3,3′-Ethyl­enebis(3,4-dihydro-6-chloro-2H-1,3-benzoxazine)

Rivera, A.; Rojas, J.J.; Ríos-Motta, J.; Dušek, M.; Fejfarová, K.

doi:10.1107/S1600536810014248

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page o1134

https://doi.org/10.1107/S1600536810014248

Open

access

3,3′-Ethylenebis(3,4-dihydro-6-chloro-2H-1,3-benzoxazine)

Augusto Rivera,^a ^* Jicli José Rojas,^a Jaime Ríos-Motta,^a Michal Dušek ^b and Karla Fejfarová ^b

^aDepartamento de Química, Universidad Nacional de Colombia, Bogotá, AA 14490, Colombia, and ^bInstitute of Physics, Na Slovance 2, 182 21 Praha 8, Czech Republic
^*Correspondence e-mail: ariverau@unal.edu.co

(Received 29 March 2010; accepted 18 April 2010; online 21 April 2010)

The asymmetric unit of the title compound, C₁₈H₁₈Cl₂N₂O₂, contains one half of an independent molecule, the other half being generated via a centre of inversion at the molecular centroid. In the crystal structure, molecular chains are formed through non-classical C—H⋯ O hydrogen bonds between an axial H atom of the oxazine ring and the O atom of a neighbouring molecule.

Related literature

For the synthesis, see: Rivera et al. (1989 ). For related structures, see: Rivera et al. (1986 ); Huerta et al. (2006 ); Chen & Wu (2007 ); Ranjith et al. (2009 ). 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

C₁₈H₁₈Cl₂N₂O₂
M_r = 365.3
Monoclinic, C 2/c
a = 18.9920 (5) Å
b = 5.8884 (2) Å
c = 17.8813 (5) Å
β = 125.449 (4)°
V = 1629.03 (12) Å³
Z = 4
Cu Kα radiation
μ = 3.70 mm⁻¹
T = 120 K
0.30 × 0.19 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with an Atlas (Gemini ultra Cu) detector
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnto, England.]$ ), using a multifaceted crystal model based on expressions derived by Clark & Reid (1995 )] T_min = 0.593, T_max = 0.787
12716 measured reflections
1442 independent reflections
1344 reflections with I > 3σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.103
S = 2.26
1442 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2B⋯O1ⁱ	0.96	2.56	3.369 (2)	142
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnto, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnto, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SIR2002 (Burla et al., 2003 ); program(s) used to refine structure: JANA2006 (Petříček et al., 2006 ); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: JANA2006.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810014248/fj2292sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810014248/fj2292Isup2.hkl

checkCIF report

Comment top

1,3-Benzoxazines are heterocyclic compound obtained from condensation between phenols, formaldehyde and a primary amine. Applications of these compounds are in polymeric and pharmacological fields. Recently the structure of these compounds has attracted much attention see Huerta et al. (2006); Chen & Wu (2007); Ranjith et al. (2009). During our investigations, a series of bis-benzoxazines were prepared by reaction of phenols, formaldehyde and ethylenediamine (Rivera et al., 1986). However, the crystallization of these compounds was difficult and led to crystals of bad quality. In the present work, the single crystals of the title compound were finally successfully prepared and its crystal structure has been determined herein.

The molecule contains two 1,3-benzoxazine units linked by an ethylene bridge. The asymmetric unit of the title compound C₁₈H₁₈Cl₂N₂O₂, contains one-half of the formula unit; a centre of inversion is located at the mid-point of the central C1—C1ⁱ bond (see Fig. 1). Both oxazine rings are in cyclohexene-like conformations with normal bond distances and angles, and their values were found in good agreement with the corresponding values in the related structures reported by Huerta et al. (2006), Chen & Wu (2007) and Ranjith et al. (2009). In the crystal structure, molecules are linked via C2—H2B···O1 weak hydrogen bonds forming a molecular slab (see Fig 2a,b). The bond involves axial-hydrogen of oxazine ring and the oxygen atom of a neighbor molecule.

There is also possibility for very weak intermolecular interaction between the hydrogen H2A and the aromatic ring C3,C4,C6, C7, C8, C9, with the distance between H2A and the centre of the ring of 2.99 Å.

Related literature top

For the synthesis, see: Rivera et al. (1989). For related structures, see: Rivera et al. (1986); Huerta et al. (2006); Chen & Wu (2007); Ranjith et al. (2009). 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

Under vigorous stirring a mixture of ethylenediamine (0.34 ml, 5 mmol) and p-chlorophenol (1.3 g 10 mmol) was dissolved in dioxane (10 ml) and (1.5 ml, 20 mmol) was slowly added. Stirring was continued for 4 h at rt until a precipitate appeared. The solid was filtered off and washed with water (1.83 g, 92%). Recrystallization from ethanol gave a white solid.

