1,3,5-Tris­(chloro­methyl)­benzene

The title compound, C₉H₉Cl₃, is being used as a platform for new tripodal receptors. Two mol­ecules make up the asymmetric unit; weak intermolecular hydrogen bonding is observed between methyl­ene H atoms and the chlorine of an adjacent mol­ecule. There are also C-H...[pi] interactions.

S1. Comment

Two molecules make up the asymmetric unit of the title compound, (I). Weak intermolecular hydrogen bonding is observed (full details in Table 1) between a methylene H atom H18B and chlorine Cl4 of an adjacent molecule. There are also C—H···πi interactions with H···ring-centroid separations of 3.07–3.31 Å (Table 1).

S2. Experimental

The title compound was prepared following literature methods (Cochrane et al., 1968) and was recrystallized from toluene.

Computing details

Data collection: CAD-4-PC (Nonius, 1993); cell refinement: CAD-4-PC (Nonius, 1993); data reduction: XCAD4 (Harms, 1995); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXTL (Siemens, 1994).

(I)

Crystal data

C9H9Cl3	Z = 4
Mr = 223.51	F(000) = 456
Triclinic, P1	Dx = 1.474 Mg m^−3
a = 8.7124 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.0659 (5) Å	Cell parameters from 25 reflections
c = 12.7901 (15) Å	θ = 10.4–14.9°
α = 87.537 (8)°	µ = 0.85 mm^−1
β = 86.992 (10)°	T = 163 K
γ = 87.873 (8)°	Fragment, colourless
V = 1007.3 (2) Å^3	0.30 × 0.30 × 0.25 mm

