supplementary materials


mw2106 scheme

Acta Cryst. (2013). E69, o1150    [ doi:10.1107/S1600536813016383 ]

1,3-Bis(chloromethyl)benzene

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

Abstract top

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.

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.

Refinement top

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

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
[Figure 1] Fig. 1. Thermal ellipsoid plot at 50% probability.
[Figure 2] 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
C8H8Cl2Dx = 1.453 Mg m3
Dm = 1.453 Mg m3
Dm measured by not measured
Mr = 175.04Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 120 reflections
a = 8.5174 (5) Åθ = 2.7–28.2°
b = 12.3094 (7) ŵ = 0.73 mm1
c = 15.2597 (9) ÅT = 100 K
V = 1599.89 (16) Å3Thick plate, colourless
Z = 80.51 × 0.50 × 0.10 mm
F(000) = 720
Data collection top
Bruker APEXII CCD
diffractometer
1949 independent reflections
Radiation source: fine-focus sealed tube1782 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
Detector resolution: 8.3333 pixels mm-1θmax = 28.6°, θmin = 2.7°
ω and φ scansh = 1111
Absorption correction: multi-scan
(SADABS; Bruker, 2011)
k = 1515
Tmin = 0.665, Tmax = 0.746l = 2020
17126 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064H-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 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C8H8Cl2V = 1599.89 (16) Å3
Mr = 175.04Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 8.5174 (5) ŵ = 0.73 mm1
b = 12.3094 (7) ÅT = 100 K
c = 15.2597 (9) Å0.51 × 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)
Tmin = 0.665, Tmax = 0.746Rint = 0.026
17126 measured reflectionsθmax = 28.6°
Refinement top
R[F2 > 2σ(F2)] = 0.023H-atom parameters constrained
wR(F2) = 0.064Δρmax = 0.39 e Å3
S = 1.04Δρmin = 0.24 e Å3
1949 reflectionsAbsolute structure: ?
91 parametersAbsolute structure parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Cl10.61622 (3)0.35365 (2)1.030229 (18)0.02078 (9)
Cl20.83843 (3)0.32450 (2)0.660472 (18)0.02164 (10)
C10.81471 (14)0.40672 (11)1.02366 (8)0.0210 (3)
H1A0.83430.45631.07360.025*
H1B0.89090.34621.02720.025*
C20.83655 (13)0.46689 (10)0.93903 (7)0.0159 (2)
C30.90389 (13)0.41528 (9)0.86690 (8)0.0161 (2)
H30.93940.34240.87220.019*
C40.91971 (13)0.46956 (9)0.78693 (7)0.0165 (2)
C50.98635 (14)0.41163 (11)0.70880 (8)0.0218 (3)
H5A1.07790.36750.72690.026*
H5B1.02240.46540.66500.026*
C60.78830 (13)0.57490 (10)0.93140 (8)0.0182 (2)
H60.74340.61100.98040.022*
C70.80570 (15)0.62972 (10)0.85252 (8)0.0209 (2)
H70.77360.70340.84780.025*
C80.87016 (14)0.57693 (10)0.78021 (8)0.0196 (2)
H80.88030.61440.72610.024*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.01567 (15)0.02646 (17)0.02020 (16)0.00530 (11)0.00008 (10)0.00373 (11)
Cl20.02070 (16)0.02609 (17)0.01814 (15)0.00366 (11)0.00164 (10)0.00641 (11)
C10.0148 (5)0.0300 (7)0.0181 (6)0.0067 (5)0.0028 (4)0.0046 (5)
C20.0113 (5)0.0219 (6)0.0145 (5)0.0039 (4)0.0025 (4)0.0009 (4)
C30.0121 (5)0.0165 (5)0.0196 (6)0.0015 (4)0.0019 (4)0.0000 (4)
C40.0117 (5)0.0216 (6)0.0162 (5)0.0028 (4)0.0004 (4)0.0022 (4)
C50.0150 (5)0.0298 (7)0.0206 (6)0.0035 (5)0.0013 (4)0.0065 (5)
C60.0158 (5)0.0216 (6)0.0173 (5)0.0008 (4)0.0018 (4)0.0041 (4)
C70.0209 (6)0.0166 (6)0.0250 (6)0.0013 (4)0.0000 (5)0.0012 (5)
C80.0192 (5)0.0227 (6)0.0171 (5)0.0017 (5)0.0000 (4)0.0039 (5)
Geometric parameters (Å, º) top
Cl1—C11.8152 (12)C4—C81.3912 (17)
Cl2—C51.8115 (12)C4—C51.5007 (16)
C1—C21.5004 (16)C5—H5A0.9900
C1—H1A0.9900C5—H5B0.9900
C1—H1B0.9900C6—C71.3879 (17)
C2—C31.3944 (16)C6—H60.9500
C2—C61.3964 (17)C7—C81.3933 (17)
C3—C41.3978 (16)C7—H70.9500
C3—H30.9500C8—H80.9500
C2—C1—Cl1109.92 (8)C4—C5—Cl2109.97 (8)
C2—C1—H1A109.7C4—C5—H5A109.7
Cl1—C1—H1A109.7Cl2—C5—H5A109.7
C2—C1—H1B109.7C4—C5—H5B109.7
Cl1—C1—H1B109.7Cl2—C5—H5B109.7
H1A—C1—H1B108.2H5A—C5—H5B108.2
C3—C2—C6119.28 (11)C7—C6—C2120.25 (11)
C3—C2—C1120.37 (11)C7—C6—H6119.9
C6—C2—C1120.35 (11)C2—C6—H6119.9
C2—C3—C4120.73 (11)C6—C7—C8120.14 (11)
C2—C3—H3119.6C6—C7—H7119.9
C4—C3—H3119.6C8—C7—H7119.9
C8—C4—C3119.29 (11)C4—C8—C7120.28 (11)
C8—C4—C5120.50 (11)C4—C8—H8119.9
C3—C4—C5120.19 (11)C7—C8—H8119.9

Experimental details

Crystal data
Chemical formulaC8H8Cl2
Mr175.04
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)100
a, b, c (Å)8.5174 (5), 12.3094 (7), 15.2597 (9)
V3)1599.89 (16)
Z8
Radiation typeMo Kα
µ (mm1)0.73
Crystal size (mm)0.51 × 0.50 × 0.10
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2011)
Tmin, Tmax0.665, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections
17126, 1949, 1782
Rint0.026
(sin θ/λ)max1)0.674
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.064, 1.04
No. of reflections1949
No. of parameters91
No. of restraints0
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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 top

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
References top

Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335–338.

Bruker (2011). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Castaner, J., Riera, J., Carilla, J., Robert, A., Molins, E. & Miravitlles, C. (1991). J. Org. Chem. 56, 103-.

CrystalMaker Software (2009). CrystalMaker for Windows. CrystalMaker Software Ltd, Oxford, England.

Hathwar, V., Roopan, S., Subashini, R., Khan, F. & Row, T. (2010). J. Chem. Sci. 122, 677–685.

Ito, A. & Tada, N. (2009). Jpn Kokai Tokkyo Koho, JP 2009242338 A 20091022

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.

Zordan, F. & Brammer, L. (2006). Cryst. Growth Des. 6, 1374–1379.