N-[(E)-1,3-Benzodioxol-5-yl­methyl­idene]-3,4-dimethyl-1,2-oxazol-5-amine

Asiri, A.M.; Khan, S.A.; Tahir, M.N.

doi:10.1107/S1600536811030327

organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2305

doi:10.1107/S1600536811030327

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N-[(E)-1,3-Benzodioxol-5-ylmethylidene]-3,4-dimethyl-1,2-oxazol-5-amine

Abdullah M. Asiri,^a Salman A. Khan ^a and M. Nawaz Tahir ^b ^*

^aDepartment of Chemistry, Faculty of Science, King Abduaziz University, Jeddah 21589, PO Box 80203, Saudi Arabia, and ^bUniversity of Sargodha, Department of Physics, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 23 July 2011; accepted 27 July 2011; online 11 August 2011)

In the title compound, C₁₃H₁₂N₂O₃, the dihedral angle between the aromatic rings is 7.94 (12)°. In the crystal, inversion dimers linked by pairs of C—H⋯O hydrogen bonds generate R₂²(6) loops. Weak π–π [centroid–centroid separations = 3.7480 (13) and 3.9047 (13) Å] and C—H⋯π interactions help to consolidate the packing.

Related literature

For background to conjugated azo-methanes, see: Asiri & Khan (2010 ). For related structures, see: Asiri et al. (2010 ); Tahir et al. (2010 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₃H₁₂N₂O₃
M_r = 244.25
Monoclinic, P 2₁ /n
a = 7.5759 (5) Å
b = 10.6980 (9) Å
c = 14.6307 (12) Å
β = 102.607 (2)°
V = 1157.19 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.28 × 0.24 × 0.22 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.975, T_max = 0.980
8018 measured reflections
2087 independent reflections
1447 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.132
S = 1.03
2087 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7B⋯O1ⁱ	0.97	2.58	3.264 (3)	128
C12—H12A⋯Cg1ⁱⁱ	0.96	2.95	3.763 (2)	143
Symmetry codes: (i) -x+1, -y, -z; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811030327/hb6330sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811030327/hb6330Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811030327/hb6330Isup3.cml

checkCIF report

Comment top

Donor-acceptor conjugated azo-methanes are used as substrates in the preparation of a large number of bioactive and industrial compounds via ring closure, cycloaddition, replacement reactions, etc (Asiri & Khan, 2010). The title compound (I, Fig. 1) has been prepared as a pharmaceutical intermediate.

The crystal structures of N-(4-chlorobenzylidene)-3,4-dimethylisoxazol -5-amine (Asiri et al., 2010) and N-[(E)-1,3-benzodioxol -5-ylmethylidene]-4-methylaniline (Tahir et al., 2010) have been published, which are related to (I).

In (I), the group A (C1–C8/O1/O2) of 1,3-benzodioxole-5-carbaldehyde moiety and the group B (C9—C12/N1/N2/O3) of 5-amino-3,4-dimethylisoxazole moiety are almost planar with r.m.s. deviations of 0.022 and 0.019 Å, respectively. The dihedral angle between A/B is 8.29 (3)°. The inter-molecular H-bondings of C—H···O type dimerize the molecules with R₂²(6) ring motif (Bernstein et al., 1995) (Table 1, Fig. 2). In stabilizing the molecules π–π interactions [separation: 3.7480 (13), 3.9047 (13) Å] and C—H···π interaction (Table 1) play important role in stabilizing the molecules.

Related literature top

For background to conjugated azo-methanes, see: Asiri & Khan (2010). For related structures, see: Asiri et al. (2010); Tahir et al. (2010). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

A mixture of 1,3-benzodioxole-5-carbaldehyde (0.50 g, 3.3 mmol) and 5-amino-3,4-dimethylisoxazole (3.3 mmol) in ethanol (15 ml) was heated for 3 h. The progress of the reaction was monitored by TLC. The solid that separated from the cooled mixture was collected and recrystallized from a methanol-chloroform mixture (8:2) to give the yellow prisms of the title compound (I).

Yield: 74%; m.p. 504–505 K.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of (I) with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The partial packing for (I), which shows that molecules form dimers with R₂²(6) ring motif.

