Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028619/lh2422sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028619/lh2422Isup2.hkl |
CCDC reference: 655003
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.004 Å
- R factor = 0.052
- wR factor = 0.135
- Data-to-parameter ratio = 8.7
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT111_ALERT_2_B ADDSYM Detects (Pseudo) Centre of Symmetry ..... 82 PerFi
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 1.02
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 1344 Count of symmetry unique reflns 1348 Completeness (_total/calc) 99.70% 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 1 ALERT level B = Potentially serious problem 1 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 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 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
For background information, see: Freifelder et al. (1958); Monguzzi et al. (1974) and for the synthetic prodedure, see: Crosby & Saffron (1976). For related literature, see: Allen et al. (1987).
The title compound was prepared by the literature method with a minor change (Crosby & Saffron, 1976). To a solution of methyl 3-nitro-4-hydroxybenzoate (21.3 g, 0.12 mol) and potassium carbonate (17.4 g, 0.13 mol) in 150 ml of DMF was dropwise added 1-bromopranpane (13.6 ml, 0.15 mol) for 1 h, The reaction mixture was stired at 383 K for 12 h. The reaction mixture was dropped into water (300 ml) and extracted with ethyl acetate (3× 100 ml). The combined ester layer was dried with sodium sulfate and evaporated, and the residue was recrystallized from ethanol and dried in vacuum at 323 K to give the title compound as white solid in 85% yield. m.p. 337–339 K (Crosby & Saffron, 1976, mp. 335–336 K), IR (KBr, cm-1): ν 3052, 2977, 1720 (C=O), 1618, 1531, 1436, 1348 (NO2), 1274. 1H NMR(300 MHz, CDCl3, p.p.m.): δ 1.10 (t, J = 5.6 Hz, 3H, CH3), 1.92(m, J=5.5 Hz, J=4.9 Hz, 2H, CH2), 3.95(s, 3H, OCH3), 4.14 (t, J=4.8 Hz, 2H, OCH2), 7.13 (d, J=6.6 Hz, 1H, Ph—H), 8.21 (d, J=5.0 Hz, 1H, Ph—H), 8.49(s, 1H, Ph—H).
The crystals were obtained by dissolving the title compound (0.3 g, 1.65 mmol) in ethyl acetate (50 ml) and evaporating the solvent slowly at room temperature for about 2 d.
In the absence of significant anomalous dispersion effects Friedel pairs were merged. H atoms were positioned geometrically, with C—H = 0.93 Å (for aromatic H), 0.97 Å (for methylene H) and 0.96 Å (for methyl H), and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.
The title compound is an important intermediate used in the synthesis of types of local anesthetics (Freifelder et al., 1958; Monguzzi et al., 1974). We report its crystal structure herein.
In the molecule of the title compound (Fig. 1) the bond lengths and angles are within normal ranges (Allen et al., 1987). As shown (Fig. 2) molecules are linked into one-dimensional chains via weak intermolecular C—H···O hydrogen bonds.
For background information, see: Freifelder et al. (1958); Monguzzi et al. (1974) and for the synthetic prodedure, see: Crosby & Saffron (1976). For related literature, see: Allen et al. (1987).
Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.
