1,3-Bis(chloro­meth­yl)benzene

Sanders, M.B.; Leon, D.; Ndichie, E.I.; Chan, B.C.

doi:10.1107/S1600536813016383

organic compounds

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ISSN: 2056-9890

Volume 69| Part 7| July 2013| Page o1150

https://doi.org/10.1107/S1600536813016383

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1,3-Bis(chloromethyl)benzene

Marisa B. Sanders,^a David Leon,^a Eddy I. Ndichie ^a and Benny C. Chan ^a ^*

^aDepartment of Chemistry, The College of New Jersey, 2000 Pennington Rd, Ewing, NJ 08628, USA
^*Correspondence e-mail: chan@tcnj.edu

(Received 5 March 2013; accepted 12 June 2013; online 26 June 2013)

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, P b c a
a = 8.5174 (5) Å
b = 12.3094 (7) Å
c = 15.2597 (9) Å
V = 1599.89 (16) Å³
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[F² > 2σ(F²)] = 0.023
wR(F²) = 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813016383/mw2106sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813016383/mw2106Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813016383/mw2106Isup3.cml

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Structure description top

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).

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT (Bruker, 2011); 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).

Figures top

	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.

1,3-Bis(chloromethyl)benzene top

Crystal data top

C₈H₈Cl₂	D_x = 1.453 Mg m⁻³ D_m = 1.453 Mg m⁻³ D_m measured by not measured
M_r = 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 top

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

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.064	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0356P)² + 0.6168P] where P = (F_o² + 2F_c²)/3
1949 reflections	(Δ/σ)_max = 0.001
91 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₈H₈Cl₂	V = 1599.89 (16) Å³
M_r = 175.04	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 8.5174 (5) Å	µ = 0.73 mm⁻¹
b = 12.3094 (7) Å	T = 100 K
c = 15.2597 (9) Å	0.51 × 0.50 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	1949 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2011)	1782 reflections with I > 2σ(I)
T_min = 0.665, T_max = 0.746	R_int = 0.026
17126 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.064	H-atom parameters constrained
S = 1.04	Δρ_max = 0.39 e Å⁻³
1949 reflections	Δρ_min = −0.24 e Å⁻³
91 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
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 (Å²) top

	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) top

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

Experimental details

Crystal data
Chemical formula	C₈H₈Cl₂
M_r	175.04
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	100
a, b, c (Å)	8.5174 (5), 12.3094 (7), 15.2597 (9)
V (Å³)	1599.89 (16)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.73
Crystal size (mm)	0.51 × 0.50 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2011)
T_min, T_max	0.665, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	17126, 1949, 1782
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.674

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.064, 1.04
No. of reflections	1949
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.24

Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CrystalMaker (CrystalMaker Software, 2009), enCIFer (Allen et al. 2004).

Acknowledgements

The authors gratefully acknowledge The College of New Jersey's School of Science for research funding and the National Science Foundation for major research instrumentation grant (NSF-0922931) for diffractometer acquisition.

References

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