2-(2-Methoxy­phen­yl)-4,4-dimethyl-4,5-dihydro-1,3-oxazole

Thiruvalluvar, A.; Butcher, R.J.; Karegoudar, P.; Holla, B.S.

doi:10.1107/S1600536807061685

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o61

https://doi.org/10.1107/S1600536807061685

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2-(2-Methoxyphenyl)-4,4-dimethyl-4,5-dihydro-1,3-oxazole

A. Thiruvalluvar,^a ^* Ray J. Butcher,^b Prakash Karegoudar ^c and B. Shivarama Holla ^d

^aPG Research Department of Physics, Rajah Serfoji Government College (Autonomous), Thanjavur 613 005, Tamil Nadu, India, ^bDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA, ^cSeQuent Scientific Limited, 120 A & B Baikampady Industrial Area, New Mangalore, India, and ^dDepartment of Chemistry, Mangalore University, Karnataka 574 199, India
^*Correspondence e-mail: athiru@vsnl.net

(Received 18 November 2007; accepted 21 November 2007; online 6 December 2007)

In the title molecule, C₁₂H₁₅NO₂, the oxazole ring adopts an envelope conformation. Overall, the molecule is approximately planar, the dihedral angle between the mean plane through all but the methylene C atom of the five-membered ring and the aromatic ring being 8.6 (1)°. A weak C—H⋯O interaction contributes to the stabilization of the crystal structure.

Related literature

For related crystal structures, see: Swaleh & Ziemer (2001 ); Rybakov et al. (2006 ).

Experimental

Crystal data

C₁₂H₁₅NO₂
M_r = 205.25
Monoclinic, P 2₁ /n
a = 8.1495 (2) Å
b = 10.9369 (3) Å
c = 12.0864 (3) Å
β = 91.305 (3)°
V = 1076.99 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 200 (2) K
0.39 × 0.31 × 0.24 mm

Data collection

Oxford Diffraction Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Versions 1.171.32. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ) T_min = 0.717, T_max = 1.000 (expected range = 0.702–0.980)
34412 measured reflections
3740 independent reflections
2596 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.163
S = 1.13
3740 reflections
139 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C26—H26⋯O1	0.93	2.35	2.7136 (12)	103

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Versions 1.171.32. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Versions 1.171.32. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807061685/tk2221sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807061685/tk2221Isup2.hkl

checkCIF report

Comment top

Swaleh and Ziemer (2001) reported the crystal structure of 2-[(2-phenyl-1,3-oxazol-4-yl)methyl]-2H-1,2,3-benzotriazole, wherein the phenyl and oxazole rings are essentially co-planar. Rybakov et al. (2006) reported the crystal structure of 5-(4-bromophenyl)-1,3-oxazol-2-amine, wherein the oxazole and the aromatic rings form a dihedral angle of 9.68 (7)°. In the title molecule, C₁₂H₁₅NO₂ (I), Fig. 1, the oxazole ring is in an envelope conformation. The dihedral angle between the mean plane through the O1/C2/N3/C5 atoms and that through the aromatic ring is 8.6 (1)°. A weak C—H···O interaction contributes to the stabilization of the crystal structure (Table 1).

Related literature top

For related crystal structures, see: Swaleh & Ziemer (2001); Rybakov et al. (2006).

Experimental top

To a solution of 2-methoxy benzyl chloride (15.8 g, 0.1 mol) in dichloromethane (50 ml), 2-amino-2-methyl-1-propanol (8.3 g, 0.11 mol) in dichloromethane (50 ml) was added at 298–303 K over 30 min. After stirring for 1 h, dichloromethane was distilled off under reduced pressure. The obtained product was recrystallized using ethyl acetate as the solvent to yield 10 g of (I) (86.5%).

Structure description top

For related crystal structures, see: Swaleh & Ziemer (2001); Rybakov et al. (2006).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis CCD (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top

Fig. 1. The molecular structure of (I) showing the atomic numbering and 50% probability displacement ellipsoids.

