





Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809052969/sj2706sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536809052969/sj2706Isup2.hkl |
CCDC reference: 755458
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean
(C-C) = 0.006 Å
- R factor = 0.095
- wR factor = 0.302
- Data-to-parameter ratio = 12.2
checkCIF/PLATON results
No syntax errors found
Alert level C RFACR01_ALERT_3_C The value of the weighted R factor is > 0.25 Weighted R factor given 0.302 PLAT084_ALERT_2_C High R2 Value .................................. 0.30 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.16 PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang .. 6 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.595 30 PLAT480_ALERT_4_C Long H...A H-Bond Reported H1B .. N1 .. 2.67 Ang. PLAT481_ALERT_4_C Long D...A H-Bond Reported C1 .. CG1 .. 4.14 Ang. PLAT731_ALERT_1_C Bond Calc 0.90(3), Rep 0.902(10) ...... 3.00 su-Ra N2 -H2 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.90(3), Rep 0.902(10) ...... 3.00 su-Ra N2 -H2 1.555 1.555 PLAT736_ALERT_1_C H...A Calc 1.98(3), Rep 1.975(13) ...... 2.31 su-Ra H2 -O2 1.555 2.566
Alert level G PLAT072_ALERT_2_G SHELXL First Parameter in WGHT Unusually Large.. 0.20 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 10 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Benzaldehyde (4.6 g,0.02 mol) and 5-methylisoxazole-4-carbonyl hydrazine (2.8 g, 0.02 mol) was mixed with glacial acetic acid (50 ml). The mixture was heated at 65° C for 3 h, the precipitate collected by filtration and washed with water, chloroform and ethanol. The product was recrystallized from ethanol, then dried under reduced pressure to give the title compound in 85% yield. Colourless, block-shaped crystals were obtained by slow evaporation of a dimethylformamide solution.
The H atom bound to N2 was located in a difference Fourier map and refined freely with the N–H distance restrained to 0.90 Å. All other H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93–0.96 Å, and with Uiso = 1.2 Uiso(C) or 1.5 Uiso(C) for methyl groups.
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C12H11N3O2 | Z = 2 |
Mr = 229.24 | F(000) = 240 |
Triclinic, P1 | Dx = 1.359 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.6562 (6) Å | Cell parameters from 1711 reflections |
b = 7.4874 (9) Å | θ = 2.7–23.4° |
c = 11.3051 (11) Å | µ = 0.10 mm−1 |
α = 87.319 (8)° | T = 293 K |
β = 84.640 (7)° | Block, colourless |
γ = 87.878 (8)° | 0.22 × 0.19 × 0.08 mm |
V = 560.04 (10) Å3 |
Bruker APEXII area-detector diffractometer | 1936 independent reflections |
Radiation source: fine-focus sealed tube | 1219 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −7→7 |
Tmin = 0.979, Tmax = 0.992 | k = −8→8 |
6763 measured reflections | l = −13→13 |
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)] = 0.095 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.302 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | w = 1/[σ2(Fo2) + (0.2P)2] where P = (Fo2 + 2Fc2)/3 |
1936 reflections | (Δ/σ)max = 0.004 |
