1-Bromo­methyl-2-iodo­benzene

The title compound, C₇H₆BrI, is a synthon for the transfer of the 2-iodo­phenyl residue. Bond lengths and angles are normal, the conformation being characterized by an almost perpendicular arrangement of the C_ipso—CH₂—Br plane and the plane of the aromatic ring. Instead of halogen–π inter­actions, the crystal structure is dictated by I...Br van-der Waals contacts [3.6943 (5) Å] and lateral contacts of parallel aromatic residues at a distance of 3.423 Å.

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.024
• wR factor = 0.056
• Data-to-parameter ratio = 22.2

checkCIF/PLATON results

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S1. Comment

1-Bromomethyl-2-iodobenzene (ortho-iodo-benzylbromide) was prepared as an intermediate in the synthesis of ortho-iodomandelic acid. The structure of the compound had been deduced upon spectroscopic data so far.

Bond lengths and angles correspond to the typical values for similar compounds. The angle between the C1—C7—Br plane and the plane of the phenyl carbons is 85.5 (3)°.

In agreement with the low melting point of the title compound of about 55 °C, the crystal structure is determined by van-der-Waals interactions. The most significant interaction in terms of a PLATON analysis (Spek, 1990) of the van-der-Waals bond distances are Br···I contacts along [0 1 0]. The phenyl rings are arranged parallel to each other and appear as π-stacked in terms of a 3.423-Å perpendicular distance (red arrows in Fig. 2). However, the mutual overlap of the rings is restricted to a single carbon–carbon bond. Though attractive intermolecular contacts between a halogen atom and a π system are common (Swierczynski et al., 2005), they are not observed in (I).

Related literature

For the synthesis of the title compound, see: Bacon & Lindsay (1958). For a related structure, see: Kirsop et al. (2006). Swierczynski et al. (2005) describe the general significance of halogen–π-system interactions.

S2. Experimental

The title compound was prepared according to a published procedure (Bacon & Lindsay, 1958) upon radical-supported bromination of 2-iodotoluene in tetrachloromethane.

Crystals suitable for X-ray analysis were obtained directly from the crystallized reaction product isolated by means of distillation from the reaction mixture.

S3. Refinement

All H atoms were located in a difference map and refined as riding on their parent atoms. One common isotropic displacement parameter for all H atoms was refined.

Computing details

Data collection: COLLECT (Nonius, 2004); cell refinement: SCALEPACK (Otwinowski & Minor 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and Spek (2003).

Figures

	Fig. 1. The molecular structure of (I), with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level) for non-H atoms.
	Fig. 2. The packing of (I) in a view close to [0 1 0]. The most significant intermolecular interactions are drawn in red: Br···I contacts that are about 0.1 Å shorter than the sum of the van-der-Waals radii (dots), and 3.4-Å contacts between the rims of parallel phenyl residues (double arrows).

1-Bromomethyl-2-iodobenzene

Crystal data

C7H6BrI	F(000) = 544
Mr = 296.93	Dx = 2.417 Mg m^−3
Monoclinic, P21/c	Melting point: 55 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.7569 (2) Å	Cell parameters from 8472 reflections
b = 12.0237 (4) Å	θ = 3.1–27.5°
c = 8.5351 (3) Å	µ = 8.73 mm^−1
β = 114.777 (2)°	T = 200 K
V = 815.94 (5) Å^3	Block, colourless
Z = 4	0.11 × 0.09 × 0.08 mm

Data collection

KappaCCD diffractometer	1867 independent reflections
Radiation source: rotating anode	1514 reflections with I > 2σ(I)
MONTEL, graded multilayered X-ray optics monochromator	Rint = 0.032
ω–scan	θmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −11→11
Tmin = 0.398, Tmax = 0.497	k = −15→15
13178 measured reflections	l = −11→11

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.024	Only H-atom displacement parameters refined
wR(F^2) = 0.056	w = 1/[σ^2(Fo^2) + (0.0252P)^2 + 0.4328P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
1867 reflections	Δρmax = 1.05 e Å^−3
84 parameters	Δρmin = −0.59 e Å^−3
0 restraints	Extinction correction: SHELXL
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0034 (3)

