


Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810049469/xu5075sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536810049469/xu5075Isup2.hkl |
CCDC reference: 803332
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean
(C-C) = 0.007 Å
- R factor = 0.040
- wR factor = 0.137
- Data-to-parameter ratio = 7.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) ..... 7.64 PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang .. 7 PLAT918_ALERT_3_C Reflection(s) # with I(obs) much smaller I(calc) 6
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 25.94 From the CIF: _reflns_number_total 924 Count of symmetry unique reflns 923 Completeness (_total/calc) 100.11% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1 Fraction of Friedel pairs measured 0.001 Are heavy atom types Z>Si present no PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 3 PLAT791_ALERT_4_G Note: The Model has Chirality at C7 (Verify) R
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound was prepared by the literature method (Qin et al., 2004). The crystals were obtained by dissolving the title compound (0.3 g) in ethanol (50 ml) and evaporating the solvent slowly at room temperature for 15 d.
The carboxyl H atom was located in a difference Fourier map and positional parameters were refined, Uiso(H) = 1.5Ueq(O). Other H atoms were positioned geometrically with C—H = 0.93-0.98 Å and O—H = 0.85 Å, and refined in ride mode with Uiso(H) = 1.5Ueq(C,O) for methyl H and hydroxyl H atoms and 1.2Ueq(C) for the other H atoms.
The title compound, (I), is an important intermediate of the highly active herbicide R-clodinafop-propargyl (Qin et al., 2004). We herein report its crystal structure.
The unit of the title compound, (I), (Fig. 1), contains one molecule and the bond lengths and angles (Table 1) are generally within normal ranges.
As can be seen from the packing diagram (Fig. 2), the intermolecular C—H···O hydrogen bonds (Table 2) link the molecules into three dimensional network, in which they may be effective in the stabilization of the crystal structure. Dipol-dipol and van der Waals interactions are also effective in the molecular packing.
For the synthesis and applications of the title compound, see: Qin et al. (2004).
Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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).
C9H10O4 | F(000) = 192 |
Mr = 182.17 | Dx = 1.349 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 25 reflections |
a = 6.205 (1) Å | θ = 10–13° |
b = 11.853 (2) Å | µ = 0.11 mm−1 |
c = 6.716 (1) Å | T = 298 K |
β = 114.78 (3)° | Block, colorless |
V = 448.47 (15) Å3 | 0.40 × 0.30 × 0.20 mm |
Z = 2 |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.018 |
Radiation source: fine-focus sealed tube | θmax = 25.9°, θmin = 3.3° |
Graphite monochromator | h = −7→6 |
ω/2θ scans | k = 0→14 |
924 measured reflections | l = 0→8 |
924 independent reflections | 3 standard reflections every 200 reflections |
829 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.137 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.05P)2 + 0.6P] where P = (Fo2 + 2Fc2)/3 |
924 reflections | (Δ/σ)max < 0.001 |
121 parameters | Δρmax = 0.24 e Å−3 |
