organic compounds
4-Formyl-3-p-tolylsydnone
aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore 574 199, India
*Correspondence e-mail: hkfun@usm.my
In the title compound, C10H8N2O3, the oxadiazole ring is essentially planar, with a maximum deviation of 0.006 (1) Å for the two-connected N atom. The mean planes through the aldehyde unit and the methyl-substituted phenyl ring make interplanar angles of 13.60 (9) and 59.69 (4)°, respectively, with the oxadiazole ring. In the adjacent molecules are interconnected into a two-dimensional array parallel to (100) by intermolecular C—H⋯O hydrogen bonds.
Related literature
For general background to and applications of sydnone compounds, see: Hedge et al. (2008); Rai et al. (2008). For related sydnone structures, see: Baker & Ollis (1957); Grossie et al. (2009). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986). For bond-length data, see: Allen et al. (1987).
Experimental
Crystal data
|
Refinement
|
Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009).
Supporting information
https://doi.org/10.1107/S1600536810016417/fj2294sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810016417/fj2294Isup2.hkl
N-Methylformanilide (0.01 mol) and phosphoryl chloride (0.01 mol) were mixed and added into 3-(p-tolyl)sydnone (0.01 mol) portion-wise. The reaction mixture was then stirred for about 1 h under cold condition. After standing overnight, it was poured into ice cold water with stirring. The solid obtained was filtered, dried and recrystallized from ethanol. Single crystals suitable for X-ray analysis were obtained from a 1:2 mixture of DMF and ethanol by slow evaporation.
All hydrogen atoms were placed in their calculated positions, with C—H = 0.93 or 0.96 Å, and refined using a riding model with Uiso = 1.2 or 1.5 Ueq(C). A rotating group model was used for the C10 methyl group.
Sydnones constitute a well-defined class of
consisting of 1,2,3-oxadiazole ring system. The introduction of the concept of mesoionic structure for certain in the year 1949 has proved to be fruitful development in heterocyclic chemistry. The study of still remains a field of interest because of their electronic structure and also because of the various types of biological activities displayed by some of them. Interest in sydnone derivatives has also been encouraged by the discovery that they exhibit various pharmacological activities (Hedge et al., 2008; Rai et al., 2008).These 4-formyl sydnone will be used for the preparation of a new series of α,β-unsaturated (namely chalcones) by condensation with appropriate or These α,β-unsaturated will be utilized for the synthesis of a variety of novel like pyrazolines, pyrazole etc carrying sydnone moiety.
Sydnones are
containing a five-membered heterocyclic ring. Generally, substitution at the N3 position by an aromatic substituent is necessary for stability. In the title sydnone compound (Fig. 1), the aromatic substituent is p-toluene. The 1,2,3-oxadiazole ring (N1/N2/O1/C7/C8) in the sydnone unit is essentially planar, with maximum deviation of -0.006 (1) Å at atom N2. The mean planes through the aldehyde moiety (C9/H9A/O3) and methyl-substituted phenyl ring (C1-C6) are inclined at dihedral angles of 13.60 (9) and 59.69 (4)°, respectively, with the 1,2,3-oxadiazole ring. As reported previously (Grossie et al., 2009), the exocyclic C7–O2 bond length of 1.2089 (9) Å is inconsistent to the formulation of Baker & Ollis (1957), which reported the delocalization of a positive charge in the ring, and a negative charge in the exocyclic oxygen. The bond lengths (Allen et al., 1987) and angles are within normal range and comparable to a related sydnone structure (Grossie et al., 2009). In the (Fig. 2), intermolecular C1—H1A···O2 and C5—H5A···O3 hydrogen bonds (Table 1) link adjacent molecules into two-dimensional arrays parallel to the (100) plane.For general background to and applications of sydnone compounds, see: Hedge et al. (2008); Rai et al. (2008). For related sydnone structures, see: Baker & Ollis (1957); Grossie et al. (2009). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986). For bond-length data, see: Allen et al. (1987).