Structure description top

For the synthesis, see: Rivera et al. (1989). For related structures, see: Rivera et al. (1986); Huerta et al. (2006); Chen & Wu (2007); Ranjith et al. (2009). 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).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: JANA2006 (Petříček et al., 2006); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: JANA2006 (Petříček et al., 2006).

Figures top

	Fig. 1. The molecular structure of title compound, showing the atomic numbering scheme with atomic displacement ellipsoids drawn at the 50%.
	Fig. 2. Perspective views of the crystal packing showing hydrogen-bonded interactions (dashed lines).

3,3'-Ethylenebis(3,4-dihydro-6-chloro-2H-1,3-benzoxazine) top

Crystal data top

C₁₈H₁₈Cl₂N₂O₂	F(000) = 760
M_r = 365.3	D_x = 1.489 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -C 2yc	Cell parameters from 10117 reflections
a = 18.9920 (5) Å	θ = 3.0–66.8°
b = 5.8884 (2) Å	µ = 3.70 mm⁻¹
c = 17.8813 (5) Å	T = 120 K
β = 125.449 (4)°	Prism, colorless
V = 1629.03 (12) Å³	0.30 × 0.19 × 0.12 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur diffractometer with an Atlas (Gemini ultra Cu) detector	1442 independent reflections
Radiation source: X-ray tube	1344 reflections with I > 3σ(I)
Mirror monochromator	R_int = 0.024
Detector resolution: 10.3784 pixels mm^-1	θ_max = 75.1°, θ_min = 5.4°
Rotation method data acquisition using ω scans	h = −22→22
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2009), using a multifaceted crystal model based on expressions derived by Clark & Reid (1995)]	k = −7→6
T_min = 0.593, T_max = 0.787	l = −19→20
12716 measured reflections

Refinement top

Refinement on F²	36 constraints
R[F > 3σ(F)] = 0.030	H-atom parameters constrained
wR(F) = 0.103	Weighting scheme based on measured s.u.'s w = 1/[σ²(I) + 0.0016I²]
S = 2.26	(Δ/σ)_max = 0.014
1442 reflections	Δρ_max = 0.25 e Å⁻³
109 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints

Crystal data top

C₁₈H₁₈Cl₂N₂O₂	V = 1629.03 (12) Å³
M_r = 365.3	Z = 4
Monoclinic, C2/c	Cu Kα radiation
a = 18.9920 (5) Å	µ = 3.70 mm⁻¹
b = 5.8884 (2) Å	T = 120 K
c = 17.8813 (5) Å	0.30 × 0.19 × 0.12 mm
β = 125.449 (4)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with an Atlas (Gemini ultra Cu) detector	1442 independent reflections
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2009), using a multifaceted crystal model based on expressions derived by Clark & Reid (1995)]	1344 reflections with I > 3σ(I)
T_min = 0.593, T_max = 0.787	R_int = 0.024
12716 measured reflections

Refinement top

R[F > 3σ(F)] = 0.030	0 restraints
wR(F) = 0.103	H-atom parameters constrained
S = 2.26	Δρ_max = 0.25 e Å⁻³
1442 reflections	Δρ_min = −0.25 e Å⁻³
109 parameters

Special details top

Experimental. CrysAlisPro (Oxford Diffraction Ltd., Version 1.171.33.51 (release 27-10-2009 CrysAlis171 .NET) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by Clark & Reid (1995)

Refinement. The refinement was carried out against all reflections. The conventional R-factor is always based on F. The goodness of fit as well as the weighted R-factor are based on F and F² for refinement carried out on F and F², respectively. The threshold expression is used only for calculating R-factors etc. and it is not relevant to the choice of reflections for refinement.

The program used for refinement, Jana2006, uses the weighting scheme based on the experimental expectations, see _refine_ls_weighting_details, that does not force S to be one. Therefore the values of S are usually larger than the ones from the SHELX program.

