Methyl 2-hy­droxy-4-iodo­benzoate

Kimble, M.J.; Myers, S.D.; Benedict, J.B.

doi:10.1107/S2414314624003948

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 9| Part 5| May 2024| x240394

https://doi.org/10.1107/S2414314624003948

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Methyl 2-hydroxy-4-iodobenzoate

Marten J. Kimble,^a ‡ Shea D. Myers ^a ‡ and Jason B Benedict ^b ^*

^a730 Natural Sciences Complex, Buffalo, NY 14260-3000, USA, and ^b771 Natural Sciences Complex, Buffalo, NY 14260, USA
^*Correspondence e-mail: jbb6@buffalo.edu

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 24 April 2024; accepted 30 April 2024; online 17 May 2024)

The structure of the title compound, C₈H₇IO₃, at 90 K has monoclinic (P2₁/c) symmetry. The extended structure is layered and displays intermolecular and intramolecular hydrogen bonding arising from the same OH group.

Keywords: crystal structure; organic; co-former.

CCDC reference: 2352344

Structure description

2-Hydroxybenzoic acid methyl ester (C₈H₈O₃), commonly known as methyl salicylate, and its derivatives have been shown to display biological effects such as anti-inflammatory, anti-fungal, and process signaling (Yoon et al., 2019 ; Li et al., 2016 ; Park et al., 2007 ). It can also be found in various foods (Duthie & Wood, 2011 ). The title compound, 2-hydroxy-4-iodobenzoic acid methyl ester (methyl 4-iodosalicylate, C₈H₇IO₃) allows for an effective way of incorporating the said methyl salicylates within larger organic molecules, using such methodologies as McClure protocols (Franchi et al., 2010 ; McClure et al., 2001 ), Stille (Yoon et al., 2019; Stille, 1986 ) and Suzuki–Miyaura reactions (Fracaroli et al., 2014 ; Miyaura et al., 1979 ), which take advantage of the iodine atom at the 4-position of the aromatic ring for the formation of carbon–carbon bonds. The iodine atom is also capable of forming supramolecular synthons, which may be useful for crystal engineering (Desiraju, 1995 ; Cherukuvada et al., 2016 ; Mitchell et al., 2023 ).

At 90 K the title compound displays monoclinic (P2₁/c) symmetry with one molecule in the asymmetric unit (Fig. 1). Intermolecular hydrogen bonding interactions occur between the hydroxy groups of one molecule and the carbonyl oxygen atom of the methyl ester of an adjacent molecule to form a centrosymmetric dimeric pair (Table 1, Fig. 2) with H⋯O = 2.53 (4) Å. An O3—H3⋯O2 intramolecular hydrogen bond also exists with an H⋯O distance of 2.05 (4) Å. The C5⋯C8 [3.326 (3) Å] and O3⋯H1C (2.51 Å) interactions provide the only short contacts between the stacks of offset ( $[\overline{1}]$ 02) parallel sheets, which make up the crystal (Fig. 3). These sheets, in turn, contain the inversion-generated hydrogen-bonded dimers (Fig. 2). The non-hydrogen atoms of the molecule are essentially coplanar with no displacement from the mean molecular plane greater than 0.132 Å (Fig. 4).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2	0.70 (4)	2.05 (4)	2.670 (3)	149 (4)
O3—H3⋯O2ⁱ	0.70 (4)	2.53 (4)	3.087 (2)	139 (4)
Symmetry code: (i) .

Figure 1
The molecular structure of the title compound showing 50% displacement ellipsoids. The intramolecular hydrogen bond is indicated by a red dashed line.

Figure 2
The dimer of title compound showing intra- and intermolecular hydrogen bonds depicted with blue dashed lines with corresponding O⋯H distances for each O—H⋯O interaction.

Figure 3
Packing diagram viewed perpendicular to ( $[\overline{1}]$ 02).

Figure 4
Packing diagram viewed along b-axis and parallel to ( $[\overline{1}]$ 02).

