Redetermination of 2,4′-methyl­ene­diphenol

Peng, W.-D.; Chen, S.-C.; An, J.; Sun, F.-A.; Chen, Q.

doi:10.1107/S1600536811044989

organic compounds

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Volume 67| Part 12| December 2011| Page o3143

https://doi.org/10.1107/S1600536811044989

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Redetermination of 2,4′-methylenediphenol

Wei-Dong Peng,^a Sheng-Chun Chen,^a Jie An,^a Fu-An Sun ^a and Qun Chen ^a ^*

^aKey Laboratory of Fine Petrochemical Technology, Changzhou University, Changzhou 213164, People's Republic of China
^*Correspondence e-mail: chenqunjpu@yahoo.com

(Received 23 October 2011; accepted 27 October 2011; online 2 November 2011)

In the previous determination [Finn & Musti (1950 ). J. Soc. Chem. Ind. (London), 69, S849] of the title compound, C₁₃H₁₂O₂, the three-dimensional coordinates and displacement parameters were not reported. This redetermination at room temperature reveals that the dihedral angle between the benzene rings is 79.73 (6)°. In the crystal, intermolecular O—H⋯O hydrogen bonds between adjacent molecules result in two-dimensional wave-like supramolecular motifs parallel to the ab plane.

Related literature

For the previous determination, see: Finn & Musti (1950). For the importance of bisphenol in industry, see: Patel & Patel (2009 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₃H₁₂O₂
M_r = 200.23
Monoclinic, P 2₁ /c
a = 5.0923 (5) Å
b = 15.3743 (14) Å
c = 13.2321 (12) Å
β = 96.660 (2)°
V = 1028.96 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.30 × 0.28 × 0.26 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.975, T_max = 0.978
5900 measured reflections
1904 independent reflections
1404 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.144
S = 1.04
1904 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.82	2.04	2.859 (2)	175
O2—H2A⋯O1ⁱⁱ	0.82	2.00	2.811 (2)	173
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 and SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 2005 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811044989/zq2130sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811044989/zq2130Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811044989/zq2130Isup3.cml

checkCIF report

Comment top

2,4'-Dihydroxydiphenylmethane is one isomer of bisphenol F which is an important chemical and/or intermediate for the preparation of useful epoxy resins, phenolic resins, and polycarbonates in the plastic and rubber industries (Patel & Patel, 2009). This structure has been solved previously but with no available three-dimensional coordinates (Finn & Musti, 1950; CSD refcode: ZZZGWU). Herein, we present a redetermination at room temperature of the crystal structure of the title compound (Fig. 1). The bond lengths (Allen et al., 1987) and angles are within normal ranges. The dihedral angle between the benzene rings is 79.73 (6)°. Intermolecular O—H···O hydrogen bonds between adjacent molecules result in two-dimensional wave-like supramolecular motifs along the ab plane (Fig. 2).

Related literature top

For the previous determination, see: Finn & Musti (1950). For the importance of bisphenol in industry, see: Patel & Patel (2009). For standard bond lengths, see: Allen et al. (1987).

Experimental top

A 37% aqueous formaldehyde (20.31 g, 0.25 mol) solution was added to phenol (47.05 g, 0.50 mol) and oxalic acid (0.18 g, 1.40 mmol) at 70 °C with stirring for 4 h. Then the reaction mixture was condensed by vacuum distillation, affording a mixture of 4,4'-methylenebisphenol, 2,4'-methylenebisphenol and 2,2'-methylenebisphenol. By dissolving the resulting mixture (0.50 g) in the mixed solution of 2-propanol (20.0 ml) and water (10.0 ml), the needle colourless single crystals suitable for X-ray analysis were obtained after a slow evaporation of the solvents at room temperature for a period of about two weeks.

Structure description top

For the previous determination, see: Finn & Musti (1950). For the importance of bisphenol in industry, see: Patel & Patel (2009). For standard bond lengths, see: Allen et al. (1987).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 and SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The two-dimensional structure of the title compound. Hydrogen atoms are omitted for clarity.

