Three closely related (2E,2'E)-3,3'-(1,4-phenyl-ene)bis-[1-(meth-oxy-phen-yl)prop-2-en-1-ones]: supra-molecular assemblies in one dimension mediated by hydrogen bonding and C-H⋯π inter-actions.

In the title compounds, (2E,2'E)-3,3'-(1,4-phenyl-ene)bis-[1-(2-meth-oxy-phen-yl)prop-2-en-1-one], C26H22O4 (I), (2E,2'E)-3,3'-(1,4-phenyl-ene)bis-[1-(3-meth-oxy-phen-yl)prop-2-en-1-one], C26H22O4 (II) and (2E,2'E)-3,3'-(1,4-phenyl-ene)bis-[1-(3,4-di-meth-oxy-phen-yl)prop-2-en-1-one], C28H26O6 (III), the asymmetric unit consists of a half-mol-ecule, completed by crystallographic inversion symmetry. The dihedral angles between the central and terminal benzene rings are 56.98 (8), 7.74 (7) and 7.73 (7)° for (I), (II) and (III), respectively. In the crystal of (I), mol-ecules are linked by pairs of C-H⋯π inter-actions into chains running parallel to [101]. The packing for (II) and (III), features inversion dimers linked by pairs of C-H⋯O hydrogen bonds, forming R22(16) and R22(14) ring motifs, respectively, as parts of [201] and [101] chains, respectively.

Chemical context

Chalcones and their derivatives are natural or synthetic 1,3-diaryl-2-propenones that may exist in cis and trans isomeric forms, the trans form being thermodynamically stable. The α,β-unsaturated enone C=C—C(=O)—C moiety in the chalcone structure plays an important role in the biological activities of these species (Husain et al., 2013 ▸; Abdel Ghani et al., 2008 ▸). As a result of the -enone system, these mol­ecules present relatively low redox potentials and have a greater probability of undergoing electron-transfer reactions. Apart from the biological activities, the photophysical properties of chalcone derivatives also attracted considerable attention from both chemists and physicists. Many chalcone derivatives have been reported in relation to non-linear optics (NLO), photorefractive polymers, holographic recording materials and fluorescent probes for sensing metal ions (Ruzié et al., 2009 ▸; Wei et al., 2011 ▸; Chandra Shekhara Shetty et al., 2016 ▸). As part of our studies in this area, we report herein the syntheses and structures of three new bis­chalcone derivatives, (2E,2′E)-3,3′-(1,4-phenyl­ene)bis­(1-(2-meth­oxy­phen­yl)prop-2-en-1-one), C26H22O4 (I), (2E,2′E)-3,3′-(1,4-phenyl­ene)bis­(1-(3-meth­oxy­phen­yl)prop-2-en-1-one), C26H22O4 (II) and (2E,2′E)-3,3′-(1,4-phenyl­ene)bis­(1-(3,4-di­meth­oxy­phen­yl)prop-2-en-1-one), C28H26O6 (III).

Structural commentary

The mol­ecular structures of (I)–(III) are shown in Figs. 1 ▸–3 ▸ ▸, respectively. The asymmetric unit of each compound consists of a half-mol­ecule, with the complete mol­ecule generated by a crystallographic inversion centre at the centroid of the central benzene ring.

Figure 1

The mol­ecular structure of (I), showing 40% probability displacement ellipsoids. [Symmetry code: (A) −x, 1 − y, −z.]

Figure 2

The mol­ecular structure of (II), showing 40% probability displacement ellipsoids. [Symmetry code: (A) 1 − x, 1 − y, 1 − z.]

Figure 3

The mol­ecular structure of (III), showing 40% probability displacement ellipsoids. [Symmetry code: (A) 2 − x, −y, 1 − z.]

Each compound is constructed from two aromatic rings (centre benzene and terminal meth­oxy­phenyl rings), which are linked by a C=C—C(=O)—C enone bridge. Despite having an extra meth­oxy substituent, the conformation of compounds (II) and (III) are very similar, as indicated by the dihedral angles between the rings of 7.74 (7) and 7.73 (7)°, respectively. The enone linkage moiety of compounds (II) and (III) has similar torsion angles [O1—C7—C8—C9 = 0.2 (2) and 7.3 (2)°, respectively], but compound (II) has a higher overall planarity than compound (III), as its enone bridge forms a smaller torsion angle with the meth­oxy­phenyl ring [C1—C6—C7—O1 = −6.5 (2)°] and benzene ring [C8—C9—C10—C11 = −1.7 (2)°; C1—C6—C7—O1 = 7.3 (2)° and C8—C9—C10—C11 = −5.6 (2)° in (III)]. Compared to the nearly coplanar arrangement of rings in compounds (II) and (III), compound (I) is substanti­ally twisted [O1—C7—C8—C9 = −13.5 (2)° and C1—C6—C7—O1 = 143.60 (15)°] about the enone bridge, which may arise from steric repulsion with the ortho-O2 atom. Hence, the dihedral angle between the 2-meth­oxy­phenyl and benzene rings in (I) increases to 56.98 (8)°. Key torsion angles are tabulated in Table 1 ▸. The C atoms of the meth­oxy groups are close to the planes of their attached rings in all cases: for (I), deviation of C13 = 0.163 (2) Å, for (II), deviation of C13 = 0.329 (2) Å, and for (III), deviations of C13 and C14 = 0.091 (2) and −0.266 (2) Å, respectively.

Table 1

Selected torsion and dihedral angles (°) for compounds (I)–(III)

Dihedral 1 is the dihedral angle between the mean planes of the terminal meth­oxy­phenyl and central benzene rings.