3 restraints | Δρmin = −0.28 e Å−3 |
C9H10O4 | V = 448.47 (15) Å3 |
Mr = 182.17 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.205 (1) Å | µ = 0.11 mm−1 |
b = 11.853 (2) Å | T = 298 K |
c = 6.716 (1) Å | 0.40 × 0.30 × 0.20 mm |
β = 114.78 (3)° |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.018 |
924 measured reflections | 3 standard reflections every 200 reflections |
924 independent reflections | intensity decay: none |
829 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.040 | 3 restraints |
wR(F2) = 0.137 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.24 e Å−3 |
924 reflections | Δρmin = −0.28 e Å−3 |
121 parameters |
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 | ||
O1 | 0.4177 (6) | 0.4704 (4) | 0.2174 (6) | 0.0527 (10) | |
H1B | 0.2918 | 0.4336 | 0.1940 | 0.079* | |
O2 | 0.8378 (5) | 0.7346 (3) | 0.9648 (5) | 0.0431 (9) | |
O3 | 1.0305 (6) | 0.9182 (3) | 0.8307 (6) | 0.0506 (10) | |
O4 | 1.3803 (5) | 0.8319 (3) | 0.9703 (6) | 0.0487 (9) | |
C1 | 0.7253 (9) | 0.5920 (5) | 0.4402 (8) | 0.0473 (13) | |
H1A | 0.7872 | 0.5876 | 0.3360 | 0.057* | |
C2 | 0.5225 (8) | 0.5344 (4) | 0.4072 (8) | 0.0381 (11) | |
C3 | 0.4318 (8) | 0.5400 (4) | 0.5642 (9) | 0.0401 (11) | |
H3A | 0.2959 | 0.4997 | 0.5449 | 0.048* | |
C4 | 0.5441 (8) | 0.6055 (4) | 0.7487 (8) | 0.0373 (10) | |
H4A | 0.4832 | 0.6092 | 0.8537 | 0.045* | |
C5 | 0.7453 (8) | 0.6655 (5) | 0.7789 (7) | 0.0375 (10) | |
C6 | 0.8398 (9) | 0.6568 (5) | 0.6261 (8) | 0.0505 (14) | |
H6A | 0.9797 | 0.6943 | 0.6483 | 0.061* | |
C7 | 1.0878 (7) | 0.7533 (4) | 1.0603 (7) | 0.0380 (11) | |
H7A | 1.1701 | 0.6824 | 1.0626 | 0.046* | |
C8 | 1.1531 (10) | 0.7924 (6) | 1.2920 (8) | 0.0538 (14) | |
H8A | 1.1081 | 0.7359 | 1.3698 | 0.081* | |
H8B | 1.0715 | 0.8616 | 1.2896 | 0.081* | |
H8C | 1.3214 | 0.8047 | 1.3643 | 0.081* | |
C9 | 1.1595 (7) | 0.8419 (4) | 0.9378 (7) | 0.0362 (10) | |
H4B | 1.448 (5) | 0.883 (3) | 0.928 (8) | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0343 (17) | 0.065 (3) | 0.059 (2) | −0.0158 (18) | 0.0201 (16) | −0.030 (2) |
O2 | 0.0322 (16) | 0.055 (2) | 0.0446 (18) | −0.0092 (16) | 0.0189 (14) | −0.0137 (17) |
O3 | 0.0359 (17) | 0.050 (2) | 0.061 (2) | 0.0072 (17) | 0.0158 (16) | 0.0174 (19) |
O4 | 0.0335 (17) | 0.048 (2) | 0.070 (2) | 0.0068 (17) | 0.0267 (16) | 0.0125 (19) |
C1 | 0.052 (3) | 0.055 (3) | 0.048 (3) | −0.015 (3) | 0.034 (2) | −0.008 (3) |
C2 | 0.030 (2) | 0.036 (2) | 0.046 (3) | 0.001 (2) | 0.015 (2) | −0.011 (2) |
C3 | 0.029 (2) | 0.035 (2) | 0.056 (3) | −0.002 (2) | 0.018 (2) | 0.000 (2) |
C4 | 0.035 (2) | 0.041 (3) | 0.040 (2) | 0.001 (2) | 0.0199 (19) | −0.001 (2) |
C5 | 0.033 (2) | 0.046 (3) | 0.035 (2) | −0.002 (2) | 0.0162 (18) | −0.011 (2) |
C6 | 0.047 (3) | 0.064 (4) | 0.051 (3) | −0.025 (3) | 0.031 (2) | −0.011 (3) |
C7 | 0.031 (2) | 0.043 (3) | 0.037 (2) | −0.006 (2) | 0.0114 (18) | 0.001 (2) |
C8 | 0.055 (3) | 0.066 (3) | 0.039 (3) | −0.014 (3) | 0.019 (2) | 0.000 (3) |
C9 | 0.028 (2) | 0.043 (3) | 0.035 (2) | 0.003 (2) | 0.0115 (17) | 0.001 (2) |
O1—C2 | 1.389 (6) | C3—H3A | 0.9300 |
O1—H1B | 0.8500 | C4—C5 | 1.376 (7) |
O2—C5 | 1.399 (5) | C4—H4A | 0.9300 |
O2—C7 | 1.426 (5) | C5—C6 | 1.382 (6) |
