Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807022787/om2124sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807022787/om2124Isup2.hkl |
CCDC reference: 651466
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.004 Å
- R factor = 0.047
- wR factor = 0.125
- Data-to-parameter ratio = 7.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) ..... 7.73 PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.54 Ratio PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.48
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 25.95 From the CIF: _reflns_number_total 861 Count of symmetry unique reflns 881 Completeness (_total/calc) 97.73% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
A solution of 3.7 g of 2,4,6-trinitroanisole in 70 ml of absolute ethanol was reduced with hydrogen at a pressure of 3 atm in the presence of platinum oxide (0.1 g). After ten minutes, the reduction mixture was filtered quickly, and the solvent removed with a water pump, at the same time slowly flowing N2(g) through the solution. The mixture was then cooled in an ice bath, the product removed by filtration and washed with small amounts of cold absolute ethanol. 2,4,6-Triaminoanisole (1.77 g, 76%) was obtained by recrystallization from hot absolute ethanol. A solution of 1.5 g of the crude triaminoanisole in 60 ml of air-free water containing 3 ml of concentrated hydrochloric acid was refluxed for 20 h in an atmosphere of carbon dioxide. After filtration, the water was removed by vacuum distillation, passing a stream of carbon dioxide. The dry residue was then thoroughly extracted with three 60 ml portions of ether. The combined ether extracts were dried over magnesium sulfate, and the ether was removed by distillation. 2,4,6-trihydroxyanisole was obtained in 65% yield. The purified products were dissolved in ethyl acetate, and petroleum ether was added carefully. The crystals suitable for X-ray analysis were obtained after 3 days by volatilization of the solvents.
H atoms bonded to C were placed in geometrically idealized positions and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C) and with C—H = 0.93 Å for the aromatic H atoms, C—H = 0.96 Å for the aliphatic H atoms. H atoms bonded to O were located from adifference electron density map and refined with a restrained O—H distance of 0.92 (2) Å.
The title compound, (I), 2,4,6-trihydroxyanisole, was first isolated by De Laire & Tiemann (1893) as a degradation product of a glucoside obtained from Iris Jorentina. Although it is a well known intermediate for synthesis of several natural isoflavones such as tectorigenin, irigenin and caviunin (Baker et al., 1970), its crystal structure has not been reported. In this article, the title comound was prepared by the method of Damschroder & Shriner (1937) with appropriate modifications.
The molecular structure is shown in Fig. 1. A l l the hydrogen atoms of the hydroxyl groups contribute to the formation of intermolecular O—H···O hydrogen bonds (Table 1), and every molecule is involved in hydrogen bond interactions with six other molecules, which leads to the formation of a three-dimensional network (Fig. 2). To our surprise, O2 was not involved in any hydrogen bond interactions. This may be due to steric hindrance around the oxygen atom. The methyl group (C7) is 1.084 (5) Å out of the plane of the benzene ring which prevents close stacking of the molecules (Fig. 3). Face to face distances between benzene rings are 4.482 (3) Å).
For related literature, see: Baker et al. (1970); Damschroder & Shriner (1937); De Laire & Tiemann (1893).
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXL97.
