1,5-Bis(4-chloro­phen­yl)-3-(4-methyl­phen­yl)pentane-1,5-dione

Chithiravel, R.; Thiruvalluvar, A.; Muthusubramanian, S.; Butcher, R.J.

doi:10.1107/S1600536813024355

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 10| October 2013| Pages o1508-o1509

doi:10.1107/S1600536813024355

Open

access

1,5-Bis(4-chlorophenyl)-3-(4-methylphenyl)pentane-1,5-dione

R. Chithiravel,^a A. Thiruvalluvar,^b ^* S. Muthusubramanian ^c and R. J. Butcher ^d

^aPostgraduate Research Department of Chemistry, Rajah Serfoji Government College (Autonomous), Thanjavur 613 005, Tamilnadu, India, ^bPostgraduate Research Department of Physics, Rajah Serfoji Government College (Autonomous), Thanjavur 613 005, Tamilnadu, India, ^cDepartment of Organic Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai 625 021, Tamilnadu, India, and ^dDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
^*Correspondence e-mail: thiruvalluvar.a@gmail.com

(Received 29 August 2013; accepted 1 September 2013; online 7 September 2013)

In the title molecule, C₂₄H₂₀Cl₂O₂, the central methylbenzene ring forms dihedral angles of 42.47 (10) and 34.34 (10)° with the terminal 4-chlorophenyl fragments. The dihedral angle between the chlorobenzene rings is 34.45 (11)°. A weak intramolecular C—H⋯O interaction generates an S(6) ring motif. The crystal packing exhibits weak C—H⋯O hydrogen bonds and C—H⋯π interactions.

Related literature

For the synthesis of 1,5-diketones, see: Yang et al. (2005 ); Hirsch & Bailey (1978 ). For the crystal structures of related compounds, see: Qiu et al. (2006 ); Insuasty et al. (2006 ); Jasinski et al. (2007 ); Huang et al. (2008 ); Lei & Bai (2009 ); Dutkiewicz et al. (2010 ); Fun et al. (2011 ). For the applications of delocalized π-systems, see: Burroughes et al. (1990 ); Smith et al. (2005 ); Li et al. (2004 ); Sariciftci et al. (1992 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₂₄H₂₀Cl₂O₂
M_r = 411.30
Monoclinic, P 2₁ /c
a = 18.6794 (11) Å
b = 7.5477 (4) Å
c = 15.5196 (8) Å
β = 103.622 (5)°
V = 2126.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 296 K
0.51 × 0.42 × 0.37 mm

Data collection

Agilent Xcalibur Ruby Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ) T_min = 0.443, T_max = 1.000
14252 measured reflections
4341 independent reflections
3735 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.146
S = 1.07
4341 reflections
255 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C31–C36 methylbenzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O1	0.97	2.56	3.130 (3)	118
C16—H16⋯O5ⁱ	0.93	2.44	3.270 (3)	149
C55—H55⋯Cg2ⁱⁱ	0.93	2.97	3.629 (2)	129
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x, y+1, z.

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: DIRDIF2008 (Beurskens et al., 2008 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL2013 and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813024355/jj2174sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813024355/jj2174Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813024355/jj2174Isup3.cdx

Supporting information file. DOI: 10.1107/S1600536813024355/jj2174Isup4.cml

checkCIF report

Comment top

A simplified green chemistry approach to the Michael-addition reaction using the "Grindstone Chemistry" method for conducting exothermic reactions in the solvent-free mode has been described (Yang et al. 2005). We tested energy saving procedures developed in our laboratory for the preparation of 1,5-diketones starting from fragrant aldehydes and fragrant ketones in the presence of NaOH under solvent-free conditions. Using this method, we obtained the title compound, (I) (Fig. 1). The synthesis of many heterocyclic compounds (Hirsch & Bailey, 1978) form an important synthetic intermediate compounds of 1,5-Diketones. Further, compared to existing methods, the main advantages of the present procedure is fast reaction times, solvent-free, mild, simple, moderately high yields and no side product formation.

The structures of related compounds viz., 3-(2-Chlorophenyl)-1,5-bis(4-nitrophenyl)pentane-1,5-dione (Qiu et al. 2006), 1,5-Bis(4-chlorophenyl)-3- (2-chloroquinolin-3-yl)pentane-1,5-dione (Insuasty et al. 2006), 3-(2-Chlorophenyl)-1,5-bis(4-chlorophenyl)pentane-1,5-dione (Jasinski et al. 2007), 1,5-Bis(4-chlorophenyl)-3-(2-thienyl)pentane-1,5-dione (Huang et al. 2008), 1,5-Bis(4-chlorophenyl)-3-[4-(dimethylamino)phenyl]pentane-1,5-dione (Lei & Bai, 2009), 3-(3-Bromo-4-methoxyphenyl)-1,5-diphenylpentane-1,5-dione (Dutkiewicz et al. 2010) and 1,5-Bis(thiophen-2-yl)-3-(2,4,5-trimethoxyphenyl) pentane-1,5-dione (Fun et al. 2011) have been reported. Many promising applications from linear π-conjugated organic molecules and polymers have attracted considerable interest for organic light-emitting diodes, non-linear optical properties, conductivity, photocells, field effect transistors, and so on due to their delocalized π systems (Burroughes et al., 1990; Smith et al., 2005; Li et al., 2004; Sariciftci et al., 1992). A new title compound was synthesized and the crystal structure is reported here.

In the title molecule, C₂₄H₂₀Cl₂O₂, (Fig. 1), the pentane-1,5-dione unit (C1—C5/O1/O5) is puckered with the torsion angles C1—C2—C3—C4 = 72.49 (19)° and C2—C3—C4—C5 = -179.02 (16)°, making the two ketone groups pointing towards opposite directions. The central methylbenzene ring forms dihedral angles of 42.47 (10) and 34.34 (10)° with the two terminal 4-chlorophenyl fragments. The dihedral angle between the two chlorobenzene rings is 34.45 (11)°. A weak intramolecular C4—H4A···O1 interaction (Table 1) which generates an S(6) ring motif (Bernstein et al., 1995) helps to stabilize this conformation. The crystal packing exhibits weak intermolecular C16—H16···O5 hydrogen bonded C(9) chains (Bernstein et al., 1995) and C55—H55···π interactions involving (C31—C36) methylbenzene ring (Table 1, Fig. 2 & Fig. 3). The C—C, C_ar—C_ar, C—Cl and C=O bond lengths in (I) are within their normal ranges (Allen et al., 1987).

Related literature top

For the synthesis of 1,5-diketones, see: Yang et al. (2005); Hirsch & Bailey (1978). For the crystal structures of related compounds, see: Qiu et al. (2006); Insuasty et al. (2006); Jasinski et al. (2007); Huang et al. (2008); Lei & Bai (2009); Dutkiewicz et al. (2010); Fun et al. (2011). For the applications of delocalized π-systems, see: Burroughes et al. (1990); Smith et al. (2005); Li et al. (2004); Sariciftci et al. (1992). For hydrogen-bond motifs, see: Bernstein et al. (1995). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was synthesized according to a modified solvent-free greener approach method (Yang et al., 2005). 4-Chloroacetophenone (0.5 g, 3 mmol), 1-(4-chlorophenyl)-3-(4-methylpenyl)prop-2-ene-1-one (0.8 g, 4 mmol) and commercial powdered NaOH (0.06 g, 1.5 mmol) were crushed together for 20 mt s, using a pestle and mortar. Recystallization from methanol gave colourless crystals. Yield: 1.1 g (90%).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: DIRDIF2008 (Beurskens et al., 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. H atoms are shown as small spheres of arbitrary radius. The dashed line indicates a weak C—H···O intramolecular hydrogen bond.
	Fig. 2. The partial packing of the title compound, viewed along the b axis. Dashed lines indicate hydrogen-bonded C(9) chains along the c axis. H atoms not involved in hydrogen bonding have been omitted for clarity.
	Fig. 3. Crystal structure of the title compound, showing the formation of a C—H···π interaction. Symmetry code (ii): x, y + 1, z.

