1,4-Bis[3-chloro-2-(chloro­meth­yl)prop­yl]benzene

Xi, H.; Gao, Y.; Sun, X.; Ma, Z.; Xiong, M.

doi:10.1107/S1600536809000609

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o473

doi:10.1107/S1600536809000609

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1,4-Bis[3-chloro-2-(chloromethyl)propyl]benzene

Haitao Xi,^a Yajun Gao,^a Xiaoqiang Sun,^a ^* Zhijun Ma ^a and Minqiu Xiong ^a

^aSchool of Chemistry and Chemical Engineering, Jiangsu Polytechnic University, Changzhou 213164, People's Republic of China
^*Correspondence e-mail: xiaoqiang_sun@yahoo.com.cn

(Received 25 December 2008; accepted 7 January 2009; online 6 February 2009)

The title molecule, C₁₄H₁₈Cl₄, possesses a crystallographically imposed inversion centre, which coincides with the centre of benzene ring. In the absence of classical intermolecular interactions, van der Waals forces help the molecules to pack in the crystal.

Related literature

For related crystal structures, see: Chen et al. (2005 ); Gao et al. (2009 ). For general background, see Amabilino & Stoddart (1995 ).

Experimental

Crystal data

C₁₄H₁₈Cl₄
M_r = 328.08
Monoclinic, P 2₁ /c
a = 6.518 (3) Å
b = 14.680 (6) Å
c = 8.433 (4) Å
β = 106.335 (5)°
V = 774.3 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.75 mm⁻¹
T = 291 (2) K
0.30 × 0.26 × 0.24 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.807, T_max = 0.842
4423 measured reflections
1679 independent reflections
1275 reflections with I > 2σ(I)
R_int = 0.066

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.113
S = 1.09
1679 reflections
82 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.32 e Å⁻³

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809000609/cv2502sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809000609/cv2502Isup2.hkl

checkCIF report

Comment top

The molecular recognition between a π-electron-rich hydroquinone ring and π-electron-deficient cyclophane has provided the inspiration for the self-assembly of a large number of catenanes (Amabilino & Stoddart, 1995). In our study of the applications of fused bipyridine cyclophane compounds in the self-assembly of supramolecular systems, we obtained tetraethyl 2,2'-(p-phenylenedimethylene)dimalonate (Chen et al., 2005), which was used in the synthesis of 2,2'-(p-phenylenedimethylene)bis(propane-1,3-diol) (Gao et al., 2009). The title compound, (I), was obtained by the chlorination of the diol. Herewith we present the crystal structure of (I) (Fig. 1).

Related literature top

For related crystal structures, see: Chen et al. (2005); Gao et al. (2009). For general background, see Amabilino & Stoddart (1995).

Experimental top

The 2,2'-(p-phenylenedimethylene)bis(propane-1,3-diol), used in this study, was obtained in accordance with the Gao et al. (2005). In a flame-dryed, round-bottomed flask was placed SOCl₂(5 mL) and p-C₆H₄[CH₂CH(CH₂OH)₂]₂(0.508 g,2 mmol) was slowly added under stirring. The mixture was heated up to 333 K. The solvent was evaporated and the resulting oil was chromatographed on a silica-gel column, yielding the title compound (0.51 g, 77%). M.p. 353–354 K.

Computing details top

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

Figures top

Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and 30% probability displacement ellipsoids [symmetry code: (A)-x, -y + 2, -z + 1].

