2-(4-Methyl-phen-yl)-7-(2-methyl-prop-oxy)-4H-chromen-4-one-6-chloro-2-(4-methyl-phen-yl)-7-(2-methyl-prop-oxy)-4H-chromen-4-one (19/1).

The title co-crystal, 0.95C(20)H(20)O(3)·0.05C(20)H(19)ClO(3), arises as the chloride carried over during the synthesis shares a position with an aromatic H atom; the partial occupancies are 0.947 (2) and 0.053 (2) for H and Cl, respectively. The mol-ecular structure is stabilized by intra-molecular C-H⋯O contacts, forming pseudo five- and six-membered rings with S(5) and S(6) graph-set motifs, respectively. The crystal structure features π-π stacking inter-actions between the centroids of the central fused ring systems [centroid-centroid distance = 3.501 (2) Å].

Related literature

For background to flavones, see: Hollman et al. (1997 ▶); Yao et al. (2004 ▶). For the biological activity of flavones, see: Harborne & Williams (2000 ▶); Khan & Hasan (2003 ▶); Qin et al. (2008 ▶); Mota et al. (2009 ▶); Prakash et al. (2009 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

0.95C20H20O3·0.05C20H19ClO3

M = 310.19

Triclinic,

a = 9.0371 (2) Å

b = 9.6216 (2) Å

c = 11.0308 (3) Å

α = 75.171 (2)°

β = 65.865 (2)°

γ = 69.833 (1)°

V = 814.20 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 293 K

0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.973, T max = 0.982

18174 measured reflections

3847 independent reflections

2737 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.136

S = 1.06

3847 reflections

219 parameters

H-atom parameters constrained

Δρmax = 0.34 e Å−3

Δρmin = −0.17 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812033430/tk5116sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812033430/tk5116Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812033430/tk5116Isup3.cml

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

0.95C20H20O3·0.05C20H19ClO3	Z = 2
Mr = 310.19	F(000) = 329.6
Triclinic, P1	Dx = 1.265 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 9.0371 (2) Å	Cell parameters from 5339 reflections
b = 9.6216 (2) Å	θ = 3.0–25.0°
c = 11.0308 (3) Å	µ = 0.09 mm−1
α = 75.171 (2)°	T = 293 K
β = 65.865 (2)°	Block, colourless
γ = 69.833 (1)°	0.30 × 0.20 × 0.20 mm
V = 814.20 (4) Å3

Bruker Kappa APEXII CCD diffractometer	3847 independent reflections
Radiation source: fine-focus sealed tube	2737 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω and φ scan	θmax = 27.8°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −11→11
Tmin = 0.973, Tmax = 0.982	k = −12→12
18174 measured reflections	l = −14→14

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.136	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0582P)2 + 0.1669P] where P = (Fo2 + 2Fc2)/3
3847 reflections	(Δ/σ)max = 0.005
219 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.17 e Å−3

