Benzene-1,2,4,5-tetrol

Weare, B.L.; Hoggett, S.; Cull, W.J.; Argent, S.P.; Khlobystov, A.N.; Brown, P.D.

doi:10.1107/S2414314624006126

Benzene-1,2,4,5-tetrol

B. L. Weare, S. Hoggett, W. J. Cull, S. P. Argent, A. N. Khlobystov and P. D. Brown

The crystal structure of the title compound was determined at 120 K. It crystallizes in the triclinic space group P $\overline{1}$ with four independent molecules in the asymmetric unit. In the crystal, each symmetry-unique molecule forms π–π stacks on itself, giving four unique π–π stacking interactions. Intermolecular hydrogen bonding is observed between each pair of independent molecules, where each hydroxy group can act as a hydrogen-bond donor and acceptor.

Keywords: benzene-1,2,4,5-tetrol; crystal structure; hydrogen bonds; covalent organic framework; hydroxyl.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2414314624006126/bx4030sup1.cif Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2414314624006126/bx4030Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2414314624006126/bx4030Isup3.cml Supplementary material

CCDC reference: 2357698

checkCIF report

Key indicators

Structure: I

Single-crystal X-ray study
T = 120 K
Mean (C-C) = 0.003 Å
R factor = 0.045
wR factor = 0.133
Data-to-parameter ratio = 10.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         31 Report
                2  8  0,   3  8  0,   1 12  0,  -1-12  1,  -3 -8  1,  -2 -8  1,
               -3 -7  1,  -2 -7  1,  -4 -5  1,  -3 -8  2,  -3 -7  2,  -3 -8  3,
               -3 -7  3,   3  9  3,  -2 -9  4,  -3 -7  4,   3 10  4,  -4 -1  5,
               -3 10  5,   2 12  5,  -2 -8  6,   2 12  7,   4  3  8,   4  4  8,
               -1 12  9,  -1 13  9,  -3  6 11,  -1 12 11,  -2  0 12,   0 12 12,
               -2  1 13,

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         16 Note
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT484_ALERT_4_G Round D-H..A Angle Rep for O5D      ..O5C      .        175 Degree
PLAT484_ALERT_4_G Round D-H..A Angle Rep for O5A      ..O5D      .        162 Degree
PLAT484_ALERT_4_G Round D-H..A Angle Rep for O4A      ..O4C      .        163 Degree
PLAT484_ALERT_4_G Round D-H..A Angle Rep for O4B      ..O4D      .        163 Degree
PLAT484_ALERT_4_G Round D-H..A Angle Rep for O4C      ..O4B      .        167 Degree
PLAT484_ALERT_4_G Round D-H..A Angle Rep for O4D      ..O5B      .        154 Degree
PLAT484_ALERT_4_G Round D-H..A Angle Rep for O5B      ..O5A      .        169 Degree
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          8 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        123 Note
PLAT933_ALERT_2_G Number of HKL-OMIT Records in Embedded .res File          4 Note
               -3  6 11,   4  3  8,   4  4  8,   4  5  8,
PLAT941_ALERT_3_G Average HKL Measurement Multiplicity ...........        3.7 Low
PLAT969_ALERT_5_G The 'Henn et al.' R-Factor-gap value ...........      2.549 Note
              Predicted wR2: Based on SigI   2  5.21 or SHELX Weight 12.21       
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          4 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  15 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   9 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Computing details top

Benzene-1,2,4,5-tetrol top

Crystal data top

C₆H₆O₄	Z = 4
M_r = 142.11	F(000) = 296
Triclinic, P1	D_x = 1.697 Mg m⁻³
a = 3.7474 (2) Å	Cu Kα radiation, λ = 1.54184 Å
b = 11.6254 (6) Å	Cell parameters from 4683 reflections
c = 13.7771 (8) Å	θ = 3.4–75.6°
α = 68.407 (5)°	µ = 1.26 mm⁻¹
β = 85.779 (4)°	T = 120 K
γ = 89.843 (4)°	Block, colourless
V = 556.37 (6) Å³	0.07 × 0.05 × 0.02 mm

Data collection top

XtalLAB PRO MM007, PILATUS3 R 200K diffractometer	2185 independent reflections
Radiation source: rotating anode, MicroMax 007 HF	1842 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.063
Detector resolution: 5.8140 pixels mm^-1	θ_max = 76.2°, θ_min = 3.5°
ω scans	h = −4→4
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2023)	k = −14→14
T_min = 0.927, T_max = 1.000	l = −17→17
8096 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.045	Hydrogen site location: mixed
wR(F²) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0799P)² + 0.1541P] where P = (F_o² + 2F_c²)/3
2185 reflections	(Δ/σ)_max < 0.001
205 parameters	Δρ_max = 0.28 e Å⁻³
8 restraints	Δρ_min = −0.33 e Å⁻³

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. All hydrogen atoms were observed in the electron difference map. All hydroxy hydrogen atoms were refined with their O-H distances restrained to a target distance of 0.84 %A (DFIX). All other hydrogen atoms were geometrically placed and refined with a riding model.

