Bis(4-hy­droxy­phen­yl) 1,4-phenyl­enebiscarbamate

Martínez-de la Luz, I.; López-Velázquez, D.; Bernès, S.; Varela Caselis, J.L.

doi:10.1107/S2414314622009191

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 7| Part 9| September 2022| x220919

https://doi.org/10.1107/S2414314622009191

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Bis(4-hydroxyphenyl) 1,4-phenylenebiscarbamate

Isabel Martínez-de la Luz,^a Delia López-Velázquez,^a Sylvain Bernès ^b ^* and Jenaro L. Varela Caselis ^c

^aFacultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Mexico, ^bInstituto de Física, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Mexico, and ^cCentro Universitario de Vinculación, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Pue., Mexico
^*Correspondence e-mail: sylvain_bernes@hotmail.com

Edited by E. R. T. Tiekink, Sunway University, Malaysia (Received 14 September 2022; accepted 15 September 2022; online 27 September 2022)

The title compound, C₂₀H₁₆N₂O₆ (systematic name: 4-hydroxyphenyl N-{4-[(4-hydroxyphenoxycarbonyl)amino]phenyl}carbamate), contains two urethane groups substituting the central benzene ring in para positions. The molecule is centrosymmetric, and displays a twisted conformation for the three aromatic rings [the dihedral angle between central benzene ring and the urethane group is 33.4 (6)°, and that between the latter and the terminal ring is 65.1 (1)°]. In the crystal, a three-dimensional framework is formed through O—H⋯O and N—H⋯O hydrogen bonds involving the hydroxy and urethane functional groups, respectively.

Keywords: crystal structure; urethane; hydrogen bond; centrosymmetric monomer.

CCDC reference: 2207709

Structure description

The title compound was obtained by reacting hydroquinone, 1,4-phenylene diisocyanate and triethylamine in dioxane. The resulting bis-urethane derivative crystallizes in the centrosymmetric space group P2₁/c, with the molecule having crystallographic inversion symmetry (Fig. 1). The urethane group displays the expected nearly planar geometry. This functional group is well represented in the CSD: 5700 hits are retrieved for organic compounds including an acyclic C—NH—(COO)—C fragment (CSD v. 5.43 with two updates, Groom et al., 2016 ). However, most of these urethane derivatives originate from boc-protected amines, using the tert-butoxycarbonyl (boc) protecting group. In contrast, benzene rings substituted by two urethane groups are less studied by X-ray diffraction. For para-substituted benzene, only five structures have been deposited to date in the CSD. These occurrences include dimethyl 1,4-phenylenebiscarbamate (Stapf et al., 2015 ), intended for anion complexation, and a dicholesterol derivative (Alegre-Requena et al., 2020 ), intended for the preparation of supramolecular gels.

Figure 1
Molecular structure of the title compound, with displacement ellipsoids shown at the 50% probability level. Non-labelled atoms are generated by symmetry operation 1 − x, −y, 1 − z.

As for dimethyl 1,4-phenylenebiscarbamate, the title molecule is not planar. The dihedral angle between the central benzene ring and the urethane group is 33.4 (6)°, hindering the formation of an intramolecular hydrogen bond C3—H3A⋯O6, although this could potentially stabilize the molecule through the formation of an S(6) ring motif. The peripheral hydroxybenzene group is also rotated with respect to the urethane group, forming a dihedral angle of 65.1 (1)°.

This twisted molecular conformation helps in the formation of two kinds of hydrogen bonds, leading to a three-dimensional supramolecular architecture. First, hydroxy groups behave both as donor and acceptor, linking molecules through O—H⋯O hydrogen bonds. The resulting two-dimensional structure is nearly parallel to the (102) plane in the crystal (Table 1, entry 1; Fig. 2). These layers are further interconnected by urethane N—H⋯O hydrogen bonds oriented nearly perpendicular to the layers (Table 1, entry 2; Fig. 3). The three-dimensional framework is thermodynamically stable, although no intermolecular π–π interactions are present in the crystal.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O14—H14⋯O14ⁱ	0.85 (4)	1.91 (5)	2.754 (2)	172 (4)
N4—H4⋯O6ⁱⁱ	0.84 (3)	2.13 (4)	2.945 (3)	163 (3)
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
Supramolecular layers formed by O—H⋯O hydrogen bonds (see entry 1 in Table 1

). Hydrogen bonds are shown as purple dashed lines, and the projection is nearly normal to [001]. Note the hanging contacts (orange dashed lines), corresponding to the hydrogen bonds described in Fig. 3

. Benzene-H atoms are omitted for clarity.

