Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108043631/lg3003sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108043631/lg3003Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108043631/lg3003IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108043631/lg3003IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108043631/lg3003IVsup5.hkl |
CCDC references: 724174; 724175; 724176; 724177
Complexes (I)–(IV) were prepared according to the procedures of Fuchita & Tsuchiya (1993) and/or Vicente et al. (1995). Light-yellow or colorless rods or blocks suitable for single-crystal X-ray diffraction were obtained by crystallization from methanol/water mixtures at room temperature. Crystals of (II) were covered with small crystallites of the same compound; as a result, an unusual second parameter in the weighting scheme, less satisfactory agreement factors and a clearly inferior Rint were encountered.
After completion of the structure models, residual maxima were found with electron densities between 1.3 and 2.2 e Å-3 and at distances between 1.3 and 1.4 Å from the corresponding chiral center (C7 in all structures), indicating disorder for the attached methyl group (C14 in all structures). A pronounced prolate anisotropic displacement parameter for the chiral C7 atom induced us to consider split positions for this atom too. The sum of both conformations was constrained to unity, and distance restraints were imposed on the bond lengths involved. Occupancies for disordered sites and interatomic distances for each individual structure are given in the supplementary material. In all structures, H atoms were treated as riding on the corresponding C (C—H = 0.98 Å) or N atoms (N—H = 0.92 Å).
For all compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Pd(C8H10N)Cl(C5H5N)] | Dx = 1.739 Mg m−3 |
Mr = 341.12 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/a | Cell parameters from 7745 reflections |
Hall symbol: -I 4ad | θ = 2.2–26.6° |
a = 18.3310 (8) Å | µ = 1.61 mm−1 |
c = 15.5123 (14) Å | T = 100 K |
V = 5212.5 (6) Å3 | Rod, light yellow |
Z = 16 | 0.23 × 0.08 × 0.04 mm |
F(000) = 2720 |
Bruker SMART APEX CCD diffractometer | 2990 independent reflections |
Radiation source: fine-focus sealed tube | 2544 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.074 |
ω scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −23→23 |
Tmin = 0.709, Tmax = 0.939 | k = −23→23 |
33317 measured reflections | l = −20→20 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0252P)2] where P = (Fo2 + 2Fc2)/3 |
2990 reflections | (Δ/σ)max = 0.001 |
153 parameters | Δρmax = 0.41 e Å−3 |
3 restraints | Δρmin = −0.50 e Å−3 |
[Pd(C8H10N)Cl(C5H5N)] | Z = 16 |
Mr = 341.12 | Mo Kα radiation |
Tetragonal, I41/a | µ = 1.61 mm−1 |
a = 18.3310 (8) Å | T = 100 K |
c = 15.5123 (14) Å | 0.23 × 0.08 × 0.04 mm |
V = 5212.5 (6) Å3 |
Bruker SMART APEX CCD diffractometer | 2990 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 2544 reflections with I > 2σ(I) |
Tmin = 0.709, Tmax = 0.939 | Rint = 0.074 |
33317 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 3 restraints |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.41 e Å−3 |
2990 reflections | Δρmin = −0.50 e Å−3 |
153 parameters |
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 of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. Minor disorder for C14/C14A and C7/C7A, see manuscript. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Pd1 | −0.002463 (16) | 0.144743 (15) | 0.326117 (17) | 0.02494 (10) | |
Cl1 | −0.09244 (5) | 0.14173 (5) | 0.21217 (6) | 0.0316 (2) | |
N1 | −0.07996 (16) | 0.10875 (17) | 0.41065 (18) | 0.0264 (7) | |
N2 | 0.07978 (15) | 0.17804 (16) | 0.24763 (18) | 0.0259 (7) | |
H2A | 0.0777 | 0.1514 | 0.1974 | 0.031* | |
H2B | 0.0721 | 0.2262 | 0.2335 | 0.031* | |
C1 | −0.1383 (2) | 0.1505 (2) | 0.4285 (3) | 0.0402 (10) | |
H1 | −0.1402 | 0.1999 | 0.4043 | 0.052* | |
C2 | −0.1954 (2) | 0.1274 (2) | 0.4789 (3) | 0.0387 (10) | |
H2 | −0.2369 | 0.1597 | 0.4900 | 0.050* | |
C3 | −0.1935 (2) | 0.0592 (2) | 0.5131 (2) | 0.0357 (10) | |
H3 | −0.2336 | 0.0415 | 0.5493 | 0.046* | |
C4 | −0.1345 (2) | 0.0157 (2) | 0.4960 (2) | 0.0384 (10) | |
H4 | −0.1315 | −0.0335 | 0.5204 | 0.050* | |
C5 | −0.0796 (2) | 0.0418 (2) | 0.4445 (2) | 0.0328 (9) | |
H5 | −0.0381 | 0.0097 | 0.4320 | 0.043* | |
C7 | 0.1561 (3) | 0.1706 (3) | 0.2855 (3) | 0.0261 (12)* | 0.717 (5) |
H7 | 0.1851 | 0.2139 | 0.2716 | 0.034* | 0.717 (5) |
C14 | 0.1937 (3) | 0.1030 (3) | 0.2520 (3) | 0.0303 (12)* | 0.717 (5) |
H14A | 0.2431 | 0.1003 | 0.2758 | 0.039* | 0.717 (5) |
H14B | 0.1962 | 0.1050 | 0.1890 | 0.039* | 0.717 (5) |
H14C | 0.1660 | 0.0597 | 0.2696 | 0.039* | 0.717 (5) |
C7A | 0.1463 (6) | 0.1441 (8) | 0.2819 (7) | 0.0261 (12)* | 0.283 (5) |
H7A | 0.1475 | 0.0912 | 0.2726 | 0.034* | 0.283 (5) |
C14A | 0.2083 (7) | 0.1830 (7) | 0.2382 (8) | 0.0303 (12)* | 0.283 (5) |
H14D | 0.2012 | 0.1816 | 0.1756 | 0.039* | 0.283 (5) |
H14E | 0.2544 | 0.1590 | 0.2529 | 0.039* | 0.283 (5) |
H14F | 0.2098 | 0.2339 | 0.2576 | 0.039* | 0.283 (5) |
C8 | 0.1454 (2) | 0.1653 (2) | 0.3806 (2) | 0.0316 (9) | |
C9 | 0.0746 (2) | 0.15690 (19) | 0.4130 (2) | 0.0273 (8) | |
C10 | 0.0642 (2) | 0.16338 (19) | 0.5023 (2) | 0.0307 (9) | |
H10 | 0.0149 | 0.1601 | 0.5266 | 0.040* | |
C11 | 0.1234 (2) | 0.1744 (2) | 0.5564 (2) | 0.0337 (9) | |
H11 | 0.1155 | 0.1791 | 0.6186 | 0.044* | |
C12 | 0.1933 (2) | 0.1790 (2) | 0.5239 (3) | 0.0376 (10) | |
H12 | 0.2350 | 0.1849 | 0.5629 | 0.049* | |
C13 | 0.2041 (2) | 0.1751 (2) | 0.4358 (3) | 0.0411 (11) | |
H13 | 0.2535 | 0.1794 | 0.4122 | 0.053* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.03454 (19) | 0.02437 (17) | 0.01590 (14) | 0.00378 (13) | 0.00342 (12) | 0.00117 (11) |
Cl1 | 0.0430 (6) | 0.0328 (5) | 0.0189 (4) | −0.0042 (4) | −0.0022 (4) | 0.0002 (4) |
N1 | 0.0296 (17) | 0.0328 (18) | 0.0167 (15) | 0.0003 (14) | 0.0003 (13) | 0.0009 (13) |
N2 | 0.0319 (18) | 0.0276 (17) | 0.0181 (16) | 0.0063 (13) | 0.0017 (13) | 0.0024 (13) |