N-[(E)-1,3-Benzodioxol-5-ylmethylidene]-3,4-dimethyl- 1,2-oxazol-5-amine top

Crystal data top

C₁₃H₁₂N₂O₃	F(000) = 512
M_r = 244.25	D_x = 1.402 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1447 reflections
a = 7.5759 (5) Å	θ = 3.4–25.3°
b = 10.6980 (9) Å	µ = 0.10 mm⁻¹
c = 14.6307 (12) Å	T = 296 K
β = 102.607 (2)°	Prism, yellow
V = 1157.19 (16) Å³	0.28 × 0.24 × 0.22 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	2087 independent reflections
Radiation source: fine-focus sealed tube	1447 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 8.10 pixels mm^-1	θ_max = 25.3°, θ_min = 3.4°
ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −12→12
T_min = 0.975, T_max = 0.980	l = −17→17
8018 measured reflections

Refinement top

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.132	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0693P)² + 0.1704P] where P = (F_o² + 2F_c²)/3
2087 reflections	(Δ/σ)_max < 0.001
165 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₃H₁₂N₂O₃	V = 1157.19 (16) Å³
M_r = 244.25	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.5759 (5) Å	µ = 0.10 mm⁻¹
b = 10.6980 (9) Å	T = 296 K
c = 14.6307 (12) Å	0.28 × 0.24 × 0.22 mm
β = 102.607 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2087 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1447 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.980	R_int = 0.032
8018 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.132	H-atom parameters constrained
S = 1.03	Δρ_max = 0.17 e Å⁻³
2087 reflections	Δρ_min = −0.18 e Å⁻³
165 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.6073 (2)	0.09898 (13)	0.08565 (10)	0.0729 (6)
O2	0.6345 (2)	0.27941 (14)	0.00426 (10)	0.0702 (6)
O3	0.6207 (2)	0.38037 (12)	0.55753 (10)	0.0699 (6)
N1	0.6338 (2)	0.23824 (15)	0.43533 (11)	0.0487 (5)
N2	0.6192 (3)	0.37712 (18)	0.65383 (13)	0.0742 (8)
C1	0.6183 (2)	0.31798 (17)	0.28025 (13)	0.0457 (6)
C2	0.6088 (3)	0.20099 (17)	0.23618 (13)	0.0493 (6)
C3	0.6150 (3)	0.19982 (17)	0.14411 (14)	0.0490 (7)
C4	0.6313 (3)	0.30805 (19)	0.09481 (13)	0.0510 (7)
C5	0.6386 (3)	0.42247 (19)	0.13520 (15)	0.0618 (8)
C6	0.6302 (3)	0.42546 (18)	0.22912 (14)	0.0572 (7)