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.96616 (14)	−0.37259 (11)	0.75225 (11)	0.0496 (3)
O2	0.73241 (16)	0.33677 (12)	0.64615 (12)	0.0611 (3)
O3	0.72302 (13)	0.01688 (10)	0.47020 (10)	0.0427 (3)
C1	0.9533 (3)	−0.6722 (2)	0.8857 (2)	0.0753 (6)
H1B	1.0079	−0.7685	0.9223	0.113*
H1C	0.8465	−0.6739	0.8881	0.113*
H1A	0.9360	−0.5981	0.9377	0.113*
C2	1.0620 (2)	−0.63483 (17)	0.74312 (17)	0.0502 (4)
H2	1.0725	−0.7099	0.6924	0.060*
C3	1.2383 (2)	−0.6446 (2)	0.7309 (3)	0.0807 (7)
H3C	1.3039	−0.6216	0.6384	0.121*
H3A	1.2900	−0.7440	0.7645	0.121*
H3B	1.2327	−0.5746	0.7820	0.121*
C4	0.9825 (2)	−0.48407 (16)	0.67936 (16)	0.0464 (4)
H4A	1.0526	−0.4655	0.5862	0.056*
H4B	0.8726	−0.4815	0.6828	0.056*
C5	0.90580 (18)	−0.22724 (16)	0.70937 (15)	0.0412 (3)
C6	0.9127 (2)	−0.12487 (17)	0.77583 (16)	0.0471 (4)
H6	0.9567	−0.1590	0.8443	0.057*	0.9470 (18)
C7	0.8550 (2)	0.02482 (17)	0.74021 (16)	0.0467 (4)
H7	0.8601	0.0919	0.7851	0.056*
C8	0.78841 (17)	0.07948 (16)	0.63740 (14)	0.0398 (3)
C9	0.78410 (17)	−0.02488 (15)	0.57358 (14)	0.0373 (3)
C10	0.84152 (17)	−0.17760 (15)	0.60726 (14)	0.0397 (3)
H10	0.8369	−0.2447	0.5623	0.048*
C11	0.72965 (19)	0.23849 (16)	0.59441 (15)	0.0446 (4)
C12	0.67062 (19)	0.27121 (16)	0.48452 (16)	0.0455 (4)
H12	0.6314	0.3707	0.4520	0.055*
C13	0.66968 (17)	0.16449 (15)	0.42691 (15)	0.0406 (3)
C14	0.61702 (18)	0.18806 (16)	0.31181 (15)	0.0425 (3)
C15	0.5271 (2)	0.32770 (17)	0.26928 (16)	0.0485 (4)
H15	0.4986	0.4081	0.3142	0.058*
C16	0.4797 (2)	0.34794 (17)	0.16082 (17)	0.0507 (4)
H16	0.4203	0.4427	0.1334	0.061*
C17	0.5174 (2)	0.23220 (18)	0.09144 (16)	0.0489 (4)
C18	0.6088 (3)	0.09398 (19)	0.13338 (19)	0.0627 (5)
H18	0.6381	0.0141	0.0877	0.075*
C19	0.6579 (2)	0.07170 (18)	0.24164 (19)	0.0587 (5)
H19	0.7191	−0.0227	0.2678	0.070*
C20	0.4595 (2)	0.2551 (2)	−0.02344 (18)	0.0628 (5)
H20A	0.5374	0.2937	−0.1039	0.094*
H20B	0.3498	0.3249	−0.0052	0.094*
