2-Phenoxy­benzoic acid at room temperature

Parkin, A.; Harte, S.M.; Carmichael, D.; Currie, S.; Drummond, L.; Haahr, A.; Haggarty, K.; Hunter, T.; Lamarque, A.; Lawton, L.; Martin, C.; Mathieson, J.E.; Mathieson, J.S.; McGlone, T.; McGregor, J.; McMillan, L.; Robertson, L.; Thatcher, R.; Vance, S.; Wilson, C.C.

doi:10.1107/S1600536805019495

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 61| Part 7| July 2005| Pages o2280-o2282

https://doi.org/10.1107/S1600536805019495

2-Phenoxybenzoic acid at room temperature

^aDepartment of Chemistry, University of Glasgow, University Avenue, Glasgow G12 8QQ, Scotland
^*Correspondence e-mail: a.parkin@chem.gla.ac.uk

(Received 24 May 2005; accepted 21 June 2005; online 30 June 2005)

In the crystal structure of the title compound, C₁₃H₁₀O₃, the molecules form classical hydrogen-bonded carboxylic acid dimers [O⋯O = 2.651 (2) Å]. These dimers are linked by C—H⋯π and π–π interactions to give a three-dimensional network.

Comment

Benzoic acid is a compound that has an elegant simplicity to its molecular structure, but its derivatives display an enormous complexity and diversity of molecular structures. The latest version of the Cambridge Structural Database (CSD, Version 5.26; Allen, 2002 ) contains 1883 structures with a benzoic acid derivative existing in the crystal structure as an isolated molecule; this does not include structures in which the molecules are either deprotonated or coordinated to metal ions. By contrast, the simple and readily available title compound, (I), is only observed in four crystal structures in the CSD, and in all of these it serves as a ligand. The 3- and 4-phenoxybenzoic acid structures are observed even less frequently, with zero and one structures of these compounds, respectively. Possibly the most closely related structure available in the CSD is that of 2-(2-carboxyphenoxy)benzoic acid (CSD refcode MIGPAT; Field & Venkataraman, 2002 ), which differs only by the presence of an extra carboxylic acid group on the second benzene ring.

The molecular geometry observed in the structure of (I) is mostly unremarkable, with the principal features of note being the prolate displacement ellipsoid of atom O10, which is consistent with a large vibration perpendicular to the plane of the benzoic acid fragment (Fig. 1). This motion is not obviously propagated in the second benzene ring; in this portion, the displacement ellipsoids are surprisingly close to spherical, although large. These observations are most likely due to the combination of three movements: a typical in-plane rotational movement around the ring, the translational movement observed for O10 in the plane of this ring and perpendicular to the O10—C11 bond vector, and a rotational movement around the O10—C11 bond vector. The average C—C bond length in this ring is slightly short, at 1.36 Å; this bond shortening can also be attributed to the effect of large thermal libration. The normals to the planes of the two benzene rings are nearly perpendicular, at 89.8 (2)°.

The molecules of (I) assemble to form a classical hydrogen-bonded dimer, in which the C7—O9 and C7—O8 bond lengths in the carboxylic acid group of 1.223 (2) and 1.3015 (18) Å, respectively, indicate a well ordered hydrogen bond. This is supported by the lack of H-atom disorder observed in the Fourier difference map (calculated with the program MAPVIEW, part of the WinGX suite; Farrugia, 1999 ) through the dimer group (Fig. 2). The single crystallographically unique hydrogen bond, viz. O8—H1⋯O9ⁱ [symmetry code: (i) 3 − x, 1 − y, −z], exhibits a typical O⋯O separation for benzoic acid dimers of 2.651 (2) Å. The remainder of the contacts lie outside the sum of the van der Waals radii of the two atoms involved, but these very weak interactions can still be used to describe the remainder of the structure. The dimers assemble into extended ribbons through C—H⋯π interactions of 3.658 Å for C4—H4⋯C12ⁱⁱ [symmetry code: (ii) x, y − 1, z] (Fig. 3a), and these ribbons form stacks defined by a π–π contact of 3.446 Å between atoms C13 and C16ⁱⁱⁱ [symmetry code: (iii) x − 1, y, z] (Fig. 3b). The stacks pack together with C—H⋯π interactions of 3.697 Å for C12—H12⋯C5^iv [symmetry code: (iv) x − 1, y + 1, z] (Fig. 4).

