5-Formyl-2-methoxy­phenyl 2-iodo­benzoate

The title compound, C₁₅H₁₁IO₄, was synthesized by the N,N'-dicyclo­hexyl­carbodiimide- and 4-dimethyl­amino­pyridine-catalyzed reaction of 3-hydr­oxy-4-methoxy­benzaldehyde and 2-iodo­benzoic acid. In the mol­ecule, the dihedral angle between the two benzene rings is 70.6 (1)°.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C)= 0.007 Å
• R factor = 0.036
• wR factor = 0.089
• Data-to-parameter ratio = 14.4

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S1. Comment

N,N'-Dicyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine (DMAP) are effective catalysts for esterification reactions (Litvin & Kirichenko, 1967; Steglich & Hofle, 1969). We have recently focused on the preparation of benzoic acid phenyl ester derivatives using these catalysts. The title compound, (I), was synthesized by the reaction of 3-hydroxy-4-methoxybenzaldehyde and 2-iodobenzoic acid in the presence of DCC and DMAP.

The molecule of (I) is shown in Fig. 1. The dihedral angle between the atoms of the central ester group (atoms C7/O1/O2) and the C1–C6 benzene ring is 88.2 (1)°, while the dihedral angle between the central ester group and the C8–C13 benzene ring is 21.4 (2)°.

In the crystal structure, molecules are linked into centrosymmetric dimers via weak C—H···O hydrogen bonds. These dimers are further linked by weak intramolecular [intermolecular?] C—H···O hydrogen bonds into one-dimensional chains along [110] (Table 1 and Fig. 2).

S2. Experimental

To a solution of 3-hydroxy-4-methoxybenzaldehyde (2 g, 13 mmol) in dry dichloromethane (25 ml, 13 mmol), 2-iodobenzoic acid (3.26 g, 13 mmol) was added in an N₂ atmosphere. N,N'-Dicyclohexylcarbodiimide (3 g, 14.5 mmol) and 4-dimethylaminopyridine (0.32 g, 2.6 mmol) were then added. The resulting mixture was stirred at room temperature for 10 h. The mixture was then filtered. The insoluble material was washed with dry dichloromethane and the combined filtrates were evaporated. Flash column chromatography [Medium and solvent?] of the residue gave a white solid, (I) (4.1 g). Colourless crystals were obtained by recrystallization of the title compound from ethyl acetate.

S3. Refinement

All H atoms were included in calculated positions and refined using a riding-model approximation, with C—H = 0.93–0.96 Å and U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C). The highest peak in the final difference Fourier map (1.05 e A⁻³) is located 0.87 Å from atom I1.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures

	Fig. 1. A view of (I), showing displacement ellipsoids drawn at the 30% probability level. H atoms are drawn as spheres of arbitrary radii.
	Fig. 2. Part of a hydrogen-bonded chain of (I). Hydrogen bonds are drawn as dashed lines.

5-Formyl-2-methoxyphenyl 2-iodobenzoate

Crystal data

C15H11IO4	Z = 2
Mr = 382.14	F(000) = 372
Triclinic, P1	Dx = 1.812 Mg m^−3
Hall symbol: -P 1	Melting point: 122 K
a = 7.4730 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.1841 (17) Å	Cell parameters from 2008 reflections
c = 11.956 (3) Å	θ = 2.4–22.3°
α = 74.517 (3)°	µ = 2.30 mm^−1
β = 86.831 (4)°	T = 294 K
γ = 84.019 (3)°	Block, colourless
V = 700.6 (3) Å^3	0.40 × 0.30 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2630 independent reflections
Radiation source: fine-focus sealed tube	2089 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ϕ and ω scans	θmax = 25.8°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→9
Tmin = 0.382, Tmax = 0.604	k = −9→9
3709 measured reflections	l = −14→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.089	w = 1/[σ^2(Fo^2) + (0.0338P)^2 + 1.0404P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.004
2630 reflections	Δρmax = 1.05 e Å^−3
183 parameters	Δρmin = −1.00 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0335 (19)

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.

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 (Ų)

