3,3′′,4,4′′-Tetra­meth­oxy-1,1′:4′,1′′-terphen­yl

Kung Pui, L.; Hung, W.W.; Yamin, B.M.; Kassim, M.B.

doi:10.1107/S1600536811025207

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o1892

doi:10.1107/S1600536811025207

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3,3′′,4,4′′-Tetramethoxy-1,1′:4′,1′′-terphenyl

Law Kung Pui,^a Wong Woei Hung,^a Bohari M. Yamin ^a and Mohammad B. Kassim ^a,^b ^*

^aSchool of Chemical Sciences & Food Technology, Faculty of Science & Technology, Universiti Kebangsaan Malaysia, 43600 Selangor, Malaysia, and ^bFuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Selangor, Malaysia
^*Correspondence e-mail: mbkassim@ukm.my

(Received 23 June 2011; accepted 27 June 2011; online 2 July 2011)

The title molecule, C₂₂H₂₂O₄, is centrosymmetric with an inversion centre located at the centre of the benzene ring. The 3,4-dimethoxybenzene fragment is essentially planar [maximum deviation = 0.400 (2) Å] and twisted relative to the central benzene ring, forming a dihedral angle of 21.25 (7)°. In the crystal, C—H⋯O hydrogen bonds link the molecules into a two-dimensional polymeric structure lying parallel to (100).

Related literature

For the synthesis, see: Bahadir et al. (2003 ). For related structures and background references, see: Krummland et al. (1997 ); Schweigert et al. (2001 ).

Experimental

Crystal data

C₂₂H₂₂O₄
M_r = 350.40
Monoclinic, P 2₁ /c
a = 13.217 (3) Å
b = 8.808 (2) Å
c = 8.058 (2) Å
β = 105.476 (4)°
V = 904.1 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.43 × 0.40 × 0.14 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.963, T_max = 0.988
5114 measured reflections
1866 independent reflections
1166 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.160
S = 1.04
1866 reflections
120 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10A⋯O1ⁱ	0.96	2.47	3.331 (3)	149
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811025207/gk2390sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025207/gk2390Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811025207/gk2390Isup3.cml

checkCIF report

Comment top

The title compound, is an analog of the previously reported 2,3,8,9-tetramethoxydibenzo[c,e][1,2]dithiin molecules (Krummland et al., 1997). The chemical and biological properties of the related chatecols were also studied by Schweigert et al. (2001).

The whole molecule is relatively flat with a maximum deviation from the mean plane at C2 [0.400 (2) Å ]. The central phenyl ring is twisted relative to the 3,4-dimethoxybenzene fragments forming a dihedral angle of 21.25 (7)°. Both methoxy fragments are essentially coplanar with the parent benzene ring with the largest deviation from the mean plane of O1/02/C3/C4/C5/C6/C7/C8/C9/C10/C11 of 0.046 (3) Å for C10.

The crystal structure is stabilized by intermolecular C10—H10A···O1 hydrogen bond linking the molecules into a two dimensional polymeric network parallel to (1 0 0) (Table 1, Fig. 2).

Related literature top

For the synthesis, see: Bahadir et al. (2003). For related structures and background references, see: Krummland et al. (1997); Schweigert et al. (2001).

Experimental top

To a 1,4-dibromobenzene (0.236 g, 1 mmol) was added Pd(PPh₃)₄ (0.07 g, 0.06 mmol) in dry toluene (6 ml) and stirred for 15 min. Then an aqueous solution of Na₂CO₃ (2 ml of 2M solution) was added, followed by a 3,4-dimethoxyphenylboronic acid (0.40 g, 2.2 mmol) in EtOH (5 ml). The mixture was refluxed at 95°C for 20 h. The reaction was quenched by adding 30% H₂O₂ (0.5 ml) slowly to oxidize the excess 3,4-dimethoxyphenylboronic acid. The reaction mixture was cleaned by NaCl solution (1M) and was extracted several times with DCM. The organic residue was washed with 30 ml of water and was dried over CaH₂. The solvent was removed in vacuo and recrystallized from DCM/n-hexane to afford white solids suitable for X-ray single-crystal diffraction (yield: 84%).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. Symmetry code for atoms with the A label: -x, 1-y, 1-z.
	Fig. 2. A packing diagram of the title compound viewed down the a-axis showing intermolecular C10—H10A···O1 hydrogen bond.