The most striking difference between the molecular structure presented here and that of MIGPAT (Field & Venkataraman, 2002) is the geometry of the carboxylic acid group. In the title compound, it is clear from the bond lengths that the C=O double bond is C7=O9, involving the O atom closest to the ether group. By contrast, the shorter C—O bond in MIGPAT is that further from the ether O atom, although the difference between the two bond lengths is much less than we report here. As the two chemically different carboxylic acids in MIGPAT are crystallographically identical, it is possible that there is some correlated structural disorder between the C—O and C=O bonds; this might explain the very similar C—O bond lengths in MIGPAT.

Figure 1
A drawing of the molecule of (I)

, showing the atomic numbering scheme. Ellipsoids for non-H atoms are shown at the 30% probability level. All H atoms take their number from the parent C atom, except for H1.

Figure 2
Fourier difference map section through the carboxylic acid dimer plane defined by atoms C7, O8, O9, C7ⁱ, O8ⁱ and O9ⁱ [symmetry code: (i) 3 − x, 1 − y, −z]. There is clearly only a single peak associated with each hydrogen bond, corresponding to an ordered H atom.

Figure 3
Packing plots of (I)

, illustrating the principal contacts in the structure. (top) The hydrogen-bond dimers link together into ribbons via C—H⋯π contacts (shown in yellow). (bottom) These ribbons stack due to π–π interactions (shown in pale green).

Figure 4
A packing plot of the entire structure. The stacks are linked by C—H⋯π interactions, shown in red.

Experimental

The title compound was used as received from Aldrich. Crystals of diffraction quality were grown from an acetone solution.

Crystal data

C₁₃H₁₀O₃
M_r = 214.22
Triclinic, $[P \overline 1]$
a = 5.2736 (5) Å
b = 7.7366 (6) Å
c = 13.6863 (10) Å
α = 89.184 (6)°
β = 83.433 (6)°
γ = 74.640 (6)°
V = 534.84 (8) Å³
Z = 2
D_x = 1.330 Mg m⁻³
Mo Kα radiation
Cell parameters from 8180 reflections
θ = 2–28°
μ = 0.10 mm⁻¹
T = 293 K
Block, colourless
0.30 × 0.15 × 0.10 mm

Data collection

Bruker APEX2 diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 1996 )T_min = 0.98, T_max = 0.99
8180 measured reflections
2565 independent reflections
1516 reflections with I > 2σ(I)
R_int = 0.028
θ_max = 28.5°
h = −6 → 7
k = −10 → 10
l = −18 → 18

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.164
S = 0.93
2565 reflections
148 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F²) + 0.08 + 0.08P], where P = [max(F_o²,0) + 2F_c²]/3
(Δ/σ)_max < 0.001
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

C1—C2	1.397 (2)
C1—C6	1.390 (2)
C1—C7	1.477 (2)
C2—O10	1.371 (2)
C2—C3	1.389 (3)
O10—C11	1.387 (2)
C11—C12	1.346 (3)
C11—C16	1.372 (4)
C12—C13	1.373 (3)
C13—C14	1.343 (4)
C14—C15	1.328 (4)
C15—C16	1.379 (3)
C3—C4	1.367 (3)
C4—C5	1.376 (3)
C5—C6	1.378 (3)
C7—O9	1.223 (2)
C7—O8	1.3015 (18)

C2—C1—C6	117.52 (16)
C2—C1—C7	122.57 (15)
C6—C1—C7	119.91 (14)
C1—C2—O10	117.58 (15)
C1—C2—C3	120.32 (16)
O10—C2—C3	122.08 (15)
C2—O10—C11	119.76 (14)
O10—C11—C12	119.5 (2)
O10—C11—C16	120.0 (2)
C12—C11—C16	120.14 (19)
C11—C12—C13	119.2 (2)
C12—C13—C14	121.1 (2)
C13—C14—C15	119.9 (2)
C14—C15—C16	120.9 (3)
C15—C16—C11	118.8 (2)
C2—C3—C4	120.45 (17)
C3—C4—C5	120.44 (19)
C4—C5—C6	119.18 (18)
C1—C6—C5	122.08 (17)
C1—C7—O9	124.03 (14)
C1—C7—O8	114.22 (15)
O9—C7—O8	121.75 (16)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H1⋯O9ⁱ	0.90 (2)	1.75 (2)	2.651 (2)	175 (2)
Symmetry code: (i) 3-x, 1-y, -z.

H atoms were positioned geometrically and refined as riding groups, with C—H = 1.0 Å and U_iso(H) = 1.2U_eq(C), except for atom H1, which was located in a Fourier difference map and refined with an O—H distance restraint of 0.90 (5) Å and a fixed U_iso(H) = 0.05 Å².