Compound	C1—C6—C7—O1	O1—C7—C8—C9	C8—C9—C10—C11	Dihedral 1
(I)	−13.5 (2)	143.60 (15)	167.44 (15)	56.98 (8)
(II)	0.2 (2)	6.5 (2)	−1.6 (2)	7.74 (7)
(III)	7.3 (2)	7.3 (2)	−5.6 (2)	7.73 (7)

Supra­molecular features

The packing of (I) is consolidated by a weak C—H⋯π contact (Table 2 ▸) involving a hydrogen atom from the phenyl ring and the centroid of the central benzene ring (C10–C12/C10A–C12A). This C—H⋯π inter­action connects the mol­ecules of (I) into chains parallel to the [101] direction with a C—H⋯π distance of 2.74 Å (Fig. 4 ▸). In the supra­molecular assemblies of compounds (II) and (III), the mol­ecules are connected by pairs of C—H⋯O hydrogen bonds (Table 2 ▸) into inversion dimers, which form (16) and (14) ring motifs, respectively. The dimers are parts of [201] chains (Fig. 5 ▸) in (II), while mol­ecules in compound (III) are parts of chains propagating in the [101] direction (Fig. 6 ▸).

Table 2

Hydrogen-bonding geometry (Å, °) for compounds (I)–(III)

Cg1 is the centroid of the C10–C12/C10A–C12A ring.

Compound	D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
(I)	C5—H5A⋯Cg1i	0.93	2.74	3.491 (3)	139
(II)	C13—H13C⋯O1ii	0.96	2.60	3.503 (3)	157
(III)	C12—H12A⋯O1iii	0.96	2.47	3.337 (3)	156

Symmetry codes: (i) 1 + x, y, 1 + z; (ii) 3 − x, 1 − y, 2 − z; (iii) 1 − x, −y, −z.

Figure 4

Fragment of a [101] chain of mol­ecules of (I) linked by pairs of weak C—H⋯π inter­actions (dashed lines).

Figure 5

Fragment of a [201] chain of mol­ecules of (II) linked by pairs of weak C—H⋯O inter­actions (dashed lines).

Figure 6

Fragment of a [101] chain of mol­ecules of (III) linked by pairs of weak C—H⋯O inter­actions (dashed lines).

Database survey

A search of the Cambridge Structural Database (CSD, Version 5.38, last update November 2016; Groom et al., 2016 ▸) using (2E,2′E)-3,3′-(1,4-phenyl­ene)bis­(1-phenyl­prop-2-en-1-one) as the main skeleton, revealed the presence of four structures containing the bis­chalcone moiety with different substituents, similar to the title compounds in this study. These include 3,3′-(1,4-phenyl­ene)bis­[1-(X)prop-2-en-1-one], where X = 2-hy­droxy­phenyl (DIDNUB; Gaur & Mishra, 2013 ▸), 4-chloro­phenyl (KIKFUG; Harrison et al., 2007 ▸), 4-meth­oxy­phenyl (UDUPUF; Harrison et al., 2007a ▸) and 3,4-meth­oxy­phenyl (UDUQAM; Harrison et al., 2007b ▸). It is notable that UDUPUF and UDUQAH are positional isomers of compounds (I) and (II), and (III), respectively, differing from them only in the location of the meth­oxy substituent (see scheme below). The dihedral angles between the central and terminal phenyl ring in these compounds vary from 10.9 to 46.3°. In terms of the title compounds, (II) and (III) are more planar [7.74 (7) and 7.73 (7)°] while compound (I) is more twisted [56.98 (8)°]. The supra­molecular assembly in UDUPUF also depends upon a single C—H⋯O hydrogen bond between inversion-related pairs of mol­ecules, forming a centrosymmetric dimer.

Synthesis and crystallization

A mixture of the corresponding meth­oxy­aceto­phenone (0.02 mol) and terephthaldi­aldehyde (0.01 mol) was dissolved in methanol (20 ml). A catalytic amount of NaOH was added to the solution dropwise with vigorous stirring. The reaction mixtures were stirred for about 5–6 h at room temperature. The resultant crude products were filtered, washed successively with distilled water and recrystallized from ethanol to obtain the title compounds. Yellow blocks [(I) and (III)] and yellow needles (II) were recrystallized using the solvents noted below.

(2 ,2′ )-3,3′-(1,4-phenyl­ene)bis­(1-(2-meth­oxy­phen­yl)prop-2-en-1-one), C

Solvent for growing crystals: acetone; yield 85%, m.p. 429–431 K. FT–IR [ATR (solid) cm−1]: 3010 (Ar, C—H, ν), 2945 (methyl, C—H, νs), 2842 (methyl, C—H, ν), 1658 (C=O, ν), 1598, 1417(Ar, C=C, ν), 1245, 1055 (C—O, ν). 1H NMR (500 MHz, CDCl3): δ ppm 7.677–7.632 (m, 8H, 5CH, 8CH, 11CH, 12CH), 7.536–7.504 (t, 2H, J = 8.0 Hz 3CH), 7.496–7.437 (d, 2H, J = 15.9 Hz, 9CH), 7.095–7.065 (t, 2H, J = 8.0 Hz, 4CH), 7.048–7.031 (d, 2H, J = 8.0 Hz, 2CH), 3.944 (s, 6H, 13CH3). 13C NMR (125 MHz, CDCl3): δ ppm 192.61 (C7), 158.23 (C1), 141.48 (C9), 136.95 (C10), 133.09 (C3), 130.47 (C5), 129.17 (C6), 128.84 (C11, C12), 127.91 (C4), 120.84 (C8), 111.69 (C2), 55.80 (C13).

