


Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810008160/sj2738sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536810008160/sj2738Isup2.hkl |
CCDC reference: 774231
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean
(C-C) = 0.004 Å
- R factor = 0.070
- wR factor = 0.203
- Data-to-parameter ratio = 16.2
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.48 Ratio PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 43 PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 2
Alert level G PLAT154_ALERT_1_G The su's on the Cell Angles are Equal (x 10000) 500 Deg. PLAT380_ALERT_4_G Check Incorrectly? Oriented X(sp2)-Methyl Moiety C12 PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels .......... 1 PLAT931_ALERT_5_G Check Twin Law ( 0 0 1)[ ] Estimated BASF 0.17
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 1 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 2 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
A mixture of 5-amino-3,4-dimethylisoxazole (0.50g, 0.0044 mol) and salicyladehyde (0.54g, 0.0044 mol) in methanol (15 mL) was refluxed for 5 h with stirring to give a light yellow precipitate. It was then filtered and washed with methanol to gives the pure Schiff base. Yield: 68%; mp. 116°C. IR (KBr) vmax cm-1: 2922(C—H), 1594 (C═O), 1562 (C═C), 1152 (C—N). 1H NMR (CDCl3) d: 8.89 (s, 1H, CH olefinic), 7.42 (d, H3, J=1.8Hz), 7.44 (dd, H4, J=7.8Hz), 7.02 (dd, H5, J=7.8Hz), 6.97 (d, H6, J=1.2 Hz), 2.25 (s, CH3), 2.05 (s, CH3).
Atom H1O2 was located from the difference Fourier map and refined freely. The remaining hydrogen atoms were positioned geometrically [C–H = 0.93 Å or 0.96 Å] and were refined using a riding model, with Uiso(H) = 1.2 or 1.5 Ueq(C). A rotating group model was applied to the methyl groups. The crystal is a non-merohedral twin with BASF = 0.166 (4).
Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
![]() | Fig. 1. The asymmetric unit of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme. |
![]() | Fig. 2. The crystal packing of the title compound (I). |
C12H12N2O2 | Z = 2 |
Mr = 216.24 | F(000) = 228 |
Triclinic, P1 | Dx = 1.307 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.3475 (14) Å | Cell parameters from 2862 reflections |
b = 8.615 (2) Å | θ = 2.4–29.7° |
c = 12.321 (3) Å | µ = 0.09 mm−1 |
α = 103.696 (5)° | T = 100 K |
β = 91.486 (5)° | Plate, yellow |
γ = 94.059 (5)° | 0.56 × 0.14 × 0.08 mm |
V = 549.6 (2) Å3 |
Bruker APEX DUO CCD area-detector diffractometer | 2467 independent reflections |
Radiation source: fine-focus sealed tube | 1946 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.000 |
ϕ and ω scans | θmax = 27.5°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −6→6 |
Tmin = 0.951, Tmax = 0.993 | k = −11→10 |
2467 measured reflections | l = −6→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)] = 0.070 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.203 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0657P)2 + 1.1217P] where P = (Fo2 + 2Fc2)/3 |
