3,3′-(p-Phenyl­ene)bis­(3,4-dihydro-2H-1,3-benzoxazine)

Ranjith, S.; Thenmozhi, S.; Manikannan, R.; Muthusubramanian, S.; Subbiahpandi, A.

doi:10.1107/S1600536809005790

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o581

doi:10.1107/S1600536809005790

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3,3′-(p-Phenylene)bis(3,4-dihydro-2H-1,3-benzoxazine)

Sekaran Ranjith,^a Sundar Thenmozhi,^a Ramaiyan Manikannan,^b Shanmugam Muthusubramanian ^b and Arunachalathevar Subbiahpandi ^a ^*

^aDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India, and ^bDepartment of Organic Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai 625 021, India
^*Correspondence e-mail: a_spandian@yahoo.com

(Received 22 December 2008; accepted 18 February 2009; online 25 February 2009)

Molecules of the title compound, C₂₂H₂₀N₂O₂, are situated on crystallographic centres of symmetry. The oxazinane ring adopts a sofa conformation. Molecules are linked into cyclic centrosymmetric dimers via C—H⋯O hydrogen bonds with the motif R₂²(6). In addition to the C—H⋯O interactions, the crystal structure is also stabilized by C—H⋯π interactions.

Related literature

For related structures, see: Huerta et al. (2006 ). For the biological activity of bis-benzoxazine compounds, see: Billmann & Dorman (1963 ); Heinisch et al. (2002 ). For puckering and asymmetry parameters, see: Cremer & Pople (1975 ); Nardelli (1983 ).

Experimental

Crystal data

C₂₂H₂₀N₂O₂
M_r = 344.40
Monoclinic, P 2₁ /c
a = 9.191 (5) Å
b = 8.794 (4) Å
c = 11.317 (5) Å
β = 113.90 (3)°
V = 836.3 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.21 × 0.19 × 0.16 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.982, T_max = 0.986
13095 measured reflections
3707 independent reflections
2762 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.164
S = 1.02
3707 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O1ⁱ	0.97	2.49	3.3469 (15)	147
C3—H3⋯Cg1ⁱⁱ	0.93	2.72	3.582 (13)	155
C3—H3⋯Cg1ⁱⁱⁱ	0.93	2.72	3.582 (13)	155
Symmetry codes: (i) -x+2, -y+2, -z; (ii) $[-x+1, y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (iii) $[x+1, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ . Cg1 is the centroid of the C9–C11/C9a–C11a ring.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: APEX2; data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809005790/fb2131sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809005790/fb2131Isup2.hkl

checkCIF report

Comment top

Bis-benzoxazine compounds exhibit various biological activities including antibacterial ( i. a. tuberculostatic), antitumor, fungicidal and plant-growth regulative properties (Billmann & Dorman, 1963; Heinisch et al., 2002). Polyoxymethylene (paraformaldehyde) undegoes a bimolecular condensation with N,N-bis-(o-hydroxybenzyl)-ethylenediamine in benzene to form 1,2-bis-[3-(3,4-dihydro-1,3–2H-benzoxazino]-ethane, which shows bacteriostatic and fungistatic activities (Billmann & Dorman, 1963). Taking into consideration these aspects, and in order to obtain a detailed information on the molecular structure in the solid state, the X-ray structure determination of the title compound has been carried out.

The molecules are situated on the crystallographic centres of symmetry and therefore have symmetry 1 (Fig. 1). The bond lengths N1—C7, O1—C5 are normal and comparable to the corresponding values observed in the related structure of 1,4-bis(8-tert-butyl-6-methyl-4H-1,3-benzoxazin-3-yl)benzene (Huerta et al., 2006).

The oxazinane ring of the benzoxazine moiety adopts the sofa conformation, with the puckering parameters q₂ and ϕ (Cremer & Pople, 1975) and the smallest displacement asymmetric parameters, Δ_s (Nardelli et al., 1983) as follows: q₂=0.3657 (11) Å, ϕ=264.71 (17)°, Δ_s(N1)=21.40 (11).