C1 | 0.042 (3) | 0.037 (2) | 0.041 (3) | 0.012 (2) | 0.007 (2) | 0.009 (2) |
C2 | 0.031 (2) | 0.048 (3) | 0.037 (2) | 0.009 (2) | 0.0071 (19) | 0.004 (2) |
C3 | 0.043 (3) | 0.041 (2) | 0.024 (2) | −0.017 (2) | 0.0068 (18) | −0.0031 (18) |
C4 | 0.058 (3) | 0.027 (2) | 0.031 (2) | −0.005 (2) | 0.011 (2) | 0.0014 (18) |
C5 | 0.048 (3) | 0.028 (2) | 0.023 (2) | 0.0062 (18) | 0.0022 (18) | 0.0014 (16) |
C8 | 0.036 (2) | 0.037 (2) | 0.022 (2) | 0.0122 (18) | 0.0021 (17) | 0.0034 (17) |
C9 | 0.035 (2) | 0.027 (2) | 0.0198 (18) | 0.0062 (16) | 0.0000 (16) | 0.0034 (15) |
C10 | 0.035 (2) | 0.031 (2) | 0.026 (2) | 0.0065 (17) | 0.0045 (17) | −0.0019 (16) |
C11 | 0.047 (3) | 0.034 (2) | 0.020 (2) | 0.0111 (19) | −0.0006 (17) | −0.0033 (16) |
C12 | 0.043 (3) | 0.039 (2) | 0.031 (2) | 0.0084 (19) | −0.0072 (19) | −0.0002 (19) |
C13 | 0.034 (2) | 0.054 (3) | 0.035 (2) | 0.014 (2) | −0.0002 (19) | 0.008 (2) |
Pd1—C9 | 1.965 (4) | C7—H7 | 0.9800 |
Pd1—N2 | 2.032 (3) | C14—H14A | 0.9801 |
Pd1—N1 | 2.043 (3) | C14—H14B | 0.9801 |
Pd1—Cl1 | 2.4183 (10) | C14—H14C | 0.9801 |
N1—C5 | 1.336 (4) | C7A—C14A | 1.505 (13) |
N1—C1 | 1.344 (5) | C7A—C8 | 1.580 (11) |
N2—C7A | 1.469 (11) | C7A—H7A | 0.9800 |
N2—C7 | 1.523 (5) | C14A—H14D | 0.9801 |
N2—H2A | 0.9200 | C14A—H14E | 0.9801 |
N2—H2B | 0.9200 | C14A—H14F | 0.9801 |
C1—C2 | 1.373 (5) | C8—C13 | 1.387 (5) |
C1—H1 | 0.9800 | C8—C9 | 1.401 (5) |
C2—C3 | 1.359 (5) | C9—C10 | 1.404 (5) |
C2—H2 | 0.9800 | C10—C11 | 1.387 (5) |
C3—C4 | 1.370 (5) | C10—H10 | 0.9800 |
C3—H3 | 0.9800 | C11—C12 | 1.380 (5) |
C4—C5 | 1.370 (5) | C11—H11 | 0.9800 |
C4—H4 | 0.9800 | C12—C13 | 1.383 (5) |
C5—H5 | 0.9800 | C12—H12 | 0.9800 |
C7—C8 | 1.491 (6) | C13—H13 | 0.9800 |
C7—C14 | 1.511 (7) | ||
C9—Pd1—N2 | 80.99 (13) | C8—C7—H7 | 110.0 |
C9—Pd1—N1 | 95.53 (13) | C14—C7—H7 | 110.0 |
N2—Pd1—N1 | 176.15 (11) | N2—C7—H7 | 110.0 |
C9—Pd1—Cl1 | 173.82 (11) | N2—C7A—C14A | 105.3 (9) |
N2—Pd1—Cl1 | 94.30 (8) | N2—C7A—C8 | 103.8 (7) |
N1—Pd1—Cl1 | 89.29 (8) | C14A—C7A—C8 | 109.1 (9) |
C5—N1—C1 | 116.6 (3) | N2—C7A—H7A | 112.7 |
C5—N1—Pd1 | 123.1 (3) | C14A—C7A—H7A | 112.7 |
C1—N1—Pd1 | 120.1 (3) | C8—C7A—H7A | 112.7 |
C7A—N2—C7 | 20.0 (6) | C7A—C14A—H14D | 109.5 |
C7A—N2—Pd1 | 105.8 (5) | C7A—C14A—H14E | 109.5 |
C7—N2—Pd1 | 115.1 (2) | H14D—C14A—H14E | 109.5 |
C7A—N2—H2A | 96.6 | C7A—C14A—H14F | 109.5 |
C7—N2—H2A | 108.5 | H14D—C14A—H14F | 109.5 |
Pd1—N2—H2A | 108.5 | H14E—C14A—H14F | 109.5 |
C7A—N2—H2B | 128.3 | C13—C8—C9 | 120.8 (4) |
C7—N2—H2B | 108.5 | C13—C8—C7 | 120.0 (4) |
Pd1—N2—H2B | 108.5 | C9—C8—C7 | 118.9 (4) |
H2A—N2—H2B | 107.5 | C13—C8—C7A | 128.5 (5) |
N1—C1—C2 | 123.2 (4) | C9—C8—C7A | 109.3 (5) |
N1—C1—H1 | 118.4 | C7—C8—C7A | 19.3 (5) |
C2—C1—H1 | 118.4 | C8—C9—C10 | 118.1 (4) |
C3—C2—C1 | 119.2 (4) | C8—C9—Pd1 | 115.6 (3) |
C3—C2—H2 | 120.4 | C10—C9—Pd1 | 126.1 (3) |
C1—C2—H2 | 120.4 | C11—C10—C9 | 120.2 (4) |
C2—C3—C4 | 118.6 (4) | C11—C10—H10 | 119.9 |
C2—C3—H3 | 120.7 | C9—C10—H10 | 119.9 |
C4—C3—H3 | 120.7 | C12—C11—C10 | 121.0 (4) |
C3—C4—C5 | 119.4 (4) | C12—C11—H11 | 119.5 |
C3—C4—H4 | 120.3 | C10—C11—H11 | 119.5 |
C5—C4—H4 | 120.3 | C11—C12—C13 | 119.4 (4) |
N1—C5—C4 | 123.0 (4) | C11—C12—H12 | 120.3 |
N1—C5—H5 | 118.5 | C13—C12—H12 | 120.3 |
C4—C5—H5 | 118.5 | C12—C13—C8 | 120.4 (4) |
C8—C7—C14 | 110.3 (4) | C12—C13—H13 | 119.8 |
C8—C7—N2 | 105.5 (4) | C8—C13—H13 | 119.8 |
C14—C7—N2 | 111.1 (4) | ||
C9—Pd1—N1—C5 | −74.6 (3) | C14—C7—C8—C9 | −110.6 (4) |
N2—Pd1—N1—C5 | −49.5 (19) | N2—C7—C8—C9 | 9.4 (5) |
Cl1—Pd1—N1—C5 | 109.3 (3) | C14—C7—C8—C7A | −46.5 (14) |
C9—Pd1—N1—C1 | 111.7 (3) | N2—C7—C8—C7A | 73.5 (14) |
N2—Pd1—N1—C1 | 136.8 (17) | N2—C7A—C8—C13 | −150.9 (5) |
Cl1—Pd1—N1—C1 | −64.4 (3) | C14A—C7A—C8—C13 | −39.1 (12) |
C9—Pd1—N2—C7A | 37.5 (6) | N2—C7A—C8—C9 | 42.9 (9) |
N1—Pd1—N2—C7A | 12 (2) | C14A—C7A—C8—C9 | 154.7 (8) |
Cl1—Pd1—N2—C7A | −146.5 (6) | N2—C7A—C8—C7 | −80.6 (15) |
C9—Pd1—N2—C7 | 18.5 (3) | C14A—C7A—C8—C7 | 31.2 (11) |
N1—Pd1—N2—C7 | −6.8 (19) | C13—C8—C9—C10 | 4.0 (5) |
Cl1—Pd1—N2—C7 | −165.5 (3) | C7—C8—C9—C10 | −170.2 (4) |
C5—N1—C1—C2 | 0.3 (6) | C7A—C8—C9—C10 | 171.4 (6) |
Pd1—N1—C1—C2 | 174.4 (3) | C13—C8—C9—Pd1 | 179.3 (3) |
N1—C1—C2—C3 | 0.2 (7) | C7—C8—C9—Pd1 | 5.0 (5) |
C1—C2—C3—C4 | 0.0 (6) | C7A—C8—C9—Pd1 | −13.3 (6) |
C2—C3—C4—C5 | −0.6 (6) | N2—Pd1—C9—C8 | −12.9 (3) |
C1—N1—C5—C4 | −0.9 (6) | N1—Pd1—C9—C8 | 165.5 (3) |
Pd1—N1—C5—C4 | −174.9 (3) | Cl1—Pd1—C9—C8 | −53.4 (11) |
C3—C4—C5—N1 | 1.1 (6) | N2—Pd1—C9—C10 | 162.0 (3) |
C7A—N2—C7—C8 | −85.5 (15) | N1—Pd1—C9—C10 | −19.7 (3) |
Pd1—N2—C7—C8 | −19.5 (4) | Cl1—Pd1—C9—C10 | 121.4 (9) |
C7A—N2—C7—C14 | 33.9 (14) | C8—C9—C10—C11 | −2.9 (5) |
Pd1—N2—C7—C14 | 99.9 (4) | Pd1—C9—C10—C11 | −177.6 (3) |
C7—N2—C7A—C14A | −45.6 (13) | C9—C10—C11—C12 | −0.3 (6) |
Pd1—N2—C7A—C14A | −166.3 (7) | C10—C11—C12—C13 | 2.4 (6) |
C7—N2—C7A—C8 | 68.9 (14) | C11—C12—C13—C8 | −1.3 (6) |
Pd1—N2—C7A—C8 | −51.7 (8) | C9—C8—C13—C12 | −1.9 (6) |
C14—C7—C8—C13 | 75.2 (5) | C7—C8—C13—C12 | 172.2 (4) |
N2—C7—C8—C13 | −164.9 (3) | C7A—C8—C13—C12 | −166.7 (7) |
[PdBr(C8H10N)(C5H5N)] | Dx = 1.899 Mg m−3 |
Mr = 385.58 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/a | Cell parameters from 2588 reflections |
Hall symbol: -I 4ad | θ = 2.2–23.5° |
a = 18.5197 (9) Å | µ = 4.32 mm−1 |
c = 15.7281 (16) Å | T = 110 K |
V = 5394.4 (7) Å3 | Rod, light yellow |
Z = 16 | 0.17 × 0.05 × 0.03 mm |
F(000) = 3008 |
Bruker SMART APEX CCD diffractometer | 2519 independent reflections |
Radiation source: fine-focus sealed tube | 1839 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.173 |
ω scans | θmax = 25.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −22→22 |
Tmin = 0.527, Tmax = 0.881 | k = −22→22 |
29977 measured reflections | l = −19→19 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.070 | H-atom parameters constrained |
wR(F2) = 0.141 | w = 1/[σ2(Fo2) + (0.0487P)2 + 37.3572P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max < 0.001 |
2519 reflections | Δρmax = 0.73 e Å−3 |
153 parameters | Δρmin = −1.34 e Å−3 |
15 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00083 (8) |
