1,4-Bis(4-chloro­phenyl­seleno)-2,5-di­methoxy­benzene

Sørensen, H.O.; Stuhr-Hansen, N.

doi:10.1107/S1600536808039469

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o13

doi:10.1107/S1600536808039469

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1,4-Bis(4-chlorophenylseleno)-2,5-dimethoxybenzene

Henning Osholm Sørensen ^a ^* and Nicolai Stuhr-Hansen ^b

^aCenter for Fundamental Research: Metal Structures in Four Dimensions, Risø National Laboratory for Sustainable Energy, Technical University of Denmark, Frederiksborgvej 399, PO 49, DK-4000 Roskilde, Denmark, and ^bDepartment of Medicinal Chemistry, University of Copenhagen, Universitetsparken 2, DK-2100 Copenhagen, Denmark
^*Correspondence e-mail: henning.sorensen@risoe.dk

(Received 27 October 2008; accepted 24 November 2008; online 3 December 2008)

The title compound, C₂₀H₁₆Cl₂O₂Se₂, utilizes the symmetry of the crystallographic inversion center. Molecular chains are formed through symmetric C—H⋯Cl interactions around inversion centers, mimicking the commonly observed symmetric hydrogen-bonded dimer pattern often found in carboxylic acids.

Related literature

For background to the electrophilic arylselenylation of reactive arenes, see: Santi et al. (2008 ); Nicolaou et al. (1979 ); Gassman et al. (1982 ); Yoshida et al. (1991 ); Tiecco et al. (1994 ); Engman & Eriksson (1996 ); Henriksen (1994 ); Henriksen & Stuhr-Hansen (1998 ). For related structures, see: Oddershede et al. (2003 ). For related supramolecular patterns, see: Gavezzotti & Filippini (1994 ); Allen et al. (1999 ); Sørensen & Larsen (2003 ); Sørensen et al. (1999 ).

Experimental

Crystal data

C₂₀H₁₆Cl₂O₂Se₂
M_r = 517.15
Monoclinic, P 2₁ /n
a = 11.7737 (17) Å
b = 6.6535 (6) Å
c = 13.438 (5) Å
β = 114.136 (16)°
V = 960.7 (4) Å³
Z = 2
Cu Kα radiation
μ = 7.47 mm⁻¹
T = 122 (1) K
0.44 × 0.15 × 0.13 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: gaussian (DeTitta, 1985 ). T_min = 0.242, T_max = 0.796
2641 measured reflections
1976 independent reflections
1919 reflections with I > 2σ(I)
R_int = 0.030
5 standard reflections frequency: 166.7 min intensity decay: 5.7%

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.075
S = 1.10
1976 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −1.20 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: DREAR (Blessing, 1987 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808039469/sg2281sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808039469/sg2281Isup2.hkl

checkCIF report

Comment top

The structure of the title compound, shown in Fig. 1, crystallized in space group P 2₁/n utilizing the crystallography inversion center in the molecular symmetry. Generally the molecular geometry of 1 is in close agreement with the related compound 1,3-dimethoxy-4,6-bis(phenylseleno)benzene, hereafter DMPSB. All bond distances and angles are the same within the experimental uncertainty. The molecular conformation of 1 is also very similar to the chloro-unsubstituted compound DMPSB having the planes of phenylseleno groups arranged perpendicular to the plane of the central benzene moiety, but rotated in opposite directions forming a Z like conformation (Fig. 1). Leading to the formation of intramolecular C_ar—H···π interactions.