Crystallization

Methyl 4-iodosalicylate (32.8 mg, 0.118 mmol) was added to a 20 ml scintillation vial to which benzene (∼2 ml) was added, and the vial shaken until the compound dissolved. The resulting solution was then left undisturbed, lightly capped, and in the dark for one week to allow for crystal formation while the solvent slowly evaporated.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₈H₇IO₃
M_r	278.04
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	90
a, b, c (Å)	4.3286 (8), 21.334 (4), 9.2941 (16)
β (°)	93.744 (4)
V (Å³)	856.4 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	3.70
Crystal size (mm)	0.80 × 0.20 × 0.02

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.564, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	23320, 3651, 3315
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.809

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.057, 1.11
No. of reflections	3651
No. of parameters	114
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.27, −1.92
Computer programs: APEX2 and SAINT V8.40B (Bruker, 2016 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2352344

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314624003948/hb4468sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314624003948/hb4468Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314624003948/hb4468Isup3.cml

checkCIF report

Computing details top

Methyl 2-hydroxy-4-iodobenzoate top

Crystal data top

C₈H₇IO₃	F(000) = 528
M_r = 278.04	D_x = 2.156 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 4.3286 (8) Å	Cell parameters from 6811 reflections
b = 21.334 (4) Å	θ = 2.9–34.1°
c = 9.2941 (16) Å	µ = 3.70 mm⁻¹
β = 93.744 (4)°	T = 90 K
V = 856.4 (3) Å³	Plate, pale yellow
Z = 4	0.80 × 0.20 × 0.02 mm

Data collection top

Bruker APEXII CCD diffractometer	3315 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.049
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 35.1°, θ_min = 2.4°
T_min = 0.564, T_max = 0.747	h = −6→6
23320 measured reflections	k = −33→34
3651 independent reflections	l = −14→15

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.057	w = 1/[σ²(F_o²) + 1.660P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.001
3651 reflections	Δρ_max = 1.27 e Å⁻³
114 parameters	Δρ_min = −1.92 e Å⁻³
0 restraints

Special details top

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.

Refinement. The O-bound H atom was located in a difference map and its position was freely refined. The C-bound H atoms were geometrically placed (C—H = 0.95–0.98 Å) and refined as riding atoms.

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

	x	y	z	U_iso*/U_eq
I1	0.05964 (3)	0.25795 (2)	0.54095 (2)	0.01430 (4)
O3	0.7859 (4)	0.39459 (9)	0.91310 (18)	0.0170 (3)
O1	0.4603 (4)	0.56516 (8)	0.72915 (18)	0.0180 (3)
O2	0.7790 (4)	0.51960 (9)	0.89865 (19)	0.0212 (4)
C6	0.2313 (5)	0.34266 (10)	0.6295 (2)	0.0127 (4)
C7	0.4516 (5)	0.34172 (10)	0.7453 (2)	0.0128 (4)
H7	0.522507	0.302965	0.785568	0.015*
C8	0.5675 (5)	0.39821 (10)	0.8018 (2)	0.0121 (3)
C1	0.5827 (6)	0.62513 (11)	0.7783 (3)	0.0203 (5)
H1A	0.499780	0.658300	0.713823	0.030*
H1B	0.809060	0.624553	0.777897	0.030*
H1C	0.522278	0.633151	0.876394	0.030*
C5	0.1189 (5)	0.39860 (11)	0.5688 (2)	0.0161 (4)
H5	−0.033554	0.398522	0.490504	0.019*
C3	0.4577 (5)	0.45534 (10)	0.7425 (2)	0.0123 (4)
C2	0.5823 (5)	0.51534 (11)	0.7990 (2)	0.0144 (4)
C4	0.2359 (5)	0.45406 (10)	0.6259 (2)	0.0156 (4)
H4	0.163744	0.492573	0.584857	0.019*
H3	0.836 (8)	0.4252 (17)	0.929 (4)	0.025 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01408 (6)	0.01099 (7)	0.01764 (7)	−0.00031 (5)	−0.00056 (4)	−0.00134 (5)
O3	0.0173 (8)	0.0173 (8)	0.0153 (7)	0.0008 (6)	−0.0061 (6)	−0.0004 (6)
O1	0.0241 (8)	0.0104 (7)	0.0188 (8)	−0.0031 (6)	−0.0048 (6)	0.0007 (6)
O2	0.0210 (8)	0.0204 (9)	0.0211 (8)	−0.0015 (6)	−0.0083 (6)	−0.0031 (6)
C6	0.0114 (8)	0.0128 (9)	0.0138 (9)	−0.0012 (7)	0.0009 (7)	−0.0017 (7)
C7	0.0128 (9)	0.0120 (9)	0.0136 (9)	0.0008 (7)	0.0011 (7)	0.0006 (7)
C8	0.0103 (8)	0.0155 (9)	0.0105 (8)	0.0020 (7)	0.0003 (6)	0.0010 (7)
C1	0.0282 (12)	0.0114 (10)	0.0211 (11)	−0.0062 (8)	0.0005 (9)	−0.0021 (8)
C5	0.0178 (10)	0.0137 (10)	0.0158 (9)	−0.0004 (7)	−0.0061 (7)	0.0005 (7)
C3	0.0132 (9)	0.0108 (9)	0.0128 (9)	0.0003 (7)	−0.0010 (7)	0.0004 (7)
C2	0.0140 (9)	0.0152 (10)	0.0138 (9)	−0.0006 (7)	0.0007 (7)	−0.0011 (7)
C4	0.0179 (10)	0.0104 (9)	0.0177 (10)	0.0002 (7)	−0.0053 (8)	0.0012 (7)