C7H8O4 | F(000) = 328 |
Mr = 156.13 | Dx = 1.397 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 558 reflections |
a = 5.231 (1) Å | θ = 2.8–26.2° |
b = 9.4010 (19) Å | µ = 0.12 mm−1 |
c = 15.095 (3) Å | T = 298 K |
V = 742.3 (3) Å3 | Block, colourless |
Z = 4 | 0.30 × 0.20 × 0.20 mm |
Bruker SMART APEX diffractometer | 736 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.041 |
Graphite monochromator | θmax = 26.0°, θmin = 2.6° |
φ and ω scans | h = 0→6 |
881 measured reflections | k = 0→11 |
861 independent reflections | l = 0→18 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.047 | w = 1/[σ2(Fo2) + (0.077P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.125 | (Δ/σ)max < 0.001 |
S = 1.08 | Δρmax = 0.20 e Å−3 |
861 reflections | Δρmin = −0.25 e Å−3 |
114 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997a), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.056 (11) |
Primary atom site location: structure-invariant direct methods | Absolute structure: indeterminate |
Secondary atom site location: difference Fourier map |
C7H8O4 | V = 742.3 (3) Å3 |
Mr = 156.13 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 5.231 (1) Å | µ = 0.12 mm−1 |
b = 9.4010 (19) Å | T = 298 K |
c = 15.095 (3) Å | 0.30 × 0.20 × 0.20 mm |
Bruker SMART APEX diffractometer | 736 reflections with I > 2σ(I) |
881 measured reflections | Rint = 0.041 |
861 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | 1 restraint |
wR(F2) = 0.125 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.20 e Å−3 |
861 reflections | Δρmin = −0.25 e Å−3 |
114 parameters | Absolute structure: indeterminate |
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. 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 > σ(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. |
x | y | z | Uiso*/Ueq | ||
O3 | 1.0972 (6) | 0.7137 (2) | 0.66584 (13) | 0.0401 (7) | |
O2 | 1.1104 (4) | 0.4545 (2) | 0.74132 (13) | 0.0318 (6) | |
O1 | 0.9108 (6) | 0.2206 (2) | 0.65022 (13) | 0.0378 (7) | |
O4 | 0.6225 (6) | 0.5306 (2) | 0.42132 (14) | 0.0474 (8) | |
C6 | 0.7719 (7) | 0.3719 (3) | 0.53482 (19) | 0.0328 (8) | |
H6 | 0.7001 | 0.2941 | 0.5061 | 0.039* | |
C4 | 0.8600 (7) | 0.6234 (3) | 0.5401 (2) | 0.0337 (8) | |
H4 | 0.8463 | 0.7134 | 0.5150 | 0.040* | |
C1 | 0.8988 (7) | 0.3553 (3) | 0.61421 (18) | 0.0276 (7) | |
C3 | 0.9875 (7) | 0.6045 (3) | 0.6196 (2) | 0.0293 (7) | |
C2 | 1.0050 (6) | 0.4702 (3) | 0.65761 (18) | 0.0267 (7) | |
C5 | 0.7536 (8) | 0.5070 (3) | 0.4988 (2) | 0.0326 (7) | |
C7 | 1.3791 (9) | 0.4384 (6) | 0.7426 (3) | 0.0679 (13) | |
H7A | 1.4238 | 0.3467 | 0.7193 | 0.102* | |
H7B | 1.4398 | 0.4464 | 0.8024 | 0.102* | |
H7C | 1.4562 | 0.5113 | 0.7069 | 0.102* | |
H3 | 1.094 (10) | 0.796 (5) | 0.633 (2) | 0.071 (14)* | |
H4A | 0.560 (8) | 0.449 (4) | 0.400 (2) | 0.062 (13)* | |
H1 | 0.902 (10) | 0.224 (5) | 0.7092 (12) | 0.070 (14)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O3 | 0.0739 (17) | 0.0161 (10) | 0.0303 (11) | −0.0086 (13) | −0.0086 (14) | 0.0010 (9) |
O2 | 0.0438 (12) | 0.0274 (11) | 0.0242 (10) | −0.0019 (11) | −0.0028 (11) | 0.0025 (9) |
O1 | 0.0757 (17) | 0.0119 (9) | 0.0256 (10) | 0.0040 (12) | −0.0020 (14) | 0.0028 (8) |
O4 | 0.085 (2) | 0.0186 (10) | 0.0383 (13) | −0.0033 (14) | −0.0263 (15) | 0.0025 (10) |
C6 | 0.055 (2) | 0.0145 (13) | 0.0291 (15) | −0.0028 (15) | −0.0009 (17) | −0.0018 (12) |
C4 | 0.055 (2) | 0.0133 (12) | 0.0329 (15) | 0.0004 (16) | −0.0041 (16) | 0.0030 (12) |
C1 | 0.0449 (17) | 0.0113 (12) | 0.0267 (13) | 0.0045 (14) | 0.0025 (15) | 0.0035 (11) |
C3 | 0.0455 (17) | 0.0142 (13) | 0.0280 (15) | −0.0026 (14) | 0.0008 (15) | −0.0023 (11) |
