The title crystals are isomorphous, with tetrameric Br⋯Br contacts as the principal packing interaction. No CN⋯Br or NC⋯Br contacts are observed.
Keywords: crystal structure, nitrile, isocyanide, Br⋯Br contacts
Abstract
In the title crystals, C8H5Br2N, which are isomorphous, the steric bulk of the methyl group causes neighboring molecules to become mutually inclined. This prevents the formation of planar or nearly planar sheets, which were observed in the trichloro and tribromo analogs. Instead of CN/NC⋯Br contacts, tetrameric Br⋯Br contacts are observed. These contacts form tetragonally puckered sheets parallel to (001). The CN/NC and methyl groups are grouped at the peaks and troughs. Both molecules lie across crystallographic mirror planes; thus, the methyl H atoms are disordered over two sets of sites with equal occupancy. The title nitrile is a redetermination. The refinement converged at R[F 2 > 2σ(F 2)] = 0.020, whereas the original determination [Gleason & Britton, (1976 ▸). Cryst. Struct. Commun. 5, 229–232] had R = 0.112.
Chemical context
As part of an ongoing study of cyano–halo short contacts, the para-Br atom of 2,4,6-tribromobenzonitrile (van Rij & Britton, 1972 ▸) was replaced by a methyl group (Gleason & Britton, 1976 ▸), giving 2,6-dibromo-4-methylbenzonitrile (RCN). The methyl group was bulky enough to disrupt the planar sheet structure that was observed in the tribromo nitrile. As of the most recent update of the Cambridge Structural Database (CSD; Version 5.37, Feb 2017; Groom et al., 2016 ▸), RCN remains the only example of a 2,6-dihalobenzonitrile with a methyl group at the 4-position. Most of the examples with polyatomic 4-substituents are fluorinated benzonitriles, with applications including tuning the fluoride affinity of phosphoranes (Solyntjes et al., 2016 ▸), study of magnetostructural correlation (Thomson et al., 2012 ▸), and use as metal ligands (Díaz-Álvarez et al., 2006 ▸). The chlorinated and brominated entries are either bis(carbonitriles) [(I), Fig. 1 ▸; Britton, 1981 ▸; Hirshfeld, 1984 ▸; van Rij & Britton, 1981 ▸] or 4-carboxy analogs [(II); Britton, 2012 ▸; Noland et al., 2017 ▸]. All of these 4-substituents have stronger interactions than a methyl group, and exhibit different packing motifs than RCN. The comparison of corresponding nitriles and isocyanides is a rare opportunity to explore the subtle differences between molecules that are both isomeric and isoelectronic. In the 2,6-dihaloaryl series, there are only three prior examples in the CSD. The trichloro and tribromo pairs [(III); Pink et al., 2000 ▸; Britton et al., 2016 ▸] are polytypic, and the pentafluoro pair [(IV), Fig. 1 ▸; Bond et al., 2001 ▸; Lentz & Preugschat, 1993 ▸] is isomorphous. The question arose as to whether RCN and its isocyanide (2,6-dibromo-4-methylphenyl isocyanide, RNC) would be isomorphous, polytypic, or polymorphic. A single crystal of RNC and a redetermination of RCN are presented.
Figure 1.
Contextual compounds.
Structural commentary
RNC and the redetermination of RCN are isomorphous with the original RCN structure (Gleason & Britton, 1976 ▸). The molecular structures of RCN (Fig. 2 ▸
a) and RNC (Fig. 2 ▸
b) are nearly planar. The two crystals described herein were pseudo-enantiomorphic, roughly being enantiomorphs with swapped cyano C and N atoms, hence the reflected ellipsoid orientations between RCN and RNC. For RCN, the mean deviation from the plane of best fit for the benzene ring (C1–C4) is 0.002 (3) Å. For RNC, this deviation (C11–C14) is 0.001 (2) Å. These planes are roughly parallel to (33
).