[PdBr(C8H10N)(C5H5N)] | Z = 16 |
Mr = 385.58 | Mo Kα radiation |
Tetragonal, I41/a | µ = 4.32 mm−1 |
a = 18.5197 (9) Å | T = 110 K |
c = 15.7281 (16) Å | 0.17 × 0.05 × 0.03 mm |
V = 5394.4 (7) Å3 |
Bruker SMART APEX CCD diffractometer | 2519 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 1839 reflections with I > 2σ(I) |
Tmin = 0.527, Tmax = 0.881 | Rint = 0.173 |
29977 measured reflections |
R[F2 > 2σ(F2)] = 0.070 | 15 restraints |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0487P)2 + 37.3572P] where P = (Fo2 + 2Fc2)/3 |
2519 reflections | Δρmax = 0.73 e Å−3 |
153 parameters | Δρmin = −1.34 e Å−3 |
Experimental. Crystals are covered with small crystallites of the same compound; as a result, an unusual second parameter in the weighting scheme, less satisfactory agreement factors and a clearly inferior Rint are encountered. |
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 of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. Minor disorder for C14/C14A and C7/C7A, see manuscript. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Pd1 | 0.00084 (4) | 0.14389 (4) | 0.33163 (5) | 0.0234 (2) | |
Br1 | −0.09194 (6) | 0.13684 (6) | 0.21267 (6) | 0.0313 (3) | |
N1 | −0.0765 (4) | 0.1072 (4) | 0.4154 (5) | 0.0244 (18) | |
N2 | 0.0818 (4) | 0.1783 (4) | 0.2536 (5) | 0.0220 (19) | |
H2A | 0.0793 | 0.1529 | 0.2034 | 0.026* | |
H2B | 0.0744 | 0.2262 | 0.2412 | 0.026* | |
C1 | −0.1319 (6) | 0.1525 (6) | 0.4354 (7) | 0.037 (3) | |
H1 | −0.1318 | 0.2024 | 0.4148 | 0.049* | |
C2 | −0.1877 (6) | 0.1278 (6) | 0.4843 (7) | 0.038 (3) | |
H2 | −0.2270 | 0.1610 | 0.4989 | 0.049* | |
C3 | −0.1904 (6) | 0.0591 (6) | 0.5133 (6) | 0.033 (3) | |
H3 | −0.2311 | 0.0420 | 0.5477 | 0.043* | |
C4 | −0.1349 (6) | 0.0150 (6) | 0.4931 (6) | 0.036 (3) | |
H4 | −0.1349 | −0.0351 | 0.5131 | 0.047* | |
C5 | −0.0778 (6) | 0.0405 (6) | 0.4440 (6) | 0.028 (2) | |
H5 | −0.0377 | 0.0080 | 0.4305 | 0.036* | |
C7 | 0.1578 (6) | 0.1695 (8) | 0.2909 (7) | 0.024 (3)* | 0.747 (13) |
H7 | 0.1878 | 0.2109 | 0.2750 | 0.031* | 0.747 (13) |
C14 | 0.1918 (7) | 0.1002 (7) | 0.2576 (8) | 0.026 (3)* | 0.747 (13) |
H14A | 0.2399 | 0.0942 | 0.2826 | 0.034* | 0.747 (13) |
H14B | 0.1959 | 0.1028 | 0.1956 | 0.034* | 0.747 (13) |
H14C | 0.1614 | 0.0589 | 0.2733 | 0.034* | 0.747 (13) |
C7A | 0.1498 (12) | 0.1464 (19) | 0.2923 (12) | 0.024 (3)* | 0.253 (13) |
H7A | 0.1528 | 0.0939 | 0.2847 | 0.031* | 0.253 (13) |
C14A | 0.2110 (18) | 0.186 (2) | 0.248 (2) | 0.026 (3)* | 0.253 (13) |
H14D | 0.2079 | 0.2378 | 0.2617 | 0.034* | 0.253 (13) |
H14E | 0.2072 | 0.1792 | 0.1868 | 0.034* | 0.253 (13) |
H14F | 0.2574 | 0.1672 | 0.2685 | 0.034* | 0.253 (13) |
C8 | 0.1484 (6) | 0.1677 (6) | 0.3833 (7) | 0.032 (3) | |
C9 | 0.0774 (6) | 0.1575 (6) | 0.4187 (6) | 0.031 (3) | |
C10 | 0.0675 (6) | 0.1649 (6) | 0.5058 (7) | 0.034 (3) | |
H10 | 0.0187 | 0.1623 | 0.5297 | 0.044* | |
C11 | 0.1260 (6) | 0.1761 (6) | 0.5591 (6) | 0.033 (3) | |
H11 | 0.1185 | 0.1792 | 0.6206 | 0.043* | |
C12 | 0.1932 (7) | 0.1826 (6) | 0.5272 (7) | 0.038 (3) | |
H12 | 0.2339 | 0.1907 | 0.5659 | 0.049* | |
C13 | 0.2058 (6) | 0.1780 (6) | 0.4397 (7) | 0.039 (3) | |
H13 | 0.2552 | 0.1821 | 0.4178 | 0.051* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.0318 (5) | 0.0241 (5) | 0.0143 (4) | 0.0021 (4) | 0.0025 (3) | 0.0006 (3) |
Br1 | 0.0425 (7) | 0.0331 (7) | 0.0184 (5) | −0.0053 (5) | −0.0030 (5) | 0.0000 (5) |
N1 | 0.032 (5) | 0.025 (4) | 0.016 (4) | −0.001 (4) | −0.001 (4) | −0.004 (4) |
N2 | 0.026 (5) | 0.027 (5) | 0.013 (4) | 0.006 (4) | 0.000 (4) | 0.001 (4) |
C1 | 0.034 (6) | 0.039 (6) | 0.039 (7) | 0.008 (5) | 0.009 (5) | 0.008 (5) |
C2 | 0.034 (6) | 0.038 (6) | 0.041 (7) | −0.001 (5) | 0.012 (5) | 0.006 (5) |
C3 | 0.040 (6) | 0.036 (6) | 0.023 (6) | −0.019 (5) | 0.014 (5) | −0.002 (5) |
C4 | 0.055 (7) | 0.035 (6) | 0.019 (6) | 0.001 (5) | 0.007 (5) | 0.002 (5) |
C5 | 0.040 (6) | 0.030 (5) | 0.013 (5) | −0.003 (5) | −0.006 (4) | 0.001 (4) |
C8 | 0.027 (6) | 0.036 (7) | 0.032 (6) | 0.007 (5) | 0.000 (5) | −0.002 (5) |
C9 | 0.036 (6) | 0.039 (7) | 0.019 (5) | 0.005 (5) | −0.003 (5) | 0.000 (5) |
C10 | 0.043 (7) | 0.037 (7) | 0.021 (6) | 0.000 (5) | 0.006 (5) | −0.006 (5) |
C11 | 0.048 (8) | 0.042 (7) | 0.010 (5) | 0.012 (6) | −0.001 (5) | −0.008 (5) |
C12 | 0.050 (8) | 0.039 (7) | 0.024 (6) | 0.017 (6) | −0.002 (6) | −0.008 (5) |
C13 | 0.032 (7) | 0.057 (8) | 0.028 (7) | 0.008 (6) | −0.002 (5) | 0.007 (6) |
Pd1—C9 | 1.987 (10) | C7—H7 | 0.9800 |
Pd1—N2 | 2.039 (7) | C14—H14A | 0.9801 |
Pd1—N1 | 2.062 (8) | C14—H14B | 0.9801 |
Pd1—Br1 | 2.5435 (13) | C14—H14C | 0.9801 |
N1—C5 | 1.314 (12) | C7A—C8 | 1.49 (2) |
N1—C1 | 1.362 (13) | C7A—C14A | 1.52 (2) |
N2—C7A | 1.52 (2) | C7A—H7A | 0.9800 |
N2—C7 | 1.533 (13) | C14A—H14D | 0.9801 |
N2—H2A | 0.9200 | C14A—H14E | 0.9801 |
N2—H2B | 0.9200 | C14A—H14F | 0.9801 |
C1—C2 | 1.366 (14) | C8—C13 | 1.398 (14) |
C1—H1 | 0.9800 | C8—C9 | 1.440 (14) |
C2—C3 | 1.353 (15) | C9—C10 | 1.389 (14) |
C2—H2 | 0.9800 | C10—C11 | 1.386 (15) |
C3—C4 | 1.350 (14) | C10—H10 | 0.9800 |
C3—H3 | 0.9800 | C11—C12 | 1.347 (15) |
C4—C5 | 1.392 (14) | C11—H11 | 0.9800 |
C4—H4 | 0.9800 | C12—C13 | 1.398 (14) |
C5—H5 | 0.9800 | C12—H12 | 0.9800 |
C7—C8 | 1.465 (15) | C13—H13 | 0.9800 |
C7—C14 | 1.522 (16) | ||
C9—Pd1—N2 | 81.4 (4) | C8—C7—H7 | 109.8 |
C9—Pd1—N1 | 95.6 (4) | C14—C7—H7 | 109.8 |
N2—Pd1—N1 | 176.7 (3) | N2—C7—H7 | 109.8 |
C9—Pd1—Br1 | 174.5 (3) | C8—C7A—C14A | 109 (2) |
N2—Pd1—Br1 | 94.0 (2) | C8—C7A—N2 | 105.5 (14) |
N1—Pd1—Br1 | 89.1 (2) | C14A—C7A—N2 | 104 (2) |
C5—N1—C1 | 119.1 (9) | C8—C7A—H7A | 112.5 |
C5—N1—Pd1 | 122.8 (7) | C14A—C7A—H7A | 112.5 |
C1—N1—Pd1 | 117.9 (7) | N2—C7A—H7A | 112.5 |
C7A—N2—C7 | 17.1 (16) | C7A—C14A—H14D | 109.5 |
C7A—N2—Pd1 | 104.3 (12) | C7A—C14A—H14E | 109.5 |
C7—N2—Pd1 | 114.3 (6) | H14D—C14A—H14E | 109.5 |
C7A—N2—H2A | 100.8 | C7A—C14A—H14F | 109.5 |
C7—N2—H2A | 108.7 | H14D—C14A—H14F | 109.5 |
Pd1—N2—H2A | 108.7 | H14E—C14A—H14F | 109.5 |
C7A—N2—H2B | 125.7 | C13—C8—C9 | 117.9 (10) |