(2 ,2′ )-3,3′-(1,4-phenyl­ene)bis­(1-(3-meth­oxy­phen­yl)prop-2-en-1-one), C

Solvent for growing crystals: chloro­form and methanol; yield 85%, m.p. 444–446 K. FT–IR [ATR (solid) cm−1]: 3074 (Ar, C—H, ν), 2952 (methyl, C—H, νs), 2839 (methyl, C—H, ν), 1658 (C=O, ν), 1582, 1414 (Ar, C=C, ν), 1259, 1022 (C—O, ν). 1H NMR (500 MHz, CDCl3): δ ppm 7.855–7.823 (d, 2H, J = 15.7 Hz, 8CH), 7.722 (s, 4H, 11CH, 12CH) , 7.650–7.635 (d, 2H, J = 8.0 Hz, 5CH), 7.606–7.574 (m, 2H, 1CH, 9CH), 7.473–441 (t, 2H, J = 8.0 Hz, 4CH), 7.189–7.172 (d, 2H, J = 8.0 Hz, 3CH), 3.924 (s, 6H, 13CH3). 13C NMR (125 MHz, CDCl3): δ ppm 189.99 (C7), 159.99 (C2), 143.57 (C9), 139.46 (C10), 136.92 (C6), 129.65 (C5), 128.98 (C11, C12), 123.14 (C8), 121.08 (C3), 119.45 (C4), 112.96 (C1), 55.53 (C13)

(2 ,2′ )-3,3′-(1,4-phenyl­ene)bis­(1-(3,4-di­meth­oxy­phen­yl)prop-2-en-1-one), C

Solvent for growing crystals: acetone; yield 85%, m.p. 479–481 K. FT–IR [ATR (solid) cm−1]: 3018 (Ar, C—H, ν), 2962 (methyl, C—H, νs), 2836 (methyl, C—H, ν), 1651 (C=O, ν), 1592, 1418 (Ar, C=C, ν), 1240, 1017 (C—O, ν). 1H NMR (500 MHz, CDCl3): δ ppm 7.857–7.826 (d, 2H, J = 15.6 Hz, 8CH), 7.740–7.720 (m, 6H, 5CH, 11CH, 12CH), 7.666 (s, 2H, 1CH), 7.651–7.619 (d, 2H, J = 15.6 Hz, 9CH), 6.984–6.967 (d, 2H, J = 8.4 Hz, 4CH), 4.012–4.009 (d, 12H, 13CH3, 14CH3). 13C NMR (125 MHz, CDCl3): δ ppm 188.34 (C7), 153.47 (C3), 149.37 (C2), 142.80 (C9), 136.94 (C10), 131.22 (C6), 128.89 (C11, C12), 123.11 (C5), 122.62 (C8), 110.82 (C4), 110.01 (C1), 56.15 (C14), 66.10 (C13)

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. In (I), (II) and (III), the C-bound H atoms were positioned geometrically [C—H = 0.93–0.96 Å] and refined using a riding model with U iso(H) = 1.5U eq(C-meth­yl) and 1.2U eq(C) for other H atoms.

Table 3

Experimental details

	(I)	(II)	(III)
Crystal data
Chemical formula	C26H22O4	C26H22O4	C28H26O6
M r	398.43	398.43	458.49
Crystal system, space group	Monoclinic, P21/c	Monoclinic, P21/c	Monoclinic, P21/n
Temperature (K)	294	294	294
a, b, c (Å)	7.1078 (11), 24.544 (4), 6.0449 (9)	5.2626 (5), 15.6157 (14), 12.4824 (11)	6.9595 (6), 21.0272 (17), 8.3297 (7)
β (°)	101.898 (2)	98.760 (2)	103.602 (2)
V (Å3)	1031.9 (3)	1013.83 (16)	1184.77 (17)
Z	2	2	2
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm−1)	0.09	0.09	0.09
Crystal size (mm)	0.39 × 0.35 × 0.18	0.90 × 0.48 × 0.09	0.35 × 0.27 × 0.16
Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector	Bruker APEXII DUO CCD area-detector	Bruker APEXII DUO CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2012 ▸)	Multi-scan (SADABS; Bruker, 2012 ▸)	Multi-scan (SADABS; Bruker, 2012 ▸)
T min, T max	0.883, 0.985	0.874, 0.992	0.890, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	8322, 2183, 1705	17791, 2458, 1574	12532, 3165, 2328
R int	0.024	0.043	0.030
(sin θ/λ)max (Å−1)	0.634	0.662	0.683
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.040, 0.119, 1.03	0.044, 0.132, 1.03	0.049, 0.136, 1.04
No. of reflections	2183	2458	3165
No. of parameters	137	137	156
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.19, −0.14	0.14, −0.14	0.20, −0.16

Computer programs: APEX2 and SAINT (Bruker, 2012 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2013 (Sheldrick, 2015 ▸), Mercury (Macrae et al., 2006 ▸) and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) global, I, II, III. DOI: 10.1107/S2056989017007460/hb7678sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017007460/hb7678Isup2.hkl

Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989017007460/hb7678IIsup3.hkl

Structure factors: contains datablock(s) III. DOI: 10.1107/S2056989017007460/hb7678IIIsup4.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989017007460/hb7678Isup5.cml

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989017007460/hb7678IIsup6.cml

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989017007460/hb7678IIIsup7.cml

CCDC references: 1449626, 1449625, 1449624

Additional supporting information: crystallographic information; 3D view; checkCIF report

C26H22O4	F(000) = 420
Mr = 398.43	Dx = 1.282 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.1078 (11) Å	Cell parameters from 3004 reflections
b = 24.544 (4) Å	θ = 2.9–26.4°
c = 6.0449 (9) Å	µ = 0.09 mm−1
β = 101.898 (2)°	T = 294 K
V = 1031.9 (3) Å3	Block, yellow
Z = 2	0.39 × 0.35 × 0.18 mm

Bruker APEXII DUO CCD area-detector diffractometer	2183 independent reflections
Radiation source: fine-focus sealed tube	1705 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
φ and ω scans	θmax = 26.8°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −8→8
Tmin = 0.883, Tmax = 0.985	k = −24→31
8322 measured reflections	l = −7→7