Data collection

Nonius CAD-4 diffractometer	3047 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
Graphite monochromator	θmax = 26.0°, θmin = 2.2°
ω–θ scans	h = −9→10
Absorption correction: ψ scan Siemens, 1994	k = −11→11
Tmin = 0.722, Tmax = 0.809	l = −15→15
6800 measured reflections	3 standard reflections every 120 min
3943 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0424P)^2 + 0.2112P] where P = (Fo^2 + 2Fc^2)/3
3943 reflections	(Δ/σ)max = 0.001
217 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.34 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 on F² for ALL reflections except for 0 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating R_factor_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	Occ. (<1)
CG1	0.7709	0.9148	0.9931	0.000*	0.00
CG2	0.4017	0.6487	0.4130	0.000*	0.00
Cl1	0.70846 (6)	1.22898 (6)	1.19291 (5)	0.04240 (15)
Cl2	0.76314 (8)	0.96538 (7)	0.68983 (5)	0.05327 (18)
Cl3	0.99777 (7)	0.60395 (7)	1.14646 (5)	0.05110 (18)
C1	0.6838 (2)	1.0217 (2)	1.04751 (16)	0.0300 (4)
C2	0.7504 (2)	1.0557 (2)	0.94906 (16)	0.0307 (4)
H2	0.7370	1.1526	0.9189	0.037*
C3	0.8365 (2)	0.9498 (2)	0.89384 (16)	0.0287 (4)
C4	0.8578 (2)	0.8088 (2)	0.93919 (16)	0.0284 (4)
H4	0.9179	0.7364	0.9023	0.034*
C5	0.7921 (2)	0.7730 (2)	1.03801 (16)	0.0285 (4)
C6	0.7045 (2)	0.8797 (2)	1.09119 (16)	0.0307 (4)
H6	0.6580	0.8554	1.1583	0.037*
C7	0.5904 (2)	1.1365 (3)	1.10597 (19)	0.0413 (6)
H7A	0.5048	1.0892	1.1471	0.050*
H7B	0.5457	1.2098	1.0555	0.050*
C8	0.9036 (3)	0.9864 (3)	0.78633 (18)	0.0405 (5)
H8A	0.9943	0.9203	0.7712	0.049*
H8B	0.9380	1.0895	0.7827	0.049*
C9	0.8161 (2)	0.6214 (2)	1.08663 (19)	0.0381 (5)
H9A	0.8125	0.5473	1.0322	0.046*
H9B	0.7324	0.6016	1.1402	0.046*
Cl4	0.78510 (8)	0.85386 (8)	0.37208 (5)	0.05551 (19)
Cl5	0.06273 (6)	0.64646 (6)	0.62442 (4)	0.03996 (15)
Cl6	0.40637 (6)	0.52473 (6)	0.12134 (4)	0.03606 (14)
C11	0.5510 (2)	0.6791 (2)	0.43654 (15)	0.0273 (4)
C12	0.4263 (2)	0.7430 (2)	0.49244 (15)	0.0294 (4)
H12	0.4434	0.8075	0.5469	0.035*
C13	0.2770 (2)	0.7131 (2)	0.46929 (15)	0.0276 (4)
C14	0.2535 (2)	0.6201 (2)	0.38843 (16)	0.0281 (4)
H14	0.1515	0.6020	0.3707	0.034*
C15	0.3768 (2)	0.5532 (2)	0.33302 (15)	0.0259 (4)
C16	0.5258 (2)	0.5834 (2)	0.35807 (15)	0.0267 (4)
