. |
x | y | z | Uiso*/Ueq | ||
S2 | −0.55860 (12) | 0.930519 (18) | 0.08151 (3) | 0.03616 (16) | |
O6A | 0.5189 (4) | 0.57139 (6) | 0.21011 (10) | 0.0457 (4) | |
H6A | 0.5829 | 0.5292 | 0.1860 | 0.069* | |
O6B | 0.1314 (4) | 0.57083 (6) | 0.04334 (10) | 0.0519 (4) | |
N1 | −0.3872 (3) | 0.80543 (6) | 0.04625 (10) | 0.0292 (3) | |
N3 | −0.0908 (4) | 0.84968 (6) | 0.21351 (10) | 0.0310 (3) | |
N4 | 0.2771 (4) | 0.75656 (6) | 0.28420 (10) | 0.0331 (3) | |
N7 | −0.2686 (4) | 0.67934 (7) | −0.02227 (10) | 0.0397 (4) | |
H7A | −0.4157 | 0.7062 | −0.0686 | 0.048* | |
H7B | −0.2271 | 0.6406 | −0.0400 | 0.048* | |
N8 | −0.1468 (3) | 0.76170 (6) | 0.10835 (9) | 0.0257 (3) | |
C2 | −0.3368 (4) | 0.85649 (7) | 0.11406 (12) | 0.0277 (3) | |
C3a | 0.0267 (4) | 0.78928 (7) | 0.20863 (11) | 0.0272 (3) | |
C5 | 0.3426 (4) | 0.69699 (7) | 0.25425 (12) | 0.0311 (4) | |
H5 | 0.5168 | 0.6735 | 0.3047 | 0.037* | |
C6 | 0.1779 (4) | 0.66538 (7) | 0.15464 (11) | 0.0284 (3) | |
C7 | −0.0857 (4) | 0.70019 (7) | 0.07569 (11) | 0.0273 (3) | |
C21 | −0.8395 (5) | 0.91335 (9) | −0.05405 (14) | 0.0392 (4) | |
H21A | −1.0199 | 0.9460 | −0.0741 | 0.059* | |
H21B | −0.9426 | 0.8707 | −0.0548 | 0.059* | |
H21C | −0.7065 | 0.9142 | −0.1058 | 0.059* | |
C61 | 0.2714 (4) | 0.59880 (8) | 0.13018 (12) | 0.0327 (4) | |
OW1 | 0.6868 (5) | 0.45674 (8) | 0.15297 (12) | 0.0718 (6) | |
HW1 | 0.8251 | 0.4267 | 0.1930 | 0.108* | |
HW2 | 0.7321 | 0.4542 | 0.0840 | 0.108* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S2 | 0.0436 (3) | 0.0246 (2) | 0.0360 (2) | 0.00448 (17) | 0.00491 (19) | −0.00044 (15) |
O6A | 0.0542 (8) | 0.0367 (7) | 0.0347 (6) | 0.0171 (6) | −0.0052 (6) | −0.0011 (5) |
O6B | 0.0711 (10) | 0.0352 (7) | 0.0351 (7) | 0.0141 (6) | −0.0068 (7) | −0.0077 (5) |
N1 | 0.0333 (7) | 0.0234 (6) | 0.0253 (6) | 0.0019 (5) | −0.0005 (5) | 0.0025 (5) |
N3 | 0.0380 (8) | 0.0245 (6) | 0.0259 (6) | −0.0047 (6) | 0.0023 (6) | −0.0019 (5) |
N4 | 0.0384 (8) | 0.0290 (7) | 0.0231 (6) | −0.0027 (6) | −0.0043 (6) | −0.0005 (5) |
N7 | 0.0527 (10) | 0.0280 (7) | 0.0248 (6) | 0.0087 (6) | −0.0101 (6) | −0.0056 (5) |
N8 | 0.0288 (7) | 0.0225 (6) | 0.0203 (5) | −0.0012 (5) | −0.0015 (5) | 0.0010 (5) |
C2 | 0.0303 (8) | 0.0236 (7) | 0.0276 (7) | −0.0029 (6) | 0.0061 (6) | 0.0026 (6) |
