Dimethyl 5,5′-methyl­enebis(2-hy­droxy­benzoate)

Guieu, S.; Brandão, P.; Rocha, J.; Silva, A.M.S.

doi:10.1107/S1600536812015760

organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1404

doi:10.1107/S1600536812015760

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Dimethyl 5,5′-methylenebis(2-hydroxybenzoate)

Samuel Guieu,^a ^* Paula Brandão,^b João Rocha ^b and Artur M. S. Silva ^a

^aUniversity of Aveiro, QOPNA, Department of Chemistry, 3810-193 Aveiro, Portugal, and ^bUniversity of Aveiro, CICECO, Department of Chemistry, 3810-193 Aveiro, Portugal
^*Correspondence e-mail: sguieu@ua.pt

(Received 27 March 2012; accepted 11 April 2012; online 18 April 2012)

In the title compound, C₁₇H₁₆O₆, the two methyl salicylate moieties are related by crystallographic twofold rotational symmetry with the two benzene rings close to being perpendicular [inter-ring dihedral angle = 86.6 (8)°]. Intramolecular phenolic O—H⋯O hydrogen bonds with carboxyl O-atom acceptors are present, with these groups also involved in centrosymmetric cyclic intermolecular O—H⋯O hydrogen-bonding associations [graph set R₂²(4)], giving infinite chains extending across (101).

Related literature

For the chemistry and applications of methylene bisphenol derivatives, see: Ogata et al. (1975 ); Méric et al. (1993 ); Shrestha et al. (2007 ); Cameron et al. (2002 ). For the preparation, see: Cushman & Kanamathareddy (1990 ); Méric et al. (1993). For the structures of similar compounds, see: Lu et al. (2011 ); Zhang et al. (2009 ); Liu et al. (2009 ). For graph-set analysis, see Etter et al. (1990 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₇H₁₆O₆
M_r = 316.31
Monoclinic, C 2/c
a = 20.4168 (13) Å
b = 4.9300 (3) Å
c = 15.5470 (12) Å
β = 111.290 (3)°
V = 1458.08 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 150 K
0.38 × 0.30 × 0.24 mm

Data collection

Bruker SMART CCD-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.953, T_max = 0.970
8440 measured reflections
1756 independent reflections
1568 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.113
S = 0.96
1756 reflections
109 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.87 (2)	1.87 (2)	2.6457 (12)	147 (2)
O1—H1⋯O2ⁱ	0.87 (2)	2.32 (1)	3.0067 (11)	134 (9)
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+{\script{5\over 2}}, -z+2]$ .

Data collection: SMART (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812015760/zs2198sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812015760/zs2198Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812015760/zs2198Isup3.cml

checkCIF report

Comment top

The title compound C₁₇H₁₆O₆ was first reported as a building block for polymer synthesis (Ogata et al., 1975). It is a useful precursor for organic polymers, metal-organic frameworks, cage compounds (Méric et al., 1993) and biologically active compounds (Shrestha et al., 2007; Cameron et al., 2002). In the title compound (Fig. 1), the two methyl salicylate moieties are related by crystallographic twofold rotational symmetry with the two phenyl rings close to perpendicular [inter-ring dihedral angle = 86.6 (8)°]. Bond lengths and angles are within normal ranges (Allen et al., 1987). Intramolecular phenolic O—H···O hydrogen bonds with carboxyl O-atom acceptors are present, with these groups also involved in centrosymmetric cyclic intermolecular hydrogen-bonding associations [graph set R²₂(4) (Etter et al., 1990)], making the ester group essentially coplanar with the phenyl ring [torsion angle C1—C6—C7—O3, 178.64 (9)°]. The molecules are involved in centrosymmetric cyclic intermolecular phenolic O—H···O_carboxyl hydrogen-bonding associations [graph set R²₂(4) giving infinite chains extending across (101) (Figs. 2, 3).

Related literature top

For the chemistry and applications of methylene bisphenol derivatives, see: Ogata et al. (1975); Méric et al. (1993); Shrestha et al. (2007); Cameron et al. (2002). For the preparation, see: Cushman & Kanamathareddy (1990); Méric et al. (1993). For the structures of similar compounds, see: Lu et al. (2011); Zhang et al. (2009); Liu et al. (2009). For graph-set analysis, see Etter et al. (1990). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was prepared in two steps starting with salicylic acid. 5,5'-Methylenebis(salicylic acid) was prepared according to a known procedure (Cushman et al., 1990), and was then esterified with methanol and a catalytic amount of sulfuric acid (Méric et al., 1993). Slow evaporation of a saturated solution in dichloromethane gave single crystals suitable for X-ray diffraction.

Computing details top

Data collection: SMART (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound showing atom numbering and displacement ellipsoids drawn at the 30% probability level. The intramolecular hydrogen bonds are shown as dashed lines. Symmetry code: (i) -x + 1, y, -z + 1/2.
	Fig. 2. The one-dimensional hydrogen-bonded chains in the title compound, with hydrogen bonds shown as dashed lines. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. The packing of the title compound in the unit cell viewed down the b axis, with hydrogen bonds and other intermolecular interactions shown as dashed lines.

