organic compounds
Methyl 5-iodo-2-methoxybenzoate
aCentre 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 cDepartment of Chemistry, University of Bergen, PO Box 7803, 5020 Bergen, Norway
*Correspondence e-mail: fredrik.lundvall@smn.uio.no
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.
CCDC reference: 992130
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2007); cell 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).
Supporting information
CCDC reference: 992130
10.1107/S1600536814005868/lr2123sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814005868/lr2123Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814005868/lr2123Isup3.cml
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.
Crystal data, data collection and structure
details are summarized in Table 1. The structure was refined by full-matrix 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).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
has not been reported so far.The structure of the title compound, C9H9IO3, has a monoclinic P21/c symmetry. The
equals one molecule of the compound, with the full content of the 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.Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).C9H9IO3 | F(000) = 560 |
Mr = 292.06 | Dx = 1.912 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 5646 reflections |
a = 4.3378 (7) Å | θ = 2.5–28.8° |
b = 7.0690 (11) Å | µ = 3.13 mm−1 |
c = 33.120 (5) Å | T = 293 K |
β = 92.727 (2)° | Plate, colourless |
V = 1014.4 (3) Å3 | 0.35 × 0.20 × 0.08 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | 2064 independent reflections |
Radiation source: fine-focus sealed tube | 1971 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
ϕ and ω scans | θmax = 26.4°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −5→5 |
Tmin = 0.407, Tmax = 0.788 | k = −8→8 |
7578 measured reflections | l = −41→41 |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.17 | w = 1/[σ2(Fo2) + (0.0267P)2 + 1.5075P] where P = (Fo2 + 2Fc2)/3 |
2064 reflections | (Δ/σ)max < 0.001 |
120 parameters | Δρmax = 0.67 e Å−3 |
0 restraints | Δρmin = −0.86 e Å−3 |
C9H9IO3 | V = 1014.4 (3) Å3 |
Mr = 292.06 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 4.3378 (7) Å | µ = 3.13 mm−1 |
b = 7.0690 (11) Å | T = 293 K |
c = 33.120 (5) Å | 0.35 × 0.20 × 0.08 mm |
β = 92.727 (2)° |
Bruker APEXII CCD diffractometer | 2064 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1971 reflections with I > 2σ(I) |
Tmin = 0.407, Tmax = 0.788 | Rint = 0.018 |
7578 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.17 | Δρmax = 0.67 e Å−3 |
2064 reflections | Δρmin = −0.86 e Å−3 |
120 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C8 | 1.2399 (13) | 0.2713 (7) | 0.00134 (13) | 0.0750 (13) | |
H8C | 1.1673 | 0.1559 | −0.0110 | 0.112* | |
H8B | 1.4608 | 0.2677 | 0.0048 | 0.112* | |
H8A | 1.1796 | 0.3764 | −0.0156 | 0.112* | |
C7 | 1.1645 (9) | 0.1539 (5) | 0.06620 (11) | 0.0513 (8) | |
C1 | 1.0379 (8) | 0.1809 (5) | 0.10720 (10) | 0.0432 (7) | |
C2 | 0.8498 (8) | 0.3314 (5) | 0.11933 (11) | 0.0467 (8) | |
C3 | 0.7587 (9) | 0.3356 (5) | 0.15924 (12) | 0.0541 (9) | |
H3 | 0.6357 | 0.4345 | 0.1676 | 0.065* | |
C4 | 0.8469 (9) | 0.1966 (6) | 0.18637 (12) | 0.0563 (9) | |
H4 | 0.7844 | 0.2022 | 0.2128 | 0.068* | |
C9 | 0.5840 (11) | 0.6212 (6) | 0.10360 (16) | 0.0719 (13) | |
H9C | 0.5652 | 0.7115 | 0.0820 | 0.108* | |
H9B | 0.6821 | 0.6798 | 0.1270 | 0.108* | |
H9A | 0.3825 | 0.5775 | 0.1100 | 0.108* | |
C5 | 1.0295 (8) | 0.0478 (5) | 0.17421 (11) | 0.0486 (8) | |
C6 | 1.1226 (8) | 0.0425 (5) | 0.13512 (10) | 0.0450 (7) | |
H6 | 1.2462 | −0.0571 | 0.1272 | 0.054* | |
O1 | 1.1074 (7) | 0.2925 (4) | 0.04032 (8) | 0.0614 (7) | |
O3 | 0.7663 (7) | 0.4639 (4) | 0.09139 (9) | 0.0652 (8) | |
O2 | 1.3145 (10) | 0.0189 (5) | 0.05808 (9) | 0.0984 (14) | |
I1 | 1.16959 (7) | −0.16619 (5) | 0.215055 (9) | 0.07304 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C8 | 0.101 (4) | 0.073 (3) | 0.053 (2) | 0.023 (3) | 0.022 (2) | 0.014 (2) |
C7 | 0.065 (2) | 0.0454 (18) | 0.0436 (18) | 0.0166 (17) | 0.0017 (16) | −0.0022 (15) |
C1 | 0.0462 (17) | 0.0391 (16) | 0.0441 (17) | 0.0076 (14) | 0.0004 (14) | −0.0047 (13) |
C2 | 0.0466 (18) | 0.0389 (17) | 0.055 (2) | 0.0056 (14) | 0.0007 (15) | −0.0076 (15) |
C3 | 0.050 (2) | 0.049 (2) | 0.064 (2) | 0.0077 (16) | 0.0127 (17) | −0.0122 (17) |
C4 | 0.054 (2) | 0.067 (2) | 0.049 (2) | 0.0002 (18) | 0.0088 (16) | −0.0088 (18) |
C9 | 0.075 (3) | 0.043 (2) | 0.098 (3) | 0.026 (2) | 0.016 (2) | −0.002 (2) |
C5 | 0.0412 (17) | 0.055 (2) | 0.0495 (19) | −0.0002 (15) | 0.0004 (14) | 0.0047 (16) |
C6 | 0.0439 (17) | 0.0421 (17) | 0.0488 (18) | 0.0071 (14) | 0.0010 (14) | −0.0018 (14) |
O1 | 0.080 (2) | 0.0538 (15) | 0.0515 (15) | 0.0239 (14) | 0.0157 (13) | 0.0088 (12) |
O3 | 0.0808 (19) | 0.0493 (15) | 0.0664 (17) | 0.0320 (14) | 0.0115 (14) | 0.0011 (13) |
O2 | 0.166 (4) | 0.076 (2) | 0.0566 (18) | 0.074 (2) | 0.032 (2) | 0.0091 (16) |
I1 | 0.05978 (19) | 0.0988 (3) | 0.06086 (19) | 0.01134 (15) | 0.00665 (13) | 0.03178 (15) |
C8—O1 | 1.446 (5) | C3—C4 | 1.373 (6) |
C8—H8C | 0.9600 | C3—H3 | 0.9300 |
C8—H8B | 0.9600 | C4—C5 | 1.388 (5) |
C8—H8A | 0.9600 | C4—H4 | 0.9300 |
C7—O2 | 1.193 (4) | C9—O3 | 1.434 (4) |
C7—O1 | 1.318 (4) | C9—H9C | 0.9600 |
C7—C1 | 1.501 (5) | C9—H9B | 0.9600 |
C1—C6 | 1.384 (5) | C9—H9A | 0.9600 |
C1—C2 | 1.411 (4) | C5—C6 | 1.375 (5) |
C2—O3 | 1.354 (4) | C5—I1 | 2.100 (4) |
C2—C3 | 1.398 (5) | C6—H6 | 0.9300 |
O1—C8—H8C | 109.5 | C3—C4—C5 | 119.8 (4) |
O1—C8—H8B | 109.5 | C3—C4—H4 | 120.1 |
H8C—C8—H8B | 109.5 | C5—C4—H4 | 120.1 |
O1—C8—H8A | 109.5 | O3—C9—H9C | 109.5 |
H8C—C8—H8A | 109.5 | O3—C9—H9B | 109.5 |
H8B—C8—H8A | 109.5 | H9C—C9—H9B | 109.5 |
O2—C7—O1 | 122.4 (3) | O3—C9—H9A | 109.5 |
O2—C7—C1 | 122.2 (3) | H9C—C9—H9A | 109.5 |
O1—C7—C1 | 115.3 (3) | H9B—C9—H9A | 109.5 |
C6—C1—C2 | 118.8 (3) | C6—C5—C4 | 119.4 (3) |
C6—C1—C7 | 114.7 (3) | C6—C5—I1 | 119.9 (3) |
C2—C1—C7 | 126.5 (3) | C4—C5—I1 | 120.7 (3) |
O3—C2—C3 | 123.6 (3) | C5—C6—C1 | 122.0 (3) |
O3—C2—C1 | 117.8 (3) | C5—C6—H6 | 119.0 |
C3—C2—C1 | 118.6 (3) | C1—C6—H6 | 119.0 |
C4—C3—C2 | 121.4 (3) | C7—O1—C8 | 115.7 (3) |
C4—C3—H3 | 119.3 | C2—O3—C9 | 118.5 (3) |
C2—C3—H3 | 119.3 | ||
O2—C7—C1—C6 | 3.2 (6) | C3—C4—C5—C6 | 0.7 (6) |
O1—C7—C1—C6 | −174.6 (3) | C3—C4—C5—I1 | 179.7 (3) |
O2—C7—C1—C2 | −177.6 (4) | C4—C5—C6—C1 | −0.5 (5) |
O1—C7—C1—C2 | 4.6 (6) | I1—C5—C6—C1 | −179.6 (3) |
C6—C1—C2—O3 | −179.1 (3) | C2—C1—C6—C5 | −0.2 (5) |
C7—C1—C2—O3 | 1.7 (6) | C7—C1—C6—C5 | 179.1 (3) |
C6—C1—C2—C3 | 0.6 (5) | O2—C7—O1—C8 | −0.3 (7) |
C7—C1—C2—C3 | −178.6 (4) | C1—C7—O1—C8 | 177.4 (4) |
O3—C2—C3—C4 | 179.3 (4) | C3—C2—O3—C9 | 2.4 (6) |
C1—C2—C3—C4 | −0.4 (6) | C1—C2—O3—C9 | −177.9 (4) |
C2—C3—C4—C5 | −0.2 (6) |
Experimental details
Crystal data | |
Chemical formula | C9H9IO3 |
Mr | 292.06 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 4.3378 (7), 7.0690 (11), 33.120 (5) |
β (°) | 92.727 (2) |
V (Å3) | 1014.4 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.13 |
Crystal size (mm) | 0.35 × 0.20 × 0.08 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.407, 0.788 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7578, 2064, 1971 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.079, 1.17 |
No. of reflections | 2064 |
No. of parameters | 120 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.67, −0.86 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008) implemented in WinGX (Farrugia, 2012), DIAMOND (Brandenburg, 2004) and ChemBioDraw Ultra (CambridgeSoft, 2009), publCIF (Westrip, 2010).
Acknowledgements
We acknowledge the support from the Norwegian Research Council (project 190980), inGAP and the Department of Chemistry, UiO.
References
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