Data collection: APEX2 (Bruker, 2009); cell
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).C10H8N2O3 | F(000) = 424 |
Mr = 204.18 | Dx = 1.448 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6788 reflections |
a = 10.5663 (4) Å | θ = 2.8–38.9° |
b = 10.4088 (3) Å | µ = 0.11 mm−1 |
c = 8.9630 (3) Å | T = 100 K |
β = 108.222 (1)° | Block, brown |
V = 936.34 (5) Å3 | 0.71 × 0.30 × 0.19 mm |
Z = 4 |
Bruker APEXII DUO CCD area-detector diffractometer | 4906 independent reflections |
Radiation source: fine-focus sealed tube | 4091 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
φ and ω scans | θmax = 37.5°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −18→18 |
Tmin = 0.926, Tmax = 0.980 | k = −17→17 |
14437 measured reflections | l = −15→14 |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0747P)2 + 0.1421P] where P = (Fo2 + 2Fc2)/3 |
4906 reflections | (Δ/σ)max = 0.001 |
137 parameters | Δρmax = 0.65 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C10H8N2O3 | V = 936.34 (5) Å3 |
Mr = 204.18 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.5663 (4) Å | µ = 0.11 mm−1 |
b = 10.4088 (3) Å | T = 100 K |
c = 8.9630 (3) Å | 0.71 × 0.30 × 0.19 mm |
β = 108.222 (1)° |
Bruker APEXII DUO CCD area-detector diffractometer | 4906 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 4091 reflections with I > 2σ(I) |
Tmin = 0.926, Tmax = 0.980 | Rint = 0.022 |
14437 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.65 e Å−3 |
4906 reflections | Δρmin = −0.31 e Å−3 |
137 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 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 > 2sigma(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 | 0.34006 (6) | 0.22147 (5) | 0.96639 (6) | 0.01912 (11) | |
O2 | 0.26550 (6) | 0.39559 (5) | 1.06918 (7) | 0.02245 (12) | |
O3 | 0.53489 (6) | 0.55203 (5) | 1.23353 (7) | 0.02190 (12) | |
N1 | 0.54958 (6) | 0.24689 (5) | 1.05402 (6) | 0.01524 (10) | |
N2 | 0.45929 (7) | 0.17063 (6) | 0.96707 (7) | 0.01825 (11) | |
C1 | 0.76823 (8) | 0.30000 (7) | 1.03217 (9) | 0.02080 (13) | |
H1A | 0.7346 | 0.3773 | 0.9839 | 0.025* | |
C2 | 0.90126 (8) | 0.26687 (7) | 1.05976 (10) | 0.02297 (14) | |
H2A | 0.9571 | 0.3228 | 1.0289 | 0.028* | |
C3 | 0.95243 (8) | 0.15115 (7) | 1.13297 (9) | 0.02082 (13) | |
C4 | 0.86671 (8) | 0.06713 (7) | 1.17625 (9) | 0.02117 (13) | |
H4A | 0.8996 | −0.0106 | 1.2238 | 0.025* | |
C5 | 0.73342 (8) | 0.09745 (6) | 1.14961 (8) | 0.01803 (12) | |
H5A | 0.6768 | 0.0411 | 1.1783 | 0.022* | |
C6 | 0.68736 (7) | 0.21424 (6) | 1.07890 (7) | 0.01561 (11) | |
C7 | 0.35989 (7) | 0.33640 (6) | 1.05605 (8) | 0.01719 (12) | |
C8 | 0.50088 (7) | 0.34990 (6) | 1.11215 (8) | 0.01566 (11) | |
C9 | 0.58136 (8) | 0.44999 (6) | 1.20780 (8) | 0.01744 (12) | |
H9A | 0.6724 | 0.4362 | 1.2517 | 0.021* | |
C10 | 1.09685 (9) | 0.11710 (10) | 1.16471 (12) | 0.03014 (17) | |
H10D | 1.1460 | 0.1928 | 1.1562 | 0.045* | |
H10A | 1.1048 | 0.0545 | 1.0895 | 0.045* | |
H10B | 1.1319 | 0.0823 | 1.2687 | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0194 (2) | 0.0159 (2) | 0.0216 (2) | 0.00027 (17) | 0.00558 (19) | −0.00320 (16) |
O2 | 0.0212 (3) | 0.0188 (2) | 0.0285 (3) | 0.00347 (18) | 0.0094 (2) | −0.00196 (18) |
O3 | 0.0306 (3) | 0.0144 (2) | 0.0250 (2) | −0.00230 (19) | 0.0148 (2) | −0.00363 (17) |
N1 | 0.0194 (3) | 0.01228 (19) | 0.0155 (2) | −0.00027 (17) | 0.00755 (19) | −0.00047 (15) |
