Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044960/sg2191sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044960/sg2191Isup2.hkl |
CCDC reference: 663811
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.002 Å
- R factor = 0.045
- wR factor = 0.120
- Data-to-parameter ratio = 17.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 500 Deg.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
A mixture of 3,4-Dimethoxybenzyl hydrazide (1 mmol) and 2,4-pentanedione (1 mmol) was refluxed in dry ethanol for 5 h. On completion of the reaction, followed by TLC examination using hexane ethyl acetate (8:2) the solvent was evaporated and reaction mixture diluted with ethyl acetate and subjected directly to thick layer chromatography on silica gel. Recrystallization from ethyl acetate yielded colourless crystals, m.p.105–107°C. IR (KBr) cm-1: 3103, 2958, 2930, 1680, 1601, 1584, 1472, 1373, 1275, 1170, 1022; 1H NMR (CDCl3) δ 7.2 (d, 8.4, 1H), 6.89 (dd, 1H), 6.7 (dd, 8.2, 3.4, 1H). 6.02 (s, 1H), 2.83 (s, 3H), 2.26 (s, 3H); EIMS m/e 260 [M+], 165 (base).
Hydrogen atoms were located in difference syntheses, refined at idealized positions riding on the C (C–H = 0.95–0.99 Å) atoms with isotropic displacement parameters Uiso(H) = 1.2U(Ceq) and 1.5(methyl-C). Methyl H atoms were refined on the basis of rigid groups allowed to rotate but not tip.
Pyrazoles represent an important class of five-membered nitrogen heterocycles exhibiting a wide range of biological activities (Mann et al., 1992, Perevalov et al., 2001). Several 1-substitued 3,5-dimethylpyrazole possess potent in vivo hypoglycemic activity (Soliman & Darwishl, 1983). The pyrazole ring is a major pharmacophoric substructure in a number of NSAIDs like phenylbutazone (Udupi et al., 1998), oxyphenbutazone, celecoxib (Smith et al., 1965) exhibiting anti-inflammatory, anti-pyretic and analgesic properties. Pyrazole derivatives being more active than the isoniazid against Mycobacterium tuberculosis have recently been reported (Ali et al., 2007). Several thiourea and urea derivatives of 4-aminopyrazoles exhibit strong anticonvulsant and antituberculosis activity. In continuation of our interest in the synthesis of bioactive heterocycles (Saeed et al., 2007) the synthesis of title compound was carried out by direct cyclocondensation of 3,4-dimethoxybenzyl hydrazide with 2,4-pentanedione.
For related literature, see: Ali et al. (2007); Mann et al. (1992); Perevalov et al. (2001); Saeed et al. (2007); Smith et al. (1965); Soliman & Darwishl (1983); Udupi et al. (1998).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Bruker, 2002); program(s) used to refine structure: SHELXTL (Bruker, 2002); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXTL (Bruker, 2002).
