1,4-Dichloro-2,3-bis­(chloro­meth­yl)butane

Cordes, D.B.; Aitken, K.M.; Aitken, R.A.

doi:10.1107/S1600536812048398

organic compounds

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Volume 68| Part 12| December 2012| Page o3495

doi:10.1107/S1600536812048398

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1,4-Dichloro-2,3-bis(chloromethyl)butane

David B. Cordes,^a ‡ Kati M. Aitken ^a and R. Alan Aitken ^a ^*

^aEaStCHEM School of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: raa@st-andrews.ac.uk

(Received 21 November 2012; accepted 25 November 2012; online 30 November 2012)

The title compound, C₆H₁₀Cl₄, adopts a geometric arrangement with two C—Cl bonds antiperiplanar to C—H bonds and the other two antiperiplanar to C—C bonds. While minimising steric replusion, this arrangement still gives rise to some intramolecular C—H⋯Cl contacts. In the crystal, molecules are connected into a three-dimensional architecture via further C—H⋯Cl contacts.

Related literature

The title compound was previously prepared by Weinges & Spänig (1968 ). For related structures of polychlorinated acylic alkanes, see: Frenzen et al. (1999 ); Frenzen & Coelhan (1998 ); Bart et al. (1979 , 1980 ); Karapetyan et al. (2008 ); Kabalka et al. (2005 ); Podsiadło & Katrusiak (2006 ); Klaeboe et al. (1986 ).

Experimental

Crystal data

C₆H₁₀Cl₄
M_r = 223.94
Orthorhombic, P b c a
a = 8.998 (3) Å
b = 8.400 (3) Å
c = 24.643 (7) Å
V = 1862.6 (10) Å³
Z = 8
Mo Kα radiation
μ = 1.20 mm⁻¹
T = 93 K
0.25 × 0.25 × 0.10 mm

Data collection

Rigaku Mercury diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2010 ) T_min = 0.746, T_max = 1.000
8405 measured reflections
1658 independent reflections
1553 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.075
S = 1.12
1658 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1B⋯Cl3	0.99	2.76	3.2097 (19)	108
C4—H4B⋯Cl4	0.99	2.80	3.2445 (19)	108
C5—H5B⋯Cl1	0.99	2.74	3.2069 (19)	109
C6—H6B⋯Cl2	0.99	2.72	3.1940 (18)	110
C2—H2⋯Cl3ⁱ	1.00	2.93	3.8599 (19)	155
C3—H3⋯Cl2ⁱⁱ	1.00	2.86	3.8092 (19)	160
C4—H4B⋯Cl3ⁱ	0.99	2.92	3.657 (2)	132
C5—H5A⋯Cl2ⁱⁱⁱ	0.99	2.90	3.6951 (19)	138
C6—H6A⋯Cl1^iv	0.99	2.84	3.655 (2)	140
Symmetry codes: (i) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iv) -x, -y, -z.

Data collection: CrystalClear (Rigaku, 2010); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ); program(s) used to refine structure: SHELXTL (Sheldrick, 2008 ); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812048398/tk5174sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812048398/tk5174Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812048398/tk5174Isup3.cml

checkCIF report

Comment top

The title compound shows a mixture of geometric arrangements of the C—Cl bonds, with two of them antiperiplanar to C—C bonds [Cl3—C5—C2—C3: 166.68 (11)°, Cl2—C4—C3—C2: 166.96 (11)°], and the other two antiperiplanar to C—H bonds [Cl1—C1—C2—H2: 178.6°, Cl4—C6—C3—H3: 175.9°]. This pattern of differing geometric arrangements has also been seen in related polychlorinated acylic alkanes (Frenzen et al., 1999; Frenzen & Coelhan, 1998; Bart et al., 1979, 1980; Karapetyan et al., 2008; Kabalka et al., 2005; Podsiadło & Katrusiak, 2006; Klaeboe et al., 1986), due to the necessity of minimizing steric repulsion in such extended structures. The arrangement of the C—Cl bonds gives rise to intramolecular C—H···Cl contacts for all four chlorines, at distances ranging from 2.72 to 2.80 Å. In addition, three of the four chlorine atoms also make intermolecular C—H···Cl contacts to adjacent molecules, at distances between 2.84 and 2.93 Å, resulting in the formation of a weakly interacting three-dimensional array.

Related literature top

The title compound was previously prepared by Weinges & Spänig (1968). For related structures of polychlorinated acylic alkanes, see: Frenzen et al. (1999); Frenzen & Coelhan (1998); Bart et al. (1979, 1980); Karapetyan et al. (2008); Kabalka et al. (2005); Podsiadło & Katrusiak (2006); Klaeboe et al. (1986).

Experimental top

The title compound was prepared by the method of Weinges and Spänig (1968). Crystals suitable for X-ray structure determination were obtained by sublimation at room temperature and ambient pressure.