Figure 2.
The molecular structures of (a) RCN and (b) RNC, with atom labeling and displacement ellipsoids at the 50% probability level. Unlabeled atoms are generated by the (−
+ y, + x, z) and ( − y, − + x, z) symmetry operations, respectively. For the methyl H atoms, only one of the two mirror-related disorder sites is shown.
Supramolecular features
The methyl group is sufficiently bulky to prevent planar ribbons or inversion dimers of the types found in the tribromo analogs. Instead, neighboring molecules of RCN and RNC adopt a mutually inclined arrangement. The inclination between best-fit planes for adjacent molecules of RCN is 38.3 (3)°, and 41.0 (2)° for RNC. This molecular arrangement prevents CN⋯Br and NC⋯Br contacts, but is probably affected by the formation of 
(4) rings of Br⋯Br contacts (Table 1 ▸). Each Br atom participates both as a donor (narrow C—Br⋯Br angle) and an acceptor (wide C—Br⋯Br angle). Each molecule participates in two such (4) rings, forming (24) rings. The result is a tetragonally puckered sheet structure parallel to (001) (Fig. 3 ▸). This is similar to the sheet structure reported for 2,6-dibromobenzonitrile (Britton et al., 2000 ▸), although without the methyl group, the sheets were nearly planar. As future work, we plan to find whether this packing motif changes when the Br atoms are replaced with I atoms.
Table 1. Contact geometry (Å, °).
| C—Br⋯Br | C—Br | Br⋯Br | C—Br⋯Br |
|---|---|---|---|
| C2—Br2⋯Br2i | 1.899 (5) | 3.5575 (7) | 96.8 (2) |
| C2—Br2⋯Br2ii | 1.899 (5) | 3.5575 (7) | 176.41 (7) |
| C12—Br12⋯Br12i | 1.895 (4) | 3.575 (1) | 97.8 (1) |
| C12—Br12⋯Br12ii | 1.895 (4) | 3.575 (1) | 175.7 (1) |
Symmetry codes: (i) 1 − y, x, 1 − z; (ii) y, 1 − x, 1 − z.
Figure 3.
The sheet structure of RNC, viewed along [0
3]. The Br⋯Br contacts are represented as pink dotted lines.
Synthesis and crystallization
The synthesis of RCN and RNC is shown in Fig. 4 ▸.
Figure 4.
The synthesis of RCN and RNC.
2,6-Dibromo-4-methylaniline (V) was prepared from 4-methylaniline based on the work of Olivier (1926 ▸).
RCN was prepared from (V) (980 mg) via the Sandmeyer cyanation procedure described by Britton et al. (2016 ▸; Fig. 4 ▸), as a tan powder (898 mg, 88%). M.p. 434–435 K (lit. 429–431 K; Gleason & Britton, 1976 ▸); R f = 0.49 (SiO2 in 2:1 hexane–ethyl acetate); 1H NMR (500 MHz, CD2Cl2) δ 7.490 (s, 2H, H3A), 2.380 (s, 3H, H6A–C); 13C NMR (126 MHz, CD2Cl2) δ 147.1 (C4), 133.2 (C3), 126.6 (C2), 116.6 (C1 or C5), 116.1 (C5 or C1), 21.7 (C6); IR (KBr, cm−1) 3062, 2231, 1582, 1451, 1197, 857, 747; MS (EI, m/z) [M]+ calculated for C8H5Br2N 274.8763, found 274.8766.