In addition to the van der Waals interactions, the crystal packing is stabilized by C–H···O and C–H···π hydrogen bonds (Tab. 1) as well as by π–π-electron interactions. The atom C8 acts as a donor to the atom O1 of the neighbour molecule. This hydrogen bond is involved in a motif C₁¹(10) forming an infinite chain along b axis. C₁¹(10) projected on the axis b corresponds to the translational period along this axis. Simultaneously a pair of C8–H8A···O1 hydrogen bonds form a cyclic centrosymmetric dimer [R₂²(6)]. The π–π-electron interactions between the rings (C1\C2···C6) at x, y, z and 1-x, -y, -z with the centroid-centroid distances equal to 3.780 (2) Å are observed in the crystal structure.

Related literature top

For related structures, see: Huerta et al. (2006). For the biological activity, see: Billmann & Dorman (1963); Heinisch et al. (2002). For puckering and asymmetry parameters, see: Cremer & Pople (1975); Nardelli (1983). Cg1 is the centroid of the C9–C11/C9a–C11a ring.

Experimental top

A mixture of 2-(4-[(2-hydroxybenzyl)amino]anilinomethyl)benzenol (0.005 mole) and methanal (0.010 mole) was irradiated under microwaves generated by IFB Microwave Oven (Frequency = 2450 MHz ~λ=122 mm; 480 W) for 4 to 6 minutes; the distance from the source to the sample was 15 cm. The progress of the reaction was monitored by a thin layer chromatography. After completion of reaction, ice-cold water (50 ml) was added to the reaction mixture and stirred. The title compound was extracted with chloroform, the combined organic layers were dried over anhydrous sodium sulfate and then the solvent was evaporated. The crude product was recrystallized in ethylacetate at room temperature. The elongated single cystals of the title compound of average length of 2 mm were grown.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title molecule with the atom labelling scheme. The displacement ellipsoids are drawn at the 30% probability level while the H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The crystal structure showing the centrosymmetric hydrogen bond motif R₂²(6). For the sake of clarity, the H atoms not involved in the motif have been omitted. The atoms marked with an asterisk (*) are situated in the position (2-x, 2-y, -z). The dashed lines indicate the hydrogen bonds.

3,3'-(p-Phenylene)bis(3,4-dihydro-2H-1,3-benzoxazine) top

Crystal data top

C₂₂H₂₀N₂O₂	F(000) = 364
M_r = 344.40	D_x = 1.368 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3779 reflections
a = 9.191 (5) Å	θ = 2.4–35.3°
b = 8.794 (4) Å	µ = 0.09 mm⁻¹
c = 11.317 (5) Å	T = 293 K
β = 113.90 (3)°	Block, colourless
V = 836.3 (7) Å³	0.21 × 0.19 × 0.16 mm
Z = 2

Data collection top

Bruker APEXII CCD area-detector diffractometer	3707 independent reflections
Radiation source: fine-focus sealed tube	2762 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 35.3°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→13
T_min = 0.982, T_max = 0.986	k = −14→14
13095 measured reflections	l = −18→16

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)] = 0.050	Hydrogen site location: difference Fourier map
wR(F²) = 0.164	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.092P)² + 0.1065P] where P = (F_o² + 2F_c²)/3
3707 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³
40 constraints

Crystal data top

C₂₂H₂₀N₂O₂	V = 836.3 (7) Å³
M_r = 344.40	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.191 (5) Å	µ = 0.09 mm⁻¹
b = 8.794 (4) Å	T = 293 K
c = 11.317 (5) Å	0.21 × 0.19 × 0.16 mm
β = 113.90 (3)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3707 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2762 reflections with I > 2σ(I)
T_min = 0.982, T_max = 0.986	R_int = 0.021
13095 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.164	H-atom parameters constrained
S = 1.02	Δρ_max = 0.42 e Å⁻³
3707 reflections	Δρ_min = −0.21 e Å⁻³
118 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.

