4-(4-Chloro­phen­yl)-7,7-dimethyl-7,8-dihydro-4H-1-benzopyran-2,5(3H,6H)-dione

Shi, H.

doi:10.1107/S1600536809051320

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o56

doi:10.1107/S1600536809051320

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4-(4-Chlorophenyl)-7,7-dimethyl-7,8-dihydro-4H-1-benzopyran-2,5(3H,6H)-dione

Hao Shi ^a ^*

^aThe College of Pharmaceutical Science, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: shihao@zjut.edu.cn

(Received 15 November 2009; accepted 28 November 2009; online 4 December 2009)

The title compound, C₁₇H₁₇ClO₃, has been synthesized by the reaction of p-chlorobenzaldehyde, isopropylidene malonate and 5,5-dimethylcyclohexane-1,3-dione with triethylbenzylammonium chloride in water as a green solvent. The six membered pyranone ring of the hexahydrocoumarin system has a screw-boat conformation while the dimethylcyclohexenone system has a distorted envelope conformation. The dihedral angle between the least-squares planes of the coumarin ring system and the benzene ring is 85.64 (9)°.

Related literature

For applications of coumarin derivatives, see: Wang et al. (1999 ); Yang (2001 ). For related structures, see: Itoh & Kanemasa (2003 ); Itoh et al. (2005 ). For ring puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₇H₁₇ClO₃
M_r = 304.76
Monoclinic, P 2₁ /n
a = 11.9005 (12) Å
b = 5.7971 (8) Å
c = 22.608 (2) Å
β = 93.972 (1)°
V = 1555.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 298 K
0.48 × 0.39 × 0.34 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.889, T_max = 0.919
7519 measured reflections
2789 independent reflections
1585 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.186
S = 1.05
2789 reflections
192 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809051320/bh2260sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809051320/bh2260Isup2.hkl

checkCIF report

Comment top

Coumarin is an important chemical having unique characteristics. It is widely used in hand soaps, detergents, lotions and laser dyes (Wang et al., 1999). Coumarin and some of its derivatives have been tested in pharmacology for treatment of HIV (Yang, 2001). To obtain coumarin in a more environment friendly way, water was used as a green solvent in the synthesis of the title compound (Fig.1 and Experimental).

In the molecule of the title compound (Fig. 2), the two six membered rings of the hexahydrocoumarin system are not planar, having screw-boat and envelope conformations respectively: the pyranone ring A (O1/C1···C4/C9) adopts the screw-boat conformation with puckering parameters (Cremer & Pople, 1975) Q= 0.430 (5) Å, θ= 61.8 (5)° and ϕ = 134.7 (6)°; the ring B (C4···C9) exists in a distorted envelope conformation [Q = 0.408 (4) Å, θ= 127.0 (6)° and ϕ= 343.4 (7)°)] with C7 displaced by 0.558 (5) Å from the plane of the other ring atoms. Ring C (C12···C17) is a benzene ring, which makes a dihedral angle of 85.64 (9)° with the least-squares plane of the coumarin ring. The analogue of the title compound including Br in place of Cl has been reported and an enantiomerically pure crystal characterized by X-ray diffraction (Itoh & Kanemasa, 2003; Itoh et al., 2005).

Related literature top

For applications of coumarin derivatives, see: Wang et al. (1999); Yang (2001). For related structures, see: Itoh & Kanemasa (2003); Itoh et al. (2005). For ring puckering parameters, see: Cremer & Pople (1975).

Experimental top

A mixture of 4-chlorobenzaldehyde (100 mmol), 5,5-dimethyl-1,3-cyclohexanedione (100 mmol), isopropylidene malonate (100 mmol), triethylbenzylammonium chloride (TEBA) (15 mmol) and 400 mL of water was transferred into a flask connected with refluxing equipment (Fig. 1). After stirring at 345 K (72°C) for 5 h, the reaction mixture was cooled to room temperature, the precipitated product was filtered and recrystallized with ethanol to give the title compound. Crystals suitable for X-ray structure analysis were obtained by slow evaporation from a solution of isopropyl alcohol at room temperature.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The preparation of the title compound.
	Fig. 2. Structure of the title compound, showing 30% probability displacement ellipsoids with atomic numbering scheme.