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

	x	y	z	U_iso*/U_eq
Cl1	0.60192 (2)	−0.00670 (6)	0.93208 (3)	0.0280 (3)
O1	0.67792 (6)	0.65142 (16)	0.72490 (7)	0.0215 (5)
N1	0.60904 (7)	0.4270 (2)	0.58616 (8)	0.0180 (5)
C1	0.53100 (8)	0.5511 (3)	0.54598 (10)	0.0185 (7)
C2	0.67854 (8)	0.5625 (3)	0.64492 (10)	0.0198 (6)
C3	0.65998 (9)	0.4905 (2)	0.77097 (11)	0.0192 (7)
C4	0.62512 (8)	0.2799 (2)	0.73128 (10)	0.0190 (6)
C5	0.61011 (8)	0.2223 (2)	0.63683 (10)	0.0191 (6)
C6	0.60690 (8)	0.1294 (2)	0.78148 (10)	0.0208 (6)
C7	0.62347 (9)	0.1873 (3)	0.86889 (10)	0.0233 (7)
C8	0.65769 (9)	0.3956 (3)	0.90753 (11)	0.0261 (7)
C9	0.67601 (10)	0.5459 (3)	0.85788 (11)	0.0246 (7)
H1a	0.54087	0.707097	0.539047	0.0222*
H1b	0.509368	0.533303	0.582633	0.0222*
H2a	0.679796	0.688363	0.61157	0.0238*
H2b	0.730991	0.479648	0.668433	0.0238*
H5a	0.65391	0.118579	0.647102	0.023*
H5b	0.556851	0.140341	0.598522	0.023*
H6	0.582529	−0.016899	0.755597	0.0249*
H8	0.668857	0.438584	0.965284	0.0313*
H9	0.700365	0.691858	0.884131	0.0295*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0306 (3)	0.0293 (3)	0.0288 (3)	0.00199 (13)	0.0199 (2)	0.00560 (14)
O1	0.0192 (5)	0.0205 (6)	0.0179 (5)	−0.0041 (4)	0.0068 (4)	−0.0012 (4)
N1	0.0124 (5)	0.0177 (6)	0.0169 (6)	0.0007 (4)	0.0044 (5)	0.0005 (5)
C1	0.0141 (6)	0.0178 (7)	0.0161 (8)	0.0023 (5)	0.0045 (6)	0.0013 (6)
C2	0.0150 (6)	0.0227 (7)	0.0174 (7)	−0.0018 (5)	0.0069 (6)	−0.0001 (6)
C3	0.0137 (6)	0.0193 (8)	0.0183 (8)	0.0015 (4)	0.0057 (6)	0.0018 (5)
C4	0.0131 (6)	0.0203 (7)	0.0172 (7)	0.0028 (5)	0.0052 (5)	0.0006 (5)
C5	0.0162 (6)	0.0173 (7)	0.0176 (7)	0.0010 (5)	0.0062 (5)	0.0011 (5)
C6	0.0146 (6)	0.0193 (7)	0.0231 (8)	0.0016 (5)	0.0079 (6)	0.0007 (6)
C7	0.0194 (6)	0.0251 (8)	0.0248 (8)	0.0042 (5)	0.0125 (6)	0.0053 (6)
C8	0.0267 (7)	0.0282 (8)	0.0210 (8)	0.0026 (6)	0.0125 (6)	−0.0014 (6)
C9	0.0233 (7)	0.0217 (7)	0.0228 (8)	−0.0005 (6)	0.0100 (6)	−0.0023 (6)

Geometric parameters (Å, º) top

Cl1—C7	1.813 (2)	C3—C9	1.437 (3)
O1—C2	1.529 (2)	C4—C5	1.578 (3)
O1—C3	1.421 (2)	C4—C6	1.439 (3)
N1—C1	1.4182 (18)	C5—H5a	0.96
N1—C2	1.3690 (16)	C5—H5b	0.96
N1—C5	1.501 (2)	C6—C7	1.445 (3)
C1—C1ⁱ	1.4853 (18)	C6—H6	0.96
C1—H1a	0.96	C7—C8	1.372 (2)
C1—H1b	0.96	C8—C9	1.432 (3)
C2—H2a	0.96	C8—H8	0.96
C2—H2b	0.96	C9—H9	0.96
C3—C4	1.3907 (19)

C2—O1—C3	116.65 (11)	C3—C4—C6	116.51 (16)
C1—N1—C2	110.35 (12)	C5—C4—C6	125.13 (12)
C1—N1—C5	111.32 (14)	N1—C5—C4	113.84 (12)
C2—N1—C5	109.60 (10)	N1—C5—H5a	109.4703
N1—C1—C1ⁱ	106.07 (13)	N1—C5—H5b	109.4713
N1—C1—H1a	109.4706	C4—C5—H5a	109.4721
N1—C1—H1b	109.4717	C4—C5—H5b	109.4707
C1ⁱ—C1—H1a	109.47	H5a—C5—H5b	104.7188
C1ⁱ—C1—H1b	109.4723	C4—C6—C7	123.28 (13)
H1a—C1—H1b	112.6688	C4—C6—H6	118.3591
O1—C2—N1	112.97 (15)	C7—C6—H6	118.3615
O1—C2—H2a	109.4708	Cl1—C7—C6	122.62 (11)
O1—C2—H2b	109.4711	Cl1—C7—C8	117.49 (15)
N1—C2—H2a	109.471	C6—C7—C8	119.88 (18)
N1—C2—H2b	109.4715	C7—C8—C9	117.04 (18)
H2a—C2—H2b	105.7297	C7—C8—H8	121.4818
O1—C3—C4	120.14 (17)	C9—C8—H8	121.4814
O1—C3—C9	120.27 (12)	C3—C9—C8	123.70 (14)
C4—C3—C9	119.58 (17)	C3—C9—H9	118.1485
C3—C4—C5	118.35 (16)	C8—C9—H9	118.1475