Special details

Refinement. RefU for hydrogen atoms: one common isotropic U for all H atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
I	0.76744 (3)	0.499318 (17)	0.15316 (3)	0.04592 (11)
Br	1.17131 (4)	0.30304 (3)	0.28843 (4)	0.04037 (12)
C1	0.8186 (4)	0.2499 (3)	0.1176 (4)	0.0325 (7)
C2	0.7165 (3)	0.3295 (2)	0.1485 (4)	0.0307 (6)
C3	0.5795 (4)	0.2968 (3)	0.1788 (4)	0.0367 (7)
H3	0.5108	0.3515	0.1978	0.053 (4)*
C4	0.5423 (4)	0.1859 (3)	0.1815 (4)	0.0432 (8)
H4	0.4485	0.1640	0.2028	0.053 (4)*
C5	0.6414 (4)	0.1067 (3)	0.1530 (4)	0.0459 (8)
H5	0.6166	0.0300	0.1562	0.053 (4)*
C6	0.7761 (4)	0.1380 (3)	0.1202 (4)	0.0415 (8)
H6	0.8419	0.0823	0.0988	0.053 (4)*
C7	0.9624 (4)	0.2805 (3)	0.0772 (4)	0.0448 (8)
H71	0.9349	0.3498	0.0080	0.053 (4)*
H72	0.9806	0.2209	0.0068	0.053 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I	0.03819 (15)	0.03381 (16)	0.06009 (18)	−0.00073 (8)	0.01501 (12)	0.00094 (10)
Br	0.02986 (17)	0.0446 (2)	0.0481 (2)	−0.00055 (14)	0.01776 (14)	0.00128 (16)
C1	0.0297 (14)	0.0391 (18)	0.0231 (15)	0.0033 (13)	0.0056 (12)	−0.0024 (12)
C2	0.0270 (13)	0.0325 (16)	0.0268 (14)	0.0022 (12)	0.0055 (11)	−0.0004 (12)
C3	0.0277 (14)	0.0436 (19)	0.0352 (16)	0.0028 (13)	0.0096 (12)	−0.0013 (14)
C4	0.0305 (15)	0.048 (2)	0.0440 (19)	−0.0097 (14)	0.0083 (14)	0.0045 (16)
C5	0.0412 (18)	0.0363 (19)	0.0441 (19)	−0.0057 (15)	0.0022 (14)	0.0029 (16)
C6	0.0404 (17)	0.039 (2)	0.0325 (17)	0.0094 (14)	0.0025 (14)	−0.0098 (14)
C7	0.0368 (17)	0.065 (2)	0.0339 (17)	0.0104 (16)	0.0164 (14)	0.0043 (16)

Geometric parameters (Å, º)

I—C2	2.087 (3)	C4—C5	1.377 (5)
Br—C7	1.977 (3)	C4—H4	0.9500
C1—C6	1.400 (5)	C5—C6	1.374 (5)
C1—C2	1.408 (4)	C5—H5	0.9500
C1—C7	1.484 (4)	C6—H6	0.9500
C2—C3	1.385 (4)	C7—H71	0.9900
C3—C4	1.376 (5)	C7—H72	0.9900
C3—H3	0.9500
Br···I^i	3.6943 (5)
C6—C1—C2	117.1 (3)	C6—C5—C4	120.3 (3)
C6—C1—C7	120.0 (3)	C6—C5—H5	119.8
C2—C1—C7	122.9 (3)	C4—C5—H5	119.8
C3—C2—C1	120.7 (3)	C5—C6—C1	121.6 (3)
C3—C2—I	117.9 (2)	C5—C6—H6	119.2
C1—C2—I	121.4 (2)	C1—C6—H6	119.2
C4—C3—C2	120.5 (3)	C1—C7—Br	111.9 (2)
C4—C3—H3	119.7	C1—C7—H71	109.2
C2—C3—H3	119.7	Br—C7—H71	109.2
C3—C4—C5	119.8 (3)	C1—C7—H72	109.2
C3—C4—H4	120.1	Br—C7—H72	109.2
C5—C4—H4	120.1	H71—C7—H72	107.9
C6—C1—C2—C3	−0.4 (4)	C3—C4—C5—C6	−0.7 (5)
C7—C1—C2—C3	177.3 (3)	C4—C5—C6—C1	1.2 (5)
C6—C1—C2—I	178.8 (2)	C2—C1—C6—C5	−0.6 (4)
C7—C1—C2—I	−3.4 (4)	C7—C1—C6—C5	−178.4 (3)
C1—C2—C3—C4	0.9 (4)	C6—C1—C7—Br	−95.8 (3)
I—C2—C3—C4	−178.4 (2)	C2—C1—C7—Br	86.4 (3)
C2—C3—C4—C5	−0.3 (5)

Symmetry code: (i) −x+2, y−1/2, −z+1/2.