organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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1,4-Bis(chloro­meth­yl)naphthalene

aDepartment of Chemistry, University of Sargodha, Sargodha, Pakistan, bDepartment of Physics, University of Sargodha, Sargodha, Pakistan, and cInstitute of Chemistry, University of the Punjab, Lahore 54590, Pakistan
*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 16 July 2008; accepted 19 July 2008; online 26 July 2008)

In the title mol­ecule, C12H10Cl2, the torsion angles Cr—Cr—Cm—Cl around the Cm—Cr bonds have values of −104.1 (4) and −101.9 (4)°, where Cm is a methylene and Cr is a ring C atom. The mol­ecules related by translation along the b axis are arranged into stacks by ππ inter­actions between unsubstituted and substituted aromatic rings of the naphthalene ring system (centroid–centroid distance = 3.940 Å).

Related literature

For related literature, see: Basaran et al. (1992[Basaran, R., Dou, S.-Q. & Weiss, A. (1992). Ber. Bunsenges. Phys. Chem. 96, 1688-1692.]); Gabe & Glusker (1971[Gabe, E. J. & Glusker, J. P. (1971). Acta Cryst. B27, 1925-1930.]); Garriz et al. (2004[Garriz, P. I., Alvarez, H. L. & Colavita, G. M. (2004). Acta Hortic. 636, 325-330.]); Ikeda et al. (1987[Ikeda, T., Uchida, T., Shimizui, T. & Aoki, K. (1987). Jpn. Patent 62 158 243.]); Kaza­kov (2003[Kazakov, P. V. (2003). Khim. Farm. Zh. 37, 23-25.]); Li et al. (2004[Li, J., Huang, X. & Huang, H. (2004). Huanan Nongye Daxue Xuebao Ziran Kexueban, 25, 10-12.]); Mitchell & Iyer (1989[Mitchell, R. H. & Iyer, V. S. (1989). Synlett, 1, 55-57.]); Tariq et al. (2008[Tariq, M. I., Siddiqui, H. L., Hussain, I. & Afzal, S. (2008). J. Chem. Soc. Pak. 30, 472-476.]); Zhang et al. (1989[Zhang, S., Xiao, S., Lai, H. & Fan, J. (1989). Shiyou Huagong, 18, 263-265.], 2007[Zhang, M., Su, P., Meng, X.-G. & Xu, X.-M. (2007). Acta Cryst. E63, o951-o952.]).

[Scheme 1]

Experimental

Crystal data
  • C12H10Cl2

  • Mr = 225.10

  • Monoclinic, P 21 /c

  • a = 13.6887 (11) Å

  • b = 4.5835 (3) Å

  • c = 17.8278 (13) Å

  • β = 109.666 (4)°

  • V = 1053.31 (13) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.57 mm−1

  • T = 296 (2) K

  • 0.25 × 0.08 × 0.04 mm

Data collection
  • Bruker Kappa APEX2 diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2005[Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.943, Tmax = 0.974

  • 10310 measured reflections

  • 2073 independent reflections

  • 1220 reflections with I > 2σ(I)

  • Rint = 0.049

Refinement
  • R[F2 > 2σ(F2)] = 0.053

  • wR(F2) = 0.167

  • S = 1.05

  • 2073 reflections

  • 127 parameters

  • H-atom parameters constrained

  • Δρmax = 0.79 e Å−3

  • Δρmin = −0.28 e Å−3

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc. Madison, Wisconsin, USA.]); cell refinement: APEX2; data reduction: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc. Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]) and PLATON.

Supporting information


Comment top

Naphthalene acetic acid (NAA) is well known growth regulator/stimulator for different varieties of fruits and vegetables (Garriz et al., 2004; Li et al., 2004). Its synthesis has developed a great interest among the chemists and several methods have been reported. One of them is chloromethylation of naphthalene using methylene chloride in the presence of catalysts (Kazakov, 2003; Mitchell & Iyer, 1989; Zhang et al., 1989). During the synthesis of NAA, using formaline and a mixture of acids as a source of insertion of methylene group (Ikeda et al., 1987; Tariq et al., 2008), the title compound has been isolated.

The crystal structures of 1,4-bis(bromomethyl)benzene (Zhang et al., 2007), 1,4-bis(chloromethyl)benzene (Basaran et al., 1992) and 9,10-bis(chloromethyl)anthracene (Gabe & Glusker, 1971) were published but no analogous derivatives of naphthalene have been reported.

