Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025895/cv2248sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025895/cv2248Isup2.hkl |
CCDC reference: 654859
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.003 Å
- R factor = 0.032
- wR factor = 0.082
- Data-to-parameter ratio = 11.2
checkCIF/PLATON results
No syntax errors found
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 25.00 From the CIF: _reflns_number_total 1630 Count of symmetry unique reflns 1019 Completeness (_total/calc) 159.96% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 611 Fraction of Friedel pairs measured 0.600 Are heavy atom types Z>Si present yes PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 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 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For the crystal structure of the related compound 3-(4-chlorophenyl)-N-methylisoxazole-5-carbaldehyde, see: Zhang et al. (2006). For details of the pharmacological properties of isoxazolyl carboxamide derivatives, see: Lee et al. (2006); Xin et al. (2005).
A mixture of 3-(2-chlorophenyl)-isoxazole-5-carboxyl acid (8 mmol) and SOCl2 (10 ml) was heated under reflux for 7 h. The excess SOCl2 was removed on a water vacuum pump and the residue was distilled in vacuo to give carbonyl chlorides (over 85% yield). The product was dissolved in 20 ml of dry acetone, which was added to excessive 30% methylamine anhydrous solution below -5° C. After stirring vigorously at the same temperature for 1 h, the mixture was extracted with CH2Cl2 and the organic layer was washed with NaHCO3 solution, H3PO4 solution, and finally with water. The solution was dried and evaporated at 308 K (15 mm H g) to yield pale powder, which was recrystallized from ethyl acetate to obtain the product (74% yield).
Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a solution of (I) in a hexane–dichloromethane mixture (1:1 v/v) at room temperature over a period of one week.
All H atoms were geometrically positioned (N—H 0.86 Å, C—H 0.93–0.96 Å) and refined as riding with Uiso(H) = 1.2–1.5Ueq(parent atom).
The derivatives of isoxazolyl carboxamides have been reported to possess various chemical and biological activities (Lee et al., 2006; Xin et al., 2005). In connection with our study of the design and synthesis of new aryl-substituted isoxazole, we prepared 3-(2-chlorophenyl)-N-methylisoxazole-5-carboxamide, (I), by a convenient method from isoxazole-5-carboxyl acid. Here, we report the crystal structure of (I).
In (I) (Fig. 1), all bond lengths and angles are normal and in a good agreement with those reported recently for 3-(4-chlorophenyl)-N-methylisoxazole-5-carbaldehyde (Zhang et al., 2006). Atoms C11/C12/N2/O2 lies in the isoxazole ring (C7/C8/C9/N1/O1) plane, and the deviations from the least-squares plane through the ring atoms are all smaller than 0.024 (3) Å. The dihedral angle between the plane of the isoxazole and benzene (C1/C2/C3/C4/C5/C6) rings is 36.80 (2)°. The relatively short distances between the centroids of benzene (Cg1) and isoxazole (Cg2) rings from the neighbouring molecules - Cg1···Cg2i 3.675 (2) Å and Cg2···Cg1i 3.801 (3) Å indicates a presence of weak π-π interactions, which form stacks of the molecules extended along the c axis. Intermolecular N—H···O and C—H···O hydrogen bonds link the molecules into zigzag chains running in the direction [101].
For the crystal structure of the related compound 3-(4-chlorophenyl)-N-methylisoxazole-5-carbaldehyde, see: Zhang et al. (2006). For details of the pharmacological properties of isoxazolyl carboxamide derivatives, see: Lee et al. (2006); Xin et al. (2005).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.
C11H9ClN2O2 | F(000) = 1952 |
Mr = 236.65 | Dx = 1.480 Mg m−3 |
Orthorhombic, Fdd2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: F 2 -2d | Cell parameters from 622 reflections |
a = 18.722 (4) Å | θ = 2.7–20.3° |
b = 31.454 (6) Å | µ = 0.34 mm−1 |
c = 7.2137 (14) Å | T = 298 K |
V = 4248.1 (14) Å3 | Block, colourless |
Z = 16 | 0.51 × 0.40 × 0.39 mm |
Bruker SMART CCD area-detector diffractometer | 1630 independent reflections |
Radiation source: fine-focus sealed tube | 1563 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
φ and ω scans | θmax = 25.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −15→22 |
Tmin = 0.844, Tmax = 0.877 | k = −37→37 |
5233 measured reflections | l = −7→8 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.082 | w = 1/[σ2(Fo2) + (0.0452P)2 + 3.3758P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.002 |
1630 reflections | Δρmax = 0.23 e Å−3 |
146 parameters | Δρmin = −0.15 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with 737 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.05 (7) |
C11H9ClN2O2 | V = 4248.1 (14) Å3 |
Mr = 236.65 | Z = 16 |
Orthorhombic, Fdd2 | Mo Kα radiation |
a = 18.722 (4) Å | µ = 0.34 mm−1 |
b = 31.454 (6) Å | T = 298 K |
c = 7.2137 (14) Å | 0.51 × 0.40 × 0.39 mm |
Bruker SMART CCD area-detector diffractometer | 1630 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 1563 reflections with I > 2σ(I) |
Tmin = 0.844, Tmax = 0.877 | Rint = 0.024 |
5233 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.082 | Δρmax = 0.23 e Å−3 |
S = 1.05 | Δρmin = −0.15 e Å−3 |
1630 reflections | Absolute structure: Flack (1983), with 737 Friedel pairs |
146 parameters | Absolute structure parameter: 0.05 (7) |
1 restraint |
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 | ||
Cl1 | 0.40451 (3) | 0.01932 (2) | 0.63140 (14) | 0.0677 (3) | |
O1 | 0.15158 (7) | 0.05205 (5) | 0.7033 (3) | 0.0466 (4) | |
C4 | 0.28830 (11) | −0.02604 (7) | 0.7458 (3) | 0.0365 (5) | |
C10 | 0.18338 (12) | 0.12278 (7) | 0.7981 (3) | 0.0397 (5) | |
O2 | 0.12321 (9) | 0.13506 (6) | 0.7591 (3) | 0.0578 (5) | |
N2 | 0.23485 (9) | 0.14753 (6) | 0.8611 (3) | 0.0445 (5) | |
H2A | 0.2762 | 0.1366 | 0.8827 | 0.053* | |
N1 | 0.17918 (10) | 0.01105 (6) | 0.6847 (3) | 0.0452 (5) | |
C7 | 0.24522 (12) | 0.01304 (7) | 0.7449 (3) | 0.0349 (5) | |
C8 | 0.26279 (11) | 0.05475 (7) | 0.8031 (3) | 0.0367 (5) | |
H8A | 0.3061 | 0.0643 | 0.8506 | 0.044* | |
C9 | 0.20348 (11) | 0.07743 (7) | 0.7747 (3) | 0.0362 (5) | |
C5 | 0.36072 (12) | −0.02668 (8) | 0.7037 (4) | 0.0428 (6) | |
C6 | 0.39989 (14) | −0.06374 (9) | 0.7098 (4) | 0.0579 (8) | |
H6A | 0.4482 | −0.0633 | 0.6804 | 0.070* | |
C3 | 0.25671 (14) | −0.06454 (8) | 0.7907 (4) | 0.0462 (6) | |
H3A | 0.2081 | −0.0653 | 0.8169 | 0.055* | |
C2 | 0.29559 (15) | −0.10164 (9) | 0.7974 (4) | 0.0570 (7) | |
H2B | 0.2731 | −0.1271 | 0.8278 | 0.068* | |
C11 | 0.22384 (14) | 0.19281 (8) | 0.8955 (5) | 0.0608 (8) | |
H11A | 0.2622 | 0.2036 | 0.9702 | 0.091* | |
H11B | 0.1794 | 0.1969 | 0.9593 | 0.091* | |
H11C | 0.2227 | 0.2078 | 0.7795 | 0.091* | |
C1 | 0.36764 (16) | −0.10126 (9) | 0.7592 (5) | 0.0611 (8) | |