2,6-Dibromo-4-methylformanilide (VI) was prepared from (V) (997 mg) via the formylation procedure described by Britton et al. (2016 ▸), performed at 60% scale, with dichloromethane instead of tetrahydrofuran. The filter cake was recrystallized from toluene, giving white needles (1.00 g, 91%). M.p. 505–506 K; R f = 0.27 (SiO2 in 2:1 hexane–ethyl acetate); 1H NMR (500 MHz, (CD3)2SO; 2 conformers obs.) δ 9.993 (s, 1H; major), 9.743 (d, J = 10.9 Hz, 1H; minor), 8.270 (s, 1H; major), 8.021 (d, J = 11.1 Hz, 1H; minor), 7.623 (s, 2H; minor), 7.571 (s, 2H; major), 2.303 (s, 3H; both); 13C NMR (126 MHz, (CD3)2SO; 2 conformers obs.) δ 164.5 (1C; minor), 159.6 (1C; major), 140.9 (1C; minor), 140.7 (1C; major), 133.0 (2C; minor), 132.6 (2C; major), 131.9 (1C; minor), 131.8 (1C; major), 123.3 (2C; minor), 123.2 (2C; major), 19.8 (1C; both); IR (KBr, cm−1) 3247, 2927, 1656, 1511, 1152, 1060, 840, 747, 684; MS (ESI, m/z) [M–H]− calculated for C8H7Br2NO 289.8822, found 289.8814.
RNC was prepared from (VI) (254 mg) via the amide dehydration procedure described by Britton et al. (2016 ▸), performed at 15% scale, as a beige powder (190 mg, 81%). M.p. 401–402 K; R f = 0.53 (SiO2 in 3:1 hexane–ethyl acetate); 1H NMR (400 MHz, CD2Cl2) δ 7.456 (s, 2H, H13), 2.346 (s, 3H, H16A–C); 13C NMR (101 MHz, CD2Cl2) δ 172.7 (C15), 142.9 (C14), 133.2 (C13), 126.0 (C11), 120.8 (C12), 21.2 (C16); IR (KBr, cm−1) 3061, 2922, 2850, 2118, 1654, 1586, 1451, 1384, 1064, 857, 748, 701; MS (EI, m/z) [M]+ calculated for C8H5Br2N 274.8783, found 274.8784.
Crystallization: RCN and RNC crystals were grown by slow evaporation of dichloromethane solutions under ambient conditions. Crystals were collected by suction filtration when a small portion of the original solvent remained, and then they were washed with pentane.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. A direct-methods solution was calculated, followed by full-matrix least squares/difference-Fourier cycles. All H atoms were placed in calculated positions (C—H = 0.95 or 0.98 Å) and refined as riding atoms with U iso(H) set to 1.2U eq(C) for aryl H atoms and 1.5U eq(C) for methyl H atoms. Because the molecules lie across mirror planes, the methyl H atoms are disordered across two sets of sites with 1:1 occupancy.
Table 2. Experimental details.
| RCN | RNC | |
|---|---|---|
| Crystal data | ||
| Chemical formula | C8H5Br2N | C8H5Br2N |
| M r | 274.95 | 274.95 |
| Crystal system, space group | Tetragonal, P
 21
m
|
Tetragonal, P
21
m
|
| Temperature (K) | 123 | 173 |
| a, c (Å) | 14.6731 (5), 3.9727 (1) | 14.690 (5), 4.0703 (15) |
| V (Å3) | 855.32 (6) | 878.3 (7) |
| Z | 4 | 4 |
| Radiation type | Cu Kα | Mo Kα |
| μ (mm−1) | 11.46 | 9.16 |
| Crystal size (mm) | 0.50 × 0.07 × 0.04 | 0.40 × 0.14 × 0.08 |
| Data collection | ||
| Diffractometer | Bruker Venture PHOTON-II | Bruker APEXII CCD |
| Absorption correction | Multi-scan (SADABS; Sheldrick, 1996 ▸) | Multi-scan (SADABS; Sheldrick, 1996 ▸) |