2-(2-Methoxyphenyl)-4,4-dimethyl-4,5-dihydro-1,3-oxazole top

Crystal data top

C₁₂H₁₅NO₂	F(000) = 440
M_r = 205.25	D_x = 1.266 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 410(1) K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 8.1495 (2) Å	Cell parameters from 14583 reflections
b = 10.9369 (3) Å	θ = 4.6–32.5°
c = 12.0864 (3) Å	µ = 0.09 mm⁻¹
β = 91.305 (3)°	T = 200 K
V = 1076.99 (5) Å³	Prism, colourless
Z = 4	0.39 × 0.31 × 0.24 mm

Data collection top

Oxford Diffraction Gemini diffractometer	3740 independent reflections
Radiation source: fine-focus sealed tube	2596 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 10.5081 pixels mm^-1	θ_max = 32.6°, θ_min = 4.6°
φ and ω scans	h = −12→12
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −16→16
T_min = 0.717, T_max = 1.000	l = −18→18
34412 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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.163	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.099P)²] where P = (F_o² + 2F_c²)/3
3740 reflections	(Δ/σ)_max < 0.001
139 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₂H₁₅NO₂	V = 1076.99 (5) Å³
M_r = 205.25	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.1495 (2) Å	µ = 0.09 mm⁻¹
b = 10.9369 (3) Å	T = 200 K
c = 12.0864 (3) Å	0.39 × 0.31 × 0.24 mm
β = 91.305 (3)°

Data collection top

Oxford Diffraction Gemini diffractometer	3740 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	2596 reflections with I > 2σ(I)
T_min = 0.717, T_max = 1.000	R_int = 0.027
34412 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.163	H-atom parameters constrained
S = 1.13	Δρ_max = 0.43 e Å⁻³
3740 reflections	Δρ_min = −0.20 e Å⁻³
139 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	0.61501 (9)	0.49026 (7)	0.33582 (5)	0.0357 (2)
O2	0.40996 (9)	0.22987 (6)	0.11696 (6)	0.0332 (2)
N3	0.65111 (10)	0.39575 (8)	0.17107 (7)	0.0325 (2)
C2	0.56870 (11)	0.40277 (7)	0.25852 (7)	0.0230 (2)
C4	0.78858 (13)	0.48460 (9)	0.18188 (8)	0.0310 (3)
C5	0.74394 (15)	0.55882 (10)	0.28508 (10)	0.0409 (3)
C12	0.33176 (17)	0.14486 (11)	0.04469 (10)	0.0445 (4)
C14	0.79827 (15)	0.56238 (11)	0.07847 (10)	0.0442 (4)
C15	0.94665 (14)	0.41267 (10)	0.20004 (11)	0.0428 (4)
C21	0.42972 (11)	0.32650 (8)	0.29281 (7)	0.0235 (2)
C22	0.35474 (11)	0.23841 (8)	0.22165 (7)	0.0254 (2)
C23	0.22969 (13)	0.16468 (9)	0.26164 (9)	0.0333 (3)
C24	0.18045 (13)	0.17635 (10)	0.37044 (10)	0.0389 (3)
C25	0.25034 (13)	0.26249 (11)	0.44046 (9)	0.0385 (3)
C26	0.37380 (12)	0.33708 (9)	0.40107 (8)	0.0300 (3)
H5A	0.83805	0.56661	0.33518	0.0491*
H5B	0.70600	0.63992	0.26448	0.0491*
H12A	0.38149	0.14833	−0.02649	0.0668*
H12B	0.21733	0.16474	0.03700	0.0668*
H12C	0.34348	0.06393	0.07459	0.0668*
H14A	0.82155	0.51117	0.01626	0.0662*
H14B	0.88401	0.62191	0.08799	0.0662*
H14C	0.69541	0.60335	0.06566	0.0662*
H15A	0.96128	0.35762	0.13920	0.0641*
H15B	0.94063	0.36683	0.26757	0.0641*
H15C	1.03780	0.46817	0.20484	0.0641*
H23	0.17905	0.10747	0.21531	0.0399*
H24	0.09887	0.12517	0.39659	0.0466*
H25	0.21528	0.27039	0.51280	0.0463*
H26	0.42061	0.39563	0.44781	0.0360*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0389 (4)	0.0352 (4)	0.0334 (4)	−0.0092 (3)	0.0072 (3)	−0.0128 (3)
O2	0.0348 (4)	0.0360 (4)	0.0288 (3)	−0.0099 (3)	0.0026 (3)	−0.0042 (3)
N3	0.0315 (4)	0.0313 (4)	0.0352 (4)	−0.0108 (3)	0.0101 (3)	−0.0042 (3)
C2	0.0250 (4)	0.0206 (4)	0.0234 (4)	0.0013 (3)	0.0010 (3)	−0.0022 (3)
C4	0.0303 (5)	0.0276 (5)	0.0352 (5)	−0.0080 (4)	0.0051 (4)	−0.0003 (4)
C5	0.0431 (6)	0.0303 (5)	0.0496 (7)	−0.0132 (5)	0.0087 (5)	−0.0089 (4)
C12	0.0492 (7)	0.0448 (6)	0.0394 (6)	−0.0134 (5)	−0.0026 (5)	−0.0095 (5)
C14	0.0402 (6)	0.0441 (6)	0.0483 (7)	−0.0097 (5)	0.0044 (5)	0.0124 (5)
C15	0.0354 (6)	0.0412 (6)	0.0519 (7)	−0.0010 (5)	0.0043 (5)	0.0036 (5)
C21	0.0220 (4)	0.0220 (4)	0.0266 (4)	0.0038 (3)	0.0031 (3)	0.0006 (3)
C22	0.0219 (4)	0.0258 (4)	0.0284 (4)	0.0018 (3)	0.0015 (3)	0.0011 (3)
C23	0.0246 (5)	0.0310 (5)	0.0443 (6)	−0.0041 (4)	0.0024 (4)	0.0026 (4)
C24	0.0267 (5)	0.0404 (6)	0.0500 (6)	−0.0010 (4)	0.0123 (4)	0.0112 (5)
C25	0.0335 (5)	0.0466 (6)	0.0361 (5)	0.0082 (5)	0.0135 (4)	0.0088 (4)
C26	0.0300 (5)	0.0328 (5)	0.0274 (4)	0.0066 (4)	0.0058 (4)	0.0037 (3)