1,5-Bis(4-chlorophenyl)-3-(4-methylphenyl)pentane-1,5-dione top

Crystal data top

C₂₄H₂₀Cl₂O₂	F(000) = 856
M_r = 411.30	D_x = 1.285 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 327(2) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 18.6794 (11) Å	Cell parameters from 5569 reflections
b = 7.5477 (4) Å	θ = 3.3–75.4°
c = 15.5196 (8) Å	µ = 0.32 mm⁻¹
β = 103.622 (5)°	T = 296 K
V = 2126.5 (2) Å³	Prism, colourless
Z = 4	0.51 × 0.42 × 0.37 mm

Data collection top

Agilent Xcalibur Ruby Gemini diffractometer	4341 independent reflections
Radiation source: Enhance (Cu) X-ray Source	3735 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
Detector resolution: 10.5081 pixels mm^-1	θ_max = 26.5°, θ_min = 2.2°
ω scans	h = −23→21
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −9→8
T_min = 0.443, T_max = 1.000	l = −19→15
14252 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.050	w = 1/[σ²(F_o²) + (0.0627P)² + 0.5487P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.146	(Δ/σ)_max = 0.001
S = 1.07	Δρ_max = 0.33 e Å⁻³
4341 reflections	Δρ_min = −0.37 e Å⁻³
255 parameters	Extinction correction: SHELXL2013 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0227 (17)

Crystal data top

C₂₄H₂₀Cl₂O₂	V = 2126.5 (2) Å³
M_r = 411.30	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.6794 (11) Å	µ = 0.32 mm⁻¹
b = 7.5477 (4) Å	T = 296 K
c = 15.5196 (8) Å	0.51 × 0.42 × 0.37 mm
β = 103.622 (5)°

Data collection top

Agilent Xcalibur Ruby Gemini diffractometer	4341 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	3735 reflections with I > 2σ(I)
T_min = 0.443, T_max = 1.000	R_int = 0.024
14252 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.146	H-atom parameters constrained
S = 1.07	Δρ_max = 0.33 e Å⁻³
4341 reflections	Δρ_min = −0.37 e Å⁻³
255 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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

