1,4-Phenyl­ene diallyl bis­(carbonate)

López-Velázquez, D.; Núñez-Méndez, I.; Bernès, S.; Martínez-de la Luz, I.; Pérez-Cruz, M.A.

doi:10.1107/S2414314623001335

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 8| Part 2| February 2023| x230133

https://doi.org/10.1107/S2414314623001335

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1,4-Phenylene diallyl bis(carbonate)

Delia López-Velázquez,^a Irma Núñez-Méndez,^b Sylvain Bernès,^c ^* Isabel Martínez-de la Luz ^b and María Ana Pérez-Cruz ^a

^aFacultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Pue., Mexico, ^bDoctorado en Ciencias Químicas, Facultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Pue., Mexico, and ^cInstituto de Física, Benemérita Universidad Autónoma de Puebla, Av. San Claudio y 18 Sur, 72570 Puebla, Pue., Mexico
^*Correspondence e-mail: sylvain_bernes@hotmail.com

Edited by R. J. Butcher, Howard University, USA (Received 13 December 2022; accepted 13 February 2023; online 21 February 2023)

The title molecule, C₁₄H₁₄O₆, is based on a benzene core di-substituted by allyl carbonate groups in the para positions. The molecule is placed on an inversion centre, and the substituents are twisted with respect to the central benzene ring plane. The crystal structure does not include significant intermolecular interactions other than weak C—H⋯O contacts between CH groups in the benzene ring and carbonate O atoms.

Keywords: crystal structure; carbonate; allyl group; monomer.

CCDC reference: 2241801

Structure description

Allylic compounds are common reagents in organic chemistry for obtaining new allyl derivatives and polymeric materials (e.g. Nair et al., 2010 ). Within this class of compounds, functional allyl aromatic carbonates (Flores Ahuactzin et al., 2009 ) are also suitable building blocks to produce diallyl carbonate compounds (López et al., 1997 ), as well as reactive homopolycarbonates or copolymers, obtained by free radical polymerization. Concerning diallyl carbonates, they can be used as cross-linking agents (Nair et al., 2010; López & Burillo, 1991 ), and they can also be polymerized to homopolymers or copolymers, such as poly[allyl(p-allylcarbonate)benzoate] (López-V et al., 2011 ) or poly[1-benzoate-2,3-diallylcarbonate glycerol] (López et al., 1997).

The reaction between allyl chloroformate (ACF) and a diol affords mono allyl carbonate and diallyl carbonate derivatives. The reaction of ACF with hydroquinone gives allyl-4-hydroxyphenyl carbonate (Flores et al., 2009) and 1,4-phenylene diallyl bis(carbonate). Herein, we report the structure of the latter. The title compound represents the first instance of a 1,4-phenylene bis(carbonate) derivative to be characterized by X-ray diffraction.

The molecule lies on an inversion centre in space group P2₁/n, with the symmetry element coinciding with the centre of the benzene ring (Fig. 1). This ring is disubstituted in the para positions by allyl carbonate groups, which are not coplanar with the ring: the dihedral angle between the mean plane of the benzene and the plane of the carbonate group O4/C5/O6/O7 is 68.69 (4)°, and the dihedral angle between the carbonate group and the allyl group C8/C9/C10 is 51.1 (2)°. This twisted conformation was previously observed for the four reported X-ray structures bearing a benzene ring substituted by an allyl carbonate group (Flores Ahuactzin et al., 2009; Herrera-González et al., 2009 ; Li et al., 2019 ; Schmid et al., 2019 ). This conformation does not promote strong intermolecular contacts in the crystal structure, as hydrogen bonds or π–π interactions. The benzene H atoms are, however, engaged in C—H⋯O contacts with neighbouring molecules. The C1—H1 group makes an almost linear contact with the carbonate O atom O7 (Table 1, entry 1; Fig. 2), while C2—H2 interacts with the carbonyl O atom O6, forming centrosymmetric R₂²(14) ring motifs in the crystal (Table 1, entry 2; Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O7ⁱ	0.93	2.59	3.5100 (16)	169
C2—H2⋯O6ⁱⁱ	0.93	2.57	3.4555 (16)	160
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) .

Figure 1
Molecular structure of the title compound. Non-H atoms are drawn at the 30% probability level. Non-labelled atoms are generated by the symmetry operation 1 − x, 1 − y, −z. The inset is the raw material as obtained from the synthesis. The edges of the hexagonal flake have dimensions of ca 5 mm.

Figure 2
Part of the crystal structure based on C1—H1⋯O7 interactions (Table 1

, entry 1). The asymmetric unit is coloured in grey, while orange, green and magenta moieties are generated by inversion, 2₁ axis and n glide plane, respectively.

Figure 3
Part of the crystal structure based on C2—H2⋯O6 interactions (Table 1

, entry 2). Grey fragments are generated from the asymmetric unit by lattice translations, and orange fragments are generated by inversion.

