Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
In the title crystal structure, C11H13NO5, mol­ecules are linked through weak C—H...O hydrogen bonds to form one-dimensional chains in the c direction.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028619/lh2422sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028619/lh2422Isup2.hkl
Contains datablock I

CCDC reference: 655003

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](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

Comment top

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.

Related literature top

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).

Experimental top

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.

Refinement top

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.

Structure description top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. A hydrogen bond is shown as a dashed line.
[Figure 2] Fig. 2. The packing of the title compound showing hydrogen bonds as dashed lines.
Methyl 3-nitro-4-propoxybenzoate top
Crystal data top
C11H13NO5Dx = 1.352 Mg m3
Mr = 239.22Melting point: 333 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 25 reflections
a = 6.9732 (6) Åθ = 10–13°
b = 12.3149 (11) ŵ = 0.11 mm1
c = 13.6851 (13) ÅT = 298 K
V = 1175.20 (18) Å3Plate, colorless
Z = 40.30 × 0.30 × 0.10 mm
F(000) = 504
Data collection top
Enraf–Nonius CAD-4
diffractometer
977 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.022
Graphite monochromatorθmax = 25.9°, θmin = 2.2°
ω/2θ scansh = 08
Absorption correction: ψ scan
(North et al., 1968)
k = 015
Tmin = 0.938, Tmax = 0.969l = 016
1368 measured reflections3 standard reflections every 200 reflections
1344 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.052H-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 reflectionsΔρmax = 0.25 e Å3
155 parametersΔρmin = 0.26 e Å3
1 restraintExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.026 (5)
Crystal data top
C11H13NO5V = 1175.20 (18) Å3
Mr = 239.22Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.9732 (6) ŵ = 0.11 mm1
b = 12.3149 (11) ÅT = 298 K
c = 13.6851 (13) Å0.30 × 0.30 × 0.10 mm
Data collection top
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 = 0.9693 standard reflections every 200 reflections
1368 measured reflections intensity decay: none
1344 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0521 restraint
wR(F2) = 0.135H-atom parameters constrained
S = 1.07Δρmax = 0.25 e Å3
1344 reflectionsΔρmin = 0.26 e Å3
155 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.7410 (4)0.02317 (14)0.42026 (13)0.0528 (6)
O20.8326 (5)0.2167 (2)0.23616 (17)0.0841 (10)
O30.6856 (5)0.0646 (2)0.24957 (17)0.0860 (10)
O40.7253 (6)0.48616 (18)0.4980 (2)0.0833 (9)
O50.6959 (4)0.41751 (17)0.64755 (19)0.0728 (8)
N0.7515 (5)0.1465 (2)0.28476 (18)0.0561 (8)
C10.6287 (8)0.2330 (3)0.3518 (3)0.0867 (14)
H1A0.66090.29820.31690.130*
H1B0.63130.17240.30780.130*
H1C0.50260.24010.37930.130*
C20.7691 (7)0.2153 (2)0.4310 (3)0.0720 (11)
H2A0.89670.21270.40290.086*
H2B0.76460.27670.47540.086*
C30.7354 (7)0.1120 (2)0.4890 (2)0.0590 (10)
H3A0.61170.11470.52140.071*
H3B0.83420.10310.53820.071*
C40.7267 (5)0.0781 (2)0.4549 (2)0.0415 (7)
C50.7335 (5)0.1646 (2)0.3898 (2)0.0426 (7)
C60.7278 (5)0.2716 (2)0.4213 (2)0.0453 (8)
H6A0.73490.32780.37600.054*
C70.7119 (5)0.2947 (2)0.5191 (2)0.0460 (7)
C80.7027 (5)0.2091 (2)0.5844 (2)0.0495 (8)
H8A0.69130.22370.65090.059*
C90.7099 (5)0.1033 (2)0.5538 (2)0.0481 (8)
H9A0.70350.04750.59960.058*
C100.7133 (5)0.4097 (2)0.5509 (3)0.0560 (9)
C110.7040 (8)0.5248 (3)0.6906 (3)0.0902 (15)
H11A0.68820.51920.76010.135*
H11B0.60320.56890.66390.135*
H11C0.82580.55740.67630.135*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0797 (16)0.0365 (10)0.0424 (11)0.0023 (13)0.0004 (13)0.0020 (8)
O20.114 (2)0.0872 (18)0.0510 (13)0.0132 (18)0.0124 (15)0.0191 (14)
O30.153 (3)0.0613 (15)0.0436 (12)0.0093 (18)0.0063 (18)0.0039 (11)
O40.107 (2)0.0401 (12)0.1029 (19)0.0009 (16)0.012 (2)0.0036 (13)
O50.095 (2)0.0493 (13)0.0745 (15)0.0003 (14)0.0025 (16)0.0210 (11)
N0.075 (2)0.0526 (14)0.0406 (13)0.0031 (18)0.0026 (15)0.0096 (12)
C10.131 (4)0.063 (2)0.066 (2)0.013 (3)0.009 (3)0.011 (2)
C20.099 (3)0.0386 (15)0.078 (2)0.001 (2)0.004 (3)0.0033 (16)
C30.089 (3)0.0378 (14)0.0498 (16)0.001 (2)0.009 (2)0.0105 (13)
C40.0474 (18)0.0334 (14)0.0438 (15)0.0011 (14)0.0009 (15)0.0013 (11)
C50.0455 (18)0.0458 (14)0.0364 (13)0.0001 (15)0.0004 (14)0.0035 (12)
C60.0466 (18)0.0409 (14)0.0483 (16)0.0018 (16)0.0038 (16)0.0094 (12)
C70.0416 (17)0.0391 (15)0.0572 (17)0.0008 (15)0.0002 (15)0.0006 (13)
C80.055 (2)0.0515 (17)0.0417 (15)0.0008 (17)0.0003 (16)0.0044 (13)
C90.062 (2)0.0403 (14)0.0421 (15)0.0012 (17)0.0032 (16)0.0073 (13)
C100.048 (2)0.0415 (17)0.078 (2)0.0022 (17)0.0007 (19)0.0087 (17)
C110.112 (4)0.056 (2)0.103 (3)0.000 (3)0.018 (3)0.039 (2)
Geometric parameters (Å, º) top
O1—C41.337 (3)C3—H3A0.9700
O1—C31.443 (3)C3—H3B0.9700
O2—N1.229 (3)C4—C51.390 (4)
O3—N1.209 (3)C4—C91.394 (4)
O4—C101.190 (4)C5—C61.386 (4)
O5—C101.332 (4)C6—C71.374 (4)
O5—C111.447 (4)C6—H6A0.9300
N—C51.460 (4)C7—C81.384 (4)
C1—C21.477 (6)C7—C101.482 (4)
C1—H1A0.9600C8—C91.370 (4)
C1—H1B0.9600C8—H8A0.9300
C1—H1C0.9600C9—H9A0.9300
C2—C31.518 (4)C11—H11A0.9600
C2—H2A0.9700C11—H11B0.9600
C2—H2B0.9700C11—H11C0.9600
C4—O1—C3118.3 (2)C5—C4—C9117.0 (2)
C10—O5—C11117.8 (3)C6—C5—C4121.9 (3)
O3—N—O2123.1 (3)C6—C5—N117.0 (2)
O3—N—C5119.1 (3)C4—C5—N121.1 (2)
O2—N—C5117.7 (3)C7—C6—C5120.1 (3)
C2—C1—H1A109.5C7—C6—H6A119.9
C2—C1—H1B109.5C5—C6—H6A119.9
H1A—C1—H1B109.5C6—C7—C8118.4 (3)
C2—C1—H1C109.5C6—C7—C10118.9 (3)
H1A—C1—H1C109.5C8—C7—C10122.7 (3)
H1B—C1—H1C109.5C9—C8—C7121.7 (3)
C1—C2—C3113.9 (4)C9—C8—H8A119.1
C1—C2—H2A108.8C7—C8—H8A119.1
C3—C2—H2A108.8C8—C9—C4120.8 (3)
C1—C2—H2B108.8C8—C9—H9A119.6
C3—C2—H2B108.8C4—C9—H9A119.6
H2A—C2—H2B107.7O4—C10—O5123.6 (3)
O1—C3—C2106.9 (2)O4—C10—C7125.3 (3)
O1—C3—H3A110.3O5—C10—C7111.1 (3)
C2—C3—H3A110.3O5—C11—H11A109.5
O1—C3—H3B110.3O5—C11—H11B109.5
C2—C3—H3B110.3H11A—C11—H11B109.5
H3A—C3—H3B108.6O5—C11—H11C109.5
O1—C4—C5119.1 (2)H11A—C11—H11C109.5
O1—C4—C9123.9 (2)H11B—C11—H11C109.5
C4—O1—C3—C2175.9 (3)C5—C6—C7—C80.3 (5)
C1—C2—C3—O157.8 (5)C5—C6—C7—C10177.8 (3)
C3—O1—C4—C5179.5 (3)C6—C7—C8—C90.3 (5)
C3—O1—C4—C91.2 (5)C10—C7—C8—C9177.1 (4)
O1—C4—C5—C6177.1 (3)C7—C8—C9—C40.1 (6)
C9—C4—C5—C61.3 (5)O1—C4—C9—C8177.6 (3)
O1—C4—C5—N1.4 (5)C5—C4—C9—C80.7 (6)
C9—C4—C5—N179.8 (3)C11—O5—C10—O43.9 (7)
O3—N—C5—C6151.7 (3)C11—O5—C10—C7177.1 (3)
O2—N—C5—C627.8 (5)C6—C7—C10—O40.9 (6)
O3—N—C5—C429.7 (5)C8—C7—C10—O4178.3 (4)
O2—N—C5—C4150.8 (3)C6—C7—C10—O5179.8 (3)
C4—C5—C6—C71.1 (5)C8—C7—C10—O52.8 (5)
N—C5—C6—C7179.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1B···O10.962.522.858 (4)101
C9—H9A···O3i0.932.593.462 (4)156
Symmetry code: (i) x+3/2, y, z+1/2.

Experimental details

Crystal data
Chemical formulaC11H13NO5
Mr239.22
Crystal system, space groupOrthorhombic, P212121
Temperature (K)298
a, b, c (Å)6.9732 (6), 12.3149 (11), 13.6851 (13)
V3)1175.20 (18)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.30 × 0.30 × 0.10
Data collection
DiffractometerEnraf–Nonius CAD-4
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.938, 0.969
No. of measured, independent and
observed [I > 2σ(I)] reflections
1368, 1344, 977
Rint0.022
(sin θ/λ)max1)0.615
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.135, 1.07
No. of reflections1344
No. of parameters155
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1B···O10.96002.52002.858 (4)101.00
C9—H9A···O3i0.93002.59003.462 (4)156.00
Symmetry code: (i) x+3/2, y, z+1/2.
 

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds