Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103027525/ta1429sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103027525/ta1429IIsup2.hkl |
CCDC reference: 231092
Colourless crystals of the title compound, prepared as reported by Canty et al. (2000), were crystallized from dichloromethane/petroleum and were found to be suitable for structural studies.
H atoms were located from difference Fourier maps and placed at idealized positions (C—H = 0.95 Å), with Uiso(H) = 1.25Ueq(C), ?N versus C being unambiguously assigned in the process.
Data collection: Syntex software; cell refinement: Syntex software; data reduction: Xtal3.5 (Hall et al., 1995); program(s) used to solve structure: Xtal3.5; program(s) used to refine structure: CRYLSQ in Xtal3.5; molecular graphics: Xtal3.5; software used to prepare material for publication: BONDLA and CIFIO in Xtal3.5.
C14H13BrN4 | Z = 2 |
Mr = 317.19 | F(000) = 320 |
Triclinic, P1 | Dx = 1.528 Mg m−3 |
Hall symbol: -p 1 | Mo Kα radiation, λ = 0.71069 Å |
a = 10.758 (6) Å | Cell parameters from 12 reflections |
b = 8.951 (5) Å | θ = 12.2–14.3° |
c = 8.425 (5) Å | µ = 2.97 mm−1 |
α = 111.24 (4)° | T = 296 K |
β = 100.94 (4)° | Plate, colourless |
γ = 105.74 (4)° | 0.67 × 0.32 × 0.12 mm |
V = 689.3 (8) Å3 |
Syntex P21 diffractometer | 1304 reflections with I > 2.00 σ(I) |
Radiation source: sealed tube | Rint = 0 |
Graphite monochromator | θmax = 25.1°, θmin = 2.1° |
2θ–ω scans | h = 0→10 |
Absorption correction: gaussian Xtal absorb | k = −10→10 |
Tmin = 0.41, Tmax = 0.72 | l = −9→9 |
2231 measured reflections | 8 standard reflections every 60 min |
2231 independent reflections | intensity decay: none |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.155 | H-atom parameters not refined |
S = 1.10 | w = 1/(σ2(F2) + 2.5F2 + .002F4) |
2231 reflections | (Δ/σ)max = 0.001 |
172 parameters | Δρmax = 0.77 e Å−3 |
0 restraints | Δρmin = −0.50 e Å−3 |
0 constraints |
C14H13BrN4 | γ = 105.74 (4)° |
Mr = 317.19 | V = 689.3 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.758 (6) Å | Mo Kα radiation |
b = 8.951 (5) Å | µ = 2.97 mm−1 |
c = 8.425 (5) Å | T = 296 K |
α = 111.24 (4)° | 0.67 × 0.32 × 0.12 mm |
β = 100.94 (4)° |
Syntex P21 diffractometer | 1304 reflections with I > 2.00 σ(I) |
Absorption correction: gaussian Xtal absorb | Rint = 0 |
Tmin = 0.41, Tmax = 0.72 | 8 standard reflections every 60 min |
2231 measured reflections | intensity decay: none |
2231 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.155 | H-atom parameters not refined |
S = 1.10 | Δρmax = 0.77 e Å−3 |
2231 reflections | Δρmin = −0.50 e Å−3 |
172 parameters |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.16921 (7) | 0.03801 (11) | 0.40814 (11) | 0.0862 (4) | |
C1 | 0.3197 (6) | 0.0461 (8) | 0.5790 (7) | 0.058 (2) | |
C2 | 0.4423 (6) | 0.1855 (7) | 0.6431 (7) | 0.055 (2) | |
C3 | 0.5526 (6) | 0.1823 (8) | 0.7590 (8) | 0.060 (2) | |
C4 | 0.5382 (6) | 0.0492 (8) | 0.8064 (8) | 0.058 (2) | |