3,3'',4,4''-Tetramethoxy-1,1':4',1''-terphenyl top

Crystal data top

C₂₂H₂₂O₄	F(000) = 372
M_r = 350.40	D_x = 1.287 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 576–578 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 13.217 (3) Å	Cell parameters from 2137 reflections
b = 8.808 (2) Å	θ = 1.6–26.5°
c = 8.058 (2) Å	µ = 0.09 mm⁻¹
β = 105.476 (4)°	T = 298 K
V = 904.1 (4) Å³	Block, colourless
Z = 2	0.43 × 0.40 × 0.14 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1866 independent reflections
Radiation source: fine-focus sealed tube	1166 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 26.5°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −16→15
T_min = 0.963, T_max = 0.988	k = −6→11
5114 measured reflections	l = −10→10

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.160	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0871P)²] where P = (F_o² + 2F_c²)/3
1866 reflections	(Δ/σ)_max < 0.001
120 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₂₂H₂₂O₄	V = 904.1 (4) Å³
M_r = 350.40	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.217 (3) Å	µ = 0.09 mm⁻¹
b = 8.808 (2) Å	T = 298 K
c = 8.058 (2) Å	0.43 × 0.40 × 0.14 mm
β = 105.476 (4)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1866 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1166 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.988	R_int = 0.029
5114 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.160	H-atom parameters constrained
S = 1.04	Δρ_max = 0.22 e Å⁻³
1866 reflections	Δρ_min = −0.13 e Å⁻³
120 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
O1	0.35830 (11)	0.46473 (15)	−0.01311 (17)	0.0655 (5)
O2	0.41248 (11)	0.60399 (17)	0.27724 (18)	0.0718 (5)
C1	0.01164 (14)	0.6080 (2)	0.6254 (2)	0.0588 (5)
H1	0.0205	0.6821	0.7103	0.071*
C2	0.07975 (14)	0.6046 (2)	0.5231 (2)	0.0576 (5)
H2	0.1332	0.6763	0.5405	0.069*
C3	0.07065 (14)	0.4961 (2)	0.3938 (2)	0.0521 (5)
C4	0.14417 (14)	0.4894 (2)	0.2832 (2)	0.0517 (5)
C5	0.24440 (15)	0.5542 (2)	0.3353 (2)	0.0523 (5)
H5	0.2648	0.6042	0.4406	0.063*
C6	0.31329 (14)	0.5458 (2)	0.2345 (2)	0.0517 (5)
C7	0.28368 (15)	0.4708 (2)	0.0755 (2)	0.0525 (5)
C8	0.18531 (16)	0.4092 (2)	0.0216 (2)	0.0626 (6)
H8	0.1644	0.3607	−0.0845	0.075*
C9	0.11677 (15)	0.4189 (2)	0.1246 (2)	0.0630 (6)
H9	0.0502	0.3765	0.0856	0.076*
C10	0.44505 (19)	0.6888 (3)	0.4319 (3)	0.0965 (9)
H10A	0.3951	0.7680	0.4316	0.145*
H10B	0.5127	0.7329	0.4402	0.145*
H10C	0.4495	0.6230	0.5285	0.145*
C11	0.33034 (18)	0.3959 (3)	−0.1786 (2)	0.0817 (7)
H11A	0.3120	0.2916	−0.1680	0.123*
H11B	0.3887	0.4012	−0.2282	0.123*
H11C	0.2714	0.4485	−0.2514	0.123*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0763 (10)	0.0667 (10)	0.0657 (9)	−0.0023 (7)	0.0402 (8)	−0.0057 (7)
O2	0.0695 (9)	0.0792 (10)	0.0783 (10)	−0.0193 (7)	0.0396 (8)	−0.0218 (8)
C1	0.0577 (12)	0.0623 (13)	0.0608 (12)	0.0026 (10)	0.0234 (10)	−0.0068 (9)
C2	0.0527 (11)	0.0603 (13)	0.0644 (13)	0.0003 (9)	0.0239 (10)	−0.0030 (10)
C3	0.0516 (11)	0.0544 (12)	0.0532 (12)	0.0090 (9)	0.0188 (9)	0.0045 (9)
C4	0.0508 (11)	0.0544 (11)	0.0521 (11)	0.0085 (9)	0.0177 (9)	0.0044 (9)
C5	0.0601 (12)	0.0500 (11)	0.0521 (11)	0.0028 (9)	0.0242 (9)	−0.0016 (8)
C6	0.0537 (11)	0.0449 (11)	0.0604 (12)	−0.0003 (8)	0.0221 (9)	0.0026 (9)
C7	0.0602 (12)	0.0492 (11)	0.0554 (12)	0.0070 (9)	0.0278 (10)	0.0072 (9)
C8	0.0647 (13)	0.0762 (14)	0.0487 (11)	0.0024 (11)	0.0181 (10)	−0.0067 (10)
C9	0.0533 (12)	0.0790 (15)	0.0593 (13)	−0.0023 (10)	0.0196 (10)	−0.0043 (10)
C10	0.0924 (17)	0.093 (2)	0.116 (2)	−0.0364 (14)	0.0489 (16)	−0.0488 (16)
C11	0.0906 (17)	0.1048 (19)	0.0606 (14)	0.0140 (14)	0.0388 (13)	−0.0016 (12)