C14H16N2O3 | Z = 2 |
Mr = 260.29 | F(000) = 276 |
Triclinic, P1 | Dx = 1.353 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.703 (2) Å | Cell parameters from 719 reflections |
b = 8.409 (2) Å | θ = 2.8–28.3° |
c = 11.454 (3) Å | µ = 0.10 mm−1 |
α = 69.970 (5)° | T = 120 K |
β = 85.267 (5)° | Prism, colourless |
γ = 66.655 (5)° | 0.44 × 0.36 × 0.25 mm |
V = 638.8 (3) Å3 |
Bruker SMART APEX diffractometer | 3011 independent reflections |
Radiation source: sealed tube | 2301 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
φ and ω scans | θmax = 27.9°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −8→10 |
Tmin = 0.959, Tmax = 0.976 | k = −10→11 |
5678 measured reflections | l = −15→15 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.120 | w = 1/[σ2(Fo2) + (0.0704P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max < 0.001 |
3011 reflections | Δρmax = 0.28 e Å−3 |
177 parameters | Δρmin = −0.28 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.013 (2) |
C14H16N2O3 | γ = 66.655 (5)° |
Mr = 260.29 | V = 638.8 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.703 (2) Å | Mo Kα radiation |
b = 8.409 (2) Å | µ = 0.10 mm−1 |
c = 11.454 (3) Å | T = 120 K |
α = 69.970 (5)° | 0.44 × 0.36 × 0.25 mm |
β = 85.267 (5)° |
Bruker SMART APEX diffractometer | 3011 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 2301 reflections with I > 2σ(I) |
Tmin = 0.959, Tmax = 0.976 | Rint = 0.053 |
5678 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.28 e Å−3 |
3011 reflections | Δρmin = −0.28 e Å−3 |
177 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.35654 (16) | 0.20752 (14) | 0.29144 (9) | 0.0318 (3) | |
O2 | 0.20118 (14) | 0.44061 (12) | 0.66198 (8) | 0.0244 (2) | |
O3 | 0.23018 (14) | 0.75359 (13) | 0.58447 (9) | 0.0256 (2) | |
N1 | 0.26483 (17) | 0.46669 (15) | 0.12170 (10) | 0.0232 (3) | |
N2 | 0.13919 (17) | 0.64924 (15) | 0.07561 (10) | 0.0253 (3) | |
C1 | 0.3239 (2) | 0.3922 (2) | 0.02736 (12) | 0.0256 (3) | |
C2 | 0.4637 (2) | 0.2008 (2) | 0.04724 (15) | 0.0346 (4) | |
H2A | 0.4951 | 0.1837 | −0.0335 | 0.052* | |
H2B | 0.4090 | 0.1134 | 0.0969 | 0.052* | |
H2C | 0.5788 | 0.1794 | 0.0914 | 0.052* | |
C3 | 0.2365 (2) | 0.5296 (2) | −0.07940 (13) | 0.0298 (3) | |
H3A | 0.2491 | 0.5231 | −0.1610 | 0.036* | |
C4 | 0.1224 (2) | 0.6848 (2) | −0.04548 (12) | 0.0266 (3) | |
C5 | −0.0039 (2) | 0.8694 (2) | −0.12837 (14) | 0.0369 (4) | |
H5A | −0.0778 | 0.9436 | −0.0778 | 0.055* | |
H5B | −0.0900 | 0.8560 | −0.1793 | 0.055* | |
H5C | 0.0727 | 0.9305 | −0.1828 | 0.055* | |
C6 | 0.30491 (19) | 0.37422 (19) | 0.25100 (12) | 0.0235 (3) | |
C7 | 0.28444 (19) | 0.48519 (18) | 0.33182 (12) | 0.0212 (3) | |
C8 | 0.30714 (19) | 0.65048 (18) | 0.29209 (12) | 0.0231 (3) | |