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040	H-atom parameters constrained
wR(F2) = 0.119	w = 1/[σ2(Fo2) + (0.0541P)2 + 0.2315P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
2183 reflections	Δρmax = 0.19 e Å−3
137 parameters	Δρmin = −0.14 e Å−3
0 restraints

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.

	x	y	z	Uiso*/Ueq
O1	0.51518 (16)	0.40818 (5)	0.74340 (18)	0.0615 (4)
O2	0.57299 (19)	0.32593 (5)	0.2133 (2)	0.0652 (4)
C1	0.7420 (2)	0.33535 (6)	0.3621 (3)	0.0492 (4)
C2	0.9148 (3)	0.31024 (8)	0.3517 (4)	0.0689 (5)
H2A	0.9237	0.2877	0.2307	0.083*
C3	1.0731 (3)	0.31908 (9)	0.5223 (4)	0.0802 (6)
H3A	1.1891	0.3026	0.5138	0.096*
C4	1.0640 (3)	0.35160 (8)	0.7040 (4)	0.0731 (6)
H4A	1.1715	0.3565	0.8194	0.088*
C5	0.8930 (2)	0.37687 (7)	0.7125 (3)	0.0545 (4)
H5A	0.8854	0.3988	0.8357	0.065*
C6	0.7315 (2)	0.37030 (6)	0.5413 (2)	0.0420 (3)
C7	0.5545 (2)	0.40138 (6)	0.5584 (2)	0.0426 (3)
C8	0.4371 (2)	0.42573 (6)	0.3525 (2)	0.0430 (3)
H8A	0.4840	0.4266	0.2198	0.052*
C9	0.2652 (2)	0.44645 (6)	0.3551 (2)	0.0416 (3)
H9A	0.2239	0.4435	0.4909	0.050*
C10	0.13276 (19)	0.47340 (5)	0.1704 (2)	0.0379 (3)
C11	−0.0569 (2)	0.48284 (6)	0.1921 (2)	0.0417 (3)
H11A	−0.0958	0.4713	0.3222	0.050*
C12	0.18710 (19)	0.49116 (6)	−0.0255 (2)	0.0413 (3)
H12A	0.3122	0.4854	−0.0442	0.050*
C13	0.5741 (4)	0.29130 (8)	0.0256 (3)	0.0783 (6)
H13A	0.4472	0.2896	−0.0672	0.117*
H13B	0.6140	0.2554	0.0785	0.117*
H13C	0.6619	0.3054	−0.0614	0.117*

	U11	U22	U33	U12	U13	U23
O1	0.0571 (7)	0.0849 (9)	0.0427 (6)	0.0192 (6)	0.0106 (5)	0.0041 (6)
O2	0.0741 (8)	0.0619 (8)	0.0550 (7)	0.0175 (6)	0.0022 (6)	−0.0104 (6)
C1	0.0528 (9)	0.0429 (8)	0.0539 (9)	0.0073 (7)	0.0153 (7)	0.0099 (7)
C2	0.0705 (12)	0.0593 (11)	0.0838 (13)	0.0179 (9)	0.0322 (11)	0.0019 (9)
C3	0.0479 (11)	0.0703 (13)	0.1266 (19)	0.0173 (9)	0.0276 (12)	0.0082 (13)
C4	0.0414 (9)	0.0636 (12)	0.1088 (16)	0.0044 (8)	0.0027 (10)	0.0043 (11)
C5	0.0437 (8)	0.0469 (9)	0.0693 (11)	0.0002 (7)	0.0032 (7)	0.0037 (7)
C6	0.0406 (7)	0.0372 (7)	0.0488 (8)	0.0027 (6)	0.0107 (6)	0.0094 (6)
C7	0.0398 (7)	0.0430 (8)	0.0448 (8)	0.0017 (6)	0.0084 (6)	0.0031 (6)
C8	0.0436 (8)	0.0441 (8)	0.0421 (8)	0.0055 (6)	0.0108 (6)	0.0051 (6)
C9	0.0436 (8)	0.0444 (8)	0.0369 (7)	0.0047 (6)	0.0082 (6)	0.0003 (6)
C10	0.0388 (7)	0.0374 (7)	0.0371 (7)	0.0033 (5)	0.0071 (5)	−0.0034 (5)
C11	0.0422 (7)	0.0478 (8)	0.0370 (7)	0.0042 (6)	0.0127 (6)	0.0026 (6)
C12	0.0339 (7)	0.0485 (8)	0.0430 (7)	0.0043 (6)	0.0116 (6)	−0.0003 (6)
C13	0.1169 (18)	0.0615 (12)	0.0537 (11)	0.0150 (11)	0.0114 (11)	−0.0064 (9)