C5 | 0.4135 (6) | −0.0827 (8) | 0.7434 (8) | 0.059 (3) | |
C6 | 0.3016 (6) | −0.0881 (7) | 0.6290 (8) | 0.054 (2) | |
C10 | 0.4582 (7) | 0.3336 (9) | 0.5910 (9) | 0.069 (3) | |
N11 | 0.5703 (6) | 0.4906 (6) | 0.7166 (7) | 0.064 (2) | |
N12 | 0.6938 (6) | 0.5228 (8) | 0.6940 (8) | 0.072 (3) | |
C13 | 0.5701 (8) | 0.6167 (9) | 0.8621 (10) | 0.074 (3) | |
C14 | 0.6972 (10) | 0.7358 (10) | 0.9406 (10) | 0.087 (4) | |
C15 | 0.7699 (8) | 0.6760 (10) | 0.8314 (12) | 0.081 (3) | |
C20 | 0.1659 (6) | −0.2331 (8) | 0.5585 (9) | 0.069 (3) | |
N21 | 0.1497 (5) | −0.3219 (7) | 0.6699 (7) | 0.062 (2) | |
N22 | 0.1199 (6) | −0.2519 (8) | 0.8223 (8) | 0.083 (3) | |
C23 | 0.1705 (7) | −0.4696 (9) | 0.6506 (9) | 0.072 (3) | |
C24 | 0.1512 (7) | −0.4978 (10) | 0.7925 (11) | 0.084 (4) | |
C25 | 0.1201 (7) | −0.3646 (12) | 0.8924 (10) | 0.088 (4) | |
H3 | 0.64111 | 0.27564 | 0.80519 | 0.07200* | |
H4 | 0.61735 | 0.04713 | 0.88427 | 0.06900* | |
H5 | 0.40558 | −0.17253 | 0.78608 | 0.07400* | |
H10a | 0.47010 | 0.29522 | 0.47346 | 0.08100* | |
H10b | 0.37284 | 0.35123 | 0.57590 | 0.08100* | |
H13 | 0.47934 | 0.58620 | 0.87577 | 0.09900* | |
H14 | 0.72893 | 0.84569 | 1.04965 | 0.10500* | |
H15 | 0.86049 | 0.70468 | 0.81830 | 0.09500* | |
H20a | 0.08188 | −0.21300 | 0.53441 | 0.08400* | |
H20b | 0.16501 | −0.31743 | 0.44858 | 0.08400* | |
H23 | 0.19258 | −0.51643 | 0.53973 | 0.08800* | |
H24 | 0.15928 | −0.59459 | 0.81656 | 0.10400* | |
H25 | 0.09824 | −0.31764 | 1.00579 | 0.10700* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0701 (5) | 0.1022 (6) | 0.0934 (6) | 0.0360 (4) | 0.0115 (4) | 0.0548 (5) |
C1 | 0.055 (4) | 0.070 (4) | 0.050 (3) | 0.030 (3) | 0.017 (3) | 0.022 (3) |
C2 | 0.063 (4) | 0.058 (3) | 0.052 (3) | 0.025 (3) | 0.027 (3) | 0.027 (3) |
C3 | 0.056 (4) | 0.065 (4) | 0.060 (3) | 0.023 (3) | 0.017 (3) | 0.029 (3) |
C4 | 0.057 (4) | 0.068 (4) | 0.061 (3) | 0.029 (3) | 0.018 (3) | 0.038 (3) |
C5 | 0.059 (4) | 0.068 (4) | 0.062 (4) | 0.027 (3) | 0.022 (3) | 0.036 (3) |
C6 | 0.051 (3) | 0.058 (3) | 0.058 (3) | 0.023 (3) | 0.022 (3) | 0.026 (3) |
C10 | 0.074 (4) | 0.079 (4) | 0.078 (4) | 0.037 (4) | 0.030 (3) | 0.048 (4) |
N11 | 0.075 (4) | 0.057 (3) | 0.072 (3) | 0.032 (3) | 0.031 (3) | 0.031 (3) |
N12 | 0.075 (4) | 0.079 (4) | 0.081 (4) | 0.038 (3) | 0.044 (3) | 0.041 (3) |
C13 | 0.094 (5) | 0.076 (4) | 0.075 (4) | 0.053 (4) | 0.041 (4) | 0.036 (4) |
C14 | 0.110 (6) | 0.078 (5) | 0.072 (5) | 0.045 (5) | 0.021 (4) | 0.027 (4) |
C15 | 0.073 (5) | 0.085 (5) | 0.106 (6) | 0.033 (4) | 0.035 (4) | 0.057 (5) |
C20 | 0.056 (4) | 0.072 (4) | 0.078 (4) | 0.017 (3) | 0.016 (3) | 0.038 (3) |
N21 | 0.047 (3) | 0.069 (3) | 0.063 (3) | 0.016 (2) | 0.016 (2) | 0.026 (3) |
N22 | 0.069 (4) | 0.092 (4) | 0.077 (4) | 0.023 (3) | 0.031 (3) | 0.028 (3) |
C23 | 0.061 (4) | 0.077 (4) | 0.077 (4) | 0.026 (3) | 0.020 (3) | 0.034 (4) |
C24 | 0.069 (5) | 0.083 (5) | 0.094 (5) | 0.016 (4) | 0.014 (4) | 0.049 (5) |