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

	x	y	z	U_iso*/U_eq
C1	0.43532 (12)	0.74937 (13)	−0.05691 (12)	0.0396 (2)
H1	0.4025	0.6810	−0.0100	0.048*
C2	0.32355 (12)	0.81402 (14)	−0.16802 (13)	0.0455 (3)
H2	0.2166	0.7884	−0.1960	0.055*
C3	0.37168 (13)	0.91652 (15)	−0.23690 (12)	0.0450 (3)
H3	0.2968	0.9594	−0.3121	0.054*
C4	0.52981 (13)	0.95635 (13)	−0.19555 (11)	0.0407 (2)
H4	0.5613	1.0267	−0.2418	0.049*
C5	0.64179 (11)	0.89038 (11)	−0.08403 (10)	0.03299 (19)
C6	0.59569 (11)	0.78485 (11)	−0.01425 (10)	0.03196 (19)
C7	0.71934 (12)	0.71327 (13)	0.10586 (11)	0.0380 (2)
H7A	0.7147	0.7601	0.1819	0.046*
H7B	0.6966	0.6058	0.1075	0.046*
C8	0.89981 (12)	0.88699 (12)	0.08050 (12)	0.0395 (2)
H8A	1.0095	0.9023	0.0928	0.047*
H8B	0.8796	0.9520	0.1415	0.047*
C9	0.93646 (9)	0.61784 (10)	0.05017 (9)	0.02906 (18)
C10	0.93371 (10)	0.46677 (11)	0.08570 (9)	0.03247 (19)
H10	0.8888	0.4429	0.1437	0.039*
C11	1.00414 (11)	0.64904 (11)	−0.03736 (10)	0.03289 (19)
H11	1.0076	0.7487	−0.0636	0.039*
N1	0.87985 (9)	0.73251 (10)	0.10900 (8)	0.03406 (18)
O1	0.79736 (9)	0.93289 (9)	−0.04855 (8)	0.0422 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0309 (4)	0.0399 (5)	0.0495 (6)	−0.0034 (4)	0.0178 (4)	−0.0027 (4)
C2	0.0291 (4)	0.0477 (6)	0.0531 (6)	−0.0014 (4)	0.0098 (4)	−0.0076 (5)
C3	0.0367 (5)	0.0511 (6)	0.0380 (5)	0.0088 (4)	0.0058 (4)	−0.0019 (4)
C4	0.0410 (5)	0.0437 (5)	0.0385 (5)	0.0057 (4)	0.0172 (4)	0.0055 (4)
C5	0.0296 (4)	0.0340 (4)	0.0369 (5)	0.0001 (3)	0.0151 (3)	−0.0001 (3)
C6	0.0282 (4)	0.0338 (4)	0.0357 (4)	0.0001 (3)	0.0149 (3)	−0.0011 (3)
C7	0.0336 (4)	0.0450 (5)	0.0392 (5)	0.0028 (4)	0.0188 (4)	0.0064 (4)
C8	0.0331 (4)	0.0361 (5)	0.0458 (6)	−0.0037 (3)	0.0121 (4)	−0.0023 (4)
C9	0.0211 (3)	0.0341 (4)	0.0281 (4)	−0.0013 (3)	0.0059 (3)	0.0035 (3)
C10	0.0287 (4)	0.0372 (4)	0.0319 (4)	−0.0008 (3)	0.0126 (3)	0.0071 (3)
C11	0.0294 (4)	0.0329 (4)	0.0359 (4)	−0.0010 (3)	0.0128 (3)	0.0076 (3)
N1	0.0281 (3)	0.0366 (4)	0.0361 (4)	−0.0003 (3)	0.0115 (3)	0.0012 (3)
O1	0.0308 (3)	0.0426 (4)	0.0526 (5)	−0.0023 (3)	0.0163 (3)	0.0117 (3)

Geometric parameters (Å, º) top

C1—C2	1.3832 (16)	C7—H7A	0.9700
C1—C6	1.3879 (13)	C7—H7B	0.9700
C1—H1	0.9300	C8—N1	1.4252 (13)
C2—C3	1.3767 (18)	C8—O1	1.4381 (14)
C2—H2	0.9300	C8—H8A	0.9700
C3—C4	1.3795 (16)	C8—H8B	0.9700
C3—H3	0.9300	C9—C10	1.3912 (13)
C4—C5	1.3915 (15)	C9—C11	1.3938 (13)
C4—H4	0.9300	C9—N1	1.4183 (12)
C5—O1	1.3713 (11)	C10—C11ⁱ	1.3841 (14)
C5—C6	1.3912 (13)	C10—H10	0.9300
C6—C7	1.5113 (14)	C11—C10ⁱ	1.3841 (14)
C7—N1	1.4709 (12)	C11—H11	0.9300