Geometric parameters (Å, º) top

O1—C2	1.3838 (11)	C5—H5A	0.9700
O1—C5	1.4393 (14)	C5—H5B	0.9700
O2—C12	1.4171 (14)	C12—H12A	0.9600
O2—C22	1.3558 (11)	C12—H12B	0.9600
N3—C2	1.2675 (12)	C12—H12C	0.9600
N3—C4	1.4865 (13)	C14—H14A	0.9600
C2—C21	1.4737 (12)	C14—H14B	0.9600
C4—C5	1.5387 (15)	C14—H14C	0.9600
C4—C14	1.5154 (16)	C15—H15A	0.9600
C4—C15	1.5211 (15)	C15—H15B	0.9600
C21—C22	1.4203 (12)	C15—H15C	0.9600
C21—C26	1.4001 (13)	C23—H23	0.9300
C22—C23	1.3946 (14)	C24—H24	0.9300
C23—C24	1.3895 (16)	C25—H25	0.9300
C24—C25	1.3807 (16)	C26—H26	0.9300
C25—C26	1.3879 (15)

O1···C12ⁱ	3.3873 (14)	H12B···H23	2.2700
O2···N3	2.7428 (11)	H12C···C23	2.7000
O1···H26ⁱⁱ	2.9200	H12C···H23	2.2400
O1···H26	2.3500	H12C···C26^xi	3.0700
O1···H23ⁱⁱⁱ	2.7800	H14A···H15A	2.5000
O2···H5A^iv	2.7700	H14A···C24^v	2.9200
O2···H25^v	2.8100	H14B···H15C	2.5100
N3···O2	2.7428 (11)	H14B···C21^x	3.0500
N3···C25^v	3.3942 (14)	H14B···C26^x	3.0700
N3···H25^v	2.7000	H14C···H5B	2.4400
C12···O1^vi	3.3873 (14)	H14C···H24ⁱⁱⁱ	2.4600
C25···N3^vii	3.3942 (14)	H14C···C12^viii	3.0700
C2···H23ⁱⁱⁱ	3.0400	H15A···H14A	2.5000
C2···H15B	3.0600	H15B···C2	3.0600
C5···H25ⁱⁱ	3.0900	H15B···C24^xii	3.1000
C12···H14C^viii	3.0700	H15B···H5A	2.4800
C12···H23	2.4700	H15B···H12Aⁱ	2.5500
C21···H14B^iv	3.0500	H15C···H5A	2.5300
C23···H12B	2.7100	H15C···H14B	2.5100
C23···H12C	2.7000	H15C···C23^x	2.8900
C23···H15C^iv	2.8900	H23···C12	2.4700
C24···H15B^ix	3.1000	H23···H12B	2.2700
C24···H14A^vii	2.9200	H23···H12C	2.2400
C26···H12Cⁱⁱⁱ	3.0700	H23···O1^xi	2.7800
C26···H14B^iv	3.0700	H23···C2^xi	3.0400
H5A···H15B	2.4800	H24···H14C^xi	2.4600
H5A···H15C	2.5300	H25···C5ⁱⁱ	3.0900
H5A···O2^x	2.7700	H25···O2^vii	2.8100
H5B···H14C	2.4400	H25···N3^vii	2.7000
H12A···H15B^vi	2.5500	H26···O1	2.3500
H12B···C23	2.7100	H26···O1ⁱⁱ	2.9200