| T min, T max | 0.314, 0.754 | 0.255, 0.746 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 8444, 904, 902 | 10248, 1074, 1001 |
| R int | 0.039 | 0.045 |
| (sin θ/λ)max (Å−1) | 0.624 | 0.652 |
| Refinement | ||
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.020, 0.057, 1.27 | 0.023, 0.051, 1.14 |
| No. of reflections | 904 | 1074 |
| No. of parameters | 60 | 59 |
| H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.37, −0.32 | 0.30, −0.51 |
| Absolute structure | Flack x determined using 348 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▸) | Flack x determined using 381 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▸) |
| Absolute structure parameter | −0.02 (3) | −0.024 (13) |
Supplementary Material
Crystal structure: contains datablock(s) RCN, RNC. DOI: 10.1107/S2056989017016395/lh5859sup1.cif
Structure factors: contains datablock(s) RCN. DOI: 10.1107/S2056989017016395/lh5859RCNsup2.hkl
Structure factors: contains datablock(s) RNC. DOI: 10.1107/S2056989017016395/lh5859RNCsup3.hkl
Supporting information file. DOI: 10.1107/S2056989017016395/lh5859RCNsup4.cml
Supporting information file. DOI: 10.1107/S2056989017016395/lh5859RNCsup5.cml
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors thank Victor G. Young, Jr. (X-Ray Crystallographic Laboratory, University of Minnesota) for assistance with the crystallographic determination, the Wayland E. Noland Research Fellowship Fund at the University of Minnesota Foundation for generous financial support of this project, and Doyle Britton (deceased July 7, 2015) for providing the basis of this project. This work was taken in large part from the PhD thesis of KJT (Tritch, 2017 ▸).
supplementary crystallographic information
3,5-Dibromo-4-methylbenzonitrile (RCN). Crystal data
| C8H5Br2N | Melting point: 434 K |
| Mr = 274.95 | Cu Kα radiation, λ = 1.54178 Å |
| Tetragonal, P421m | Cell parameters from 2980 reflections |
| a = 14.6731 (5) Å | θ = 4.3–74.0° |
| c = 3.9727 (1) Å | µ = 11.46 mm−1 |
| V = 855.32 (6) Å3 | T = 123 K |
| Z = 4 | Needle, colourless |
| F(000) = 520 | 0.50 × 0.07 × 0.04 mm |
| Dx = 2.135 Mg m−3 |
3,5-Dibromo-4-methylbenzonitrile (RCN). Data collection
| Bruker Venture PHOTON-II diffractometer | 902 reflections with I > 2σ(I) |
| Radiation source: ImuS micro-focus | Rint = 0.039 |
| φ and ω scans | θmax = 74.2°, θmin = 6.0° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −18→18 |
| Tmin = 0.314, Tmax = 0.754 | k = −17→17 |
| 8444 measured reflections | l = −4→4 |
| 904 independent reflections |
3,5-Dibromo-4-methylbenzonitrile (RCN). Refinement
| Refinement on F2 | H-atom parameters constrained |
| Least-squares matrix: full | w = 1/[σ2(Fo2) + 2.1952P] where P = (Fo2 + 2Fc2)/3 |
| R[F2 > 2σ(F2)] = 0.020 | (Δ/σ)max = 0.001 |
| wR(F2) = 0.057 | Δρmax = 0.37 e Å−3 |
| S = 1.27 | Δρmin = −0.32 e Å−3 |
| 904 reflections | Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 60 parameters | Extinction coefficient: 0.0055 (4) |