C2—C1—C6	121.12 (10)	C6—C7—H7B	109.5
C2—C1—H1	119.4	H7A—C7—H7B	108.1
C6—C1—H1	119.4	N1—C8—O1	113.95 (9)
C3—C2—C1	119.55 (10)	N1—C8—H8A	108.8
C3—C2—H2	120.2	O1—C8—H8A	108.8
C1—C2—H2	120.2	N1—C8—H8B	108.8
C2—C3—C4	120.67 (10)	O1—C8—H8B	108.8
C2—C3—H3	119.7	H8A—C8—H8B	107.7
C4—C3—H3	119.7	C10—C9—C11	117.32 (9)
C3—C4—C5	119.50 (10)	C10—C9—N1	119.36 (8)
C3—C4—H4	120.3	C11—C9—N1	123.22 (8)
C5—C4—H4	120.3	C11ⁱ—C10—C9	121.98 (8)
O1—C5—C4	116.89 (9)	C11ⁱ—C10—H10	119.0
O1—C5—C6	122.47 (9)	C9—C10—H10	119.0
C4—C5—C6	120.63 (9)	C10ⁱ—C11—C9	120.70 (8)
C1—C6—C5	118.50 (9)	C10ⁱ—C11—H11	119.7
C1—C6—C7	121.66 (9)	C9—C11—H11	119.7
C5—C6—C7	119.83 (8)	C9—N1—C8	117.79 (8)
N1—C7—C6	110.80 (8)	C9—N1—C7	117.51 (8)
N1—C7—H7A	109.5	C8—N1—C7	108.90 (8)
C6—C7—H7A	109.5	C5—O1—C8	113.39 (8)
N1—C7—H7B	109.5

C6—C1—C2—C3	−0.69 (17)	N1—C9—C10—C11ⁱ	−176.14 (8)
C1—C2—C3—C4	−0.61 (18)	C10—C9—C11—C10ⁱ	−0.28 (14)
C2—C3—C4—C5	0.91 (17)	N1—C9—C11—C10ⁱ	175.99 (8)
C3—C4—C5—O1	179.20 (10)	C10—C9—N1—C8	173.54 (9)
C3—C4—C5—C6	0.07 (16)	C11—C9—N1—C8	−2.67 (13)
C2—C1—C6—C5	1.63 (16)	C10—C9—N1—C7	−53.04 (11)
C2—C1—C6—C7	−179.07 (10)	C11—C9—N1—C7	130.75 (10)
O1—C5—C6—C1	179.60 (9)	O1—C8—N1—C9	71.79 (11)
C4—C5—C6—C1	−1.32 (15)	O1—C8—N1—C7	−65.29 (11)
O1—C5—C6—C7	0.29 (15)	C6—C7—N1—C9	−89.66 (10)
C4—C5—C6—C7	179.37 (9)	C6—C7—N1—C8	47.56 (11)
C1—C6—C7—N1	163.06 (9)	C4—C5—O1—C8	167.11 (9)
C5—C6—C7—N1	−17.65 (13)	C6—C5—O1—C8	−13.78 (14)
C11—C9—C10—C11ⁱ	0.29 (15)	N1—C8—O1—C5	47.26 (12)

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O1ⁱⁱ	0.97	2.49	3.3469 (15)	147
C3—H3···Cg1ⁱⁱⁱ	0.93	2.72	3.582 (13)	155
C3—H3···Cg1^iv	0.93	2.72	3.582 (13)	155

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

Experimental details

Crystal data
Chemical formula	C₂₂H₂₀N₂O₂
M_r	344.40
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.191 (5), 8.794 (4), 11.317 (5)
β (°)	113.90 (3)
V (Å³)	836.3 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.21 × 0.19 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.982, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	13095, 3707, 2762
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.814

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.164, 1.02
No. of reflections	3707
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.21

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O1ⁱ	0.97	2.49	3.3469 (15)	147
C3—H3···Cg1ⁱⁱ	0.93	2.72	3.582 (13)	155
C3—H3···Cg1ⁱⁱⁱ	0.93	2.72	3.582 (13)	155

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

Acknowledgements

SR and ASP thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the X-ray data collection.

References

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