Methyl 5-iodo-2-methoxybenzoate

organic compounds Acta Crystallographica Section E Monoclinic, P21 =n a = 4.3378 (7) Å b = 7.0690 (11) Å c = 33.120 (5) Å = 92.727 (2) V = 1014.4 (3) Å3 Structure Reports Online ISSN 1600-5368 Methyl 5-iodo-2-methoxybenzoate Data collection Fredrik Lundvall,a* David Stephen Wragg,b Pascal D. C. Dietzelc and Helmer Fjellvåga Bruker APEXII CCD diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.407, Tmax = 0.788 Z=4 Mo K radiation  = 3.13 mm 1 T = 293 K 0.35  0.20  0.08 mm 7578 measured reflections 2064 independent reflections 1971 reflections with I > 2(I) Rint = 0.018 a Centre for Materials Science and Nanotechnology, Department of Chemistry, University of Oslo, PO Box 1126, 0315 Oslo, Norway, bCentre for Materials Science and Nanotechnology, University of Oslo, PO Box 1033, 0315 Oslo, and c Department of Chemistry, University of Bergen, PO Box 7803, 5020 Bergen, Norway Correspondence e-mail: [email protected] Refinement R[F 2 > 2(F 2)] = 0.033 wR(F 2) = 0.079 S = 1.17 2064 reflections 120 parameters H-atom parameters constrained
max = 0.67 e Å 3
min = 0.86 e Å 3 Received 5 March 2014; accepted 17 March 2014 Key indicators: single-crystal X-ray study; T = 293 K; mean (C–C) = 0.005 Å; R factor = 0.033; wR factor = 0.079; data-to-parameter ratio = 17.2. In the title compound, C9H9IO3, the molecules are close to planar [maximum deviation from benzene ring plane = 0.229 (5) Å for the methyl carboxylate C atom] with the methyl groups oriented away from each other. In the crystal, molecules form stacked layers parallel to the ab plane, where every layer has either the iodine or methoxy/methyl carboxylate substituents pointing towards each other in an alternating fashion. Related literature For the synthesis, see Wang et al. (2009). Experimental Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) implemented in WinGX (Farrugia, 2012); molecular graphics: DIAMOND (Brandenburg, 2004) and ChemBioDraw Ultra (CambridgeSoft, 2009); software used to prepare material for publication: publCIF (Westrip, 2010). We acknowledge the support from the Norwegian Research Council (project 190980), inGAP and the Department of Chemistry, UiO. Supporting information for this paper is available from the IUCr electronic archives (Reference: LR2123). References Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. Brandenburg, K. (2004). DIAMOND. Crystal Impact GbR, Bonn, Germany. Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. CambridgeSoft (2009). ChemBioDraw Ultra. CambridgeSoft Corporation, Cambridge, Massachusetts, USA. Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Wang, L., Xiao, Z.-Y., Hou, J.-L., Wang, G.-T., Jiang, X.-K. & Li, Z.-T. (2009). Tetrahedron, 65, 10544–10551. Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Crystal data C9H9IO3 o462 Mr = 292.06 Lundvall et al. doi:10.1107/S1600536814005868 Acta Cryst. (2014). E70, o462 supporting information supporting information Acta Cryst. (2014). E70, o462 [doi:10.1107/S1600536814005868] Methyl 5-iodo-2-methoxybenzoate Fredrik Lundvall, David Stephen Wragg, Pascal D. C. Dietzel and Helmer Fjellvåg S1. Experimental S1.1. Synthesis and crystallization The title compound was synthesized by the method used by Wang et al. (2009), only differing slightly in the reaction time which was increased from 30 to 60 minutes. The 1H NMR spectrum of the title compound is in good agreement with what was reported by Wang et al. (2009). The title compound was dissolved in CDCl3 for NMR-analysis, and slow evaporation of the solvent yielded single crystals suitable for X-ray diffraction. S1.2. Refinement Crystal data, data collection and structure refinement details are summarized in Table 1. The structure was refined by fullmatrix least squares using SHELXL97 (Sheldrick, 2008) as implemented in the WinGX suite (Farrugia, 2012). H-atoms were positioned geometrically at distances of 0.93 (CH) and 0.96 Å (CH3) and refined using a riding model with Uiso (H)=1.2 Ueq (CH) and Uiso (H)=1.5 Ueq (CH3). S2. Results and discussion The title compound is an intermediate in the synthesis of 4,4′-dimethoxy-3,3′-biphenyldicarboxylic acid, a novel organic linker for use in MOFs (Metal-Organic Frameworks). The title compound is a known intermediate from the literature (Wang et al., 2009), but the crystal structure has not been reported so far. The structure of the title compound, C9H9IO3, has a monoclinic P21/c symmetry. The asymmetric unit equals one molecule of the compound, with the full content of the unit cell generated by symmetry operations. The molecule has a planar motif where the methyl groups are oriented away from each other to accommodate the sterical demands of these groups. To further increase the distance between the methyl groups, an alternative configuration of the molecule could theoretically be achieved by rotating the methyl carboxylate group 180° around the C1–C7 bond. This however appears not to be an energetically favourable configuration in the solid state. The asymmetric units are packed to form layers parallel to the C plane, which results in a layered structure where every other layer has either an iodine or a methoxy/methyl carboxylate interface. Acta Cryst. (2014). E70, o462 sup-1 supporting information Figure 1 One molecular unit of the title compound with 50% probability displacement ellipsoids. Hydrogen atoms are omitted for clarity. Acta Cryst. (2014). E70, o462 sup-2 supporting information Figure 2 Packing diagram of the title compound viewed along the a axis. Hydrogen atoms are omitted for clarity. Acta Cryst. (2014). E70, o462 sup-3 supporting information Figure 3 Packing diagram of the title compound viewed along the b axis. Hydrogen atoms are omitted for clarity. Methyl 5-iodo-2-methoxybenzoate Crystal data C9H9IO3 Mr = 292.06 Monoclinic, P21/n Hall symbol: -P 2yn a = 4.3378 (7) Å b = 7.0690 (11) Å c = 33.120 (5) Å β = 92.727 (2)° V = 1014.4 (3) Å3 Z=4 Acta Cryst. (2014). E70, o462 F(000) = 560 Dx = 1.912 Mg m−3 Mo Kα radiation, λ = 0.71073 Å Cell parameters from 5646 reflections θ = 2.5–28.8° µ = 3.13 mm−1 T = 293 K Plate, colourless 0.35 × 0.20 × 0.08 mm sup-4 supporting information Data collection Bruker APEXII CCD diffractometer Radiation source: fine-focus sealed tube Graphite monochromator φ and ω scans Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.407, Tmax = 0.788 7578 measured reflections 2064 independent reflections 1971 reflections with I > 2σ(I) Rint = 0.018 θmax = 26.4°, θmin = 2.5° h = −5→5 k = −8→8 l = −41→41 Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.033 wR(F2) = 0.079 S = 1.17 2064 reflections 120 parameters 0 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ2(Fo2) + (0.0267P)2 + 1.5075P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001 Δρmax = 0.67 e Å−3 Δρmin = −0.86 e Å−3 Special details Experimental. The recrystallization was performed in deuterated solvent, CDCl3. 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) C8 H8C H8B H8A C7 C1 C2 C3 H3 C4 H4 C9 H9C H9B H9A x y z Uiso*/Ueq 1.2399 (13) 1.1673 1.4608 1.1796 1.1645 (9) 1.0379 (8) 0.8498 (8) 0.7587 (9) 0.6357 0.8469 (9) 0.7844 0.5840 (11) 0.5652 0.6821 0.3825 0.2713 (7) 0.1559 0.2677 0.3764 0.1539 (5) 0.1809 (5) 0.3314 (5) 0.3356 (5) 0.4345 0.1966 (6) 0.2022 0.6212 (6) 0.7115 0.6798 0.5775 0.00134 (13) −0.0110 0.0048 −0.0156 0.06620 (11) 0.10720 (10) 0.11933 (11) 0.15924 (12) 0.1676 0.18637 (12) 0.2128 0.10360 (16) 0.0820 0.1270 0.1100 0.0750 (13) 0.112* 0.112* 0.112* 0.0513 (8) 0.0432 (7) 0.0467 (8) 0.0541 (9) 0.065* 0.0563 (9) 0.068* 0.0719 (13) 0.108* 0.108* 0.108* Acta Cryst. (2014). E70, o462 sup-5 supporting information C5 C6 H6 O1 O3 O2 I1 1.0295 (8) 1.1226 (8) 1.2462 1.1074 (7) 0.7663 (7) 1.3145 (10) 1.16959 (7) 0.0478 (5) 0.0425 (5) −0.0571 0.2925 (4) 0.4639 (4) 0.0189 (5) −0.16619 (5) 0.17421 (11) 0.13512 (10) 0.1272 0.04032 (8) 0.09139 (9) 0.05808 (9) 0.215055 (9) 0.0486 (8) 0.0450 (7) 0.054* 0.0614 (7) 0.0652 (8) 0.0984 (14) 0.07304 (14) Atomic displacement parameters (Å2) C8 C7 C1 C2 C3 C4 C9 C5 C6 O1 O3 O2 I1 U11 U22 U33 U12 U13 U23 0.101 (4) 0.065 (2) 0.0462 (17) 0.0466 (18) 0.050 (2) 0.054 (2) 0.075 (3) 0.0412 (17) 0.0439 (17) 0.080 (2) 0.0808 (19) 0.166 (4) 0.05978 (19) 0.073 (3) 0.0454 (18) 0.0391 (16) 0.0389 (17) 0.049 (2) 0.067 (2) 0.043 (2) 0.055 (2) 0.0421 (17) 0.0538 (15) 0.0493 (15) 0.076 (2) 0.0988 (3) 0.053 (2) 0.0436 (18) 0.0441 (17) 0.055 (2) 0.064 (2) 0.049 (2) 0.098 (3) 0.0495 (19) 0.0488 (18) 0.0515 (15) 0.0664 (17) 0.0566 (18) 0.06086 (19) 0.023 (3) 0.0166 (17) 0.0076 (14) 0.0056 (14) 0.0077 (16) 0.0002 (18) 0.026 (2) −0.0002 (15) 0.0071 (14) 0.0239 (14) 0.0320 (14) 0.074 (2) 0.01134 (15) 0.022 (2) 0.0017 (16) 0.0004 (14) 0.0007 (15) 0.0127 (17) 0.0088 (16) 0.016 (2) 0.0004 (14) 0.0010 (14) 0.0157 (13) 0.0115 (14) 0.032 (2) 0.00665 (13) 0.014 (2) −0.0022 (15) −0.0047 (13) −0.0076 (15) −0.0122 (17) −0.0088 (18) −0.002 (2) 0.0047 (16) −0.0018 (14) 0.0088 (12) 0.0011 (13) 0.0091 (16) 0.03178 (15) Geometric parameters (Å, º) C8—O1 C8—H8C C8—H8B C8—H8A C7—O2 C7—O1 C7—C1 C1—C6 C1—C2 C2—O3 C2—C3 1.446 (5) 0.9600 0.9600 0.9600 1.193 (4) 1.318 (4) 1.501 (5) 1.384 (5) 1.411 (4) 1.354 (4) 1.398 (5) C3—C4 C3—H3 C4—C5 C4—H4 C9—O3 C9—H9C C9—H9B C9—H9A C5—C6 C5—I1 C6—H6 1.373 (6) 0.9300 1.388 (5) 0.9300 1.434 (4) 0.9600 0.9600 0.9600 1.375 (5) 2.100 (4) 0.9300 O1—C8—H8C O1—C8—H8B H8C—C8—H8B O1—C8—H8A H8C—C8—H8A H8B—C8—H8A O2—C7—O1 O2—C7—C1 O1—C7—C1 109.5 109.5 109.5 109.5 109.5 109.5 122.4 (3) 122.2 (3) 115.3 (3) C3—C4—C5 C3—C4—H4 C5—C4—H4 O3—C9—H9C O3—C9—H9B H9C—C9—H9B O3—C9—H9A H9C—C9—H9A H9B—C9—H9A 119.8 (4) 120.1 120.1 109.5 109.5 109.5 109.5 109.5 109.5 Acta Cryst. (2014). E70, o462 sup-6 supporting information C6—C1—C2 C6—C1—C7 C2—C1—C7 O3—C2—C3 O3—C2—C1 C3—C2—C1 C4—C3—C2 C4—C3—H3 C2—C3—H3 118.8 (3) 114.7 (3) 126.5 (3) 123.6 (3) 117.8 (3) 118.6 (3) 121.4 (3) 119.3 119.3 C6—C5—C4 C6—C5—I1 C4—C5—I1 C5—C6—C1 C5—C6—H6 C1—C6—H6 C7—O1—C8 C2—O3—C9 119.4 (3) 119.9 (3) 120.7 (3) 122.0 (3) 119.0 119.0 115.7 (3) 118.5 (3) O2—C7—C1—C6 O1—C7—C1—C6 O2—C7—C1—C2 O1—C7—C1—C2 C6—C1—C2—O3 C7—C1—C2—O3 C6—C1—C2—C3 C7—C1—C2—C3 O3—C2—C3—C4 C1—C2—C3—C4 C2—C3—C4—C5 3.2 (6) −174.6 (3) −177.6 (4) 4.6 (6) −179.1 (3) 1.7 (6) 0.6 (5) −178.6 (4) 179.3 (4) −0.4 (6) −0.2 (6) C3—C4—C5—C6 C3—C4—C5—I1 C4—C5—C6—C1 I1—C5—C6—C1 C2—C1—C6—C5 C7—C1—C6—C5 O2—C7—O1—C8 C1—C7—O1—C8 C3—C2—O3—C9 C1—C2—O3—C9 0.7 (6) 179.7 (3) −0.5 (5) −179.6 (3) −0.2 (5) 179.1 (3) −0.3 (7) 177.4 (4) 2.4 (6) −177.9 (4) Acta Cryst. (2014). E70, o462 sup-7