4-(4-Chlorophenyl)-7,7-dimethyl-7,8-dihydro-4H-1-benzopyran- 2,5(3H,6H)-dione top

Crystal data top

C₁₇H₁₇ClO₃	F(000) = 640
M_r = 304.76	D_x = 1.301 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1909 reflections
a = 11.9005 (12) Å	θ = 2.7–23.0°
b = 5.7971 (8) Å	µ = 0.25 mm⁻¹
c = 22.608 (2) Å	T = 298 K
β = 93.972 (1)°	Prism, colorless
V = 1555.9 (3) Å³	0.48 × 0.39 × 0.34 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2789 independent reflections
Radiation source: fine-focus sealed tube	1585 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 25.2°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −12→14
T_min = 0.889, T_max = 0.919	k = −6→6
7519 measured reflections	l = −27→20

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.186	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0667P)² + 1.4872P] where P = (F_o² + 2F_c²)/3
2789 reflections	(Δ/σ)_max < 0.001
192 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.51 e Å⁻³
0 constraints

Crystal data top

C₁₇H₁₇ClO₃	V = 1555.9 (3) Å³
M_r = 304.76	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.9005 (12) Å	µ = 0.25 mm⁻¹
b = 5.7971 (8) Å	T = 298 K
c = 22.608 (2) Å	0.48 × 0.39 × 0.34 mm
β = 93.972 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2789 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	1585 reflections with I > 2σ(I)
T_min = 0.889, T_max = 0.919	R_int = 0.034
7519 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.186	H-atom parameters constrained
S = 1.05	Δρ_max = 0.49 e Å⁻³
2789 reflections	Δρ_min = −0.51 e Å⁻³
192 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	−0.43477 (9)	0.5886 (3)	0.12137 (6)	0.1069 (6)
O1	0.1778 (2)	0.6708 (5)	0.18437 (12)	0.0681 (8)
O2	0.1132 (3)	0.5408 (7)	0.26641 (15)	0.1127 (13)
O3	0.0220 (3)	1.3042 (5)	0.07706 (14)	0.0936 (10)
C1	0.1180 (4)	0.7039 (10)	0.2336 (2)	0.0765 (13)
C2	0.0708 (4)	0.9367 (9)	0.24091 (17)	0.0810 (14)
H2A	0.1305	1.0395	0.2559	0.097*
H2B	0.0149	0.9303	0.2701	0.097*
C3	0.0160 (3)	1.0357 (7)	0.18295 (16)	0.0598 (10)
H3	0.0049	1.2017	0.1883	0.072*
C4	0.0969 (3)	1.0017 (6)	0.13547 (15)	0.0505 (9)
C5	0.0888 (3)	1.1459 (7)	0.08223 (17)	0.0602 (10)
C6	0.1584 (3)	1.0799 (8)	0.03203 (18)	0.0751 (12)
H6A	0.1720	1.2168	0.0089	0.090*
H6B	0.1156	0.9727	0.0064	0.090*
C7	0.2710 (3)	0.9703 (7)	0.05132 (16)	0.0580 (10)
C8	0.2544 (3)	0.7783 (7)	0.09489 (18)	0.0631 (10)
H8A	0.2291	0.6416	0.0731	0.076*
H8B	0.3265	0.7424	0.1155	0.076*
C9	0.1725 (3)	0.8325 (6)	0.13923 (16)	0.0518 (9)
C10	0.3488 (4)	1.1568 (8)	0.0813 (2)	0.0812 (13)
H10A	0.3137	1.2211	0.1145	0.122*
H10B	0.3616	1.2767	0.0532	0.122*
H10C	0.4195	1.0883	0.0947	0.122*
C11	0.3302 (4)	0.8824 (9)	−0.0017 (2)	0.0955 (15)
H11A	0.4020	0.8187	0.0115	0.143*
H11B	0.3409	1.0077	−0.0285	0.143*
H11C	0.2849	0.7653	−0.0217	0.143*
C12	−0.0981 (3)	0.9254 (6)	0.16736 (15)	0.0524 (9)
C13	−0.1075 (3)	0.7218 (7)	0.13616 (17)	0.0585 (10)
H13	−0.0428	0.6531	0.1235	0.070*
C14	−0.2100 (3)	0.6170 (7)	0.12320 (17)	0.0636 (10)
H14	−0.2141	0.4778	0.1027	0.076*
C15	−0.3048 (3)	0.7190 (8)	0.14062 (17)	0.0638 (11)
C16	−0.3001 (3)	0.9189 (9)	0.17169 (18)	0.0719 (12)
H16	−0.3658	0.9854	0.1838	0.086*
C17	−0.1966 (3)	1.0245 (7)	0.18543 (17)	0.0666 (11)
H17	−0.1932	1.1618	0.2068	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0534 (6)	0.1496 (13)	0.1172 (11)	−0.0213 (7)	0.0011 (6)	0.0253 (9)
O1	0.0610 (16)	0.0693 (18)	0.0721 (18)	−0.0014 (13)	−0.0099 (14)	0.0155 (15)
O2	0.128 (3)	0.132 (3)	0.075 (2)	−0.020 (2)	−0.0128 (19)	0.040 (2)
O3	0.110 (2)	0.074 (2)	0.097 (2)	0.0438 (19)	0.0137 (19)	0.0108 (18)
C1	0.072 (3)	0.101 (4)	0.054 (3)	−0.020 (3)	−0.017 (2)	0.008 (3)
C2	0.081 (3)	0.110 (4)	0.050 (2)	−0.024 (3)	−0.004 (2)	−0.018 (3)
C3	0.064 (2)	0.057 (2)	0.059 (2)	−0.0037 (19)	0.0033 (18)	−0.0186 (19)
C4	0.0476 (18)	0.048 (2)	0.055 (2)	−0.0025 (16)	−0.0024 (15)	−0.0082 (18)
C5	0.060 (2)	0.053 (2)	0.067 (3)	0.0078 (19)	−0.0015 (19)	−0.001 (2)
C6	0.073 (3)	0.091 (3)	0.061 (2)	0.014 (2)	0.002 (2)	0.007 (2)
C7	0.055 (2)	0.062 (2)	0.057 (2)	0.0042 (18)	0.0022 (17)	−0.002 (2)
C8	0.051 (2)	0.055 (2)	0.084 (3)	0.0043 (18)	0.0070 (19)	0.001 (2)
C9	0.0462 (19)	0.051 (2)	0.057 (2)	−0.0052 (17)	−0.0076 (16)	0.0054 (19)
C10	0.073 (3)	0.069 (3)	0.101 (3)	−0.013 (2)	0.002 (2)	0.005 (3)
C11	0.092 (3)	0.110 (4)	0.087 (3)	0.014 (3)	0.025 (3)	−0.007 (3)
C12	0.056 (2)	0.054 (2)	0.047 (2)	0.0089 (17)	0.0058 (16)	−0.0044 (18)
C13	0.0450 (19)	0.062 (2)	0.068 (2)	0.0058 (17)	0.0046 (17)	−0.014 (2)
C14	0.053 (2)	0.066 (3)	0.071 (3)	−0.0035 (19)	−0.0004 (18)	−0.002 (2)
C15	0.050 (2)	0.081 (3)	0.061 (2)	−0.002 (2)	0.0028 (18)	0.018 (2)
C16	0.053 (2)	0.094 (3)	0.071 (3)	0.020 (2)	0.022 (2)	0.018 (3)
C17	0.077 (3)	0.064 (3)	0.060 (2)	0.015 (2)	0.015 (2)	−0.004 (2)