	x	y	z	Uiso*/Ueq
I1	0.31507 (5)	−0.29425 (4)	0.91220 (3)	0.0703 (2)
O1	0.1224 (4)	0.2544 (3)	0.6875 (2)	0.0459 (7)
O2	0.2894 (5)	0.0109 (4)	0.6940 (3)	0.0617 (9)
O3	0.4798 (7)	0.5482 (6)	0.3195 (4)	0.0948 (14)
O4	−0.1533 (4)	0.1476 (4)	0.6065 (3)	0.0576 (8)
C1	−0.0377 (6)	0.2285 (5)	0.5256 (4)	0.0453 (10)
C2	−0.0549 (6)	0.2620 (6)	0.4072 (4)	0.0516 (11)
H2	−0.1521	0.2270	0.3771	0.062*
C3	0.0731 (7)	0.3475 (6)	0.3340 (4)	0.0533 (12)
H3	0.0614	0.3693	0.2542	0.064*
C4	0.2184 (6)	0.4017 (5)	0.3757 (3)	0.0486 (10)
C5	0.2361 (6)	0.3686 (5)	0.4954 (4)	0.0472 (10)
H5	0.3323	0.4051	0.5252	0.057*
C6	0.1115 (6)	0.2826 (5)	0.5674 (3)	0.0424 (9)
C7	0.2183 (5)	0.1096 (5)	0.7432 (3)	0.0378 (9)
C8	0.2240 (5)	0.0955 (5)	0.8690 (3)	0.0379 (9)
C9	0.1897 (6)	0.2426 (5)	0.9069 (4)	0.0478 (10)
H9	0.1653	0.3468	0.8527	0.057*
C10	0.1913 (7)	0.2372 (6)	1.0225 (4)	0.0617 (13)
H10	0.1695	0.3367	1.0466	0.074*
C11	0.2252 (8)	0.0834 (7)	1.1019 (4)	0.0744 (16)
H11	0.2240	0.0785	1.1806	0.089*
C12	0.2608 (8)	−0.0623 (6)	1.0675 (4)	0.0664 (14)
H12	0.2845	−0.1655	1.1228	0.080*
C13	0.2622 (6)	−0.0592 (5)	0.9511 (4)	0.0460 (10)
C14	0.3505 (9)	0.4945 (7)	0.2945 (4)	0.0700 (15)
H14	0.3310	0.5130	0.2158	0.084*
C15	−0.3131 (7)	0.1016 (8)	0.5670 (5)	0.0716 (14)
H15A	−0.3798	0.2019	0.5219	0.107*
H15B	−0.3857	0.0481	0.6327	0.107*
H15C	−0.2813	0.0239	0.5200	0.107*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0942 (3)	0.0360 (2)	0.0753 (3)	0.00180 (15)	−0.01319 (19)	−0.00616 (14)
O1	0.0613 (18)	0.0454 (15)	0.0297 (14)	0.0120 (13)	−0.0089 (13)	−0.0123 (12)
O2	0.090 (2)	0.0490 (18)	0.0423 (17)	0.0203 (16)	−0.0043 (16)	−0.0151 (14)
O3	0.108 (4)	0.113 (4)	0.067 (3)	−0.043 (3)	0.012 (2)	−0.020 (2)
O4	0.057 (2)	0.065 (2)	0.0506 (18)	−0.0056 (16)	−0.0016 (15)	−0.0152 (15)
C1	0.053 (3)	0.039 (2)	0.043 (2)	0.0096 (18)	−0.006 (2)	−0.0126 (18)
C2	0.063 (3)	0.049 (2)	0.045 (2)	0.006 (2)	−0.015 (2)	−0.018 (2)
C3	0.079 (3)	0.047 (2)	0.033 (2)	0.011 (2)	−0.012 (2)	−0.0137 (18)
C4	0.070 (3)	0.041 (2)	0.033 (2)	0.006 (2)	−0.002 (2)	−0.0091 (17)
C5	0.059 (3)	0.040 (2)	0.043 (2)	0.0065 (19)	−0.010 (2)	−0.0134 (18)
C6	0.057 (3)	0.038 (2)	0.030 (2)	0.0105 (18)	−0.0087 (18)	−0.0107 (16)
C7	0.043 (2)	0.0350 (19)	0.035 (2)	−0.0033 (16)	−0.0028 (17)	−0.0077 (16)
C8	0.043 (2)	0.0374 (19)	0.0324 (19)	−0.0091 (16)	−0.0036 (17)	−0.0050 (15)
C9	0.066 (3)	0.040 (2)	0.036 (2)	−0.0110 (19)	−0.004 (2)	−0.0064 (17)
C10	0.092 (4)	0.059 (3)	0.042 (2)	−0.023 (3)	−0.003 (2)	−0.019 (2)
C11	0.122 (5)	0.070 (3)	0.035 (2)	−0.031 (3)	−0.007 (3)	−0.010 (2)
C12	0.101 (4)	0.053 (3)	0.038 (2)	−0.018 (3)	−0.013 (2)	0.008 (2)
C13	0.053 (3)	0.039 (2)	0.044 (2)	−0.0095 (18)	−0.0072 (19)	−0.0032 (17)
C14	0.102 (5)	0.065 (3)	0.043 (3)	−0.006 (3)	0.004 (3)	−0.015 (2)
C15	0.054 (3)	0.085 (4)	0.078 (4)	−0.006 (3)	−0.003 (3)	−0.025 (3)

Geometric parameters (Å, º)