The bond lengths in the naphthalene system are in the range of 1.344 (6)–1.425 (5) Å. The Cl atoms deviate in opposite directions from the plane of the naphthalene ring by 1.660 (6) Å and 1.559 (6) Å. The closest contacts of Cl atoms with neighbouring molecules are: 3.491 (5) Å for Cl1···C9i and 3.5581 (16) Å for Cl2···Cl2ii [symmetry codes: (i) -x, 1 - y, -z; (ii) 1 - x, 1 - y, 1 - z].

Related literature top

For related literature, see: Basaran et al. (1992); Gabe & Glusker (1971); Garriz et al. (2004); Ikeda et al. (1987); Kazakov (2003); Li et al. (2004); Mitchell & Iyer (1989); Tariq et al. (2008); Zhang et al. (1989, 2007).

Experimental top

A mixture of naphthalene (40.0 g), paraformaldehyde (35.0 g), glacial acetic acid (82.0 ml), H3PO4 (52.0 ml) and concentrated HCl (114.0 ml) was heated in a water bath at 358 K with vigorous stirring for 2 h. Thereafter, the mixture was cooled to room temperature. A solid product was obtained and isolated. It was thoroughly washed with water, ether and n-hexane, respectively in order to remove unreacted material. The product was further purified in hot methanol. Needle-shaped colorless crystals (m.p. 394-396 K) were obtained by recrystallization from ethyl acetate.

