1,3-Bis(chloro­meth­yl)benzene

Abstract

The title compound, C₈H₈Cl₂, used in the synthesis of many pharmaceutical inter­mediates, forms a three-dimensional network through chlorine–chlorine inter­actions in the solid-state that measure 3.513 (1) and 3.768 (3) Å.

Related literature  

For background information on the applications of halogenated xylenes, see: Ito & Tada (2009 ▶); Zordan & Brammer (2006 ▶). For related structures, see: Castaner et al. (1991 ▶). For halogen–halogen inter­actions, see: Hathwar et al. (2010 ▶). For additional information on how the space group of the structure was solved, see Spek (2009 ▶).

Experimental  

Crystal data  

• C₈H₈Cl₂

• M _r = 175.04

• Orthorhombic,

• a = 8.5174 (5) Å

• b = 12.3094 (7) Å

• c = 15.2597 (9) Å

• V = 1599.89 (16) ų

• Z = 8

• Mo Kα radiation

• μ = 0.73 mm⁻¹

• T = 100 K

• 0.51 × 0.50 × 0.10 mm

Data collection  

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2011 ▶) T _min = 0.665, T _max = 0.746

• 17126 measured reflections

• 1949 independent reflections

• 1782 reflections with I > 2σ(I)

• R _int = 0.026

Refinement  

• R[F ² > 2σ(F ²)] = 0.023

• wR(F ²) = 0.064

• S = 1.04

• 1949 reflections

• 91 parameters

• H-atom parameters constrained

• Δρ_max = 0.39 e Å⁻³

• Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2011 ▶); cell refinement: SAINT (Bruker, 2011 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalMaker (CrystalMaker Software, 2009 ▶); software used to prepare material for publication: enCIFer (Allen et al. 2004 ▶).

Supplementary Material

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

supplementary crystallographic information

Comment

Halogenated xylenes, including the title compound, have a variety of applications in agrochemicals, drugs, and macromolecular materials (Ito and Tada, 2009). Most recently, these compounds have shown potential for their use in hard-coated film for optical devices (Ito and Tada, 2009). Compounds such as the title one that contain networks of halogen-halogen contacts also have a variety of applications in liquid crystals, topochemical reactions, conducting materials, and anion receptors (Zordan and Brammer, 2006). 1,3-Bis(chloromethyl)benzene is stabilized by chlorine-chlorine interactions of 3.513 (1) Å and 3.768 (3) Å. These contacts are within the normal range of chlorine-chlorine interactions, which are typically 3.546 Å to 3.813 Å (Hathwar et al., 2010).

Experimental

Approximately 100 mg of the title compound was dissolved in 2 ml of hexanes. The solution was evaporated slowly over one week to produce large, clear, block crystals.

Refinement

The structure was solved using direct methods (Bruker, 2011).

Figures

Fig. 1.

Thermal ellipsoid plot at 50% probability.

Fig. 2.

The title structure is stabilized by chlorine-chlorine interactions that measure 3.513 (1) Å and 3.768 (3) Å to form a three dimensional network. Carbon atoms are shown in black, hydrogen atoms in pink, and chlorine atoms in green.

Crystal data

C8H8Cl2	Dx = 1.453 Mg m−3Dm = 1.453 Mg m−3Dm measured by not measured
Mr = 175.04	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 120 reflections
a = 8.5174 (5) Å	θ = 2.7–28.2°
b = 12.3094 (7) Å	µ = 0.73 mm−1
c = 15.2597 (9) Å	T = 100 K
V = 1599.89 (16) Å3	Thick plate, colourless
Z = 8	0.51 × 0.50 × 0.10 mm
F(000) = 720

Data collection

Bruker APEXII CCD diffractometer	1949 independent reflections
Radiation source: fine-focus sealed tube	1782 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 8.3333 pixels mm-1	θmax = 28.6°, θmin = 2.7°
ω and φ scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2011)	k = −15→15
Tmin = 0.665, Tmax = 0.746	l = −20→20
17126 measured reflections

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0356P)2 + 0.6168P] where P = (Fo2 + 2Fc2)/3
1949 reflections	(Δ/σ)max = 0.001
91 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.24 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.