C3a | 0.0320 (8) | 0.0238 (7) | 0.0218 (6) | −0.0063 (6) | 0.0015 (6) | −0.0008 (5) |
C5 | 0.0340 (9) | 0.0297 (8) | 0.0228 (7) | −0.0019 (7) | −0.0020 (6) | 0.0029 (6) |
C6 | 0.0312 (8) | 0.0272 (7) | 0.0227 (7) | −0.0007 (6) | 0.0016 (6) | 0.0023 (6) |
C7 | 0.0328 (8) | 0.0241 (7) | 0.0216 (7) | −0.0031 (6) | 0.0025 (6) | −0.0004 (5) |
C21 | 0.0365 (9) | 0.0376 (9) | 0.0383 (9) | 0.0034 (8) | 0.0026 (7) | 0.0036 (7) |
C61 | 0.0382 (9) | 0.0303 (8) | 0.0256 (7) | 0.0039 (7) | 0.0030 (7) | 0.0021 (6) |
OW1 | 0.1166 (16) | 0.0547 (9) | 0.0430 (8) | 0.0443 (10) | 0.0217 (9) | 0.0136 (7) |
S2—C2 | 1.7356 (15) | N7—H7B | 0.8487 |
S2—C21 | 1.7932 (17) | N8—C7 | 1.3619 (19) |
O6A—C61 | 1.3174 (18) | N8—C3a | 1.3782 (17) |
O6A—H6A | 0.9695 | C5—C6 | 1.3992 (19) |
O6B—C61 | 1.2209 (18) | C5—H5 | 0.9300 |
N1—C2 | 1.3255 (19) | C6—C7 | 1.415 (2) |
N1—N8 | 1.3773 (17) | C6—C61 | 1.462 (2) |
N3—C3a | 1.323 (2) | C21—H21A | 0.9600 |
N3—C2 | 1.3624 (18) | C21—H21B | 0.9600 |
N4—C5 | 1.319 (2) | C21—H21C | 0.9600 |
N4—C3a | 1.3442 (19) | OW1—HW1 | 0.8798 |
N7—C7 | 1.3149 (18) | OW1—HW2 | 0.9456 |
N7—H7A | 0.8886 | ||
C2—S2—C21 | 101.19 (8) | N4—C5—H5 | 116.5 |
C61—O6A—H6A | 109.9 | C6—C5—H5 | 116.5 |
C2—N1—N8 | 100.72 (11) | C5—C6—C7 | 117.86 (14) |
C3a—N3—C2 | 102.85 (12) | C5—C6—C61 | 122.29 (13) |
C5—N4—C3a | 114.79 (12) | C7—C6—C61 | 119.85 (13) |
C7—N7—H7A | 120.4 | N7—C7—N8 | 118.90 (13) |
C7—N7—H7B | 116.8 | N7—C7—C6 | 127.06 (15) |
H7A—N7—H7B | 122.6 | N8—C7—C6 | 114.05 (12) |
C7—N8—N1 | 125.23 (11) | S2—C21—H21A | 109.5 |
C7—N8—C3a | 124.56 (12) | S2—C21—H21B | 109.5 |
N1—N8—C3a | 110.21 (12) | H21A—C21—H21B | 109.5 |
N1—C2—N3 | 116.94 (13) | S2—C21—H21C | 109.5 |
N1—C2—S2 | 123.67 (11) | H21A—C21—H21C | 109.5 |
N3—C2—S2 | 119.37 (11) | H21B—C21—H21C | 109.5 |
N3—C3a—N4 | 128.90 (13) | O6B—C61—O6A | 122.79 (15) |
N3—C3a—N8 | 109.27 (12) | O6B—C61—C6 | 122.96 (14) |
N4—C3a—N8 | 121.82 (14) | O6A—C61—C6 | 114.25 (13) |
N4—C5—C6 | 126.92 (14) | HW1—OW1—HW2 | 103.7 |
D—H···A | D—H | H···A | D···A | D—H···A |
O6A—H6A···OW1 | 0.97 | 1.62 | 2.5880 (19) | 176 |
N7—H7A···N4i | 0.89 | 2.06 | 2.9032 (18) | 159 |
N7—H7B···O6B | 0.85 | 2.08 | 2.7117 (19) | 131 |