Refinement top

H atoms were positioned geometrically, with C—H = 0.93 and 0.97 Å for aromatic and methylene C-atoms, respectively, and constrained to ride on their parent atoms with Uiso(H)=1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The ORTEP diagram of the title compound with displacement ellipsoids at the 50% probability level. H-atoms are shown by small circles of arbitrary radii.
[Figure 2] Fig. 2. The crystal packing diagram.
1,4-Bis(chloromethyl)naphthalene top
Crystal data top
C12H10Cl2F(000) = 464
Mr = 225.10Dx = 1.419 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2073 reflections
a = 13.6887 (11) Åθ = 1.6–26.0°
b = 4.5835 (3) ŵ = 0.57 mm1
c = 17.8278 (13) ÅT = 296 K
β = 109.666 (4)°Needle, colourless
V = 1053.31 (13) Å30.25 × 0.08 × 0.04 mm
Z = 4
Data collection top
Bruker Kappa APEX2
diffractometer
2073 independent reflections
Radiation source: fine-focus sealed tube1220 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.049
Detector resolution: 7.40 pixels mm-1θmax = 26.0°, θmin = 1.6°
ω scansh = 1616
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
k = 55
Tmin = 0.943, Tmax = 0.974l = 2121
10310 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)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.167H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0763P)2 + 0.5487P]
where P = (Fo2 + 2Fc2)/3
2073 reflections(Δ/σ)max < 0.001
127 parametersΔρmax = 0.79 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C12H10Cl2V = 1053.31 (13) Å3
Mr = 225.10Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.6887 (11) ŵ = 0.57 mm1
b = 4.5835 (3) ÅT = 296 K
c = 17.8278 (13) Å0.25 × 0.08 × 0.04 mm
β = 109.666 (4)°
Data collection top
Bruker Kappa APEX2
diffractometer
2073 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
1220 reflections with I > 2σ(I)
Tmin = 0.943, Tmax = 0.974Rint = 0.049
10310 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.167H-atom parameters constrained
S = 1.05Δρmax = 0.79 e Å3
2073 reflectionsΔρmin = 0.28 e Å3
127 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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
Cl10.15383 (10)0.5096 (3)0.06255 (6)0.0825 (5)
Cl20.41801 (9)0.6216 (3)0.40488 (6)0.0694 (4)
C10.2211 (3)0.3836 (7)0.1364 (2)0.0438 (11)
C20.2846 (3)0.4596 (8)0.0908 (2)0.0479 (12)
C30.3638 (3)0.6492 (9)0.1214 (2)0.0566 (14)
C40.3843 (3)0.7720 (8)0.1975 (3)0.0572 (14)
C50.3249 (3)0.7058 (7)0.2432 (2)0.0472 (11)
C60.2416 (3)0.5067 (7)0.2133 (2)0.0428 (11)
C70.1764 (3)0.4271 (8)0.2572 (2)0.0537 (12)
C80.0976 (3)0.2349 (10)0.2267 (3)0.0635 (16)
C90.0776 (3)0.1120 (9)0.1520 (3)0.0642 (16)
C100.1366 (3)0.1849 (8)0.1080 (2)0.0546 (12)
C110.2650 (3)0.3370 (10)0.0095 (2)0.0681 (17)
C120.3470 (3)0.8534 (9)0.3220 (2)0.0631 (16)
H30.405490.699240.091610.0680*
H40.439490.901010.217110.0681*
H70.187690.507450.307370.0642*
H80.056090.184320.256560.0759*
H90.023560.020560.132420.0771*
H100.121790.103480.057620.0655*
H11A0.252900.128680.010170.0818*
H11B0.325750.366930.006050.0818*
H12A0.281930.910870.328220.0755*
H12B0.386921.029040.322980.0755*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0917 (9)0.0956 (9)0.0466 (7)0.0066 (7)0.0055 (6)0.0041 (6)
Cl20.0783 (8)0.0692 (7)0.0492 (6)0.0150 (5)0.0065 (5)0.0007 (5)
C10.043 (2)0.0421 (18)0.042 (2)0.0109 (16)0.0085 (16)0.0062 (16)
C20.050 (2)0.050 (2)0.043 (2)0.0115 (18)0.0149 (17)0.0073 (17)
C30.053 (2)0.064 (2)0.055 (3)0.005 (2)0.021 (2)0.015 (2)
C40.048 (2)0.049 (2)0.064 (3)0.0019 (18)0.005 (2)0.010 (2)
C50.053 (2)0.0411 (19)0.041 (2)0.0119 (17)0.0071 (18)0.0081 (16)
C60.041 (2)0.0400 (18)0.044 (2)0.0095 (16)0.0097 (16)0.0065 (16)
C70.052 (2)0.058 (2)0.051 (2)0.0138 (19)0.0173 (19)0.0106 (18)
C80.051 (2)0.069 (3)0.075 (3)0.009 (2)0.027 (2)0.020 (2)
C90.054 (3)0.061 (2)0.070 (3)0.005 (2)0.011 (2)0.011 (2)
C100.056 (2)0.051 (2)0.049 (2)0.0012 (18)0.0074 (19)0.0033 (18)