C25 | 0.060 (4) | 0.121 (7) | 0.070 (5) | 0.013 (4) | 0.019 (3) | 0.044 (5) |
Br1—C1 | 1.917 (7) | N12—C15 | 1.331 (8) |
C1—C2 | 1.392 (8) | C13—C14 | 1.341 (10) |
C1—C6 | 1.389 (11) | C13—H13 | 0.981 |
C2—C3 | 1.401 (10) | C14—C15 | 1.374 (14) |
C2—C10 | 1.519 (11) | C14—H14 | 0.986 |
C3—C4 | 1.368 (11) | C15—H15 | 0.976 |
C3—H3 | 0.974 | C20—N21 | 1.439 (11) |
C4—C5 | 1.375 (8) | C20—H20a | 0.967 |
C4—H4 | 0.980 | C20—H20b | 0.956 |
C5—C6 | 1.370 (9) | N21—N22 | 1.352 (9) |
C5—H5 | 0.983 | N21—C23 | 1.357 (11) |
C6—C20 | 1.501 (8) | N22—C25 | 1.341 (15) |
C10—N11 | 1.438 (7) | C23—C24 | 1.349 (14) |
C10—H10a | 0.970 | C23—H23 | 0.980 |
C10—H10b | 0.966 | C24—C25 | 1.356 (13) |
N11—N12 | 1.346 (9) | C24—H24 | 0.980 |
N11—C13 | 1.333 (9) | C25—H25 | 0.996 |
Br1—C1—C2 | 117.6 (6) | N11—C13—C14 | 107.3 (8) |
Br1—C1—C6 | 118.6 (4) | N11—C13—H13 | 109.5 |
C2—C1—C6 | 123.7 (6) | C14—C13—H13 | 143.2 |
C1—C2—C3 | 116.3 (7) | C13—C14—C15 | 105.3 (6) |
C1—C2—C10 | 122.7 (6) | C13—C14—H14 | 126.6 |
C3—C2—C10 | 121.0 (5) | C15—C14—H14 | 128.0 |
C2—C3—C4 | 121.0 (5) | N12—C15—C14 | 111.7 (7) |
C2—C3—H3 | 119.4 | N12—C15—H15 | 105.8 |
C4—C3—H3 | 119.6 | C14—C15—H15 | 142.5 |
C3—C4—C5 | 120.3 (6) | C6—C20—N21 | 113.5 (5) |
C3—C4—H4 | 119.8 | C6—C20—H20a | 120.9 |
C5—C4—H4 | 119.9 | C6—C20—H20b | 105.6 |
C4—C5—C6 | 121.8 (7) | N21—C20—H20a | 103.6 |
C4—C5—H5 | 118.0 | N21—C20—H20b | 104.5 |
C6—C5—H5 | 120.1 | H20a—C20—H20b | 107.5 |
C1—C6—C5 | 116.9 (5) | C20—N21—N22 | 120.2 (6) |
C1—C6—C20 | 121.3 (6) | C20—N21—C23 | 128.0 (6) |
C5—C6—C20 | 121.8 (7) | N22—N21—C23 | 111.6 (7) |
C2—C10—N11 | 113.9 (6) | N21—N22—C25 | 103.0 (7) |
C2—C10—H10a | 107.1 | N21—C23—C24 | 107.0 (7) |
C2—C10—H10b | 107.6 | N21—C23—H23 | 109.5 |
N11—C10—H10a | 110.0 | C24—C23—H23 | 143.5 |
N11—C10—H10b | 111.3 | C23—C24—C25 | 105.5 (9) |
H10a—C10—H10b | 106.5 | C23—C24—H24 | 126.3 |
C10—N11—N12 | 120.0 (6) | C25—C24—H24 | 128.2 |
C10—N11—C13 | 127.8 (7) | N22—C25—C24 | 112.9 (8) |
N12—N11—C13 | 112.2 (5) | N22—C25—H25 | 105.7 |
N11—N12—C15 | 103.4 (6) | C24—C25—H25 | 141.4 |
Experimental details
Crystal data | |
Chemical formula | C14H13BrN4 |
Mr | 317.19 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 10.758 (6), 8.951 (5), 8.425 (5) |
α, β, γ (°) | 111.24 (4), 100.94 (4), 105.74 (4) |
V (Å3) | 689.3 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.97 |
Crystal size (mm) | 0.67 × 0.32 × 0.12 |
Data collection | |
Diffractometer | Syntex P21 diffractometer |
Absorption correction | Gaussian Xtal absorb |
Tmin, Tmax | 0.41, 0.72 |
No. of measured, independent and observed [I > 2.00 σ(I)] reflections | 2231, 2231, 1304 |
Rint | 0 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.155, 1.10 |
No. of reflections | 2231 |
No. of parameters | 172 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.77, −0.50 |
Computer programs: Syntex software, Xtal3.5 (Hall et al., 1995), CRYLSQ in Xtal3.5, BONDLA and CIFIO in Xtal3.5.