C7—N2—H2B | 108.7 | C13—C8—C7 | 122.4 (10) |
Pd1—N2—H2B | 108.7 | C9—C8—C7 | 119.7 (10) |
H2A—N2—H2B | 107.6 | C13—C8—C7A | 129.3 (12) |
N1—C1—C2 | 119.6 (10) | C9—C8—C7A | 110.7 (13) |
N1—C1—H1 | 120.2 | C7—C8—C7A | 17.7 (16) |
C2—C1—H1 | 120.2 | C10—C9—C8 | 119.2 (10) |
C3—C2—C1 | 122.2 (11) | C10—C9—Pd1 | 126.7 (8) |
C3—C2—H2 | 118.9 | C8—C9—Pd1 | 113.7 (7) |
C1—C2—H2 | 118.9 | C11—C10—C9 | 120.5 (10) |
C4—C3—C2 | 117.4 (10) | C11—C10—H10 | 119.7 |
C4—C3—H3 | 121.3 | C9—C10—H10 | 119.7 |
C2—C3—H3 | 121.3 | C12—C11—C10 | 120.7 (10) |
C3—C4—C5 | 120.3 (10) | C12—C11—H11 | 119.6 |
C3—C4—H4 | 119.9 | C10—C11—H11 | 119.6 |
C5—C4—H4 | 119.9 | C11—C12—C13 | 121.0 (11) |
N1—C5—C4 | 121.5 (10) | C11—C12—H12 | 119.5 |
N1—C5—H5 | 119.3 | C13—C12—H12 | 119.5 |
C4—C5—H5 | 119.3 | C12—C13—C8 | 120.4 (11) |
C8—C7—C14 | 111.8 (10) | C12—C13—H13 | 119.8 |
C8—C7—N2 | 105.8 (9) | C8—C13—H13 | 119.8 |
C14—C7—N2 | 109.7 (10) | ||
C9—Pd1—N1—C5 | −79.2 (8) | C14—C7—C8—C9 | −105.5 (12) |
N2—Pd1—N1—C5 | −55 (6) | N2—C7—C8—C9 | 14.0 (15) |
Br1—Pd1—N1—C5 | 103.8 (7) | C14—C7—C8—C7A | −42 (3) |
C9—Pd1—N1—C1 | 106.9 (8) | N2—C7—C8—C7A | 77 (3) |
N2—Pd1—N1—C1 | 131 (5) | C14A—C7A—C8—C13 | −41 (3) |
Br1—Pd1—N1—C1 | −70.1 (7) | N2—C7A—C8—C13 | −152.7 (14) |
C9—Pd1—N2—C7A | 35.3 (13) | C14A—C7A—C8—C9 | 155.7 (19) |
N1—Pd1—N2—C7A | 11 (6) | N2—C7A—C8—C9 | 44 (2) |
Br1—Pd1—N2—C7A | −147.8 (12) | C14A—C7A—C8—C7 | 32 (3) |
C9—Pd1—N2—C7 | 20.6 (7) | N2—C7A—C8—C7 | −80 (3) |
N1—Pd1—N2—C7 | −3 (6) | C13—C8—C9—C10 | 6.0 (16) |
Br1—Pd1—N2—C7 | −162.5 (7) | C7—C8—C9—C10 | −172.0 (11) |
C5—N1—C1—C2 | −0.2 (15) | C7A—C8—C9—C10 | 171.2 (16) |
Pd1—N1—C1—C2 | 173.9 (8) | C13—C8—C9—Pd1 | 179.7 (8) |
N1—C1—C2—C3 | −0.7 (18) | C7—C8—C9—Pd1 | 1.8 (13) |
C1—C2—C3—C4 | 0.9 (17) | C7A—C8—C9—Pd1 | −15.0 (17) |
C2—C3—C4—C5 | −0.2 (16) | N2—Pd1—C9—C10 | 160.9 (10) |
C1—N1—C5—C4 | 0.9 (14) | N1—Pd1—C9—C10 | −20.4 (10) |
Pd1—N1—C5—C4 | −172.9 (7) | Br1—Pd1—C9—C10 | 127 (3) |
C3—C4—C5—N1 | −0.7 (16) | N2—Pd1—C9—C8 | −12.3 (8) |
C7A—N2—C7—C8 | −80 (3) | N1—Pd1—C9—C8 | 166.3 (8) |
Pd1—N2—C7—C8 | −23.5 (11) | Br1—Pd1—C9—C8 | −46 (4) |
C7A—N2—C7—C14 | 40 (3) | C8—C9—C10—C11 | −5.4 (16) |
Pd1—N2—C7—C14 | 97.3 (9) | Pd1—C9—C10—C11 | −178.2 (8) |
C7—N2—C7A—C8 | 76 (3) | C9—C10—C11—C12 | 2.5 (17) |
Pd1—N2—C7A—C8 | −52 (2) | C10—C11—C12—C13 | −0.3 (17) |
C7—N2—C7A—C14A | −38 (3) | C11—C12—C13—C8 | 1.0 (17) |
Pd1—N2—C7A—C14A | −166.5 (18) | C9—C8—C13—C12 | −3.8 (16) |
C14—C7—C8—C13 | 76.7 (15) | C7—C8—C13—C12 | 174.0 (11) |
N2—C7—C8—C13 | −163.9 (10) | C7A—C8—C13—C12 | −166 (2) |
[PdBr(C8H9BrN)(C6H7N)] | Dx = 2.048 Mg m−3 |
Mr = 478.51 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/a | Cell parameters from 1895 reflections |
Hall symbol: -I 4ad | θ = 2.7–23.2° |
a = 18.5329 (13) Å | µ = 6.33 mm−1 |
c = 18.071 (3) Å | T = 100 K |
V = 6206.8 (12) Å3 | Block, colorless |
Z = 16 | 0.31 × 0.23 × 0.13 mm |
F(000) = 3680 |
Bruker SMART APEX CCD diffractometer | 3374 independent reflections |
Radiation source: fine-focus sealed tube | 1916 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.067 |
ω scans | θmax = 27.1°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −22→23 |
Tmin = 0.244, Tmax = 0.493 | k = −22→22 |
13256 measured reflections | l = −23→6 |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.075 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.020P)2] where P = (Fo2 + 2Fc2)/3 |
3374 reflections | (Δ/σ)max = 0.005 |
172 parameters | Δρmax = 0.69 e Å−3 |
3 restraints | Δρmin = −0.59 e Å−3 |
[PdBr(C8H9BrN)(C6H7N)] | Z = 16 |
Mr = 478.51 | Mo Kα radiation |
Tetragonal, I41/a | µ = 6.33 mm−1 |
a = 18.5329 (13) Å | T = 100 K |
c = 18.071 (3) Å | 0.31 × 0.23 × 0.13 mm |
V = 6206.8 (12) Å3 |
Bruker SMART APEX CCD diffractometer | 3374 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 1916 reflections with I > 2σ(I) |
Tmin = 0.244, Tmax = 0.493 | Rint = 0.067 |
13256 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 3 restraints |
wR(F2) = 0.075 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.69 e Å−3 |
3374 reflections | Δρmin = −0.59 e Å−3 |
172 parameters |
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 of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. Minor disorder for C14/C14A and C7/C7A, see manuscript. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Pd1 | 0.00428 (2) | 0.14605 (2) | 0.30708 (2) | 0.04295 (15) | |
Br1 | −0.09198 (3) | 0.13378 (3) | 0.20809 (3) | 0.05454 (19) | |
Br2 | 0.13075 (4) | 0.19745 (4) | 0.59829 (4) | 0.0838 (3) | |
N1 | −0.0643 (2) | 0.1079 (2) | 0.3863 (2) | 0.0417 (11) | |
N2 | 0.0816 (2) | 0.1808 (2) | 0.2347 (2) | 0.0500 (13) | |
H2A | 0.0775 | 0.1546 | 0.1917 | 0.060* | |
H2B | 0.0725 | 0.2284 | 0.2233 | 0.060* | |
C1 | −0.1233 (3) | 0.1435 (3) | 0.4062 (3) | 0.0568 (17) | |
H1 | −0.1336 | 0.1899 | 0.3825 | 0.074* | |
C2 | −0.1710 (3) | 0.1175 (4) | 0.4594 (3) | 0.0640 (18) | |
H2 | −0.2137 | 0.1460 | 0.4724 | 0.083* | |
C3 | −0.1591 (4) | 0.0531 (3) | 0.4935 (3) | 0.0525 (16) | |
C4 | −0.1013 (3) | 0.0172 (3) | 0.4704 (3) | 0.0567 (17) | |
H4 | −0.0917 | −0.0308 | 0.4908 | 0.074* | |
C5 | −0.0544 (3) | 0.0451 (3) | 0.4185 (3) | 0.0542 (17) | |
H5 | −0.0117 | 0.0168 | 0.4051 | 0.070* | |
C6 | −0.2067 (4) | 0.0258 (3) | 0.5536 (3) | 0.091 (2) | |
H6A | −0.2028 | −0.0268 | 0.5565 | 0.136* | |
H6B | −0.2568 | 0.0392 | 0.5429 | 0.136* | |
H6C | −0.1920 | 0.0471 | 0.6008 | 0.136* | |
C7 | 0.1586 (4) | 0.1748 (5) | 0.2625 (4) | 0.046 (2)* | 0.650 (6) |
H7 | 0.1896 | 0.2159 | 0.2459 | 0.055* | 0.650 (6) |
C14 | 0.1877 (5) | 0.1034 (4) | 0.2395 (5) | 0.054 (2)* | 0.650 (6) |
H14A | 0.1553 | 0.0651 | 0.2566 | 0.081* | 0.650 (6) |
H14B | 0.2356 | 0.0965 | 0.2612 | 0.081* | 0.650 (6) |
H14C | 0.1913 | 0.1017 | 0.1854 | 0.081* | 0.650 (6) |
C7A | 0.1486 (7) | 0.1422 (9) | 0.2624 (7) | 0.046 (2)* | 0.350 (6) |
H7A | 0.1434 | 0.0886 | 0.2599 | 0.055* | 0.350 (6) |
C14A | 0.2097 (8) | 0.1680 (9) | 0.2175 (8) | 0.054 (2)* | 0.350 (6) |
H14D | 0.2024 | 0.1541 | 0.1657 | 0.081* | 0.350 (6) |
H14E | 0.2546 | 0.1465 | 0.2359 | 0.081* | 0.350 (6) |