Computing details top

Data collection: CrystalClear (Rigaku, 2010); cell refinement: CrystalClear (Rigaku, 2010); data reduction: CrystalClear (Rigaku, 2010); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

1,4-Dichloro-2,3-bis(chloromethyl)butane top

Crystal data top

C₆H₁₀Cl₄	F(000) = 912
M_r = 223.94	D_x = 1.597 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5355 reflections
a = 8.998 (3) Å	θ = 1.7–28.6°
b = 8.400 (3) Å	µ = 1.20 mm⁻¹
c = 24.643 (7) Å	T = 93 K
V = 1862.6 (10) Å³	Prism, colourless
Z = 8	0.25 × 0.25 × 0.10 mm

Data collection top

Rigaku Mercury diffractometer	1658 independent reflections
Radiation source: rotating anode	1553 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.050
Detector resolution: 14.7059 pixels mm^-1	θ_max = 25.4°, θ_min = 2.8°
ω and ϕ scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2010)	k = −9→10
T_min = 0.746, T_max = 1.000	l = −25→29
8405 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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0315P)² + 0.758P] where P = (F_o² + 2F_c²)/3
1658 reflections	(Δ/σ)_max < 0.001
91 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₆H₁₀Cl₄	V = 1862.6 (10) Å³
M_r = 223.94	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 8.998 (3) Å	µ = 1.20 mm⁻¹
b = 8.400 (3) Å	T = 93 K
c = 24.643 (7) Å	0.25 × 0.25 × 0.10 mm

Data collection top

Rigaku Mercury diffractometer	1658 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2010)	1553 reflections with I > 2σ(I)
T_min = 0.746, T_max = 1.000	R_int = 0.050
8405 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.075	H-atom parameters constrained
S = 1.12	Δρ_max = 0.29 e Å⁻³
1658 reflections	Δρ_min = −0.26 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	−0.07005 (5)	−0.12175 (5)	0.063173 (16)	0.02498 (15)
Cl2	0.32971 (5)	0.25183 (6)	0.190640 (17)	0.02602 (15)
Cl3	−0.33730 (5)	0.06538 (6)	0.184618 (18)	0.02712 (15)
Cl4	0.08315 (5)	0.40738 (5)	0.056565 (18)	0.02950 (15)
C1	−0.1427 (2)	0.0759 (2)	0.07550 (7)	0.0210 (4)
H1A	−0.1140	0.1468	0.0452	0.025*
H1B	−0.2526	0.0714	0.0768	0.025*
C2	−0.08431 (17)	0.14452 (19)	0.12866 (6)	0.0177 (4)
H2	−0.1265	0.2541	0.1324	0.021*
C3	0.08737 (17)	0.16035 (19)	0.13078 (6)	0.0174 (4)
H3	0.1284	0.0520	0.1383	0.021*
C4	0.13327 (19)	0.2676 (2)	0.17793 (6)	0.0215 (4)
H4A	0.0777	0.2367	0.2110	0.026*
H4B	0.1079	0.3795	0.1693	0.026*
C5	−0.13917 (19)	0.0475 (2)	0.17705 (7)	0.0216 (4)
H5A	−0.0896	0.0855	0.2105	0.026*
H5B	−0.1126	−0.0658	0.1718	0.026*
C6	0.15708 (18)	0.2177 (2)	0.07798 (7)	0.0207 (4)
H6A	0.1388	0.1378	0.0492	0.025*
H6B	0.2659	0.2273	0.0829	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0309 (3)	0.0212 (3)	0.0228 (2)	−0.00077 (18)	0.00016 (16)	−0.00473 (16)
Cl2	0.0180 (3)	0.0320 (3)	0.0281 (3)	−0.00443 (16)	−0.00639 (15)	0.00751 (18)
Cl3	0.0168 (3)	0.0315 (3)	0.0331 (3)	−0.00376 (17)	0.00498 (16)	−0.00645 (18)
Cl4	0.0355 (3)	0.0231 (3)	0.0299 (3)	−0.00145 (18)	−0.00172 (17)	0.00903 (18)
C1	0.0210 (9)	0.0203 (8)	0.0215 (8)	0.0006 (7)	−0.0031 (7)	0.0003 (7)
C2	0.0157 (9)	0.0173 (8)	0.0201 (8)	0.0012 (6)	−0.0019 (6)	−0.0006 (7)
C3	0.0167 (9)	0.0167 (8)	0.0188 (8)	0.0017 (6)	−0.0003 (6)	0.0010 (6)
C4	0.0141 (8)	0.0286 (9)	0.0219 (8)	−0.0014 (7)	−0.0021 (6)	−0.0004 (7)
C5	0.0157 (8)	0.0275 (9)	0.0217 (8)	0.0002 (7)	0.0012 (6)	−0.0022 (7)
C6	0.0210 (10)	0.0196 (8)	0.0213 (8)	0.0012 (7)	0.0010 (6)	0.0013 (7)

Geometric parameters (Å, º) top

Cl1—C1	1.8103 (18)	C3—C6	1.523 (2)
Cl2—C4	1.7999 (18)	C3—C4	1.528 (2)
Cl3—C5	1.7987 (18)	C3—H3	1.0000
Cl4—C6	1.8054 (18)	C4—H4A	0.9900
C1—C2	1.525 (2)	C4—H4B	0.9900
C1—H1A	0.9900	C5—H5A	0.9900
C1—H1B	0.9900	C5—H5B	0.9900
C2—C5	1.526 (2)	C6—H6A	0.9900
C2—C3	1.551 (2)	C6—H6B	0.9900
C2—H2	1.0000