The molecular packing arrangement is dominated by molecular chains (see Fig. 2) formed by cyclic C_ar—H···Cl interactions [H7···Cl_i = 2.96 Å, C7—H7···Cl_i = 166.0°; symmetry code: (i) 2 - x,1 - y,1 - z] around an inversion center leading to a pattern, which highly resembles the cyclic hydrogen-bonded dimers frequently observed in carboxylic acids. The C_ar—H···Cl type of cyclic interaction found in 1 has also been observed in other compounds having a p-chlorosubstituted phenyl group, e.g. in the structure of racemic p-chlorophenoxypropionic acid, where the distance H···Cl is 2.92 Å [C—H···Cl 175°]. The chains are stacked such that the π-π interactions between the phenelseleno groups and between the benzene rings along the diagonal of the b and c-axes, respectively. Due to the chain formation in 1 the packing arrangement is rather different from the pattern found in DMPSB, where interactions with chlorine cannot be formed.

Related literature top

For background to the electrophilic arylselenylation of reactive arenes, see: Santi et al. (2008); Nicolaou et al. (1979); Gassman et al. (1982); Yoshida et al. (1991); Tiecco et al. (1994); Engman & Eriksson (1996); Henriksen (1994); Henriksen & Stuhr-Hansen (1998). For related structures, see: Oddershede et al. (2003). For related supramolecular patterns, see: Gavezzotti & Filippini (1994); Allen et al. (1999); Sørensen & Larsen (2003); Sørensen et al. (1999).

Experimental top

Crystals suitable for an X-ray diffraction experiment were obtained by slow crystallization from hot toluene.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: DREAR (Blessing, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Thermal elipsoid plot of (1) including labelling of the atoms. The displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as spheres with an arbitrary radii.
	Fig. 2. A view of the cyclic C—H···Cl interactions linking the molecules into a chain.
	Fig. 3. Packing diagram of viewed down the b axis.

1,4-Bis(4-chlorophenylseleno)-2,5-dimethoxybenzene top

Crystal data top

C₂₀H₁₆Cl₂O₂Se₂	F(000) = 508
M_r = 517.15	D_x = 1.788 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 193 K
Hall symbol: -P 2yn	Cu Kα radiation, λ = 1.54184 Å
a = 11.7737 (17) Å	Cell parameters from 20 reflections
b = 6.6535 (6) Å	θ = 39.3–40.7°
c = 13.438 (5) Å	µ = 7.47 mm⁻¹
β = 114.136 (16)°	T = 122 K
V = 960.7 (4) Å³	Block, white
Z = 2	0.44 × 0.15 × 0.13 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1919 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.030
Graphite monochromator	θ_max = 74.9°, θ_min = 4.2°
ω–2θ scans	h = −14→14
Absorption correction: gaussian (DeTitta, 1985).	k = −7→8
T_min = 0.242, T_max = 0.796	l = 0→16
2641 measured reflections	5 standard reflections every 166.7 min
1976 independent reflections	intensity decay: 5.7%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.028	H-atom parameters constrained
wR(F²) = 0.076	w = 1/[σ²(F_o²) + (0.0433P)² + 0.9774P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
1976 reflections	Δρ_max = 0.60 e Å⁻³
119 parameters	Δρ_min = −1.20 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0029 (3)