H8A | 0.3328 | 0.7009 | 0.2080 | 0.028* | |
C9 | 0.29251 (19) | 0.74323 (18) | 0.37492 (12) | 0.0224 (3) | |
H9A | 0.3094 | 0.8560 | 0.3473 | 0.027* | |
C10 | 0.25345 (18) | 0.67149 (18) | 0.49716 (12) | 0.0203 (3) | |
C11 | 0.23435 (18) | 0.50109 (18) | 0.53931 (11) | 0.0196 (3) | |
C12 | 0.25064 (18) | 0.40966 (18) | 0.45652 (12) | 0.0202 (3) | |
H12A | 0.2388 | 0.2944 | 0.4845 | 0.024* | |
C13 | 0.2007 (2) | 0.26019 (18) | 0.71111 (12) | 0.0257 (3) | |
H13A | 0.1006 | 0.2550 | 0.6668 | 0.039* | |
H13B | 0.1775 | 0.2312 | 0.7999 | 0.039* | |
H13C | 0.3238 | 0.1704 | 0.7004 | 0.039* | |
C14 | 0.2499 (2) | 0.92627 (19) | 0.54465 (14) | 0.0310 (3) | |
H14A | 0.3768 | 0.9098 | 0.5150 | 0.046* | |
H14B | 0.2318 | 0.9719 | 0.6147 | 0.046* | |
H14C | 0.1546 | 1.0153 | 0.4770 | 0.046* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0463 (7) | 0.0205 (5) | 0.0244 (5) | −0.0079 (5) | 0.0000 (5) | −0.0083 (4) |
O2 | 0.0340 (6) | 0.0219 (5) | 0.0192 (4) | −0.0116 (4) | 0.0047 (4) | −0.0092 (4) |
O3 | 0.0336 (6) | 0.0208 (5) | 0.0259 (5) | −0.0104 (4) | 0.0020 (4) | −0.0124 (4) |
N1 | 0.0281 (6) | 0.0206 (6) | 0.0195 (5) | −0.0067 (5) | 0.0024 (5) | −0.0089 (5) |
N2 | 0.0275 (6) | 0.0210 (6) | 0.0224 (6) | −0.0051 (5) | −0.0014 (5) | −0.0059 (5) |
C1 | 0.0318 (8) | 0.0292 (8) | 0.0238 (7) | −0.0159 (6) | 0.0067 (6) | −0.0147 (6) |
C2 | 0.0410 (9) | 0.0303 (8) | 0.0354 (8) | −0.0124 (7) | 0.0123 (7) | −0.0188 (7) |
C3 | 0.0404 (9) | 0.0343 (8) | 0.0219 (7) | −0.0199 (7) | 0.0044 (6) | −0.0127 (6) |
C4 | 0.0308 (8) | 0.0277 (8) | 0.0228 (7) | −0.0143 (6) | −0.0008 (6) | −0.0065 (6) |
C5 | 0.0416 (9) | 0.0335 (9) | 0.0284 (8) | −0.0130 (7) | −0.0082 (7) | −0.0018 (7) |
C6 | 0.0251 (7) | 0.0228 (7) | 0.0209 (6) | −0.0069 (6) | 0.0019 (5) | −0.0084 (6) |
C7 | 0.0205 (6) | 0.0205 (7) | 0.0203 (6) | −0.0041 (5) | −0.0013 (5) | −0.0082 (5) |
C8 | 0.0229 (7) | 0.0244 (7) | 0.0182 (6) | −0.0074 (6) | 0.0005 (5) | −0.0049 (5) |
C9 | 0.0222 (7) | 0.0181 (6) | 0.0248 (7) | −0.0073 (5) | −0.0012 (5) | −0.0050 (5) |
C10 | 0.0183 (6) | 0.0187 (6) | 0.0230 (6) | −0.0039 (5) | −0.0031 (5) | −0.0091 (5) |
C11 | 0.0177 (6) | 0.0191 (6) | 0.0183 (6) | −0.0036 (5) | −0.0006 (5) | −0.0056 (5) |
C12 | 0.0203 (6) | 0.0166 (6) | 0.0219 (6) | −0.0047 (5) | −0.0006 (5) | −0.0068 (5) |
C13 | 0.0337 (8) | 0.0201 (7) | 0.0211 (6) | −0.0099 (6) | 0.0047 (6) | −0.0059 (5) |
C14 | 0.0365 (8) | 0.0219 (7) | 0.0386 (8) | −0.0114 (6) | 0.0007 (7) | −0.0148 (6) |
O1—C6 | 1.2171 (17) | C5—H5B | 0.9800 |
O2—C11 | 1.3610 (15) | C5—H5C | 0.9800 |
O2—C13 | 1.4274 (16) | C6—C7 | 1.4844 (18) |
O3—C10 | 1.3616 (15) | C7—C8 | 1.3841 (19) |
O3—C14 | 1.4314 (16) | C7—C12 | 1.3998 (18) |
N1—N2 | 1.3869 (16) | C8—C9 | 1.3931 (18) |