C7	0.6271 (3)	0.1475 (2)	−0.00210 (15)	0.0687 (8)
C8	0.6190 (2)	0.33074 (18)	0.37881 (13)	0.0497 (7)
C9	0.6331 (3)	0.26031 (18)	0.52782 (13)	0.0478 (7)
C10	0.6405 (2)	0.18039 (18)	0.60027 (13)	0.0477 (7)
C11	0.6292 (3)	0.2593 (2)	0.67649 (14)	0.0556 (7)
C12	0.6270 (3)	0.2203 (2)	0.77363 (15)	0.0716 (9)
C13	0.6585 (3)	0.0425 (2)	0.60257 (15)	0.0697 (9)
H2	0.59873	0.12747	0.26857	0.0591*
H5	0.64865	0.49515	0.10183	0.0741*
H6	0.63264	0.50254	0.25877	0.0686*
H7A	0.73721	0.11561	−0.01717	0.0824*
H7B	0.52555	0.12203	−0.05118	0.0824*
H8	0.60811	0.41048	0.40229	0.0596*
H12A	0.51285	0.18213	0.77471	0.1074*
H12B	0.64420	0.29227	0.81383	0.1074*
H12C	0.72268	0.16145	0.79518	0.1074*
H13A	0.69485	0.01447	0.54709	0.1045*
H13B	0.54443	0.00536	0.60531	0.1045*
H13C	0.74801	0.01816	0.65679	0.1045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1287 (13)	0.0486 (9)	0.0459 (9)	−0.0125 (8)	0.0292 (9)	−0.0072 (7)
O2	0.1149 (12)	0.0587 (10)	0.0411 (8)	−0.0105 (8)	0.0259 (8)	−0.0007 (7)
O3	0.1182 (12)	0.0479 (9)	0.0477 (9)	0.0126 (8)	0.0273 (8)	−0.0003 (7)
N1	0.0606 (10)	0.0462 (9)	0.0407 (9)	−0.0010 (7)	0.0143 (7)	0.0013 (7)
N2	0.1179 (16)	0.0650 (13)	0.0447 (11)	0.0151 (10)	0.0288 (10)	−0.0032 (9)
C1	0.0549 (11)	0.0427 (10)	0.0424 (10)	0.0009 (8)	0.0170 (8)	0.0031 (8)
C2	0.0648 (12)	0.0409 (10)	0.0445 (11)	−0.0023 (9)	0.0172 (9)	0.0050 (9)
C3	0.0631 (12)	0.0423 (11)	0.0432 (11)	−0.0035 (9)	0.0148 (9)	−0.0020 (9)
C4	0.0652 (12)	0.0526 (12)	0.0373 (10)	−0.0033 (9)	0.0157 (9)	0.0023 (9)
C5	0.0975 (16)	0.0443 (12)	0.0495 (12)	−0.0033 (10)	0.0291 (11)	0.0083 (9)
C6	0.0860 (15)	0.0407 (11)	0.0497 (12)	−0.0020 (10)	0.0253 (10)	−0.0009 (9)
C7	0.1030 (17)	0.0597 (14)	0.0456 (12)	−0.0082 (12)	0.0210 (11)	−0.0036 (10)
C8	0.0656 (13)	0.0431 (10)	0.0434 (11)	−0.0004 (9)	0.0186 (9)	−0.0022 (9)
C9	0.0591 (12)	0.0446 (11)	0.0410 (11)	0.0003 (8)	0.0140 (9)	−0.0023 (9)
C10	0.0517 (11)	0.0505 (12)	0.0404 (11)	−0.0020 (8)	0.0091 (8)	0.0009 (9)
C11	0.0582 (12)	0.0666 (14)	0.0426 (12)	0.0025 (10)	0.0122 (9)	0.0005 (10)
C12	0.0825 (16)	0.0934 (18)	0.0410 (12)	−0.0012 (13)	0.0179 (11)	0.0039 (12)
C13	0.0987 (17)	0.0543 (13)	0.0523 (14)	−0.0088 (11)	0.0083 (12)	0.0070 (10)