C2—O1—C5	105.25 (7)	H5A—C5—H5B	109.00
C12—O2—C22	117.79 (8)	O2—C12—H12A	109.00
C2—N3—C4	107.44 (8)	O2—C12—H12B	109.00
O1—C2—N3	117.61 (8)	O2—C12—H12C	109.00
O1—C2—C21	113.65 (7)	H12A—C12—H12B	109.00
N3—C2—C21	128.72 (8)	H12A—C12—H12C	109.00
N3—C4—C5	102.97 (8)	H12B—C12—H12C	109.00
N3—C4—C14	110.35 (8)	C4—C14—H14A	109.00
N3—C4—C15	107.98 (8)	C4—C14—H14B	109.00
C5—C4—C14	112.96 (9)	C4—C14—H14C	109.00
C5—C4—C15	111.78 (9)	H14A—C14—H14B	109.00
C14—C4—C15	110.46 (9)	H14A—C14—H14C	109.00
O1—C5—C4	105.01 (8)	H14B—C14—H14C	109.00
C2—C21—C22	122.44 (8)	C4—C15—H15A	109.00
C2—C21—C26	118.99 (8)	C4—C15—H15B	109.00
C22—C21—C26	118.51 (8)	C4—C15—H15C	109.00
O2—C22—C21	117.68 (8)	H15A—C15—H15B	109.00
O2—C22—C23	122.98 (8)	H15A—C15—H15C	109.00
C21—C22—C23	119.34 (8)	H15B—C15—H15C	109.00
C22—C23—C24	120.26 (9)	C22—C23—H23	120.00
C23—C24—C25	121.25 (10)	C24—C23—H23	120.00
C24—C25—C26	118.88 (10)	C23—C24—H24	119.00
C21—C26—C25	121.73 (9)	C25—C24—H24	119.00
O1—C5—H5A	111.00	C24—C25—H25	121.00
O1—C5—H5B	111.00	C26—C25—H25	121.00
C4—C5—H5A	111.00	C21—C26—H26	119.00
C4—C5—H5B	111.00	C25—C26—H26	119.00

C5—O1—C2—N3	5.16 (11)	N3—C4—C5—O1	12.97 (10)
C5—O1—C2—C21	−176.76 (8)	C14—C4—C5—O1	132.00 (9)
C2—O1—C5—C4	−11.14 (10)	C15—C4—C5—O1	−102.69 (10)
C12—O2—C22—C21	−177.98 (9)	C2—C21—C22—O2	−3.21 (13)
C12—O2—C22—C23	2.38 (13)	C2—C21—C22—C23	176.46 (8)
C4—N3—C2—O1	3.72 (11)	C26—C21—C22—O2	179.69 (8)
C4—N3—C2—C21	−174.03 (9)	C26—C21—C22—C23	−0.65 (13)
C2—N3—C4—C5	−10.28 (10)	C2—C21—C26—C25	−175.91 (9)
C2—N3—C4—C14	−131.11 (9)	C22—C21—C26—C25	1.29 (14)
C2—N3—C4—C15	108.08 (9)	O2—C22—C23—C24	178.86 (9)
O1—C2—C21—C22	174.63 (8)	C21—C22—C23—C24	−0.79 (14)
O1—C2—C21—C26	−8.28 (12)	C22—C23—C24—C25	1.65 (16)
N3—C2—C21—C22	−7.55 (15)	C23—C24—C25—C26	−1.01 (16)
N3—C2—C21—C26	169.54 (9)	C24—C25—C26—C21	−0.48 (16)

Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x+1/2, y+1/2, −z+1/2; (iv) −x+3/2, y−1/2, −z+1/2; (v) x+1/2, −y+1/2, z−1/2; (vi) x−1/2, −y+1/2, z−1/2; (vii) x−1/2, −y+1/2, z+1/2; (viii) −x+1, −y+1, −z; (ix) x−1, y, z; (x) −x+3/2, y+1/2, −z+1/2; (xi) −x+1/2, y−1/2, −z+1/2; (xii) x+1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C26—H26···O1	0.93	2.35	2.7136 (12)	103

Experimental details

Crystal data
Chemical formula	C₁₂H₁₅NO₂
M_r	205.25
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	200
a, b, c (Å)	8.1495 (2), 10.9369 (3), 12.0864 (3)
β (°)	91.305 (3)
V (Å³)	1076.99 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.39 × 0.31 × 0.24

Data collection
Diffractometer	Oxford Diffraction Gemini
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
T_min, T_max	0.717, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	34412, 3740, 2596
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.758

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.163, 1.13
No. of reflections	3740
No. of parameters	139
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.20

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C26—H26···O1	0.93	2.35	2.7136 (12)	103

Acknowledgements

RJB acknowledges the NSF–MRI program for funding to purchase the X-ray CCD diffractometer.

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