N1—C1 | 1.3870 (16) | C8—H8A | 0.9500 |
N1—C6 | 1.4106 (17) | C9—C10 | 1.3823 (18) |
N2—C4 | 1.3209 (17) | C9—H9A | 0.9500 |
C1—C3 | 1.355 (2) | C10—C11 | 1.4105 (18) |
C1—C2 | 1.489 (2) | C11—C12 | 1.3818 (17) |
C2—H2A | 0.9800 | C12—H12A | 0.9500 |
C2—H2B | 0.9800 | C13—H13A | 0.9800 |
C2—H2C | 0.9800 | C13—H13B | 0.9800 |
C3—C4 | 1.418 (2) | C13—H13C | 0.9800 |
C3—H3A | 0.9500 | C14—H14A | 0.9800 |
C4—C5 | 1.484 (2) | C14—H14B | 0.9800 |
C5—H5A | 0.9800 | C14—H14C | 0.9800 |
C11—O2—C13 | 116.84 (9) | C8—C7—C12 | 119.57 (12) |
C10—O3—C14 | 116.39 (10) | C8—C7—C6 | 123.72 (12) |
N2—N1—C1 | 111.43 (11) | C12—C7—C6 | 116.61 (12) |
N2—N1—C6 | 120.77 (10) | C7—C8—C9 | 120.30 (12) |
C1—N1—C6 | 127.52 (12) | C7—C8—H8A | 119.9 |
C4—N2—N1 | 104.43 (11) | C9—C8—H8A | 119.9 |
C3—C1—N1 | 105.93 (13) | C10—C9—C8 | 120.15 (12) |
C3—C1—C2 | 130.03 (13) | C10—C9—H9A | 119.9 |
N1—C1—C2 | 123.97 (13) | C8—C9—H9A | 119.9 |
C1—C2—H2A | 109.5 | O3—C10—C9 | 124.91 (12) |
C1—C2—H2B | 109.5 | O3—C10—C11 | 115.09 (11) |
H2A—C2—H2B | 109.5 | C9—C10—C11 | 120.00 (11) |
C1—C2—H2C | 109.5 | O2—C11—C12 | 125.47 (12) |
H2A—C2—H2C | 109.5 | O2—C11—C10 | 115.23 (11) |
H2B—C2—H2C | 109.5 | C12—C11—C10 | 119.30 (11) |
C1—C3—C4 | 106.59 (12) | C11—C12—C7 | 120.64 (12) |
C1—C3—H3A | 126.7 | C11—C12—H12A | 119.7 |
C4—C3—H3A | 126.7 | C7—C12—H12A | 119.7 |
N2—C4—C3 | 111.61 (13) | O2—C13—H13A | 109.5 |
N2—C4—C5 | 120.63 (13) | O2—C13—H13B | 109.5 |
C3—C4—C5 | 127.76 (13) | H13A—C13—H13B | 109.5 |
C4—C5—H5A | 109.5 | O2—C13—H13C | 109.5 |
C4—C5—H5B | 109.5 | H13A—C13—H13C | 109.5 |
H5A—C5—H5B | 109.5 | H13B—C13—H13C | 109.5 |
C4—C5—H5C | 109.5 | O3—C14—H14A | 109.5 |
H5A—C5—H5C | 109.5 | O3—C14—H14B | 109.5 |
H5B—C5—H5C | 109.5 | H14A—C14—H14B | 109.5 |
O1—C6—N1 | 118.94 (12) | O3—C14—H14C | 109.5 |
O1—C6—C7 | 122.82 (12) | H14A—C14—H14C | 109.5 |
N1—C6—C7 | 118.23 (12) | H14B—C14—H14C | 109.5 |
C1—N1—N2—C4 | 0.04 (15) | N1—C6—C7—C12 | 155.47 (12) |
C6—N1—N2—C4 | −174.31 (12) | C12—C7—C8—C9 | −1.3 (2) |
N2—N1—C1—C3 | 0.66 (15) | C6—C7—C8—C9 | −177.61 (12) |
C6—N1—C1—C3 | 174.54 (12) | C7—C8—C9—C10 | −0.6 (2) |
N2—N1—C1—C2 | 177.94 (12) | C14—O3—C10—C9 | −0.54 (19) |
C6—N1—C1—C2 | −8.2 (2) | C14—O3—C10—C11 | 179.64 (11) |
N1—C1—C3—C4 | −1.04 (16) | C8—C9—C10—O3 | −177.77 (12) |
C2—C1—C3—C4 | −178.10 (14) | C8—C9—C10—C11 | 2.0 (2) |
N1—N2—C4—C3 | −0.72 (15) | C13—O2—C11—C12 | 6.10 (19) |
N1—N2—C4—C5 | 179.43 (12) | C13—O2—C11—C10 | −173.65 (11) |
C1—C3—C4—N2 | 1.15 (17) | O3—C10—C11—O2 | −1.92 (17) |
C1—C3—C4—C5 | −179.01 (14) | C9—C10—C11—O2 | 178.25 (12) |
N2—N1—C6—O1 | 154.03 (13) | O3—C10—C11—C12 | 178.31 (11) |
C1—N1—C6—O1 | −19.3 (2) | C9—C10—C11—C12 | −1.52 (19) |
N2—N1—C6—C7 | −26.76 (18) | O2—C11—C12—C7 | 179.82 (12) |