Dimethyl 5,5'-methylenebis(2-hydroxybenzoate) top

Crystal data top

C₁₇H₁₆O₆	F(000) = 664
M_r = 316.31	D_x = 1.441 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8440 reflections
a = 20.4168 (13) Å	θ = 2.8–27.9°
b = 4.9300 (3) Å	µ = 0.11 mm⁻¹
c = 15.5470 (12) Å	T = 150 K
β = 111.290 (3)°	Block, colourless
V = 1458.08 (17) Å³	0.38 × 0.30 × 0.24 mm
Z = 4

Data collection top

Bruker SMART CCD-detector diffractometer	1756 independent reflections
Radiation source: fine-focus sealed tube	1568 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω and ϕ scans	θ_max = 27.9°, θ_min = 4.1°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −26→21
T_min = 0.953, T_max = 0.970	k = −6→6
8440 measured reflections	l = −19→20

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	w = 1/[σ²(F_o²) + (0.0724P)² + 0.9516P] where P = (F_o² + 2F_c²)/3
1756 reflections	(Δ/σ)_max = 0.049
109 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₁₇H₁₆O₆	V = 1458.08 (17) Å³
M_r = 316.31	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 20.4168 (13) Å	µ = 0.11 mm⁻¹
b = 4.9300 (3) Å	T = 150 K
c = 15.5470 (12) Å	0.38 × 0.30 × 0.24 mm
β = 111.290 (3)°

Data collection top

Bruker SMART CCD-detector diffractometer	1756 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1568 reflections with I > 2σ(I)
T_min = 0.953, T_max = 0.970	R_int = 0.025
8440 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	Δρ_max = 0.23 e Å⁻³
1756 reflections	Δρ_min = −0.33 e Å⁻³
109 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	Occ. (<1)
H1	0.2434 (10)	1.009 (5)	0.9251 (15)	0.070 (6)*
O2	0.18996 (4)	1.12860 (16)	0.99304 (5)	0.0260 (2)
O1	0.24736 (4)	0.89366 (17)	0.88455 (6)	0.0265 (2)
O3	0.08604 (4)	0.98089 (17)	0.99095 (6)	0.0284 (2)
C5	0.07384 (5)	0.6081 (2)	0.85532 (7)	0.0212 (2)
H5	0.0372	0.6288	0.8789	0.025*
C6	0.13366 (5)	0.7717 (2)	0.89054 (7)	0.0189 (2)
C2	0.18118 (6)	0.5483 (2)	0.78810 (8)	0.0269 (3)
H2	0.2178	0.5240	0.7648	0.032*
C7	0.14042 (5)	0.9762 (2)	0.96221 (7)	0.0196 (2)
C3	0.12105 (6)	0.3904 (2)	0.75449 (8)	0.0277 (3)
H3	0.1170	0.2602	0.7078	0.033*
C1	0.18813 (5)	0.7425 (2)	0.85599 (7)	0.0212 (2)
C4	0.06631 (5)	0.4174 (2)	0.78730 (7)	0.0238 (2)
C9	0.0000	0.2479 (3)	0.7500	0.0296 (4)
H9A	−0.0029	0.1295	0.7999	0.036*	0.50
H9B	0.0029	0.1295	0.7001	0.036*	0.50
C8	0.09263 (7)	1.1785 (3)	1.06230 (9)	0.0350 (3)
H8A	0.0510	1.1700	1.0796	0.053*
H8B	0.0966	1.3604	1.0393	0.053*
H8C	0.1347	1.1389	1.1165	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0226 (4)	0.0255 (4)	0.0290 (4)	−0.0081 (3)	0.0084 (3)	−0.0051 (3)
O1	0.0221 (4)	0.0265 (4)	0.0335 (5)	−0.0035 (3)	0.0132 (3)	−0.0013 (3)
O3	0.0247 (4)	0.0324 (5)	0.0315 (4)	−0.0085 (3)	0.0142 (3)	−0.0101 (3)
C5	0.0180 (4)	0.0180 (5)	0.0235 (5)	0.0006 (4)	0.0027 (4)	0.0024 (4)
C6	0.0178 (4)	0.0171 (5)	0.0188 (5)	0.0007 (3)	0.0031 (4)	0.0023 (4)
C2	0.0289 (5)	0.0259 (5)	0.0266 (5)	0.0049 (4)	0.0110 (4)	0.0009 (4)
C7	0.0175 (4)	0.0200 (5)	0.0191 (5)	−0.0013 (3)	0.0043 (4)	0.0025 (4)
C3	0.0335 (6)	0.0207 (5)	0.0235 (5)	0.0050 (4)	0.0039 (4)	−0.0024 (4)
C1	0.0200 (5)	0.0199 (5)	0.0218 (5)	0.0014 (4)	0.0052 (4)	0.0045 (4)
C4	0.0227 (5)	0.0157 (5)	0.0242 (5)	0.0020 (4)	−0.0021 (4)	0.0026 (4)
C9	0.0247 (7)	0.0162 (7)	0.0350 (8)	0.000	−0.0045 (6)	0.000
C8	0.0396 (7)	0.0382 (7)	0.0338 (6)	−0.0085 (5)	0.0211 (5)	−0.0124 (5)