2,4'-methylenediphenol top

Crystal data top

C₁₃H₁₂O₂	F(000) = 424
M_r = 200.23	D_x = 1.293 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1692 reflections
a = 5.0923 (5) Å	θ = 3.1–24.9°
b = 15.3743 (14) Å	µ = 0.09 mm⁻¹
c = 13.2321 (12) Å	T = 296 K
β = 96.660 (2)°	Block, colourless
V = 1028.96 (17) Å³	0.30 × 0.28 × 0.26 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	1904 independent reflections
Radiation source: fine-focus sealed tube	1404 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
phi and ω scans	θ_max = 25.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −6→6
T_min = 0.975, T_max = 0.978	k = −16→18
5900 measured reflections	l = −13→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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.144	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0749P)² + 0.2818P] where P = (F_o² + 2F_c²)/3
1904 reflections	(Δ/σ)_max < 0.001
138 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₃H₁₂O₂	V = 1028.96 (17) Å³
M_r = 200.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.0923 (5) Å	µ = 0.09 mm⁻¹
b = 15.3743 (14) Å	T = 296 K
c = 13.2321 (12) Å	0.30 × 0.28 × 0.26 mm
β = 96.660 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1904 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1404 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.978	R_int = 0.025
5900 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.144	H-atom parameters constrained
S = 1.04	Δρ_max = 0.16 e Å⁻³
1904 reflections	Δρ_min = −0.20 e Å⁻³
138 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	0.4293 (4)	1.00937 (12)	0.83972 (14)	0.0379 (5)
C2	0.2466 (4)	0.94424 (14)	0.84369 (15)	0.0441 (5)
H2	0.1297	0.9454	0.8927	0.053*
C3	0.2377 (4)	0.87678 (13)	0.77407 (15)	0.0441 (5)
H3	0.1138	0.8327	0.7769	0.053*
C4	0.4087 (4)	0.87356 (12)	0.70047 (14)	0.0393 (5)
C5	0.5900 (4)	0.94019 (14)	0.69828 (15)	0.0455 (5)
H5	0.7077	0.9392	0.6495	0.055*
C6	0.6006 (4)	1.00814 (13)	0.76676 (15)	0.0438 (5)
H6	0.7227	1.0528	0.7636	0.053*
C7	0.3999 (4)	0.79840 (14)	0.62684 (17)	0.0548 (6)
H7A	0.3855	0.7447	0.6644	0.066*
H7B	0.5656	0.7966	0.5974	0.066*
C8	0.1742 (4)	0.80219 (12)	0.54106 (14)	0.0384 (5)
C9	0.0121 (4)	0.73108 (12)	0.51658 (14)	0.0381 (5)
C10	−0.1909 (4)	0.73465 (14)	0.43729 (15)	0.0469 (5)
H10	−0.2967	0.6861	0.4214	0.056*
C11	−0.2353 (4)	0.81017 (15)	0.38226 (16)	0.0538 (6)
H11	−0.3720	0.8128	0.3292	0.065*
C12	−0.0785 (5)	0.88160 (15)	0.40538 (16)	0.0563 (6)
H12	−0.1087	0.9327	0.3682	0.068*
C13	0.1238 (4)	0.87742 (14)	0.48385 (17)	0.0514 (6)
H13	0.2294	0.9261	0.4990	0.062*
O1	0.4294 (3)	1.07617 (10)	0.90993 (12)	0.0556 (4)
H1	0.5765	1.0985	0.9185	0.083*
O2	0.0601 (3)	0.65582 (10)	0.57267 (12)	0.0551 (4)
H2A	−0.0787	0.6291	0.5742	0.083*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0381 (10)	0.0335 (10)	0.0397 (10)	0.0055 (8)	−0.0058 (8)	−0.0021 (8)
C2	0.0392 (10)	0.0521 (12)	0.0416 (11)	−0.0007 (9)	0.0075 (8)	−0.0011 (9)
C3	0.0379 (11)	0.0413 (11)	0.0516 (12)	−0.0055 (8)	−0.0012 (9)	0.0010 (9)
C4	0.0345 (10)	0.0409 (11)	0.0396 (10)	0.0086 (8)	−0.0083 (8)	−0.0030 (8)
C5	0.0349 (10)	0.0595 (13)	0.0421 (11)	0.0011 (9)	0.0046 (8)	−0.0029 (9)
C6	0.0379 (10)	0.0425 (11)	0.0498 (12)	−0.0069 (8)	0.0008 (9)	0.0003 (9)
C7	0.0519 (13)	0.0518 (13)	0.0559 (13)	0.0186 (10)	−0.0146 (10)	−0.0147 (10)
C8	0.0382 (10)	0.0401 (11)	0.0358 (10)	0.0070 (8)	−0.0005 (8)	−0.0064 (8)
C9	0.0383 (10)	0.0390 (11)	0.0376 (10)	0.0056 (8)	0.0071 (8)	0.0017 (8)
C10	0.0421 (11)	0.0485 (13)	0.0480 (12)	−0.0038 (9)	−0.0031 (9)	−0.0053 (9)
C11	0.0525 (13)	0.0639 (15)	0.0409 (11)	0.0062 (11)	−0.0118 (9)	0.0020 (10)
C12	0.0654 (15)	0.0503 (14)	0.0503 (13)	0.0064 (11)	−0.0054 (11)	0.0125 (10)
C13	0.0530 (13)	0.0403 (12)	0.0584 (13)	−0.0035 (10)	−0.0038 (10)	0.0025 (10)
O1	0.0550 (9)	0.0489 (9)	0.0616 (10)	0.0010 (7)	0.0004 (8)	−0.0201 (7)
O2	0.0504 (9)	0.0460 (9)	0.0671 (10)	−0.0005 (7)	−0.0008 (7)	0.0169 (7)