Geometric parameters (Å, º) top

O1—C7	1.364 (2)	C5—C6	1.374 (2)
O1—C11	1.421 (2)	C5—H5	0.9300
O2—C6	1.364 (2)	C6—C7	1.401 (3)
O2—C10	1.418 (2)	C7—C8	1.368 (3)
C1—C2	1.373 (3)	C8—C9	1.385 (3)
C1—C3ⁱ	1.400 (3)	C8—H8	0.9300
C1—H1	0.9300	C9—H9	0.9300
C2—C3	1.395 (3)	C10—H10A	0.9600
C2—H2	0.9300	C10—H10B	0.9600
C3—C1ⁱ	1.400 (3)	C10—H10C	0.9600
C3—C4	1.484 (3)	C11—H11A	0.9600
C4—C9	1.380 (3)	C11—H11B	0.9600
C4—C5	1.400 (3)	C11—H11C	0.9600

C7—O1—C11	117.68 (15)	O1—C7—C6	115.63 (17)
C6—O2—C10	117.78 (15)	C8—C7—C6	119.13 (17)
C2—C1—C3ⁱ	122.27 (18)	C7—C8—C9	120.26 (18)
C2—C1—H1	118.9	C7—C8—H8	119.9
C3ⁱ—C1—H1	118.9	C9—C8—H8	119.9
C1—C2—C3	121.59 (18)	C4—C9—C8	122.05 (19)
C1—C2—H2	119.2	C4—C9—H9	119.0
C3—C2—H2	119.2	C8—C9—H9	119.0
C2—C3—C1ⁱ	116.14 (17)	O2—C10—H10A	109.5
C2—C3—C4	122.42 (18)	O2—C10—H10B	109.5
C1ⁱ—C3—C4	121.43 (17)	H10A—C10—H10B	109.5
C9—C4—C5	117.06 (17)	O2—C10—H10C	109.5
C9—C4—C3	121.46 (17)	H10A—C10—H10C	109.5
C5—C4—C3	121.48 (17)	H10B—C10—H10C	109.5
C6—C5—C4	121.58 (18)	O1—C11—H11A	109.5
C6—C5—H5	119.2	O1—C11—H11B	109.5
C4—C5—H5	119.2	H11A—C11—H11B	109.5
O2—C6—C5	125.06 (17)	O1—C11—H11C	109.5
O2—C6—C7	115.03 (16)	H11A—C11—H11C	109.5
C5—C6—C7	119.90 (17)	H11B—C11—H11C	109.5
O1—C7—C8	125.24 (18)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···O1ⁱⁱ	0.96	2.47	3.331 (3)	149

Symmetry code: (ii) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₂H₂₂O₄
M_r	350.40
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	13.217 (3), 8.808 (2), 8.058 (2)
β (°)	105.476 (4)
V (Å³)	904.1 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.43 × 0.40 × 0.14

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.963, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	5114, 1866, 1166
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.160, 1.04
No. of reflections	1866
No. of parameters	120
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.13

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···O1ⁱ	0.96	2.47	3.331 (3)	149

Symmetry code: (i) x, −y+3/2, z+1/2.

Acknowledgements

The authors thank Universiti Kebangsaan Malaysia for the grants UKM-GUP-BTT-07–30–190 and UKM-OUP-TK-16–73/2011 and for sabbatical leave for MBK. The authors thank also the Akademi Sains Malaysia for the ST-027–2004-GL research fund. LKP thanks the Kementerian Pengajian Tinggi, Malaysia, for the MyPhD fund.

References

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