	x	y	z	U_iso*/U_eq
Cl14	0.50733 (5)	0.76817 (14)	0.95387 (6)	0.1283 (4)
Cl54	0.08862 (5)	1.03187 (11)	0.11762 (5)	0.1154 (3)
O1	0.32422 (10)	0.76750 (19)	0.53035 (12)	0.0873 (6)
O5	0.27979 (11)	0.3043 (2)	0.26076 (12)	0.0939 (7)
C1	0.32982 (10)	0.6468 (3)	0.58359 (14)	0.0638 (6)
C2	0.29189 (10)	0.4711 (2)	0.55773 (13)	0.0621 (6)
C3	0.25188 (9)	0.4591 (2)	0.46011 (12)	0.0555 (5)
C4	0.30797 (10)	0.4435 (3)	0.40126 (13)	0.0647 (6)
C5	0.27264 (11)	0.4342 (3)	0.30405 (14)	0.0644 (6)
C11	0.37394 (9)	0.6711 (3)	0.67653 (14)	0.0626 (6)
C12	0.40855 (12)	0.8328 (3)	0.70082 (17)	0.0809 (8)
C13	0.44906 (13)	0.8624 (4)	0.7860 (2)	0.0933 (10)
C14	0.45523 (12)	0.7294 (4)	0.84725 (17)	0.0838 (9)
C15	0.42146 (13)	0.5692 (3)	0.82660 (16)	0.0813 (8)
C16	0.38072 (11)	0.5404 (3)	0.74081 (14)	0.0705 (7)
C31	0.19689 (9)	0.3081 (2)	0.44168 (11)	0.0525 (5)
C32	0.21576 (10)	0.1365 (2)	0.46994 (12)	0.0596 (5)
C33	0.16507 (11)	0.0008 (3)	0.45037 (13)	0.0649 (6)
C34	0.09424 (12)	0.0296 (3)	0.40097 (13)	0.0676 (6)
C35	0.07564 (11)	0.1993 (3)	0.37249 (15)	0.0754 (7)
C36	0.12561 (10)	0.3367 (3)	0.39251 (14)	0.0668 (6)
C37	0.04025 (16)	−0.1219 (4)	0.3772 (2)	0.1036 (10)
C51	0.22673 (10)	0.5860 (2)	0.25994 (12)	0.0591 (6)
C52	0.17530 (13)	0.5558 (3)	0.18151 (14)	0.0766 (8)
C53	0.13217 (14)	0.6916 (4)	0.13849 (15)	0.0844 (9)
C54	0.14217 (13)	0.8596 (3)	0.17322 (14)	0.0739 (7)
C55	0.19288 (12)	0.8948 (3)	0.25063 (14)	0.0701 (7)
C56	0.23502 (11)	0.7562 (2)	0.29495 (13)	0.0619 (6)
H2A	0.25663	0.45128	0.59369	0.0745*
H2B	0.32834	0.37735	0.57095	0.0745*
H3	0.22450	0.56978	0.44428	0.0666*
H4A	0.34075	0.54492	0.41221	0.0776*
H4B	0.33758	0.33800	0.41830	0.0776*
H12	0.40425	0.92255	0.65885	0.0970*
H13	0.47188	0.97108	0.80159	0.1118*
H15	0.42573	0.48107	0.86937	0.0975*
H16	0.35758	0.43174	0.72612	0.0846*
H32	0.26327	0.11248	0.50255	0.0714*
H33	0.17890	−0.11285	0.47092	0.0778*
H35	0.02834	0.22220	0.33896	0.0905*
H36	0.11120	0.45041	0.37267	0.0802*
H37A	0.01457	−0.13765	0.42342	0.1553*
H37B	0.06642	−0.22851	0.37049	0.1553*
H37C	0.00548	−0.09558	0.32250	0.1553*
H52	0.16976	0.44229	0.15749	0.0920*
H53	0.09667	0.66994	0.08653	0.1012*
H55	0.19902	1.00942	0.27314	0.0842*
H56	0.26892	0.77754	0.34828	0.0742*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl14	0.1032 (5)	0.1647 (9)	0.1004 (5)	−0.0240 (5)	−0.0091 (4)	−0.0387 (5)
Cl54	0.1193 (6)	0.1104 (6)	0.1139 (6)	0.0419 (4)	0.0225 (4)	0.0407 (4)
O1	0.0932 (11)	0.0590 (8)	0.0993 (11)	−0.0099 (8)	0.0019 (9)	0.0133 (8)
O5	0.1211 (14)	0.0656 (9)	0.1022 (12)	0.0217 (9)	0.0405 (11)	−0.0103 (8)
C1	0.0529 (9)	0.0552 (10)	0.0820 (12)	0.0002 (8)	0.0131 (8)	0.0033 (9)
C2	0.0566 (10)	0.0565 (10)	0.0712 (11)	−0.0045 (8)	0.0112 (8)	0.0022 (8)
C3	0.0497 (8)	0.0505 (9)	0.0668 (10)	0.0040 (7)	0.0150 (7)	0.0062 (7)
C4	0.0532 (9)	0.0616 (10)	0.0823 (12)	0.0055 (8)	0.0222 (9)	0.0091 (9)
C5	0.0671 (11)	0.0552 (10)	0.0787 (12)	0.0025 (8)	0.0326 (9)	0.0011 (9)
C11	0.0463 (9)	0.0605 (10)	0.0822 (12)	−0.0050 (8)	0.0174 (8)	−0.0064 (9)
C12	0.0711 (13)	0.0719 (13)	0.1003 (16)	−0.0206 (10)	0.0214 (11)	−0.0078 (12)
C13	0.0734 (14)	0.0910 (17)	0.115 (2)	−0.0313 (13)	0.0215 (13)	−0.0300 (15)
C14	0.0568 (11)	0.1059 (18)	0.0862 (15)	−0.0097 (11)	0.0121 (10)	−0.0243 (14)
C15	0.0712 (13)	0.0886 (15)	0.0796 (14)	−0.0029 (11)	0.0088 (10)	−0.0025 (12)
C16	0.0611 (11)	0.0675 (12)	0.0801 (13)	−0.0088 (9)	0.0109 (9)	−0.0048 (10)
C31	0.0515 (8)	0.0530 (9)	0.0538 (9)	0.0018 (7)	0.0142 (7)	0.0021 (7)
C32	0.0578 (9)	0.0564 (9)	0.0618 (10)	0.0035 (8)	0.0088 (7)	0.0024 (8)
C33	0.0763 (12)	0.0512 (9)	0.0673 (11)	−0.0017 (8)	0.0174 (9)	0.0012 (8)
C34	0.0693 (11)	0.0680 (11)	0.0656 (11)	−0.0139 (9)	0.0161 (9)	−0.0065 (9)
C35	0.0532 (10)	0.0831 (14)	0.0836 (14)	−0.0055 (10)	0.0034 (9)	0.0072 (11)
C36	0.0554 (10)	0.0615 (10)	0.0802 (12)	0.0041 (8)	0.0094 (9)	0.0126 (9)
C37	0.0965 (18)	0.0865 (16)	0.120 (2)	−0.0326 (15)	0.0096 (15)	−0.0107 (15)
C51	0.0632 (10)	0.0577 (10)	0.0627 (10)	0.0011 (8)	0.0274 (8)	0.0007 (8)
C52	0.0894 (15)	0.0721 (13)	0.0706 (12)	0.0036 (11)	0.0232 (11)	−0.0134 (10)
C53	0.0842 (15)	0.1014 (17)	0.0645 (12)	0.0120 (13)	0.0116 (10)	−0.0041 (12)
C54	0.0799 (13)	0.0783 (13)	0.0691 (12)	0.0179 (11)	0.0291 (10)	0.0167 (10)
C55	0.0856 (13)	0.0558 (10)	0.0752 (12)	0.0018 (9)	0.0313 (10)	0.0071 (9)
C56	0.0692 (11)	0.0561 (10)	0.0632 (10)	−0.0044 (8)	0.0214 (8)	0.0026 (8)

