4-Chloro-2-phenyl-2H-chromene-3-carbaldehyde

Punithavalli, B.; Alphonsa, A.T.

doi:10.1107/S2414314625006571

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 10| Part 7| July 2025| x250657

https://doi.org/10.1107/S2414314625006571

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access

4-Chloro-2-phenyl-2H-chromene-3-carbaldehyde

B. Punithavalli ^a and A. Therasa Alphonsa ^a ^*

^aDepartment of Chemistry, Annamalai University, Annamalai Nagar-608002, Tamilnadu, India
^*Correspondence e-mail: [email protected]

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 3 July 2025; accepted 21 July 2025; online 29 July 2025)

The title compound, 4-chloro-2-phenyl-2H-chromene-3-carbaldehyde (PCC), C₁₆H₁₁ClO₂, was obtained in good yield by a standard one-pot method. The molecule has the following substituents: a chlorine atom at the 4-position, a phenyl group at the 2-position, and an aldehyde (–CHO) group at the 3-position of the 2H-chromene ring system.

Keywords: crystal structure; chromene; topology.

CCDC reference: 2474588

Structure description

Heterocyclic compounds containing nitrogen and oxygen have attracted a lot of interest because of their diverse pharmacological activities (Swamy & Agasimundin, 2008 ; Tanaka & Sugino, 2001 ). The basic flavonoid structure is a flavone nucleus, which consists of 15 carbon atoms arranged in rings and is available as flavones, flavonols, flavanones, isoflavones, chalcones and their derivatives. In organic chemistry, 4-chloro-2-phenyl-2H-chromene-3-carbaldehyde is a noteworthy compound that is especially well-known for being synthesized from flavanone. This substance is a member of the chromene class, which includes a range of physiologically active compounds with uses in drug development and medicinal chemistry. The chromene ring with a phenyl substituent and an aldehyde functional group is part of the structural framework of 4-chloro-2-phenyl-2H-chromene-3-carbaldehyde (PCC), which makes it useful in a variety of chemical reactions, including nucleophilic interactions and electrophilic substitutions (Najmanová et al., 2020 ).

Single crystal X-ray analysis confirmed that the 4-chloro-2-phenyl-2H-chromene-3-carbaldehyde crystallizes in the triclinic system in space group P $[\overline{1}]$ . The title chromene derivative has the following substituents: a chlorine atom at the 4-position, a phenyl group at the 2-position, and an aldehyde (–CHO) group at the 3-position of the 2H-chromene ring system. The molecular structure is shown in Fig. 1 and the unit-cell contents in Fig. 2.

Figure 1
The molecular structure of 4-chloro-2-phenyl-2H-chromene-3-carbaldehyde. Displacement ellipsoids are at the 50% probability level.

Figure 2
Packing of 4-chloro-2-phenyl-2H-chromene-3-carbaldehyde.

Synthesis and crystallization

The starting materials 2-phenylchroman-4-one, phosphoryl trichloride and dimethyl furan were purchased from Sigma-Aldrich chemical company with a stated purity and were used as such without further purification. The title compound was synthesized according to Fig. 3. In a round-bottom flask, flavanone (0.1 g) was added with phosphorus oxychloride (16 ml) and stirred well for 6-7 h. The completion of the reaction was monitored by TLC. After that, the reaction mixture was poured into ice-cold water. The resulting precipitate was washed with water and dried. The crude product was recrystallized from ethanol solution.

Figure 3
Reaction scheme for the synthesis of the title compound.

Refinement

The crystal data and structure refinement parameters are listed in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₁₆H₁₁ClO₂
M_r	270.70
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	300
a, b, c (Å)	7.0108 (4), 8.7716 (5), 11.1285 (6)
α, β, γ (°)	75.127 (2), 83.188 (2), 73.584 (2)
V (Å³)	633.68 (6)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.30
Crystal size (mm)	0.30 × 0.20 × 0.13

Data collection
Diffractometer	Bruker D8 QUEST diffractometer with PHOTON II detector
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.702, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	24536, 3133, 2488
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.105, 1.03
No. of reflections	3133
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.21
Computer programs: APEX4 and SAINT (Bruker, 2021 ), SHELXT2019/1 (Sheldrick, 2015a ), SHELXL2019/1 (Sheldrick, 2015b ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 2474588