I1—C13	2.091 (4)	C5—H5	0.9300
O1—C7	1.347 (5)	C7—C8	1.480 (5)
O1—C6	1.398 (4)	C8—C9	1.391 (6)
O2—C7	1.188 (5)	C8—C13	1.393 (5)
O3—C14	1.187 (7)	C9—C10	1.372 (6)
O4—C1	1.343 (5)	C9—H9	0.9300
O4—C15	1.428 (6)	C10—C11	1.368 (7)
C1—C2	1.380 (6)	C10—H10	0.9300
C1—C6	1.404 (6)	C11—C12	1.359 (7)
C2—C3	1.375 (7)	C11—H11	0.9300
C2—H2	0.9300	C12—C13	1.384 (6)
C3—C4	1.380 (7)	C12—H12	0.9300
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.394 (6)	C15—H15A	0.9600
C4—C14	1.467 (7)	C15—H15B	0.9600
C5—C6	1.352 (6)	C15—H15C	0.9600
C7—O1—C6	116.0 (3)	C13—C8—C7	122.7 (4)
C1—O4—C15	117.5 (4)	C10—C9—C8	121.3 (4)
O4—C1—C2	125.4 (4)	C10—C9—H9	119.3
O4—C1—C6	116.1 (4)	C8—C9—H9	119.3
C2—C1—C6	118.5 (4)	C11—C10—C9	119.1 (5)
C3—C2—C1	119.3 (4)	C11—C10—H10	120.4
C3—C2—H2	120.3	C9—C10—H10	120.4
C1—C2—H2	120.3	C12—C11—C10	120.9 (4)
C2—C3—C4	121.8 (4)	C12—C11—H11	119.5
C2—C3—H3	119.1	C10—C11—H11	119.5
C4—C3—H3	119.1	C11—C12—C13	120.8 (4)
C3—C4—C5	119.1 (4)	C11—C12—H12	119.6
C3—C4—C14	120.0 (4)	C13—C12—H12	119.6
C5—C4—C14	120.9 (4)	C12—C13—C8	119.2 (4)
C6—C5—C4	119.1 (4)	C12—C13—I1	116.3 (3)
C6—C5—H5	120.4	C8—C13—I1	124.5 (3)
C4—C5—H5	120.4	O3—C14—C4	126.3 (5)
C5—C6—O1	120.1 (4)	O3—C14—H14	116.8
C5—C6—C1	122.1 (4)	C4—C14—H14	116.8
O1—C6—C1	117.7 (4)	O4—C15—H15A	109.5
O2—C7—O1	122.5 (3)	O4—C15—H15B	109.5
O2—C7—C8	126.4 (4)	H15A—C15—H15B	109.5
O1—C7—C8	111.2 (3)	O4—C15—H15C	109.5
C9—C8—C13	118.6 (4)	H15A—C15—H15C	109.5
C9—C8—C7	118.7 (3)	H15B—C15—H15C	109.5
C15—O4—C1—C2	−4.1 (6)	C6—O1—C7—C8	178.7 (3)
C15—O4—C1—C6	175.6 (4)	O2—C7—C8—C9	158.0 (4)
O4—C1—C2—C3	179.4 (4)	O1—C7—C8—C9	−20.9 (5)
C6—C1—C2—C3	−0.3 (6)	O2—C7—C8—C13	−22.0 (7)
C1—C2—C3—C4	−0.3 (6)	O1—C7—C8—C13	159.1 (4)
C2—C3—C4—C5	0.1 (6)	C13—C8—C9—C10	−0.7 (7)
C2—C3—C4—C14	−179.2 (4)	C7—C8—C9—C10	179.3 (4)
C3—C4—C5—C6	0.7 (6)	C8—C9—C10—C11	−0.7 (8)
C14—C4—C5—C6	−180.0 (4)	C9—C10—C11—C12	1.3 (9)
C4—C5—C6—O1	−177.3 (3)	C10—C11—C12—C13	−0.5 (9)
C4—C5—C6—C1	−1.4 (6)	C11—C12—C13—C8	−0.9 (8)
C7—O1—C6—C5	−90.2 (4)	C11—C12—C13—I1	−179.1 (4)
C7—O1—C6—C1	93.8 (4)	C9—C8—C13—C12	1.5 (6)
O4—C1—C6—C5	−178.6 (4)	C7—C8—C13—C12	−178.5 (4)
C2—C1—C6—C5	1.2 (6)	C9—C8—C13—I1	179.5 (3)
O4—C1—C6—O1	−2.6 (5)	C7—C8—C13—I1	−0.6 (6)
C2—C1—C6—O1	177.2 (3)	C3—C4—C14—O3	179.6 (6)
C6—O1—C7—O2	−0.3 (6)	C5—C4—C14—O3	0.3 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O3^i	0.93	2.52	3.391 (7)	156
C15—H15B···O2^ii	0.96	2.52	3.322 (6)	141

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z.