H1B | 0.3942 | −0.1262 | 0.7669 | 0.073* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0399 (3) | 0.0536 (4) | 0.1097 (6) | −0.0067 (3) | 0.0177 (4) | 0.0027 (4) |
O1 | 0.0300 (8) | 0.0444 (9) | 0.0654 (12) | −0.0012 (7) | −0.0097 (8) | 0.0011 (8) |
C4 | 0.0362 (11) | 0.0388 (12) | 0.0343 (13) | −0.0019 (9) | −0.0011 (9) | −0.0029 (10) |
C10 | 0.0305 (11) | 0.0451 (13) | 0.0433 (13) | 0.0060 (9) | −0.0012 (9) | 0.0059 (11) |
O2 | 0.0368 (9) | 0.0509 (10) | 0.0857 (14) | 0.0104 (8) | −0.0167 (9) | −0.0006 (10) |
N2 | 0.0298 (9) | 0.0379 (10) | 0.0659 (14) | 0.0076 (7) | −0.0068 (10) | −0.0005 (10) |
N1 | 0.0337 (10) | 0.0418 (11) | 0.0602 (14) | −0.0029 (8) | −0.0036 (9) | −0.0025 (10) |
C7 | 0.0311 (11) | 0.0394 (12) | 0.0343 (12) | −0.0035 (9) | −0.0017 (8) | 0.0009 (10) |
C8 | 0.0284 (11) | 0.0383 (12) | 0.0433 (13) | 0.0007 (9) | −0.0043 (9) | −0.0020 (10) |
C9 | 0.0288 (10) | 0.0409 (12) | 0.0389 (12) | −0.0025 (9) | −0.0008 (9) | 0.0036 (11) |
C5 | 0.0357 (11) | 0.0432 (13) | 0.0495 (15) | −0.0019 (10) | 0.0001 (10) | −0.0055 (11) |
C6 | 0.0440 (14) | 0.0522 (16) | 0.078 (2) | 0.0093 (11) | 0.0085 (13) | −0.0110 (15) |
C3 | 0.0475 (13) | 0.0405 (12) | 0.0507 (16) | −0.0059 (10) | 0.0026 (11) | −0.0019 (11) |
C2 | 0.0723 (18) | 0.0367 (13) | 0.0621 (18) | −0.0026 (12) | 0.0087 (15) | 0.0014 (12) |
C11 | 0.0513 (14) | 0.0430 (14) | 0.088 (2) | 0.0085 (11) | −0.0083 (15) | −0.0117 (16) |
C1 | 0.0654 (17) | 0.0452 (15) | 0.073 (2) | 0.0159 (13) | 0.0044 (15) | −0.0035 (15) |
Cl1—C5 | 1.743 (3) | C8—C9 | 1.336 (3) |
O1—C9 | 1.359 (3) | C8—H8A | 0.9300 |
O1—N1 | 1.396 (3) | C5—C6 | 1.378 (3) |
C4—C3 | 1.386 (3) | C6—C1 | 1.373 (4) |
C4—C5 | 1.390 (3) | C6—H6A | 0.9300 |
C4—C7 | 1.470 (3) | C3—C2 | 1.376 (4) |
C10—O2 | 1.224 (3) | C3—H3A | 0.9300 |
C10—N2 | 1.320 (3) | C2—C1 | 1.377 (4) |
C10—C9 | 1.485 (3) | C2—H2B | 0.9300 |
N2—C11 | 1.460 (3) | C11—H11A | 0.9600 |
N2—H2A | 0.8600 | C11—H11B | 0.9600 |
N1—C7 | 1.312 (3) | C11—H11C | 0.9600 |
C7—C8 | 1.416 (3) | C1—H1B | 0.9300 |
C9—O1—N1 | 108.32 (16) | C6—C5—Cl1 | 117.47 (19) |
C3—C4—C5 | 117.0 (2) | C4—C5—Cl1 | 120.82 (17) |
C3—C4—C7 | 119.8 (2) | C1—C6—C5 | 120.1 (2) |
C5—C4—C7 | 123.1 (2) | C1—C6—H6A | 120.0 |
O2—C10—N2 | 124.4 (2) | C5—C6—H6A | 120.0 |
O2—C10—C9 | 120.7 (2) | C2—C3—C4 | 121.6 (2) |
N2—C10—C9 | 114.88 (19) | C2—C3—H3A | 119.2 |
C10—N2—C11 | 122.0 (2) | C4—C3—H3A | 119.2 |
C10—N2—H2A | 119.0 | C3—C2—C1 | 120.3 (3) |
C11—N2—H2A | 119.0 | C3—C2—H2B | 119.9 |
C7—N1—O1 | 105.85 (18) | C1—C2—H2B | 119.9 |
N1—C7—C8 | 111.17 (19) | N2—C11—H11A | 109.5 |
N1—C7—C4 | 118.6 (2) | N2—C11—H11B | 109.5 |
C8—C7—C4 | 130.2 (2) | H11A—C11—H11B | 109.5 |
C9—C8—C7 | 104.85 (19) | N2—C11—H11C | 109.5 |
C9—C8—H8A | 127.6 | H11A—C11—H11C | 109.5 |
C7—C8—H8A | 127.6 | H11B—C11—H11C | 109.5 |
C8—C9—O1 | 109.8 (2) | C6—C1—C2 | 119.4 (2) |
C8—C9—C10 | 134.9 (2) | C6—C1—H1B | 120.3 |
O1—C9—C10 | 115.23 (18) | C2—C1—H1B | 120.3 |
C6—C5—C4 | 121.7 (2) | ||
O2—C10—N2—C11 | 1.6 (5) | O2—C10—C9—C8 | 179.7 (3) |
C9—C10—N2—C11 | −178.9 (2) | N2—C10—C9—C8 | 0.2 (4) |
C9—O1—N1—C7 | 0.2 (2) | O2—C10—C9—O1 | 1.9 (3) |
O1—N1—C7—C8 | −0.3 (3) | N2—C10—C9—O1 | −177.7 (2) |