Geometric parameters (Å, º) top

Cl14—C14	1.736 (3)	C51—C56	1.389 (2)
Cl54—C54	1.741 (2)	C52—C53	1.376 (4)
O1—C1	1.218 (3)	C53—C54	1.373 (4)
O5—C5	1.214 (3)	C54—C55	1.369 (3)
C1—C2	1.513 (3)	C55—C56	1.390 (3)
C1—C11	1.495 (3)	C2—H2A	0.9700
C2—C3	1.526 (3)	C2—H2B	0.9700
C3—C4	1.548 (3)	C3—H3	0.9800
C3—C31	1.516 (2)	C4—H4A	0.9700
C4—C5	1.499 (3)	C4—H4B	0.9700
C5—C51	1.497 (3)	C12—H12	0.9300
C11—C12	1.391 (3)	C13—H13	0.9300
C11—C16	1.387 (3)	C15—H15	0.9300
C12—C13	1.378 (4)	C16—H16	0.9300
C13—C14	1.369 (4)	C32—H32	0.9300
C14—C15	1.367 (4)	C33—H33	0.9300
C15—C16	1.386 (3)	C35—H35	0.9300
C31—C32	1.386 (2)	C36—H36	0.9300
C31—C36	1.387 (3)	C37—H37A	0.9600
C32—C33	1.379 (3)	C37—H37B	0.9600
C33—C34	1.381 (3)	C37—H37C	0.9600
C34—C35	1.373 (3)	C52—H52	0.9300
C34—C37	1.512 (4)	C53—H53	0.9300
C35—C36	1.381 (3)	C55—H55	0.9300
C51—C52	1.381 (3)	C56—H56	0.9300

