Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025238/hk2257sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025238/hk2257Isup2.hkl |
CCDC reference: 651520
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.002 Å
- R factor = 0.037
- wR factor = 0.076
- Data-to-parameter ratio = 15.6
checkCIF/PLATON results
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0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 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 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For general background, see: Qadeer et al. (2007); Zheng et al. (2003); Al-Talib et al. (1990); Yousif et al. (1986); Ahmad et al. (2001); Al-Soud et al. (2004); El-Emam et al. (2004); Weinstock et al. (1991); Bruno et al. (2004).
For the preparation of (I), a mixture of methyl-2,6-dimethoxybenzoate (1.96 g, 10 mmol) and hydrazine hydrate (80%, 15 ml) in absolute ethanol (50 ml) was refluxed for 5 h at 413–423 K. The excess solvent was removed by distillation. The solid residue was filtered off, washed with water and recrystallized from ethanol (30%) to give the title compound (yield: 91%). Colorless single crystals of (I) were obtained by slow evaporation of an ethanol solution at room temperature.
H atoms were positioned geometrically, with C—H = 0.95 and 0.98 Å for aromatic and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,N), where x = 1.5 for methyl H, and x = 1.2 for aromatic H atoms.
The title compound, (I), is a lachrymator and a drug intermediate. It is widely employed in synthetic organic chemistry for example; 2,6-dimehthoxybenzohydr- azide (Qadeer et al., 2007), 2,5-disubstituted-1,3,4-oxadiazoles (Zheng et al., 2003; Al-Talib et al., 1990) and 5-substituted-2-mercapto-1,3,4-oxadiazoles (Yousif et al., 1986; Ahmad et al., 2001; Al-Soud et al., 2004; El-Emam et al., 2004). In addition, methyl 4-(bromomethyl)benzoate has been used in the synthesis of 1-(carboxybenzyl)imidazole-5-acrylic acids, which are potent and selective angiotensin II receptor antagonists (Weinstock et al., 1991). In view of the versatility of these compounds, we have synthesized the title compound, (I), and reported its crystal structure.
The title molecule (Fig. 1) shows no unusual features when compared with the Mogul norms (Bruno et al., 2004). The dihedral angle between the planar ester group and benzene ring is 81.46 (3)°.
As can be seen from the packing diagram (Fig. 2), the molecules of (I) are stacked along the a axis and elongated along the b axis. Dipole-dipole and van der Waals interactions are effective in the molecular packing.
For general background, see: Qadeer et al. (2007); Zheng et al. (2003); Al-Talib et al. (1990); Yousif et al. (1986); Ahmad et al. (2001); Al-Soud et al. (2004); El-Emam et al. (2004); Weinstock et al. (1991); Bruno et al. (2004).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.
C10H12O4 | Dx = 1.317 Mg m−3 |
Mr = 196.20 | Melting point: 450(1) K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 1609 reflections |
a = 7.2306 (9) Å | θ = 2.9–23.6° |
b = 14.1058 (17) Å | µ = 0.10 mm−1 |
c = 19.403 (2) Å | T = 100 K |
V = 1978.9 (4) Å3 | Block, colourless |
Z = 8 | 0.40 × 0.30 × 0.30 mm |
F(000) = 832 |
Bruker APEXII diffractometer | 2033 independent reflections |
Radiation source: fine-focus sealed tube | 1271 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
φ and ω scans | θmax = 26.4°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→9 |
Tmin = 0.960, Tmax = 0.970 | k = −17→15 |
10579 measured reflections | l = −24→22 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 0.85 | w = 1/[σ2(Fo2) + (0.0303P)2] where P = (Fo2 + 2Fc2)/3 |
