Acta Crystallographica Section E: Crystallographic Communications

Acta Crystallogr E Crystallogr Commun. 72(Pt 10): 1509-1511

Crystal structure and C—H⋯F hydrogen bonding in the fluorinated bis-benzoxazine: 3,3′-(ethane-1,2-diyl)bis(6-fluoro-3,4-dihydro-2H-1,3-benzoxazine)

Augusto Riveraa*, Jicli José Rojasa, Jaime Ríos-Mottaa, Michael Bolteb

a. Universidad Nacional de Colombia, Sede Bogotá, Facultad de Ciencias, Departamento de Química, Cra 30 No. 45-03, Bogotá, Código Postal 111321, Colombia

b. Institut für Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von Laue-Strasse, 7, 60438 Frankfurt/Main, Germany

Correspondence e-mail: ariverau@unal.edu.co

© Rivera et al. 2016

DOI: 10.1107/S2056989016015243

Published online: 30 September 2016

Abstract

The packing of the title benzoxazine derivative features C—H⋯F hydrogen bonds, which form a sheet structure further linked via weak C—H⋯π hydrogen bonds.

Abstract

The title fluorinated bisbenzoxazine, C₁₈H₁₈F₂N₂O₂, crystallizes with one half-molecule in the asymmetric unit, which is completed by inversion symmetry. The fused oxazine ring adopts an approximately half-chair conformation. The two benzoxazine rings are oriented anti to one another around the central C—C bond. The dominant intermolecular interaction in the crystal structure is a C—H⋯F hydrogen bond between the F atoms and the axial H atoms of the OCH₂N methylene group in the oxazine rings of neighbouring molecules. C—H⋯π contacts further stabilize the crystal packing.

Chemical context  

Even though benzoxazines have been known for more than 60 years, a cursory look at the literature cited in relation to the polybenzoxazines in recent years reveals increasing interest in polybenzoxazine chemistry (Demir et al., 2013 ▸). Mannich condensation of a phenol and a primary amine with formaldehyde is perhaps the best synthetic route widely employed for the preparation of a variety of benzoxazine monomers. Mono-functional benzoxazines with one oxazine ring yield linear polymers, while bi- and polyfunctional benzoxazines produce cross-linked polymers. As a result, many kinds of benzoxazine monomers, including both mono-benzoxazines and bis-benzoxazines, have been synthesized. For composite applications, bifunctional benzoxazines are important as they produce fillers with good adhesion properties that in turn give high modulus composite materials (Santhosh-Kumar & Reghunadhan-Nair, 2014 ▸).

Much work in our group has been directed at the synthesis of a wide variety of bis-benzoxazines from ethylendiamine, formaldehyde and phenols in the molar ratio of 1:4:2 using a conventional method and solvent-free conditions (Rivera et al., 1989 ▸). Recently, we have also investigated the crystal structures of several bis-benzoxazines namely 3,3′-(ethane-1,2-diyl)bis(6-substituted-3,4-dihydro-2H-1,3-benzoxazine) derivatives (Rivera et al., 2010 ▸, 2011 ▸, 2012a ▸,b ▸). These were prepared to determine whether replacement of the substituents at the para position of the phenol affects the molecular conformation and possible supramolecular aggregation. In this context, the title compound is a model for studying non-conventional molecular interactions where the halogen atom may act as a hydrogen-bond acceptor. Although debate has surrounded the role of fluorine as a hydrogen-bond (HB) acceptor, the presence of such weak molecular interactions in the solid state has been the subject of both theoretical and spectroscopic studies (Dalvit & Vulpetti, 2016 ▸). However, to the best of our knowledge, there are few examples of X-ray studies. On the other hand, polymers containing fluorinated aromatic systems often exhibit exceptional thermal stability and show good water-repellent properties (Su & Chang, 2003 ▸). Therefore we report herein the crystal structure of 3,3′-(ethane-1,2-diyl)bis(6-fluoro-3,4-dihydro-2H-1,3-benzoxazine) (I), which is a very good candidate as a monomer for the investigation of the polymerization of fluorine-containing bis-benzoxazine monomers.

Structural commentary  

The molecular structure of the title compound is illustrated in Fig. 1 ▸. The asymmetric unit contains one-half of the formula unit; a centre of inversion located at the mid-point of the central C1—C1i bond generates the other half of the bis-benzoxazine compound [symmetry code: (i) 1 − x, 1 − y, 1 − z]. Bond lengths in the benzoxazine moiety in (I) are within normal ranges and are comparable to those found in related structures (Rivera et al., 2012a ▸,b ▸, 2011 ▸; Chen & Wu, 2007 ▸).