C11H13NO5 | Dx = 1.352 Mg m−3 |
Mr = 239.22 | Melting point: 333 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 6.9732 (6) Å | θ = 10–13° |
b = 12.3149 (11) Å | µ = 0.11 mm−1 |
c = 13.6851 (13) Å | T = 298 K |
V = 1175.20 (18) Å3 | Plate, colorless |
Z = 4 | 0.30 × 0.30 × 0.10 mm |
F(000) = 504 |
Enraf–Nonius CAD-4 diffractometer | 977 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.022 |
Graphite monochromator | θmax = 25.9°, θmin = 2.2° |
ω/2θ scans | h = 0→8 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→15 |
Tmin = 0.938, Tmax = 0.969 | l = 0→16 |
1368 measured reflections | 3 standard reflections every 200 reflections |
1344 independent reflections | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.135 | w = 1/[σ2(Fo2) + (0.08P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
1344 reflections | Δρmax = 0.25 e Å−3 |
155 parameters | Δρmin = −0.26 e Å−3 |
1 restraint | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.026 (5) |
C11H13NO5 | V = 1175.20 (18) Å3 |
Mr = 239.22 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.9732 (6) Å | µ = 0.11 mm−1 |
b = 12.3149 (11) Å | T = 298 K |
c = 13.6851 (13) Å | 0.30 × 0.30 × 0.10 mm |
Enraf–Nonius CAD-4 diffractometer | 977 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.022 |
Tmin = 0.938, Tmax = 0.969 | 3 standard reflections every 200 reflections |
1368 measured reflections | intensity decay: none |
1344 independent reflections |
R[F2 > 2σ(F2)] = 0.052 | 1 restraint |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.25 e Å−3 |
1344 reflections | Δρmin = −0.26 e Å−3 |
155 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 | 0.7410 (4) | −0.02317 (14) | 0.42026 (13) | 0.0528 (6) | |
O2 | 0.8326 (5) | 0.2167 (2) | 0.23616 (17) | 0.0841 (10) | |
O3 | 0.6856 (5) | 0.0646 (2) | 0.24957 (17) | 0.0860 (10) | |
O4 | 0.7253 (6) | 0.48616 (18) | 0.4980 (2) | 0.0833 (9) | |
O5 | 0.6959 (4) | 0.41751 (17) | 0.64755 (19) | 0.0728 (8) | |
N | 0.7515 (5) | 0.1465 (2) | 0.28476 (18) | 0.0561 (8) | |
C1 | 0.6287 (8) | −0.2330 (3) | 0.3518 (3) | 0.0867 (14) | |
H1A | 0.6609 | −0.2982 | 0.3169 | 0.130* | |
H1B | 0.6313 | −0.1724 | 0.3078 | 0.130* | |
H1C | 0.5026 | −0.2401 | 0.3793 | 0.130* | |
C2 | 0.7691 (7) | −0.2153 (2) | 0.4310 (3) | 0.0720 (11) | |
H2A | 0.8967 | −0.2127 | 0.4029 | 0.086* | |
H2B | 0.7646 | −0.2767 | 0.4754 | 0.086* | |
C3 | 0.7354 (7) | −0.1120 (2) | 0.4890 (2) | 0.0590 (10) | |
H3A | 0.6117 | −0.1147 | 0.5214 | 0.071* | |
H3B | 0.8342 | −0.1031 | 0.5382 | 0.071* | |
C4 | 0.7267 (5) | 0.0781 (2) | 0.4549 (2) | 0.0415 (7) | |
C5 | 0.7335 (5) | 0.1646 (2) | 0.3898 (2) | 0.0426 (7) | |
C6 | 0.7278 (5) | 0.2716 (2) | 0.4213 (2) | 0.0453 (8) | |
H6A | 0.7349 | 0.3278 | 0.3760 | 0.054* | |
C7 | 0.7119 (5) | 0.2947 (2) | 0.5191 (2) | 0.0460 (7) | |
C8 | 0.7027 (5) | 0.2091 (2) | 0.5844 (2) | 0.0495 (8) | |
H8A | 0.6913 | 0.2237 | 0.6509 | 0.059* | |