Crystal data top

C₂₀H₁₆Cl₂O₂Se₂	V = 960.7 (4) Å³
M_r = 517.15	Z = 2
Monoclinic, P2₁/n	Cu Kα radiation
a = 11.7737 (17) Å	µ = 7.47 mm⁻¹
b = 6.6535 (6) Å	T = 122 K
c = 13.438 (5) Å	0.44 × 0.15 × 0.13 mm
β = 114.136 (16)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1919 reflections with I > 2σ(I)
Absorption correction: gaussian (DeTitta, 1985).	R_int = 0.030
T_min = 0.242, T_max = 0.796	5 standard reflections every 166.7 min
2641 measured reflections	intensity decay: 5.7%
1976 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.076	H-atom parameters constrained
S = 1.10	Δρ_max = 0.60 e Å⁻³
1976 reflections	Δρ_min = −1.20 e Å⁻³
119 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
Se1	0.745362 (19)	0.19839 (3)	0.007848 (17)	0.01812 (12)
Cl	1.00097 (5)	0.82041 (8)	0.40315 (5)	0.02427 (15)
O1	1.23891 (13)	0.1213 (2)	0.13084 (12)	0.0192 (3)
C1	1.2567 (2)	0.2869 (3)	0.20396 (19)	0.0232 (5)
H1A	1.3459	0.3140	0.2431	0.035*
H1B	1.2213	0.2535	0.2564	0.035*
H1C	1.2150	0.4063	0.1623	0.035*
C2	1.11846 (19)	0.0668 (3)	0.06767 (16)	0.0160 (4)
C3	1.0144 (2)	0.1577 (3)	0.07253 (17)	0.0168 (4)
H3	1.0245	0.2653	0.1219	0.020*
C4	0.89557 (19)	0.0910 (3)	0.00514 (16)	0.0159 (4)
C5	0.82080 (19)	0.3830 (3)	0.12694 (17)	0.0172 (4)
C6	0.8614 (2)	0.3181 (3)	0.23448 (19)	0.0194 (4)
H6	0.8506	0.1815	0.2493	0.023*
C7	0.9173 (2)	0.4513 (3)	0.32023 (17)	0.0197 (4)
H7	0.9457	0.4067	0.3936	0.024*
C8	0.93109 (19)	0.6504 (3)	0.29699 (17)	0.0174 (4)
C9	0.8891 (2)	0.7196 (3)	0.19057 (19)	0.0211 (5)
H9	0.8985	0.8570	0.1762	0.025*
C10	0.8331 (2)	0.5850 (3)	0.10537 (17)	0.0201 (4)
H10	0.8030	0.6308	0.0321	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Se1	0.01674 (16)	0.01956 (17)	0.01817 (16)	0.00021 (7)	0.00723 (11)	−0.00363 (7)
Cl	0.0267 (3)	0.0243 (3)	0.0206 (3)	−0.0041 (2)	0.0084 (2)	−0.00601 (18)
O1	0.0174 (7)	0.0196 (7)	0.0194 (7)	−0.0023 (6)	0.0063 (6)	−0.0059 (6)
C1	0.0242 (11)	0.0227 (11)	0.0217 (11)	−0.0045 (9)	0.0084 (9)	−0.0084 (8)
C2	0.0178 (9)	0.0154 (9)	0.0145 (9)	−0.0025 (8)	0.0064 (7)	0.0012 (7)
C3	0.0215 (10)	0.0136 (9)	0.0164 (9)	−0.0016 (8)	0.0089 (8)	−0.0014 (7)
C4	0.0192 (9)	0.0143 (9)	0.0156 (9)	0.0004 (7)	0.0084 (8)	0.0013 (7)
C5	0.0169 (9)	0.0178 (10)	0.0196 (10)	0.0013 (8)	0.0103 (8)	−0.0016 (8)
C6	0.0211 (10)	0.0160 (10)	0.0216 (11)	0.0022 (8)	0.0091 (9)	0.0024 (8)
C7	0.0208 (10)	0.0215 (11)	0.0170 (9)	0.0033 (8)	0.0080 (8)	0.0037 (8)
C8	0.0169 (9)	0.0173 (10)	0.0189 (10)	0.0001 (8)	0.0080 (8)	−0.0038 (8)
C9	0.0255 (11)	0.0163 (10)	0.0213 (11)	−0.0001 (8)	0.0093 (9)	0.0018 (8)
C10	0.0245 (11)	0.0196 (10)	0.0170 (10)	0.0017 (8)	0.0093 (8)	0.0031 (8)