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
Cl1	0.61622 (3)	0.35365 (2)	1.030229 (18)	0.02078 (9)
Cl2	0.83843 (3)	0.32450 (2)	0.660472 (18)	0.02164 (10)
C1	0.81471 (14)	0.40672 (11)	1.02366 (8)	0.0210 (3)
H1A	0.8343	0.4563	1.0736	0.025*
H1B	0.8909	0.3462	1.0272	0.025*
C2	0.83655 (13)	0.46689 (10)	0.93903 (7)	0.0159 (2)
C3	0.90389 (13)	0.41528 (9)	0.86690 (8)	0.0161 (2)
H3	0.9394	0.3424	0.8722	0.019*
C4	0.91971 (13)	0.46956 (9)	0.78693 (7)	0.0165 (2)
C5	0.98635 (14)	0.41163 (11)	0.70880 (8)	0.0218 (3)
H5A	1.0779	0.3675	0.7269	0.026*
H5B	1.0224	0.4654	0.6650	0.026*
C6	0.78830 (13)	0.57490 (10)	0.93140 (8)	0.0182 (2)
H6	0.7434	0.6110	0.9804	0.022*
C7	0.80570 (15)	0.62972 (10)	0.85252 (8)	0.0209 (2)
H7	0.7736	0.7034	0.8478	0.025*
C8	0.87016 (14)	0.57693 (10)	0.78021 (8)	0.0196 (2)
H8	0.8803	0.6144	0.7261	0.024*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.01567 (15)	0.02646 (17)	0.02020 (16)	−0.00530 (11)	0.00008 (10)	0.00373 (11)
Cl2	0.02070 (16)	0.02609 (17)	0.01814 (15)	−0.00366 (11)	0.00164 (10)	−0.00641 (11)
C1	0.0148 (5)	0.0300 (7)	0.0181 (6)	−0.0067 (5)	−0.0028 (4)	0.0046 (5)
C2	0.0113 (5)	0.0219 (6)	0.0145 (5)	−0.0039 (4)	−0.0025 (4)	0.0009 (4)
C3	0.0121 (5)	0.0165 (5)	0.0196 (6)	−0.0015 (4)	−0.0019 (4)	0.0000 (4)
C4	0.0117 (5)	0.0216 (6)	0.0162 (5)	−0.0028 (4)	−0.0004 (4)	−0.0022 (4)
C5	0.0150 (5)	0.0298 (7)	0.0206 (6)	−0.0035 (5)	0.0013 (4)	−0.0065 (5)
C6	0.0158 (5)	0.0216 (6)	0.0173 (5)	−0.0008 (4)	0.0018 (4)	−0.0041 (4)
C7	0.0209 (6)	0.0166 (6)	0.0250 (6)	0.0013 (4)	0.0000 (5)	0.0012 (5)
C8	0.0192 (5)	0.0227 (6)	0.0171 (5)	−0.0017 (5)	0.0000 (4)	0.0039 (5)

Geometric parameters (Å, º)

Cl1—C1	1.8152 (12)	C4—C8	1.3912 (17)
Cl2—C5	1.8115 (12)	C4—C5	1.5007 (16)
C1—C2	1.5004 (16)	C5—H5A	0.9900
C1—H1A	0.9900	C5—H5B	0.9900
C1—H1B	0.9900	C6—C7	1.3879 (17)
C2—C3	1.3944 (16)	C6—H6	0.9500
C2—C6	1.3964 (17)	C7—C8	1.3933 (17)
C3—C4	1.3978 (16)	C7—H7	0.9500
C3—H3	0.9500	C8—H8	0.9500
C2—C1—Cl1	109.92 (8)	C4—C5—Cl2	109.97 (8)
C2—C1—H1A	109.7	C4—C5—H5A	109.7
Cl1—C1—H1A	109.7	Cl2—C5—H5A	109.7
C2—C1—H1B	109.7	C4—C5—H5B	109.7
Cl1—C1—H1B	109.7	Cl2—C5—H5B	109.7
H1A—C1—H1B	108.2	H5A—C5—H5B	108.2
C3—C2—C6	119.28 (11)	C7—C6—C2	120.25 (11)
C3—C2—C1	120.37 (11)	C7—C6—H6	119.9
C6—C2—C1	120.35 (11)	C2—C6—H6	119.9
C2—C3—C4	120.73 (11)	C6—C7—C8	120.14 (11)
C2—C3—H3	119.6	C6—C7—H7	119.9
C4—C3—H3	119.6	C8—C7—H7	119.9
C8—C4—C3	119.29 (11)	C4—C8—C7	120.28 (11)
C8—C4—C5	120.50 (11)	C4—C8—H8	119.9
C3—C4—C5	120.19 (11)	C7—C8—H8	119.9