C9 | 0.7099 (5) | 0.1033 (2) | 0.5538 (2) | 0.0481 (8) | |
H9A | 0.7035 | 0.0475 | 0.5996 | 0.058* | |
C10 | 0.7133 (5) | 0.4097 (2) | 0.5509 (3) | 0.0560 (9) | |
C11 | 0.7040 (8) | 0.5248 (3) | 0.6906 (3) | 0.0902 (15) | |
H11A | 0.6882 | 0.5192 | 0.7601 | 0.135* | |
H11B | 0.6032 | 0.5689 | 0.6639 | 0.135* | |
H11C | 0.8258 | 0.5574 | 0.6763 | 0.135* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0797 (16) | 0.0365 (10) | 0.0424 (11) | 0.0023 (13) | −0.0004 (13) | 0.0020 (8) |
O2 | 0.114 (2) | 0.0872 (18) | 0.0510 (13) | −0.0132 (18) | 0.0124 (15) | 0.0191 (14) |
O3 | 0.153 (3) | 0.0613 (15) | 0.0436 (12) | −0.0093 (18) | −0.0063 (18) | −0.0039 (11) |
O4 | 0.107 (2) | 0.0401 (12) | 0.1029 (19) | 0.0009 (16) | 0.012 (2) | 0.0036 (13) |
O5 | 0.095 (2) | 0.0493 (13) | 0.0745 (15) | −0.0003 (14) | −0.0025 (16) | −0.0210 (11) |
N | 0.075 (2) | 0.0526 (14) | 0.0406 (13) | 0.0031 (18) | 0.0026 (15) | 0.0096 (12) |
C1 | 0.131 (4) | 0.063 (2) | 0.066 (2) | −0.013 (3) | 0.009 (3) | −0.011 (2) |
C2 | 0.099 (3) | 0.0386 (15) | 0.078 (2) | −0.001 (2) | 0.004 (3) | 0.0033 (16) |
C3 | 0.089 (3) | 0.0378 (14) | 0.0498 (16) | −0.001 (2) | −0.009 (2) | 0.0105 (13) |
C4 | 0.0474 (18) | 0.0334 (14) | 0.0438 (15) | −0.0011 (14) | −0.0009 (15) | 0.0013 (11) |
C5 | 0.0455 (18) | 0.0458 (14) | 0.0364 (13) | 0.0001 (15) | −0.0004 (14) | 0.0035 (12) |
C6 | 0.0466 (18) | 0.0409 (14) | 0.0483 (16) | 0.0018 (16) | 0.0038 (16) | 0.0094 (12) |
C7 | 0.0416 (17) | 0.0391 (15) | 0.0572 (17) | −0.0008 (15) | −0.0002 (15) | 0.0006 (13) |
C8 | 0.055 (2) | 0.0515 (17) | 0.0417 (15) | 0.0008 (17) | −0.0003 (16) | −0.0044 (13) |
C9 | 0.062 (2) | 0.0403 (14) | 0.0421 (15) | −0.0012 (17) | 0.0032 (16) | 0.0073 (13) |
C10 | 0.048 (2) | 0.0415 (17) | 0.078 (2) | −0.0022 (17) | −0.0007 (19) | −0.0087 (17) |
C11 | 0.112 (4) | 0.056 (2) | 0.103 (3) | 0.000 (3) | −0.018 (3) | −0.039 (2) |
O1—C4 | 1.337 (3) | C3—H3A | 0.9700 |
O1—C3 | 1.443 (3) | C3—H3B | 0.9700 |
O2—N | 1.229 (3) | C4—C5 | 1.390 (4) |
O3—N | 1.209 (3) | C4—C9 | 1.394 (4) |
O4—C10 | 1.190 (4) | C5—C6 | 1.386 (4) |
O5—C10 | 1.332 (4) | C6—C7 | 1.374 (4) |
O5—C11 | 1.447 (4) | C6—H6A | 0.9300 |
N—C5 | 1.460 (4) | C7—C8 | 1.384 (4) |
C1—C2 | 1.477 (6) | C7—C10 | 1.482 (4) |
C1—H1A | 0.9600 | C8—C9 | 1.370 (4) |
C1—H1B | 0.9600 | C8—H8A | 0.9300 |
C1—H1C | 0.9600 | C9—H9A | 0.9300 |
C2—C3 | 1.518 (4) | C11—H11A | 0.9600 |
C2—H2A | 0.9700 | C11—H11B | 0.9600 |
C2—H2B | 0.9700 | C11—H11C | 0.9600 |
C4—O1—C3 | 118.3 (2) | C5—C4—C9 | 117.0 (2) |
C10—O5—C11 | 117.8 (3) | C6—C5—C4 | 121.9 (3) |
O3—N—O2 | 123.1 (3) | C6—C5—N | 117.0 (2) |
O3—N—C5 | 119.1 (3) | C4—C5—N | 121.1 (2) |
O2—N—C5 | 117.7 (3) | C7—C6—C5 | 120.1 (3) |
C2—C1—H1A | 109.5 | C7—C6—H6A | 119.9 |
C2—C1—H1B | 109.5 | C5—C6—H6A | 119.9 |
H1A—C1—H1B | 109.5 | C6—C7—C8 | 118.4 (3) |
C2—C1—H1C | 109.5 | C6—C7—C10 | 118.9 (3) |
H1A—C1—H1C | 109.5 | C8—C7—C10 | 122.7 (3) |