Geometric parameters (Å, º) top

Se1—C4	1.921 (2)	C4—C2ⁱ	1.398 (3)
Se1—C5	1.923 (2)	C5—C6	1.393 (3)
Cl—C8	1.741 (2)	C5—C10	1.395 (3)
O1—C2	1.371 (2)	C6—C7	1.388 (3)
O1—C1	1.433 (2)	C6—H6	0.9500
C1—H1A	0.9800	C7—C8	1.386 (3)
C1—H1B	0.9800	C7—H7	0.9500
C1—H1C	0.9800	C8—C9	1.387 (3)
C2—C3	1.391 (3)	C9—C10	1.389 (3)
C2—C4ⁱ	1.398 (3)	C9—H9	0.9500
C3—C4	1.392 (3)	C10—H10	0.9500
C3—H3	0.9500

C4—Se1—C5	97.92 (9)	C6—C5—Se1	120.74 (16)
C2—O1—C1	116.88 (17)	C10—C5—Se1	119.64 (16)
O1—C1—H1A	109.5	C7—C6—C5	120.6 (2)
O1—C1—H1B	109.5	C7—C6—H6	119.7
H1A—C1—H1B	109.5	C5—C6—H6	119.7
O1—C1—H1C	109.5	C8—C7—C6	118.9 (2)
H1A—C1—H1C	109.5	C8—C7—H7	120.6
H1B—C1—H1C	109.5	C6—C7—H7	120.6
O1—C2—C3	124.29 (19)	C7—C8—C9	121.7 (2)
O1—C2—C4ⁱ	115.37 (18)	C7—C8—Cl	119.75 (17)
C3—C2—C4ⁱ	120.34 (19)	C9—C8—Cl	118.60 (17)
C2—C3—C4	120.07 (19)	C8—C9—C10	119.0 (2)
C2—C3—H3	120.0	C8—C9—H9	120.5
C4—C3—H3	120.0	C10—C9—H9	120.5
C3—C4—C2ⁱ	119.60 (19)	C9—C10—C5	120.3 (2)
C3—C4—Se1	123.88 (16)	C9—C10—H10	119.9
C2ⁱ—C4—Se1	116.50 (15)	C5—C10—H10	119.9
C6—C5—C10	119.6 (2)

C1—O1—C2—C3	−1.8 (3)	C10—C5—C6—C7	−2.0 (3)
C1—O1—C2—C4ⁱ	178.06 (18)	Se1—C5—C6—C7	179.10 (16)
O1—C2—C3—C4	−179.78 (19)	C5—C6—C7—C8	0.6 (3)
C4ⁱ—C2—C3—C4	0.4 (3)	C6—C7—C8—C9	0.8 (3)
C2—C3—C4—C2ⁱ	−0.4 (3)	C6—C7—C8—Cl	179.98 (16)
C2—C3—C4—Se1	177.83 (15)	C7—C8—C9—C10	−0.7 (3)
C5—Se1—C4—C3	−3.27 (19)	Cl—C8—C9—C10	−179.91 (17)
C5—Se1—C4—C2ⁱ	174.97 (16)	C8—C9—C10—C5	−0.8 (3)
C4—Se1—C5—C6	−83.67 (18)	C6—C5—C10—C9	2.1 (3)
C4—Se1—C5—C10	97.46 (18)	Se1—C5—C10—C9	−179.02 (17)

Symmetry code: (i) −x+2, −y, −z.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₆Cl₂O₂Se₂
M_r	517.15
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	122
a, b, c (Å)	11.7737 (17), 6.6535 (6), 13.438 (5)
β (°)	114.136 (16)
V (Å³)	960.7 (4)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	7.47
Crystal size (mm)	0.44 × 0.15 × 0.13

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	Gaussian (DeTitta, 1985).
T_min, T_max	0.242, 0.796
No. of measured, independent and observed [I > 2σ(I)] reflections	2641, 1976, 1919
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.076, 1.10
No. of reflections	1976
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.60, −1.20

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), DREAR (Blessing, 1987), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Acknowledgements

The authors thank Flemming Hansen, Centre of Crystallographic Studies, University of Copenhagen, for obtaining the crystallographic data. The Danish National Research Foundation is acknowledged for supporting the Center for Fundamental Research: Metal Structures in Four Dimensions.

References

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