OW1—HW1···N3ii | 0.88 | 2.06 | 2.9371 (18) | 173 |
OW1—HW2···O6Biii | 0.95 | 1.92 | 2.849 (2) | 167 |
Symmetry codes: (i) x−1, −y+3/2, z−1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C7H7N5O2S·C3H7NO | C7H7N5O2S·H2O |
Mr | 298.33 | 243.26 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 12.1365 (6), 11.2180 (7), 10.3559 (5) | 4.0134 (3), 20.3287 (12), 12.6897 (7) |
β (°) | 108.570 (3) | 107.039 (6) |
V (Å3) | 1336.52 (12) | 989.87 (11) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.26 | 0.33 |
Crystal size (mm) | 0.25 × 0.25 × 0.10 | 0.28 × 0.16 × 0.05 |
Data collection | ||
Diffractometer | Nonius Kappa CCD area-detector diffractometer | Oxford Supernova CCD area-detector diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3215, 3215, 2605 | 6449, 2242, 1816 |
Rint | 0.000 | 0.026 |
(sin θ/λ)max (Å−1) | 0.664 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.120, 1.16 | 0.037, 0.108, 1.11 |
No. of reflections | 3214 | 2242 |
No. of parameters | 184 | 146 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.31 | 0.39, −0.34 |
Computer programs: COLLECT (Nonius, 1998), CrysAlis CCD (Oxford Diffraction, 2004), CrysAlis RED (Oxford Diffraction, 2004), HKL (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1993), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997).
N1—C2 | 1.330 (3) | N4—C3a | 1.350 (3) |
N1—N8 | 1.370 (2) | N8—C7 | 1.360 (3) |
N3—C3a | 1.337 (3) | N8—C3a | 1.376 (3) |
N3—C2 | 1.357 (3) | C5—C6 | 1.404 (3) |
N4—C5 | 1.333 (3) | C6—C7 | 1.408 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O6A—H6A···O11 | 0.91 | 1.71 | 2.584 (2) | 161.7 |
N7—H7A···O11i | 0.88 | 2.11 | 2.870 (2) | 144.6 |
N7—H7B···O6B | 0.86 | 2.06 | 2.718 (2) | 132.2 |
N7—H7B···O6Ai | 0.86 | 2.36 | 2.899 (2) | 121.2 |
C5—H5···O6Bii | 0.93 | 2.44 | 3.340 (3) | 163.0 |
C9—H9B···N1ii | 0.96 | 2.59 | 3.462 (3) | 152.0 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2. |
N1—C2 | 1.3255 (19) | N4—C3a | 1.3442 (19) |
N1—N8 | 1.3773 (17) | N8—C7 | 1.3619 (19) |
N3—C3a | 1.323 (2) | N8—C3a | 1.3782 (17) |
N3—C2 | 1.3624 (18) | C5—C6 | 1.3992 (19) |
N4—C5 | 1.319 (2) | C6—C7 | 1.415 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O6A—H6A···OW1 | 0.97 | 1.62 | 2.5880 (19) | 176.3 |