H20C	0.4543	0.1615	−0.0348	0.094*
Cl1	0.9913 (10)	−0.1791 (10)	0.9090 (9)	0.060 (3)	0.0530 (18)

	U11	U22	U33	U12	U13	U23
O1	0.0659 (7)	0.0342 (6)	0.0515 (7)	−0.0061 (5)	−0.0312 (6)	−0.0029 (5)
O2	0.0839 (9)	0.0380 (6)	0.0665 (8)	−0.0159 (6)	−0.0280 (7)	−0.0138 (5)
O3	0.0506 (6)	0.0282 (5)	0.0497 (6)	−0.0065 (4)	−0.0231 (5)	−0.0029 (4)
C1	0.1004 (16)	0.0513 (11)	0.0633 (12)	−0.0210 (11)	−0.0291 (12)	0.0109 (9)
C2	0.0599 (10)	0.0339 (8)	0.0580 (10)	−0.0101 (7)	−0.0277 (8)	−0.0004 (7)
C3	0.0635 (12)	0.0462 (10)	0.132 (2)	−0.0063 (9)	−0.0503 (13)	0.0042 (11)
C4	0.0549 (9)	0.0370 (8)	0.0483 (9)	−0.0088 (7)	−0.0225 (7)	−0.0050 (7)
C5	0.0415 (8)	0.0339 (7)	0.0433 (8)	−0.0072 (6)	−0.0135 (7)	−0.0037 (6)
C6	0.0529 (9)	0.0455 (9)	0.0457 (9)	−0.0121 (7)	−0.0212 (7)	−0.0062 (7)
C7	0.0517 (9)	0.0428 (9)	0.0487 (9)	−0.0137 (7)	−0.0164 (7)	−0.0121 (7)
C8	0.0381 (7)	0.0348 (7)	0.0422 (8)	−0.0108 (6)	−0.0075 (6)	−0.0079 (6)
C9	0.0356 (7)	0.0344 (7)	0.0382 (8)	−0.0092 (6)	−0.0102 (6)	−0.0039 (6)
C10	0.0424 (8)	0.0325 (7)	0.0428 (8)	−0.0091 (6)	−0.0142 (7)	−0.0055 (6)
C11	0.0455 (8)	0.0356 (8)	0.0477 (9)	−0.0117 (6)	−0.0086 (7)	−0.0099 (6)
C12	0.0479 (9)	0.0287 (7)	0.0521 (9)	−0.0057 (6)	−0.0146 (7)	−0.0045 (6)
C13	0.0376 (7)	0.0305 (7)	0.0459 (8)	−0.0066 (6)	−0.0111 (6)	−0.0021 (6)
C14	0.0424 (8)	0.0321 (7)	0.0478 (9)	−0.0083 (6)	−0.0149 (7)	−0.0010 (6)
C15	0.0510 (9)	0.0331 (8)	0.0560 (10)	−0.0065 (7)	−0.0190 (8)	−0.0040 (7)
C16	0.0494 (9)	0.0361 (8)	0.0589 (10)	−0.0077 (7)	−0.0224 (8)	0.0062 (7)
C17	0.0473 (9)	0.0475 (9)	0.0483 (9)	−0.0161 (7)	−0.0169 (7)	0.0039 (7)
C18	0.0868 (13)	0.0410 (9)	0.0661 (12)	−0.0078 (9)	−0.0392 (11)	−0.0094 (8)
C19	0.0780 (12)	0.0320 (8)	0.0685 (11)	0.0000 (8)	−0.0408 (10)	−0.0060 (7)
C20	0.0691 (12)	0.0642 (12)	0.0582 (11)	−0.0207 (9)	−0.0303 (9)	0.0033 (9)
Cl1	0.053 (5)	0.061 (6)	0.059 (5)	−0.016 (4)	−0.016 (4)	−0.001 (4)