Geometric parameters (Å, º) top

O2—C7	1.2104 (13)	C2—C1	1.3938 (15)
O1—C1	1.3508 (13)	C2—H2	0.9500
O1—H1	0.87 (2)	C3—C4	1.3932 (17)
O3—C7	1.3390 (12)	C3—H3	0.9500
O3—C8	1.4455 (14)	C4—C9	1.5157 (13)
C5—C4	1.3811 (15)	C9—C4ⁱ	1.5157 (13)
C5—C6	1.3989 (14)	C9—H9A	0.9900
C5—H5	0.9500	C9—H9B	0.9900
C6—C1	1.4071 (14)	C8—H8A	0.9800
C6—C7	1.4715 (14)	C8—H8B	0.9800
C2—C3	1.3857 (16)	C8—H8C	0.9800

C1—O1—H1	106.9 (13)	O1—C1—C6	123.74 (10)
C7—O3—C8	114.23 (8)	C2—C1—C6	118.82 (10)
C4—C5—C6	122.07 (10)	C5—C4—C3	117.65 (10)
C4—C5—H5	119.0	C5—C4—C9	120.26 (10)
C6—C5—H5	119.0	C3—C4—C9	122.08 (9)
C5—C6—C1	119.36 (9)	C4—C9—C4ⁱ	113.07 (12)
C5—C6—C7	121.34 (9)	C4—C9—H9A	109.0
C1—C6—C7	119.30 (9)	C4ⁱ—C9—H9A	109.0
C3—C2—C1	120.27 (10)	C4—C9—H9B	109.0
C3—C2—H2	119.9	C4ⁱ—C9—H9B	109.0
C1—C2—H2	119.9	H9A—C9—H9B	107.8
O2—C7—O3	122.15 (9)	O3—C8—H8A	109.5
O2—C7—C6	124.07 (9)	O3—C8—H8B	109.5
O3—C7—C6	113.78 (8)	H8A—C8—H8B	109.5
C2—C3—C4	121.81 (10)	O3—C8—H8C	109.5
C2—C3—H3	119.1	H8A—C8—H8C	109.5
C4—C3—H3	119.1	H8B—C8—H8C	109.5
O1—C1—C2	117.44 (9)

C8—O3—C7—O2	−1.07 (15)	C3—C4—C5—C6	0.43 (15)
C8—O3—C7—C6	179.17 (9)	C9—C4—C5—C6	−178.93 (9)
O1—C1—C2—C3	−178.69 (10)	C3—C4—C9—C4ⁱ	−123.32 (10)
C6—C1—C2—C3	1.01 (16)	C5—C4—C9—C4ⁱ	56.01 (11)
O1—C1—C6—C5	178.95 (10)	C4—C5—C6—C1	0.00 (16)
O1—C1—C6—C7	−0.29 (15)	C4—C5—C6—C7	179.24 (10)
C2—C1—C6—C5	−0.73 (15)	C1—C6—C7—O2	1.60 (16)
C2—C1—C6—C7	−179.97 (10)	C1—C6—C7—O3	−178.64 (9)
C1—C2—C3—C4	−0.58 (17)	C5—C6—C7—O2	−177.63 (10)
C2—C3—C4—C5	−0.15 (16)	C5—C6—C7—O3	2.13 (14)
C2—C3—C4—C9	179.20 (10)

Symmetry code: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.87 (2)	1.87 (2)	2.6457 (12)	147 (2)
O1—H1···O2ⁱⁱ	0.87 (2)	2.32 (1)	3.0067 (11)	134 (9)

Symmetry code: (ii) −x+1/2, −y+5/2, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₆O₆
M_r	316.31
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	20.4168 (13), 4.9300 (3), 15.5470 (12)
β (°)	111.290 (3)
V (Å³)	1458.08 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.38 × 0.30 × 0.24

Data collection
Diffractometer	Bruker SMART CCD-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.953, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	8440, 1756, 1568
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.659

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.113, 0.96
No. of reflections	1756
No. of parameters	109
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.33

Computer programs: SMART (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.87 (2)	1.87 (2)	2.6457 (12)	147 (2)
O1—H1···O2ⁱ	0.87 (2)	2.32 (1)	3.0067 (11)	134 (9)

Symmetry code: (i) −x+1/2, −y+5/2, −z+2.

Acknowledgements

Thanks are due to the University of Aveiro and the Portuguese Fundação para a Ciência e a Tecnologia (FCT) for funding the Organic Chemistry Research Unit (project PEst-C/QUI/UI0062/2011) and the CICECO Associate Laboratory (PEst-C/CTM/LA0011/2011). SG also thanks the FCT for a postdoctoral grant (SFRH/BPD/70702/2010).

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