N7—H7A···N4i | 0.89 | 2.06 | 2.9032 (18) | 158.8 |
N7—H7B···O6B | 0.85 | 2.08 | 2.7117 (19) | 131.2 |
OW1—HW1···N3ii | 0.88 | 2.06 | 2.9371 (18) | 172.5 |
OW1—HW2···O6Biii | 0.95 | 1.92 | 2.849 (2) | 166.5 |
Symmetry codes: (i) x−1, −y+3/2, z−1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z. |
(a) Odabaşoğlu & Büyükgüngör (2006); (b) Surdykowski et al. (1999); (c) Vas'kevich et al. (2006); (d) Kleschick & Bordner (1989); (e) Britsun et al. (2006); (f) Lokaj et al. (2006); (g) Wendt et al. (2007); (h) Rusinov et al. (2007). |
R1 | R2 | R3 | R4 | C5–C6 | C6–C7 | Reference |
-NH2 | -COOH | -H | -SCH3 | 1.404 | 1.408 | (I) |
-NH2 | -COOH | -H | -SCH3 | 1.399 | 1.415 | (II) |
-Me | -H | -Me | -H | 1.408–1.414 | 1.349-1.351 | (a) |
-Ph | -H | -Ph | -H | 1.427 | 1.370 | (b) |
-Me | -H | -Me | -NHPh | 1.400 | 1.355 | (c) |
-Me | -H | -Ph | -SCH2Ph | 1.396 | 1.374 | (d) |
-Me | -H | -NHPh | -SCH3 | 1.400 | 1.377 | (e) |
-Me | -CN | -H | -H | 1.414 | 1.372 | (f) |
-NH2 | -CN | -Ph | -H | 1.416 | 1.393 | (g) |
-NHPh | -NO2 | -CH3 | -H | 1.414 | 1.400 | (h) |
Given the similarity between the skeleton of (I) and the purine ring, 1,2,4-triazolo-[1,5-a]pyrimidines can be considered as model systems for various coordination compounds that exist in nature (Salas et al., 1999). In addition, 1,2,4-triazolo[1,5-a]pyrimidines are known to possess a variety of biological properties (Ram, 1988), antitumour activity being one of the most important. 7-Amino-2-methylsulfanyl-1,2,4-triazolo[1,5-a]pyrimidine-6-carboxylic acid is an amino acid with carboxylic acid and amine groups in positions 7 and 6, respectively, and an S—CH3 group in position 2 (Figs. 1 and 2 for numbering scheme). The presence of all these groups makes the molecule a more versatile ligand than the triazolopyrimidines already known in the literature (Salas et al., 1999; Haasnoot, 2000). The 1,2,4-triazolo[1,5-a]pyrimidine molecule crystallizes with either dimethylformamide (DMF) [(I)] or water [(II)] molecules, in the monoclinic system (space group P21/c ). Crystal structure determinations were carried out for (I) and (II) at room temperature. In both cases, the asymmetric unit contains one 1,2,4-triazolo[1,5-a]pyrimidine molecule and one solvent molecule.