O1—C7	1.2187 (17)	C7—C8	1.474 (2)
O2—C1	1.364 (2)	C8—C9	1.3267 (19)
O2—C13	1.419 (2)	C8—H8A	0.9300
C1—C2	1.387 (2)	C9—C10	1.4616 (19)
C1—C6	1.396 (2)	C9—H9A	0.9300
C2—C3	1.378 (3)	C10—C12	1.3897 (19)
C2—H2A	0.9300	C10—C11	1.4002 (19)
C3—C4	1.370 (3)	C11—C12i	1.3760 (19)
C3—H3A	0.9300	C11—H11A	0.9300
C4—C5	1.375 (2)	C12—C11i	1.3761 (19)
C4—H4A	0.9300	C12—H12A	0.9300
C5—C6	1.387 (2)	C13—H13A	0.9600
C5—H5A	0.9300	C13—H13B	0.9600
C6—C7	1.4932 (19)	C13—H13C	0.9600
C1—O2—C13	118.66 (14)	C9—C8—C7	120.50 (13)
O2—C1—C2	124.22 (16)	C9—C8—H8A	119.8
O2—C1—C6	115.79 (13)	C7—C8—H8A	119.8
C2—C1—C6	119.87 (16)	C8—C9—C10	127.89 (13)
C3—C2—C1	119.34 (18)	C8—C9—H9A	116.1
C3—C2—H2A	120.3	C10—C9—H9A	116.1
C1—C2—H2A	120.3	C12—C10—C11	118.03 (13)
C4—C3—C2	121.72 (17)	C12—C10—C9	122.99 (12)
C4—C3—H3A	119.1	C11—C10—C9	118.97 (12)
C2—C3—H3A	119.1	C12i—C11—C10	121.57 (12)
C3—C4—C5	118.73 (19)	C12i—C11—H11A	119.2
C3—C4—H4A	120.6	C10—C11—H11A	119.2
C5—C4—H4A	120.6	C11i—C12—C10	120.40 (12)
C4—C5—C6	121.43 (18)	C11i—C12—H12A	119.8
C4—C5—H5A	119.3	C10—C12—H12A	119.8
C6—C5—H5A	119.3	O2—C13—H13A	109.5
C5—C6—C1	118.81 (14)	O2—C13—H13B	109.5
C5—C6—C7	117.92 (14)	H13A—C13—H13B	109.5
C1—C6—C7	123.27 (14)	O2—C13—H13C	109.5
O1—C7—C8	121.49 (13)	H13A—C13—H13C	109.5
O1—C7—C6	119.30 (13)	H13B—C13—H13C	109.5
C8—C7—C6	119.12 (12)
C13—O2—C1—C2	−4.7 (2)	C5—C6—C7—O1	−36.6 (2)
C13—O2—C1—C6	179.21 (14)	C1—C6—C7—O1	143.60 (15)
O2—C1—C2—C3	−174.24 (17)	C5—C6—C7—C8	140.06 (15)
C6—C1—C2—C3	1.7 (3)	C1—C6—C7—C8	−39.8 (2)
C1—C2—C3—C4	0.8 (3)	O1—C7—C8—C9	−13.5 (2)
C2—C3—C4—C5	−1.5 (3)	C6—C7—C8—C9	169.90 (14)
C3—C4—C5—C6	−0.4 (3)	C7—C8—C9—C10	178.03 (14)
C4—C5—C6—C1	2.8 (2)	C8—C9—C10—C12	−13.8 (2)
C4—C5—C6—C7	−177.02 (15)	C8—C9—C10—C11	167.44 (15)
O2—C1—C6—C5	172.83 (13)	C12—C10—C11—C12i	0.1 (2)
C2—C1—C6—C5	−3.4 (2)	C9—C10—C11—C12i	178.90 (13)
O2—C1—C6—C7	−7.4 (2)	C11—C10—C12—C11i	−0.1 (2)
C2—C1—C6—C7	176.38 (14)	C9—C10—C12—C11i	−178.84 (13)

C26H22O4	F(000) = 420
Mr = 398.43	Dx = 1.305 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.2626 (5) Å	Cell parameters from 2940 reflections
b = 15.6157 (14) Å	θ = 2.6–27.7°
c = 12.4824 (11) Å	µ = 0.09 mm−1
β = 98.760 (2)°	T = 294 K
V = 1013.83 (16) Å3	Needle, yellow
Z = 2	0.90 × 0.48 × 0.09 mm

Bruker APEXII DUO CCD area-detector diffractometer	2458 independent reflections
Radiation source: fine-focus sealed tube	1574 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
φ and ω scans	θmax = 28.1°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −6→6
Tmin = 0.874, Tmax = 0.992	k = −20→20
17791 measured reflections	l = −16→16

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044	H-atom parameters constrained
wR(F2) = 0.132	w = 1/[σ2(Fo2) + (0.0567P)2 + 0.138P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
2458 reflections	Δρmax = 0.14 e Å−3
137 parameters	Δρmin = −0.14 e Å−3
0 restraints

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.

	x	y	z	Uiso*/Ueq
O1	1.3466 (2)	0.50160 (7)	0.83740 (9)	0.0753 (4)
O2	2.0704 (2)	0.69588 (8)	1.00094 (10)	0.0771 (4)
C1	1.6959 (3)	0.63162 (9)	0.89251 (12)	0.0502 (4)
H1A	1.6962	0.5856	0.9399	0.060*
C2	1.8795 (3)	0.69465 (10)	0.91308 (12)	0.0552 (4)
C3	1.8786 (3)	0.76279 (11)	0.84322 (15)	0.0680 (5)
H3A	2.0034	0.8052	0.8572	0.082*
C4	1.6943 (3)	0.76859 (11)	0.75284 (16)	0.0723 (5)
H4A	1.6945	0.8150	0.7062	0.087*
C5	1.5086 (3)	0.70582 (10)	0.73089 (13)	0.0583 (4)
H5A	1.3841	0.7100	0.6697	0.070*
C6	1.5086 (3)	0.63679 (9)	0.80022 (11)	0.0461 (3)
C7	1.3200 (3)	0.56519 (9)	0.78002 (11)	0.0499 (4)
C8	1.1041 (3)	0.57169 (10)	0.69022 (12)	0.0525 (4)
H8A	1.0879	0.6207	0.6473	0.063*
C9	0.9345 (3)	0.51020 (9)	0.66922 (11)	0.0505 (4)
H9A	0.9579	0.4629	0.7149	0.061*
C10	0.7126 (2)	0.50652 (9)	0.58281 (10)	0.0450 (3)
C11	0.6491 (3)	0.57310 (9)	0.50998 (11)	0.0514 (4)
H11A	0.7478	0.6228	0.5161	0.062*
C12	0.5587 (3)	0.43363 (10)	0.57116 (11)	0.0522 (4)
H12A	0.5971	0.3884	0.6194	0.063*
C13	2.1228 (4)	0.61900 (12)	1.05960 (15)	0.0766 (6)
H13A	2.2657	0.6275	1.1163	0.115*
H13B	2.1640	0.5748	1.0117	0.115*
H13C	1.9743	0.6024	1.0908	0.115*