Figure 3
The two-dimensional supramolecular motif formed by N—H⋯O hydrogen bonds (see entry 2 in Table 1

). Two neighbouring molecules are related by the glide plane of space group P2₁/c. The projection is nearly normal to [010]. Benzene-H atoms are omitted for clarity.

The synthesized molecule is a potential useful intermediate for obtaining other monomers, or cross-linking agents (Kothandaraman & Sultan Nasar, 1995 ; Lamba et al., 1998 ): such diols are used for polycondensation reactions affording polymeric materials. On the other hand, some classes of urethane derivatives show diverse biological activity and have been used as fungicides, bactericides or analgesics, among other applications (Lamba et al., 1998; Yagci et al., 2011 ; Wang et al., 2022 ).

Synthesis and crystallization

The synthesis was performed in a 100 ml three-mouth flask, sealed with silicone grease and evacuated with argon. In 5 ml of dry dioxane, hydroquinone (0.316 g), triethylamine (0.207 ml) and 1,4-phenylene diisocyanate (0.222 g) were added. The reaction was carried out at 353–363 K, under constant stirring. After a few minutes, it was observed that the reaction medium turned white. After 6 h, the reaction product was purified by column chromatography, using ethyl acetate:hexane (60:40) as the eluant. Once the purified monomer was obtained, it was dried in a furnace at 313 K for 24 h. Single crystals were obtained by evaporation of a saturated solution of the compound in an ethanol/dichloromethane mixture (4:1, v:v).

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₂₀H₁₆N₂O₆
M_r	380.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	19.0804 (17), 4.6758 (3), 10.1189 (8)
β (°)	101.169 (7)
V (Å³)	885.67 (12)
Z	2
Radiation type	Ag Kα, λ = 0.56083 Å
μ (mm⁻¹)	0.07
Crystal size (mm)	0.26 × 0.20 × 0.03

Data collection
Diffractometer	Stoe Stadivari
Absorption correction	Multi-scan (X-AREA; Stoe & Cie, 2019 )
T_min, T_max	0.450, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15028, 1678, 984
R_int	0.074
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.165, 1.06
No. of reflections	1678
No. of parameters	133
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.20
Computer programs: X-AREA (Stoe & Cie, 2019), 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: 2207709

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314622009191/tk4084sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314622009191/tk4084Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314622009191/tk4084Isup3.cml

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2019); cell refinement: X-AREA (Stoe & Cie, 2019); data reduction: X-AREA (Stoe & Cie, 2019); 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).

4-Hydroxyphenyl N-{4-[(4-hydroxyphenoxycarbonyl)amino]phenyl}carbamate top

Crystal data top

C₂₀H₁₆N₂O₆	F(000) = 396
M_r = 380.35	D_x = 1.426 Mg m⁻³
Monoclinic, P2₁/c	Ag Kα radiation, λ = 0.56083 Å
a = 19.0804 (17) Å	Cell parameters from 8468 reflections
b = 4.6758 (3) Å	θ = 2.6–25.0°
c = 10.1189 (8) Å	µ = 0.07 mm⁻¹
β = 101.169 (7)°	T = 295 K
V = 885.67 (12) Å³	Plate, colourless
Z = 2	0.26 × 0.20 × 0.03 mm

Data collection top

Stoe Stadivari diffractometer	1678 independent reflections
Radiation source: Sealed X-ray tube, Axo Astix-f Microfocus source	984 reflections with I > 2σ(I)
Graded multilayer mirror monochromator	R_int = 0.074
Detector resolution: 5.81 pixels mm^-1	θ_max = 20.0°, θ_min = 2.6°
ω scans	h = −23→23
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2019)	k = −5→5
T_min = 0.450, T_max = 1.000	l = −12→11
15028 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.051	Hydrogen site location: mixed
wR(F²) = 0.165	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0826P)²] where P = (F_o² + 2F_c²)/3
1678 reflections	(Δ/σ)_max < 0.001
133 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³
0 constraints

Special details top

Refinement. H atoms bonded to heteroatoms were refined freely, while H atoms of aromatic CH groups were placed in calculated positions and refined as riding to their carrier C atom.

