3,3′-(Ethane-1,2-di­yl)bis­(6-methyl-3,4-dihydro-2H-1,3-benzoxazine)

Rivera, A.; Camacho, J.; Ríos-Motta, J.; Pojarová, M.; Dušek, M.

doi:10.1107/S1600536811027139

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2028

doi:10.1107/S1600536811027139

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3,3′-(Ethane-1,2-diyl)bis(6-methyl-3,4-dihydro-2H-1,3-benzoxazine)

Augusto Rivera,^a ^* Jairo Camacho,^a Jaime Ríos-Motta,^a Michaela Pojarová ^b and Michal Dušek ^b

^aDepartamento de Química, Universidad Nacional de Colombia, Ciudad, Universitaria, Bogotá, Colombia, and ^bInstitute of Physics, v.v.i, AS CR, Na Slovance 2, 182 21 Prague 8, Czech Republic
^*Correspondence e-mail: ariverau@unal.edu.co

(Received 1 July 2011; accepted 6 July 2011; online 13 July 2011)

The asymmetric unit of the title compound, C₂₀H₂₄N₂O₂, contains one half-molecule, which is completed by inversion symmetry. In the crystal, molecular chains are formed through non-classical C—H⋯O hydrogen bonds, formed between axial H atoms of the oxazine ring and a O atom of a neighboring molecule.

Related literature

For the synthesis, see: Rivera et al. (1994 ). For a related structure, see: Rivera et al. (2010 ). For uses of benzoxazines in polymer science, see Yaggi et al. (2009 ). For the biological activity of bis-benzoxazine compounds, see: Billmann & Dorman (1963 ); Heinisch et al. (2002 ).

Experimental

Crystal data

C₂₀H₂₄N₂O₂
M_r = 324.41
Monoclinic, P 2₁ /n
a = 8.5042 (1) Å
b = 5.8558 (1) Å
c = 16.5519 (2) Å
β = 95.899 (1)°
V = 819.90 (2) Å³
Z = 2
Cu Kα radiation
μ = 0.68 mm⁻¹
T = 130 K
0.50 × 0.33 × 0.20 mm

Data collection

Xcalibur, Atlas, Gemini ultra diffractometer
Absorption correction: analytical (CrysAlis PRO; Agilent, 2011 ) T_min = 0.384, T_max = 0.668
7156 measured reflections
1452 independent reflections
1429 reflections with I > 2σ(I)
R_int = 0.013

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.087
S = 1.03
1452 reflections
111 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O1ⁱ	0.97	2.57	3.425 (1)	147
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811027139/qm2015sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811027139/qm2015Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811027139/qm2015Isup3.cml

checkCIF report

Comment top

In the title compound, C₂₀H₂₄N₂O₂, the asymmetric unit contains one-half of the molecule, which is related to the other half by a centre of inversion located at the mid-point of the central C12—C12a bond (see Fig.1). The unit cell contains two molecules. Unlike the related structure Rivera et al. (2010), which crystallized in space group C2/c the title compound crystallizes in the P2_1./n space group.

The molecule contains two 1,3-benzoxazine units linked by a CH₂CH₂ spacer at the 3 position of heterocyclic ring. The bond lengths and angles are within normal ranges, whereas the observed C—O bond length [1.376 (1) Å and 1.453 (1) Å] are considerably shortened in relation to related structure (Rivera et al., 2010) [1.421 (2) Å and 1.529 (2) Å]. The C—N bond length [1.429 (1) Å] in the N—CH₂—O segment is more agreement with the typical than the related structure (Rivera et al., 2010) [1.369 (2) Å]. This information indicates minor influence of the anomeric effect in the title compound. The heterocyclic ring adopts a cyclohexene-like half chair conformation. In the crystal structure, molecules are linked by non clasical intermolecular C—H···.O interactions between H2A and O1 of a neighboring molecule. This establishes crystal packing into 1-D extended chains along the b-axis (see Fig. 2).

Related literature top

For the synthesis, see: Rivera et al. (1994). For a related structure, see: Rivera et al. (2010). For uses of benzoxazines in polymer science, see Yaggi et al. (2009). For the biological activity of bis-benzoxazine compounds, see: Billmann & Dorman (1963); Heinisch et al. (2002).

Experimental top

To a stirred solution of 1,3-bis(2'-hydroxy-5'-methyl-benzyl)imidazolidine (1 mmol) in dioxne is added slowly dropwise formaldehyde solution 40% (1 mmol) (8 ml, 0.11 mmol) and the mixture gently warned at 40–42 °C until a precipitate appeared. The product was filtered and washed with alcohol and water. Recrystallization of solid from ethyl acetate gives title compound (yield 82%). M.p. 401–402 K.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecule of the title compound with atom-labeling scheme.
	Fig. 2. Packing of the molecules of the title compound view along b.

