Benzene-1,3,5-triol at 105 K

Görbitz, C.H.; Kaboli, M.; Read, M.L.; Vestli, K.

doi:10.1107/S1600536808030638

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page o2023

doi:10.1107/S1600536808030638

Open

access

Benzene-1,3,5-triol at 105 K

Carl Henrik Görbitz,^a ^* Massoud Kaboli,^a Matthew Lovell Read ^a and Kristian Vestli ^a

^aDepartment of Chemistry, University of Oslo, PO Box 1033 Blindern, N-0315 Oslo, Norway
^*Correspondence e-mail: c.h.gorbitz@kjemi.uio.no

(Received 16 September 2008; accepted 23 September 2008; online 27 September 2008)

The structure of the title compound, C₆H₆O₃, has been redetermined at low temperature [room-temperature structure: Maartmann-Moe (1965 ). Acta Cryst. 19, 155–157]. The molecule is planar with approximate D_3h point symmetry, yet it crystallizes in the chiral orthorhombic space group P2₁2₁2₁ with a three-dimensional hydrogen-bonding network containing infinite O—H⋯O—H⋯O—H chains.

Related literature

For the structure at room temperature, see: Maartmann-Moe (1965). For the hydrate structure, see: Wallwork & Powell (1957 ).

Experimental

Crystal data

C₆H₆O₃
M_r = 126.11
Orthorhombic, P 2₁ 2₁ 2₁
a = 4.7778 (2) Å
b = 9.3581 (4) Å
c = 12.4433 (6) Å
V = 556.35 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 105 (2) K
0.20 × 0.08 × 0.05 mm

Data collection

Siemens SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.916, T_max = 0.997
6178 measured reflections
743 independent reflections
728 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.081
S = 1.13
743 reflections
91 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 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⋯O3ⁱ	0.83 (2)	1.94 (2)	2.7426 (13)	164 (2)
O2—H2⋯O1ⁱⁱ	0.79 (2)	1.97 (2)	2.7424 (14)	169 (2)
O3—H3⋯O2ⁱⁱⁱ	0.86 (2)	1.85 (2)	2.7086 (16)	173.3 (17)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT-Plus (Bruker, 2001 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808030638/bi2305sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808030638/bi2305Isup2.hkl

checkCIF report

Comment top

The structure of the benzene-1,3,5-triol, commonly known as phloroglucinol, is shown in Fig. 1. The molecule is essentially planar, with D₃_h point symmetry, having only small out-of-plane rotations for the hydroxyl groups. Rather than forming a layer-like structure, a folded molecular aggregation pattern is observed in the crystal (Fig. 2) giving a three-dimensional hydrogen-bonding pattern. The three hydrogen bonds listed in Table 1 form an infinite zigzag chain along the b axis as shown in Fig. 3. The agreement with the original structure determination (Maartmann-Moe, 1965) is generally good, but with some significant changes in the hydrogen bonding geometries.

Benzene-1,3,5-triol has also been crystallized as a dihydrate, which is divided into layers with water molecules as connectors (Wallwork & Powell, 1957).

Related literature top

For the structure at room temperature, see: Maartmann-Moe (1965). For the hydrate structure, see: Wallwork & Powell (1957).

Experimental top

The title compound was obtained from Fluka. Crystals were grown by diffusion of hexane into 30 µl of a solution containing 2.1 mg benzene-1,3,5-triol and 1.3 mg triazin in 3-methyl-2-butanone.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are shown at the 50% probability level and H-atoms are shown as spheres of arbitrary size.
	Fig. 2. Molecular packing and unit cell of the title compound viewed along the b axis. Hydrogen bonding is indicated by dashed lines, H-atoms bonded to C have been omitted for clarity. The three different hydroxylic O atoms have been depicted in different colours.
	Fig. 3. Detail of the hydrogen bonding pattern showing infinite hydrogen-bonded chains.