H14F | 0.2128 | 0.2207 | 0.2210 | 0.081* | 0.350 (6) |
C8 | 0.1521 (3) | 0.1703 (3) | 0.3451 (3) | 0.0584 (18) | |
C9 | 0.0844 (3) | 0.1623 (3) | 0.3779 (3) | 0.0439 (14) | |
C10 | 0.0775 (3) | 0.1706 (3) | 0.4535 (3) | 0.0447 (14) | |
H10 | 0.0305 | 0.1657 | 0.4779 | 0.058* | |
C11 | 0.1403 (3) | 0.1863 (3) | 0.4945 (3) | 0.0486 (15) | |
C12 | 0.2071 (3) | 0.1944 (3) | 0.4636 (3) | 0.0556 (17) | |
H12 | 0.2495 | 0.2056 | 0.4939 | 0.072* | |
C13 | 0.2120 (3) | 0.1862 (3) | 0.3885 (4) | 0.0631 (18) | |
H13 | 0.2591 | 0.1917 | 0.3646 | 0.082* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.0381 (3) | 0.0485 (3) | 0.0422 (2) | 0.0083 (2) | −0.0001 (2) | −0.0008 (2) |
Br1 | 0.0499 (4) | 0.0663 (5) | 0.0475 (4) | −0.0003 (3) | −0.0063 (3) | 0.0004 (3) |
Br2 | 0.0723 (5) | 0.1181 (7) | 0.0608 (5) | −0.0186 (5) | −0.0091 (4) | −0.0258 (4) |
N1 | 0.036 (3) | 0.045 (3) | 0.044 (3) | 0.002 (2) | 0.000 (2) | −0.008 (2) |
N2 | 0.029 (3) | 0.075 (3) | 0.046 (3) | 0.016 (2) | −0.006 (2) | 0.005 (2) |
C1 | 0.060 (4) | 0.044 (4) | 0.066 (4) | 0.012 (4) | 0.008 (4) | 0.003 (3) |
C2 | 0.053 (4) | 0.065 (5) | 0.073 (5) | −0.003 (4) | 0.021 (4) | −0.014 (4) |
C3 | 0.060 (5) | 0.047 (4) | 0.050 (4) | −0.015 (4) | 0.009 (3) | −0.004 (3) |
C4 | 0.078 (5) | 0.039 (4) | 0.053 (4) | −0.007 (4) | 0.005 (3) | 0.008 (3) |
C5 | 0.070 (5) | 0.034 (4) | 0.059 (4) | 0.019 (3) | −0.006 (3) | 0.002 (3) |
C6 | 0.106 (6) | 0.074 (5) | 0.092 (6) | −0.023 (5) | 0.029 (5) | 0.009 (4) |
C8 | 0.039 (4) | 0.083 (5) | 0.053 (4) | 0.025 (3) | −0.004 (3) | 0.010 (3) |
C9 | 0.031 (3) | 0.048 (4) | 0.052 (4) | 0.008 (3) | −0.002 (3) | 0.007 (3) |
C10 | 0.042 (4) | 0.041 (4) | 0.051 (4) | −0.002 (3) | −0.005 (3) | 0.002 (3) |
C11 | 0.059 (4) | 0.039 (4) | 0.048 (3) | −0.001 (3) | −0.008 (3) | 0.004 (3) |
C12 | 0.028 (4) | 0.063 (4) | 0.075 (5) | 0.002 (3) | −0.008 (3) | 0.016 (4) |
C13 | 0.032 (4) | 0.093 (5) | 0.064 (4) | 0.015 (4) | −0.001 (3) | 0.021 (4) |
Pd1—C9 | 1.983 (5) | C6—H6C | 0.9800 |
Pd1—N1 | 2.042 (4) | C7—C14 | 1.488 (10) |
Pd1—N2 | 2.044 (4) | C7—C8 | 1.499 (9) |
Pd1—Br1 | 2.5365 (7) | C7—H7 | 1.0000 |
Br2—C11 | 1.895 (5) | C14—H14A | 0.9800 |
N1—C5 | 1.314 (6) | C14—H14B | 0.9800 |
N1—C1 | 1.326 (6) | C14—H14C | 0.9800 |
N2—C7 | 1.517 (8) | C7A—C14A | 1.472 (14) |
N2—C7A | 1.519 (12) | C7A—C8 | 1.584 (13) |
N2—H2A | 0.9200 | C7A—H7A | 1.0000 |
N2—H2B | 0.9200 | C14A—H14D | 0.9800 |
C1—C2 | 1.392 (7) | C14A—H14E | 0.9800 |
C1—H1 | 0.9800 | C14A—H14F | 0.9800 |
C2—C3 | 1.363 (8) | C8—C13 | 1.391 (7) |
C2—H2 | 0.9800 | C8—C9 | 1.397 (7) |
C3—C4 | 1.327 (7) | C9—C10 | 1.381 (7) |
C3—C6 | 1.487 (7) | C10—C11 | 1.410 (7) |
C4—C5 | 1.380 (7) | C10—H10 | 0.9800 |
C4—H4 | 0.9800 | C11—C12 | 1.366 (7) |
C5—H5 | 0.9800 | C12—C13 | 1.369 (8) |
C6—H6A | 0.9800 | C12—H12 | 0.9800 |
C6—H6B | 0.9800 | C13—H13 | 0.9800 |
C9—Pd1—N1 | 93.80 (19) | C14—C7—C8 | 105.0 (6) |
C9—Pd1—N2 | 80.83 (19) | C14—C7—N2 | 108.3 (6) |
N1—Pd1—N2 | 174.04 (16) | C8—C7—N2 | 105.0 (6) |
C9—Pd1—Br1 | 174.41 (16) | C14—C7—H7 | 112.7 |
N1—Pd1—Br1 | 91.46 (12) | C8—C7—H7 | 112.7 |
N2—Pd1—Br1 | 94.01 (11) | N2—C7—H7 | 112.7 |
C5—N1—C1 | 115.9 (5) | C14A—C7A—N2 | 107.2 (11) |
C5—N1—Pd1 | 122.0 (4) | C14A—C7A—C8 | 112.4 (11) |
C1—N1—Pd1 | 122.0 (4) | N2—C7A—C8 | 100.9 (8) |
C7—N2—C7A | 24.0 (7) | C14A—C7A—H7A | 111.9 |
C7—N2—Pd1 | 115.1 (4) | N2—C7A—H7A | 111.9 |
C7A—N2—Pd1 | 102.4 (6) | C8—C7A—H7A | 111.9 |
C7—N2—H2A | 108.5 | C7A—C14A—H14D | 109.5 |
C7A—N2—H2A | 95.5 | C7A—C14A—H14E | 109.5 |
Pd1—N2—H2A | 108.5 | H14D—C14A—H14E | 109.5 |
C7—N2—H2B | 108.5 | C7A—C14A—H14F | 109.5 |
C7A—N2—H2B | 132.4 | H14D—C14A—H14F | 109.5 |
Pd1—N2—H2B | 108.5 | H14E—C14A—H14F | 109.5 |
H2A—N2—H2B | 107.5 | C13—C8—C9 | 120.0 (5) |
N1—C1—C2 | 122.6 (6) | C13—C8—C7 | 119.1 (6) |
N1—C1—H1 | 118.7 | C9—C8—C7 | 120.0 (6) |
C2—C1—H1 | 118.7 | C13—C8—C7A | 129.4 (7) |
C3—C2—C1 | 120.8 (6) | C9—C8—C7A | 109.2 (7) |
C3—C2—H2 | 119.6 | C7—C8—C7A | 23.4 (7) |
C1—C2—H2 | 119.6 | C10—C9—C8 | 119.4 (5) |
C4—C3—C2 | 115.3 (6) | C10—C9—Pd1 | 125.9 (4) |
C4—C3—C6 | 122.6 (6) | C8—C9—Pd1 | 114.5 (4) |
C2—C3—C6 | 122.1 (6) | C9—C10—C11 | 117.8 (5) |
C3—C4—C5 | 122.3 (6) | C9—C10—H10 | 121.1 |
C3—C4—H4 | 118.8 | C11—C10—H10 | 121.1 |
C5—C4—H4 | 118.8 | C12—C11—C10 | 123.8 (5) |
N1—C5—C4 | 123.0 (6) | C12—C11—Br2 | 118.5 (4) |
N1—C5—H5 | 118.5 | C10—C11—Br2 | 117.7 (4) |
C4—C5—H5 | 118.5 | C11—C12—C13 | 117.0 (5) |
C3—C6—H6A | 109.5 | C11—C12—H12 | 121.5 |
C3—C6—H6B | 109.5 | C13—C12—H12 | 121.5 |
H6A—C6—H6B | 109.5 | C12—C13—C8 | 122.0 (6) |
C3—C6—H6C | 109.5 | C12—C13—H13 | 119.0 |
H6A—C6—H6C | 109.5 | C8—C13—H13 | 119.0 |
H6B—C6—H6C | 109.5 | ||
C9—Pd1—N1—C5 | −69.9 (4) | C14—C7—C8—C9 | −105.3 (7) |
N2—Pd1—N1—C5 | −44.4 (18) | N2—C7—C8—C9 | 8.8 (8) |
Br1—Pd1—N1—C5 | 112.1 (4) | C14—C7—C8—C7A | −37.5 (13) |
C9—Pd1—N1—C1 | 113.0 (4) | N2—C7—C8—C7A | 76.6 (14) |
N2—Pd1—N1—C1 | 138.4 (16) | C14A—C7A—C8—C13 | −30.8 (16) |
Br1—Pd1—N1—C1 | −65.1 (4) | N2—C7A—C8—C13 | −144.7 (7) |
C9—Pd1—N2—C7 | 20.2 (4) | C14A—C7A—C8—C9 | 162.9 (10) |
N1—Pd1—N2—C7 | −5.5 (19) | N2—C7A—C8—C9 | 49.0 (10) |
Br1—Pd1—N2—C7 | −161.9 (4) | C14A—C7A—C8—C7 | 41.0 (13) |
C9—Pd1—N2—C7A | 41.8 (6) | N2—C7A—C8—C7 | −72.9 (14) |
N1—Pd1—N2—C7A | 16.1 (19) | C13—C8—C9—C10 | 0.2 (9) |
Br1—Pd1—N2—C7A | −140.4 (6) | C7—C8—C9—C10 | −169.0 (6) |
C5—N1—C1—C2 | 1.8 (8) | C7A—C8—C9—C10 | 168.0 (7) |
Pd1—N1—C1—C2 | 179.1 (4) | C13—C8—C9—Pd1 | 176.2 (5) |
N1—C1—C2—C3 | −0.3 (10) | C7—C8—C9—Pd1 | 7.0 (8) |
C1—C2—C3—C4 | −2.4 (9) | C7A—C8—C9—Pd1 | −15.9 (8) |
C1—C2—C3—C6 | 176.5 (6) | N1—Pd1—C9—C10 | −21.5 (5) |
C2—C3—C4—C5 | 3.7 (9) | N2—Pd1—C9—C10 | 161.1 (5) |
C6—C3—C4—C5 | −175.2 (6) | Br1—Pd1—C9—C10 | 138.4 (14) |
C1—N1—C5—C4 | −0.5 (8) | N1—Pd1—C9—C8 | 162.8 (4) |
Pd1—N1—C5—C4 | −177.8 (4) | N2—Pd1—C9—C8 | −14.6 (4) |
C3—C4—C5—N1 | −2.4 (10) | Br1—Pd1—C9—C8 | −37.3 (19) |
C7A—N2—C7—C14 | 29.3 (12) | C8—C9—C10—C11 | −0.6 (8) |
Pd1—N2—C7—C14 | 91.3 (6) | Pd1—C9—C10—C11 | −176.1 (4) |
C7A—N2—C7—C8 | −82.4 (14) | C9—C10—C11—C12 | 0.6 (8) |