	U11	U22	U33	U12	U13	U23
O1	0.0691 (8)	0.0679 (7)	0.0765 (8)	−0.0179 (6)	−0.0289 (6)	0.0158 (6)
O2	0.0662 (8)	0.0728 (8)	0.0805 (8)	−0.0176 (6)	−0.0268 (6)	−0.0033 (6)
C1	0.0443 (8)	0.0523 (8)	0.0509 (8)	−0.0004 (6)	−0.0027 (6)	−0.0046 (6)
C2	0.0451 (8)	0.0557 (9)	0.0609 (9)	−0.0035 (7)	−0.0040 (7)	−0.0106 (7)
C3	0.0536 (10)	0.0573 (10)	0.0894 (12)	−0.0104 (8)	−0.0009 (9)	−0.0014 (9)
C4	0.0619 (11)	0.0631 (10)	0.0882 (13)	−0.0042 (8)	−0.0010 (9)	0.0156 (9)
C5	0.0494 (9)	0.0604 (9)	0.0612 (9)	0.0040 (7)	−0.0042 (7)	0.0039 (7)
C6	0.0369 (7)	0.0511 (8)	0.0480 (7)	0.0035 (6)	−0.0007 (6)	−0.0063 (6)
C7	0.0418 (8)	0.0558 (8)	0.0486 (8)	0.0010 (6)	−0.0044 (6)	−0.0040 (7)
C8	0.0435 (8)	0.0583 (8)	0.0513 (8)	0.0010 (7)	−0.0072 (6)	−0.0015 (6)
C9	0.0450 (8)	0.0561 (8)	0.0464 (7)	0.0026 (6)	−0.0063 (6)	−0.0029 (6)
C10	0.0366 (7)	0.0524 (8)	0.0432 (7)	0.0042 (6)	−0.0031 (6)	−0.0071 (6)
C11	0.0442 (8)	0.0511 (8)	0.0550 (8)	−0.0035 (6)	−0.0048 (7)	−0.0032 (6)
C12	0.0453 (8)	0.0549 (8)	0.0516 (8)	0.0015 (6)	−0.0076 (6)	0.0035 (6)
C13	0.0648 (11)	0.0864 (13)	0.0689 (11)	−0.0082 (9)	−0.0214 (9)	0.0006 (9)

O1—C7	1.2199 (17)	C7—C8	1.4729 (18)
O2—C2	1.3698 (17)	C8—C9	1.310 (2)
O2—C13	1.411 (2)	C8—H8A	0.9300
C1—C2	1.376 (2)	C9—C10	1.4652 (17)
C1—C6	1.3998 (18)	C9—H9A	0.9300
C1—H1A	0.9300	C10—C11	1.3882 (19)
C2—C3	1.375 (2)	C10—C12	1.392 (2)
C3—C4	1.374 (2)	C11—C12i	1.3765 (18)
C3—H3A	0.9300	C11—H11A	0.9300
C4—C5	1.382 (2)	C12—C11i	1.3766 (18)
C4—H4A	0.9300	C12—H12A	0.9300
C5—C6	1.382 (2)	C13—H13A	0.9600
C5—H5A	0.9300	C13—H13B	0.9600
C6—C7	1.491 (2)	C13—H13C	0.9600
C2—O2—C13	117.70 (12)	C9—C8—C7	121.65 (14)
C2—C1—C6	119.92 (14)	C9—C8—H8A	119.2
C2—C1—H1A	120.0	C7—C8—H8A	119.2
C6—C1—H1A	120.0	C8—C9—C10	128.20 (14)
O2—C2—C3	115.34 (13)	C8—C9—H9A	115.9
O2—C2—C1	124.61 (14)	C10—C9—H9A	115.9
C3—C2—C1	120.05 (14)	C11—C10—C12	117.76 (12)
C4—C3—C2	120.36 (15)	C11—C10—C9	122.57 (13)
C4—C3—H3A	119.8	C12—C10—C9	119.67 (13)
C2—C3—H3A	119.8	C12i—C11—C10	120.65 (13)
C3—C4—C5	120.36 (16)	C12i—C11—H11A	119.7
C3—C4—H4A	119.8	C10—C11—H11A	119.7
C5—C4—H4A	119.8	C11i—C12—C10	121.59 (13)
C4—C5—C6	119.78 (14)	C11i—C12—H12A	119.2
C4—C5—H5A	120.1	C10—C12—H12A	119.2
C6—C5—H5A	120.1	O2—C13—H13A	109.5
C5—C6—C1	119.53 (13)	O2—C13—H13B	109.5
C5—C6—C7	122.86 (12)	H13A—C13—H13B	109.5
C1—C6—C7	117.59 (13)	O2—C13—H13C	109.5
O1—C7—C8	120.62 (13)	H13A—C13—H13C	109.5
O1—C7—C6	119.81 (12)	H13B—C13—H13C	109.5
C8—C7—C6	119.57 (13)
C13—O2—C2—C3	−164.12 (17)	C1—C6—C7—O1	−6.5 (2)
C13—O2—C2—C1	16.2 (2)	C5—C6—C7—C8	−7.6 (2)
C6—C1—C2—O2	179.81 (14)	C1—C6—C7—C8	173.97 (13)
C6—C1—C2—C3	0.2 (2)	O1—C7—C8—C9	0.2 (2)
O2—C2—C3—C4	−179.41 (16)	C6—C7—C8—C9	179.71 (14)
C1—C2—C3—C4	0.3 (3)	C7—C8—C9—C10	−179.20 (14)
C2—C3—C4—C5	−0.3 (3)	C8—C9—C10—C11	−1.7 (2)
C3—C4—C5—C6	0.0 (3)	C8—C9—C10—C12	177.64 (16)
C4—C5—C6—C1	0.5 (2)	C12—C10—C11—C12i	−0.4 (2)
C4—C5—C6—C7	−177.93 (16)	C9—C10—C11—C12i	178.90 (14)
C2—C1—C6—C5	−0.5 (2)	C11—C10—C12—C11i	0.4 (2)
C2—C1—C6—C7	177.94 (14)	C9—C10—C12—C11i	−178.91 (14)
C5—C6—C7—O1	171.91 (15)