Geometric parameters (Å, º) top

Cl1—C15	1.749 (4)	C7—C10	1.549 (5)
O1—C1	1.374 (5)	C8—C9	1.480 (5)
O1—C9	1.384 (4)	C8—H8A	0.9700
O2—C1	1.206 (5)	C8—H8B	0.9700
O3—C5	1.214 (4)	C10—H10A	0.9600
C1—C2	1.475 (7)	C10—H10B	0.9600
C2—C3	1.534 (6)	C10—H10C	0.9600
C2—H2A	0.9700	C11—H11A	0.9600
C2—H2B	0.9700	C11—H11B	0.9600
C3—C4	1.503 (5)	C11—H11C	0.9600
C3—C12	1.520 (5)	C12—C13	1.376 (5)
C3—H3	0.9800	C12—C17	1.392 (5)
C4—C9	1.330 (5)	C13—C14	1.375 (5)
C4—C5	1.463 (5)	C13—H13	0.9300
C5—C6	1.501 (5)	C14—C15	1.357 (5)
C6—C7	1.519 (5)	C14—H14	0.9300
C6—H6A	0.9700	C15—C16	1.354 (6)
C6—H6B	0.9700	C16—C17	1.391 (6)
C7—C8	1.509 (5)	C16—H16	0.9300
C7—C11	1.520 (6)	C17—H17	0.9300