159 parameters | Δρmax = 0.53 e Å−3 |
1 restraint | Δρmin = −0.34 e Å−3 |
C12H11N3O2 | γ = 87.878 (8)° |
Mr = 229.24 | V = 560.04 (10) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.6562 (6) Å | Mo Kα radiation |
b = 7.4874 (9) Å | µ = 0.10 mm−1 |
c = 11.3051 (11) Å | T = 293 K |
α = 87.319 (8)° | 0.22 × 0.19 × 0.08 mm |
β = 84.640 (7)° |
Bruker APEXII area-detector diffractometer | 1936 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 1219 reflections with I > 2σ(I) |
Tmin = 0.979, Tmax = 0.992 | Rint = 0.040 |
6763 measured reflections |
R[F2 > 2σ(F2)] = 0.095 | 1 restraint |
wR(F2) = 0.302 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.53 e Å−3 |
1936 reflections | Δρmin = −0.34 e Å−3 |
159 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 | ||
C1 | 0.1634 (6) | 0.4088 (7) | 0.0931 (4) | 0.0719 (13) | |
H1A | 0.1434 | 0.5364 | 0.0932 | 0.108* | |
H1B | 0.0435 | 0.3528 | 0.1282 | 0.108* | |
H1C | 0.1922 | 0.3726 | 0.0128 | 0.108* | |
C2 | 0.3348 (5) | 0.3544 (5) | 0.1625 (3) | 0.0564 (11) | |
C3 | 0.5697 (5) | 0.2840 (6) | 0.2794 (3) | 0.0617 (11) | |
H3 | 0.6344 | 0.2629 | 0.3484 | 0.074* | |
C4 | 0.3642 (5) | 0.3410 (5) | 0.2793 (3) | 0.0504 (10) | |
C5 | 0.2072 (5) | 0.3862 (5) | 0.3748 (3) | 0.0522 (10) | |
C6 | 0.4198 (6) | 0.2675 (5) | 0.6388 (3) | 0.0569 (10) | |
H6 | 0.3092 | 0.3072 | 0.6882 | 0.068* | |
C7 | 0.5963 (6) | 0.1885 (5) | 0.6923 (3) | 0.0535 (10) | |
C8 | 0.7688 (6) | 0.1292 (6) | 0.6238 (4) | 0.0636 (11) | |
H8 | 0.7727 | 0.1374 | 0.5413 | 0.076* | |
C9 | 0.9325 (6) | 0.0591 (6) | 0.6767 (4) | 0.0726 (13) | |
H9 | 1.0466 | 0.0202 | 0.6299 | 0.087* | |
C10 | 0.9299 (7) | 0.0456 (6) | 0.7985 (4) | 0.0741 (13) | |
H10 | 1.0417 | −0.0017 | 0.8342 | 0.089* | |
C11 | 0.7604 (7) | 0.1027 (6) | 0.8669 (4) | 0.0785 (14) | |
H11 | 0.7569 | 0.0934 | 0.9493 | 0.094* | |
C12 | 0.5962 (7) | 0.1736 (6) | 0.8140 (4) | 0.0684 (12) | |
H12 | 0.4826 | 0.2122 | 0.8613 | 0.082* | |
H2 | 0.150 (5) | 0.408 (5) | 0.545 (3) | 0.075 (12)* | |
N1 | 0.6576 (5) | 0.2644 (5) | 0.1742 (3) | 0.0742 (12) | |
N2 | 0.2397 (4) | 0.3615 (4) | 0.4894 (3) | 0.0578 (9) | |
N3 | 0.4137 (5) | 0.2831 (4) | 0.5270 (3) | 0.0546 (9) | |
O1 | 0.5060 (4) | 0.3099 (4) | 0.0977 (2) | 0.0689 (10) | |
O2 | 0.0417 (4) | 0.4503 (4) | 0.3494 (2) | 0.0672 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.052 (2) | 0.111 (3) | 0.051 (2) | 0.007 (2) | −0.0067 (19) | 0.012 (2) |
C2 | 0.039 (2) | 0.072 (2) | 0.054 (2) | 0.0057 (17) | 0.0052 (16) | 0.0055 (18) |
C3 | 0.041 (2) | 0.095 (3) | 0.046 (2) | 0.0154 (19) | 0.0029 (16) | −0.0016 (19) |
C4 | 0.0349 (19) | 0.065 (2) | 0.049 (2) | 0.0093 (15) | 0.0018 (15) | 0.0009 (16) |
C5 | 0.037 (2) | 0.068 (2) | 0.051 (2) | 0.0094 (16) | 0.0003 (15) | −0.0050 (17) |
C6 | 0.045 (2) | 0.072 (2) | 0.051 (2) | 0.0075 (17) | 0.0048 (17) | −0.0029 (17) |
C7 | 0.050 (2) | 0.062 (2) | 0.047 (2) | 0.0037 (17) | 0.0017 (16) | −0.0022 (16) |
C8 | 0.054 (2) | 0.084 (3) | 0.051 (2) | 0.010 (2) | 0.0017 (18) | −0.0024 (19) |
C9 | 0.053 (2) | 0.086 (3) | 0.077 (3) | 0.017 (2) | −0.002 (2) | −0.003 (2) |