2033 reflections | (Δ/σ)max < 0.001 |
130 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C10H12O4 | V = 1978.9 (4) Å3 |
Mr = 196.20 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 7.2306 (9) Å | µ = 0.10 mm−1 |
b = 14.1058 (17) Å | T = 100 K |
c = 19.403 (2) Å | 0.40 × 0.30 × 0.30 mm |
Bruker APEXII diffractometer | 2033 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1271 reflections with I > 2σ(I) |
Tmin = 0.960, Tmax = 0.970 | Rint = 0.064 |
10579 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 0.85 | Δρmax = 0.17 e Å−3 |
2033 reflections | Δρmin = −0.17 e Å−3 |
130 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 | 0.32641 (14) | 0.23587 (7) | 0.03432 (5) | 0.0274 (3) | |
O2 | 0.52183 (14) | 0.26194 (7) | 0.12196 (5) | 0.0305 (3) | |
O3 | 0.57947 (15) | 0.04433 (7) | 0.08234 (5) | 0.0343 (3) | |
O4 | 0.07719 (14) | 0.21697 (7) | 0.16359 (5) | 0.0272 (3) | |
C1 | 0.3235 (2) | 0.12555 (11) | 0.12428 (7) | 0.0230 (4) | |
C2 | 0.4173 (2) | 0.03933 (11) | 0.11826 (7) | 0.0276 (4) | |
C3 | 0.3440 (2) | −0.04231 (11) | 0.14695 (8) | 0.0323 (4) | |
H3 | 0.4061 | −0.1013 | 0.1422 | 0.039* | |
C4 | 0.1787 (2) | −0.03647 (12) | 0.18270 (8) | 0.0344 (4) | |
H4 | 0.1288 | −0.0924 | 0.2026 | 0.041* | |
C5 | 0.0838 (2) | 0.04769 (11) | 0.19046 (7) | 0.0303 (4) | |
H5 | −0.0287 | 0.0500 | 0.2157 | 0.036* | |
C6 | 0.1568 (2) | 0.12911 (11) | 0.16044 (7) | 0.0245 (4) | |
C7 | 0.4041 (2) | 0.21447 (10) | 0.09467 (7) | 0.0226 (4) | |
C8 | 0.3873 (2) | 0.32382 (11) | 0.00241 (8) | 0.0297 (4) | |
H8A | 0.3664 | 0.3767 | 0.0343 | 0.045* | |
H8B | 0.3171 | 0.3346 | −0.0401 | 0.045* | |
H8C | 0.5194 | 0.3195 | −0.0085 | 0.045* | |
C9 | 0.6844 (2) | −0.04143 (12) | 0.07533 (9) | 0.0462 (5) | |
H9A | 0.7218 | −0.0639 | 0.1210 | 0.069* | |
H9B | 0.7948 | −0.0291 | 0.0474 | 0.069* | |
H9C | 0.6084 | −0.0899 | 0.0528 | 0.069* | |
C10 | −0.0943 (2) | 0.22482 (12) | 0.20085 (8) | 0.0341 (4) | |
H10A | −0.1840 | 0.1796 | 0.1821 | 0.051* | |
H10B | −0.1429 | 0.2894 | 0.1962 | 0.051* | |
H10C | −0.0728 | 0.2109 | 0.2497 | 0.051* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0275 (6) | 0.0282 (7) | 0.0267 (5) | −0.0047 (5) | −0.0031 (5) | 0.0051 (5) |
O2 | 0.0282 (6) | 0.0268 (7) | 0.0364 (6) | −0.0056 (5) | −0.0072 (5) | 0.0012 (5) |
O3 | 0.0338 (7) | 0.0246 (7) | 0.0446 (7) | 0.0085 (5) | 0.0067 (6) | 0.0003 (5) |
O4 | 0.0242 (6) | 0.0274 (7) | 0.0301 (6) | 0.0005 (5) | 0.0052 (5) | 0.0022 (5) |
C1 | 0.0247 (9) | 0.0221 (9) | 0.0221 (8) | −0.0016 (7) | −0.0039 (7) | −0.0006 (6) |
C2 | 0.0288 (10) | 0.0266 (10) | 0.0273 (8) | −0.0016 (8) | −0.0045 (8) | −0.0004 (7) |
C3 | 0.0395 (11) | 0.0221 (10) | 0.0352 (9) | 0.0000 (8) | −0.0078 (8) | −0.0005 (7) |
C4 | 0.0421 (11) | 0.0263 (10) | 0.0350 (9) | −0.0121 (8) | −0.0094 (8) | 0.0057 (8) |
C5 | 0.0300 (10) | 0.0320 (10) | 0.0289 (8) | −0.0085 (8) | −0.0013 (7) | 0.0037 (7) |
C6 | 0.0257 (9) | 0.0242 (9) | 0.0237 (8) | −0.0030 (7) | −0.0047 (7) | −0.0006 (7) |
C7 | 0.0198 (8) | 0.0221 (9) | 0.0260 (8) | 0.0044 (7) | 0.0012 (7) | −0.0039 (7) |
C8 | 0.0292 (10) | 0.0279 (10) | 0.0320 (9) | 0.0000 (8) | 0.0035 (7) | 0.0091 (7) |
C9 | 0.0456 (12) | 0.0309 (11) | 0.0622 (12) | 0.0143 (9) | 0.0069 (10) | −0.0013 (9) |
C10 | 0.0269 (9) | 0.0396 (11) | 0.0358 (9) | 0.0027 (8) | 0.0091 (7) | 0.0041 (8) |
O1—C7 | 1.3335 (16) | C4—C5 | 1.379 (2) |
O1—C8 | 1.4548 (17) | C4—H4 | 0.9500 |
O2—C7 | 1.2055 (17) | C5—C6 | 1.392 (2) |
O3—C2 | 1.3658 (18) | C5—H5 | 0.9500 |
O3—C9 | 1.4345 (17) | C8—H8A | 0.9800 |
O4—C6 | 1.3680 (17) | C8—H8B | 0.9800 |
O4—C10 | 1.4397 (17) | C8—H8C | 0.9800 |
C1—C6 | 1.3951 (19) | C9—H9A | 0.9800 |
C1—C2 | 1.398 (2) | C9—H9B | 0.9800 |