Pd1—N2—C7—C8 | −20.4 (7) | C9—C10—C11—Br2 | −179.9 (4) |
C7—N2—C7A—C14A | −50.4 (13) | C10—C11—C12—C13 | −0.3 (9) |
Pd1—N2—C7A—C14A | −175.5 (10) | Br2—C11—C12—C13 | −179.8 (4) |
C7—N2—C7A—C8 | 67.4 (13) | C11—C12—C13—C8 | 0.0 (9) |
Pd1—N2—C7A—C8 | −57.8 (9) | C9—C8—C13—C12 | 0.1 (9) |
C14—C7—C8—C13 | 85.3 (8) | C7—C8—C13—C12 | 169.4 (6) |
N2—C7—C8—C13 | −160.6 (6) | C7A—C8—C13—C12 | −165.0 (9) |
[Pd(C8H9BrN)I(C6H7N)] | Dx = 2.151 Mg m−3 |
Mr = 525.50 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/a | Cell parameters from 4379 reflections |
Hall symbol: -I 4ad | θ = 2.2–21.7° |
a = 18.8243 (9) Å | µ = 5.50 mm−1 |
c = 18.3193 (17) Å | T = 110 K |
V = 6491.5 (7) Å3 | Rod, colorless |
Z = 16 | 0.13 × 0.09 × 0.08 mm |
F(000) = 3968 |
Bruker SMART APEX CCD diffractometer | 3338 independent reflections |
Radiation source: fine-focus sealed tube | 2302 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.088 |
ω scans | θmax = 26.4°, θmin = 2.2° |
Absorption correction: multi-scan MULABS as implemented in PLATON (Spek, 2003) | h = −23→23 |
Tmin = 0.535, Tmax = 0.668 | k = −23→23 |
38236 measured reflections | l = −22→22 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.059 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.020P)2] where P = (Fo2 + 2Fc2)/3 |
3338 reflections | (Δ/σ)max = 0.001 |
172 parameters | Δρmax = 0.69 e Å−3 |
3 restraints | Δρmin = −0.52 e Å−3 |
[Pd(C8H9BrN)I(C6H7N)] | Z = 16 |
Mr = 525.50 | Mo Kα radiation |
Tetragonal, I41/a | µ = 5.50 mm−1 |
a = 18.8243 (9) Å | T = 110 K |
c = 18.3193 (17) Å | 0.13 × 0.09 × 0.08 mm |
V = 6491.5 (7) Å3 |
Bruker SMART APEX CCD diffractometer | 3338 independent reflections |
Absorption correction: multi-scan MULABS as implemented in PLATON (Spek, 2003) | 2302 reflections with I > 2σ(I) |
Tmin = 0.535, Tmax = 0.668 | Rint = 0.088 |
38236 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 3 restraints |
wR(F2) = 0.059 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.69 e Å−3 |
3338 reflections | Δρmin = −0.52 e Å−3 |
172 parameters |
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 of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. Minor disorder for C14/C14A and C7/C7A, see manuscript. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Pd1 | 0.006586 (19) | 0.14501 (2) | 0.31335 (2) | 0.03317 (11) | |
I1 | −0.092583 (18) | 0.125984 (18) | 0.208469 (19) | 0.04190 (11) | |
Br1 | 0.13019 (3) | 0.19494 (3) | 0.60213 (3) | 0.05639 (18) | |
N1 | −0.0601 (2) | 0.1064 (2) | 0.3910 (2) | 0.0320 (10) | |
N2 | 0.08125 (18) | 0.1808 (2) | 0.2424 (2) | 0.0378 (11) | |
H2A | 0.0768 | 0.1564 | 0.1991 | 0.045* | |
H2B | 0.0729 | 0.2280 | 0.2329 | 0.045* | |
C1 | −0.1153 (3) | 0.1435 (3) | 0.4177 (3) | 0.0478 (15) | |
H1 | −0.1226 | 0.1922 | 0.4006 | 0.062* | |
C2 | −0.1618 (3) | 0.1161 (3) | 0.4681 (3) | 0.0489 (15) | |
H2 | −0.2020 | 0.1451 | 0.4847 | 0.064* | |
C3 | −0.1530 (3) | 0.0491 (3) | 0.4954 (3) | 0.0409 (13) | |
C4 | −0.0974 (3) | 0.0121 (3) | 0.4677 (3) | 0.0552 (16) | |
H4 | −0.0893 | −0.0368 | 0.4841 | 0.072* | |
C5 | −0.0518 (3) | 0.0418 (3) | 0.4169 (3) | 0.0466 (15) | |
H5 | −0.0115 | 0.0134 | 0.3995 | 0.061* | |
C6 | −0.2007 (3) | 0.0198 (3) | 0.5537 (3) | 0.0645 (18) | |
H6A | −0.1974 | −0.0321 | 0.5541 | 0.097* | |
H6B | −0.2499 | 0.0340 | 0.5437 | 0.097* | |
H6C | −0.1861 | 0.0386 | 0.6013 | 0.097* | |
C7 | 0.1562 (3) | 0.1725 (3) | 0.2702 (3) | 0.0376 (18)* | 0.792 (6) |
H7 | 0.1873 | 0.2113 | 0.2511 | 0.045* | 0.792 (6) |
C14 | 0.1843 (3) | 0.1005 (3) | 0.2480 (4) | 0.0426 (17)* | 0.792 (6) |
H14A | 0.1538 | 0.0632 | 0.2683 | 0.064* | 0.792 (6) |
H14B | 0.2328 | 0.0946 | 0.2665 | 0.064* | 0.792 (6) |
H14C | 0.1846 | 0.0968 | 0.1946 | 0.064* | 0.792 (6) |
C7A | 0.1489 (9) | 0.1465 (13) | 0.2726 (8) | 0.0376 (18)* | 0.208 (6) |
H7A | 0.1469 | 0.0934 | 0.2714 | 0.045* | 0.208 (6) |
C14A | 0.2079 (12) | 0.1763 (12) | 0.2248 (12) | 0.0426 (17)* | 0.208 (6) |
H14D | 0.2493 | 0.1876 | 0.2551 | 0.064* | 0.208 (6) |
H14E | 0.1911 | 0.2196 | 0.2005 | 0.064* | 0.208 (6) |
H14F | 0.2212 | 0.1410 | 0.1880 | 0.064* | 0.208 (6) |
C8 | 0.1510 (3) | 0.1761 (3) | 0.3512 (3) | 0.0410 (13) | |
C9 | 0.0842 (2) | 0.1640 (2) | 0.3835 (3) | 0.0349 (12) | |
C10 | 0.0786 (3) | 0.1708 (2) | 0.4588 (3) | 0.0353 (12) | |
H10 | 0.0326 | 0.1645 | 0.4830 | 0.046* | |
C11 | 0.1391 (3) | 0.1867 (3) | 0.4996 (3) | 0.0410 (13) | |
C12 | 0.2043 (3) | 0.1976 (3) | 0.4683 (3) | 0.0397 (13) | |
H12 | 0.2459 | 0.2090 | 0.4983 | 0.052* | |
C13 | 0.2102 (3) | 0.1920 (3) | 0.3931 (3) | 0.0459 (14) | |
H13 | 0.2563 | 0.1993 | 0.3695 | 0.060* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.0279 (2) | 0.0326 (2) | 0.0390 (2) | 0.00570 (18) | −0.00202 (18) | −0.00062 (18) |
I1 | 0.0374 (2) | 0.0434 (2) | 0.0449 (2) | 0.00203 (16) | −0.00832 (17) | −0.00009 (17) |
Br1 | 0.0491 (4) | 0.0698 (4) | 0.0502 (4) | −0.0099 (3) | −0.0076 (3) | −0.0140 (3) |
N1 | 0.029 (2) | 0.028 (2) | 0.040 (3) | 0.0043 (19) | −0.003 (2) | −0.005 (2) |
N2 | 0.028 (2) | 0.044 (3) | 0.041 (3) | 0.012 (2) | −0.002 (2) | 0.002 (2) |
C1 | 0.040 (3) | 0.032 (3) | 0.071 (4) | 0.000 (3) | 0.008 (3) | 0.002 (3) |
C2 | 0.033 (3) | 0.042 (3) | 0.071 (4) | −0.005 (3) | 0.020 (3) | 0.000 (3) |
C3 | 0.044 (3) | 0.034 (3) | 0.044 (3) | −0.013 (3) | 0.000 (3) | −0.007 (3) |
C4 | 0.069 (4) | 0.037 (3) | 0.060 (4) | 0.005 (3) | 0.004 (3) | 0.008 (3) |
C5 | 0.059 (4) | 0.028 (3) | 0.053 (4) | 0.012 (3) | 0.012 (3) | −0.001 (3) |
C6 | 0.067 (4) | 0.058 (4) | 0.068 (5) | −0.015 (3) | 0.010 (4) | 0.010 (3) |
C8 | 0.031 (3) | 0.049 (3) | 0.042 (3) | 0.006 (2) | −0.006 (3) | 0.001 (3) |
C9 | 0.029 (3) | 0.028 (3) | 0.048 (3) | 0.004 (2) | −0.004 (2) | 0.001 (2) |
C10 | 0.034 (3) | 0.029 (3) | 0.043 (3) | 0.003 (2) | 0.000 (3) | −0.005 (2) |
C11 | 0.047 (4) | 0.030 (3) | 0.046 (3) | 0.006 (2) | −0.006 (3) | −0.001 (3) |
C12 | 0.030 (3) | 0.038 (3) | 0.052 (4) | 0.004 (2) | −0.010 (3) | 0.002 (3) |
C13 | 0.025 (3) | 0.056 (4) | 0.057 (4) | 0.009 (3) | −0.001 (3) | 0.004 (3) |
Pd1—C9 | 1.979 (5) | C6—H6C | 0.9800 |