benzene-1,3,5-triol top

Crystal data top

C₆H₆O₃	F(000) = 264
M_r = 126.11	D_x = 1.506 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4652 reflections
a = 4.7778 (2) Å	θ = 2.7–27.1°
b = 9.3581 (4) Å	µ = 0.12 mm⁻¹
c = 12.4433 (6) Å	T = 105 K
V = 556.35 (4) Å³	Needle, colourless
Z = 4	0.20 × 0.08 × 0.05 mm

Data collection top

Siemens SMART CCD diffractometer	743 independent reflections
Radiation source: fine-focus sealed tube	728 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
ω scans	θ_max = 27.1°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→6
T_min = 0.916, T_max = 0.997	k = −11→11
6178 measured reflections	l = −15→15

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ²(F_o²) + (0.054P)² + 0.1017P] where P = (F_o² + 2F_c²)/3
743 reflections	(Δ/σ)_max < 0.001
91 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₆H₆O₃	V = 556.35 (4) Å³
M_r = 126.11	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 4.7778 (2) Å	µ = 0.12 mm⁻¹
b = 9.3581 (4) Å	T = 105 K
c = 12.4433 (6) Å	0.20 × 0.08 × 0.05 mm

Data collection top

Siemens SMART CCD diffractometer	743 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	728 reflections with I > 2σ(I)
T_min = 0.916, T_max = 0.997	R_int = 0.014
6178 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	Δρ_max = 0.27 e Å⁻³
743 reflections	Δρ_min = −0.20 e Å⁻³
91 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. Data were collected by measuring three sets of exposures with the detector set at 2θ = 29°, crystal-to-detector distance 5.00 cm. Refinement of F² against ALL reflections.

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

	x	y	z	U_iso*/U_eq
O1	0.2140 (2)	0.48267 (10)	0.56722 (8)	0.0160 (3)
H1	0.189 (5)	0.560 (2)	0.5979 (15)	0.024*
O2	0.8083 (3)	0.25657 (10)	0.31075 (8)	0.0167 (3)
H2	0.760 (5)	0.189 (2)	0.3432 (14)	0.025*
O3	0.7415 (2)	0.76483 (10)	0.32139 (8)	0.0160 (3)
H3	0.884 (5)	0.7549 (19)	0.2792 (16)	0.024*
C1	0.3967 (3)	0.49437 (14)	0.48167 (11)	0.0135 (3)
C2	0.5004 (3)	0.36808 (13)	0.43819 (11)	0.0141 (3)
H21	0.4423	0.2779	0.4652	0.017*
C3	0.6913 (3)	0.37730 (13)	0.35413 (10)	0.0135 (3)
C4	0.7758 (3)	0.50800 (15)	0.31202 (11)	0.0150 (3)
H41	0.9054	0.5126	0.2542	0.018*
C5	0.6651 (3)	0.63152 (13)	0.35689 (10)	0.0134 (3)
C6	0.4732 (3)	0.62700 (13)	0.44129 (11)	0.0137 (3)
H61	0.3970	0.7124	0.4704	0.016*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0199 (5)	0.0107 (5)	0.0173 (5)	−0.0003 (4)	0.0057 (4)	−0.0006 (3)
O2	0.0217 (5)	0.0090 (5)	0.0194 (5)	0.0017 (4)	0.0058 (4)	0.0000 (4)
O3	0.0209 (6)	0.0093 (5)	0.0177 (5)	−0.0015 (4)	0.0054 (5)	0.0009 (3)
C1	0.0127 (6)	0.0142 (6)	0.0136 (6)	−0.0006 (6)	−0.0006 (5)	−0.0004 (5)
C2	0.0152 (6)	0.0109 (6)	0.0161 (6)	−0.0009 (5)	−0.0003 (6)	0.0017 (5)
C3	0.0142 (6)	0.0108 (6)	0.0154 (6)	0.0014 (6)	−0.0013 (6)	−0.0012 (5)
C4	0.0158 (6)	0.0141 (6)	0.0150 (6)	0.0000 (5)	0.0032 (5)	0.0003 (5)
C5	0.0152 (7)	0.0104 (6)	0.0145 (6)	−0.0017 (6)	−0.0014 (6)	0.0012 (5)
C6	0.0151 (6)	0.0110 (6)	0.0152 (6)	0.0005 (5)	0.0008 (6)	−0.0020 (5)