The fused six-membered heterocyclic rings exist in an approximately half-chair conformation, characterized by a puckering amplitude Q = 0.4913 (15) Å, and θ = 52.03 (17)° and φ = 98.3 (2)°, with C2 and N1 displaced from the mean plane by −0.299 (2) and 0.331 (1) Å, respectively. The C1—C1A bond is in an axial position with a C5—N1—C1—C1A torsion angle of 75.45 (18)°. The two benzoxazine rings are oriented anti to one another about the central C1—C1A bond, with an N1—C1—C1A—N1A torsion angle of 180.0 (2)°.

Supramolecular features  

The packing of title compound is dominated by C2—H2A⋯F1 hydrogen bonds (Table 1 ▸), that connect the molecules into a sheet structure, Fig. 2 ▸. Symmetry dictates that both F atoms are involved in these hydrogen bonds. The crystal structure also features two weak C—H⋯π interactions (Table 1 ▸), as indicated in PLATON (Spek, 2009 ▸), with C—H⋯Cg distances of 3.527 (2) and 3.577 (2) Å and with C—H⋯Cg angles of 126 and 129°, respectively.

Database survey  

A database search yielded four comparable structures, 3,3′-(ethane-1,2-diyl)bis(6-methyl-3,4-dihydro-2H-1,3-benzoxazine) (AXAKAM; Rivera et al., 2011 ▸), 3,3′-ethylenebis(3,4-dihydro-6-chloro-2H-1,3-benzoxazine) (NUQKAM; Rivera et al., 2010 ▸), 3,3′-(ethane-1,2-diyl)-bis(6-methoxy-3,4-dihydro-2H-1,3-benzoxazine) monohydrate (QEDDOU; Rivera et al., 2012b ▸), and 3,3′-(ethane-1,2-diyl)bis(3,4-dihydro-2H-1,3-benzoxazine) (SAGPUN; Rivera et al., 2012a ▸).

Synthesis and crystallization  

The title compound was synthesized according to the literature procedure (Rivera et al.,1989 ▸), and single crystals were obtained by slow evaporation from an ethyl acetate/benzene 1:3 solvent mixture at room temperature.

Refinement details  

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. All H atoms were located in difference electron-density maps. C-bound H atoms were fixed geometrically (C—H = 0.95 or 0.99 Å) and refined using a riding-model approximation, with U iso(H) set to 1.2U eq of the parent atom.

Figure 1View larger versionFigure 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. Atoms labelled with the suffix A are generated using the symmetry operator (−x + 1, −y + 1, −z + 1).

Figure 2View larger versionFigure 2. Packing diagram for title compound, viewed along the b axis. C—H⋯F and C—F⋯π contacts are drawn as dashed lines.

See full tableTable 1. Hydrogen-bond geometry (Å, °) Cg2 is the centroid of the C3/C4/C6/C7/C8/C9 ring

See full table Table 2. Experimental details

Supplementary Material

Open In Web Browser

Acknowledgments

We acknowledge the Dirección de Investigaciones, Sede Bogotá (DIB) de la Universidad Nacional de Colombia for financial support of this work (research project No. 28427). JJR is also grateful to COLCIENCIAS for his doctoral scholarship.

supplementary crystallographic information

Crystal data

See full table

Data collection

See full table

Refinement

See full table

Special details

See full table

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

See full table

Atomic displacement parameters (Å²)

See full table

Geometric parameters (Å, º)

See full table

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

Cg2 is the centroid of the C3/C4/C6/C7/C8/C9 ring

See full table

Symmetry codes: (ii) −x+2, y−1/2, −z+3/2; (iii) −x+2, y+1/2, −z+3/2; (iv) −x+1, y−1/2, −z+3/2.

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References

Chen, X.-L. & Wu, M.-H. (2007). Acta Cryst. E63, o3684.

Dalvit, C. & Vulpetti, A. (2016). Chem. Eur. J. 22, 7592–7601.

Demir, K. D., Kiskan, B., Aydogan, B. & Yagci, Y. (2013). React. Funct. Polym. 73, 346–359.