C110.079 (3)0.072 (3)0.055 (3)0.014 (2)0.025 (2)0.004 (2)
C120.072 (3)0.049 (2)0.057 (3)0.010 (2)0.007 (2)0.0009 (19)
Geometric parameters (Å, º) top
Cl1—C111.810 (4)C8—C91.386 (7)
Cl2—C121.814 (4)C9—C101.344 (6)
C1—C21.419 (6)C3—H30.9300
C1—C61.421 (5)C4—H40.9300
C1—C101.425 (5)C7—H70.9300
C2—C31.353 (6)C8—H80.9300
C2—C111.492 (5)C9—H90.9300
C3—C41.407 (6)C10—H100.9300
C4—C51.365 (6)C11—H11A0.9700
C5—C61.417 (5)C11—H11B0.9700
C5—C121.496 (5)C12—H12A0.9700
C6—C71.419 (6)C12—H12B0.9700
C7—C81.357 (6)
Cl1···C103.464 (4)C10···H11A2.7400
Cl1···C9i3.491 (5)C11···H102.6200
Cl2···Cl2ii3.5581 (16)C12···H72.6400
Cl2···C73.578 (4)H3···H11B2.2900
Cl1···H12Aiii3.0500H3···Cl2viii3.0800
Cl1···H102.9800H4···H12B2.3100
Cl2···H12Biv3.0400H4···C4viii2.9200
Cl2···H3v3.0800H7···Cl23.0900
Cl2···H73.0900H7···C122.6400
C1···C4iv3.521 (5)H7···H12A2.2100
C4···C1vi3.521 (5)H8···C8ix3.0300
C6···C9vi3.504 (6)H10···Cl12.9800
C6···C12iv3.595 (5)H10···C112.6200
C7···Cl23.578 (4)H10···H11A2.2300
C7···C12iv3.448 (6)H11A···C3iv3.0100
C9···C6iv3.504 (6)H11A···C102.7400
C9···Cl1i3.491 (5)H11A···H102.2300
C10···Cl13.464 (4)H11B···H32.2900
C12···C7vi3.448 (6)H12A···C72.7200
C12···C6vi3.595 (5)H12A···C7vi2.8400
C3···H11Avi3.0100H12A···C8vi2.9600
C4···H4v2.9200H12A···H72.2100
C7···H12A2.7200H12A···Cl1x3.0500
C7···H12Aiv2.8400H12B···Cl2vi3.0400
C8···H8vii3.0300H12B···H42.3100
C8···H12Aiv2.9600
C2—C1—C6119.7 (3)C4—C3—H3119.00
C2—C1—C10122.3 (3)C3—C4—H4119.00
C6—C1—C10118.0 (3)C5—C4—H4119.00
C1—C2—C3119.3 (3)C6—C7—H7120.00
C1—C2—C11121.3 (3)C8—C7—H7120.00
C3—C2—C11119.4 (4)C7—C8—H8119.00
C2—C3—C4121.2 (4)C9—C8—H8119.00
C3—C4—C5121.4 (4)C8—C9—H9120.00
C4—C5—C6119.0 (3)C10—C9—H9120.00
C4—C5—C12119.2 (4)C1—C10—H10119.00
C6—C5—C12121.8 (4)C9—C10—H10119.00
C1—C6—C5119.4 (4)Cl1—C11—H11A109.00
C1—C6—C7118.3 (3)Cl1—C11—H11B109.00
C5—C6—C7122.3 (3)C2—C11—H11A110.00
C6—C7—C8120.6 (3)C2—C11—H11B109.00
C7—C8—C9121.5 (4)H11A—C11—H11B108.00
C8—C9—C10119.8 (4)Cl2—C12—H12A109.00
C1—C10—C9121.8 (3)Cl2—C12—H12B109.00
Cl1—C11—C2111.0 (3)C5—C12—H12A109.00
Cl2—C12—C5112.6 (3)C5—C12—H12B109.00
C2—C3—H3119.00H12A—C12—H12B108.00
C6—C1—C2—C30.1 (5)C2—C3—C4—C50.3 (6)
C6—C1—C2—C11179.5 (3)C3—C4—C5—C60.7 (6)
C10—C1—C2—C3179.8 (4)C3—C4—C5—C12177.1 (4)
C10—C1—C2—C110.8 (6)C4—C5—C6—C10.7 (5)
C2—C1—C6—C50.5 (5)C4—C5—C6—C7180.0 (4)
C2—C1—C6—C7179.8 (3)C12—C5—C6—C1177.0 (3)
C10—C1—C6—C5179.8 (3)C12—C5—C6—C72.3 (5)
C10—C1—C6—C70.5 (5)C4—C5—C12—Cl2101.9 (4)
C2—C1—C10—C9179.3 (4)C6—C5—C12—Cl280.4 (4)
C6—C1—C10—C90.4 (6)C1—C6—C7—C81.0 (6)
C1—C2—C3—C40.0 (6)C5—C6—C7—C8179.8 (4)
C11—C2—C3—C4179.4 (4)C6—C7—C8—C90.5 (6)
C1—C2—C11—Cl175.3 (4)C7—C8—C9—C100.5 (7)
C3—C2—C11—Cl1104.1 (4)C8—C9—C10—C11.0 (6)
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+1, z+1; (iii) x, y+3/2, z1/2; (iv) x, y1, z; (v) x+1, y1/2, z+1/2; (vi) x, y+1, z; (vii) x, y+1/2, z+1/2; (viii) x+1, y+1/2, z+1/2; (ix) x, y1/2, z+1/2; (x) x, y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC12H10Cl2
Mr225.10
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)13.6887 (11), 4.5835 (3), 17.8278 (13)
β (°) 109.666 (4)
V3)1053.31 (13)
Z4
Radiation typeMo Kα
µ (mm1)0.57
Crystal size (mm)0.25 × 0.08 × 0.04
Data collection
DiffractometerBruker Kappa APEX2
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2005)
Tmin, Tmax0.943, 0.974
No. of measured, independent and
observed [I > 2σ(I)] reflections
10310, 2073, 1220
Rint0.049
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.167, 1.05
No. of reflections2073
No. of parameters127
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.79, 0.28

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

 

Acknowledgements

The authors acknowledge the Higher Education Commission, Islamabad, Pakistan, for funding the purchase of the diffractometer at GCU, Lahore.

References

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