3-(4-Iodo­phen­yl)-2,3-di­hydro-1H-benzo[f]chromen-1-one

Dean, R.; Miller, C.N.; Zingales, S.K.; Padgett, C.W.

doi:10.1107/S2414314620001108

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 5| Part 1| January 2020| x200110

https://doi.org/10.1107/S2414314620001108

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3-(4-Iodophenyl)-2,3-dihydro-1H-benzo[f]chromen-1-one

Raven Dean,^a Chelsea N. Miller,^a Sarah K. Zingales ^a ^* and Clifford W. Padgett ^a

^aGeorgia Southern University, 11935 Abercorn St, Department of Chemistry and Biochemistry, Savannah GA 31419, USA
^*Correspondence e-mail: szingales@georgiasouthern.edu

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 13 December 2019; accepted 27 January 2020; online 31 January 2020)

In the title compound, C₁₉H₁₃IO₂, the dihedral angle between the naphthyl ring system and the pendant iodophenyl ring is 72.48 (11)°. In the crystal, C—H⋯π interactions and I⋯O [3.293 (2) Å] halogen bonds are observed, which combine to generate a herringbone packing motif.

Keywords: crystal structure; naphthopyran; flavone; halogen bond.

CCDC reference: 1980111

Structure description

Traditional CORMS (carbon monoxide-releasing molecules) contain metal carbonyls whereas photoCORMS have recently become of interest because of their ability to release CO in biological systems. Our group is particularly interested in the extended flavonol motif as it has been shown to release CO quantitatively with visible light (Popova et al., 2017 ). Typically, we synthesize these flavonols in two steps from an acetyl naphthol and an aromatic aldehyde. The first step is an aldol condensation, followed by oxidative cyclization. However, if no oxidant is added, the 2′–hydroxychalcone intermediate can cyclize to a flavanone under basic conditions (Furlong et al., 1985 ). In our quest to synthesize a novel flavonol (2-hydroxy-3-(4-iodophenyl)-1H-naphtho[2,1-b]pyran-1-one), we serendipitously synthesized the title flavanone.

In the title molecule (Fig. 1), the iodophenyl ring is tilted by 72.48 (11)° with respect to the naphthyl ring system. No hydrogen bonding is observed in the extended structure. T-shaped π-stacking with Cg1⋯Cg2ⁱ = 4.929 (2) Å [symmetry code: (i) 1 − x, 1 − y, 1 − z] and C6—H6⋯Cg2ⁱ = 154.5 (3)°, where Cg1 is the centroid of the pyranone ring containing atoms C4–C7/C12/C13 and Cg2 is the centroid of the iodophenyl ring containing atoms C14–C19 (Burley & Petsko, 1985 ). I⋯O halogen bonds between neighboring molecules form a chain that runs parallel to the b-axis direction. The I1⋯O2ⁱⁱ distance is 3.293 (2) Å, with C17—I1⋯O2ⁱⁱ and I1⋯O2ⁱⁱ—C1ⁱⁱ angles of 177.21 (10) and 127.9 (2)°, respectively [symmetry code: (ii) − $[{1\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z]. This I⋯O separation is some 0.25 Å shorter than van der Waals'interaction distance of 3.5 Å (Rissanen, 2008 ) The crystal structure exhibits a herringbone pattern (Fig. 2) with molecules linked into [010] chains by the halogen bonding; neighboring layers are held together with van der Waals interactions along with T-shaped π-stacking.

Figure 1
A view of the molecular structure of the title compound, showing the atom labeling. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
Crystal packing diagram of the title compound, viewed along the a axis. O⋯I halogen bonds are indicated has red lines.

Synthesis and crystallization

1-Acetyl-2-naphthol (164 mg, 0.88 mmol) and 4-iodobenzaldehyde (205 mg, 0.88 mmol) were dissolved in ethanol (5 ml). An NaOH solution (5 M, 0.76 ml) was added and the reaction was stirred until a precipitate formed. The reaction mixture was acidified to pH 4 with glacial acetic acid. The solids were filtered and taken directly to the next step. (E)-1-(2-Hydroxynaphthalen-1-yl)-3-(4-iodophenyl)prop-2-en-1-one was then suspended in ethanol (10 ml). An NaOH solution (5 M, 0.12 ml) was added and the reaction stirred until a precipitate formed. The reaction mixture was acidified to pH 1 with HCl (6 M). The white solid was collected by filtration and slow evaporation of a solution of the title compound in ethyl acetate gave colorless crystals (108 mg, 30% yield over two steps).

¹H NMR (300 MHz, (CDCl₂) δ = 9.46 (d, J = 8.6 Hz, 1H), 7.95 (d, J = 8.9 Hz, 1H), 7.80–7.75 (m, 3H), 7.65 (t, J = 7.9 Hz, 1H), 7.44 (t, J = 7.6 Hz, 1H), 7.26 (d, J = 8.6 Hz, 2H), 7.16 (d, J = 8.9 Hz, 1H), 5.54 (dd, J = 13.4, 3.1 Hz, 1H), 3.16 (dd, J = 16.5, 13.2 Hz, 1H), 2.95 (dd, J = 16.5, 3.0 Hz, 1H) ppm.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₁₉H₁₃IO₂
M_r	400.19
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	170
a, b, c (Å)	7.0481 (3), 18.2185 (8), 12.6391 (6)
β (°)	104.947 (4)
V (Å³)	1568.02 (12)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.05
Crystal size (mm)	0.77 × 0.34 × 0.34

Data collection
Diffractometer	Rigaku XtaLAB mini
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2018 $[Rigaku OD (2018). CrysAlis PRO. Oxford Diffraction/Agilent Technologies UK Ltd, Yarnton, England.]$ )
T_min, T_max	0.738, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	23424, 5656, 3493
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.768

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.096, 1.12
No. of reflections	5656
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.72, −0.81
Computer programs: CrysAlis PRO (Rigaku OD, 2018 $[Rigaku OD (2018). CrysAlis PRO. Oxford Diffraction/Agilent Technologies UK Ltd, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1980111

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314620001108/hb4334sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620001108/hb4334Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314620001108/hb4334Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

3-(4-Iodophenyl)-2,3-dihydro-1H-benzo[f]chromen-1-one top

Crystal data top

C₁₉H₁₃IO₂	F(000) = 784
M_r = 400.19	D_x = 1.695 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.0481 (3) Å	Cell parameters from 5447 reflections
b = 18.2185 (8) Å	θ = 2.0–28.8°
c = 12.6391 (6) Å	µ = 2.05 mm⁻¹
β = 104.947 (4)°	T = 170 K
V = 1568.02 (12) Å³	Prism, colorless
Z = 4	0.77 × 0.34 × 0.34 mm

Data collection top

Rigaku XtaLAB mini diffractometer	3493 reflections with I > 2σ(I)
Detector resolution: 13.6612 pixels mm^-1	R_int = 0.035
profile data from ω–scans	θ_max = 33.1°, θ_min = 2.0°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2018)	h = −10→10
T_min = 0.738, T_max = 1.000	k = −27→25
23424 measured reflections	l = −19→18
5656 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.096	w = 1/[σ²(F_o²) + (0.0197P)² + 1.6677P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max = 0.001
5656 reflections	Δρ_max = 0.72 e Å⁻³
199 parameters	Δρ_min = −0.81 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. All C–bound H atoms were positioned geometrically and refined as riding, with C—H = 0.93 or 0.96 Å and U_iso(H) = 1.2U_eq(C) or U_iso(H) = 1.5U_eq(C) for C(H) and CH₃ groups, respectively.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
I1	−0.50948 (3)	0.43392 (2)	0.16336 (2)	0.06235 (10)
O1	0.3551 (3)	0.60041 (12)	0.4492 (2)	0.0521 (6)
C1	0.3838 (5)	0.75621 (18)	0.4302 (3)	0.0500 (8)
O2	0.3855 (4)	0.82269 (13)	0.4246 (3)	0.0732 (8)
C2	0.2006 (5)	0.71359 (18)	0.3764 (3)	0.0579 (9)
H2A	0.111796	0.713332	0.425697	0.069*
H2B	0.131632	0.738742	0.307874	0.069*
C3	0.2426 (4)	0.63579 (18)	0.3505 (3)	0.0482 (8)
H3	0.323461	0.636549	0.296041	0.058*
C4	0.5196 (4)	0.63685 (16)	0.5048 (3)	0.0418 (7)
C5	0.6575 (5)	0.59171 (18)	0.5759 (3)	0.0522 (8)
H5	0.631204	0.540920	0.581550	0.063*
C6	0.8277 (5)	0.6209 (2)	0.6361 (3)	0.0556 (9)
H6	0.916930	0.590867	0.687195	0.067*
C7	0.8749 (4)	0.69535 (18)	0.6244 (3)	0.0471 (7)
C8	1.0575 (5)	0.7242 (2)	0.6837 (3)	0.0610 (10)
H8	1.146842	0.693508	0.733673	0.073*
C9	1.1078 (6)	0.7950 (2)	0.6704 (4)	0.0708 (11)
H9	1.231105	0.813773	0.710556	0.085*
C10	0.9759 (6)	0.8396 (2)	0.5970 (4)	0.0716 (12)
H10	1.012377	0.888683	0.586249	0.086*
C11	0.7944 (5)	0.81461 (19)	0.5397 (3)	0.0559 (9)
H11	0.706231	0.846849	0.491926	0.067*
C12	0.7382 (4)	0.74111 (17)	0.5516 (3)	0.0423 (7)
C13	0.5495 (4)	0.71092 (16)	0.4953 (2)	0.0387 (6)
C14	0.0648 (4)	0.58838 (18)	0.3059 (3)	0.0474 (7)
C15	0.0197 (5)	0.56413 (19)	0.1993 (3)	0.0537 (8)
H15	0.101446	0.577554	0.153307	0.064*
C16	−0.1444 (5)	0.5201 (2)	0.1580 (3)	0.0546 (8)
H16	−0.174482	0.503502	0.084224	0.066*
C17	−0.2617 (4)	0.50090 (18)	0.2245 (3)	0.0488 (8)
C18	−0.2188 (5)	0.5240 (2)	0.3317 (3)	0.0591 (9)
H18	−0.299918	0.509947	0.377662	0.071*
C19	−0.0551 (5)	0.5683 (2)	0.3719 (3)	0.0592 (9)
H19	−0.025515	0.584942	0.445616	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.04458 (13)	0.06445 (16)	0.06874 (17)	−0.00698 (11)	−0.00216 (10)	−0.01116 (13)
O1	0.0414 (11)	0.0401 (11)	0.0626 (15)	−0.0048 (9)	−0.0087 (10)	0.0070 (10)
C1	0.0424 (16)	0.0458 (18)	0.056 (2)	0.0027 (14)	0.0030 (14)	0.0040 (15)
O2	0.0588 (15)	0.0414 (13)	0.103 (2)	0.0045 (11)	−0.0094 (14)	0.0091 (14)
C2	0.0417 (16)	0.0484 (19)	0.072 (2)	0.0019 (14)	−0.0065 (16)	0.0077 (17)
C3	0.0384 (15)	0.0525 (19)	0.0481 (19)	−0.0004 (14)	0.0010 (13)	0.0027 (14)
C4	0.0364 (14)	0.0397 (15)	0.0469 (17)	−0.0030 (12)	0.0065 (12)	0.0027 (13)
C5	0.0466 (17)	0.0386 (16)	0.062 (2)	−0.0029 (13)	−0.0030 (15)	0.0093 (15)
C6	0.0420 (16)	0.054 (2)	0.061 (2)	0.0007 (15)	−0.0045 (15)	0.0114 (17)
C7	0.0366 (14)	0.0510 (18)	0.0487 (18)	−0.0045 (13)	0.0020 (13)	−0.0002 (14)
C8	0.0463 (18)	0.068 (2)	0.059 (2)	−0.0095 (17)	−0.0036 (16)	0.0030 (18)
C9	0.055 (2)	0.073 (3)	0.073 (3)	−0.023 (2)	−0.0036 (19)	−0.002 (2)
C10	0.068 (2)	0.063 (2)	0.073 (3)	−0.028 (2)	0.000 (2)	0.001 (2)
C11	0.0565 (19)	0.0462 (18)	0.060 (2)	−0.0087 (15)	0.0055 (16)	0.0028 (16)
C12	0.0408 (15)	0.0427 (16)	0.0421 (16)	−0.0056 (13)	0.0083 (12)	−0.0004 (13)
C13	0.0375 (14)	0.0400 (15)	0.0358 (15)	0.0013 (12)	0.0042 (11)	−0.0036 (12)
C14	0.0369 (15)	0.0473 (17)	0.0529 (19)	−0.0003 (13)	0.0023 (13)	0.0029 (14)
C15	0.0447 (17)	0.060 (2)	0.054 (2)	−0.0026 (16)	0.0096 (14)	−0.0012 (17)
C16	0.0472 (17)	0.064 (2)	0.0464 (19)	0.0016 (16)	0.0003 (14)	−0.0047 (16)
C17	0.0377 (15)	0.0493 (18)	0.0514 (19)	0.0005 (13)	−0.0027 (13)	−0.0035 (15)
C18	0.0506 (19)	0.075 (2)	0.049 (2)	−0.0139 (18)	0.0083 (15)	−0.0055 (18)
C19	0.0509 (19)	0.075 (2)	0.0453 (19)	−0.0140 (18)	0.0012 (15)	−0.0091 (18)