Rivera, A., Aguilar, Z., Clavijo, D. & Joseph-Nathan, P. (1989). An. Quim. Ser. C, 85, 9–10

Rivera, A., Camacho, J., Ríos-Motta, J., Fejfarová, K. & Dušek, M. (2012a). Acta Cryst. E68, o148.

Rivera, A., Camacho, J., Ríos-Motta, J., Kučeraková, M. & Dušek, M. (2012b). Acta Cryst. E68, o2734.

Rivera, A., Camacho, J., Ríos-Motta, J., Pojarová, M. & Dušek, M. (2011). Acta Cryst. E67, o2028.

Rivera, A., Rojas, J. J., Ríos-Motta, J., Dušek, M. & Fejfarová, K. (2010). Acta Cryst. E66, o1134.

Santhosh-Kumar, K. S. & Reghunadhan-Nair, C. P. (2014). 3-Polybenzoxazine – new generation phenolics, in Handbook of Thermoset Plastics, 3rd ed., edited by H. Dodiuk & S. H. Goodman, pp. 45–73. Amsterdam: Elsevier Inc.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.

Stoe & Cie (2001). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany.

Su, Y. C. & Chang, F. C. (2003). Polymer, 44, 7989–7996.

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C₁₈H₁₈F₂N₂O₂ | F(000) = 348
Mr = 332.34 | Dx = 1.470 Mg m⁻³
Monoclinic, P2₁/c | Mo Kα radiation, λ = 0.71073 Å
a = 7.0242 (6) Å | Cell parameters from 7746 reflections
b = 6.2316 (6) Å | θ = 3.5–27.8°
c = 17.1574 (15) Å | µ = 0.11 mm⁻¹
β = 91.473 (7)° | T = 173 K
V = 750.77 (12) Å³ | Plate, colourless
Z = 2 | 0.17 × 0.13 × 0.04 mm

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Stoe IPDS II two-circle diffractometer | 1285 reflections with I > 2σ(I)
Radiation source: Genix 3D IµS microfocus X-ray source | Rint = 0.036
ω scans | θmax = 26.4°, θmin = 3.5°
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001) | h = −8→8
Tmin = 0.362, Tmax = 1.000 | k = −7→7
7746 measured reflections | l = −20→21
1532 independent reflections |

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Refinement on F² | 0 restraints
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041 | H-atom parameters constrained
wR(F²) = 0.101 | w = 1/[σ²(Fo²) + (0.0538P)² + 0.1464P] where P = (Fo² + 2Fc²)/3
S = 1.08 | (Δ/σ)max < 0.001
1532 reflections | Δρmax = 0.18 e Å⁻³
109 parameters | Δρmin = −0.16 e Å⁻³

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Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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| x | y | z | Uiso*/Ueq |
F1 | 0.80087 (14) | 0.60837 (18) | 0.86796 (5) | 0.0408 (3) |
O1 | 0.69940 (16) | 0.06550 (17) | 0.61834 (6) | 0.0293 (3) |
N1 | 0.73058 (17) | 0.3605 (2) | 0.52754 (7) | 0.0256 (3) |
C1 | 0.5232 (2) | 0.3961 (2) | 0.52148 (8) | 0.0260 (3) |
H1A | 0.4706 | 0.4020 | 0.5744 | 0.031* |
H1B | 0.4624 | 0.2743 | 0.4934 | 0.031* |
C2 | 0.7756 (2) | 0.1410 (3) | 0.54504 (9) | 0.0294 (4) |
H2A | 0.9158 | 0.1242 | 0.5471 | 0.035* |
H2B | 0.7249 | 0.0493 | 0.5022 | 0.035* |
C3 | 0.72790 (19) | 0.2069 (2) | 0.67944 (8) | 0.0237 (3) |
C4 | 0.79289 (19) | 0.4168 (2) | 0.66810 (8) | 0.0228 (3) |
C5 | 0.8283 (2) | 0.4965 (3) | 0.58624 (8) | 0.0267 (3) |
H5A | 0.7820 | 0.6459 | 0.5809 | 0.032* |
H5B | 0.9668 | 0.4961 | 0.5770 | 0.032* |
C6 | 0.81932 (19) | 0.5507 (3) | 0.73252 (8) | 0.0250 (3) |
H6 | 0.8647 | 0.6931 | 0.7263 | 0.030* |
C7 | 0.7786 (2) | 0.4732 (3) | 0.80519 (8) | 0.0273 (3) |
C8 | 0.7114 (2) | 0.2675 (3) | 0.81752 (9) | 0.0293 (4) |
H8 | 0.6837 | 0.2193 | 0.8685 | 0.035* |
C9 | 0.6854 (2) | 0.1337 (3) | 0.75374 (9) | 0.0269 (3) |
H9 | 0.6386 | −0.0079 | 0.7606 | 0.032* |

