4-(4-Chloro-phen-yl)-7,7-dimethyl-7,8-dihydro-4H-1-benzopyran-2,5(3H,6H)-dione.

The title compound, C(17)H(17)ClO(3), has been synthesized by the reaction of p-chloro-benzaldehyde, isopropyl-idene malonate and 5,5-dimethyl-cyclo-hexane-1,3-dione with triethyl-benzyl-ammonium chloride in water as a green solvent. The six membered pyran-one ring of the hexa-hydro-coumarin system has a screw-boat conformation while the dimethyl-cyclo-hexenone 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 = 304.76

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.062

wR(F 2) = 0.186

S = 1.05

2789 reflections

192 parameters

H-atom parameters constrained

Δρmax = 0.49 e Å−3

Δρmin = −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.

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C17H17ClO3	F(000) = 640
Mr = 304.76	Dx = 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

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

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(Fo2) + (0.0667P)2 + 1.4872P] where P = (Fo2 + 2Fc2)/3
2789 reflections	(Δ/σ)max < 0.001
192 parameters	Δρmax = 0.49 e Å−3
0 restraints	Δρmin = −0.51 e Å−3
0 constraints

	x	y	z	Uiso*/Ueq
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*

	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)

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)