3,3'-(Ethane-1,2-diyl)bis(6-methyl-3,4-dihydro-2H-1,3-benzoxazine) top

Crystal data top

C₂₀H₂₄N₂O₂	F(000) = 348
M_r = 324.41	D_x = 1.314 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: -P 2yn	Cell parameters from 6632 reflections
a = 8.5042 (1) Å	θ = 5.2–67.0°
b = 5.8558 (1) Å	µ = 0.68 mm⁻¹
c = 16.5519 (2) Å	T = 130 K
β = 95.899 (1)°	Plate, colourless
V = 819.90 (2) Å³	0.50 × 0.33 × 0.20 mm
Z = 2

Data collection top

Xcalibur, Atlas, Gemini ultra diffractometer	1452 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	1429 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.013
Detector resolution: 10.3784 pixels mm^-1	θ_max = 67.1°, θ_min = 5.4°
Rotation method data acquisition using ω scans	h = −10→10
Absorption correction: analytical (CrysAlis PRO; Agilent, 2011)	k = −7→6
T_min = 0.384, T_max = 0.668	l = −18→19
7156 measured reflections

Refinement top

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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.087	w = 1/[σ²(F_o²) + (0.0446P)² + 0.3441P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
1452 reflections	Δρ_max = 0.21 e Å⁻³
111 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.033 (2)

Crystal data top

C₂₀H₂₄N₂O₂	V = 819.90 (2) Å³
M_r = 324.41	Z = 2
Monoclinic, P2₁/n	Cu Kα radiation
a = 8.5042 (1) Å	µ = 0.68 mm⁻¹
b = 5.8558 (1) Å	T = 130 K
c = 16.5519 (2) Å	0.50 × 0.33 × 0.20 mm
β = 95.899 (1)°

Data collection top

Xcalibur, Atlas, Gemini ultra diffractometer	1452 independent reflections
Absorption correction: analytical (CrysAlis PRO; Agilent, 2011)	1429 reflections with I > 2σ(I)
T_min = 0.384, T_max = 0.668	R_int = 0.013
7156 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 1.03	Δρ_max = 0.21 e Å⁻³
1452 reflections	Δρ_min = −0.16 e Å⁻³
111 parameters

Special details top

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. The H atoms were all located in a difference map, but those attached to carbon atoms were repositioned geometrically. The isotropic temperature parameters of hydrogen atoms were calculated as 1.2*U_eq of the parent atom.

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

	x	y	z	U_iso*/U_eq
O1	0.72879 (9)	0.13355 (13)	0.81920 (5)	0.0219 (2)
C2	0.88891 (13)	0.0460 (2)	0.82084 (7)	0.0207 (3)
H2A	0.8959	−0.0491	0.7734	0.025*
H2B	0.9608	0.1735	0.8174	0.025*
N3	0.93877 (10)	−0.08416 (16)	0.89191 (5)	0.0191 (3)
C4	0.84012 (13)	−0.29037 (19)	0.89165 (6)	0.0196 (3)
H4A	0.8583	−0.3650	0.9441	0.023*
H4B	0.8708	−0.3956	0.8508	0.023*
C5	0.66601 (13)	−0.23570 (19)	0.87416 (6)	0.0189 (3)
C6	0.54855 (13)	−0.3874 (2)	0.89236 (6)	0.0205 (3)
H6	0.5781	−0.5261	0.9168	0.025*
C7	0.38861 (13)	−0.3384 (2)	0.87522 (7)	0.0220 (3)
C8	0.34747 (13)	−0.1288 (2)	0.83884 (7)	0.0245 (3)
H8	0.2412	−0.0917	0.8271	0.029*
C9	0.46154 (14)	0.0245 (2)	0.81998 (7)	0.0232 (3)
H9	0.4319	0.1630	0.7955	0.028*
C10	0.62084 (13)	−0.02829 (19)	0.83767 (6)	0.0195 (3)
C11	0.26270 (14)	−0.5038 (2)	0.89513 (7)	0.0261 (3)
H11A	0.2123	−0.5685	0.8458	0.031*
H11B	0.1856	−0.4250	0.9232	0.031*
H11C	0.3099	−0.6234	0.9291	0.031*
C12	0.94008 (13)	0.04830 (19)	0.96715 (6)	0.0205 (3)
H12A	0.8357	0.0451	0.9858	0.025*
H12B	0.9662	0.2060	0.9566	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0200 (4)	0.0209 (4)	0.0243 (4)	0.0001 (3)	0.0000 (3)	0.0041 (3)
C2	0.0187 (5)	0.0238 (6)	0.0194 (6)	−0.0003 (4)	0.0012 (4)	0.0010 (4)
N3	0.0195 (5)	0.0195 (5)	0.0180 (5)	−0.0007 (4)	0.0001 (4)	−0.0003 (4)
C4	0.0204 (6)	0.0183 (6)	0.0195 (5)	0.0008 (4)	0.0001 (4)	−0.0005 (4)
C5	0.0202 (6)	0.0207 (6)	0.0155 (5)	0.0008 (4)	0.0003 (4)	−0.0030 (4)
C6	0.0238 (6)	0.0195 (6)	0.0179 (5)	0.0005 (4)	0.0010 (4)	−0.0018 (4)
C7	0.0217 (6)	0.0251 (6)	0.0193 (5)	−0.0018 (5)	0.0028 (4)	−0.0048 (5)
C8	0.0176 (6)	0.0291 (7)	0.0263 (6)	0.0026 (5)	0.0000 (4)	−0.0029 (5)
C9	0.0234 (6)	0.0217 (6)	0.0239 (6)	0.0035 (5)	−0.0008 (4)	0.0004 (5)
C10	0.0212 (6)	0.0209 (6)	0.0164 (5)	−0.0013 (4)	0.0012 (4)	−0.0023 (4)
C11	0.0216 (6)	0.0295 (7)	0.0275 (6)	−0.0021 (5)	0.0040 (5)	−0.0023 (5)
C12	0.0205 (5)	0.0196 (6)	0.0208 (6)	0.0012 (4)	−0.0007 (4)	−0.0017 (4)

Geometric parameters (Å, º) top

O1—C10	1.3755 (14)	C6—H6	0.9300
O1—C2	1.4525 (13)	C7—C8	1.3958 (18)
C2—N3	1.4291 (14)	C7—C11	1.5052 (16)
C2—H2A	0.9700	C8—C9	1.3808 (17)
C2—H2B	0.9700	C8—H8	0.9300
N3—C12	1.4663 (14)	C9—C10	1.3910 (16)
N3—C4	1.4701 (14)	C9—H9	0.9300
C4—C5	1.5134 (15)	C11—H11A	0.9600
C4—H4A	0.9700	C11—H11B	0.9600
C4—H4B	0.9700	C11—H11C	0.9600
C5—C6	1.3926 (16)	C12—C12ⁱ	1.521 (2)
C5—C10	1.3928 (16)	C12—H12A	0.9700
C6—C7	1.3905 (16)	C12—H12B	0.9700

C10—O1—C2	113.49 (8)	C6—C7—C11	121.71 (11)
N3—C2—O1	113.69 (8)	C8—C7—C11	120.52 (10)
N3—C2—H2A	108.8	C9—C8—C7	121.23 (10)
O1—C2—H2A	108.8	C9—C8—H8	119.4
N3—C2—H2B	108.8	C7—C8—H8	119.4
O1—C2—H2B	108.8	C8—C9—C10	119.98 (11)
H2A—C2—H2B	107.7	C8—C9—H9	120.0
C2—N3—C12	113.12 (9)	C10—C9—H9	120.0
C2—N3—C4	108.35 (8)	O1—C10—C9	117.26 (10)
C12—N3—C4	113.04 (8)	O1—C10—C5	122.45 (10)
N3—C4—C5	111.94 (9)	C9—C10—C5	120.28 (11)
N3—C4—H4A	109.2	C7—C11—H11A	109.5
C5—C4—H4A	109.2	C7—C11—H11B	109.5
N3—C4—H4B	109.2	H11A—C11—H11B	109.5
C5—C4—H4B	109.2	C7—C11—H11C	109.5
H4A—C4—H4B	107.9	H11A—C11—H11C	109.5
C6—C5—C10	118.56 (10)	H11B—C11—H11C	109.5
C6—C5—C4	122.21 (10)	N3—C12—C12ⁱ	110.89 (11)
C10—C5—C4	119.22 (10)	N3—C12—H12A	109.5
C7—C6—C5	122.18 (11)	C12ⁱ—C12—H12A	109.5
C7—C6—H6	118.9	N3—C12—H12B	109.5
C5—C6—H6	118.9	C12ⁱ—C12—H12B	109.5
C6—C7—C8	117.77 (10)	H12A—C12—H12B	108.1

Symmetry code: (i) −x+2, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1ⁱⁱ	0.97	2.57	3.425 (1)	147

Symmetry code: (ii) −x+3/2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₂₀H₂₄N₂O₂
M_r	324.41
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	130
a, b, c (Å)	8.5042 (1), 5.8558 (1), 16.5519 (2)
β (°)	95.899 (1)
V (Å³)	819.90 (2)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	0.68
Crystal size (mm)	0.50 × 0.33 × 0.20

Data collection
Diffractometer	Xcalibur, Atlas, Gemini ultra diffractometer
Absorption correction	Analytical (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.384, 0.668
No. of measured, independent and observed [I > 2σ(I)] reflections	7156, 1452, 1429
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.087, 1.03
No. of reflections	1452
No. of parameters	111
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.16

Computer programs: CrysAlis PRO (Agilent, 2011), CrysAlis PRO (Agilent 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

O1—C10

1.3755 (14)

O1—C2

1.4525 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1ⁱ	0.97	2.57	3.425 (1)	147

Symmetry code: (i) −x+3/2, y−1/2, −z+3/2.

Acknowledgements

We acknowledge the Dirección de Investigaciones, Sede Bogotá (DIB) de La Universidad Nacional de Colombia, for financial support of this work, as well as the Institutional research plan No. AVOZ10100521 of the Institute of Physics and the Praemium Academiae project of the Academy of Science of the Czech Republic.

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