N2 | 0.0206 (3) | 0.0153 (2) | 0.0194 (2) | −0.00021 (19) | 0.0070 (2) | −0.00313 (17) |
C1 | 0.0255 (3) | 0.0152 (2) | 0.0263 (3) | −0.0009 (2) | 0.0148 (3) | 0.0028 (2) |
C2 | 0.0243 (3) | 0.0202 (3) | 0.0294 (3) | −0.0039 (2) | 0.0157 (3) | −0.0007 (2) |
C3 | 0.0195 (3) | 0.0230 (3) | 0.0216 (3) | −0.0007 (2) | 0.0089 (2) | −0.0034 (2) |
C4 | 0.0220 (3) | 0.0192 (3) | 0.0237 (3) | 0.0025 (2) | 0.0091 (3) | 0.0025 (2) |
C5 | 0.0207 (3) | 0.0143 (2) | 0.0211 (3) | 0.0000 (2) | 0.0095 (2) | 0.00184 (19) |
C6 | 0.0186 (3) | 0.0133 (2) | 0.0172 (2) | −0.00044 (19) | 0.0088 (2) | −0.00029 (17) |
C7 | 0.0210 (3) | 0.0134 (2) | 0.0179 (2) | 0.0007 (2) | 0.0072 (2) | −0.00046 (18) |
C8 | 0.0195 (3) | 0.0127 (2) | 0.0166 (2) | 0.0000 (2) | 0.0083 (2) | −0.00152 (17) |
C9 | 0.0220 (3) | 0.0149 (2) | 0.0178 (2) | −0.0033 (2) | 0.0097 (2) | −0.00218 (19) |
C10 | 0.0195 (3) | 0.0387 (4) | 0.0328 (4) | 0.0012 (3) | 0.0091 (3) | −0.0044 (3) |
O1—N2 | 1.3647 (8) | C3—C4 | 1.3983 (11) |
O1—C7 | 1.4197 (8) | C3—C10 | 1.5046 (12) |
O2—C7 | 1.2089 (9) | C4—C5 | 1.3893 (11) |
O3—C9 | 1.2220 (9) | C4—H4A | 0.9300 |
N1—N2 | 1.2971 (8) | C5—C6 | 1.3870 (9) |
N1—C8 | 1.3615 (8) | C5—H5A | 0.9300 |
N1—C6 | 1.4428 (9) | C7—C8 | 1.4225 (10) |
C1—C6 | 1.3878 (9) | C8—C9 | 1.4448 (9) |
C1—C2 | 1.3924 (11) | C9—H9A | 0.9300 |
C1—H1A | 0.9300 | C10—H10D | 0.9600 |
C2—C3 | 1.3971 (11) | C10—H10A | 0.9600 |
C2—H2A | 0.9300 | C10—H10B | 0.9600 |
N2—O1—C7 | 110.58 (5) | C4—C5—H5A | 121.0 |
N2—N1—C8 | 114.64 (6) | C5—C6—C1 | 122.72 (7) |
N2—N1—C6 | 117.76 (5) | C5—C6—N1 | 118.03 (6) |
C8—N1—C6 | 127.60 (6) | C1—C6—N1 | 119.25 (6) |
N1—N2—O1 | 105.66 (5) | O2—C7—O1 | 120.29 (7) |
C6—C1—C2 | 118.02 (7) | O2—C7—C8 | 136.05 (6) |
C6—C1—H1A | 121.0 | O1—C7—C8 | 103.66 (5) |
C2—C1—H1A | 121.0 | N1—C8—C7 | 105.44 (6) |
C1—C2—C3 | 121.19 (7) | N1—C8—C9 | 124.90 (6) |
C1—C2—H2A | 119.4 | C7—C8—C9 | 129.64 (6) |
C3—C2—H2A | 119.4 | O3—C9—C8 | 122.82 (7) |
C2—C3—C4 | 118.71 (7) | O3—C9—H9A | 118.6 |
C2—C3—C10 | 120.83 (7) | C8—C9—H9A | 118.6 |
C4—C3—C10 | 120.45 (7) | C3—C10—H10D | 109.5 |
C5—C4—C3 | 121.34 (7) | C3—C10—H10A | 109.5 |
C5—C4—H4A | 119.3 | H10D—C10—H10A | 109.5 |
C3—C4—H4A | 119.3 | C3—C10—H10B | 109.5 |
C6—C5—C4 | 118.01 (6) | H10D—C10—H10B | 109.5 |
C6—C5—H5A | 121.0 | H10A—C10—H10B | 109.5 |
C8—N1—N2—O1 | −1.23 (7) | N2—N1—C6—C1 | 120.44 (7) |
C6—N1—N2—O1 | 178.51 (5) | C8—N1—C6—C1 | −59.85 (9) |
C7—O1—N2—N1 | 1.09 (7) | N2—O1—C7—O2 | 179.97 (6) |
C6—C1—C2—C3 | −0.31 (11) | N2—O1—C7—C8 | −0.58 (7) |
C1—C2—C3—C4 | 1.07 (12) | N2—N1—C8—C7 | 0.88 (7) |
C1—C2—C3—C10 | −178.99 (8) | C6—N1—C8—C7 | −178.84 (6) |
C2—C3—C4—C5 | −0.81 (11) | N2—N1—C8—C9 | −178.07 (6) |
C10—C3—C4—C5 | 179.25 (7) | C6—N1—C8—C9 | 2.22 (10) |
C3—C4—C5—C6 | −0.19 (11) | O2—C7—C8—N1 | 179.18 (8) |
C4—C5—C6—C1 | 1.01 (11) | O1—C7—C8—N1 | −0.13 (7) |
C4—C5—C6—N1 | −178.80 (6) | O2—C7—C8—C9 | −1.94 (13) |
C2—C1—C6—C5 | −0.76 (11) | O1—C7—C8—C9 | 178.74 (6) |
C2—C1—C6—N1 | 179.05 (6) | N1—C8—C9—O3 | 166.06 (6) |
N2—N1—C6—C5 | −59.74 (8) | C7—C8—C9—O3 | −12.62 (11) |
C8—N1—C6—C5 | 119.96 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···O2i | 0.93 | 2.41 | 3.2847 (9) | 156 |
C5—H5A···O3ii | 0.93 | 2.60 | 3.3489 (11) | 138 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, y−1/2, −z+5/2. |
Experimental details
Crystal data | |