1,4-Bis[3-chloro-2-(chloromethyl)propyl]benzene top

Crystal data top

C₁₄H₁₈Cl₄	F(000) = 340
M_r = 328.08	D_x = 1.407 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1607 reflections
a = 6.518 (3) Å	θ = 2.8–26.1°
b = 14.680 (6) Å	µ = 0.75 mm⁻¹
c = 8.433 (4) Å	T = 291 K
β = 106.335 (5)°	Block, colourless
V = 774.3 (6) Å³	0.30 × 0.26 × 0.24 mm
Z = 2

Data collection top

Bruker SMART APEX CCD diffractometer	1679 independent reflections
Radiation source: sealed tube	1275 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
ϕ and ω scans	θ_max = 27.0°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→7
T_min = 0.807, T_max = 0.842	k = −18→14
4423 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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0483P)² + 0.0345P] where P = (F_o² + 2F_c²)/3
1679 reflections	(Δ/σ)_max < 0.001
82 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₄H₁₈Cl₄	V = 774.3 (6) Å³
M_r = 328.08	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.518 (3) Å	µ = 0.75 mm⁻¹
b = 14.680 (6) Å	T = 291 K
c = 8.433 (4) Å	0.30 × 0.26 × 0.24 mm
β = 106.335 (5)°

Data collection top

Bruker SMART APEX CCD diffractometer	1679 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1275 reflections with I > 2σ(I)
T_min = 0.807, T_max = 0.842	R_int = 0.066
4423 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.09	Δρ_max = 0.32 e Å⁻³
1679 reflections	Δρ_min = −0.32 e Å⁻³
82 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.

The structures were solved with direct methods and refined with full-matrix least-squares techniques using the SHELXTL. The coordinates of the non-hydrogen atoms were refined anisotropically, and the positions of the H atoms were positioned geometrically and refined using a riding model with C—H = 0.93–0.97 Å, and with U_iso(H) = 1.2 timesU_eq(C).

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
C1	0.1873 (3)	0.97482 (12)	0.6208 (2)	0.0415 (4)
C2	0.0205 (4)	1.01687 (13)	0.6634 (2)	0.0482 (5)
H2	0.0327	1.0284	0.7741	0.058*
C3	−0.1637 (3)	1.04196 (13)	0.5447 (3)	0.0477 (5)
H3	−0.2733	1.0705	0.5764	0.057*
C4	0.3901 (3)	0.94730 (13)	0.7505 (3)	0.0489 (5)
H7A	0.3999	0.9812	0.8511	0.059*
H7B	0.5123	0.9638	0.7122	0.059*
C5	0.4008 (3)	0.84467 (13)	0.7898 (2)	0.0410 (4)
H8	0.3984	0.8123	0.6877	0.049*
C6	0.6155 (3)	0.82501 (15)	0.9136 (3)	0.0543 (5)
H9A	0.6174	0.8515	1.0194	0.065*
H9B	0.7275	0.8539	0.8764	0.065*
C7	0.2135 (3)	0.81085 (13)	0.8444 (2)	0.0444 (5)
H10A	0.2273	0.7456	0.8629	0.053*
H10B	0.0828	0.8218	0.7571	0.053*
Cl1	0.67066 (10)	0.70596 (4)	0.94037 (8)	0.0736 (3)
Cl2	0.19547 (9)	0.86582 (4)	1.03025 (7)	0.0635 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0465 (11)	0.0298 (9)	0.0488 (11)	−0.0015 (8)	0.0141 (9)	0.0050 (8)
C2	0.0586 (13)	0.0437 (11)	0.0440 (11)	0.0046 (9)	0.0172 (10)	−0.0002 (8)
C3	0.0535 (12)	0.0389 (11)	0.0560 (12)	0.0063 (9)	0.0241 (10)	0.0036 (9)
C4	0.0424 (11)	0.0438 (11)	0.0570 (12)	−0.0062 (8)	0.0082 (9)	0.0026 (9)
C5	0.0389 (10)	0.0396 (10)	0.0443 (10)	0.0017 (8)	0.0114 (8)	−0.0017 (8)
C6	0.0368 (11)	0.0513 (12)	0.0718 (14)	0.0052 (9)	0.0101 (10)	0.0022 (10)
C7	0.0397 (11)	0.0414 (11)	0.0480 (11)	−0.0012 (8)	0.0058 (9)	0.0009 (8)
Cl1	0.0629 (4)	0.0603 (4)	0.0915 (5)	0.0227 (3)	0.0119 (3)	0.0086 (3)
Cl2	0.0614 (4)	0.0795 (4)	0.0538 (4)	0.0101 (3)	0.0228 (3)	0.0004 (3)