Geometric parameters (Å, º) top

C1—C2	1.372 (3)	C7—H7B	0.9700
C1—C6	1.374 (3)	C8—C9	1.386 (3)
C1—O1	1.385 (2)	C8—C13	1.390 (3)
C2—C3	1.384 (3)	C9—O2	1.381 (2)
C2—H2	0.9300	C9—C10	1.386 (3)
C3—C4	1.381 (3)	C10—C11	1.375 (3)
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.382 (3)	C11—C12	1.371 (3)
C4—C7	1.509 (3)	C11—H11	0.9300
C5—C6	1.380 (3)	C12—C13	1.377 (3)
C5—H5	0.9300	C12—H12	0.9300
C6—H6	0.9300	C13—H13	0.9300
C7—C8	1.520 (3)	O1—H1	0.8200
C7—H7A	0.9700	O2—H2A	0.8200

C2—C1—C6	120.35 (18)	C8—C7—H7B	108.6
C2—C1—O1	117.60 (18)	H7A—C7—H7B	107.6
C6—C1—O1	122.04 (18)	C9—C8—C13	117.51 (17)
C1—C2—C3	119.42 (19)	C9—C8—C7	121.52 (18)
C1—C2—H2	120.3	C13—C8—C7	120.97 (18)
C3—C2—H2	120.3	O2—C9—C8	118.16 (17)
C4—C3—C2	121.45 (19)	O2—C9—C10	120.67 (18)
C4—C3—H3	119.3	C8—C9—C10	121.17 (18)
C2—C3—H3	119.3	C11—C10—C9	119.79 (19)
C3—C4—C5	117.77 (18)	C11—C10—H10	120.1
C3—C4—C7	120.60 (19)	C9—C10—H10	120.1
C5—C4—C7	121.62 (19)	C12—C11—C10	120.15 (19)
C6—C5—C4	121.51 (19)	C12—C11—H11	119.9
C6—C5—H5	119.2	C10—C11—H11	119.9
C4—C5—H5	119.2	C11—C12—C13	119.8 (2)
C1—C6—C5	119.49 (19)	C11—C12—H12	120.1
C1—C6—H6	120.3	C13—C12—H12	120.1
C5—C6—H6	120.3	C12—C13—C8	121.6 (2)
C4—C7—C8	114.59 (16)	C12—C13—H13	119.2
C4—C7—H7A	108.6	C8—C13—H13	119.2
C8—C7—H7A	108.6	C1—O1—H1	109.5
C4—C7—H7B	108.6	C9—O2—H2A	109.5

C6—C1—C2—C3	0.6 (3)	C4—C7—C8—C13	49.1 (3)
O1—C1—C2—C3	179.23 (16)	C13—C8—C9—O2	179.89 (18)
C1—C2—C3—C4	−0.1 (3)	C7—C8—C9—O2	0.2 (3)
C2—C3—C4—C5	−0.1 (3)	C13—C8—C9—C10	0.7 (3)
C2—C3—C4—C7	178.59 (17)	C7—C8—C9—C10	−179.05 (18)
C3—C4—C5—C6	−0.3 (3)	O2—C9—C10—C11	−179.92 (19)
C7—C4—C5—C6	−178.93 (18)	C8—C9—C10—C11	−0.7 (3)
C2—C1—C6—C5	−0.9 (3)	C9—C10—C11—C12	0.3 (3)
O1—C1—C6—C5	−179.51 (17)	C10—C11—C12—C13	0.1 (4)
C4—C5—C6—C1	0.8 (3)	C11—C12—C13—C8	−0.1 (4)
C3—C4—C7—C8	77.4 (3)	C9—C8—C13—C12	−0.3 (3)
C5—C4—C7—C8	−104.0 (2)	C7—C8—C13—C12	179.5 (2)
C4—C7—C8—C9	−131.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	2.04	2.859 (2)	175
O2—H2A···O1ⁱⁱ	0.82	2.00	2.811 (2)	173

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₂O₂
M_r	200.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	5.0923 (5), 15.3743 (14), 13.2321 (12)
β (°)	96.660 (2)
V (Å³)	1028.96 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.28 × 0.26

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.975, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	5900, 1904, 1404
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.144, 1.04
No. of reflections	1904
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.20

Computer programs: APEX2 (Bruker, 2007), APEX2 and SAINT (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	2.04	2.859 (2)	175
O2—H2A···O1ⁱⁱ	0.82	2.00	2.811 (2)	173

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

Acknowledgements

We gratefully acknowledge financial support from the Open Foundation of Jiangsu Province Key Laboratory of Fine Petrochemical Technology (KF1005) and the Analysis Center of Changzhou University.

References

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