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

	x	y	z	U_iso*/U_eq
C1A	−0.1468 (5)	1.09568 (17)	0.02598 (13)	0.0161 (4)
H1A	−0.249116	1.160936	0.043654	0.019*
C2A	−0.0561 (4)	0.98695 (17)	0.10428 (13)	0.0161 (4)
C3A	0.0876 (5)	0.89114 (17)	0.07847 (13)	0.0159 (4)
O4A	−0.1011 (3)	0.96812 (13)	0.20910 (9)	0.0204 (3)
H4A	−0.224 (6)	1.024 (2)	0.2205 (19)	0.031*
O5A	0.1865 (4)	0.78369 (12)	0.15524 (10)	0.0223 (3)
H5A	0.055 (6)	0.767 (2)	0.2104 (15)	0.033*
C1B	0.3702 (5)	0.38074 (17)	0.02176 (14)	0.0176 (4)
H1B	0.280395	0.299234	0.036481	0.021*
C2B	0.3851 (5)	0.42502 (17)	0.10209 (13)	0.0164 (4)
C3B	0.5136 (5)	0.54465 (17)	0.08035 (14)	0.0167 (4)
O4B	0.2720 (4)	0.34746 (13)	0.20260 (10)	0.0231 (3)
H4B	0.192 (7)	0.388 (2)	0.2403 (18)	0.035*
O5B	0.5337 (4)	0.58394 (13)	0.16233 (10)	0.0225 (3)
H5B	0.434 (7)	0.6521 (18)	0.1517 (19)	0.034*
C1C	0.5825 (5)	0.12616 (17)	0.45145 (13)	0.0168 (4)
H1C	0.639580	0.212043	0.418210	0.020*
C2C	0.4847 (5)	0.05791 (17)	0.39276 (13)	0.0167 (4)
C3C	0.4038 (5)	−0.06764 (17)	0.44063 (13)	0.0161 (4)
O4C	0.4713 (4)	0.10954 (12)	0.28510 (9)	0.0195 (3)
H4C	0.421 (6)	0.1868 (16)	0.2668 (18)	0.029*
O5C	0.3112 (3)	−0.13754 (12)	0.38383 (9)	0.0185 (3)
H5C	0.226 (6)	−0.093 (2)	0.3286 (14)	0.028*
C1D	1.0908 (4)	0.38787 (17)	0.49271 (13)	0.0159 (4)
H1D	1.153969	0.310947	0.487689	0.019*
C2D	0.9455 (4)	0.47869 (17)	0.40886 (13)	0.0149 (4)
C3D	0.8562 (4)	0.59139 (17)	0.41683 (13)	0.0151 (4)
O4D	0.8906 (4)	0.45066 (13)	0.32286 (9)	0.0202 (3)
H4D	0.773 (6)	0.509 (2)	0.2812 (17)	0.030*
O5D	0.7198 (3)	0.68082 (12)	0.33076 (9)	0.0180 (3)
H5D	0.611 (6)	0.7358 (19)	0.3477 (18)	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1A	0.0121 (8)	0.0164 (9)	0.0193 (9)	0.0051 (7)	−0.0046 (7)	−0.0052 (7)
C2A	0.0106 (8)	0.0201 (10)	0.0156 (8)	0.0037 (7)	−0.0036 (6)	−0.0039 (7)
C3A	0.0126 (8)	0.0159 (9)	0.0153 (8)	0.0037 (7)	−0.0049 (6)	−0.0003 (7)
O4A	0.0238 (7)	0.0217 (7)	0.0146 (6)	0.0096 (6)	−0.0051 (5)	−0.0046 (5)
O5A	0.0267 (7)	0.0185 (7)	0.0153 (6)	0.0120 (6)	−0.0023 (5)	0.0012 (5)
C1B	0.0142 (8)	0.0154 (9)	0.0215 (9)	0.0067 (7)	−0.0072 (7)	−0.0036 (7)
C2B	0.0128 (8)	0.0166 (9)	0.0162 (8)	0.0056 (7)	−0.0055 (7)	−0.0009 (7)
C3B	0.0136 (8)	0.0191 (9)	0.0183 (8)	0.0092 (7)	−0.0096 (7)	−0.0065 (7)
O4B	0.0302 (8)	0.0182 (7)	0.0171 (6)	0.0073 (6)	−0.0010 (5)	−0.0022 (5)
O5B	0.0309 (8)	0.0196 (7)	0.0195 (7)	0.0136 (6)	−0.0128 (6)	−0.0083 (6)
C1C	0.0143 (8)	0.0162 (9)	0.0172 (8)	0.0063 (7)	−0.0036 (7)	−0.0024 (7)
C2C	0.0130 (8)	0.0194 (10)	0.0133 (8)	0.0072 (7)	−0.0039 (6)	−0.0005 (7)
C3C	0.0119 (8)	0.0176 (9)	0.0171 (8)	0.0058 (7)	−0.0040 (6)	−0.0041 (7)
O4C	0.0264 (7)	0.0157 (7)	0.0138 (6)	0.0074 (6)	−0.0068 (5)	−0.0013 (5)
O5C	0.0210 (7)	0.0175 (7)	0.0154 (6)	0.0051 (6)	−0.0080 (5)	−0.0032 (5)
C1D	0.0123 (8)	0.0145 (9)	0.0183 (8)	0.0043 (7)	−0.0036 (7)	−0.0026 (7)
C2D	0.0103 (8)	0.0180 (9)	0.0148 (8)	0.0026 (7)	−0.0033 (6)	−0.0037 (7)
C3D	0.0120 (8)	0.0144 (9)	0.0150 (8)	0.0041 (7)	−0.0045 (6)	0.0000 (7)
O4D	0.0237 (7)	0.0210 (7)	0.0164 (6)	0.0107 (6)	−0.0094 (5)	−0.0062 (5)
O5D	0.0194 (6)	0.0171 (7)	0.0148 (6)	0.0092 (5)	−0.0075 (5)	−0.0015 (5)