2467 reflections | (Δ/σ)max = 0.001 |
152 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
C12H12N2O2 | γ = 94.059 (5)° |
Mr = 216.24 | V = 549.6 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.3475 (14) Å | Mo Kα radiation |
b = 8.615 (2) Å | µ = 0.09 mm−1 |
c = 12.321 (3) Å | T = 100 K |
α = 103.696 (5)° | 0.56 × 0.14 × 0.08 mm |
β = 91.486 (5)° |
Bruker APEX DUO CCD area-detector diffractometer | 2467 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 1946 reflections with I > 2σ(I) |
Tmin = 0.951, Tmax = 0.993 | Rint = 0.000 |
2467 measured reflections |
R[F2 > 2σ(F2)] = 0.070 | 0 restraints |
wR(F2) = 0.203 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.40 e Å−3 |
2467 reflections | Δρmin = −0.34 e Å−3 |
152 parameters |
Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K. |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 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 | ||
O1 | 1.0387 (4) | 1.1305 (2) | 0.41739 (17) | 0.0228 (5) | |
O2 | 0.6135 (4) | 0.7350 (3) | 0.08828 (18) | 0.0262 (5) | |
N1 | 0.8330 (5) | 0.9521 (3) | 0.2591 (2) | 0.0194 (5) | |
N2 | 1.2481 (5) | 1.2478 (3) | 0.4414 (2) | 0.0252 (6) | |
C1 | 0.2930 (5) | 0.7387 (3) | 0.3499 (3) | 0.0201 (6) | |
H1A | 0.3082 | 0.7892 | 0.4256 | 0.024* | |
C2 | 0.0960 (5) | 0.6240 (3) | 0.3108 (3) | 0.0221 (6) | |
H2A | −0.0224 | 0.5990 | 0.3593 | 0.026* | |
C3 | 0.0782 (6) | 0.5468 (4) | 0.1976 (3) | 0.0249 (7) | |
H3A | −0.0529 | 0.4691 | 0.1710 | 0.030* | |
C4 | 0.2512 (6) | 0.5831 (4) | 0.1235 (3) | 0.0250 (7) | |
H4A | 0.2362 | 0.5296 | 0.0484 | 0.030* | |
C5 | 0.4491 (5) | 0.7008 (3) | 0.1626 (2) | 0.0199 (6) | |
C6 | 0.4711 (5) | 0.7802 (3) | 0.2771 (2) | 0.0186 (6) | |
C7 | 0.6723 (5) | 0.9024 (3) | 0.3225 (2) | 0.0191 (6) | |
H7A | 0.6859 | 0.9462 | 0.3992 | 0.023* | |
C8 | 1.0225 (5) | 1.0682 (3) | 0.3052 (2) | 0.0176 (6) | |
C9 | 1.2091 (5) | 1.1366 (3) | 0.2539 (2) | 0.0192 (6) | |
C10 | 1.3428 (5) | 1.2479 (3) | 0.3446 (2) | 0.0195 (6) | |
C11 | 1.2629 (6) | 1.1010 (4) | 0.1327 (3) | 0.0276 (7) | |
H11A | 1.1457 | 1.0163 | 0.0921 | 0.041* | |
H11C | 1.4305 | 1.0685 | 0.1229 | 0.041* | |
H11D | 1.2470 | 1.1953 | 0.1051 | 0.041* | |
C12 | 1.5687 (5) | 1.3582 (4) | 0.3386 (3) | 0.0243 (7) | |
H12A | 1.6191 | 1.4202 | 0.4124 | 0.036* | |
H12D | 1.5285 | 1.4287 | 0.2920 | 0.036* | |
H12B | 1.7034 | 1.2963 | 0.3075 | 0.036* | |
H1O2 | 0.722 (11) | 0.820 (7) | 0.132 (5) | 0.080 (18)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0194 (11) | 0.0238 (11) | 0.0233 (11) | −0.0060 (8) | 0.0019 (8) | 0.0042 (8) |
O2 | 0.0250 (12) | 0.0281 (11) | 0.0232 (11) | −0.0040 (9) | 0.0061 (9) | 0.0028 (9) |
N1 | 0.0170 (12) | 0.0148 (11) | 0.0261 (13) | 0.0009 (9) | 0.0020 (9) | 0.0041 (9) |
N2 | 0.0207 (13) | 0.0246 (13) | 0.0290 (14) | −0.0061 (10) | −0.0003 (10) | 0.0062 (10) |