H16	0.6110	0.5379	0.3210	0.032*
C17	0.7125 (2)	0.7122 (2)	0.46102 (17)	0.0347 (5)
H17A	0.7789	0.6216	0.4551	0.042*
H17B	0.7141	0.7448	0.5338	0.042*
C18	0.1429 (3)	0.7802 (2)	0.53021 (19)	0.0381 (5)
H18A	0.0633	0.8153	0.4817	0.046*
H18B	0.1765	0.8663	0.5671	0.046*
C19	0.3500 (2)	0.4480 (2)	0.24951 (16)	0.0308 (4)
H19A	0.2397	0.4250	0.2517	0.037*
H19B	0.4097	0.3547	0.2630	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0360 (3)	0.0463 (3)	0.0466 (3)	0.0067 (2)	−0.0108 (2)	−0.0194 (3)
Cl2	0.0716 (4)	0.0566 (4)	0.0310 (3)	−0.0024 (3)	−0.0043 (3)	0.0066 (3)
Cl3	0.0445 (3)	0.0404 (3)	0.0701 (4)	0.0031 (2)	−0.0273 (3)	0.0045 (3)
C1	0.0199 (9)	0.0382 (11)	0.0328 (11)	0.0010 (8)	−0.0039 (8)	−0.0104 (9)
C2	0.0257 (10)	0.0291 (10)	0.0374 (11)	−0.0008 (8)	−0.0031 (9)	0.0000 (9)
C3	0.0231 (10)	0.0349 (11)	0.0280 (10)	−0.0046 (8)	0.0007 (8)	−0.0006 (8)
C4	0.0206 (9)	0.0307 (10)	0.0341 (11)	0.0005 (8)	−0.0005 (8)	−0.0062 (8)
C5	0.0213 (9)	0.0324 (10)	0.0322 (11)	−0.0031 (8)	−0.0059 (8)	0.0019 (8)
C6	0.0209 (10)	0.0475 (12)	0.0239 (10)	−0.0037 (9)	−0.0015 (8)	−0.0026 (9)
C7	0.0257 (11)	0.0541 (14)	0.0459 (14)	0.0055 (10)	−0.0059 (10)	−0.0225 (11)
C8	0.0390 (12)	0.0450 (13)	0.0363 (12)	−0.0047 (10)	0.0081 (10)	0.0024 (10)
C9	0.0282 (11)	0.0393 (12)	0.0467 (13)	−0.0053 (9)	−0.0074 (10)	0.0098 (10)
Cl4	0.0556 (4)	0.0688 (4)	0.0441 (3)	−0.0393 (3)	−0.0075 (3)	0.0128 (3)
Cl5	0.0300 (3)	0.0498 (3)	0.0399 (3)	−0.0083 (2)	0.0105 (2)	−0.0096 (2)
Cl6	0.0323 (3)	0.0493 (3)	0.0265 (3)	−0.0026 (2)	0.0009 (2)	−0.0015 (2)
C11	0.0235 (10)	0.0327 (10)	0.0251 (10)	−0.0049 (8)	−0.0016 (8)	0.0077 (8)
C12	0.0338 (11)	0.0287 (10)	0.0257 (10)	−0.0041 (8)	−0.0010 (8)	0.0008 (8)
C13	0.0250 (10)	0.0269 (10)	0.0301 (11)	−0.0010 (8)	0.0034 (8)	0.0034 (8)
C14	0.0211 (9)	0.0323 (10)	0.0306 (11)	−0.0037 (8)	−0.0006 (8)	0.0032 (8)
C15	0.0255 (10)	0.0278 (10)	0.0239 (10)	−0.0034 (8)	0.0009 (8)	0.0039 (8)
C16	0.0222 (9)	0.0314 (10)	0.0255 (10)	−0.0009 (8)	0.0040 (8)	0.0045 (8)
C17	0.0285 (11)	0.0425 (12)	0.0332 (11)	−0.0098 (9)	−0.0033 (9)	0.0049 (9)
C18	0.0326 (11)	0.0372 (12)	0.0432 (13)	0.0008 (9)	0.0095 (10)	−0.0021 (10)
C19	0.0275 (10)	0.0356 (11)	0.0290 (10)	−0.0048 (8)	0.0024 (8)	0.0002 (9)