Pd1—N2 | 2.029 (4) | C7—C8 | 1.488 (8) |
Pd1—N1 | 2.031 (4) | C7—C14 | 1.511 (8) |
Pd1—I1 | 2.7028 (5) | C7—H7 | 1.0000 |
Br1—C11 | 1.893 (5) | C14—H14A | 0.9800 |
N1—C5 | 1.315 (6) | C14—H14B | 0.9800 |
N1—C1 | 1.344 (6) | C14—H14C | 0.9800 |
N2—C7 | 1.508 (6) | C7A—C14A | 1.522 (18) |
N2—C7A | 1.531 (16) | C7A—C8 | 1.544 (16) |
N2—H2A | 0.9200 | C7A—H7A | 1.0000 |
N2—H2B | 0.9200 | C14A—H14D | 0.9800 |
C1—C2 | 1.373 (7) | C14A—H14E | 0.9800 |
C1—H1 | 0.9800 | C14A—H14F | 0.9800 |
C2—C3 | 1.368 (7) | C8—C13 | 1.385 (7) |
C2—H2 | 0.9800 | C8—C9 | 1.408 (7) |
C3—C4 | 1.356 (7) | C9—C10 | 1.389 (7) |
C3—C6 | 1.499 (7) | C10—C11 | 1.394 (6) |
C4—C5 | 1.385 (7) | C10—H10 | 0.9800 |
C4—H4 | 0.9800 | C11—C12 | 1.372 (7) |
C5—H5 | 0.9800 | C12—C13 | 1.385 (7) |
C6—H6A | 0.9800 | C12—H12 | 0.9800 |
C6—H6B | 0.9800 | C13—H13 | 0.9800 |
C9—Pd1—N2 | 81.04 (19) | C8—C7—N2 | 105.7 (4) |
C9—Pd1—N1 | 93.83 (18) | C8—C7—C14 | 109.4 (5) |
N2—Pd1—N1 | 174.34 (15) | N2—C7—C14 | 109.2 (5) |
C9—Pd1—I1 | 174.73 (15) | C8—C7—H7 | 110.8 |
N2—Pd1—I1 | 93.84 (11) | N2—C7—H7 | 110.8 |
N1—Pd1—I1 | 91.33 (11) | C14—C7—H7 | 110.8 |
C5—N1—C1 | 116.2 (5) | C14A—C7A—N2 | 104.1 (15) |
C5—N1—Pd1 | 120.7 (3) | C14A—C7A—C8 | 112.6 (16) |
C1—N1—Pd1 | 123.2 (3) | N2—C7A—C8 | 101.9 (10) |
C7—N2—C7A | 19.3 (10) | C14A—C7A—H7A | 112.5 |
C7—N2—Pd1 | 113.4 (3) | N2—C7A—H7A | 112.5 |
C7A—N2—Pd1 | 101.8 (8) | C8—C7A—H7A | 112.5 |
C7—N2—H2A | 108.9 | C7A—C14A—H14D | 109.5 |
C7A—N2—H2A | 100.1 | C7A—C14A—H14E | 109.5 |
Pd1—N2—H2A | 108.9 | H14D—C14A—H14E | 109.5 |
C7—N2—H2B | 108.9 | C7A—C14A—H14F | 109.5 |
C7A—N2—H2B | 128.2 | H14D—C14A—H14F | 109.5 |
Pd1—N2—H2B | 108.9 | H14E—C14A—H14F | 109.5 |
H2A—N2—H2B | 107.7 | C13—C8—C9 | 121.3 (5) |
N1—C1—C2 | 122.9 (5) | C13—C8—C7 | 120.7 (5) |
N1—C1—H1 | 118.5 | C9—C8—C7 | 118.0 (5) |
C2—C1—H1 | 118.5 | C13—C8—C7A | 128.0 (8) |
C3—C2—C1 | 121.0 (5) | C9—C8—C7A | 108.1 (8) |
C3—C2—H2 | 119.5 | C7—C8—C7A | 19.3 (10) |
C1—C2—H2 | 119.5 | C10—C9—C8 | 118.1 (5) |
C4—C3—C2 | 115.5 (5) | C10—C9—Pd1 | 127.2 (4) |
C4—C3—C6 | 122.7 (5) | C8—C9—Pd1 | 114.6 (4) |
C2—C3—C6 | 121.8 (5) | C9—C10—C11 | 119.3 (5) |
C3—C4—C5 | 121.6 (5) | C9—C10—H10 | 120.3 |
C3—C4—H4 | 119.2 | C11—C10—H10 | 120.3 |
C5—C4—H4 | 119.2 | C12—C11—C10 | 122.7 (5) |
N1—C5—C4 | 122.8 (5) | C12—C11—Br1 | 118.8 (4) |
N1—C5—H5 | 118.6 | C10—C11—Br1 | 118.5 (4) |
C4—C5—H5 | 118.6 | C11—C12—C13 | 118.4 (5) |
C3—C6—H6A | 109.5 | C11—C12—H12 | 120.8 |
C3—C6—H6B | 109.5 | C13—C12—H12 | 120.8 |
H6A—C6—H6B | 109.5 | C12—C13—C8 | 120.3 (5) |
C3—C6—H6C | 109.5 | C12—C13—H13 | 119.9 |
H6A—C6—H6C | 109.5 | C8—C13—H13 | 119.9 |
H6B—C6—H6C | 109.5 | ||
C9—Pd1—N1—C5 | −77.3 (4) | N2—C7—C8—C9 | 18.9 (7) |
N2—Pd1—N1—C5 | −52.3 (17) | C14—C7—C8—C9 | −98.6 (6) |
I1—Pd1—N1—C5 | 103.8 (4) | N2—C7—C8—C7A | 82 (2) |
C9—Pd1—N1—C1 | 104.1 (4) | C14—C7—C8—C7A | −35.9 (19) |
N2—Pd1—N1—C1 | 129.1 (15) | C14A—C7A—C8—C13 | −37 (2) |
I1—Pd1—N1—C1 | −74.9 (4) | N2—C7A—C8—C13 | −147.6 (7) |
C9—Pd1—N2—C7 | 23.7 (3) | C14A—C7A—C8—C9 | 161.8 (13) |
N1—Pd1—N2—C7 | −1.5 (17) | N2—C7A—C8—C9 | 50.9 (14) |
I1—Pd1—N2—C7 | −157.5 (3) | C14A—C7A—C8—C7 | 37.5 (18) |
C9—Pd1—N2—C7A | 40.0 (8) | N2—C7A—C8—C7 | −73.4 (19) |
N1—Pd1—N2—C7A | 14.7 (19) | C13—C8—C9—C10 | 2.1 (7) |
I1—Pd1—N2—C7A | −141.3 (8) | C7—C8—C9—C10 | −176.9 (5) |
C5—N1—C1—C2 | −1.3 (8) | C7A—C8—C9—C10 | 165.1 (9) |
Pd1—N1—C1—C2 | 177.4 (4) | C13—C8—C9—Pd1 | 178.3 (4) |
N1—C1—C2—C3 | 1.8 (9) | C7—C8—C9—Pd1 | −0.7 (6) |
C1—C2—C3—C4 | −2.0 (8) | C7A—C8—C9—Pd1 | −18.7 (10) |
C1—C2—C3—C6 | 176.3 (5) | N2—Pd1—C9—C10 | 163.1 (4) |
C2—C3—C4—C5 | 1.9 (8) | N1—Pd1—C9—C10 | −19.3 (4) |
C6—C3—C4—C5 | −176.3 (5) | I1—Pd1—C9—C10 | 149.5 (12) |
C1—N1—C5—C4 | 1.3 (8) | N2—Pd1—C9—C8 | −12.7 (3) |
Pd1—N1—C5—C4 | −177.5 (4) | N1—Pd1—C9—C8 | 164.9 (4) |
C3—C4—C5—N1 | −1.7 (9) | I1—Pd1—C9—C8 | −26.3 (17) |
C7A—N2—C7—C8 | −84 (2) | C8—C9—C10—C11 | −2.2 (7) |
Pd1—N2—C7—C8 | −28.5 (5) | Pd1—C9—C10—C11 | −177.9 (3) |
C7A—N2—C7—C14 | 33.3 (18) | C9—C10—C11—C12 | 1.5 (7) |
Pd1—N2—C7—C14 | 89.1 (5) | C9—C10—C11—Br1 | −179.5 (3) |
C7—N2—C7A—C14A | −46.6 (19) | C10—C11—C12—C13 | −0.5 (8) |
Pd1—N2—C7A—C14A | −175.7 (13) | Br1—C11—C12—C13 | −179.5 (4) |
C7—N2—C7A—C8 | 70.7 (19) | C11—C12—C13—C8 | 0.3 (8) |
Pd1—N2—C7A—C8 | −58.4 (13) | C9—C8—C13—C12 | −1.1 (8) |
N2—C7—C8—C13 | −160.1 (5) | C7—C8—C13—C12 | 177.8 (5) |
C14—C7—C8—C13 | 82.3 (7) | C7A—C8—C13—C12 | −160.5 (12) |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | [Pd(C8H10N)Cl(C5H5N)] | [PdBr(C8H10N)(C5H5N)] | [PdBr(C8H9BrN)(C6H7N)] | [Pd(C8H9BrN)I(C6H7N)] |
Mr | 341.12 | 385.58 | 478.51 | 525.50 |
Crystal system, space group | Tetragonal, I41/a | Tetragonal, I41/a | Tetragonal, I41/a | Tetragonal, I41/a |
Temperature (K) | 100 | 110 | 100 | 110 |
a, c (Å) | 18.3310 (8), 15.5123 (14) | 18.5197 (9), 15.7281 (16) | 18.5329 (13), 18.071 (3) | 18.8243 (9), 18.3193 (17) |
V (Å3) | 5212.5 (6) | 5394.4 (7) | 6206.8 (12) | 6491.5 (7) |
Z | 16 | 16 | 16 | 16 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 1.61 | 4.32 | 6.33 | 5.50 |
Crystal size (mm) | 0.23 × 0.08 × 0.04 | 0.17 × 0.05 × 0.03 | 0.31 × 0.23 × 0.13 | 0.13 × 0.09 × 0.08 |
Data collection | ||||
Diffractometer | Bruker SMART APEX CCD diffractometer | Bruker SMART APEX CCD diffractometer | Bruker SMART APEX CCD diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) | Multi-scan (SADABS; Bruker, 2004) | Multi-scan (SADABS; Bruker, 2004) | Multi-scan MULABS as implemented in PLATON (Spek, 2003) |
Tmin, Tmax | 0.709, 0.939 | 0.527, 0.881 | 0.244, 0.493 | 0.535, 0.668 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 33317, 2990, 2544 | 29977, 2519, 1839 | 13256, 3374, 1916 | 38236, 3338, 2302 |
Rint | 0.074 | 0.173 | 0.067 | 0.088 |
(sin θ/λ)max (Å−1) | 0.649 | 0.606 | 0.641 | 0.626 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.073, 1.11 | 0.070, 0.141, 1.11 | 0.042, 0.075, 1.00 | 0.032, 0.059, 1.01 |
No. of reflections | 2990 | 2519 | 3374 | 3338 |
No. of parameters | 153 | 153 | 172 | 172 |