Synthesis and crystallization

To a three-neck round-bottom flask connected to an addition funnel, hydroquinone (2.28 g, 20.7 mmol) was added and dissolved in 20 ml of THF under an argon atmosphere. After continuous agitation, a homogeneous phase was observed in the reaction flask, and NaHCO₃ (0.86 g, 10.3 mmol), previously dissolved in 5 ml of distilled water, was added. Then, the reaction flask was placed in an ice bath and allyl chloroformate (1.09 ml, 10.3 mmol) was slowly added dropwise, maintaining the agitation. After complete addition, the reaction was left for 5–10 minutes at 273 K, and then at room temperature for 2 h. After completion of the reaction, the products were extracted in a separation funnel using CH₂Cl₂, and dried over anhydrous Na₂SO₄. The reaction mixture was filtered and concentrated. The resulting concentrated solution was precipitated into hexane. The precipitate was collected, washed with hexane, and dried in vacuo (yield: 1.152 g, 20%). Transparent prismatic single crystals were recovered from this material for X-ray study (see Fig. 1, inset). ¹H NMR (500 MHz, CDCl₃), δ (p.p.m.): 4.75 (d, J = 5.0 Hz, 4H), 5.34 (d, J = 10.0 Hz, 2H), 5.44 (dd, J = 17.5, 1.5 Hz, 2H), 5.90 (m, 2H), 7.21 (s, 4H); ¹³C NMR (125 MHz, CDCl₃), δ (p.p.m.): 69.3 (–CH₂–), 119.7 (=CH₂), 122.0 (benzene), 131.1 (=CH), 148.6 (benzene), 154.3 (C=O); FTIR (ATR, ν, cm⁻¹): 3082 (Csp²—H), 2960 (Csp³—H), 1757 (C=O), 1649 (C=C, allyl), 1602 (C=C, aromatic), 770 (aromatic ring), 730 (Csp³—H).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₄O₆
M_r	278.25
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	253
a, b, c (Å)	10.2808 (13), 5.4764 (6), 12.7396 (15)
β (°)	104.070 (9)
V (Å³)	695.74 (14)
Z	2
Radiation type	Ag Kα, λ = 0.56083 Å
μ (mm⁻¹)	0.06
Crystal size (mm)	0.60 × 0.50 × 0.50

Data collection
Diffractometer	Stoe Stadivari
Absorption correction	Multi-scan (X-AREA; Stoe & Cie, 2018 )
T_min, T_max	0.536, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	16744, 1620, 1305
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.653

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.102, 1.04
No. of reflections	1620
No. of parameters	98
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.15
Computer programs: X-AREA (Stoe & Cie, 2018), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), XP in SHELXTL-Plus (Sheldrick, 2008 ), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2241801

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314623001335/bv4045sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314623001335/bv4045Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314623001335/bv4045Isup3.cml

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2018); cell refinement: X-AREA (Stoe & Cie, 2018); data reduction: X-AREA (Stoe & Cie, 2018); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008) and Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).

1,4-Phenylene diallyl bis(carbonate) top

Crystal data top

C₁₄H₁₄O₆	F(000) = 292
M_r = 278.25	D_x = 1.328 Mg m⁻³
Monoclinic, P2₁/n	Ag Kα radiation, λ = 0.56083 Å
a = 10.2808 (13) Å	Cell parameters from 19549 reflections
b = 5.4764 (6) Å	θ = 2.3–31.6°
c = 12.7396 (15) Å	µ = 0.06 mm⁻¹
β = 104.070 (9)°	T = 253 K
V = 695.74 (14) Å³	Prism, colourless
Z = 2	0.60 × 0.50 × 0.50 mm

Data collection top

Stoe Stadivari diffractometer	1620 independent reflections
Radiation source: Sealed X-ray tube, Axo Astix-f Microfocus source	1305 reflections with I > 2σ(I)
Graded multilayer mirror monochromator	R_int = 0.029
Detector resolution: 5.81 pixels mm^-1	θ_max = 21.5°, θ_min = 2.3°
ω scans	h = −13→13
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2018)	k = −7→7
T_min = 0.536, T_max = 1.000	l = −16→16
16744 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0441P)² + 0.1879P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
1620 reflections	Δρ_max = 0.18 e Å⁻³
98 parameters	Δρ_min = −0.15 e Å⁻³
0 restraints	Extinction correction: SHELXL-2018/3 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.023 (6)
Primary atom site location: dual

Special details top

Refinement. Allyl H atoms (H10a and H10b) were refined with free coordinates, and other H atoms were placed on calculated positions. All H atoms were refined with isotropic displacements, calculated as U_iso(H) = 1.2×U_eq(carrier C atom).