C2—C1—Cl1	111.49 (11)	C3—C4—Cl2	110.75 (12)
C2—C1—H1A	109.3	C3—C4—H4A	109.5
Cl1—C1—H1A	109.3	Cl2—C4—H4A	109.5
C2—C1—H1B	109.3	C3—C4—H4B	109.5
Cl1—C1—H1B	109.3	Cl2—C4—H4B	109.5
H1A—C1—H1B	108.0	H4A—C4—H4B	108.1
C1—C2—C5	110.98 (14)	C2—C5—Cl3	110.91 (12)
C1—C2—C3	113.87 (13)	C2—C5—H5A	109.5
C5—C2—C3	109.97 (13)	Cl3—C5—H5A	109.5
C1—C2—H2	107.2	C2—C5—H5B	109.5
C5—C2—H2	107.2	Cl3—C5—H5B	109.5
C3—C2—H2	107.2	H5A—C5—H5B	108.0
C6—C3—C4	110.60 (14)	C3—C6—Cl4	112.17 (11)
C6—C3—C2	114.11 (13)	C3—C6—H6A	109.2
C4—C3—C2	110.21 (13)	Cl4—C6—H6A	109.2
C6—C3—H3	107.2	C3—C6—H6B	109.2
C4—C3—H3	107.2	Cl4—C6—H6B	109.2
C2—C3—H3	107.2	H6A—C6—H6B	107.9

Cl1—C1—C2—C5	−64.59 (16)	C2—C3—C4—Cl2	166.96 (11)
Cl1—C1—C2—C3	60.14 (17)	C1—C2—C5—Cl3	−66.41 (15)
C1—C2—C3—C6	40.2 (2)	C3—C2—C5—Cl3	166.68 (11)
C5—C2—C3—C6	165.43 (14)	C4—C3—C6—Cl4	−67.52 (15)
C1—C2—C3—C4	165.31 (13)	C2—C3—C6—Cl4	57.41 (17)
C5—C2—C3—C4	−69.43 (18)	Cl1—C1—C2—H2	178.6
C6—C3—C4—Cl2	−65.92 (15)	Cl4—C6—C3—H3	175.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···Cl3	0.99	2.76	3.2097 (19)	108
C4—H4B···Cl4	0.99	2.80	3.2445 (19)	108
C5—H5B···Cl1	0.99	2.74	3.2069 (19)	109
C6—H6B···Cl2	0.99	2.72	3.1940 (18)	110
C2—H2···Cl3ⁱ	1.00	2.93	3.8599 (19)	155
C3—H3···Cl2ⁱⁱ	1.00	2.86	3.8092 (19)	160
C4—H4B···Cl3ⁱ	0.99	2.92	3.657 (2)	132
C5—H5A···Cl2ⁱⁱⁱ	0.99	2.90	3.6951 (19)	138
C6—H6A···Cl1^iv	0.99	2.84	3.655 (2)	140

Symmetry codes: (i) −x−1/2, y+1/2, z; (ii) −x+1/2, y−1/2, z; (iii) x−1/2, y, −z+1/2; (iv) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	C₆H₁₀Cl₄
M_r	223.94
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	93
a, b, c (Å)	8.998 (3), 8.400 (3), 24.643 (7)
V (Å³)	1862.6 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.20
Crystal size (mm)	0.25 × 0.25 × 0.10

Data collection
Diffractometer	Rigaku Mercury diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2010)
T_min, T_max	0.746, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8405, 1658, 1553
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.075, 1.12
No. of reflections	1658
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.26

Computer programs: CrystalClear (Rigaku, 2010), SIR2004 (Burla et al., 2005), SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···Cl3	0.99	2.76	3.2097 (19)	108
C4—H4B···Cl4	0.99	2.80	3.2445 (19)	108
C5—H5B···Cl1	0.99	2.74	3.2069 (19)	109
C6—H6B···Cl2	0.99	2.72	3.1940 (18)	110
C2—H2···Cl3ⁱ	1.00	2.93	3.8599 (19)	155
C3—H3···Cl2ⁱⁱ	1.00	2.86	3.8092 (19)	160
C4—H4B···Cl3ⁱ	0.99	2.92	3.657 (2)	132
C5—H5A···Cl2ⁱⁱⁱ	0.99	2.90	3.6951 (19)	138
C6—H6A···Cl1^iv	0.99	2.84	3.655 (2)	140

Symmetry codes: (i) −x−1/2, y+1/2, z; (ii) −x+1/2, y−1/2, z; (iii) x−1/2, y, −z+1/2; (iv) −x, −y, −z.

Footnotes

‡Department of Chemistry & Biochemistry, Texas Tech University, Lubbock, TX, USA.

Acknowledgements

The authors are grateful to the University of St Andrews and the Engineering and Physical Sciences Research Council (EPSRC, UK) for financial support.

References

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