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| U ¹¹ | U ²² | U ³³ | U ¹² | U ¹³ | U ²³
F1 | 0.0442 (6) | 0.0526 (7) | 0.0255 (5) | −0.0053 (5) | 0.0007 (4) | −0.0122 (4)
O1 | 0.0393 (6) | 0.0227 (6) | 0.0258 (6) | −0.0001 (4) | 0.0008 (4) | −0.0013 (4)
N1 | 0.0251 (6) | 0.0299 (7) | 0.0217 (6) | 0.0008 (5) | 0.0008 (4) | 0.0007 (5)
C1 | 0.0248 (7) | 0.0289 (8) | 0.0243 (7) | −0.0015 (6) | 0.0006 (5) | 0.0018 (6)
C2 | 0.0338 (8) | 0.0310 (8) | 0.0233 (7) | 0.0046 (6) | 0.0025 (6) | −0.0032 (6)
C3 | 0.0227 (7) | 0.0253 (8) | 0.0231 (7) | 0.0034 (6) | −0.0003 (5) | 0.0000 (6)
C4 | 0.0202 (6) | 0.0264 (8) | 0.0220 (7) | 0.0014 (5) | 0.0008 (5) | 0.0018 (6)
C5 | 0.0273 (7) | 0.0296 (8) | 0.0232 (7) | −0.0033 (6) | 0.0000 (5) | 0.0032 (6)
C6 | 0.0210 (6) | 0.0269 (8) | 0.0271 (7) | −0.0004 (5) | 0.0000 (5) | 0.0003 (6)
C7 | 0.0245 (7) | 0.0351 (9) | 0.0223 (7) | 0.0020 (6) | −0.0019 (5) | −0.0057 (6)
C8 | 0.0262 (7) | 0.0399 (9) | 0.0218 (7) | 0.0026 (6) | 0.0036 (6) | 0.0059 (7)
C9 | 0.0252 (7) | 0.0269 (8) | 0.0287 (8) | 0.0014 (6) | 0.0024 (6) | 0.0060 (6)