C1—O1—C9	120.2 (3)	C9—C8—H8B	108.7
O2—C1—O1	116.0 (5)	C7—C8—H8B	108.7
O2—C1—C2	127.8 (5)	H8A—C8—H8B	107.6
O1—C1—C2	116.2 (4)	C4—C9—O1	122.9 (3)
C1—C2—C3	112.9 (3)	C4—C9—C8	126.0 (3)
C1—C2—H2A	109.0	O1—C9—C8	110.9 (3)
C3—C2—H2A	109.0	C7—C10—H10A	109.5
C1—C2—H2B	109.0	C7—C10—H10B	109.5
C3—C2—H2B	109.0	H10A—C10—H10B	109.5
H2A—C2—H2B	107.8	C7—C10—H10C	109.5
C4—C3—C12	112.6 (3)	H10A—C10—H10C	109.5
C4—C3—C2	107.8 (3)	H10B—C10—H10C	109.5
C12—C3—C2	111.1 (3)	C7—C11—H11A	109.5
C4—C3—H3	108.4	C7—C11—H11B	109.5
C12—C3—H3	108.4	H11A—C11—H11B	109.5
C2—C3—H3	108.4	C7—C11—H11C	109.5
C9—C4—C5	118.7 (3)	H11A—C11—H11C	109.5
C9—C4—C3	121.0 (3)	H11B—C11—H11C	109.5
C5—C4—C3	120.2 (3)	C13—C12—C17	117.7 (3)
O3—C5—C4	121.1 (4)	C13—C12—C3	121.3 (3)
O3—C5—C6	120.8 (4)	C17—C12—C3	121.0 (3)
C4—C5—C6	117.9 (3)	C14—C13—C12	121.9 (3)
C5—C6—C7	114.3 (3)	C14—C13—H13	119.1
C5—C6—H6A	108.7	C12—C13—H13	119.1
C7—C6—H6A	108.7	C15—C14—C13	119.2 (4)
C5—C6—H6B	108.7	C15—C14—H14	120.4
C7—C6—H6B	108.7	C13—C14—H14	120.4
H6A—C6—H6B	107.6	C16—C15—C14	121.2 (4)
C8—C7—C6	110.1 (3)	C16—C15—Cl1	120.2 (3)
C8—C7—C11	110.9 (3)	C14—C15—Cl1	118.6 (4)
C6—C7—C11	111.2 (3)	C15—C16—C17	119.8 (4)
C8—C7—C10	109.3 (3)	C15—C16—H16	120.1
C6—C7—C10	108.8 (3)	C17—C16—H16	120.1
C11—C7—C10	106.5 (3)	C16—C17—C12	120.2 (4)
C9—C8—C7	114.1 (3)	C16—C17—H17	119.9
C9—C8—H8A	108.7	C12—C17—H17	119.9
C7—C8—H8A	108.7

C9—O1—C1—O2	169.1 (3)	C5—C4—C9—O1	−172.3 (3)
C9—O1—C1—C2	−12.9 (5)	C3—C4—C9—O1	3.8 (5)
O2—C1—C2—C3	−138.5 (4)	C5—C4—C9—C8	2.4 (5)
O1—C1—C2—C3	43.7 (5)	C3—C4—C9—C8	178.5 (3)
C1—C2—C3—C4	−48.0 (5)	C1—O1—C9—C4	−12.2 (5)
C1—C2—C3—C12	75.9 (4)	C1—O1—C9—C8	172.4 (3)
C12—C3—C4—C9	−97.0 (4)	C7—C8—C9—C4	16.7 (5)
C2—C3—C4—C9	26.0 (5)	C7—C8—C9—O1	−168.1 (3)
C12—C3—C4—C5	79.1 (4)	C4—C3—C12—C13	35.1 (5)
C2—C3—C4—C5	−157.9 (3)	C2—C3—C12—C13	−86.0 (4)
C9—C4—C5—O3	−179.1 (4)	C4—C3—C12—C17	−146.4 (3)
C3—C4—C5—O3	4.7 (5)	C2—C3—C12—C17	92.5 (4)
C9—C4—C5—C6	6.0 (5)	C17—C12—C13—C14	−0.3 (5)
C3—C4—C5—C6	−170.1 (3)	C3—C12—C13—C14	178.2 (4)
O3—C5—C6—C7	152.0 (4)	C12—C13—C14—C15	1.3 (6)
C4—C5—C6—C7	−33.1 (5)	C13—C14—C15—C16	−1.6 (6)
C5—C6—C7—C8	49.9 (5)	C13—C14—C15—Cl1	177.7 (3)
C5—C6—C7—C11	173.2 (4)	C14—C15—C16—C17	0.9 (6)
C5—C6—C7—C10	−69.9 (5)	Cl1—C15—C16—C17	−178.3 (3)
C6—C7—C8—C9	−41.4 (4)	C15—C16—C17—C12	0.0 (6)
C11—C7—C8—C9	−164.8 (3)	C13—C12—C17—C16	−0.3 (5)
C10—C7—C8—C9	78.1 (4)	C3—C12—C17—C16	−178.8 (3)

Experimental details

Crystal data
Chemical formula	C₁₇H₁₇ClO₃
M_r	304.76
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	11.9005 (12), 5.7971 (8), 22.608 (2)
β (°)	93.972 (1)
V (Å³)	1555.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.48 × 0.39 × 0.34

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.889, 0.919
No. of measured, independent and observed [I > 2σ(I)] reflections	7519, 2789, 1585
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.186, 1.05
No. of reflections	2789
No. of parameters	192
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.51

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Acknowledgements

The research was supported by the Open Foundation of Key Disciplines within the Zhejiang Provincial Key Disciplines.

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