Geometric parameters (Å, º)

Cl1—C7	1.806 (2)	Cl4—C17	1.790 (2)
Cl2—C8	1.803 (2)	Cl5—C18	1.805 (2)
Cl3—C9	1.793 (2)	Cl6—C19	1.804 (2)
C1—C2	1.386 (3)	C11—C16	1.386 (3)
C1—C6	1.390 (3)	C11—C12	1.391 (3)
C1—C7	1.498 (3)	C11—C17	1.501 (3)
C2—C3	1.390 (3)	C12—C13	1.388 (3)
C2—H2	0.9500	C12—H12	0.9500
C3—C4	1.391 (3)	C13—C14	1.390 (3)
C3—C8	1.494 (3)	C13—C18	1.495 (3)
C4—C5	1.391 (3)	C14—C15	1.391 (3)
C4—H4	0.9500	C14—H14	0.9500
C5—C6	1.389 (3)	C15—C16	1.393 (3)
C5—C9	1.496 (3)	C15—C19	1.495 (3)
C6—H6	0.9500	C16—H16	0.9500
C7—H7A	0.9900	C17—H17A	0.9900
C7—H7B	0.9900	C17—H17B	0.9900
C8—H8A	0.9900	C18—H18A	0.9900
C8—H8B	0.9900	C18—H18B	0.9900
C9—H9A	0.9900	C19—H19A	0.9900
C9—H9B	0.9900	C19—H19B	0.9900
C2—C1—C6	119.20 (19)	C16—C11—C12	119.67 (18)
C2—C1—C7	120.3 (2)	C16—C11—C17	119.75 (18)
C6—C1—C7	120.5 (2)	C12—C11—C17	120.58 (19)
C1—C2—C3	120.84 (19)	C13—C12—C11	120.52 (18)
C1—C2—H2	119.6	C13—C12—H12	119.7
C3—C2—H2	119.6	C11—C12—H12	119.7
C2—C3—C4	119.28 (19)	C12—C13—C14	119.18 (18)
C2—C3—C8	120.34 (19)	C12—C13—C18	120.53 (19)
C4—C3—C8	120.37 (19)	C14—C13—C18	120.29 (18)
C5—C4—C3	120.59 (19)	C13—C14—C15	121.05 (18)
C5—C4—H4	119.7	C13—C14—H14	119.5
C3—C4—H4	119.7	C15—C14—H14	119.5
C6—C5—C4	119.22 (19)	C14—C15—C16	118.92 (18)
C6—C5—C9	120.4 (2)	C14—C15—C19	120.58 (18)
C4—C5—C9	120.36 (19)	C16—C15—C19	120.49 (18)
C5—C6—C1	120.86 (19)	C11—C16—C15	120.62 (18)
C5—C6—H6	119.6	C11—C16—H16	119.7
C1—C6—H6	119.6	C15—C16—H16	119.7
C1—C7—Cl1	110.59 (14)	C11—C17—Cl4	110.06 (14)
C1—C7—H7A	109.5	C11—C17—H17A	109.6
Cl1—C7—H7A	109.5	Cl4—C17—H17A	109.6
C1—C7—H7B	109.5	C11—C17—H17B	109.6
Cl1—C7—H7B	109.5	Cl4—C17—H17B	109.6
H7A—C7—H7B	108.1	H17A—C17—H17B	108.2
C3—C8—Cl2	110.50 (15)	C13—C18—Cl5	110.43 (15)
C3—C8—H8A	109.5	C13—C18—H18A	109.6
Cl2—C8—H8A	109.5	Cl5—C18—H18A	109.6
C3—C8—H8B	109.5	C13—C18—H18B	109.6
Cl2—C8—H8B	109.5	Cl5—C18—H18B	109.6
H8A—C8—H8B	108.1	H18A—C18—H18B	108.1
C5—C9—Cl3	110.81 (14)	C15—C19—Cl6	111.25 (14)
C5—C9—H9A	109.5	C15—C19—H19A	109.4
Cl3—C9—H9A	109.5	Cl6—C19—H19A	109.4
C5—C9—H9B	109.5	C15—C19—H19B	109.4
Cl3—C9—H9B	109.5	Cl6—C19—H19B	109.4
H9A—C9—H9B	108.1	H19A—C19—H19B	108.0
C6—C1—C2—C3	0.2 (3)	C16—C11—C12—C13	−0.9 (3)
C7—C1—C2—C3	−179.63 (18)	C17—C11—C12—C13	179.60 (17)
C1—C2—C3—C4	−1.1 (3)	C11—C12—C13—C14	−0.9 (3)
C1—C2—C3—C8	178.05 (19)	C11—C12—C13—C18	179.25 (18)
C2—C3—C4—C5	0.9 (3)	C12—C13—C14—C15	2.2 (3)
C8—C3—C4—C5	−178.20 (18)	C18—C13—C14—C15	−178.05 (18)
C3—C4—C5—C6	0.0 (3)	C13—C14—C15—C16	−1.5 (3)
C3—C4—C5—C9	−179.68 (18)	C13—C14—C15—C19	177.16 (18)
C4—C5—C6—C1	−0.9 (3)	C12—C11—C16—C15	1.5 (3)
C9—C5—C6—C1	178.81 (18)	C17—C11—C16—C15	−178.96 (17)
C2—C1—C6—C5	0.8 (3)	C14—C15—C16—C11	−0.3 (3)
C7—C1—C6—C5	−179.36 (18)	C19—C15—C16—C11	−179.01 (17)
C2—C1—C7—Cl1	−93.8 (2)	C16—C11—C17—Cl4	83.0 (2)
C6—C1—C7—Cl1	86.3 (2)	C12—C11—C17—Cl4	−97.5 (2)
C2—C3—C8—Cl2	−83.9 (2)	C12—C13—C18—Cl5	−102.3 (2)
C4—C3—C8—Cl2	95.2 (2)	C14—C13—C18—Cl5	77.9 (2)
C6—C5—C9—Cl3	−98.0 (2)	C14—C15—C19—Cl6	111.33 (18)
C4—C5—C9—Cl3	81.8 (2)	C16—C15—C19—Cl6	−70.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18B···Cl4^i	0.99	2.72	3.682 (2)	163
C7—H7A···CG1^ii	0.99	3.07	3.509 (2)	108
C7—H7B···CG1^ii	0.99	3.12	3.509 (2)	105
C17—H17A···CG2^iii	0.99	3.31	3.729 (2)	107

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