No. of restraints | 3 | 15 | 3 | 3 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0252P)2] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0487P)2 + 37.3572P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.020P)2] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.020P)2] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.41, −0.50 | 0.73, −1.34 | 0.69, −0.59 | 0.69, −0.52 |
Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).
Complex | D-H–A | D-H | H–A | D–A | D-H–A |
(I) | N2-H2A-Cl1i | 0.92 | 2.54 | 3.318 (3) | 142 |
(I) | N2-H2B-Cl1ii | 0.92 | 2.47 | 3.357 (3) | 161 |
(II) | N2-H2A-Br1i | 0.92 | 2.68 | 3.471 (8) | 144 |
(II) | N2-H2B-Br1ii | 0.92 | 2.59 | 3.494 (8) | 166 |
(III) | N2-H2A-Br1i | 0.92 | 2.80 | 3.568 (4) | 142 |
(III) | N2-H2B-Br1ii | 0.92 | 2.60 | 3.475 (4) | 160 |
(IV) | N2-H2A-I1i | 0.92 | 3.02 | 3.793 (4) | 143 |
(IV) | N2-H2B-I1ii | 0.92 | 2.81 | 3.696 (4) | 162 |
Symmetry codes: (i) -y+1/4, x+1/4, -z+1/4; (ii) -x, -y+1/2,z. |
Ortho-palladation was first reported by Cope & Friedrich (1968) and was originally restricted to activated tertiary amines. Contributions by Dunina et al. (1999), Fuchita and co-workers (Fuchita & Tsuchiya, 1993; Fuchita et al., 1995, 1997) and Vicente et al. (1993, 1995, 1997, 2003) paved the way towards more general substrates. We have structurally characterized reaction products and intermediates (Calmuschi & Englert, 2002; Calmuschi, Alesi & Englert, 2004 and/or??? Calmuschi, Jonas & Englert, 2004; Calmuschi-Cula et al., 2005) and have used the target molecules in crystal engineering (Calmuschi, Alesi & Englert, 2004 and/or??? Calmuschi, Jonas & Englert, 2004; Calmuschi & Englert, 2005). In this context, we previously reported (Calmuschi & Englert, 2002) pronounced pseudosymmetry in the crystal structure of the enantiomerically pure complex (SP-4–4)-(R)-[2-(1-aminoethyl)phenyl-κ2-C1,N] chlorido(pyridine-κN)palladium(II), R-(I). Complex (I) crystallizes in space group I41, and we suggested that the centrosymmetric supergroup I41/a might represent the appropriate space group in the case of the racemate of this compound, rac-(I). In the present contribution, we confirm our earlier assumption: rac-(I) indeed crystallizes in I41/a, with lattice parameters very similar to those of the pure enantiomers. The results of a seeding experiment underline the similarity in the molecular arrangement of R-(I) and rac-(I). A crystal of the former was immerged in a saturated solution of the latter and allowed to grow under slow stirring while the temperature was gradually reduced from 292 to 282 K over a period of three months. IR spectroscopy on small peripheric fragments of the resulting large object revealed that the racemic solid grew on top of the enantiomerically pure seeded crystal. The IR spectra (KBr pellets) of rac-(I) show one strong and one much weaker band, while those of R-(I) exhibit two bands of equal intensity around 1600 cm-1.
The remaining three complexes, (II)–(IV), represented in the scheme, albeit different with respect to the metal-bonded halogen ligands X and the substituents both on the chelating ligand (R1) and on the pyridine ring (R2), also crystallize in the space group I41/a, with very similar packing and closely related lattice parameters a. Their unit-cell parameters c, however, cover a much wider range, between 15.5123 (14) and 18.3193 (17) Å, according to the space filling requirements of the substituents. [The structure of (III) is illustrated in Fig. 1.] The underlying packing pattern of both the racemic and the enantiomerically pure palladium complexes is particularly robust and extends to a recently published series of chiral platinum derivatives (Calmuschi-Cula & Englert, 2008). Their racemic counterparts have not yet been structurally characterized but will most likely also crystallize in the t2 supergroup I41/a. We note that chemically related compounds with different substituents in the periphery do not generally show the same packing in the solid, in particular when more than one modification is made to a given structure. Comparisons of packing patterns on a sound statistical basis are not very popular because they usually imply extensive manual intervention in addition to database searches. However, van der Streek & Motherwell (2005) have recently published the GRX search algorithm and applied it to the question of isomorphism between chloro- and methyl-substituted compounds. They found that approximately 25% of their crystal structures are isostructural. Our complexes (I) and (IV) share the same packing pattern, although they differ in three positions, with an iodide replacing a chloride ligand at the metal, a Br substituent instead of an H atom in the cyclopalladated amine, and a methyl group rather than an H atom on the coordinated pyridine ring. Fig. 2 shows this similarity with respect to packing.
Complexes (I)–(IV) all exhibit classical intermolecular hydrogen bonds between the only relevant donors, namely the amine H atoms and the halide ligands of neighbouring molecules. A summary of these interactions is provided in Table 1. Comparison with the Cambridge Structural Database (CSD; Allen, 2002) confirms that these hydrogen bonds are not exceptional. We searched the CSD for intermolecular contacts between NH donors and halogen atom acceptors bonded to any other atom. The search was restricted to contacts with donor–hydrogen–acceptor angles greater than or equal to 140° and to error-free entries without disorder, and resulted in the following mean hydrogen–acceptor distances: H···Cl = 2.460 Å, 5555 observations; H···Br = 2.460 Å, 1053 observations; H···I = 2.843 Å, 530 observations. The compounds described here are typical molecular crystals. Their packing coefficient – defined as the ratio between the filled volume, based on the van der Waals radii for all atoms, and the total volume of the unit cell – ranges from 68.6% for (IV) to 71.9% for (I). According to Kitaigorodsky (1973), `the overwhelming majority of crystals' have packing coefficients between 65 and 77%.