O1—N1—C7—C4 | 178.9 (2) | C3—C4—C5—C6 | −1.3 (4) |
C3—C4—C7—N1 | −37.5 (3) | C7—C4—C5—C6 | 178.6 (2) |
C5—C4—C7—N1 | 142.7 (2) | C3—C4—C5—Cl1 | 175.96 (18) |
C3—C4—C7—C8 | 141.5 (2) | C7—C4—C5—Cl1 | −4.2 (3) |
C5—C4—C7—C8 | −38.4 (4) | C4—C5—C6—C1 | −0.3 (4) |
N1—C7—C8—C9 | 0.2 (3) | Cl1—C5—C6—C1 | −177.7 (2) |
C4—C7—C8—C9 | −178.8 (2) | C5—C4—C3—C2 | 1.4 (4) |
C7—C8—C9—O1 | 0.0 (3) | C7—C4—C3—C2 | −178.4 (2) |
C7—C8—C9—C10 | −178.0 (3) | C4—C3—C2—C1 | 0.0 (4) |
N1—O1—C9—C8 | −0.1 (3) | C5—C6—C1—C2 | 1.8 (5) |
N1—O1—C9—C10 | 178.25 (19) | C3—C2—C1—C6 | −1.7 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O2i | 0.86 | 2.14 | 2.983 (3) | 165 |
C8—H8A···O2i | 0.93 | 2.33 | 3.173 (3) | 151 |
Symmetry code: (i) x+1/4, −y+1/4, z+1/4. |
Experimental details
Crystal data | |
Chemical formula | C11H9ClN2O2 |
Mr | 236.65 |
Crystal system, space group | Orthorhombic, Fdd2 |
Temperature (K) | 298 |
a, b, c (Å) | 18.722 (4), 31.454 (6), 7.2137 (14) |
V (Å3) | 4248.1 (14) |
Z | 16 |
Radiation type | Mo Kα |
µ (mm−1) | 0.34 |
Crystal size (mm) | 0.51 × 0.40 × 0.39 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.844, 0.877 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5233, 1630, 1563 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.082, 1.05 |
No. of reflections | 1630 |
No. of parameters | 146 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.15 |
Absolute structure | Flack (1983), with 737 Friedel pairs |
Absolute structure parameter | 0.05 (7) |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Sheldrick, 2001), SHELXTL and local programs.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O2i | 0.86 | 2.14 | 2.983 (3) | 164.9 |
C8—H8A···O2i | 0.93 | 2.33 | 3.173 (3) | 150.6 |
Symmetry code: (i) x+1/4, −y+1/4, z+1/4. |
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The derivatives of isoxazolyl carboxamides have been reported to possess various chemical and biological activities (Lee et al., 2006; Xin et al., 2005). In connection with our study of the design and synthesis of new aryl-substituted isoxazole, we prepared 3-(2-chlorophenyl)-N-methylisoxazole-5-carboxamide, (I), by a convenient method from isoxazole-5-carboxyl acid. Here, we report the crystal structure of (I).
In (I) (Fig. 1), all bond lengths and angles are normal and in a good agreement with those reported recently for 3-(4-chlorophenyl)-N-methylisoxazole-5-carbaldehyde (Zhang et al., 2006). Atoms C11/C12/N2/O2 lies in the isoxazole ring (C7/C8/C9/N1/O1) plane, and the deviations from the least-squares plane through the ring atoms are all smaller than 0.024 (3) Å. The dihedral angle between the plane of the isoxazole and benzene (C1/C2/C3/C4/C5/C6) rings is 36.80 (2)°. The relatively short distances between the centroids of benzene (Cg1) and isoxazole (Cg2) rings from the neighbouring molecules - Cg1···Cg2i 3.675 (2) Å and Cg2···Cg1i 3.801 (3) Å indicates a presence of weak π-π interactions, which form stacks of the molecules extended along the c axis. Intermolecular N—H···O and C—H···O hydrogen bonds link the molecules into zigzag chains running in the direction [101].