C1—N1—C6—C7 | 159.88 (13) | C10—C11—C12—C7 | −0.4 (2) |
O1—C6—C7—C8 | 151.01 (14) | C8—C7—C12—C11 | 1.9 (2) |
N1—C6—C7—C8 | −28.17 (19) | C6—C7—C12—C11 | 178.39 (12) |
O1—C6—C7—C12 | −25.4 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8A···N2 | 0.95 | 2.46 | 2.8948 (18) | 108 |
C3—H3A···O2i | 0.95 | 2.45 | 3.3496 (18) | 157 |
Symmetry code: (i) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C14H16N2O3 |
Mr | 260.29 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 120 |
a, b, c (Å) | 7.703 (2), 8.409 (2), 11.454 (3) |
α, β, γ (°) | 69.970 (5), 85.267 (5), 66.655 (5) |
V (Å3) | 638.8 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.44 × 0.36 × 0.25 |
Data collection | |
Diffractometer | Bruker SMART APEX |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.959, 0.976 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5678, 3011, 2301 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.120, 0.97 |
No. of reflections | 3011 |
No. of parameters | 177 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.28 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXTL (Bruker, 2002).
O1—C6 | 1.2171 (17) | N1—N2 | 1.3869 (16) |
O2—C11 | 1.3610 (15) | N1—C1 | 1.3870 (16) |
O2—C13 | 1.4274 (16) | N1—C6 | 1.4106 (17) |
O3—C10 | 1.3616 (15) | N2—C4 | 1.3209 (17) |
O3—C14 | 1.4314 (16) | ||
C11—O2—C13 | 116.84 (9) | C4—N2—N1 | 104.43 (11) |
C10—O3—C14 | 116.39 (10) | O1—C6—N1 | 118.94 (12) |
N2—N1—C1 | 111.43 (11) | O1—C6—C7 | 122.82 (12) |
N2—N1—C6 | 120.77 (10) | N1—C6—C7 | 118.23 (12) |
C1—N1—C6 | 127.52 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8A···N2 | 0.95 | 2.46 | 2.8948 (18) | 107.8 |
C3—H3A···O2i | 0.95 | 2.45 | 3.3496 (18) | 157.4 |
Symmetry code: (i) x, y, z−1. |
Pyrazoles represent an important class of five-membered nitrogen heterocycles exhibiting a wide range of biological activities (Mann et al., 1992, Perevalov et al., 2001). Several 1-substitued 3,5-dimethylpyrazole possess potent in vivo hypoglycemic activity (Soliman & Darwishl, 1983). The pyrazole ring is a major pharmacophoric substructure in a number of NSAIDs like phenylbutazone (Udupi et al., 1998), oxyphenbutazone, celecoxib (Smith et al., 1965) exhibiting anti-inflammatory, anti-pyretic and analgesic properties. Pyrazole derivatives being more active than the isoniazid against Mycobacterium tuberculosis have recently been reported (Ali et al., 2007). Several thiourea and urea derivatives of 4-aminopyrazoles exhibit strong anticonvulsant and antituberculosis activity. In continuation of our interest in the synthesis of bioactive heterocycles (Saeed et al., 2007) the synthesis of title compound was carried out by direct cyclocondensation of 3,4-dimethoxybenzyl hydrazide with 2,4-pentanedione.