Geometric parameters (Å, º) top

I1—C6	2.101 (2)	C8—C3	1.407 (3)
O3—C8	1.357 (3)	C1—H1A	0.9800
O3—H3	0.70 (4)	C1—H1B	0.9800
O1—C1	1.447 (3)	C1—H1C	0.9800
O1—C2	1.336 (3)	C5—H5	0.9500
O2—C2	1.220 (3)	C5—C4	1.379 (3)
C6—C7	1.391 (3)	C3—C2	1.472 (3)
C6—C5	1.394 (3)	C3—C4	1.400 (3)
C7—H7	0.9500	C4—H4	0.9500
C7—C8	1.395 (3)

C8—O3—H3	107 (3)	H1A—C1—H1C	109.5
C2—O1—C1	115.15 (18)	H1B—C1—H1C	109.5
C7—C6—I1	119.85 (16)	C6—C5—H5	121.0
C7—C6—C5	121.9 (2)	C4—C5—C6	118.0 (2)
C5—C6—I1	118.20 (15)	C4—C5—H5	121.0
C6—C7—H7	120.3	C8—C3—C2	120.44 (19)
C6—C7—C8	119.4 (2)	C4—C3—C8	118.89 (19)
C8—C7—H7	120.3	C4—C3—C2	120.63 (19)
O3—C8—C7	116.94 (19)	O1—C2—C3	113.23 (18)
O3—C8—C3	123.3 (2)	O2—C2—O1	122.9 (2)
C7—C8—C3	119.80 (19)	O2—C2—C3	123.8 (2)
O1—C1—H1A	109.5	C5—C4—C3	122.0 (2)
O1—C1—H1B	109.5	C5—C4—H4	119.0
O1—C1—H1C	109.5	C3—C4—H4	119.0
H1A—C1—H1B	109.5

I1—C6—C7—C8	178.99 (15)	C8—C3—C2—O1	178.4 (2)
I1—C6—C5—C4	−179.01 (17)	C8—C3—C2—O2	−1.0 (3)
O3—C8—C3—C2	1.0 (3)	C8—C3—C4—C5	0.9 (3)
O3—C8—C3—C4	178.8 (2)	C1—O1—C2—O2	1.2 (3)
C6—C7—C8—O3	−178.90 (19)	C1—O1—C2—C3	−178.26 (19)
C6—C7—C8—C3	0.9 (3)	C5—C6—C7—C8	−0.8 (3)
C6—C5—C4—C3	−0.9 (4)	C2—C3—C4—C5	178.8 (2)
C7—C6—C5—C4	0.8 (3)	C4—C3—C2—O1	0.6 (3)
C7—C8—C3—C2	−178.8 (2)	C4—C3—C2—O2	−178.8 (2)
C7—C8—C3—C4	−0.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.70 (4)	2.05 (4)	2.670 (3)	149 (4)
O3—H3···O2ⁱ	0.70 (4)	2.53 (4)	3.087 (2)	139 (4)

Symmetry code: (i) −x+2, −y+1, −z+2.

Footnotes

‡Both authors contributed equally to this work.

Funding information

Funding for this research was provided by: National Science Foundation (award No. DMR-2003932).

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