Geometric parameters (Å, º) top

C1A—H1A	0.9500	C1C—H1C	0.9500
C1A—C2A	1.388 (2)	C1C—C2C	1.391 (3)
C1A—C3Aⁱ	1.391 (2)	C1C—C3Cⁱⁱⁱ	1.394 (2)
C2A—C3A	1.385 (3)	C2C—C3C	1.386 (3)
C2A—O4A	1.376 (2)	C2C—O4C	1.385 (2)
C3A—O5A	1.378 (2)	C3C—O5C	1.379 (2)
O4A—H4A	0.852 (17)	O4C—H4C	0.863 (17)
O5A—H5A	0.835 (17)	O5C—H5C	0.832 (16)
C1B—H1B	0.9500	C1D—H1D	0.9500
C1B—C2B	1.386 (2)	C1D—C2D	1.392 (2)
C1B—C3Bⁱⁱ	1.391 (3)	C1D—C3D^iv	1.382 (2)
C2B—C3B	1.390 (3)	C2D—C3D	1.392 (3)
C2B—O4B	1.381 (2)	C2D—O4D	1.368 (2)
C3B—O5B	1.372 (2)	C3D—O5D	1.3881 (19)
O4B—H4B	0.861 (16)	O4D—H4D	0.858 (16)
O5B—H5B	0.843 (17)	O5D—H5D	0.851 (16)