Data collection: APEX2 (Bruker, 2005 ); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: ORTEP3 for Windows (Farrugia, 1997 ) and MERCURY (Bruno et al., 2002 ); software used to prepare material for publication: CRYSTALS.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536805019495/cf6429sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805019495/cf6429Isup2.hkl

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Bruno et al., 2002); software used to prepare material for publication: CRYSTALS.

2-Phenoxybenzoic acid top

Crystal data top

C₁₃H₁₀O₃	Z = 2
M_r = 214.22	F(000) = 224
Triclinic, P1	D_x = 1.330 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.2736 (5) Å	Cell parameters from 8180 reflections
b = 7.7366 (6) Å	θ = 2–28°
c = 13.6863 (10) Å	µ = 0.10 mm⁻¹
α = 89.184 (6)°	T = 293 K
β = 83.433 (6)°	Block, colourless
γ = 74.640 (6)°	0.30 × 0.15 × 0.10 mm
V = 534.84 (8) Å³

Data collection top

Bruker APEX2 diffractometer	1516 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
φ and ω scans	θ_max = 28.5°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→7
T_min = 0.98, T_max = 0.99	k = −10→10
8180 measured reflections	l = −18→18
2565 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.164	w = 1/[σ²(F²) + 0.08 + 0.08P], where P = [max(F_o²,0) + 2F_c²]/3
S = 0.93	(Δ/σ)_max = 0.000159
2565 reflections	Δρ_max = 0.38 e Å⁻³
148 parameters	Δρ_min = −0.29 e Å⁻³
1 restraint

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

	x	y	z	U_iso*/U_eq
C1	1.0774 (3)	0.2871 (2)	0.12595 (11)	0.0538
C2	0.8810 (4)	0.3698 (2)	0.20060 (13)	0.0663
O10	0.8556 (4)	0.54655 (19)	0.22196 (13)	0.1192
C11	0.6892 (5)	0.6279 (2)	0.30383 (16)	0.0787
C12	0.4462 (5)	0.7320 (3)	0.29248 (17)	0.0909
C13	0.2911 (5)	0.8241 (4)	0.3725 (2)	0.0970
C14	0.3793 (5)	0.8138 (3)	0.46118 (19)	0.0911
C15	0.6204 (6)	0.7129 (4)	0.47235 (19)	0.1149
C16	0.7826 (5)	0.6184 (4)	0.3938 (2)	0.1112
C3	0.7150 (4)	0.2753 (3)	0.24872 (15)	0.0760
C4	0.7430 (4)	0.1000 (3)	0.22415 (16)	0.0772
C5	0.9367 (4)	0.0147 (3)	0.15164 (16)	0.0781
C6	1.1009 (4)	0.1085 (2)	0.10356 (14)	0.0673
C7	1.2568 (3)	0.3820 (2)	0.07145 (11)	0.0558
O9	1.2443 (3)	0.54022 (17)	0.08452 (10)	0.0788
O8	1.4326 (3)	0.28285 (19)	0.00646 (10)	0.0819
H12	0.3789	0.7416	0.2267	0.1076*
H13	0.1095	0.9007	0.3647	0.1114*
H14	0.2637	0.8818	0.5187	0.1056*
H15	0.6847	0.7053	0.5386	0.1326*
H16	0.9651	0.5443	0.4023	0.1243*
H3	0.5743	0.3357	0.3018	0.0891*
H4	0.6217	0.0335	0.2590	0.0934*
H5	0.9583	−0.1138	0.1341	0.0941*
H6	1.2412	0.0460	0.0508	0.0791*
H1	1.535 (3)	0.348 (2)	−0.0246 (12)	0.0500*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0574 (9)	0.0501 (9)	0.0474 (8)	−0.0055 (7)	0.0014 (7)	−0.0040 (7)
C2	0.0805 (12)	0.0475 (9)	0.0618 (10)	−0.0113 (8)	0.0168 (9)	−0.0063 (8)
O10	0.1579 (16)	0.0575 (8)	0.1224 (13)	−0.0398 (9)	0.0961 (12)	−0.0311 (8)
C11	0.0982 (15)	0.0472 (9)	0.0814 (14)	−0.0263 (10)	0.0472 (12)	−0.0152 (9)
C12	0.0975 (17)	0.0935 (16)	0.0768 (14)	−0.0243 (14)	0.0109 (12)	−0.0181 (12)
C13	0.0789 (15)	0.0970 (17)	0.0991 (18)	−0.0059 (12)	0.0176 (13)	−0.0198 (14)
C14	0.0976 (17)	0.0790 (14)	0.0869 (16)	−0.0231 (12)	0.0335 (13)	−0.0306 (12)
C15	0.112 (2)	0.143 (3)	0.0750 (16)	−0.0165 (19)	0.0088 (15)	−0.0134 (15)
C16	0.0877 (17)	0.113 (2)	0.108 (2)	0.0039 (15)	0.0198 (15)	0.0077 (16)
C3	0.0873 (14)	0.0593 (11)	0.0732 (12)	−0.0190 (10)	0.0252 (10)	−0.0048 (9)
C4	0.0891 (14)	0.0625 (12)	0.0803 (13)	−0.0275 (10)	0.0066 (11)	0.0009 (10)
C5	0.0920 (15)	0.0551 (11)	0.0859 (14)	−0.0215 (10)	0.0018 (11)	−0.0131 (10)
C6	0.0723 (12)	0.0571 (10)	0.0664 (11)	−0.0115 (9)	0.0051 (9)	−0.0151 (8)
C7	0.0576 (9)	0.0532 (9)	0.0481 (9)	−0.0041 (7)	0.0046 (7)	−0.0082 (7)
O9	0.0870 (9)	0.0578 (8)	0.0806 (9)	−0.0182 (6)	0.0350 (7)	−0.0159 (6)
O8	0.0886 (10)	0.0656 (8)	0.0801 (9)	−0.0197 (7)	0.0387 (8)	−0.0198 (7)