C1—C7 | 1.498 (2) | C9—H9C | 0.9800 |
C2—C3 | 1.384 (2) | C10—H10A | 0.9800 |
C3—C4 | 1.385 (2) | C10—H10B | 0.9800 |
C3—H3 | 0.9500 | C10—H10C | 0.9800 |
C7—O1—C8 | 116.06 (12) | O2—C7—O1 | 123.88 (14) |
C2—O3—C9 | 117.32 (12) | O2—C7—C1 | 124.86 (13) |
C6—O4—C10 | 117.04 (12) | O1—C7—C1 | 111.25 (13) |
C6—C1—C2 | 119.51 (14) | O1—C8—H8A | 109.5 |
C6—C1—C7 | 119.94 (13) | O1—C8—H8B | 109.5 |
C2—C1—C7 | 120.50 (14) | H8A—C8—H8B | 109.5 |
O3—C2—C3 | 125.22 (15) | O1—C8—H8C | 109.5 |
O3—C2—C1 | 114.49 (14) | H8A—C8—H8C | 109.5 |
C3—C2—C1 | 120.29 (15) | H8B—C8—H8C | 109.5 |
C4—C3—C2 | 118.84 (16) | O3—C9—H9A | 109.5 |
C4—C3—H3 | 120.6 | O3—C9—H9B | 109.5 |
C2—C3—H3 | 120.6 | H9A—C9—H9B | 109.5 |
C5—C4—C3 | 122.38 (16) | O3—C9—H9C | 109.5 |
C5—C4—H4 | 118.8 | H9A—C9—H9C | 109.5 |
C3—C4—H4 | 118.8 | H9B—C9—H9C | 109.5 |
C4—C5—C6 | 118.39 (16) | O4—C10—H10A | 109.5 |
C4—C5—H5 | 120.8 | O4—C10—H10B | 109.5 |
C6—C5—H5 | 120.8 | H10A—C10—H10B | 109.5 |
O4—C6—C5 | 124.68 (14) | O4—C10—H10C | 109.5 |
O4—C6—C1 | 114.74 (13) | H10A—C10—H10C | 109.5 |
C5—C6—C1 | 120.57 (15) | H10B—C10—H10C | 109.5 |
C9—O3—C2—C3 | −1.7 (2) | C4—C5—C6—O4 | 179.56 (13) |
C9—O3—C2—C1 | 178.89 (13) | C4—C5—C6—C1 | −0.9 (2) |
C6—C1—C2—O3 | −179.47 (12) | C2—C1—C6—O4 | 179.59 (13) |
C7—C1—C2—O3 | −1.9 (2) | C7—C1—C6—O4 | 2.00 (19) |
C6—C1—C2—C3 | 1.1 (2) | C2—C1—C6—C5 | 0.0 (2) |
C7—C1—C2—C3 | 178.67 (13) | C7—C1—C6—C5 | −177.57 (13) |
O3—C2—C3—C4 | 179.34 (13) | C8—O1—C7—O2 | −2.0 (2) |
C1—C2—C3—C4 | −1.3 (2) | C8—O1—C7—C1 | 176.88 (12) |
C2—C3—C4—C5 | 0.4 (2) | C6—C1—C7—O2 | 96.75 (18) |
C3—C4—C5—C6 | 0.7 (2) | C2—C1—C7—O2 | −80.82 (19) |
C10—O4—C6—C5 | 0.1 (2) | C6—C1—C7—O1 | −82.08 (16) |
C10—O4—C6—C1 | −179.47 (12) | C2—C1—C7—O1 | 100.35 (16) |
Experimental details
Crystal data | |
Chemical formula | C10H12O4 |
Mr | 196.20 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 100 |
a, b, c (Å) | 7.2306 (9), 14.1058 (17), 19.403 (2) |
V (Å3) | 1978.9 (4) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.40 × 0.30 × 0.30 |
Data collection | |
Diffractometer | Bruker APEXII |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.960, 0.970 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10579, 2033, 1271 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.076, 0.85 |
No. of reflections | 2033 |
No. of parameters | 130 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.17 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999), SHELXTL.
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The title compound, (I), is a lachrymator and a drug intermediate. It is widely employed in synthetic organic chemistry for example; 2,6-dimehthoxybenzohydr- azide (Qadeer et al., 2007), 2,5-disubstituted-1,3,4-oxadiazoles (Zheng et al., 2003; Al-Talib et al., 1990) and 5-substituted-2-mercapto-1,3,4-oxadiazoles (Yousif et al., 1986; Ahmad et al., 2001; Al-Soud et al., 2004; El-Emam et al., 2004). In addition, methyl 4-(bromomethyl)benzoate has been used in the synthesis of 1-(carboxybenzyl)imidazole-5-acrylic acids, which are potent and selective angiotensin II receptor antagonists (Weinstock et al., 1991). In view of the versatility of these compounds, we have synthesized the title compound, (I), and reported its crystal structure.
The title molecule (Fig. 1) shows no unusual features when compared with the Mogul norms (Bruno et al., 2004). The dihedral angle between the planar ester group and benzene ring is 81.46 (3)°.
As can be seen from the packing diagram (Fig. 2), the molecules of (I) are stacked along the a axis and elongated along the b axis. Dipole-dipole and van der Waals interactions are effective in the molecular packing.