O1—C1—C2	121.06 (19)	C1—C2—H2B	109.00
O1—C1—C11	120.2 (2)	C3—C2—H2A	109.00
C2—C1—C11	118.76 (18)	C3—C2—H2B	109.00
C1—C2—C3	113.88 (15)	H2A—C2—H2B	108.00
C2—C3—C4	110.43 (15)	C2—C3—H3	108.00
C2—C3—C31	112.56 (14)	C4—C3—H3	108.00
C4—C3—C31	110.75 (14)	C31—C3—H3	108.00
C3—C4—C5	113.49 (16)	C3—C4—H4A	109.00
O5—C5—C4	121.0 (2)	C3—C4—H4B	109.00
O5—C5—C51	119.42 (19)	C5—C4—H4A	109.00
C4—C5—C51	119.57 (18)	C5—C4—H4B	109.00
C1—C11—C12	119.0 (2)	H4A—C4—H4B	108.00
C1—C11—C16	122.9 (2)	C11—C12—H12	119.00
C12—C11—C16	118.1 (2)	C13—C12—H12	119.00
C11—C12—C13	121.2 (2)	C12—C13—H13	120.00
C12—C13—C14	119.0 (3)	C14—C13—H13	121.00
Cl14—C14—C13	118.4 (2)	C14—C15—H15	121.00
Cl14—C14—C15	119.8 (2)	C16—C15—H15	121.00
C13—C14—C15	121.8 (2)	C11—C16—H16	119.00
C14—C15—C16	118.9 (2)	C15—C16—H16	119.00
C11—C16—C15	121.0 (2)	C31—C32—H32	120.00
C3—C31—C32	122.17 (15)	C33—C32—H32	120.00
C3—C31—C36	120.46 (15)	C32—C33—H33	119.00
C32—C31—C36	117.34 (17)	C34—C33—H33	119.00
C31—C32—C33	120.93 (18)	C34—C35—H35	119.00
C32—C33—C34	121.6 (2)	C36—C35—H35	119.00
C33—C34—C35	117.5 (2)	C31—C36—H36	119.00
C33—C34—C37	120.9 (2)	C35—C36—H36	119.00
C35—C34—C37	121.6 (2)	C34—C37—H37A	109.00
C34—C35—C36	121.5 (2)	C34—C37—H37B	109.00
C31—C36—C35	121.2 (2)	C34—C37—H37C	109.00
C5—C51—C52	118.80 (17)	H37A—C37—H37B	110.00
C5—C51—C56	122.00 (17)	H37A—C37—H37C	109.00
C52—C51—C56	119.20 (17)	H37B—C37—H37C	109.00
C51—C52—C53	120.8 (2)	C51—C52—H52	120.00
C52—C53—C54	119.2 (2)	C53—C52—H52	120.00
Cl54—C54—C53	119.08 (18)	C52—C53—H53	120.00
Cl54—C54—C55	119.21 (18)	C54—C53—H53	120.00
C53—C54—C55	121.7 (2)	C54—C55—H55	121.00
C54—C55—C56	118.8 (2)	C56—C55—H55	121.00
C51—C56—C55	120.30 (18)	C51—C56—H56	120.00
C1—C2—H2A	109.00	C55—C56—H56	120.00

O1—C1—C2—C3	3.7 (3)	C12—C13—C14—Cl14	179.28 (19)
C11—C1—C2—C3	−177.04 (16)	C12—C13—C14—C15	−1.0 (4)
O1—C1—C11—C12	−0.3 (3)	Cl14—C14—C15—C16	−179.36 (18)
O1—C1—C11—C16	178.2 (2)	C13—C14—C15—C16	0.9 (4)
C2—C1—C11—C12	−179.59 (18)	C14—C15—C16—C11	−0.1 (3)
C2—C1—C11—C16	−1.1 (3)	C3—C31—C32—C33	−178.41 (17)
C1—C2—C3—C4	72.49 (19)	C36—C31—C32—C33	−0.6 (3)
C1—C2—C3—C31	−163.18 (15)	C3—C31—C36—C35	177.69 (18)
C2—C3—C4—C5	−179.02 (16)	C32—C31—C36—C35	−0.1 (3)
C31—C3—C4—C5	55.6 (2)	C31—C32—C33—C34	1.0 (3)
C2—C3—C31—C32	−51.0 (2)	C32—C33—C34—C35	−0.6 (3)
C2—C3—C31—C36	131.25 (18)	C32—C33—C34—C37	177.7 (2)
C4—C3—C31—C32	73.1 (2)	C33—C34—C35—C36	−0.2 (3)
C4—C3—C31—C36	−104.60 (19)	C37—C34—C35—C36	−178.4 (2)
C3—C4—C5—O5	−117.3 (2)	C34—C35—C36—C31	0.5 (3)
C3—C4—C5—C51	61.6 (2)	C5—C51—C52—C53	−179.7 (2)
O5—C5—C51—C52	20.8 (3)	C56—C51—C52—C53	−0.5 (3)
O5—C5—C51—C56	−158.4 (2)	C5—C51—C56—C55	178.05 (19)
C4—C5—C51—C52	−158.1 (2)	C52—C51—C56—C55	−1.1 (3)
C4—C5—C51—C56	22.7 (3)	C51—C52—C53—C54	1.8 (4)
C1—C11—C12—C13	179.2 (2)	C52—C53—C54—Cl54	178.90 (19)
C16—C11—C12—C13	0.6 (3)	C52—C53—C54—C55	−1.4 (4)
C1—C11—C16—C15	−179.2 (2)	Cl54—C54—C55—C56	179.52 (17)
C12—C11—C16—C15	−0.7 (3)	C53—C54—C55—C56	−0.1 (4)
C11—C12—C13—C14	0.2 (4)	C54—C55—C56—C51	1.4 (3)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the (C31-C36) methylbenzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O1	0.97	2.56	3.130 (3)	118
C16—H16···O5ⁱ	0.93	2.44	3.270 (3)	149
C55—H55···Cg2ⁱⁱ	0.93	2.97	3.629 (2)	129