Geometric parameters (Å, º) top

O1—C1	1.3808 (17)	C2—C3	1.3905 (19)
O1—H1	0.83 (2)	C2—H21	0.9500
O2—C3	1.3712 (16)	C3—C4	1.3905 (18)
O2—H2	0.79 (2)	C4—C5	1.3884 (19)
O3—C5	1.3730 (15)	C4—H41	0.9500
O3—H3	0.86 (2)	C5—C6	1.3945 (19)
C1—C6	1.3881 (17)	C6—H61	0.9500
C1—C2	1.3910 (18)

C1—O1—H1	112.2 (14)	C2—C3—C4	121.90 (12)
C3—O2—H2	109.9 (14)	C5—C4—C3	118.05 (12)
C5—O3—H3	107.9 (12)	C5—C4—H41	121.0
O1—C1—C6	121.10 (11)	C3—C4—H41	121.0
O1—C1—C2	117.24 (11)	O3—C5—C4	121.72 (12)
C6—C1—C2	121.67 (12)	O3—C5—C6	116.41 (11)
C3—C2—C1	118.27 (12)	C4—C5—C6	121.87 (12)
C3—C2—H21	120.9	C1—C6—C5	118.22 (12)
C1—C2—H21	120.9	C1—C6—H61	120.9
O2—C3—C2	120.83 (12)	C5—C6—H61	120.9
O2—C3—C4	117.26 (12)

O1—C1—C2—C3	−178.06 (12)	O1—C1—C6—C5	178.09 (12)
C6—C1—C2—C3	1.8 (2)	C2—C1—C6—C5	−1.8 (2)
C1—C2—C3—O2	177.59 (12)	O3—C5—C6—C1	−178.14 (12)
C1—C2—C3—C4	−1.1 (2)	C4—C5—C6—C1	1.0 (2)
O2—C3—C4—C5	−178.32 (13)	H1—O1—C1—C6	−13.0 (16)
C2—C3—C4—C5	0.4 (2)	H2—O2—C3—C2	−4.3 (16)
C3—C4—C5—O3	178.75 (13)	H3—O3—C5—C4	−10.8 (14)
C3—C4—C5—C6	−0.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.83 (2)	1.94 (2)	2.7426 (13)	164 (2)
O2—H2···O1ⁱⁱ	0.79 (2)	1.97 (2)	2.7424 (14)	169 (2)
O3—H3···O2ⁱⁱⁱ	0.86 (2)	1.85 (2)	2.7086 (16)	173.3 (17)

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

Experimental details

Crystal data
Chemical formula	C₆H₆O₃
M_r	126.11
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	105
a, b, c (Å)	4.7778 (2), 9.3581 (4), 12.4433 (6)
V (Å³)	556.35 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.20 × 0.08 × 0.05

Data collection
Diffractometer	Siemens SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.916, 0.997
No. of measured, independent and observed [I > 2σ(I)] reflections	6178, 743, 728
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.081, 1.13
No. of reflections	743
No. of parameters	91
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.20

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008).

Selected torsion angles (º) top

H1—O1—C1—C6	−13.0 (16)	H3—O3—C5—C4	−10.8 (14)
H2—O2—C3—C2	−4.3 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.83 (2)	1.94 (2)	2.7426 (13)	164 (2)
O2—H2···O1ⁱⁱ	0.79 (2)	1.97 (2)	2.7424 (14)	169 (2)
O3—H3···O2ⁱⁱⁱ	0.86 (2)	1.85 (2)	2.7086 (16)	173.3 (17)

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

Acknowledgements

The purchase of the diffractometer was made possible through support from the Research Council of Norway (NFR).

References

Bruker (1998). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2001). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Maartmann-Moe, K. (1965). Acta Cryst. 19, 155–157. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wallwork, S. C. & Powell, H. M. (1957). Acta Cryst. 10, 48–52. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar