(3E)-3-{(2E)-3-[4-(Di­methyl­amino)­phen­yl]prop-2-enyl­idene}-3,4-di­hydro-2H-chromen-4-one

Biruntha, K.; Reuben Jonathan, D.; Mohamooda Sumaya, U.; Dravida Thendral, E.R.A.; Usha, G.

doi:10.1107/S2414314618012737

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 9| September 2018| x181273

https://doi.org/10.1107/S2414314618012737

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(3E)-3-{(2E)-3-[4-(Dimethylamino)phenyl]prop-2-enylidene}-3,4-dihydro-2H-chromen-4-one

K. Biruntha,^a D. Reuben Jonathan,^b U. Mohamooda Sumaya,^a E. R. A. Dravida Thendral ^c and G. Usha ^c ^*

^aDepartment of Physics, Bharathi Women's College, Chennai-108, Tamilnadu, India, ^bDepartment of Chemistry, Madras Christian College, Chennai-59, Tamilnadu, India, and ^cPG and Research Department of Physics, Queen Mary's College, Chennai-4, Tamilnadu, India
^*Correspondence e-mail: guqmc@yahoo.com

Edited by R. J. Butcher, Howard University, USA (Received 6 August 2018; accepted 8 September 2018; online 14 September 2018)

In the title compound, C₂₀H₁₉NO₂, the (dimethylamino)phenyl ring and the chromanone ring system are linked via an α-β unsaturated carbon bridge. The dihedral angle between the two terminal phenyl rings is 29.66 (6)°. The tetrahydro-4H-pyran-4 one ring in the chromanone moiety adopts a sofa conformation. The crystal packing is stabilized only by van der Waals forces.

Keywords: crystal structure; chalcone derivative; crystal packing; van der Waals forces.

CCDC reference: 1846995

Structure description

Chalcones are open chain flavonoids having a variety of biological activities, including antioxidant, anti-inflammation, antimicrobial, antiprotozoal and antiulcer properties (Dimmock et al., 1999 ). More importantly, chalcones have also shown anticancer activity as inhibitors of cancer cell proliferation, carcinogenesis and metastasis (Zi & Simoneau, 2005 ). The Claisen–Schmidt condensation reaction between substituted acetophenones and aryl aldehydes under basic conditions has been widely used to synthesize chalcone derivatives (Robinson et al., 2013 ; Tiwari et al., 2010 ). As part of our studies in this area, the title compound (Fig. 1) was synthesized and its crystal structure determined.

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. H atoms are shown as small circles of arbitrary radii.

The C—N distances in the (dimethylamino)phenyl moiety are in the range 1.366 (2) to 1.447 (2) Å and are comparable with the values reported for a similar structure (Adam et al., 2015 ). The C—O and C=O distances in the chromanone moiety [1.365 (2)–1.441 (2) Å and 1.227 (2) Å, respectively] are typical of those in reported structures (Gopaul et al., 2012 ). In the molecule, neither the α-β unsaturated carbon bridge nor the dimethylamino substituent are coplanar with their attached phenyl ring; the dihedral angle between the phenyl ring and the dimethylamino group is 10.3 (2)° while that between the α-β unsaturated carbon bridge and the phenyl ring is 8.58 (9)°. This is also true of the phenyl and tetrahydro-4H-pyran-4-one rings of the chromanone ring system, which make a dihedral angle of 6.2 (1)°. As a result of these dihedral angles which are all in the same direction, even though most of the title compound makes up a single conjugated system, there is a significant twist between the two end phenyl rings, which make a dihedral angle of 29.66 (6)°. The sum of the angles around the N atom is 359.61°, indicating sp² hybridization. The tetrahydro-4H-pyran-4-one ring in the chromanone moiety adopts a sofa conformation with atom C13 displaced from the other ring atoms by 0.5656 (15) Å and with puckering parameters of q2 = 0.3795 (15) Å, φ2 = 71.43 (2)°, q3 = 0.1835 (15) Å, Q_T = 0.4216 (14) Å and θ2 = 64.20 (2)°.

It is well known that the ketone atom in chalcones is usually an active participant in hydrogen-bond formation or C—H⋯O interactions. However, in the present compound this is not the case and the crystal structure is stabilized only by van der Waals forces (Fig. 2).

Figure 2
The packing of the molecules in the unit cell.

Synthesis and crystallization

In a 250 ml round-bottomed flask, 4-chromanone (0.9 g, 0.006 mol) and 4-dimethylaminocinnamaldehyde (1 g, 0.006 mol) were added to absolute alcohol and stirred for 5 min. Then a solution of NaOH (0.3 g,10 ml) was added and stirred for 2 h. The mixture was kept overnight at room temperature and the precipitate was generated by adding a sufficient amount of crushed ice. The yield was filtered and washed with distilled water several times to remove any trace of NaOH remaining in the product. The crude chalcone derivative was recrystallized twice from ethyl methylketone to give red block-shaped diffraction-quality crystals of the title compound (yield 70%; m.p. 175°C).

Refinement

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

Table 1
Experimental details

Crystal data
Chemical formula	C₂₀H₁₉NO₂
M_r	305.36
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	9.3620 (4), 11.6073 (5), 15.0732 (7)
β (°)	98.859 (2)
V (Å³)	1618.43 (12)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.20 × 0.20 × 0.15

Data collection
Diffractometer	Bruker Kappa APEX3 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.984, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	12086, 3331, 2487
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.133, 1.05
No. of reflections	3275
No. of parameters	210
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.14
Computer programs: APEX3, SAINT and XPREP (Bruker, 2016), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2014/7 (Sheldrick, 2015b ) and ORTEP-3 for Windows (Farrugia, 2012 ).

Structural data

CCDC reference: 1846995

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618012737/bv4020sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618012737/bv4020Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618012737/bv4020Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: APEX3 and SAINT (Bruker, 2016); data reduction: SAINT and XPREP (Bruker, 2016); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2014/7 (Sheldrick, 2015b).

(3E)-3-{(2E)-3-[4-(Dimethylamino)phenyl]prop-2-enylidene}-3,4-dihydro-2H-chromen-4-one top

Crystal data top

C₂₀H₁₉NO₂	F(000) = 648
M_r = 305.36	D_x = 1.253 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.3620 (4) Å	Cell parameters from 5210 reflections
b = 11.6073 (5) Å	θ = 3.2–26.4°
c = 15.0732 (7) Å	µ = 0.08 mm⁻¹
β = 98.859 (2)°	T = 296 K
V = 1618.43 (12) Å³	Block, red
Z = 4	0.20 × 0.20 × 0.15 mm

Data collection top

Bruker Kappa APEX3 CMOS diffractometer	2487 reflections with I > 2σ(I)
ω and φ scan	R_int = 0.037
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 26.4°, θ_min = 3.7°
T_min = 0.984, T_max = 0.988	h = −10→11
12086 measured reflections	k = −14→14
3331 independent reflections	l = −18→16

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.044	H-atom parameters constrained
wR(F²) = 0.133	w = 1/[σ²(F_o²) + (0.0692P)² + 0.2609P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3275 reflections	Δρ_max = 0.16 e Å⁻³
210 parameters	Δρ_min = −0.14 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. H atoms were positioned geometrically and treated as riding on their parent atoms and refined with, C—H distances of 0.93–0.97 Å, with U_iso(H) = 1.5 U_eq(CH₃), and U_iso(H) = 1.2U_eq(C) for all other H atoms.

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

	x	y	z	U_iso*/U_eq
C1	0.0964 (2)	0.68888 (17)	0.79247 (11)	0.0640 (5)
H1A	0.0838	0.7306	0.8457	0.096*
H1B	0.1727	0.6335	0.8067	0.096*
H1C	0.0082	0.6497	0.7693	0.096*
C2	0.0885 (2)	0.88711 (17)	0.73183 (13)	0.0720 (5)
H2A	0.0361	0.8954	0.7814	0.108*
H2B	0.0275	0.9086	0.6772	0.108*
H2C	0.1723	0.9360	0.7409	0.108*
C3	0.19368 (15)	0.73066 (12)	0.65409 (9)	0.0419 (3)
C4	0.21389 (15)	0.61255 (12)	0.63836 (9)	0.0433 (3)
H4	0.1859	0.5583	0.6777	0.052*
C5	0.27444 (15)	0.57621 (12)	0.56564 (9)	0.0416 (3)
H5	0.2842	0.4975	0.5566	0.050*
C6	0.32198 (15)	0.65288 (11)	0.50480 (9)	0.0395 (3)
C7	0.30258 (16)	0.77064 (12)	0.52103 (9)	0.0438 (3)
H7	0.3331	0.8245	0.4823	0.053*
C8	0.24020 (16)	0.80844 (12)	0.59197 (9)	0.0459 (3)
H8	0.2280	0.8871	0.5996	0.055*
C9	0.38700 (15)	0.60951 (12)	0.43012 (9)	0.0430 (3)
H9	0.3857	0.5300	0.4227	0.052*
C10	0.44891 (16)	0.67015 (12)	0.37032 (9)	0.0437 (3)
H10	0.4570	0.7497	0.3767	0.052*
C11	0.50278 (16)	0.61550 (12)	0.29683 (9)	0.0427 (3)
H11	0.4934	0.5358	0.2935	0.051*
C12	0.56533 (15)	0.66574 (11)	0.23197 (8)	0.0394 (3)
C13	0.58723 (16)	0.79282 (12)	0.22502 (10)	0.0444 (3)
H13A	0.5089	0.8247	0.1825	0.053*
H13B	0.5830	0.8278	0.2830	0.053*
C14	0.74836 (15)	0.76685 (12)	0.12115 (9)	0.0425 (3)
C15	0.68871 (16)	0.65880 (12)	0.09684 (9)	0.0428 (3)
C16	0.60480 (16)	0.59667 (12)	0.15718 (9)	0.0432 (3)
C17	0.7188 (2)	0.60855 (15)	0.01730 (11)	0.0606 (4)
H17	0.6778	0.5378	−0.0010	0.073*
C18	0.8080 (2)	0.66229 (17)	−0.03405 (13)	0.0723 (5)
H18	0.8262	0.6284	−0.0871	0.087*
C19	0.8709 (2)	0.76745 (17)	−0.00662 (13)	0.0667 (5)
H19	0.9342	0.8024	−0.0403	0.080*
C20	0.84022 (17)	0.81996 (15)	0.06980 (11)	0.0553 (4)
H20	0.8810	0.8911	0.0871	0.066*
N1	0.13334 (15)	0.76841 (12)	0.72573 (9)	0.0556 (4)
O1	0.72288 (11)	0.82258 (9)	0.19689 (7)	0.0509 (3)
O2	0.57429 (15)	0.49431 (9)	0.14612 (8)	0.0648 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0704 (11)	0.0793 (12)	0.0468 (9)	−0.0040 (9)	0.0230 (8)	−0.0043 (8)
C2	0.0828 (13)	0.0659 (11)	0.0727 (12)	0.0152 (9)	0.0286 (10)	−0.0171 (9)
C3	0.0403 (7)	0.0463 (8)	0.0395 (7)	−0.0012 (6)	0.0078 (6)	−0.0048 (6)
C4	0.0474 (8)	0.0423 (7)	0.0416 (7)	−0.0044 (6)	0.0115 (6)	0.0035 (6)
C5	0.0483 (8)	0.0347 (7)	0.0423 (7)	−0.0006 (5)	0.0088 (6)	0.0003 (5)
C6	0.0444 (7)	0.0382 (7)	0.0361 (7)	0.0009 (5)	0.0067 (6)	−0.0003 (5)
C7	0.0531 (8)	0.0384 (7)	0.0413 (7)	−0.0019 (6)	0.0114 (6)	0.0030 (6)
C8	0.0554 (9)	0.0352 (7)	0.0485 (8)	0.0007 (6)	0.0126 (7)	−0.0032 (6)
C9	0.0523 (8)	0.0385 (7)	0.0390 (7)	0.0036 (6)	0.0094 (6)	0.0009 (5)
C10	0.0532 (8)	0.0376 (7)	0.0416 (7)	0.0033 (6)	0.0109 (6)	−0.0006 (6)
C11	0.0545 (8)	0.0351 (7)	0.0397 (7)	0.0060 (6)	0.0107 (6)	0.0020 (5)
C12	0.0461 (8)	0.0350 (7)	0.0377 (7)	0.0058 (5)	0.0081 (6)	0.0000 (5)
C13	0.0515 (8)	0.0366 (7)	0.0477 (8)	0.0020 (6)	0.0162 (6)	−0.0028 (6)
C14	0.0393 (7)	0.0449 (7)	0.0438 (7)	0.0050 (6)	0.0079 (6)	0.0015 (6)
C15	0.0475 (8)	0.0417 (7)	0.0406 (7)	0.0078 (6)	0.0112 (6)	0.0004 (6)
C16	0.0548 (8)	0.0360 (7)	0.0402 (7)	0.0049 (6)	0.0112 (6)	−0.0002 (5)
C17	0.0826 (12)	0.0519 (9)	0.0526 (9)	0.0027 (8)	0.0271 (8)	−0.0065 (7)
C18	0.0941 (14)	0.0718 (12)	0.0598 (10)	0.0076 (10)	0.0401 (10)	−0.0050 (9)
C19	0.0667 (11)	0.0730 (12)	0.0680 (11)	0.0031 (9)	0.0346 (9)	0.0088 (9)
C20	0.0487 (9)	0.0566 (9)	0.0633 (10)	−0.0017 (7)	0.0171 (7)	0.0027 (7)
N1	0.0654 (8)	0.0558 (8)	0.0507 (7)	−0.0001 (6)	0.0251 (6)	−0.0083 (6)
O1	0.0528 (6)	0.0498 (6)	0.0527 (6)	−0.0102 (5)	0.0164 (5)	−0.0122 (5)
O2	0.1039 (10)	0.0350 (6)	0.0621 (7)	−0.0063 (5)	0.0341 (7)	−0.0080 (5)

Geometric parameters (Å, º) top

C1—N1	1.446 (2)	C10—C11	1.4338 (19)
C1—H1A	0.9600	C10—H10	0.9300
C1—H1B	0.9600	C11—C12	1.3474 (19)
C1—H1C	0.9600	C11—H11	0.9300
C2—N1	1.447 (2)	C12—C16	1.4759 (18)
C2—H2A	0.9600	C12—C13	1.4951 (18)
C2—H2B	0.9600	C13—O1	1.4414 (18)
C2—H2C	0.9600	C13—H13A	0.9700
C3—N1	1.3658 (18)	C13—H13B	0.9700
C3—C4	1.409 (2)	C14—O1	1.3647 (17)
C3—C8	1.417 (2)	C14—C20	1.387 (2)
C4—C5	1.376 (2)	C14—C15	1.399 (2)
C4—H4	0.9300	C15—C17	1.400 (2)
C5—C6	1.3988 (19)	C15—C16	1.478 (2)
C5—H5	0.9300	C16—O2	1.2272 (17)
C6—C7	1.4054 (19)	C17—C18	1.373 (2)
C6—C9	1.4499 (19)	C17—H17	0.9300
C7—C8	1.367 (2)	C18—C19	1.390 (3)
C7—H7	0.9300	C18—H18	0.9300
C8—H8	0.9300	C19—C20	1.372 (2)
C9—C10	1.3434 (19)	C19—H19	0.9300
C9—H9	0.9300	C20—H20	0.9300

N1—C1—H1A	109.5	C12—C11—H11	116.1
N1—C1—H1B	109.5	C10—C11—H11	116.1
H1A—C1—H1B	109.5	C11—C12—C16	120.46 (12)
N1—C1—H1C	109.5	C11—C12—C13	123.88 (12)
H1A—C1—H1C	109.5	C16—C12—C13	115.42 (12)
H1B—C1—H1C	109.5	O1—C13—C12	113.18 (11)
N1—C2—H2A	109.5	O1—C13—H13A	108.9
N1—C2—H2B	109.5	C12—C13—H13A	108.9
H2A—C2—H2B	109.5	O1—C13—H13B	108.9
N1—C2—H2C	109.5	C12—C13—H13B	108.9
H2A—C2—H2C	109.5	H13A—C13—H13B	107.8
H2B—C2—H2C	109.5	O1—C14—C20	117.34 (13)
N1—C3—C4	121.86 (13)	O1—C14—C15	122.01 (13)
N1—C3—C8	121.65 (13)	C20—C14—C15	120.61 (14)
C4—C3—C8	116.49 (13)	C14—C15—C17	118.23 (14)
C5—C4—C3	120.99 (13)	C14—C15—C16	120.32 (12)
C5—C4—H4	119.5	C17—C15—C16	121.31 (13)
C3—C4—H4	119.5	O2—C16—C12	123.32 (13)
C4—C5—C6	122.62 (13)	O2—C16—C15	121.56 (13)
C4—C5—H5	118.7	C12—C16—C15	115.10 (12)
C6—C5—H5	118.7	C18—C17—C15	120.89 (16)
C5—C6—C7	116.23 (12)	C18—C17—H17	119.6
C5—C6—C9	120.14 (12)	C15—C17—H17	119.6
C7—C6—C9	123.63 (12)	C17—C18—C19	119.88 (16)
C8—C7—C6	122.04 (13)	C17—C18—H18	120.1
C8—C7—H7	119.0	C19—C18—H18	120.1
C6—C7—H7	119.0	C20—C19—C18	120.36 (16)
C7—C8—C3	121.62 (13)	C20—C19—H19	119.8
C7—C8—H8	119.2	C18—C19—H19	119.8
C3—C8—H8	119.2	C19—C20—C14	119.94 (16)
C10—C9—C6	127.97 (13)	C19—C20—H20	120.0
C10—C9—H9	116.0	C14—C20—H20	120.0
C6—C9—H9	116.0	C3—N1—C1	121.17 (14)
C9—C10—C11	121.74 (13)	C3—N1—C2	120.99 (14)
C9—C10—H10	119.1	C1—N1—C2	117.45 (14)
C11—C10—H10	119.1	C14—O1—C13	114.07 (11)
C12—C11—C10	127.81 (13)

N1—C3—C4—C5	179.78 (13)	C11—C12—C16—O2	5.5 (2)
C8—C3—C4—C5	−0.6 (2)	C13—C12—C16—O2	−169.17 (14)
C3—C4—C5—C6	1.4 (2)	C11—C12—C16—C15	−172.74 (12)
C4—C5—C6—C7	−1.0 (2)	C13—C12—C16—C15	12.58 (18)
C4—C5—C6—C9	179.05 (12)	C14—C15—C16—O2	−166.30 (14)
C5—C6—C7—C8	−0.3 (2)	C17—C15—C16—O2	9.4 (2)
C9—C6—C7—C8	179.70 (13)	C14—C15—C16—C12	11.97 (19)
C6—C7—C8—C3	1.1 (2)	C17—C15—C16—C12	−172.32 (13)
N1—C3—C8—C7	179.00 (13)	C14—C15—C17—C18	1.9 (3)
C4—C3—C8—C7	−0.6 (2)	C16—C15—C17—C18	−173.87 (15)
C5—C6—C9—C10	−173.96 (14)	C15—C17—C18—C19	0.7 (3)
C7—C6—C9—C10	6.1 (2)	C17—C18—C19—C20	−2.4 (3)
C6—C9—C10—C11	−176.87 (13)	C18—C19—C20—C14	1.4 (3)
C9—C10—C11—C12	179.21 (14)	O1—C14—C20—C19	179.38 (14)
C10—C11—C12—C16	−175.39 (13)	C15—C14—C20—C19	1.3 (2)
C10—C11—C12—C13	−1.2 (2)	C4—C3—N1—C1	4.3 (2)
C11—C12—C13—O1	141.69 (13)	C8—C3—N1—C1	−175.22 (14)
C16—C12—C13—O1	−43.83 (17)	C4—C3—N1—C2	−168.28 (15)
O1—C14—C15—C17	179.08 (13)	C8—C3—N1—C2	12.2 (2)
C20—C14—C15—C17	−2.9 (2)	C20—C14—O1—C13	154.73 (13)
O1—C14—C15—C16	−5.1 (2)	C15—C14—O1—C13	−27.24 (18)
C20—C14—C15—C16	172.89 (13)	C12—C13—O1—C14	51.19 (16)

Acknowledgements

The authors thank Central Instrumentation Facility, Queen Mary's College, Chennai-4 for computing facilities and SAIF, IIT, Madras, for the X-ray data collection.

References

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