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314625006571/bt4178sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314625006571/bt4178Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314625006571/bt4178Isup3.cml

checkCIF report

Computing details top

4-Chloro-2-phenyl-2H-chromene-3-carbaldehyde top

Crystal data top

C₁₆H₁₁ClO₂	Z = 2
M_r = 270.70	F(000) = 280
Triclinic, P1	D_x = 1.419 Mg m⁻³
a = 7.0108 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.7716 (5) Å	Cell parameters from 9898 reflections
c = 11.1285 (6) Å	θ = 2.5–27.4°
α = 75.127 (2)°	µ = 0.30 mm⁻¹
β = 83.188 (2)°	T = 300 K
γ = 73.584 (2)°	Block, yellow
V = 633.68 (6) Å³	0.30 × 0.20 × 0.13 mm

Data collection top

Bruker D8 QUEST diffractometer with PHOTON II detector	2488 reflections with I > 2σ(I)
Radiation source: i-mu-s microfocus source	R_int = 0.039
φ and ω scans	θ_max = 28.3°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −9→9
T_min = 0.702, T_max = 0.746	k = −11→11
24536 measured reflections	l = −14→14
3133 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.105	w = 1/[σ²(F_o²) + (0.0403P)² + 0.2009P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3133 reflections	Δρ_max = 0.22 e Å⁻³
172 parameters	Δρ_min = −0.21 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. Hydrogen atoms were located in a difference map and refined as riding on their parent atoms with U(H)=1.2U_eq(C) and with C_tertiary-H=0.98Å or with C-H=0.93Å.