O3—C9 | 1.221 (6) | C6—H6A | 0.9300 |
O4—C9 | 1.300 (5) | C7—C8 | 1.508 (7) |
O4—H4B | 0.85 (4) | C7—C9 | 1.511 (6) |
C1—C2 | 1.366 (6) | C7—H7A | 0.9800 |
C1—C6 | 1.382 (7) | C8—H8A | 0.9600 |
C1—H1A | 0.9300 | C8—H8B | 0.9600 |
C2—C3 | 1.389 (6) | C8—H8C | 0.9600 |
C3—C4 | 1.378 (7) | ||
C2—O1—H1B | 119.4 | C1—C6—C5 | 119.7 (4) |
C5—O2—C7 | 117.0 (4) | C1—C6—H6A | 120.2 |
C9—O4—H4B | 121 (3) | C5—C6—H6A | 120.2 |
C2—C1—C6 | 120.9 (4) | O2—C7—C8 | 106.5 (4) |
C2—C1—H1A | 119.5 | O2—C7—C9 | 112.1 (4) |
C6—C1—H1A | 119.5 | C8—C7—C9 | 109.6 (4) |
C1—C2—O1 | 117.8 (4) | O2—C7—H7A | 109.6 |
C1—C2—C3 | 119.5 (4) | C8—C7—H7A | 109.6 |
O1—C2—C3 | 122.7 (4) | C9—C7—H7A | 109.6 |
C4—C3—C2 | 119.8 (4) | C7—C8—H8A | 109.5 |
C4—C3—H3A | 120.1 | C7—C8—H8B | 109.5 |
C2—C3—H3A | 120.1 | H8A—C8—H8B | 109.5 |
C5—C4—C3 | 120.6 (4) | C7—C8—H8C | 109.5 |
C5—C4—H4A | 119.7 | H8A—C8—H8C | 109.5 |
C3—C4—H4A | 119.7 | H8B—C8—H8C | 109.5 |
C4—C5—C6 | 119.5 (4) | O3—C9—O4 | 123.4 (4) |
C4—C5—O2 | 116.2 (4) | O3—C9—C7 | 124.4 (4) |
C6—C5—O2 | 124.3 (4) | O4—C9—C7 | 112.0 (4) |
C6—C1—C2—O1 | −179.6 (5) | C2—C1—C6—C5 | −1.4 (9) |
C6—C1—C2—C3 | −0.8 (8) | C4—C5—C6—C1 | 2.9 (9) |
C1—C2—C3—C4 | 1.5 (7) | O2—C5—C6—C1 | −175.5 (5) |
O1—C2—C3—C4 | −179.8 (5) | C5—O2—C7—C8 | −160.4 (5) |
C2—C3—C4—C5 | 0.0 (7) | C5—O2—C7—C9 | 79.9 (6) |
C3—C4—C5—C6 | −2.2 (8) | O2—C7—C9—O3 | 26.7 (7) |
C3—C4—C5—O2 | 176.3 (4) | C8—C7—C9—O3 | −91.3 (6) |
C7—O2—C5—C4 | 150.4 (4) | O2—C7—C9—O4 | −157.2 (4) |
C7—O2—C5—C6 | −31.1 (7) | C8—C7—C9—O4 | 84.8 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1B···O3i | 0.85 | 1.94 | 2.733 (6) | 154 |
O4—H4B···O1ii | 0.85 (4) | 1.84 (4) | 2.679 (6) | 166 (4) |
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) −x+2, y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C9H10O4 |
Mr | 182.17 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 298 |
a, b, c (Å) | 6.205 (1), 11.853 (2), 6.716 (1) |
β (°) | 114.78 (3) |
V (Å3) | 448.47 (15) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.40 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 924, 924, 829 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.615 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.137, 1.02 |
No. of reflections | 924 |
No. of parameters | 121 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.28 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1B···O3i | 0.85 | 1.94 | 2.733 (6) | 154 |
O4—H4B···O1ii | 0.85 (4) | 1.84 (4) | 2.679 (6) | 166 (4) |
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) −x+2, y+1/2, −z+1. |
The title compound, (I), is an important intermediate of the highly active herbicide R-clodinafop-propargyl (Qin et al., 2004). We herein report its crystal structure.
The unit of the title compound, (I), (Fig. 1), contains one molecule and the bond lengths and angles (Table 1) are generally within normal ranges.
As can be seen from the packing diagram (Fig. 2), the intermolecular C—H···O hydrogen bonds (Table 2) link the molecules into three dimensional network, in which they may be effective in the stabilization of the crystal structure. Dipol-dipol and van der Waals interactions are also effective in the molecular packing.