| 0 restraints | Absolute structure: Flack x determined using 348 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
| Hydrogen site location: inferred from neighbouring sites | Absolute structure parameter: −0.02 (3) |
3,5-Dibromo-4-methylbenzonitrile (RCN). Special details
| Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
3,5-Dibromo-4-methylbenzonitrile (RCN). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| C1 | 0.2722 (3) | 0.7722 (3) | 0.357 (2) | 0.0156 (13) | |
| C2 | 0.2985 (3) | 0.6837 (4) | 0.2695 (13) | 0.0177 (10) | |
| Br2 | 0.41762 (3) | 0.64354 (3) | 0.38319 (19) | 0.0222 (2) | |
| C3 | 0.2404 (3) | 0.6240 (3) | 0.1067 (15) | 0.0185 (9) | |
| H3A | 0.2605 | 0.5645 | 0.0486 | 0.022* | |
| C4 | 0.1517 (3) | 0.6517 (3) | 0.0283 (18) | 0.0189 (15) | |
| C5 | 0.3328 (4) | 0.8328 (4) | 0.532 (2) | 0.0223 (17) | |
| N1 | 0.3806 (3) | 0.8806 (3) | 0.676 (2) | 0.0309 (17) | |
| C6 | 0.0866 (3) | 0.5866 (3) | −0.138 (2) | 0.0212 (13) | |
| H6A | 0.0306 | 0.6190 | −0.1991 | 0.032* | 0.5 |
| H6B | 0.0720 | 0.5369 | 0.0175 | 0.032* | 0.5 |
| H6C | 0.1148 | 0.5615 | −0.3417 | 0.032* | 0.5 |
3,5-Dibromo-4-methylbenzonitrile (RCN). Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0183 (18) | 0.0183 (18) | 0.010 (3) | −0.003 (2) | 0.000 (2) | 0.000 (2) |
| C2 | 0.015 (2) | 0.019 (2) | 0.019 (3) | 0.0001 (19) | 0.0034 (19) | 0.0025 (19) |
| Br2 | 0.0147 (3) | 0.0236 (3) | 0.0282 (3) | 0.00002 (17) | −0.0017 (2) | 0.0042 (3) |
| C3 | 0.018 (2) | 0.015 (2) | 0.022 (2) | −0.0001 (17) | 0.002 (3) | −0.003 (2) |
| C4 | 0.018 (2) | 0.018 (2) | 0.020 (4) | −0.005 (3) | 0.0031 (18) | 0.0031 (18) |
| C5 | 0.022 (2) | 0.022 (2) | 0.024 (4) | −0.002 (3) | 0.000 (2) | 0.000 (2) |
| N1 | 0.031 (2) | 0.031 (2) | 0.030 (4) | −0.009 (3) | −0.003 (2) | −0.003 (2) |
| C6 | 0.023 (2) | 0.023 (2) | 0.017 (3) | −0.005 (3) | 0.000 (2) | 0.000 (2) |
3,5-Dibromo-4-methylbenzonitrile (RCN). Geometric parameters (Å, º)
| C1—C2i | 1.399 (6) | C4—C3i | 1.398 (6) |
| C1—C2 | 1.399 (6) | C4—C6 | 1.505 (10) |
| C1—C5 | 1.437 (10) | C5—N1 | 1.145 (11) |
| C2—C3 | 1.383 (8) | C6—H6A | 0.9800 |
| C2—Br2 | 1.899 (5) | C6—H6B | 0.9800 |
| C3—C4 | 1.398 (6) | C6—H6C | 0.9800 |
| C3—H3A | 0.9500 | ||
| C2i—C1—C2 | 116.8 (7) | C3i—C4—C6 | 120.3 (3) |
| C2i—C1—C5 | 121.6 (3) | C3—C4—C6 | 120.3 (3) |
| C2—C1—C5 | 121.6 (3) | N1—C5—C1 | 179.0 (9) |
| C3—C2—C1 | 122.3 (5) | C4—C6—H6A | 109.5 |
| C3—C2—Br2 | 118.8 (4) | C4—C6—H6B | 109.5 |
| C1—C2—Br2 | 118.9 (4) | H6A—C6—H6B | 109.5 |
| C2—C3—C4 | 119.6 (5) | C4—C6—H6C | 109.5 |
| C2—C3—H3A | 120.2 | H6A—C6—H6C | 109.5 |
| C4—C3—H3A | 120.2 | H6B—C6—H6C | 109.5 |
| C3i—C4—C3 | 119.5 (6) | ||
| C2i—C1—C2—C3 | −0.5 (10) | C1—C2—C3—C4 | −0.7 (9) |
| C5—C1—C2—C3 | 178.7 (7) | Br2—C2—C3—C4 | 178.5 (5) |
| C2i—C1—C2—Br2 | −179.7 (4) | C2—C3—C4—C3i | 1.9 (11) |
| C5—C1—C2—Br2 | −0.5 (9) | C2—C3—C4—C6 | −178.0 (6) |
Symmetry code: (i) y−1/2, x+1/2, z.