The molecular structures of (I) and (II) are shown in Figs. 1 and 2, respectively. It is known that the association of triazole and pyrimidine rings involves a loss of aromaticity in the latter (Boulanger et al., 1988; Surdykowski et al., 1999). This is indeed observed in (I) and (II), as indicated by the increase in the bond lengths C6—C5 [1.403 (7) and 1.399 (2) Å, respectively, in (I) and (II)] and N8—C3a [1.376 (2) and 1.378 (2) Å] with respect to the characteristic distances observed in non-conjugated aryl-substituted pyrimidine compounds (1.377 and 1.333 Å, respectively; Surdykowski et al., 1999). In both 1,2,4-triazolo[1,5-a]pyrimidine molecules, the carboxyl group adopts a synplanar conformation (Leiserowitz, 1976), as shown by the lengths of the C═O [1.227 (2) and 1.221 (2) Å] and C—O(H) [1.322 (2) and 1.317 (2) Å] bonds and the O═C—O bond angle [122.6 (2) and 122.8 (2)°]. The thiolic CH3 and the NH2 group are parallel in both molecular structures. However, while in (I) they point opposite to each other, in (II) they point in the same direction, as shown by the C21—S2—C2—N1 torsion angles of 177.1 (2) and 1.2 (2)° in (I) and (II), respectively. Except for the orientation of the thiolic CH3 group, the molecular structures of the 1,2,4-triazolo[1,5-a]pyrimidine molecules are almost equivalent within both crystal environments as far as angles and bond distances are concerned. In addition, the molecule exhibits a planar conformation in both cases [r.m.s. deviations 0.0315 and 0.0202 Å for (I) and (II), respectively, when all non-H atoms are used in the calculation]. It is known that the presence of substituents in a triazolopyrimidine ring does not lead to radical changes in bond distances (Lokaj et al., 2006). However, we can make some observations (see Table 5). When the pyridine is substituted in the meta position by electron-donating groups, the C6—C7 bond length is shorter than that of a typical C—C aromatic bond. This also happens if an electron donor or acceptor is in the ortho position. The introduction of a group in position 2 does not change the electronic distribution in the pyridine. In our case, we have two substituents in the ortho position, namely the amino group and the carboxylate. It follows that the bond distances C5—C6 and C6—C7 are close to each other, owing to the synergy of the two groups.
The molecular geometry of the 1,2,4-triazolo[1,5-a]pyrimidine molecule is very similar in both crystal structures, with the exception of the N1—C2—S2—C21 torsion angle. The different orientation of the S—CH3 group found in the crystal structures of (I) and (II) leads to a radically different crystal packing in these cases. This effect is due to distinct hydrogen-bonding networks (see Tables 2 and 4) formed upon the influence of the cocrystallized solvent molecules, which lead to strongly different supramolecular architectures. Thus, in (I), each amino group is involved in three N···O hydrogen bonds: one intramolecular bond with the carbonyl group [2.719 (3) Å] and two intermolecular bonds, one with a carboxyl group of a neighbouring molecule [2.900 (3) Å] and one with the DMF carbonyl group [2.870 (3) Å]. The DMF also forms hydrogen bonds with an adjacent carboxyl group [2.587 (2) Å]. These interactions lead to a two-dimensional hydrogen-bonding pattern, as displayed in Fig. 3. Short contacts in the structure are also generated by (C═O···C—H)solvent (2.790 Å), C—Hsolvent··· π (2.847 Å), S···π (3.448 Å) and π–π stacking (3.326 Å) interactions. In (II), atoms N3 and N4 are involved in hydrogen bonds with one water molecule [N···O = 2.937 (2) Å] and one neighbouring amino group [N···N = 2.902 (2) Å]. The water molecule further participates in a hydrogen bond with the carboxyl O atom to provide the three-dimensional structure (Fig. 4). The backbone hydrogen-bonding network is completed with an intramolecular N···O6B [2.712 (2) Å] interaction. Additional short lattice contacts are assisted by S···S [3.6125 (5) Å] and π–π stacking interactions, which form columns of parallel molecules stacked in a head-to-head arrangement along the crystallographic a axis (π–π = 3.381 Å between the mean-square planes of two neighbouring molecules). The π–π interactions involve the triazole ring of one molecule and the pyrimidine ring of a neighbouring molecule related by the (1 + x, y, z) symmetry element, with a separation distance of 3.5150 (9) Å between the corresponding ring centroids; the angle between the ring planes is as low as 0.88 (5)°.