C10 | 0.066 (3) | 0.080 (3) | 0.078 (3) | 0.015 (2) | −0.021 (2) | 0.004 (2) |
C11 | 0.078 (3) | 0.099 (3) | 0.057 (3) | 0.020 (3) | −0.011 (2) | 0.002 (2) |
C12 | 0.065 (3) | 0.087 (3) | 0.052 (2) | 0.016 (2) | 0.0003 (19) | −0.004 (2) |
N1 | 0.0411 (19) | 0.121 (3) | 0.057 (2) | 0.0189 (18) | 0.0007 (15) | 0.0025 (19) |
N2 | 0.0372 (17) | 0.087 (2) | 0.0468 (19) | 0.0153 (15) | 0.0002 (13) | −0.0059 (16) |
N3 | 0.0408 (17) | 0.073 (2) | 0.0486 (19) | 0.0090 (14) | −0.0024 (13) | −0.0020 (14) |
O1 | 0.0457 (16) | 0.113 (2) | 0.0448 (16) | 0.0136 (14) | 0.0042 (12) | 0.0022 (14) |
O2 | 0.0419 (16) | 0.104 (2) | 0.0547 (17) | 0.0250 (14) | −0.0063 (12) | −0.0128 (14) |
C1—C2 | 1.478 (5) | C7—C12 | 1.375 (5) |
C1—H1A | 0.9600 | C7—C8 | 1.394 (5) |
C1—H1B | 0.9600 | C8—C9 | 1.368 (5) |
C1—H1C | 0.9600 | C8—H8 | 0.9300 |
C2—O1 | 1.337 (4) | C9—C10 | 1.374 (6) |
C2—C4 | 1.352 (5) | C9—H9 | 0.9300 |
C3—N1 | 1.288 (5) | C10—C11 | 1.373 (6) |
C3—C4 | 1.417 (5) | C10—H10 | 0.9300 |
C3—H3 | 0.9300 | C11—C12 | 1.373 (6) |
C4—C5 | 1.473 (5) | C11—H11 | 0.9300 |
C5—O2 | 1.239 (4) | C12—H12 | 0.9300 |
C5—N2 | 1.336 (5) | N1—O1 | 1.412 (4) |
C6—N3 | 1.269 (5) | N2—N3 | 1.373 (4) |
C6—C7 | 1.464 (5) | N2—H2 | 0.902 (10) |
C6—H6 | 0.9300 | ||
C2—C1—H1A | 109.5 | C8—C7—C6 | 122.2 (3) |
C2—C1—H1B | 109.5 | C9—C8—C7 | 120.7 (4) |
H1A—C1—H1B | 109.5 | C9—C8—H8 | 119.7 |
C2—C1—H1C | 109.5 | C7—C8—H8 | 119.7 |
H1A—C1—H1C | 109.5 | C8—C9—C10 | 120.6 (4) |
H1B—C1—H1C | 109.5 | C8—C9—H9 | 119.7 |
O1—C2—C4 | 109.7 (3) | C10—C9—H9 | 119.7 |
O1—C2—C1 | 115.1 (3) | C11—C10—C9 | 119.2 (4) |
C4—C2—C1 | 135.3 (4) | C11—C10—H10 | 120.4 |
N1—C3—C4 | 113.2 (3) | C9—C10—H10 | 120.4 |
N1—C3—H3 | 123.4 | C12—C11—C10 | 120.3 (4) |
C4—C3—H3 | 123.4 | C12—C11—H11 | 119.9 |
C2—C4—C3 | 103.5 (3) | C10—C11—H11 | 119.9 |
C2—C4—C5 | 123.5 (3) | C11—C12—C7 | 121.3 (4) |
C3—C4—C5 | 133.0 (3) | C11—C12—H12 | 119.4 |
O2—C5—N2 | 118.7 (3) | C7—C12—H12 | 119.4 |
O2—C5—C4 | 119.9 (3) | C3—N1—O1 | 104.4 (3) |
N2—C5—C4 | 121.4 (3) | C5—N2—N3 | 123.3 (3) |
N3—C6—C7 | 121.8 (3) | C5—N2—H2 | 119 (3) |
N3—C6—H6 | 119.1 | N3—N2—H2 | 118 (3) |
C7—C6—H6 | 119.1 | C6—N3—N2 | 115.5 (3) |
C12—C7—C8 | 117.9 (4) | C2—O1—N1 | 109.3 (3) |
C12—C7—C6 | 119.8 (4) | ||
O1—C2—C4—C3 | 0.0 (4) | C7—C8—C9—C10 | 0.0 (7) |
C1—C2—C4—C3 | −178.5 (5) | C8—C9—C10—C11 | 0.3 (7) |
O1—C2—C4—C5 | 178.0 (3) | C9—C10—C11—C12 | −0.4 (8) |
C1—C2—C4—C5 | −0.5 (8) | C10—C11—C12—C7 | 0.3 (8) |
N1—C3—C4—C2 | 0.0 (5) | C8—C7—C12—C11 | 0.1 (7) |
N1—C3—C4—C5 | −177.7 (4) | C6—C7—C12—C11 | −179.0 (4) |
C2—C4—C5—O2 | −4.5 (6) | C4—C3—N1—O1 | 0.0 (5) |
C3—C4—C5—O2 | 172.8 (4) | O2—C5—N2—N3 | 176.6 (3) |
C2—C4—C5—N2 | 176.3 (4) | C4—C5—N2—N3 | −4.2 (6) |
C3—C4—C5—N2 | −6.4 (7) | C7—C6—N3—N2 | −179.3 (3) |
N3—C6—C7—C12 | −179.8 (4) | C5—N2—N3—C6 | −179.1 (4) |
N3—C6—C7—C8 | 1.2 (6) | C4—C2—O1—N1 | 0.0 (5) |
C12—C7—C8—C9 | −0.2 (7) | C1—C2—O1—N1 | 178.8 (3) |
C6—C7—C8—C9 | 178.8 (4) | C3—N1—O1—C2 | 0.0 (5) |
Cg1 is the centroid of the C7–C12 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···N3 | 0.93 | 2.39 | 2.893 (5) | 114 |