2,6-Dibromo-4-methylphenyl isocyanide (RNC). Crystal data
| C8H5Br2N | Melting point: 401 K |
| Mr = 274.95 | Mo Kα radiation, λ = 0.71073 Å |
| Tetragonal, P421m | Cell parameters from 2995 reflections |
| a = 14.690 (5) Å | θ = 2.8–26.9° |
| c = 4.0703 (15) Å | µ = 9.16 mm−1 |
| V = 878.3 (7) Å3 | T = 173 K |
| Z = 4 | Needle, colourless |
| F(000) = 520 | 0.40 × 0.14 × 0.08 mm |
| Dx = 2.079 Mg m−3 |
2,6-Dibromo-4-methylphenyl isocyanide (RNC). Data collection
| Bruker APEXII CCD diffractometer | 1001 reflections with I > 2σ(I) |
| Radiation source: sealed tube | Rint = 0.045 |
| φ and ω scans | θmax = 27.6°, θmin = 2.0° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −18→19 |
| Tmin = 0.255, Tmax = 0.746 | k = −19→19 |
| 10248 measured reflections | l = −5→5 |
| 1074 independent reflections |
2,6-Dibromo-4-methylphenyl isocyanide (RNC). Refinement
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.023 | w = 1/[σ2(Fo2) + (0.0267P)2 + 0.0073P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.051 | (Δ/σ)max < 0.001 |
| S = 1.14 | Δρmax = 0.30 e Å−3 |
| 1074 reflections | Δρmin = −0.51 e Å−3 |
| 59 parameters | Absolute structure: Flack x determined using 381 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
| 0 restraints | Absolute structure parameter: −0.024 (13) |
2,6-Dibromo-4-methylphenyl isocyanide (RNC). Special details
| Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
2,6-Dibromo-4-methylphenyl isocyanide (RNC). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Br12 | 0.64344 (3) | 0.58324 (2) | 0.38265 (14) | 0.03268 (14) | |
| N11 | 0.8281 (2) | 0.6719 (2) | 0.5307 (11) | 0.0278 (11) | |
| C11 | 0.7708 (2) | 0.7292 (2) | 0.3538 (15) | 0.0228 (11) | |
| C12 | 0.6845 (3) | 0.7013 (3) | 0.2671 (9) | 0.0245 (8) | |
| C13 | 0.6256 (2) | 0.7587 (2) | 0.0981 (10) | 0.0243 (8) | |
| H13A | 0.5664 | 0.7382 | 0.0402 | 0.029* | |
| C14 | 0.6535 (3) | 0.8465 (3) | 0.0132 (13) | 0.0237 (11) | |
| C15 | 0.8753 (3) | 0.6247 (3) | 0.6829 (18) | 0.0474 (18) | |
| C16 | 0.5894 (3) | 0.9106 (3) | −0.1624 (14) | 0.0328 (12) | |
| H16A | 0.5318 | 0.8793 | −0.2065 | 0.049* | 0.5 |
| H16B | 0.6169 | 0.9300 | −0.3703 | 0.049* | 0.5 |
| H16C | 0.5781 | 0.9640 | −0.0241 | 0.049* | 0.5 |
2,6-Dibromo-4-methylphenyl isocyanide (RNC). Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br12 | 0.0337 (2) | 0.02125 (19) | 0.0431 (2) | −0.00062 (15) | 0.0071 (2) | 0.0013 (2) |
