Methyl 2-amino-4,5-dimethoxybenzoate

organic compounds Acta Crystallographica Section E Data collection Structure Reports Online Bruker APEXII CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2004) Tmin = 0.948, Tmax = 0.974 ISSN 1600-5368 Methyl 2-amino-4,5-dimethoxybenzoate Tania N. Hill* and Naadiya Patel Molecular Sciences Institute, School of Chemistry, University of the Witwatersrand, PO WITS 2050, Johannesburg, South Africa Correspondence e-mail: [email protected] Received 7 November 2013; accepted 11 November 2013 9994 measured reflections 2543 independent reflections 2080 reflections with I > 2(I) Rint = 0.035 Refinement R[F 2 > 2(F 2)] = 0.038 wR(F 2) = 0.109 S = 1.05 2543 reflections 147 parameters H atoms treated by a mixture of independent and constrained refinement
max = 0.27 e Å3
min = 0.25 e Å3 Table 1 Hydrogen-bond geometry (Å,  ). Key indicators: single-crystal X-ray study; T = 173 K; mean (C–C) = 0.002 Å; R factor = 0.038; wR factor = 0.109; data-to-parameter ratio = 17.3. The title compound, C10H13NO4, is essentially planar, with an r.m.s. deviation of 0.049 Å. An intramolecular C—H  O hydrogen bond occurs and the amino group forms an intramolecular N—H  Oester hydrogen bond; the other H atom forms an intermolecular N—H  Ocarbonyl hydrogen bond, leading to the formation of a helical chain that runs along the b-axis direction. D—H  A D—H H  A D  A D—H  A C6—H6  O2 N1—H1A  O1 N1—H1B  O1i 0.95 0.90 (2) 0.88 (2) 2.37 2.03 (2) 2.10 (2) 2.7131 (14) 2.702 (2) 2.947 (1) 101 131 (2) 162 (1) Symmetry code: (i) x; y þ 12; z  12. Data collection: APEX2 (Bruker, 2005); cell refinement: SAINTPlus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 2012). Related literature For similar crystal structures, see: Zhang et al. (2009); Smith & Elsegood (2002). The University of the Witwatersrand and the Molecular Sciences Institute are thanked for providing the infrastructure and financial support. Special thanks go to Dr Andreas Lemmerer of the University of the Witwatersrand for his contributions and insights toward this project. TNH wishes to thank the University of the Witwatersrand research committee for a postdoctoral fellowship. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG5347). References Experimental Crystal data C10H13NO4 Mr = 211.21 Monoclinic, P21 =c a = 11.1933 (4) Å b = 7.7564 (3) Å c = 13.7728 (5) Å = 121.741 (2) Acta Cryst. (2013). E69, o1779 V = 1016.91 (7) Å3 Z=4 Mo K radiation  = 0.11 mm1 T = 173 K 0.5  0.29  0.25 mm Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Imapct GbR, Bonn, Germany. Bruker (2004). SAINT-Plus, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin. USA. Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Smith, M. B. & Elsegood, M. R. J. (2002). Tetrahedron Lett. 43, 1299–1301. Zhang, M., Lu, R., Han, L., Wei, W. & Wang, H. (2009). Acta Cryst. E65, o942. doi:10.1107/S1600536813030894 Hill and Patel o1779 supplementary materials supplementary materials Acta Cryst. (2013). E69, o1779 [doi:10.1107/S1600536813030894] Methyl 2-amino-4,5-dimethoxybenzoate Tania N. Hill and Naadiya Patel 1. Comment The molecular structure of (I) is presented in Figure 1, and was obtained by recrystallization of the commercially available compound. The title compound consists of an amino (C2) and methoxy (C4 and C5) substituted benzoate which was found to be essentially planar with an r.m.s. deviation of 0.049 Å; the dihedral angles shown in Table 1 further reinforce the planarity of (I). The maximum deviation observed below the calculated mean plane was found for the carbonyl oxygen (O1) at -0.136 (1) Å. Two intramolecular hydrogen bonds found between the phenyl carbon (C6), the amino (N1) and the ester O atoms (O1 and O2) with distances of 2.713 (1) Å and 2.702 (2) Å, effectively lock the ester into the molecular plane. The last hydrogen bond interaction observed between the amino (N1) and an adjacent carbonyl oxygen (O1) (symmetry operator [-x, y + 1/2, -z - 1/2]) with a distance of 2.947 (1) Å results in a helical chain along [0 1 0] (Figure 2). 2. Experimental Methyl 2-amino-4,5-dimethoxybenzoate was obtained commercially. (I) was redissolved in warm MeOH and allowed to cool to room terperature. Yellow crystals suitable for single-crystal diffraction were obtained by slow evaporation over a few days. 3. Refinement All hydrogen atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å Uiso(H)= 1.2 Ueq(C) for the aromatic H and with C—H = 0.98 Å Uiso(H)= 1.5 Ueq(C)for methyl H atoms. The methyl groups were allowed to rotate with a fixed angle arround the C—C bond to best fit the experimental electron density. The amino hydrogens were freely refined. Computing details Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 2012). Acta Cryst. (2013). E69, o1779 sup-1 supplementary materials Figure 1 View of (I) (50% probability displacement ellipsoids) Acta Cryst. (2013). E69, o1779 sup-2 supplementary materials Figure 2 Packing of (I) viewed along [0 1 0]. H atoms omitted. Methyl 2-amino-4,5-dimethoxybenzoate Crystal data C10H13NO4 Mr = 211.21 Monoclinic, P21/c Hall symbol: -P 2ybc a = 11.1933 (4) Å b = 7.7564 (3) Å c = 13.7728 (5) Å β = 121.741 (2)° V = 1016.91 (7) Å3 Z=4 Acta Cryst. (2013). E69, o1779 F(000) = 448 Dx = 1.38 Mg m−3 Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3834 reflections θ = 3.0–28.3° µ = 0.11 mm−1 T = 173 K Cuboid, yellow 0.5 × 0.29 × 0.25 mm sup-3 supplementary materials Data collection Bruker APEXII CCD area-detector diffractometer Radiation source: fine-focus sealed tube Graphite monochromator Detector resolution: 512 pixels mm-1 ω scans Absorption correction: multi-scan (SADABS; Bruker, 2004) Tmin = 0.948, Tmax = 0.974 9994 measured reflections 2543 independent reflections 2080 reflections with I > 2σ(I) Rint = 0.035 θmax = 28.3°, θmin = 2.1° h = −14→14 k = −10→10 l = −18→18 Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.038 wR(F2) = 0.109 S = 1.05 2543 reflections 147 parameters 0 restraints H atoms treated by a mixture of independent and constrained refinement w = 1/[σ2(Fo2) + (0.0501P)2 + 0.2646P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001 Δρmax = 0.27 e Å−3 Δρmin = −0.25 e Å−3 Special details 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. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) C1 C2 C3 H3 C4 C5 C6 H6 C7 C8 H8A H8B H8C C9 H9A H9B H9C C10 H10A H10B H10C N1 x y z Uiso*/Ueq 0.19769 (12) 0.16865 (12) 0.22538 (12) 0.2062 0.30761 (12) 0.33814 (12) 0.28295 (12) 0.3024 0.13820 (12) 0.13103 (15) 0.0291 0.1763 0.1531 0.33489 (15) 0.3706 0.3805 0.2331 0.44564 (14) 0.3554 0.5049 0.4927 0.09141 (12) 0.09141 (14) 0.16680 (14) 0.33134 (15) 0.3839 0.41704 (14) 0.34050 (14) 0.18137 (14) 0.1301 −0.07648 (14) −0.30520 (15) −0.3006 −0.3421 −0.3875 0.66056 (17) 0.591 0.7738 0.6751 0.36738 (17) 0.3526 0.4467 0.2554 0.08643 (15) −0.01177 (10) −0.11496 (10) −0.11104 (10) −0.1801 −0.00949 (10) 0.09484 (9) 0.09202 (9) 0.1615 −0.01151 (10) 0.09811 (12) 0.064 0.1779 0.0558 −0.10146 (11) −0.1402 −0.0826 −0.1518 0.29532 (10) 0.29 0.3579 0.31 −0.21889 (9) 0.0237 (2) 0.0243 (2) 0.0250 (2) 0.03* 0.0239 (2) 0.0234 (2) 0.0235 (2) 0.028* 0.0256 (2) 0.0340 (3) 0.051* 0.051* 0.051* 0.0345 (3) 0.052* 0.052* 0.052* 0.0328 (3) 0.049* 0.049* 0.049* 0.0326 (3) Acta Cryst. (2013). E69, o1779 sup-4 supplementary materials O1 O2 O3 O4 H1B H1A 0.05611 (10) 0.18202 (10) 0.36486 (9) 0.42222 (9) 0.0560 (16) 0.0410 (18) −0.15847 (12) −0.13617 (11) 0.57535 (10) 0.43624 (10) 0.1496 (19) −0.007 (3) −0.09659 (8) 0.09315 (7) 0.00121 (7) 0.19078 (7) −0.2812 (14) −0.2225 (15) 0.0376 (2) 0.0324 (2) 0.0293 (2) 0.0279 (2) 0.037 (4)* 0.056 (5)* Atomic displacement parameters (Å2) C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 N1 O1 O2 O3 O4 U11 U22 U33 U12 U13 U23 0.0235 (5) 0.0221 (5) 0.0261 (6) 0.0248 (6) 0.0236 (5) 0.0255 (6) 0.0250 (6) 0.0438 (8) 0.0402 (7) 0.0398 (7) 0.0371 (6) 0.0411 (5) 0.0431 (5) 0.0363 (5) 0.0341 (5) 0.0231 (5) 0.0261 (5) 0.0278 (6) 0.0229 (5) 0.0249 (5) 0.0237 (5) 0.0246 (5) 0.0221 (5) 0.0328 (6) 0.0348 (6) 0.0324 (6) 0.0323 (5) 0.0241 (4) 0.0258 (4) 0.0271 (4) 0.0239 (5) 0.0232 (5) 0.0223 (5) 0.0268 (5) 0.0219 (5) 0.0216 (5) 0.0272 (6) 0.0417 (7) 0.0336 (6) 0.0218 (6) 0.0211 (5) 0.0305 (5) 0.0295 (4) 0.0271 (4) 0.0215 (4) 0.0032 (4) 0.0050 (4) 0.0056 (4) 0.0033 (4) 0.0017 (4) 0.0021 (4) 0.0032 (4) −0.0015 (5) 0.0003 (5) −0.0095 (5) −0.0008 (5) −0.0088 (4) −0.0050 (4) −0.0031 (3) −0.0063 (3) 0.0121 (4) 0.0110 (4) 0.0137 (5) 0.0155 (5) 0.0121 (4) 0.0127 (4) 0.0137 (5) 0.0263 (6) 0.0214 (6) 0.0148 (5) 0.0102 (5) 0.0127 (4) 0.0188 (4) 0.0176 (4) 0.0140 (4) −0.0001 (4) −0.0010 (4) 0.0038 (4) 0.0024 (4) −0.0004 (4) 0.0011 (4) −0.0011 (4) 0.0015 (5) 0.0092 (5) −0.0019 (5) −0.0008 (4) −0.0055 (4) −0.0004 (3) 0.0029 (3) −0.0018 (3) Geometric parameters (Å, º) C1—C2 C1—C6 C1—C7 C2—N1 C2—C3 C3—C4 C3—H3 C4—O3 C4—C5 C5—O4 C5—C6 C6—H6 C7—O1 C7—O2 1.4077 (15) 1.4162 (15) 1.4634 (16) 1.3722 (15) 1.4138 (16) 1.3751 (16) 0.95 1.3568 (13) 1.4203 (15) 1.3692 (13) 1.3716 (15) 0.95 1.2202 (14) 1.3374 (14) C8—O2 C8—H8A C8—H8B C8—H8C C9—O3 C9—H9A C9—H9B C9—H9C C10—O4 C10—H10A C10—H10B C10—H10C N1—H1B N1—H1A 1.4458 (14) 0.98 0.98 0.98 1.4317 (14) 0.98 0.98 0.98 1.4247 (14) 0.98 0.98 0.98 0.881 (16) 0.90 (2) C2—C1—C6 C2—C1—C7 C6—C1—C7 N1—C2—C1 N1—C2—C3 C1—C2—C3 C4—C3—C2 119.31 (10) 120.56 (10) 120.12 (10) 123.27 (11) 118.28 (10) 118.42 (10) 121.47 (10) H8A—C8—H8B O2—C8—H8C H8A—C8—H8C H8B—C8—H8C O3—C9—H9A O3—C9—H9B H9A—C9—H9B 109.5 109.5 109.5 109.5 109.5 109.5 109.5 Acta Cryst. (2013). E69, o1779 sup-5 supplementary materials C4—C3—H3 C2—C3—H3 O3—C4—C3 O3—C4—C5 C3—C4—C5 O4—C5—C6 O4—C5—C4 C6—C5—C4 C5—C6—C1 C5—C6—H6 C1—C6—H6 O1—C7—O2 O1—C7—C1 O2—C7—C1 O2—C8—H8A O2—C8—H8B 119.3 119.3 124.97 (10) 114.83 (10) 120.20 (10) 125.87 (10) 115.28 (10) 118.85 (10) 121.75 (10) 119.1 119.1 121.23 (11) 125.11 (11) 113.66 (10) 109.5 109.5 O3—C9—H9C H9A—C9—H9C H9B—C9—H9C O4—C10—H10A O4—C10—H10B H10A—C10—H10B O4—C10—H10C H10A—C10—H10C H10B—C10—H10C C2—N1—H1B C2—N1—H1A H1B—N1—H1A C7—O2—C8 C4—O3—C9 C5—O4—C10 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 118.5 (10) 117.0 (12) 116.4 (15) 115.77 (9) 117.30 (9) 116.08 (9) C6—C1—C2—N1 C7—C1—C2—N1 C6—C1—C2—C3 C7—C1—C2—C3 N1—C2—C3—C4 C1—C2—C3—C4 C2—C3—C4—O3 C2—C3—C4—C5 O3—C4—C5—O4 C3—C4—C5—O4 O3—C4—C5—C6 C3—C4—C5—C6 O4—C5—C6—C1 177.57 (11) −3.72 (17) −0.46 (16) 178.25 (10) −177.87 (11) 0.26 (16) −179.49 (10) 0.33 (17) −0.88 (14) 179.28 (10) 179.10 (10) −0.73 (17) −179.48 (10) C4—C5—C6—C1 C2—C1—C6—C5 C7—C1—C6—C5 C2—C1—C7—O1 C6—C1—C7—O1 C2—C1—C7—O2 C6—C1—C7—O2 O1—C7—O2—C8 C1—C7—O2—C8 C3—C4—O3—C9 C5—C4—O3—C9 C6—C5—O4—C10 C4—C5—O4—C10 0.54 (17) 0.06 (17) −178.65 (10) −3.96 (18) 174.73 (11) 176.09 (10) −5.22 (15) 2.67 (16) −177.38 (10) 1.26 (16) −178.57 (10) −4.40 (16) 175.59 (10) Hydrogen-bond geometry (Å, º) D—H···A D—H H···A D···A D—H···A C6—H6···O2 N1—H1A···O1 N1—H1B···O1i 0.95 0.90 (2) 0.88 (2) 2.37 2.03 (2) 2.10 (2) 2.7131 (14) 2.702 (2) 2.947 (1) 101 131 (2) 162 (1) Symmetry code: (i) −x, y+1/2, −z−1/2. Acta Cryst. (2013). E69, o1779 sup-6