C1 | 0.0155 (14) | 0.0176 (13) | 0.0270 (15) | 0.0054 (10) | 0.0036 (11) | 0.0036 (11) |
C2 | 0.0152 (14) | 0.0204 (14) | 0.0318 (16) | 0.0021 (11) | 0.0054 (11) | 0.0078 (12) |
C3 | 0.0159 (14) | 0.0225 (14) | 0.0353 (17) | −0.0013 (11) | −0.0012 (12) | 0.0063 (12) |
C4 | 0.0247 (16) | 0.0227 (15) | 0.0246 (15) | −0.0006 (12) | −0.0007 (12) | 0.0004 (12) |
C5 | 0.0164 (14) | 0.0194 (14) | 0.0242 (14) | 0.0026 (11) | 0.0021 (11) | 0.0052 (11) |
C6 | 0.0154 (13) | 0.0155 (13) | 0.0256 (14) | 0.0033 (10) | 0.0019 (11) | 0.0054 (11) |
C7 | 0.0199 (14) | 0.0158 (13) | 0.0216 (14) | 0.0058 (11) | 0.0019 (11) | 0.0034 (10) |
C8 | 0.0140 (13) | 0.0163 (13) | 0.0237 (14) | 0.0051 (10) | 0.0029 (10) | 0.0056 (10) |
C9 | 0.0159 (13) | 0.0169 (13) | 0.0262 (15) | 0.0037 (10) | 0.0033 (11) | 0.0074 (11) |
C10 | 0.0136 (13) | 0.0169 (13) | 0.0296 (15) | 0.0038 (10) | 0.0020 (11) | 0.0079 (11) |
C11 | 0.0272 (16) | 0.0291 (16) | 0.0260 (16) | 0.0009 (13) | 0.0080 (12) | 0.0055 (12) |
C12 | 0.0137 (13) | 0.0215 (14) | 0.0392 (17) | 0.0005 (11) | 0.0038 (12) | 0.0100 (12) |
O1—C8 | 1.357 (3) | C4—H4A | 0.9300 |
O1—N2 | 1.429 (3) | C5—C6 | 1.412 (4) |
O2—C5 | 1.353 (4) | C6—C7 | 1.452 (4) |
O2—H1O2 | 0.95 (6) | C7—H7A | 0.9300 |
N1—C7 | 1.293 (4) | C8—C9 | 1.367 (4) |
N1—C8 | 1.381 (4) | C9—C10 | 1.426 (4) |
N2—C10 | 1.308 (4) | C9—C11 | 1.491 (4) |
C1—C2 | 1.385 (4) | C10—C12 | 1.498 (4) |
C1—C6 | 1.410 (4) | C11—H11A | 0.9600 |
C1—H1A | 0.9300 | C11—H11C | 0.9600 |
C2—C3 | 1.394 (4) | C11—H11D | 0.9600 |
C2—H2A | 0.9300 | C12—H12A | 0.9600 |
C3—C4 | 1.387 (4) | C12—H12D | 0.9600 |
C3—H3A | 0.9300 | C12—H12B | 0.9600 |
C4—C5 | 1.404 (4) | ||
C8—O1—N2 | 107.7 (2) | N1—C7—H7A | 119.1 |
C5—O2—H1O2 | 103 (3) | C6—C7—H7A | 119.1 |
C7—N1—C8 | 120.3 (2) | O1—C8—C9 | 110.8 (2) |
C10—N2—O1 | 105.3 (2) | O1—C8—N1 | 119.7 (2) |
C2—C1—C6 | 121.2 (3) | C9—C8—N1 | 129.5 (3) |
C2—C1—H1A | 119.4 | C8—C9—C10 | 103.2 (3) |
C6—C1—H1A | 119.4 | C8—C9—C11 | 128.4 (3) |
C1—C2—C3 | 118.9 (3) | C10—C9—C11 | 128.4 (3) |
C1—C2—H2A | 120.6 | N2—C10—C9 | 112.9 (3) |
C3—C2—H2A | 120.6 | N2—C10—C12 | 119.8 (3) |
C4—C3—C2 | 121.6 (3) | C9—C10—C12 | 127.3 (3) |
C4—C3—H3A | 119.2 | C9—C11—H11A | 109.5 |
C2—C3—H3A | 119.2 | C9—C11—H11C | 109.5 |
C3—C4—C5 | 119.7 (3) | H11A—C11—H11C | 109.5 |
C3—C4—H4A | 120.2 | C9—C11—H11D | 109.5 |
C5—C4—H4A | 120.2 | H11A—C11—H11D | 109.5 |
O2—C5—C4 | 118.4 (3) | H11C—C11—H11D | 109.5 |
O2—C5—C6 | 121.9 (3) | C10—C12—H12A | 109.5 |
C4—C5—C6 | 119.6 (3) | C10—C12—H12D | 109.5 |
C1—C6—C5 | 119.0 (3) | H12A—C12—H12D | 109.5 |
C1—C6—C7 | 118.8 (3) | C10—C12—H12B | 109.5 |
C5—C6—C7 | 122.2 (3) | H12A—C12—H12B | 109.5 |
N1—C7—C6 | 121.8 (3) | H12D—C12—H12B | 109.5 |
C8—O1—N2—C10 | −0.3 (3) | N2—O1—C8—C9 | 0.3 (3) |
C6—C1—C2—C3 | 1.3 (4) | N2—O1—C8—N1 | −179.4 (2) |
C1—C2—C3—C4 | −0.6 (5) | C7—N1—C8—O1 | −0.3 (4) |
C2—C3—C4—C5 | −0.3 (5) | C7—N1—C8—C9 | −179.9 (3) |
C3—C4—C5—O2 | −179.3 (3) | O1—C8—C9—C10 | −0.2 (3) |
C3—C4—C5—C6 | 0.5 (4) | N1—C8—C9—C10 | 179.4 (3) |
C2—C1—C6—C5 | −1.1 (4) | O1—C8—C9—C11 | 178.7 (3) |
C2—C1—C6—C7 | 179.4 (3) | N1—C8—C9—C11 | −1.7 (5) |
O2—C5—C6—C1 | 180.0 (3) | O1—N2—C10—C9 | 0.1 (3) |
C4—C5—C6—C1 | 0.2 (4) | O1—N2—C10—C12 | −179.8 (2) |
O2—C5—C6—C7 | −0.5 (4) | C8—C9—C10—N2 | 0.0 (3) |
C4—C5—C6—C7 | 179.7 (3) | C11—C9—C10—N2 | −178.9 (3) |
C8—N1—C7—C6 | −179.7 (2) | C8—C9—C10—C12 | 180.0 (3) |
C1—C6—C7—N1 | −176.1 (3) | C11—C9—C10—C12 | 1.1 (5) |
C5—C6—C7—N1 | 4.4 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1O2···N1 | 1.00 (9) | 1.71 (8) | 2.648 (5) | 154 (8) |
Experimental details
Crystal data | |
Chemical formula | C12H12N2O2 |
Mr | 216.24 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 5.3475 (14), 8.615 (2), 12.321 (3) |
α, β, γ (°) | 103.696 (5), 91.486 (5), 94.059 (5) |
V (Å3) | 549.6 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.56 × 0.14 × 0.08 |
Data collection | |
Diffractometer | Bruker APEX DUO CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.951, 0.993 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2467, 2467, 1946 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.070, 0.203, 1.06 |
No. of reflections | 2467 |
No. of parameters | 152 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40, −0.34 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1O2···N1 | 1.00 (9) | 1.71 (8) | 2.648 (5) | 154 (8) |
Heterocyclic compounds, especially isoxazoles, are one of the key building elements of natural products. Among the numerous heterocyclic systems of biological and pharmacological interest, the oxazole ring is endowed with various activities, including hypoglycemic (Spinelli, 1999), analgesic (Conti et al., 1998), anti-inflammatory (Mishra et al., 1998), anti-bacterial (Ko et al., 1998) and anti-tumor (Kang et al., 2000) properties. In view of the importance of the title compound as a pharmaceutical intermediate, the paper reports its synthesis and crystal structure.
In the title compound (Fig. 1), the isoxazole ring is essentially planar with a maximum deviation of 0.002 (2) Å for atom C8. The dihedral angle between the isoxazole ring (N2/O1/C8–C10) and the phenyl ring (C1–C6) is 4.30 (15)°. The methyl groups at C9 and C10 deviate from the isoxazole mean plane by 0.056 (3) Å and 0.013 (4) Å , respectively. The C5—O2 and C7═N1 bond lengths are 1.353 (4) Å and 1.293 (4) Å, respectively, and agree with the corresponding values in 4-{[(1E)-(3,5-dibromo-2-hydroxyphenyl) methylene]-amino}-1,5-dimethyl-2-phenyl-1,2-dihydro- 3H-pyrazol-3-one [1.344 (3) and 1.292 (4) Å; Huang & Chen, 2005].
In the crystal structure (Fig. 2), the imino N atoms are linked to the phenol O atoms and act as hydrogen-bond acceptors in intramolecular O2—H1O2···N1 interactions (Table 1) (Jeffrey & Saenger, 1991; Jeffrey, 1997; Scheiner, 1997), which generate S(6) ring motifs (Bernstein et al., 1995).