N2—H2···O2i | 0.90 (1) | 1.98 (1) | 2.867 (4) | 170 (4) |
C1—H1B···N1ii | 0.96 | 2.67 | 3.598 (6) | 162 |
C1—H1A···Cg1iii | 0.96 | 3.35 | 4.136 (7) | 140 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x−1, y, z; (iii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C12H11N3O2 |
Mr | 229.24 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.6562 (6), 7.4874 (9), 11.3051 (11) |
α, β, γ (°) | 87.319 (8), 84.640 (7), 87.878 (8) |
V (Å3) | 560.04 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.22 × 0.19 × 0.08 |
Data collection | |
Diffractometer | Bruker APEXII area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.979, 0.992 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6763, 1936, 1219 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.095, 0.302, 1.10 |
No. of reflections | 1936 |
No. of parameters | 159 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.53, −0.34 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Cg1 is the centroid of the C7–C12 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···N3 | 0.93 | 2.39 | 2.893 (5) | 113.7 |
N2—H2···O2i | 0.902 (10) | 1.975 (13) | 2.867 (4) | 170 (4) |
C1—H1B···N1ii | 0.96 | 2.67 | 3.598 (6) | 161.8 |
C1—H1A···Cg1iii | 0.96 | 3.352 | 4.136 (7) | 140.2 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x−1, y, z; (iii) −x+1, −y+1, −z+1. |
A large number of hydrazone derivatives have been reported recently (Fun et al. 2008; Wei et al. 2009; Khaledi et al. 2008) and their biological activity (Molina et al. 1994; Khattab 2005) and coordination ability (Reiter et al.1985) have also been noted. Isoxazole compounds have also attracted much interest as they exhibit some fungicidal, plant-growth regulating and antibacterial activity (Stevens et al.1984). In order to study the properties of a new compound containing both the hydrazine and isoxazole groups, we synthesized the title compound and report its crystal structure here, Fig 1.
The title compound C12H11N3O2, is approximately planar (rms deviation 0.0814 from the plane through all non-hydrogen atoms)with a dihedral angle of 6.88 (16)°. between the C7···C12 benzene and C2···C4,N1,O1 isoxazole rings. The molecule displays an E configuration with respect to the C6═N3 double bond, with a C7—C6—N3—N2 torsion angle of -179.3 (3)°. The dihedral angle formed by the benzene and isoxazole rings is 2.457 (114)°. An intramolecular C—H···N hydrogen bond generates an S6 ring motif (Bernstein et al. 1997) and locks the molecule into a planar configuration. Bond lengths (Allen et al.,1987) and angles are unexceptional and similar to those found in related stuctures (Fun et al., 2008; Wei et al., 2009; Khaledi et al., 2008).
In the crystal structure (Fig. 2), intermolecular N2—H2···O2 hydrogen bonds form centrosymmetric dimers. These are further linked by weak C1—H1B···N1 interactions augmented by very weak, inversion related C1—H1A···Cg1 contacts to form layers parallel to [120] (Cg1 is the centroid of the C7···C12 phenyl ring).