Geometric parameters (Å, º) top

C1—C2	1.397 (2)	C15—C16	1.379 (3)
C1—C6	1.390 (2)	C15—H15	1.000
C1—C7	1.477 (2)	C16—H16	1.000
C2—O10	1.371 (2)	C3—C4	1.367 (3)
C2—C3	1.389 (3)	C3—H3	1.000
O10—C11	1.387 (2)	C4—C5	1.376 (3)
C11—C12	1.346 (3)	C4—H4	1.000
C11—C16	1.372 (4)	C5—C6	1.378 (3)
C12—C13	1.373 (3)	C5—H5	1.000
C12—H12	1.000	C6—H6	1.000
C13—C14	1.343 (4)	C7—O9	1.223 (2)
C13—H13	1.000	C7—O8	1.3015 (18)
C14—C15	1.328 (4)	O8—H1	0.901 (17)
C14—H14	1.000

C2—C1—C6	117.52 (16)	C16—C15—H15	119.7
C2—C1—C7	122.57 (15)	C15—C16—C11	118.8 (2)
C6—C1—C7	119.91 (14)	C15—C16—H16	120.6
C1—C2—O10	117.58 (15)	C11—C16—H16	120.6
C1—C2—C3	120.32 (16)	C2—C3—C4	120.45 (17)
O10—C2—C3	122.08 (15)	C2—C3—H3	119.8
C2—O10—C11	119.76 (14)	C4—C3—H3	119.8
O10—C11—C12	119.5 (2)	C3—C4—C5	120.44 (19)
O10—C11—C16	120.0 (2)	C3—C4—H4	119.8
C12—C11—C16	120.14 (19)	C5—C4—H4	119.8
C11—C12—C13	119.2 (2)	C4—C5—C6	119.18 (18)
C11—C12—H12	120.4	C4—C5—H5	120.4
C13—C12—H12	120.4	C6—C5—H5	120.4
C12—C13—C14	121.1 (2)	C1—C6—C5	122.08 (17)
C12—C13—H13	119.6	C1—C6—H6	119.0
C14—C13—H13	119.3	C5—C6—H6	118.9
C13—C14—C15	119.9 (2)	C1—C7—O9	124.03 (14)
C13—C14—H14	120.0	C1—C7—O8	114.22 (15)
C15—C14—H14	120.1	O9—C7—O8	121.75 (16)
C14—C15—C16	120.9 (3)	C7—O8—H1	110.1 (10)
C14—C15—H15	119.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H1···O9ⁱ	0.90 (2)	1.75 (2)	2.651 (2)	175 (2)

Symmetry code: (i) −x+3, −y+1, −z.

Acknowledgements

This paper is the result of an optional undergraduate class project entitled `Frontiers of Crystallography', designed to show some of the sort of research that can be undertaken in crystallography. The data collection, structure solution, refinement and post-refinement analysis of the unknown title structure were all undertaken in parallel by the undergraduate students, who are all co-authors, and the collated information has resulted in this paper.

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