C28H26O6	F(000) = 484
Mr = 458.49	Dx = 1.285 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.9595 (6) Å	Cell parameters from 3549 reflections
b = 21.0272 (17) Å	θ = 2.7–28.5°
c = 8.3297 (7) Å	µ = 0.09 mm−1
β = 103.602 (2)°	T = 294 K
V = 1184.77 (17) Å3	Block, yellow
Z = 2	0.35 × 0.27 × 0.16 mm

Bruker APEXII DUO CCD area-detector diffractometer	3165 independent reflections
Radiation source: fine-focus sealed tube	2328 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
φ and ω scans	θmax = 29.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −9→8
Tmin = 0.890, Tmax = 0.985	k = −28→26
12532 measured reflections	l = −11→11

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049	H-atom parameters constrained
wR(F2) = 0.136	w = 1/[σ2(Fo2) + (0.0557P)2 + 0.2808P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
3165 reflections	Δρmax = 0.20 e Å−3
156 parameters	Δρmin = −0.16 e Å−3
0 restraints

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.

	x	y	z	Uiso*/Ueq
O1	0.26810 (16)	0.04480 (7)	0.05640 (13)	0.0667 (4)
O2	−0.37696 (15)	0.15896 (5)	0.01870 (14)	0.0560 (3)
O3	−0.33472 (18)	0.22511 (6)	0.28240 (17)	0.0694 (4)
C1	−0.04399 (19)	0.11677 (6)	0.10365 (16)	0.0377 (3)
H1A	−0.0610	0.0919	0.0090	0.045*
C2	−0.1959 (2)	0.15447 (6)	0.12601 (17)	0.0399 (3)
C3	−0.1726 (2)	0.19126 (7)	0.2696 (2)	0.0459 (3)
C4	0.0049 (2)	0.19044 (7)	0.3851 (2)	0.0525 (4)
H4A	0.0217	0.2154	0.4796	0.063*
C5	0.1585 (2)	0.15265 (7)	0.36105 (18)	0.0469 (4)
H5A	0.2779	0.1525	0.4398	0.056*
C6	0.13686 (19)	0.11510 (6)	0.22134 (16)	0.0369 (3)
C7	0.2924 (2)	0.07224 (7)	0.18910 (16)	0.0413 (3)
C8	0.4765 (2)	0.06233 (7)	0.31697 (16)	0.0419 (3)
H8A	0.4879	0.0794	0.4218	0.050*
C9	0.62488 (19)	0.02971 (7)	0.28517 (16)	0.0385 (3)
H9A	0.6062	0.0140	0.1782	0.046*
C10	0.81526 (18)	0.01514 (6)	0.39711 (15)	0.0348 (3)
C11	0.8724 (2)	0.03954 (7)	0.55600 (16)	0.0422 (3)
H11A	0.7872	0.0664	0.5947	0.051*
C12	0.9466 (2)	−0.02452 (7)	0.34276 (16)	0.0429 (3)
H12A	0.9117	−0.0412	0.2364	0.051*
C13	−0.4046 (3)	0.12540 (11)	−0.1316 (2)	0.0727 (6)
H13A	−0.5375	0.1316	−0.1950	0.109*
H13B	−0.3816	0.0809	−0.1092	0.109*
H13C	−0.3135	0.1409	−0.1929	0.109*
C14	−0.3309 (3)	0.25570 (12)	0.4350 (3)	0.0920 (8)
H14A	−0.4595	0.2727	0.4331	0.138*
H14B	−0.2360	0.2896	0.4516	0.138*
H14C	−0.2948	0.2255	0.5234	0.138*

	U11	U22	U33	U12	U13	U23
O1	0.0427 (6)	0.1049 (10)	0.0443 (6)	0.0272 (6)	−0.0066 (5)	−0.0257 (6)
O2	0.0389 (6)	0.0653 (7)	0.0565 (6)	0.0185 (5)	−0.0031 (5)	−0.0026 (5)
O3	0.0576 (7)	0.0680 (8)	0.0820 (9)	0.0234 (6)	0.0149 (6)	−0.0190 (7)
C1	0.0349 (7)	0.0413 (7)	0.0355 (6)	0.0040 (5)	0.0056 (5)	0.0013 (5)
C2	0.0344 (7)	0.0387 (7)	0.0443 (7)	0.0040 (5)	0.0048 (5)	0.0051 (6)
C3	0.0434 (8)	0.0380 (7)	0.0578 (9)	0.0059 (6)	0.0149 (7)	−0.0026 (6)
C4	0.0523 (9)	0.0492 (9)	0.0544 (9)	−0.0001 (7)	0.0092 (7)	−0.0169 (7)
C5	0.0378 (7)	0.0522 (8)	0.0469 (8)	−0.0014 (6)	0.0024 (6)	−0.0087 (7)
C6	0.0308 (6)	0.0414 (7)	0.0372 (6)	0.0006 (5)	0.0052 (5)	0.0015 (5)
C7	0.0306 (7)	0.0553 (8)	0.0357 (6)	0.0048 (6)	0.0030 (5)	−0.0022 (6)
C8	0.0327 (7)	0.0572 (8)	0.0325 (6)	0.0042 (6)	0.0010 (5)	−0.0027 (6)
C9	0.0303 (7)	0.0504 (8)	0.0316 (6)	0.0003 (5)	0.0010 (5)	0.0006 (5)
C10	0.0274 (6)	0.0443 (7)	0.0306 (6)	−0.0005 (5)	0.0026 (5)	0.0037 (5)
C11	0.0323 (7)	0.0559 (8)	0.0365 (7)	0.0091 (6)	0.0040 (5)	−0.0049 (6)
C12	0.0358 (7)	0.0574 (9)	0.0316 (6)	0.0054 (6)	0.0004 (5)	−0.0066 (6)
C13	0.0523 (11)	0.0953 (14)	0.0582 (10)	0.0179 (10)	−0.0117 (8)	−0.0150 (10)
C14	0.0722 (14)	0.0934 (16)	0.1191 (19)	0.0054 (12)	0.0398 (13)	−0.0499 (15)