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

	x	y	z	U_iso*/U_eq
Cl1	0.15627 (6)	0.98500 (5)	0.71969 (4)	0.05455 (15)
O1	0.77862 (15)	0.76830 (13)	0.58422 (10)	0.0452 (3)
O2	0.6807 (2)	0.95248 (17)	0.89832 (13)	0.0695 (4)
C1	0.8078 (2)	0.60085 (18)	0.79480 (14)	0.0432 (3)
C2	1.0062 (3)	0.5239 (2)	0.81560 (18)	0.0655 (5)
H2	1.102219	0.579734	0.782252	0.079*
C3	1.0636 (4)	0.3651 (3)	0.8853 (2)	0.0828 (7)
H3	1.197400	0.315453	0.899833	0.099*
C4	0.9247 (4)	0.2807 (2)	0.93297 (19)	0.0754 (6)
H4	0.963825	0.173161	0.978827	0.090*
C5	0.7274 (4)	0.3548 (2)	0.9131 (2)	0.0747 (6)
H5	0.632676	0.297137	0.945091	0.090*
C6	0.6681 (3)	0.5158 (2)	0.84521 (17)	0.0592 (5)
H6	0.533599	0.566230	0.833782	0.071*
C7	0.7540 (2)	0.77322 (18)	0.71423 (14)	0.0407 (3)
H7	0.850791	0.827483	0.728683	0.049*
C8	0.5509 (2)	0.87461 (17)	0.74512 (14)	0.0400 (3)
C9	0.3969 (2)	0.88283 (17)	0.68077 (14)	0.0390 (3)
C10	0.4248 (2)	0.80733 (17)	0.57576 (13)	0.0394 (3)
C11	0.6219 (2)	0.74966 (17)	0.53280 (13)	0.0395 (3)
C12	0.5371 (3)	0.9571 (2)	0.84591 (15)	0.0506 (4)
H12	0.412489	1.015614	0.870651	0.061*
C13	0.2713 (2)	0.7949 (2)	0.51259 (16)	0.0487 (4)
H13	0.139474	0.833098	0.539225	0.058*
C14	0.3141 (3)	0.7262 (2)	0.41102 (17)	0.0573 (4)
H14	0.211223	0.717625	0.369606	0.069*
C15	0.5087 (3)	0.6702 (2)	0.37072 (16)	0.0565 (4)
H15	0.536306	0.624245	0.301928	0.068*
C16	0.6630 (3)	0.68122 (19)	0.43080 (15)	0.0489 (4)
H16	0.794096	0.642888	0.402954	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0411 (2)	0.0541 (3)	0.0653 (3)	−0.00800 (17)	0.00581 (18)	−0.0173 (2)
O1	0.0397 (5)	0.0553 (6)	0.0401 (6)	−0.0157 (5)	0.0023 (4)	−0.0085 (5)
O2	0.0744 (9)	0.0788 (9)	0.0638 (8)	−0.0161 (7)	−0.0156 (7)	−0.0305 (7)
C1	0.0508 (8)	0.0403 (8)	0.0374 (7)	−0.0065 (6)	−0.0038 (6)	−0.0124 (6)
C2	0.0532 (10)	0.0599 (11)	0.0650 (12)	0.0034 (8)	0.0055 (9)	−0.0064 (9)
C3	0.0729 (14)	0.0676 (13)	0.0742 (14)	0.0201 (11)	0.0018 (11)	−0.0031 (11)
C4	0.1089 (18)	0.0433 (10)	0.0546 (11)	0.0067 (11)	−0.0072 (11)	−0.0059 (8)
C5	0.1052 (18)	0.0531 (11)	0.0657 (13)	−0.0318 (12)	−0.0130 (12)	0.0022 (9)
C6	0.0670 (11)	0.0474 (9)	0.0620 (11)	−0.0193 (8)	−0.0173 (9)	0.0004 (8)
C7	0.0415 (8)	0.0406 (8)	0.0419 (8)	−0.0128 (6)	−0.0034 (6)	−0.0098 (6)
C8	0.0449 (8)	0.0339 (7)	0.0398 (7)	−0.0111 (6)	−0.0009 (6)	−0.0057 (6)
C9	0.0386 (7)	0.0326 (7)	0.0418 (8)	−0.0099 (6)	0.0028 (6)	−0.0033 (6)
C10	0.0435 (8)	0.0342 (7)	0.0384 (7)	−0.0120 (6)	−0.0019 (6)	−0.0030 (6)
C11	0.0449 (8)	0.0341 (7)	0.0368 (7)	−0.0128 (6)	−0.0014 (6)	−0.0012 (6)
C12	0.0591 (10)	0.0465 (9)	0.0454 (9)	−0.0100 (7)	−0.0048 (7)	−0.0129 (7)
C13	0.0455 (8)	0.0484 (9)	0.0515 (9)	−0.0138 (7)	−0.0068 (7)	−0.0068 (7)
C14	0.0677 (11)	0.0553 (10)	0.0543 (10)	−0.0213 (9)	−0.0161 (8)	−0.0105 (8)
C15	0.0762 (12)	0.0515 (10)	0.0451 (9)	−0.0179 (9)	−0.0050 (8)	−0.0147 (7)
C16	0.0570 (10)	0.0440 (8)	0.0425 (8)	−0.0118 (7)	0.0034 (7)	−0.0088 (7)

Geometric parameters (Å, º) top

Cl1—C9	1.7343 (15)	C7—C8	1.504 (2)
O1—C11	1.3641 (18)	C7—H7	0.9800
O1—C7	1.4470 (18)	C8—C9	1.341 (2)
O2—C12	1.207 (2)	C8—C12	1.464 (2)
C1—C6	1.378 (2)	C9—C10	1.453 (2)
C1—C2	1.381 (2)	C10—C13	1.397 (2)
C1—C7	1.515 (2)	C10—C11	1.402 (2)
C2—C3	1.381 (3)	C11—C16	1.381 (2)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.364 (3)	C13—C14	1.377 (2)
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.369 (3)	C14—C15	1.376 (3)
C4—H4	0.9300	C14—H14	0.9300
C5—C6	1.390 (3)	C15—C16	1.375 (2)
C5—H5	0.9300	C15—H15	0.9300
C6—H6	0.9300	C16—H16	0.9300