Geometric parameters (Å, º) top

O1—C3	1.370 (2)	C9—C10	1.353 (3)
O1—C7	1.423 (3)	C10—C11	1.416 (3)
O2—C4	1.365 (2)	C10—C13	1.481 (3)
O2—C7	1.415 (3)	C11—C12	1.485 (3)
O3—N2	1.412 (2)	C2—H2	0.9300
O3—C9	1.366 (2)	C5—H5	0.9300
N1—C8	1.279 (2)	C6—H6	0.9300
N1—C9	1.375 (2)	C7—H7A	0.9700
N2—C11	1.301 (3)	C7—H7B	0.9700
C1—C2	1.403 (3)	C8—H8	0.9300
C1—C6	1.385 (3)	C12—H12A	0.9600
C1—C8	1.447 (3)	C12—H12B	0.9600
C2—C3	1.358 (3)	C12—H12C	0.9600
C3—C4	1.384 (3)	C13—H13A	0.9600
C4—C5	1.355 (3)	C13—H13B	0.9600
C5—C6	1.390 (3)	C13—H13C	0.9600

C3—O1—C7	106.12 (15)	C10—C11—C12	126.98 (19)
C4—O2—C7	106.20 (16)	C1—C2—H2	121.00
N2—O3—C9	108.09 (14)	C3—C2—H2	121.00
C8—N1—C9	119.01 (17)	C4—C5—H5	122.00
O3—N2—C11	105.39 (17)	C6—C5—H5	122.00
C2—C1—C6	119.69 (17)	C1—C6—H6	119.00
C2—C1—C8	122.06 (17)	C5—C6—H6	119.00
C6—C1—C8	118.24 (17)	O1—C7—H7A	110.00
C1—C2—C3	117.05 (17)	O1—C7—H7B	110.00
O1—C3—C2	128.35 (17)	O2—C7—H7A	110.00
O1—C3—C4	109.26 (17)	O2—C7—H7B	110.00
C2—C3—C4	122.39 (18)	H7A—C7—H7B	108.00
O2—C4—C3	109.91 (17)	N1—C8—H8	118.00
O2—C4—C5	128.19 (19)	C1—C8—H8	118.00
C3—C4—C5	121.89 (18)	C11—C12—H12A	109.00
C4—C5—C6	116.46 (19)	C11—C12—H12B	109.00
C1—C6—C5	122.49 (18)	C11—C12—H12C	109.00
O1—C7—O2	108.37 (16)	H12A—C12—H12B	109.00
N1—C8—C1	123.51 (17)	H12A—C12—H12C	110.00
O3—C9—N1	119.35 (16)	H12B—C12—H12C	109.00
O3—C9—C10	109.80 (16)	C10—C13—H13A	109.00
N1—C9—C10	130.84 (18)	C10—C13—H13B	110.00
C9—C10—C11	103.94 (17)	C10—C13—H13C	109.00
C9—C10—C13	129.41 (18)	H13A—C13—H13B	109.00
C11—C10—C13	126.65 (18)	H13A—C13—H13C	109.00
N2—C11—C10	112.77 (18)	H13B—C13—H13C	109.00
N2—C11—C12	120.26 (19)

C7—O1—C3—C2	−177.5 (2)	C6—C1—C8—N1	−170.00 (18)
C7—O1—C3—C4	2.4 (2)	C1—C2—C3—O1	−179.6 (2)
C3—O1—C7—O2	−3.8 (2)	C1—C2—C3—C4	0.5 (3)
C7—O2—C4—C3	−2.4 (2)	O1—C3—C4—O2	0.0 (3)
C7—O2—C4—C5	178.9 (2)	O1—C3—C4—C5	178.8 (2)
C4—O2—C7—O1	3.8 (2)	C2—C3—C4—O2	179.9 (2)
C9—O3—N2—C11	−0.4 (2)	C2—C3—C4—C5	−1.3 (4)
N2—O3—C9—N1	178.87 (19)	O2—C4—C5—C6	179.1 (2)
N2—O3—C9—C10	−0.3 (2)	C3—C4—C5—C6	0.5 (3)
C9—N1—C8—C1	179.97 (18)	C4—C5—C6—C1	1.1 (3)
C8—N1—C9—O3	−1.4 (3)	O3—C9—C10—C11	0.8 (2)
C8—N1—C9—C10	177.5 (2)	O3—C9—C10—C13	−178.49 (18)
O3—N2—C11—C10	0.9 (3)	N1—C9—C10—C11	−178.2 (2)
O3—N2—C11—C12	−178.74 (19)	N1—C9—C10—C13	2.5 (4)
C6—C1—C2—C3	1.1 (3)	C9—C10—C11—N2	−1.1 (3)
C8—C1—C2—C3	−177.91 (18)	C9—C10—C11—C12	178.5 (2)
C2—C1—C6—C5	−2.0 (3)	C13—C10—C11—N2	178.2 (2)
C8—C1—C6—C5	177.09 (19)	C13—C10—C11—C12	−2.2 (3)
C2—C1—C8—N1	9.0 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O1ⁱ	0.97	2.58	3.264 (3)	128
C12—H12A···Cg1ⁱⁱ	0.96	2.95	3.763 (2)	143

Symmetry codes: (i) −x+1, −y, −z; (ii) x−1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₂N₂O₃
M_r	244.25
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	7.5759 (5), 10.6980 (9), 14.6307 (12)
β (°)	102.607 (2)
V (Å³)	1157.19 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.28 × 0.24 × 0.22

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.975, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	8018, 2087, 1447
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.132, 1.03
No. of reflections	2087
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.18

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O1ⁱ	0.97	2.58	3.264 (3)	128
C12—H12A···Cg1ⁱⁱ	0.96	2.95	3.763 (2)	143

Symmetry codes: (i) −x+1, −y, −z; (ii) x−1/2, −y+1/2, z+1/2.

Acknowledgements

The authors would like to thank the Chemistry Department, King Abdulaziz University, Jeddah, Saudi Arabia, for providing the research facilities.

References

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2305

doi:10.1107/S1600536811030327

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