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F1—C7 | 1.3731 (17) | C3—C4 | 1.401 (2)
O1—C3 | 1.3803 (18) | C4—C6 | 1.393 (2)
O1—C2 | 1.4574 (18) | C4—C5 | 1.5161 (19)
N1—C2 | 1.434 (2) | C5—H5A | 0.9900
N1—C5 | 1.4721 (19) | C5—H5B | 0.9900
N1—C1 | 1.4746 (18) | C6—C7 | 1.374 (2)
C1—C1i | 1.522 (3) | C6—H6 | 0.9500
C1—H1A | 0.9900 | C7—C8 | 1.384 (2)
C1—H1B | 0.9900 | C8—C9 | 1.384 (2)
C2—H2A | 0.9900 | C8—H8 | 0.9500
C2—H2B | 0.9900 | C9—H9 | 0.9500
C3—C9 | 1.393 (2) |  |
C3—O1—C2 | 113.57 (12) | C6—C4—C5 | 121.16 (14)
C2—N1—C5 | 108.03 (12) | C3—C4—C5 | 119.75 (13)
C2—N1—C1 | 111.72 (12) | N1—C5—C4 | 111.15 (12)
C5—N1—C1 | 113.84 (12) | N1—C5—H5A | 109.4
N1—C1—C1i | 111.15 (14) | C4—C5—H5A | 109.4
N1—C1—H1A | 109.4 | N1—C5—H5B | 109.4
C1i—C1—H1A | 109.4 | C4—C5—H5B | 109.4
N1—C1—H1B | 109.4 | H5A—C5—H5B | 108.0
C1i—C1—H1B | 109.4 | C7—C6—C4 | 118.88 (15)
H1A—C1—H1B | 108.0 | C7—C6—H6 | 120.6
N1—C2—O1 | 113.88 (12) | C4—C6—H6 | 120.6
N1—C2—H2A | 108.8 | F1—C7—C6 | 118.28 (15)
O1—C2—H2A | 108.8 | F1—C7—C8 | 118.74 (13)
N1—C2—H2B | 108.8 | C6—C7—C8 | 122.95 (14)
O1—C2—H2B | 108.8 | C7—C8—C9 | 118.40 (13)
H2A—C2—H2B | 107.7 | C7—C8—H8 | 120.8
O1—C3—C9 | 117.09 (14) | C9—C8—H8 | 120.8
O1—C3—C4 | 122.16 (13) | C8—C9—C3 | 119.93 (15)
C9—C3—C4 | 120.75 (14) | C8—C9—H9 | 120.0
C6—C4—C3 | 119.07 (13) | C3—C9—H9 | 120.0
C2—N1—C1—C1i | −161.85 (15) | C1—N1—C5—C4 | 75.31 (15)
C5—N1—C1—C1i | 75.45 (18) | C6—C4—C5—N1 | −160.16 (12)
C5—N1—C2—O1 | 65.92 (15) | C3—C4—C5—N1 | 18.20 (18)
C1—N1—C2—O1 | −60.03 (16) | C3—C4—C6—C7 | −0.8 (2)
C3—O1—C2—N1 | −45.71 (17) | C5—C4—C6—C7 | 177.62 (13)
C2—O1—C3—C9 | −170.60 (12) | C4—C6—C7—F1 | −178.47 (12)
C2—O1—C3—C4 | 10.67 (19) | C4—C6—C7—C8 | −0.3 (2)
O1—C3—C4—C6 | −179.71 (12) | F1—C7—C8—C9 | 178.65 (13)
C9—C3—C4—C6 | 1.6 (2) | C6—C7—C8—C9 | 0.5 (2)
O1—C3—C4—C5 | 1.9 (2) | C7—C8—C9—C3 | 0.4 (2)
C9—C3—C4—C5 | −176.79 (13) | O1—C3—C9—C8 | 179.82 (13)
C2—N1—C5—C4 | −49.39 (15) | C4—C3—C9—C8 | −1.4 (2)

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D—H···A | D—H | H···A | D···A | D—H···A
C2—H2A···F1ii | 0.99 | 2.44 | 3.300 (2) | 145
C6—H6···Cg2iii | 0.95 | 2.88 | 3.527 (2) | 126
C9—H9···Cg2iv | 0.95 | 2.90 | 3.577 (2) | 129

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Figure 1.

The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. Atoms labelled with the suffix A are generated using the symmetry operator (−x + 1, −y + 1, −z + 1).

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Figure 2.

Packing diagram for title compound, viewed along the b axis. C—H⋯F and C—F⋯π contacts are drawn as dashed lines.

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Table 1. Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C3/C4/C6/C7/C8/C9 ring

D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A
C2—H2A⋯F1i | 0.99 | 2.44 | 3.300 (2) | 145
C6—H6⋯Cg2ii | 0.95 | 2.88 | 3.527 (2) | 126
C9—H9⋯Cg2iii | 0.95 | 2.90 | 3.577 (2) | 129

Symmetry codes: (i) ; (ii) ; (iii) .

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Table 2. Experimental details

Crystal data
Chemical formula | C₁₈H₁₈F₂N₂O₂
M r | 332.34
Crystal system, space group | Monoclinic, P2₁/c
Temperature (K) | 173
a, b, c (Å) | 7.0242 (6), 6.2316 (6), 17.1574 (15)
β (°) | 91.473 (7)
V (Å³) | 750.77 (12)
Z | 2
Radiation type | Mo Kα
μ (mm⁻¹) | 0.11
Crystal size (mm) | 0.17 × 0.13 × 0.04
Data collection
Diffractometer | Stoe IPDS II two-circle
Absorption correction | Multi-scan (X-AREA; Stoe & Cie, 2001 ▸)
T min, T max | 0.362, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections | 7746, 1532, 1285
R int | 0.036
(sin θ/λ)max (Å⁻¹) | 0.625
Refinement
R[F ² > 2σ(F ²)], wR(F ²), S | 0.041, 0.101, 1.08
No. of reflections | 1532
No. of parameters | 109
H-atom treatment | H-atom parameters constrained
Δρmax, Δρmin (e Å⁻³) | 0.18, −0.16

Computer programs: X-AREA (Stoe & Cie, 2001 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸) and XP in SHELXTL-Plus (Sheldrick, 2008 ▸).

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