Br1—C1 | 1.917 (7) | ||
Br1—C1—C2 | 117.6 (6) | C1—C6—C5 | 116.9 (5) |
Br1—C1—C6 | 118.6 (4) | C1—C6—C20 | 121.3 (6) |
C2—C1—C6 | 123.7 (6) | C5—C6—C20 | 121.8 (7) |
C1—C2—C3 | 116.3 (7) | C2—C10—N11 | 113.9 (6) |
C1—C2—C10 | 122.7 (6) | C6—C20—N21 | 113.5 (5) |
C3—C2—C10 | 121.0 (5) |
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Aryl halides containing nitrogen donor groups are useful reagents for the synthesis of organometallic compounds with interesting stability, structural and reactivity properties (Canty & van Koten, 1995; Albrecht & van Koten, 2001). The most extensively explored reagent is 2,6-bis[(dimethylamino)methyl]bromobenzene, 2,6-(Me2CH2)2C6H3Br, (I), which gives a wide range of organometallic compounds, including square-planar palladium(II) and platinum(II) complexes, and octahedral platinum(IV) complexes. In these complexes, the [N—C—N]− ligand normally acts in a planar tridentate fashion, e.g. square-planar PtI{2,6-(Me2NCH2)2C6H3—N,C,N} (Smeets et al., 1987) and mer-PtCl3{2,6-(Me2CH2)2C6H3—N,C,N} (van Koten et al., 1990). We have reported that the closely related reagent 2,6-bis[(pyrazol-1-yl)methyl]bromobenzene, (II), undergoes an oxidative addition reaction with [PtMe2(SEt2)]2 to form fac-PtBrMe2[2,6-(pzCH2)2C6H3—N,C,N], a platinum(IV) complex with the [N—C—N]− group as a tripodal tridentate ligand (Canty et al., 1990; Canty et al., 2000). Additional interest in these ligand systems has arisen from the discovery that 2,6-(3,5-Me2pz)2C6H3Br reacts with [Pt(p-Tol)2(SEt2)]2 to form PtBr{2,6-(3,5-Me2pz)2C6H3—N,C,N}, rather than a PtIV complex, providing a new and facile route to PtII complexes containing [N—C—N]− ligands that coordinate in a planar rather than a tripodal mode. Nevertheless, the puckering of the five-membered chelate rings is such that the ligand as a whole is not planar, having symmetry degraded to quasi-2 rather than m (Canty et al., 2000). This methodology has been extended to 2,6-(Me2CH2)2C6H3Br, resulting in a wide range of applications, e.g. the synthesis of nanosize multimetallic catalysts (Dijkstra et al., 2001). The precursor (II) itself is of interest, the Br atom occupying the position of the coordinated metal atom in the above, with the possibility of interaction of? the position of the coordinated metal with the pyrazole N atom or CH components should the peripheral rings lie quasi-coplanar with the central ring. A structure determination was therefore undertaken in order to explore this point.
In the event, the structure was found to be otherwise. The asymmetric unit of the structure comprises a single molecule, devoid of crystallographic symmetry, the planes of the peripheral pyrazolyl rings lying quasi-normal to the central ring [the interplanar dihedral angles are 83.3 (3) and 89.3 (3)°]. In the central ring, the C2—C1—C6 angle is enlarged to greater than 120°, at the expense of the pair of exocyclic angles. The capability of derivative ligands to coordinate in planar or tripodal tridentate modes is a consequence of the latitude available in terms of free rotation about the bonds to either side of Cn0 in the pendants, with the capacity to adjust chelate bite in the resultant six-membered rings by puckering of the latter, degrading the overall symmetry as above. In this mode in the present ?, pyrazole atoms Nn2 may lie in proximity to the Br atom or, by virtue of the exocyclic asymmetry at atom Nn1, ?to the CHn3 group?, directed away, as extremes. In the event, the C1—C2—C10—N11 and C1—C6—C20—N21 angles are 157.7 (6) and −157.7 (6)°, with C2—C10—N11—N12 and C6—C20—N21—N22 angles of 91.5 (9) and 78.4 (8)°, the ambience of the Br atom being the pair of methylene H atoms, H10b and H20a, at ca 2.7 and 2.8 Å. The angles at atoms C10 and C20 [113.9 (6) and 113.5 (5)°] are appreciably higher than the tetrahedral values, perhaps in consequence of repulsion between the faces of the pyrazole rings and atoms H3 and H5 (N11···H3 and N21—H5 = 2.5 Å). The exocyclic angles at atoms C2 and C6 are essentially equivalent.