Geometric parameters (Å, º) top

I1—C17	2.107 (3)	C8—H8	0.9500
O1—C3	1.446 (4)	C8—C9	1.360 (5)
O1—C4	1.364 (3)	C9—H9	0.9500
C1—O2	1.213 (4)	C9—C10	1.393 (6)
C1—C2	1.510 (4)	C10—H10	0.9500
C1—C13	1.492 (4)	C10—C11	1.375 (5)
C2—H2A	0.9900	C11—H11	0.9500
C2—H2B	0.9900	C11—C12	1.415 (4)
C2—C3	1.502 (5)	C12—C13	1.445 (4)
C3—H3	1.0000	C14—C15	1.374 (5)
C3—C14	1.507 (4)	C14—C19	1.381 (5)
C4—C5	1.406 (4)	C15—H15	0.9500
C4—C13	1.376 (4)	C15—C16	1.394 (5)
C5—H5	0.9500	C16—H16	0.9500
C5—C6	1.353 (4)	C16—C17	1.368 (5)
C6—H6	0.9500	C17—C18	1.376 (5)
C6—C7	1.413 (5)	C18—H18	0.9500
C7—C8	1.413 (4)	C18—C19	1.392 (5)
C7—C12	1.419 (4)	C19—H19	0.9500

C4—O1—C3	115.6 (2)	C8—C9—C10	119.0 (3)
O2—C1—C2	120.5 (3)	C10—C9—H9	120.5
O2—C1—C13	124.5 (3)	C9—C10—H10	119.1
C13—C1—C2	114.9 (3)	C11—C10—C9	121.9 (4)
C1—C2—H2A	109.0	C11—C10—H10	119.1
C1—C2—H2B	109.0	C10—C11—H11	119.8
H2A—C2—H2B	107.8	C10—C11—C12	120.3 (3)
C3—C2—C1	112.9 (3)	C12—C11—H11	119.8
C3—C2—H2A	109.0	C7—C12—C13	118.7 (3)
C3—C2—H2B	109.0	C11—C12—C7	117.6 (3)
O1—C3—C2	109.1 (3)	C11—C12—C13	123.7 (3)
O1—C3—H3	108.5	C4—C13—C1	118.4 (3)
O1—C3—C14	106.6 (3)	C4—C13—C12	118.2 (3)
C2—C3—H3	108.5	C12—C13—C1	123.4 (3)
C2—C3—C14	115.5 (3)	C15—C14—C3	120.7 (3)
C14—C3—H3	108.5	C15—C14—C19	119.0 (3)
O1—C4—C5	113.6 (3)	C19—C14—C3	120.3 (3)
O1—C4—C13	124.2 (3)	C14—C15—H15	119.6
C13—C4—C5	122.2 (3)	C14—C15—C16	120.8 (3)
C4—C5—H5	120.1	C16—C15—H15	119.6
C6—C5—C4	119.7 (3)	C15—C16—H16	120.3
C6—C5—H5	120.1	C17—C16—C15	119.4 (3)
C5—C6—H6	119.4	C17—C16—H16	120.3
C5—C6—C7	121.1 (3)	C16—C17—I1	119.9 (2)
C7—C6—H6	119.4	C16—C17—C18	120.8 (3)
C6—C7—C12	119.5 (3)	C18—C17—I1	119.3 (3)
C8—C7—C6	120.5 (3)	C17—C18—H18	120.4
C8—C7—C12	119.9 (3)	C17—C18—C19	119.2 (3)
C7—C8—H8	119.4	C19—C18—H18	120.4
C9—C8—C7	121.2 (3)	C14—C19—C18	120.7 (3)
C9—C8—H8	119.4	C14—C19—H19	119.6
C8—C9—H9	120.5	C18—C19—H19	119.6

Acknowledgements

The authors thank Georgia Southern University for support of this work.

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