C2 | 0.0399 (16) | 0.0186 (14) | 0.0215 (13) | 0.0010 (14) | 0.0034 (14) | −0.0008 (12) |
C5 | 0.0491 (18) | 0.0220 (14) | 0.0266 (14) | 0.0010 (13) | −0.0073 (16) | 0.0015 (11) |
C7 | 0.053 (2) | 0.089 (3) | 0.061 (3) | 0.010 (3) | −0.009 (3) | 0.003 (3) |
O3—C3 | 1.368 (4) | C6—H6 | 0.9300 |
O3—H3 | 0.92 (4) | C4—C5 | 1.377 (4) |
O2—C2 | 1.386 (3) | C4—C3 | 1.384 (4) |
O2—C7 | 1.414 (5) | C4—H4 | 0.9300 |
O1—C1 | 1.379 (3) | C1—C2 | 1.381 (4) |
O1—H1 | 0.892 (18) | C3—C2 | 1.390 (4) |
O4—C5 | 1.374 (4) | C7—H7A | 0.9600 |
O4—H4A | 0.89 (4) | C7—H7B | 0.9600 |
C6—C1 | 1.379 (4) | C7—H7C | 0.9600 |
C6—C5 | 1.384 (4) | ||
C3—O3—H3 | 110 (3) | O3—C3—C2 | 116.3 (3) |
C2—O2—C7 | 114.8 (3) | C4—C3—C2 | 120.5 (3) |
C1—O1—H1 | 111 (3) | C1—C2—O2 | 120.6 (2) |
C5—O4—H4A | 111 (2) | C1—C2—C3 | 119.2 (3) |
C1—C6—C5 | 118.6 (3) | O2—C2—C3 | 120.0 (3) |
C1—C6—H6 | 120.7 | O4—C5—C4 | 117.3 (3) |
C5—C6—H6 | 120.7 | O4—C5—C6 | 121.2 (3) |
C5—C4—C3 | 119.0 (3) | C4—C5—C6 | 121.5 (3) |
C5—C4—H4 | 120.5 | O2—C7—H7A | 109.5 |
C3—C4—H4 | 120.5 | O2—C7—H7B | 109.5 |
C6—C1—O1 | 117.9 (3) | H7A—C7—H7B | 109.5 |
C6—C1—C2 | 121.1 (2) | O2—C7—H7C | 109.5 |
O1—C1—C2 | 120.9 (3) | H7A—C7—H7C | 109.5 |
O3—C3—C4 | 123.2 (2) | H7B—C7—H7C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4A···O1i | 0.89 (4) | 1.93 (4) | 2.823 (3) | 177 (4) |
O3—H3···O4ii | 0.92 (4) | 1.83 (4) | 2.743 (3) | 172 (4) |
O1—H1···O3iii | 0.89 (2) | 1.89 (2) | 2.778 (3) | 174 (5) |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x+1/2, −y+3/2, −z+1; (iii) −x+2, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C7H8O4 |
Mr | 156.13 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 298 |
a, b, c (Å) | 5.231 (1), 9.4010 (19), 15.095 (3) |
V (Å3) | 742.3 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART APEX |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 881, 861, 736 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.125, 1.08 |
No. of reflections | 861 |
No. of parameters | 114 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.25 |
Absolute structure | Indeterminate |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4A···O1i | 0.89 (4) | 1.93 (4) | 2.823 (3) | 177 (4) |
O3—H3···O4ii | 0.92 (4) | 1.83 (4) | 2.743 (3) | 172 (4) |
O1—H1···O3iii | 0.892 (18) | 1.889 (19) | 2.778 (3) | 174 (5) |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x+1/2, −y+3/2, −z+1; (iii) −x+2, y−1/2, −z+3/2. |
The title compound, (I), 2,4,6-trihydroxyanisole, was first isolated by De Laire & Tiemann (1893) as a degradation product of a glucoside obtained from Iris Jorentina. Although it is a well known intermediate for synthesis of several natural isoflavones such as tectorigenin, irigenin and caviunin (Baker et al., 1970), its crystal structure has not been reported. In this article, the title comound was prepared by the method of Damschroder & Shriner (1937) with appropriate modifications.
The molecular structure is shown in Fig. 1. A l l the hydrogen atoms of the hydroxyl groups contribute to the formation of intermolecular O—H···O hydrogen bonds (Table 1), and every molecule is involved in hydrogen bond interactions with six other molecules, which leads to the formation of a three-dimensional network (Fig. 2). To our surprise, O2 was not involved in any hydrogen bond interactions. This may be due to steric hindrance around the oxygen atom. The methyl group (C7) is 1.084 (5) Å out of the plane of the benzene ring which prevents close stacking of the molecules (Fig. 3). Face to face distances between benzene rings are 4.482 (3) Å).