C11—O1—C7	116.95 (11)	C9—C8—C7	118.92 (13)
C6—C1—C2	118.58 (16)	C12—C8—C7	116.38 (13)
C6—C1—C7	122.85 (15)	C8—C9—C10	121.45 (13)
C2—C1—C7	118.54 (15)	C8—C9—Cl1	121.05 (12)
C3—C2—C1	120.8 (2)	C10—C9—Cl1	117.50 (11)
C3—C2—H2	119.6	C13—C10—C11	118.49 (14)
C1—C2—H2	119.6	C13—C10—C9	124.97 (14)
C4—C3—C2	120.2 (2)	C11—C10—C9	116.48 (13)
C4—C3—H3	119.9	O1—C11—C16	117.44 (14)
C2—C3—H3	119.9	O1—C11—C10	121.73 (13)
C3—C4—C5	119.78 (19)	C16—C11—C10	120.70 (14)
C3—C4—H4	120.1	O2—C12—C8	122.83 (16)
C5—C4—H4	120.1	O2—C12—H12	118.6
C4—C5—C6	120.3 (2)	C8—C12—H12	118.6
C4—C5—H5	119.8	C14—C13—C10	120.32 (16)
C6—C5—H5	119.8	C14—C13—H13	119.8
C1—C6—C5	120.26 (19)	C10—C13—H13	119.8
C1—C6—H6	119.9	C15—C14—C13	120.12 (16)
C5—C6—H6	119.9	C15—C14—H14	119.9
O1—C7—C8	111.67 (12)	C13—C14—H14	119.9
O1—C7—C1	109.74 (12)	C16—C15—C14	120.88 (16)
C8—C7—C1	114.24 (12)	C16—C15—H15	119.6
O1—C7—H7	106.9	C14—C15—H15	119.6
C8—C7—H7	106.9	C15—C16—C11	119.49 (16)
C1—C7—H7	106.9	C15—C16—H16	120.3
C9—C8—C12	124.70 (14)	C11—C16—H16	120.3

C6—C1—C2—C3	0.0 (3)	C7—C8—C9—Cl1	175.11 (10)
C7—C1—C2—C3	−178.08 (18)	C8—C9—C10—C13	172.68 (14)
C1—C2—C3—C4	1.2 (3)	Cl1—C9—C10—C13	−7.6 (2)
C2—C3—C4—C5	−1.0 (3)	C8—C9—C10—C11	−10.2 (2)
C3—C4—C5—C6	−0.4 (3)	Cl1—C9—C10—C11	169.61 (10)
C2—C1—C6—C5	−1.4 (3)	C7—O1—C11—C16	−154.86 (13)
C7—C1—C6—C5	176.64 (16)	C7—O1—C11—C10	29.37 (18)
C4—C5—C6—C1	1.6 (3)	C13—C10—C11—O1	175.26 (13)
C11—O1—C7—C8	−42.03 (16)	C9—C10—C11—O1	−2.10 (19)
C11—O1—C7—C1	85.70 (15)	C13—C10—C11—C16	−0.4 (2)
C6—C1—C7—O1	−95.72 (17)	C9—C10—C11—C16	−177.74 (13)
C2—C1—C7—O1	82.32 (17)	C9—C8—C12—O2	−176.79 (16)
C6—C1—C7—C8	30.6 (2)	C7—C8—C12—O2	3.7 (2)
C2—C1—C7—C8	−151.40 (15)	C11—C10—C13—C14	0.5 (2)
O1—C7—C8—C9	30.37 (18)	C9—C10—C13—C14	177.57 (14)
C1—C7—C8—C9	−94.90 (16)	C10—C13—C14—C15	−0.4 (3)
O1—C7—C8—C12	−150.09 (13)	C13—C14—C15—C16	0.2 (3)
C1—C7—C8—C12	84.64 (16)	C14—C15—C16—C11	−0.1 (3)
C12—C8—C9—C10	175.37 (13)	O1—C11—C16—C15	−175.62 (14)
C7—C8—C9—C10	−5.1 (2)	C10—C11—C16—C15	0.2 (2)
C12—C8—C9—Cl1	−4.4 (2)

References

Bruker (2021). APEX4 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
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ISSN: 2414-3146

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4-Chloro-2-phenyl-2H-chromene-3-carbaldehyde

Structure description

Synthesis and crystallization

Refinement

Structural data

References

organic compounds