O1—C7	1.2229 (17)	C8—C9	1.318 (2)
O2—C2	1.3660 (16)	C8—H8A	0.9300
O2—C13	1.410 (2)	C9—C10	1.4621 (16)
O3—C3	1.3593 (18)	C9—H9A	0.9300
O3—C14	1.419 (2)	C10—C11	1.3877 (18)
C1—C2	1.3688 (19)	C10—C12	1.3893 (19)
C1—C6	1.4022 (18)	C11—C12i	1.3781 (18)
C1—H1A	0.9300	C11—H11A	0.9300
C2—C3	1.401 (2)	C12—C11i	1.3780 (18)
C3—C4	1.376 (2)	C12—H12A	0.9300
C4—C5	1.384 (2)	C13—H13A	0.9600
C4—H4A	0.9300	C13—H13B	0.9600
C5—C6	1.3848 (19)	C13—H13C	0.9600
C5—H5A	0.9300	C14—H14A	0.9600
C6—C7	1.4807 (19)	C14—H14B	0.9600
C7—C8	1.4756 (17)	C14—H14C	0.9600
C2—O2—C13	117.30 (12)	C7—C8—H8A	119.4
C3—O3—C14	117.82 (15)	C8—C9—C10	128.07 (12)
C2—C1—C6	120.95 (13)	C8—C9—H9A	116.0
C2—C1—H1A	119.5	C10—C9—H9A	116.0
C6—C1—H1A	119.5	C11—C10—C12	118.04 (11)
O2—C2—C1	125.04 (13)	C11—C10—C9	122.96 (12)
O2—C2—C3	115.10 (12)	C12—C10—C9	119.00 (12)
C1—C2—C3	119.85 (12)	C12i—C11—C10	120.96 (13)
O3—C3—C4	125.24 (14)	C12i—C11—H11A	119.5
O3—C3—C2	115.11 (13)	C10—C11—H11A	119.5
C4—C3—C2	119.65 (13)	C11i—C12—C10	121.00 (12)
C3—C4—C5	120.21 (14)	C11i—C12—H12A	119.5
C3—C4—H4A	119.9	C10—C12—H12A	119.5
C5—C4—H4A	119.9	O2—C13—H13A	109.5
C4—C5—C6	120.91 (13)	O2—C13—H13B	109.5
C4—C5—H5A	119.5	H13A—C13—H13B	109.5
C6—C5—H5A	119.5	O2—C13—H13C	109.5
C5—C6—C1	118.41 (12)	H13A—C13—H13C	109.5
C5—C6—C7	124.03 (12)	H13B—C13—H13C	109.5
C1—C6—C7	117.55 (12)	O3—C14—H14A	109.5
O1—C7—C8	119.85 (12)	O3—C14—H14B	109.5
O1—C7—C6	119.98 (12)	H14A—C14—H14B	109.5
C8—C7—C6	120.17 (12)	O3—C14—H14C	109.5
C9—C8—C7	121.13 (12)	H14A—C14—H14C	109.5
C9—C8—H8A	119.4	H14B—C14—H14C	109.5
C13—O2—C2—C1	−4.5 (2)	C2—C1—C6—C5	−0.1 (2)
C13—O2—C2—C3	176.83 (15)	C2—C1—C6—C7	178.99 (13)
C6—C1—C2—O2	−179.73 (13)	C5—C6—C7—O1	−173.70 (15)
C6—C1—C2—C3	−1.1 (2)	C1—C6—C7—O1	7.3 (2)
C14—O3—C3—C4	−8.5 (3)	C5—C6—C7—C8	6.5 (2)
C14—O3—C3—C2	170.79 (17)	C1—C6—C7—C8	−172.50 (13)
O2—C2—C3—O3	1.14 (19)	O1—C7—C8—C9	7.3 (2)
C1—C2—C3—O3	−177.63 (13)	C6—C7—C8—C9	−172.95 (14)
O2—C2—C3—C4	−179.52 (14)	C7—C8—C9—C10	−179.46 (13)
C1—C2—C3—C4	1.7 (2)	C8—C9—C10—C11	−5.6 (2)
O3—C3—C4—C5	178.13 (15)	C8—C9—C10—C12	174.89 (15)
C2—C3—C4—C5	−1.1 (2)	C12—C10—C11—C12i	−0.4 (2)
C3—C4—C5—C6	0.0 (2)	C9—C10—C11—C12i	−179.97 (14)
C4—C5—C6—C1	0.7 (2)	C11—C10—C12—C11i	0.4 (2)
C4—C5—C6—C7	−178.35 (14)	C9—C10—C12—C11i	179.98 (13)