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

	x	y	z	U_iso*/U_eq
C1	0.47748 (17)	0.1997 (8)	0.4010 (3)	0.0515 (9)
H1A	0.462350	0.335166	0.334332	0.062*
C2	0.42963 (15)	0.0948 (7)	0.4754 (3)	0.0429 (8)
C3	0.45239 (16)	−0.1062 (8)	0.5758 (3)	0.0476 (8)
H3A	0.420723	−0.177251	0.626969	0.057*
N4	0.35804 (14)	0.1974 (7)	0.4457 (3)	0.0519 (8)
H4	0.3413 (19)	0.235 (8)	0.365 (4)	0.062*
C5	0.31708 (16)	0.2435 (7)	0.5367 (3)	0.0431 (8)
O6	0.33018 (11)	0.1848 (5)	0.65433 (18)	0.0521 (7)
O7	0.25538 (11)	0.3727 (6)	0.47506 (19)	0.0613 (8)
C8	0.20244 (17)	0.4238 (8)	0.5511 (3)	0.0462 (8)
C9	0.13914 (17)	0.2829 (8)	0.5162 (3)	0.0487 (8)
H9A	0.133664	0.144948	0.448748	0.058*
C10	0.08313 (17)	0.3420 (7)	0.5796 (3)	0.0461 (8)
H10A	0.039714	0.247497	0.554220	0.055*
C11	0.09221 (16)	0.5420 (7)	0.6806 (3)	0.0398 (7)
C12	0.15670 (17)	0.6839 (7)	0.7167 (3)	0.0479 (8)
H12A	0.162645	0.819364	0.785254	0.058*
C13	0.21180 (17)	0.6259 (8)	0.6520 (3)	0.0507 (9)
H13A	0.255094	0.721890	0.675983	0.061*
O14	0.03802 (12)	0.6086 (5)	0.7487 (2)	0.0505 (6)
H14	0.011 (2)	0.464 (10)	0.749 (4)	0.076*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0432 (19)	0.073 (3)	0.0396 (15)	0.0162 (17)	0.0118 (14)	0.0108 (15)
C2	0.0348 (17)	0.060 (2)	0.0349 (14)	0.0080 (15)	0.0093 (13)	−0.0035 (14)
C3	0.0380 (18)	0.066 (2)	0.0420 (16)	0.0044 (16)	0.0162 (14)	0.0038 (15)
N4	0.0366 (16)	0.086 (2)	0.0351 (12)	0.0135 (14)	0.0118 (12)	0.0053 (14)
C5	0.0351 (17)	0.058 (2)	0.0359 (15)	0.0054 (15)	0.0059 (13)	−0.0010 (15)
O6	0.0419 (13)	0.0833 (19)	0.0320 (11)	0.0149 (12)	0.0097 (9)	0.0029 (10)
O7	0.0401 (13)	0.105 (2)	0.0415 (11)	0.0267 (13)	0.0142 (10)	0.0150 (12)
C8	0.0367 (18)	0.067 (2)	0.0364 (15)	0.0132 (16)	0.0117 (13)	0.0128 (15)
C9	0.0443 (19)	0.062 (2)	0.0386 (15)	0.0063 (16)	0.0056 (14)	−0.0052 (15)
C10	0.0347 (17)	0.054 (2)	0.0502 (17)	−0.0009 (15)	0.0100 (14)	−0.0042 (15)
C11	0.0373 (17)	0.0401 (19)	0.0446 (15)	0.0056 (14)	0.0145 (13)	0.0050 (14)
C12	0.047 (2)	0.047 (2)	0.0518 (18)	−0.0047 (16)	0.0141 (15)	−0.0109 (15)
C13	0.0343 (17)	0.064 (2)	0.0541 (18)	−0.0046 (16)	0.0092 (15)	0.0063 (17)
O14	0.0458 (13)	0.0474 (15)	0.0659 (14)	0.0011 (11)	0.0294 (11)	−0.0022 (11)