O1—C5	1.3503 (17)	C7—H7	0.9300
O1—C4	1.4333 (17)	C8—C9	1.3844 (19)
O2—C11	1.2348 (17)	C8—C11	1.457 (2)
O3—C13	1.3589 (16)	C9—C10	1.3852 (19)
O3—C9	1.3762 (17)	C10—H10	0.9300
C1—C2	1.503 (3)	C11—C12	1.439 (2)
C1—H1B	0.9600	C12—C13	1.343 (2)
C1—H1C	0.9600	C12—H12	0.9300
C1—H1A	0.9600	C13—C14	1.470 (2)
C2—C4	1.513 (2)	C14—C19	1.383 (2)
C2—C3	1.514 (2)	C14—C15	1.386 (2)
C2—H2	0.9800	C15—C16	1.377 (2)
C3—H3C	0.9600	C15—H15	0.9300
C3—H3A	0.9600	C16—C17	1.380 (2)
C3—H3B	0.9600	C16—H16	0.9300
C4—H4A	0.9700	C17—C18	1.380 (2)
C4—H4B	0.9700	C17—C20	1.499 (2)
C5—C10	1.379 (2)	C18—C19	1.380 (2)
C5—C6	1.401 (2)	C18—H18	0.9300
C6—C7	1.364 (2)	C19—H19	0.9300
C6—Cl1	1.772 (9)	C20—H20A	0.9600
C6—H6	0.9300	C20—H20B	0.9600
C7—C8	1.400 (2)	C20—H20C	0.9600
C5—O1—C4	118.87 (11)	O3—C9—C8	121.81 (12)
C13—O3—C9	119.23 (11)	O3—C9—C10	115.07 (12)
C2—C1—H1B	109.5	C8—C9—C10	123.12 (13)
C2—C1—H1C	109.5	C5—C10—C9	118.11 (13)
H1B—C1—H1C	109.5	C5—C10—H10	120.9
C2—C1—H1A	109.5	C9—C10—H10	120.9
H1B—C1—H1A	109.5	O2—C11—C12	122.81 (14)
H1C—C1—H1A	109.5	O2—C11—C8	123.12 (14)
C1—C2—C4	112.08 (15)	C12—C11—C8	114.06 (12)
C1—C2—C3	112.10 (17)	C13—C12—C11	122.91 (13)
C4—C2—C3	110.95 (14)	C13—C12—H12	118.5
C1—C2—H2	107.1	C11—C12—H12	118.5
C4—C2—H2	107.1	C12—C13—O3	121.86 (13)
C3—C2—H2	107.1	C12—C13—C14	126.37 (13)
C2—C3—H3C	109.5	O3—C13—C14	111.77 (12)
C2—C3—H3A	109.5	C19—C14—C15	118.04 (14)
H3C—C3—H3A	109.5	C19—C14—C13	120.87 (13)
C2—C3—H3B	109.5	C15—C14—C13	121.09 (14)
H3C—C3—H3B	109.5	C16—C15—C14	120.31 (14)
H3A—C3—H3B	109.5	C16—C15—H15	119.8
O1—C4—C2	107.95 (12)	C14—C15—H15	119.8
O1—C4—H4A	110.1	C15—C16—C17	122.14 (14)
C2—C4—H4A	110.1	C15—C16—H16	118.9
O1—C4—H4B	110.1	C17—C16—H16	118.9
C2—C4—H4B	110.1	C16—C17—C18	117.17 (15)
H4A—C4—H4B	108.4	C16—C17—C20	121.40 (15)
O1—C5—C10	124.33 (13)	C18—C17—C20	121.43 (16)
O1—C5—C6	115.33 (13)	C19—C18—C17	121.49 (16)
C10—C5—C6	120.34 (13)	C19—C18—H18	119.3
C7—C6—C5	120.05 (14)	C17—C18—H18	119.3
C7—C6—Cl1	116.7 (3)	C18—C19—C14	120.84 (15)
C5—C6—Cl1	123.2 (3)	C18—C19—H19	119.6
C7—C6—H6	120.0	C14—C19—H19	119.6
C5—C6—H6	120.0	C17—C20—H20A	109.5
C6—C7—C8	121.26 (13)	C17—C20—H20B	109.5
C6—C7—H7	119.4	H20A—C20—H20B	109.5
C8—C7—H7	119.4	C17—C20—H20C	109.5
C9—C8—C7	117.11 (13)	H20A—C20—H20C	109.5
C9—C8—C11	120.11 (13)	H20B—C20—H20C	109.5
C7—C8—C11	122.75 (13)
C5—O1—C4—C2	176.62 (13)	C7—C8—C11—O2	−0.8 (2)
C1—C2—C4—O1	62.80 (18)	C9—C8—C11—C12	0.0 (2)
C3—C2—C4—O1	−63.37 (19)	C7—C8—C11—C12	178.16 (14)
C4—O1—C5—C10	7.0 (2)	O2—C11—C12—C13	179.05 (15)
C4—O1—C5—C6	−172.61 (13)	C8—C11—C12—C13	0.1 (2)
O1—C5—C6—C7	179.97 (14)	C11—C12—C13—O3	0.9 (2)
C10—C5—C6—C7	0.3 (2)	C11—C12—C13—C14	−177.83 (14)
O1—C5—C6—Cl1	−1.0 (4)	C9—O3—C13—C12	−1.8 (2)
C10—C5—C6—Cl1	179.3 (3)	C9—O3—C13—C14	177.06 (12)
C5—C6—C7—C8	−0.1 (2)	C12—C13—C14—C19	164.68 (16)
Cl1—C6—C7—C8	−179.2 (3)	O3—C13—C14—C19	−14.1 (2)
C6—C7—C8—C9	−0.1 (2)	C12—C13—C14—C15	−14.5 (2)
C6—C7—C8—C11	−178.39 (14)	O3—C13—C14—C15	166.74 (13)
C13—O3—C9—C8	1.8 (2)	C19—C14—C15—C16	0.4 (2)
C13—O3—C9—C10	−177.59 (12)	C13—C14—C15—C16	179.60 (14)
C7—C8—C9—O3	−179.21 (13)	C14—C15—C16—C17	0.6 (2)
C11—C8—C9—O3	−0.9 (2)	C15—C16—C17—C18	−1.4 (2)
C7—C8—C9—C10	0.2 (2)	C15—C16—C17—C20	177.83 (15)
C11—C8—C9—C10	178.47 (13)	C16—C17—C18—C19	1.2 (3)
O1—C5—C10—C9	−179.90 (13)	C20—C17—C18—C19	−178.04 (17)
C6—C5—C10—C9	−0.3 (2)	C17—C18—C19—C14	−0.2 (3)
O3—C9—C10—C5	179.46 (12)	C15—C14—C19—C18	−0.6 (3)
C8—C9—C10—C5	0.0 (2)	C13—C14—C19—C18	−179.81 (16)
C9—C8—C11—O2	−179.02 (14)

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19···O3	0.93	2.38	2.702 (2)	100
C1—H1A···O1	0.96	2.58	2.900 (2)	100

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C19—H19⋯O3	0.93	2.38	2.702 (2)	100
C1—H1A⋯O1	0.96	2.58	2.900 (2)	100