C2A—C1A—H1A	120.1	C2C—C1C—H1C	120.2
C2A—C1A—C3Aⁱ	119.82 (17)	C2C—C1C—C3Cⁱⁱⁱ	119.53 (18)
C3Aⁱ—C1A—H1A	120.1	C3Cⁱⁱⁱ—C1C—H1C	120.2
C3A—C2A—C1A	120.03 (16)	C3C—C2C—C1C	120.55 (16)
O4A—C2A—C1A	123.07 (16)	O4C—C2C—C1C	122.61 (17)
O4A—C2A—C3A	116.90 (15)	O4C—C2C—C3C	116.82 (16)
C2A—C3A—C1Aⁱ	120.14 (16)	C2C—C3C—C1Cⁱⁱⁱ	119.92 (17)
O5A—C3A—C1Aⁱ	119.11 (16)	O5C—C3C—C1Cⁱⁱⁱ	118.51 (17)
O5A—C3A—C2A	120.70 (15)	O5C—C3C—C2C	121.57 (15)
C2A—O4A—H4A	112.3 (16)	C2C—O4C—H4C	109.5 (15)
C3A—O5A—H5A	111.3 (17)	C3C—O5C—H5C	110.6 (17)
C2B—C1B—H1B	119.9	C2D—C1D—H1D	119.7
C2B—C1B—C3Bⁱⁱ	120.17 (18)	C3D^iv—C1D—H1D	119.7
C3Bⁱⁱ—C1B—H1B	119.9	C3D^iv—C1D—C2D	120.58 (17)
C1B—C2B—C3B	119.88 (17)	C1D—C2D—C3D	119.20 (16)
O4B—C2B—C1B	118.40 (17)	O4D—C2D—C1D	117.50 (16)
O4B—C2B—C3B	121.71 (16)	O4D—C2D—C3D	123.28 (15)
C2B—C3B—C1Bⁱⁱ	119.95 (17)	C1D^iv—C3D—C2D	120.22 (15)
O5B—C3B—C1Bⁱⁱ	121.84 (18)	C1D^iv—C3D—O5D	122.17 (16)
O5B—C3B—C2B	118.17 (16)	O5D—C3D—C2D	117.60 (15)
C2B—O4B—H4B	111.8 (18)	C2D—O4D—H4D	108.3 (17)
C3B—O5B—H5B	112.5 (16)	C3D—O5D—H5D	111.5 (16)

C1A—C2A—C3A—C1Aⁱ	1.1 (3)	C1C—C2C—C3C—C1Cⁱⁱⁱ	0.5 (3)
C1A—C2A—C3A—O5A	178.53 (16)	C1C—C2C—C3C—O5C	−179.04 (15)
C3Aⁱ—C1A—C2A—C3A	−1.0 (3)	C3Cⁱⁱⁱ—C1C—C2C—C3C	−0.5 (3)
C3Aⁱ—C1A—C2A—O4A	178.86 (16)	C3Cⁱⁱⁱ—C1C—C2C—O4C	−178.89 (15)
O4A—C2A—C3A—C1Aⁱ	−178.86 (16)	O4C—C2C—C3C—C1Cⁱⁱⁱ	178.98 (15)
O4A—C2A—C3A—O5A	−1.4 (3)	O4C—C2C—C3C—O5C	−0.6 (2)
C1B—C2B—C3B—C1Bⁱⁱ	−0.5 (3)	C1D—C2D—C3D—C1D^iv	−0.4 (3)
C1B—C2B—C3B—O5B	−178.19 (14)	C1D—C2D—C3D—O5D	178.51 (15)
C3Bⁱⁱ—C1B—C2B—C3B	0.5 (3)	C3D^iv—C1D—C2D—C3D	0.4 (3)
C3Bⁱⁱ—C1B—C2B—O4B	−179.07 (15)	C3D^iv—C1D—C2D—O4D	−178.16 (16)
O4B—C2B—C3B—C1Bⁱⁱ	179.06 (15)	O4D—C2D—C3D—C1D^iv	178.07 (17)
O4B—C2B—C3B—O5B	1.4 (2)	O4D—C2D—C3D—O5D	−3.0 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4A—H4A···O4C^v	0.85 (2)	1.89 (2)	2.715 (2)	163 (2)
O4B—H4B···O4D^vi	0.86 (2)	1.88 (2)	2.708 (2)	163 (3)
O4B—H4B···O5B	0.86 (2)	2.45 (2)	2.764 (2)	102 (2)
O4C—H4C···O4B	0.86 (2)	1.85 (2)	2.702 (2)	167 (2)
O4D—H4D···O5B	0.86 (2)	1.85 (2)	2.6425 (19)	154 (2)
O4D—H4D···O5D	0.86 (2)	2.34 (2)	2.789 (2)	113 (2)
O5A—H5A···O4A	0.83 (2)	2.40 (2)	2.711 (2)	103 (2)
O5A—H5A···O5D^vi	0.83 (2)	1.95 (2)	2.7562 (18)	162 (2)
O5B—H5B···O5A	0.84 (2)	1.80 (2)	2.633 (2)	169 (2)
O5C—H5C···O4A^vii	0.83 (2)	2.04 (2)	2.8376 (16)	161 (2)
O5C—H5C···O4C	0.83 (2)	2.38 (2)	2.734 (2)	107 (2)
O5D—H5D···O5C^viii	0.85 (2)	2.03 (2)	2.8796 (19)	175 (2)

Symmetry codes: (v) x−1, y+1, z; (vi) x−1, y, z; (vii) x, y−1, z; (viii) x, y+1, z.

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