Methyl 5-iodo-2-meth­oxy­benzoate

Lundvall, F.; Wragg, D.S.; Dietzel, P.D.C.; Fjellvåg, H.

doi:10.1107/S1600536814005868

organic compounds

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doi:10.1107/S1600536814005868

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Methyl 5-iodo-2-methoxybenzoate

Fredrik Lundvall,^a ^* David Stephen Wragg,^b Pascal D. C. Dietzel ^c and Helmer Fjellvåg ^a

^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

(Received 5 March 2014; accepted 17 March 2014; online 22 March 2014)

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

Related literature

For the synthesis, see Wang et al. (2009 ).

Experimental

Crystal data

C₉H₉IO₃
M_r = 292.06
Monoclinic, P 2₁ /n
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
Mo Kα radiation
μ = 3.13 mm⁻¹
T = 293 K
0.35 × 0.20 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.407, T_max = 0.788
7578 measured reflections
2064 independent reflections
1971 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.079
S = 1.17
2064 reflections
120 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.86 e Å⁻³

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 ).

Supporting information

CCDC reference: 992130

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814005868/lr2123sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814005868/lr2123Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814005868/lr2123Isup3.cml

checkCIF report

Experimental top

Synthesis and crystallization top

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.

Refinement top

Crystal data, data collection and structure refinement 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 U_iso (H)=1.2 U_eq (CH) and U_iso (H)=1.5 U_eq (CH₃).

Results and discussion top

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.

Related literature top

For the synthesis, see Wang et al. (2009).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: 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).

Figures top

	Fig. 1. One molecular unit of the title compound with 50% probability displacement ellipsoids. Hydrogen atoms are omitted for clarity.
	Fig. 2. Packing diagram of the title compound viewed along the a axis. Hydrogen atoms are omitted for clarity.
	Fig. 3. Packing diagram of the title compound viewed along the b axis. Hydrogen atoms are omitted for clarity.

Methyl 5-iodo-2-methoxybenzoate top

Crystal data top

C₉H₉IO₃	F(000) = 560
M_r = 292.06	D_x = 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

Data collection top

Bruker APEXII CCD diffractometer	2064 independent reflections
Radiation source: fine-focus sealed tube	1971 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ϕ and ω scans	θ_max = 26.4°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→5
T_min = 0.407, T_max = 0.788	k = −8→8
7578 measured reflections	l = −41→41

Refinement top

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(F_o²) + (0.0267P)² + 1.5075P] where P = (F_o² + 2F_c²)/3
2064 reflections	(Δ/σ)_max < 0.001
120 parameters	Δρ_max = 0.67 e Å⁻³
0 restraints	Δρ_min = −0.86 e Å⁻³

Crystal data top

C₉H₉IO₃	V = 1014.4 (3) Å³
M_r = 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)°

Data collection top

Bruker APEXII CCD diffractometer	2064 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1971 reflections with I > 2σ(I)
T_min = 0.407, T_max = 0.788	R_int = 0.018
7578 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.079	H-atom parameters constrained
S = 1.17	Δρ_max = 0.67 e Å⁻³
2064 reflections	Δρ_min = −0.86 e Å⁻³
120 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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
M_r	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)
T_min, T_max	0.407, 0.788
No. of measured, independent and observed [I > 2σ(I)] reflections	7578, 2064, 1971
R_int	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
Δρ_max, Δρ_min (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

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 4| April 2014| Page o462

doi:10.1107/S1600536814005868

Open

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