C2—N1—C1—C1ⁱ	150.21 (14)	C9—C3—C4—C6	0.2 (3)
C5—N1—C1—C1ⁱ	−87.87 (15)	O1—C3—C9—C8	178.38 (17)
C3—O1—C2—N1	46.41 (18)	C4—C3—C9—C8	−0.3 (3)
C2—O1—C3—C4	−14.6 (2)	C3—C4—C5—N1	−18.4 (2)
C2—O1—C3—C9	166.66 (16)	C6—C4—C5—N1	162.77 (15)
C1—N1—C2—O1	61.58 (16)	C3—C4—C6—C7	−0.3 (3)
C5—N1—C2—O1	−61.37 (17)	C5—C4—C6—C7	178.57 (16)
C1—N1—C5—C4	−74.43 (16)	C4—C6—C7—Cl1	−178.83 (13)
C2—N1—C5—C4	47.92 (19)	C4—C6—C7—C8	0.5 (3)
N1—C1—C1ⁱ—N1ⁱ	180.00 (13)	Cl1—C7—C8—C9	178.84 (14)
O1—C3—C4—C5	2.6 (2)	C6—C7—C8—C9	−0.5 (3)
O1—C3—C4—C6	−178.46 (15)	C7—C8—C9—C3	0.5 (3)
C9—C3—C4—C5	−178.74 (16)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···O1ⁱⁱ	0.96	2.56	3.369 (2)	142

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

Experimental details

Crystal data
Chemical formula	C₁₈H₁₈Cl₂N₂O₂
M_r	365.3
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	120
a, b, c (Å)	18.9920 (5), 5.8884 (2), 17.8813 (5)
β (°)	125.449 (4)
V (Å³)	1629.03 (12)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	3.70
Crystal size (mm)	0.30 × 0.19 × 0.12

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with an Atlas (Gemini ultra Cu) detector
Absorption correction	Analytical [CrysAlis PRO (Oxford Diffraction, 2009), using a multifaceted crystal model based on expressions derived by Clark & Reid (1995)]
T_min, T_max	0.593, 0.787
No. of measured, independent and observed [I > 3σ(I)] reflections	12716, 1442, 1344
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.627

Refinement
R[F > 3σ(F)], wR(F), S	0.030, 0.103, 2.26
No. of reflections	1442
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.25

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SIR2002 (Burla et al., 2003), JANA2006 (Petříček et al., 2006), DIAMOND (Brandenburg & Putz, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···O1ⁱ	0.96	2.56	3.369 (2)	142

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

Acknowledgements

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

References

Billmann, J. H. & Dorman, L. C. (1963). J. Med. Chem. 6, 701–708. CrossRef PubMed Web of Science Google Scholar
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Burla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Polidori, G. & Spagna, R. (2003). J. Appl. Cryst. 36, 1103. CrossRef IUCr Journals Google Scholar
Chen, X.-L. & Wu, M.-H. (2007). Acta Cryst. E63, o3684. Web of Science CSD CrossRef IUCr Journals Google Scholar
Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897. CrossRef CAS Web of Science IUCr Journals Google Scholar
Heinisch, L., Wittmann, S., Stoiber, T., Berg, A., Ankel-Fuchs, D. & Mollmann, U. (2002). J. Med. Chem. 45, 3032–3039. Web of Science CrossRef PubMed CAS Google Scholar
Huerta, R., Toscano, R. A. & Castillo, I. (2006). Acta Cryst. E62, o2938–o2940. Web of Science CSD CrossRef IUCr Journals Google Scholar
Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnto, England. Google Scholar
Petříček, V., Dušek, M. & Palatinus, L. (2006). JANA2006. Institute of Physics, Praha, Czech Republic. Google Scholar
Ranjith, S., Thenmozhi, S., Manikannan, R., Muthusubramanian, S. & Subbiahpandi, A. (2009). Acta Cryst. E65, o581. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rivera, A., Aguilar, Z., Clavijo, D. & Joseph-Nathan, P. (1989). Anal. Quim. 85, 9–10. CAS Google Scholar
Rivera, A., Ospina, E., Sanchez, A. & Joseph-Nathan, P. (1986). Heterocycles, 24, 2507–2510. CrossRef CAS Google Scholar
Yaggi, Y., Kiskan, B. & Ghosh, N. N. (2009). J. Polym. Sci. Part A Polym. Chem. 47, 5565–5576. Google Scholar