Geometric parameters (Å, º) top

C1—C2	1.381 (4)	C8—C13	1.377 (5)
C1—C3ⁱ	1.384 (4)	C9—C10	1.377 (4)
C1—H1A	0.9300	C9—H9A	0.9300
C2—C3	1.390 (5)	C10—C11	1.371 (4)
C2—N4	1.424 (4)	C10—H10A	0.9300
C3—H3A	0.9300	C11—C12	1.383 (4)
N4—C5	1.336 (4)	C11—O14	1.385 (3)
N4—H4	0.84 (3)	C12—C13	1.369 (4)
C5—O6	1.199 (3)	C12—H12A	0.9300
C5—O7	1.362 (4)	C13—H13A	0.9300
O7—C8	1.404 (3)	O14—H14	0.85 (4)
C8—C9	1.361 (5)

C2—C1—C3ⁱ	121.0 (3)	C13—C8—O7	121.3 (3)
C2—C1—H1A	119.5	C8—C9—C10	120.8 (3)
C3ⁱ—C1—H1A	119.5	C8—C9—H9A	119.6
C1—C2—C3	119.5 (3)	C10—C9—H9A	119.6
C1—C2—N4	118.3 (3)	C11—C10—C9	119.1 (3)
C3—C2—N4	122.2 (3)	C11—C10—H10A	120.4
C1ⁱ—C3—C2	119.5 (3)	C9—C10—H10A	120.4
C1ⁱ—C3—H3A	120.3	C10—C11—C12	120.1 (3)
C2—C3—H3A	120.3	C10—C11—O14	121.7 (3)
C5—N4—C2	125.1 (3)	C12—C11—O14	118.2 (3)
C5—N4—H4	118 (2)	C13—C12—C11	120.3 (3)
C2—N4—H4	117 (2)	C13—C12—H12A	119.8
O6—C5—N4	127.6 (3)	C11—C12—H12A	119.8
O6—C5—O7	123.5 (3)	C12—C13—C8	119.3 (3)
N4—C5—O7	109.0 (2)	C12—C13—H13A	120.4
C5—O7—C8	118.3 (2)	C8—C13—H13A	120.4
C9—C8—C13	120.4 (3)	C11—O14—H14	110 (3)
C9—C8—O7	118.2 (3)

C3ⁱ—C1—C2—C3	0.5 (6)	C5—O7—C8—C13	69.9 (4)
C3ⁱ—C1—C2—N4	−179.3 (3)	C13—C8—C9—C10	0.9 (5)
C1—C2—C3—C1ⁱ	−0.5 (6)	O7—C8—C9—C10	−174.5 (3)
N4—C2—C3—C1ⁱ	179.3 (3)	C8—C9—C10—C11	−1.2 (5)
C1—C2—N4—C5	−144.0 (3)	C9—C10—C11—C12	0.7 (5)
C3—C2—N4—C5	36.2 (5)	C9—C10—C11—O14	−179.4 (3)
C2—N4—C5—O6	−7.1 (6)	C10—C11—C12—C13	0.0 (5)
C2—N4—C5—O7	172.8 (3)	O14—C11—C12—C13	−179.8 (3)
O6—C5—O7—C8	−4.1 (5)	C11—C12—C13—C8	−0.3 (5)
N4—C5—O7—C8	175.9 (3)	C9—C8—C13—C12	−0.2 (5)
C5—O7—C8—C9	−114.7 (4)	O7—C8—C13—C12	175.1 (3)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O6	0.93	2.47	2.939 (4)	111
C13—H13A···O6ⁱⁱ	0.93	2.63	3.451 (4)	148
O14—H14···O14ⁱⁱⁱ	0.85 (4)	1.91 (5)	2.754 (2)	172 (4)
N4—H4···O6^iv	0.84 (3)	2.13 (4)	2.945 (3)	163 (3)

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

Funding information

Funding for this research was provided by: Consejo Nacional de Ciencia y Tecnología (scholarship No. 820488 to I. Martínez-de la Luz; grant No. 268178).

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