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

	x	y	z	U_iso*/U_eq
C1	0.41290 (13)	0.3086 (2)	−0.03895 (10)	0.0404 (3)
H1	0.354051	0.182011	−0.066169	0.049*
C2	0.47808 (13)	0.3163 (2)	0.06961 (10)	0.0401 (3)
H2	0.464542	0.194551	0.116732	0.048*
C3	0.56326 (12)	0.5078 (2)	0.10622 (9)	0.0365 (3)
O4	0.63189 (9)	0.50484 (17)	0.21618 (7)	0.0450 (3)
C5	0.59396 (12)	0.6762 (2)	0.27902 (9)	0.0366 (3)
O6	0.51476 (10)	0.83464 (18)	0.24966 (7)	0.0498 (3)
O7	0.66007 (9)	0.63120 (18)	0.37984 (6)	0.0440 (3)
C8	0.62690 (13)	0.7968 (3)	0.45975 (10)	0.0444 (3)
H8A	0.532199	0.785459	0.457866	0.053*
H8B	0.646954	0.964013	0.444160	0.053*
C9	0.70837 (14)	0.7236 (3)	0.56723 (10)	0.0476 (3)
H9	0.799945	0.700847	0.575414	0.057*
C10	0.6593 (2)	0.6888 (3)	0.65149 (13)	0.0630 (4)
H10A	0.7141 (18)	0.644 (4)	0.7198 (16)	0.076*
H10B	0.5653 (19)	0.700 (4)	0.6461 (14)	0.076*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0448 (6)	0.0346 (6)	0.0399 (7)	−0.0038 (5)	0.0063 (5)	−0.0041 (5)
C2	0.0516 (7)	0.0331 (6)	0.0356 (6)	0.0008 (5)	0.0109 (5)	0.0029 (5)
C3	0.0409 (6)	0.0367 (6)	0.0290 (6)	0.0076 (5)	0.0031 (4)	−0.0027 (5)
O4	0.0532 (5)	0.0449 (5)	0.0309 (4)	0.0150 (4)	−0.0012 (4)	−0.0038 (4)
C5	0.0368 (6)	0.0387 (6)	0.0320 (6)	0.0025 (5)	0.0040 (4)	0.0004 (5)
O6	0.0567 (6)	0.0520 (6)	0.0366 (5)	0.0203 (4)	0.0035 (4)	0.0010 (4)
O7	0.0472 (5)	0.0508 (5)	0.0291 (4)	0.0135 (4)	0.0000 (3)	−0.0038 (4)
C8	0.0470 (7)	0.0497 (7)	0.0343 (6)	0.0064 (6)	0.0057 (5)	−0.0070 (5)
C9	0.0469 (7)	0.0544 (8)	0.0371 (7)	0.0016 (6)	0.0019 (5)	−0.0077 (6)
C10	0.0770 (11)	0.0669 (10)	0.0434 (8)	0.0006 (9)	0.0112 (7)	0.0051 (7)

Geometric parameters (Å, º) top

C1—C3ⁱ	1.3811 (17)	O7—C8	1.4640 (15)
C1—C2	1.3830 (17)	C8—C9	1.4763 (17)
C1—H1	0.9300	C8—H8A	0.9700
C2—C3	1.3733 (18)	C8—H8B	0.9700
C2—H2	0.9300	C9—C10	1.306 (2)
C3—O4	1.4071 (14)	C9—H9	0.9300
O4—C5	1.3513 (14)	C10—H10A	0.947 (19)
C5—O6	1.1863 (14)	C10—H10B	0.954 (18)
C5—O7	1.3221 (14)

C3ⁱ—C1—C2	118.84 (11)	C5—O7—C8	114.10 (9)
C3ⁱ—C1—H1	120.6	O7—C8—C9	107.53 (10)
C2—C1—H1	120.6	O7—C8—H8A	110.2
C3—C2—C1	118.48 (11)	C9—C8—H8A	110.2
C3—C2—H2	120.8	O7—C8—H8B	110.2
C1—C2—H2	120.8	C9—C8—H8B	110.2
C2—C3—C1ⁱ	122.68 (11)	H8A—C8—H8B	108.5
C2—C3—O4	116.95 (11)	C10—C9—C8	123.81 (14)
C1ⁱ—C3—O4	120.30 (11)	C10—C9—H9	118.1
C5—O4—C3	115.77 (9)	C8—C9—H9	118.1
O6—C5—O7	126.45 (11)	C9—C10—H10A	122.1 (12)
O6—C5—O4	126.58 (11)	C9—C10—H10B	121.3 (11)
O7—C5—O4	106.96 (9)	H10A—C10—H10B	116.6 (16)

C3ⁱ—C1—C2—C3	0.5 (2)	C3—O4—C5—O7	174.50 (10)
C1—C2—C3—C1ⁱ	−0.5 (2)	O6—C5—O7—C8	0.88 (19)
C1—C2—C3—O4	−177.58 (11)	O4—C5—O7—C8	−177.99 (10)
C2—C3—O4—C5	−110.62 (12)	C5—O7—C8—C9	−179.91 (11)
C1ⁱ—C3—O4—C5	72.25 (15)	O7—C8—C9—C10	−130.59 (16)
C3—O4—C5—O6	−4.37 (19)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O7ⁱⁱ	0.93	2.59	3.5100 (16)	169
C2—H2···O6ⁱⁱⁱ	0.93	2.57	3.4555 (16)	160

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

Funding information

Funding for this research was provided by: Consejo Nacional de Ciencia y Tecnología (grant No. 268178; scholarship No. 820488 to I. Martínez-de la Luz; scholarship No. 1003328 to I. Núñez-Méndez); Secretaría de Educación Pública (award No. PROFOCIE 2018-20).

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