| N11 | 0.0268 (15) | 0.0268 (15) | 0.030 (3) | 0.009 (2) | 0.0005 (13) | −0.0005 (13) |
| C11 | 0.0238 (15) | 0.0238 (15) | 0.021 (3) | 0.0067 (19) | 0.0031 (16) | −0.0031 (16) |
| C12 | 0.0267 (19) | 0.0202 (18) | 0.027 (2) | 0.0008 (16) | 0.0080 (16) | −0.0028 (15) |
| C13 | 0.0214 (17) | 0.0240 (17) | 0.0273 (19) | 0.0001 (14) | 0.0017 (18) | −0.0043 (19) |
| C14 | 0.0245 (16) | 0.0245 (16) | 0.022 (3) | 0.007 (2) | 0.0038 (14) | −0.0038 (14) |
| C15 | 0.048 (2) | 0.048 (2) | 0.046 (5) | 0.016 (3) | −0.002 (2) | 0.002 (2) |
| C16 | 0.0329 (18) | 0.0329 (18) | 0.033 (3) | 0.009 (3) | −0.0013 (18) | 0.0013 (18) |
2,6-Dibromo-4-methylphenyl isocyanide (RNC). Geometric parameters (Å, º)
| Br12—C12 | 1.896 (4) | C13—H13A | 0.9500 |
| N11—C15 | 1.161 (8) | C14—C13i | 1.396 (4) |
| N11—C11 | 1.391 (7) | C14—C16 | 1.511 (7) |
| C11—C12 | 1.379 (5) | C16—H16A | 0.9800 |
| C11—C12i | 1.379 (5) | C16—H16B | 0.9800 |
| C12—C13 | 1.389 (6) | C16—H16C | 0.9800 |
| C13—C14 | 1.396 (4) | ||
| C15—N11—C11 | 178.9 (6) | C13—C14—C13i | 118.7 (5) |
| C12—C11—C12i | 118.7 (5) | C13—C14—C16 | 120.6 (2) |
| C12—C11—N11 | 120.6 (3) | C13i—C14—C16 | 120.6 (2) |
| C12i—C11—N11 | 120.6 (3) | C14—C16—H16A | 109.5 |
| C11—C12—C13 | 121.3 (4) | C14—C16—H16B | 109.5 |
| C11—C12—Br12 | 120.0 (3) | H16A—C16—H16B | 109.5 |
| C13—C12—Br12 | 118.7 (3) | C14—C16—H16C | 109.5 |
| C12—C13—C14 | 120.0 (4) | H16A—C16—H16C | 109.5 |
| C12—C13—H13A | 120.0 | H16B—C16—H16C | 109.5 |
| C14—C13—H13A | 120.0 | ||
| C12i—C11—C12—C13 | −0.5 (8) | C11—C12—C13—C14 | −0.1 (6) |
| N11—C11—C12—C13 | 178.2 (4) | Br12—C12—C13—C14 | 179.2 (3) |
| C12i—C11—C12—Br12 | −179.8 (3) | C12—C13—C14—C13i | 0.7 (7) |
| N11—C11—C12—Br12 | −1.1 (7) | C12—C13—C14—C16 | −178.3 (4) |
Symmetry code: (i) −y+3/2, −x+3/2, z.
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) RCN, RNC. DOI: 10.1107/S2056989017016395/lh5859sup1.cif
Structure factors: contains datablock(s) RCN. DOI: 10.1107/S2056989017016395/lh5859RCNsup2.hkl
Structure factors: contains datablock(s) RNC. DOI: 10.1107/S2056989017016395/lh5859RNCsup3.hkl
Supporting information file. DOI: 10.1107/S2056989017016395/lh5859RCNsup4.cml
Supporting information file. DOI: 10.1107/S2056989017016395/lh5859RNCsup5.cml
Additional supporting information: crystallographic information; 3D view; checkCIF report