H1B—C1—H1C | 109.5 | C9—C8—C7 | 121.7 (3) |
C1—C2—C3 | 113.9 (4) | C9—C8—H8A | 119.1 |
C1—C2—H2A | 108.8 | C7—C8—H8A | 119.1 |
C3—C2—H2A | 108.8 | C8—C9—C4 | 120.8 (3) |
C1—C2—H2B | 108.8 | C8—C9—H9A | 119.6 |
C3—C2—H2B | 108.8 | C4—C9—H9A | 119.6 |
H2A—C2—H2B | 107.7 | O4—C10—O5 | 123.6 (3) |
O1—C3—C2 | 106.9 (2) | O4—C10—C7 | 125.3 (3) |
O1—C3—H3A | 110.3 | O5—C10—C7 | 111.1 (3) |
C2—C3—H3A | 110.3 | O5—C11—H11A | 109.5 |
O1—C3—H3B | 110.3 | O5—C11—H11B | 109.5 |
C2—C3—H3B | 110.3 | H11A—C11—H11B | 109.5 |
H3A—C3—H3B | 108.6 | O5—C11—H11C | 109.5 |
O1—C4—C5 | 119.1 (2) | H11A—C11—H11C | 109.5 |
O1—C4—C9 | 123.9 (2) | H11B—C11—H11C | 109.5 |
C4—O1—C3—C2 | −175.9 (3) | C5—C6—C7—C8 | 0.3 (5) |
C1—C2—C3—O1 | −57.8 (5) | C5—C6—C7—C10 | 177.8 (3) |
C3—O1—C4—C5 | 179.5 (3) | C6—C7—C8—C9 | 0.3 (5) |
C3—O1—C4—C9 | 1.2 (5) | C10—C7—C8—C9 | −177.1 (4) |
O1—C4—C5—C6 | −177.1 (3) | C7—C8—C9—C4 | −0.1 (6) |
C9—C4—C5—C6 | 1.3 (5) | O1—C4—C9—C8 | 177.6 (3) |
O1—C4—C5—N | 1.4 (5) | C5—C4—C9—C8 | −0.7 (6) |
C9—C4—C5—N | 179.8 (3) | C11—O5—C10—O4 | −3.9 (7) |
O3—N—C5—C6 | −151.7 (3) | C11—O5—C10—C7 | 177.1 (3) |
O2—N—C5—C6 | 27.8 (5) | C6—C7—C10—O4 | 0.9 (6) |
O3—N—C5—C4 | 29.7 (5) | C8—C7—C10—O4 | 178.3 (4) |
O2—N—C5—C4 | −150.8 (3) | C6—C7—C10—O5 | 179.8 (3) |
C4—C5—C6—C7 | −1.1 (5) | C8—C7—C10—O5 | −2.8 (5) |
N—C5—C6—C7 | −179.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···O1 | 0.96 | 2.52 | 2.858 (4) | 101 |
C9—H9A···O3i | 0.93 | 2.59 | 3.462 (4) | 156 |
Symmetry code: (i) −x+3/2, −y, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C11H13NO5 |
Mr | 239.22 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 298 |
a, b, c (Å) | 6.9732 (6), 12.3149 (11), 13.6851 (13) |
V (Å3) | 1175.20 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.30 × 0.30 × 0.10 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.938, 0.969 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1368, 1344, 977 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.615 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.135, 1.07 |
No. of reflections | 1344 |
No. of parameters | 155 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.26 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1985), CAD-4 Software, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···O1 | 0.9600 | 2.5200 | 2.858 (4) | 101.00 |
C9—H9A···O3i | 0.9300 | 2.5900 | 3.462 (4) | 156.00 |
Symmetry code: (i) −x+3/2, −y, z+1/2. |
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The title compound is an important intermediate used in the synthesis of types of local anesthetics (Freifelder et al., 1958; Monguzzi et al., 1974). We report its crystal structure herein.
In the molecule of the title compound (Fig. 1) the bond lengths and angles are within normal ranges (Allen et al., 1987). As shown (Fig. 2) molecules are linked into one-dimensional chains via weak intermolecular C—H···O hydrogen bonds.