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

Abstract

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,

• a = 6.518 (3) Å

• b = 14.680 (6) Å

• c = 8.433 (4) Å

• β = 106.335 (5)°

• V = 774.3 (6) ų

• 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[F ² > 2σ(F ²)] = 0.040

• wR(F ²) = 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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

All H atoms were geometrically positioned (C–H 0.93-0.98%A) and treated as riding, with Uiso(H) = 1.2Ueq(C).

Figures

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].

Crystal data

C14H18Cl4	F(000) = 340
Mr = 328.08	Dx = 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

Bruker SMART APEX CCD diffractometer	1679 independent reflections
Radiation source: sealed tube	1275 reflections with I > 2σ(I)
graphite	Rint = 0.066
φ and ω scans	θmax = 27.0°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→7
Tmin = 0.807, Tmax = 0.842	k = −18→14
4423 measured reflections	l = −10→10

Refinement

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(Fo2) + (0.0483P)2 + 0.0345P] where P = (Fo2 + 2Fc2)/3
1679 reflections	(Δ/σ)max < 0.001
82 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.32 e Å−3

Special details

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 Uiso(H) = 1.2 timesUeq(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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x, −y+2, −z+1.