Geometric parameters (Å, º) top

C1—C3ⁱ	1.382 (3)	C5—C7	1.504 (3)
C1—C2	1.383 (3)	C5—C6	1.520 (3)
C1—C4	1.515 (3)	C5—H8	0.9800
C2—C3	1.380 (3)	C6—Cl1	1.786 (2)
C2—H2	0.9300	C6—H9A	0.9700
C3—C1ⁱ	1.382 (3)	C6—H9B	0.9700
C3—H3	0.9300	C7—Cl2	1.796 (2)
C4—C5	1.540 (3)	C7—H10A	0.9700
C4—H7A	0.9700	C7—H10B	0.9700
C4—H7B	0.9700

C3ⁱ—C1—C2	118.01 (19)	C6—C5—C4	108.10 (16)
C3ⁱ—C1—C4	120.55 (19)	C7—C5—H8	107.2
C2—C1—C4	121.44 (18)	C6—C5—H8	107.2
C3—C2—C1	121.17 (19)	C4—C5—H8	107.2
C3—C2—H2	119.4	C5—C6—Cl1	112.74 (15)
C1—C2—H2	119.4	C5—C6—H9A	109.0
C2—C3—C1ⁱ	120.82 (19)	Cl1—C6—H9A	109.0
C2—C3—H3	119.6	C5—C6—H9B	109.0
C1ⁱ—C3—H3	119.6	Cl1—C6—H9B	109.0
C1—C4—C5	113.20 (15)	H9A—C6—H9B	107.8
C1—C4—H7A	108.9	C5—C7—Cl2	112.11 (13)
C5—C4—H7A	108.9	C5—C7—H10A	109.2
C1—C4—H7B	108.9	Cl2—C7—H10A	109.2
C5—C4—H7B	108.9	C5—C7—H10B	109.2
H7A—C4—H7B	107.8	Cl2—C7—H10B	109.2
C7—C5—C6	113.40 (16)	H10A—C7—H10B	107.9
C7—C5—C4	113.42 (15)

C3ⁱ—C1—C2—C3	−0.4 (3)	C1—C4—C5—C6	176.91 (17)
C4—C1—C2—C3	179.85 (17)	C7—C5—C6—Cl1	64.6 (2)
C1—C2—C3—C1ⁱ	0.4 (3)	C4—C5—C6—Cl1	−168.74 (14)
C3ⁱ—C1—C4—C5	−77.5 (2)	C6—C5—C7—Cl2	62.71 (19)
C2—C1—C4—C5	102.2 (2)	C4—C5—C7—Cl2	−61.10 (19)
C1—C4—C5—C7	−56.4 (2)

Symmetry code: (i) −x, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₈Cl₄
M_r	328.08
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	6.518 (3), 14.680 (6), 8.433 (4)
β (°)	106.335 (5)
V (Å³)	774.3 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.75
Crystal size (mm)	0.30 × 0.26 × 0.24

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.807, 0.842
No. of measured, independent and observed [I > 2σ(I)] reflections	4423, 1679, 1275
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.113, 1.09
No. of reflections	1679
No. of parameters	82
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.32

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors acknowledge the financial support of Jiangsu Polytechnic University, the Natural Science Foundation of China (grant No. 20872051) and the Key Laboratory of Fine Petrochemical Engineering of Jiangsu Province (grant No. KF0503).

References

Amabilino, D. B. & Stoddart, J. F. (1995). Chem. Rev. 95, 2725–2737. CrossRef CAS Web of Science Google Scholar
Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Chen, A.-H., Wang, Z.-G., Yin, G.-D. & Wu, A.-X. (2005). Acta Cryst. E61, o3240–o3241. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122. Web of Science CrossRef CAS IUCr Journals Google Scholar