The hydrogen-bond patterns observed in both crystal structures can be described using graph-set theory (Etter, 1990). In addition, based on topological analyses of the electron-density distribution experimentally characterized for 83 X—H···O (X = C, N, O) hydrogen-bonding interactions (Espinosa et al., 1998), graph and molecular binding energies involving H···O interactions can be estimated from the H···O distances. Indeed, supported by previous results on ice (Espinosa & Molins, 2000), the energy associated with each interaction can be estimated from the function Ei ≈ 25000exp(-3.6dH···O), where Ei and dH···O are in kJ mol-1 and Å, respectively. As the H-atom positions have been here derived from X-ray data, they are expected to be systematically too close from their bound atom, therefore leading to an overestimation of the H···O distance with a concomitant underestimation of the corresponding Ei value. Thus, to calculate Ei we have shifted the H-atom positions along their bond direction according to the mean X—H bond lengths observed from neutron diffraction analyses: (O═ Csp2—)O—H = 1.018, (Car—)N—H2 = 1.011, Car—H = 1.083, (Z—)Csp3—H3 = 1.077 (Allen & Bruno, 2010) and OW—H = 0.97 Å (Espinosa et al., 1996).
In (I), the two-dimensional arrangement of molecules, which is parallel to the (101) plane, involves graph sets R32(6) (after replacement of H atoms, the actual hydrogen-bond distances are N—H···O = 1.97 and 2.29, and O—H···O = 1.59 Å), R32(7) (N—H···O = 1.96 and 2.29, and C—H···O = 2.29 Å), R22(10) (N—H···O = 1.97 and C—H···N = 2.46 Å) and S(6) (N—H···O = 1.96 Å) (Fig. 3). The R32(6) motif shares one interaction with R32(7) and another with R22(10). Within a graph, the addition of the interaction energies corresponding to the hydrogen bonds building the motif leads to the total interaction energy of the pattern embedded in the crystal structure (Egraph = ΣjEij). For R32(6), R32(7) and S(6), the estimated Egraph values are 109.0, 34.7 and 21.6 kJ mol-1, respectively. The hydrogen-bond energy component of the total molecular binding energy of 7-amino-2-methylsulfanyl-1,2,4-triazolo[1,5-a]pyrimidine-6-carboxylic acid within the crystal structure of (I) is roughly 116 kJ mol-1, this result being obtained by adding the contributions of the four main intermolecular hydrogen-bond interactions (O—H···O = 1.59, N—H···O = 1.97 and 2.29 and C—H···O = 2.29 Å), while longer contacts involving C—H···O and C—H···N interactions (C—H···X > 2.45 Å) were not taken into account.
In the case of (II), S(6), R43(10) and R44(12) graphs are exhibited (Fig. 4). The last of these involves four hydrogen-bond interactions (two equivalent interactions corresponding to each hydrogen-bond distance O—H···O = 1.57 and 1.90 Å, after replacement of H atoms) and links asymmetric units that lie in parallel planes. Here, the estimated Egraph value is 141 kJ mol-1. The intramolecular hydrogen-bond interaction is shared by the S(6) and R43(10) graphs. The hydrogen-bond distance (N—H···O = 1.96 Å, after replacement of the H atom) is equivalent to that found in (I), therefore leading to the same estimated S(6) graph energy (21.6 kJ mol-1). The main hydrogen-bond interactions contributing to the molecular binding energy of 7-amino-2-methylsulfanyl-1,2,4-triazolo[1,5-a]pyrimidine-6-carboxylic acid within (II) belong to the R43(10) and R44(12) graphs and involve two O—H···O (O—H···O = 1.57 and 1.90 Å), one N—H···N (N—H···N = 1.94 Å) and one O—H···N (O—H···N = 1.98 Å) contacts, the first two leading to an energetic contribution of roughly 70 kJ mol-1.
Even though the method used here to derive Ei is expected to give approximate values only, it can be used to extract tendencies. For molecules involving X—H···O (X = C, N, O) hydrogen-bonding interactions, the dependence of Ei on H···O quickly enables the characterization of graph energies and the estimation of hydrogen-bond contributions to molecular binding energies from structural information only. In particular, the method could be applied to classify graphs, or higher hierarchical patterns formed by the addition of several graphs, exhibiting the same number of hydrogen-bonds.