Chemical formula | C10H8N2O3 |
Mr | 204.18 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 10.5663 (4), 10.4088 (3), 8.9630 (3) |
β (°) | 108.222 (1) |
V (Å3) | 936.34 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.71 × 0.30 × 0.19 |
Data collection | |
Diffractometer | Bruker APEXII DUO CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.926, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14437, 4906, 4091 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.857 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.132, 1.07 |
No. of reflections | 4906 |
No. of parameters | 137 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.65, −0.31 |
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 |
C1—H1A···O2i | 0.9300 | 2.4100 | 3.2847 (9) | 156.00 |
C5—H5A···O3ii | 0.9300 | 2.6000 | 3.3489 (11) | 138.00 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, y−1/2, −z+5/2. |
Acknowledgements
The authors thank Universiti Sains Malaysia (USM) for the Research University Golden Goose grant (No. 1001/PFIZIK/811012). JHG also thanks USM for the award of a USM fellowship.
References
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Sydnones constitute a well-defined class of mesoionic compounds consisting of 1,2,3-oxadiazole ring system. The introduction of the concept of mesoionic structure for certain heterocyclic compounds in the year 1949 has proved to be fruitful development in heterocyclic chemistry. The study of sydnones still remains a field of interest because of their electronic structure and also because of the various types of biological activities displayed by some of them. Interest in sydnone derivatives has also been encouraged by the discovery that they exhibit various pharmacological activities (Hedge et al., 2008; Rai et al., 2008).
These 4-formyl sydnone will be used for the preparation of a new series of α,β-unsaturated carbonyl compounds (namely chalcones) by condensation with appropriate ketones or aldehydes. These α,β-unsaturated carbonyl compounds will be utilized for the synthesis of a variety of novel heterocyclic compounds like pyrazolines, pyrazole etc carrying sydnone moiety.
Sydnones are mesoionic compounds containing a five-membered heterocyclic ring. Generally, substitution at the N3 position by an aromatic substituent is necessary for stability. In the title sydnone compound (Fig. 1), the aromatic substituent is p-toluene. The 1,2,3-oxadiazole ring (N1/N2/O1/C7/C8) in the sydnone unit is essentially planar, with maximum deviation of -0.006 (1) Å at atom N2. The mean planes through the aldehyde moiety (C9/H9A/O3) and methyl-substituted phenyl ring (C1-C6) are inclined at dihedral angles of 13.60 (9) and 59.69 (4)°, respectively, with the 1,2,3-oxadiazole ring. As reported previously (Grossie et al., 2009), the exocyclic C7–O2 bond length of 1.2089 (9) Å is inconsistent to the formulation of Baker & Ollis (1957), which reported the delocalization of a positive charge in the ring, and a negative charge in the exocyclic oxygen. The bond lengths (Allen et al., 1987) and angles are within normal range and comparable to a related sydnone structure (Grossie et al., 2009). In the crystal structure (Fig. 2), intermolecular C1—H1A···O2 and C5—H5A···O3 hydrogen bonds (Table 1) link adjacent molecules into two-dimensional arrays parallel to the (100) plane.