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

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the (C31-C36) methylbenzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O1	0.97	2.56	3.130 (3)	118
C16—H16···O5ⁱ	0.93	2.44	3.270 (3)	149
C55—H55···Cg2ⁱⁱ	0.93	2.97	3.629 (2)	129

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

Acknowledgements

RJB acknowledges the NSF–MRI program (grant No. CHE0619278) for funds to purchase the X-ray diffractometer.

References

Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England. Google Scholar
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Beurskens, P. T., Beurskens, G., de Gelder, R., Smits, J. M. M., García-Granda, S. & Gould, R. O. (2008). DIRDIF2008. Crystallography Laboratory, Radboud University Nijmegen, The Netherlands. Google Scholar
Burroughes, J. H., Bradley, D. D. C., Brown, A. R., Marks, R. N., Mackay, K., Friend, R. H., Burns, P. L. & Holmes, A. B. (1990). Nature (London), 347, 539–541. CrossRef CAS Web of Science Google Scholar
Dutkiewicz, G., Chidan Kumar, C. S., Yathirajan, H. S., Narayana, B. & Kubicki, M. (2010). Acta Cryst. E66, o816. Web of Science CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Fun, H.-K., Suwunwong, T., Boonnak, N. & Chantrapromma, S. (2011). Acta Cryst. E67, o3416–o3417. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Hirsch, S. S. & Bailey, W. J. (1978). J. Org. Chem. 43, 4090–4094. CrossRef CAS Web of Science Google Scholar
Huang, X., Xin, F., Shi, Q.-L., Wang, Y. & Wei, G.-D. (2008). Acta Cryst. E64, o2454. Web of Science CSD CrossRef IUCr Journals Google Scholar
Insuasty, B., Torres, H., Cobo, J., Low, J. N. & Glidewell, C. (2006). Acta Cryst. C62, o39–o41. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Jasinski, J. P., Butcher, R. J., Yathirajan, H. S., Narayana, B. & Swamy, M. T. (2007). Acta Cryst. E63, o4808–o4809. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Lei, X. & Bai, X. (2009). Acta Cryst. E65, o514. Web of Science CSD CrossRef IUCr Journals Google Scholar
Li, Y. N., Ding, J. F., Day, M., Tao, Y., Lu, J. P. & D'iorio, M. (2004). Chem. Mater. 16, 2165–2173. Web of Science CrossRef CAS Google Scholar
Qiu, X.-Y., Ma, J.-L. & Liu, W.-S. (2006). Acta Cryst. E62, o4565–o4566. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sariciftci, N. S., Smilowitz, L. & Heeger, A. J. (1992). Science, 258, 1474–1476. CrossRef PubMed CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Smith, C. B., Raston, C. L. & Sobolev, A. N. (2005). Green Chem. 7, 650–654. Web of Science CSD CrossRef CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yang, J.-X., Tao, X.-T., Yuan, C. X., Yan, Y. X., Wang, L., Liu, Z., Ren, Y. & Jiang, M. H. (2005). J. Am. Chem. Soc. 127, 3278–3279. Web of Science CrossRef PubMed CAS Google Scholar