Buy article online - an online subscription or single-article purchase is required to access this article.
The title compound, C
7H
6BrI, 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—CH
2—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.
Supporting information
CCDC reference: 672972
Key indicators
- Single-crystal X-ray study
- T = 200 K
- Mean (C-C) = 0.005 Å
- R factor = 0.024
- wR factor = 0.056
- Data-to-parameter ratio = 22.2
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
1 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
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.
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.
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).
1-Bromomethyl-2-iodobenzene
top
Crystal data top
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) Å3 | Block, colourless |
Z = 4 | 0.11 × 0.09 × 0.08 mm |
Data collection top
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 top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.024 | Only H-atom displacement parameters refined |
wR(F2) = 0.056 | w = 1/[σ2(Fo2) + (0.0252P)2 + 0.4328P] where P = (Fo2 + 2Fc2)/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) |
Crystal data top
C7H6BrI | V = 815.94 (5) Å3 |
Mr = 296.93 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.7569 (2) Å | µ = 8.73 mm−1 |
b = 12.0237 (4) Å | T = 200 K |
c = 8.5351 (3) Å | 0.11 × 0.09 × 0.08 mm |
β = 114.777 (2)° | |
Data collection top
KappaCCD diffractometer | 1867 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 1514 reflections with I > 2σ(I) |
Tmin = 0.398, Tmax = 0.497 | Rint = 0.032 |
13178 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.056 | Only H-atom displacement parameters refined |
S = 1.09 | Δρmax = 1.05 e Å−3 |
1867 reflections | Δρmin = −0.59 e Å−3 |
84 parameters | |
Special details top
Refinement. RefU for hydrogen atoms: one common isotropic U for all H atoms. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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···Ii | 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. |
Experimental details
Crystal data |
Chemical formula | C7H6BrI |
Mr | 296.93 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 200 |
a, b, c (Å) | 8.7569 (2), 12.0237 (4), 8.5351 (3) |
β (°) | 114.777 (2) |
V (Å3) | 815.94 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 8.73 |
Crystal size (mm) | 0.11 × 0.09 × 0.08 |
|
Data collection |
Diffractometer | KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.398, 0.497 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13178, 1867, 1514 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.056, 1.09 |
No. of reflections | 1867 |
No. of parameters | 84 |
H-atom treatment | Only H-atom displacement parameters refined |
Δρmax, Δρmin (e Å−3) | 1.05, −0.59 |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
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).