Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047745/dn2236sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047745/dn2236Isup2.hkl |
CCDC reference: 667131
A solution of di(ttbutylamino-methyl-mesityl)methane (178 mg, 0.42 mmol) and [PdCl2(C6H5CN)2] (322 mg, 0.84 mmol) in dichloromethane (80 ml) was stirred during 18 h. After that period the solvent was evaporated and the residue filtered through a short silicagel column using dichloromethane as eluent. The filtrate was evaporated to dryness and the orange product was washed with diethylether (10 ml) (78% yield).
Complex 1 was disolved in chloroform, and crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of the chloroform solution.
1H NMR (400 MHz, CDCl3): 7.09 (s, 2H), 4.59 (d, 3J = 11.4 Hz, 2H), 4.38 (s, 2H), 3.81 (dd, 2J = 12.7 Hz, 2H), 3.14 (d, 2J = 12.7 Hz, 2H), 2.60 (s, 6H), 2.49 (s, 6H), 2.37 (s, 6H), 1.57 (s, 18H) p.p.m.. 13C {1H} NMR (100 MHz, CDCl3): 138.23, 137.67, 137.42, 135.05, 132.27, 130.18, 60.83, 47.11, 33.94, 29.35, 22.68, 20.72, 19.24 p.p.m.. Calcd. for C29H46Cl4N2Pd2: C 44.81 H 5.96 N 3.60 Found: C 44.56 H 5.92 N 3.57.
The H atoms were included in calculated positions and refined using a riding model, with C—H (N—H)= 0.93–0.96 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C).
The title compound [PdCl(µ-Cl) (NHtBu—CH2-2,4,6-C6HMe3—CH2-2,4,6-C6HMe3—CH2—NHtBu)]2 (1) is prepared from N,N'-{3,3'-methylenebis(2,4,6-trimethyl-3,1-phenylene)}bis(methylene)bis (2-methylpropan-2-amine) (Chahen et al., 2007) and 2 eq. of [PdCl2(C6H5CN)2]. The molecular structure of 1 shows the palladium atoms to be surrounded by a terminal chloro ligand, a nitrogen atom of the bidentate amine ligand, NHtBu—CH2-2,4,6-C6HMe3—CH2-2,4,6-C6HMe3—CH2—NHtBu, and two bridging chloro ligands. Each Pd atom and the four atoms comprising its square-planar coordination sphere are planar with a mean deviation of the fitted atoms of 0.009Å for Pd1 and 0.03Å for Pd2. The angle between these two planes is 152.67 (3)°. The intramolecular Pd—Pd distance of 3.3625 (5) Å is slightly longer then those observed for the pyrazolyl analogues [3.2004 (6) to 3.2569 (6) Å] (Guzei et al., 2003).
A characteristic helical conformation of the diphenyl methane moiety (Barnes et al., 1981), which occurs as enantiomeric pairs, is observed in the bis-amine ligand. The two C6HMe3 planes are inclined at an angle of 74.9 (1)° to each other.
For similar dinuclear chloro-bridged palladium complexes, see: Guzei et al. (2003). For the synthesis of NHtBu—CH2-2,4,6-C6HMe3—CH2-2,4,6-C6HMe3—CH2—NHtBu, see: Chahen et al. (2007). For structural information, see: Barnes et al. (1981).
Data collection: EXPOSE in IPDS Software (Stoe & Cie, 2000); cell refinement: CELL in IPDS Software (Stoe & Cie, 2000); data reduction: INTEGRATE in IPDS Software (Stoe & Cie, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[Pd2Cl4(C29H46N2)] | F(000) = 3152 |
Mr = 777.28 | Dx = 1.607 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 8003 reflections |
a = 18.7173 (11) Å | θ = 2.1–26.0° |
b = 14.7968 (8) Å | µ = 1.47 mm−1 |
c = 23.1967 (18) Å | T = 173 K |
V = 6424.5 (7) Å3 | Plate, yellow |
Z = 8 | 0.22 × 0.19 × 0.16 mm |
Stoe IPDS diffractometer | 4450 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.106 |
Graphite monochromator | θmax = 25.9°, θmin = 2.2° |
φ oscillation scans | h = −23→22 |
47318 measured reflections | k = −17→17 |
6218 independent reflections | l = −28→28 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 0.92 | w = 1/[σ2(Fo2) + (0.0695P)2] where P = (Fo2 + 2Fc2)/3 |
6218 reflections | (Δ/σ)max = 0.001 |
346 parameters | Δρmax = 0.83 e Å−3 |
0 restraints | Δρmin = −1.24 e Å−3 |
[Pd2Cl4(C29H46N2)] | V = 6424.5 (7) Å3 |
Mr = 777.28 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 18.7173 (11) Å | µ = 1.47 mm−1 |
b = 14.7968 (8) Å | T = 173 K |
c = 23.1967 (18) Å | 0.22 × 0.19 × 0.16 mm |
Stoe IPDS diffractometer | 4450 reflections with I > 2σ(I) |
47318 measured reflections | Rint = 0.106 |
6218 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 0.92 | Δρmax = 0.83 e Å−3 |
6218 reflections | Δρmin = −1.24 e Å−3 |
346 parameters |
Experimental. A crystal was mounted at 173 K on a Stoe Image Plate Diffraction System (Stoe & Cie, 2000) using Mo Kα graphite monochromated radiation. Image plate distance 70 mm, φ oscillation scans 0 - 100°, step Δφ = 0.8°, 5 minutes per frame. |
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. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.5736 (2) | 0.4144 (3) | 0.31830 (17) | 0.0296 (9) | |
H1A | 0.6244 | 0.4184 | 0.3103 | 0.036* | |
H1B | 0.5554 | 0.4753 | 0.3230 | 0.036* | |
C2 | 0.5361 (2) | 0.3695 (3) | 0.26755 (17) | 0.0271 (9) | |
C3 | 0.5634 (2) | 0.2868 (3) | 0.24702 (17) | 0.0288 (9) | |
C4 | 0.5300 (2) | 0.2459 (3) | 0.20064 (18) | 0.0328 (10) | |
H4 | 0.5491 | 0.1923 | 0.1864 | 0.039* | |
C5 | 0.4696 (2) | 0.2807 (3) | 0.17434 (18) | 0.0316 (9) | |
C6 | 0.4423 (2) | 0.3634 (3) | 0.19445 (17) | 0.0303 (9) | |
C7 | 0.4773 (2) | 0.4101 (3) | 0.23907 (17) | 0.0289 (9) | |
C8 | 0.3776 (2) | 0.4033 (4) | 0.16409 (18) | 0.0389 (11) | |
H8A | 0.3563 | 0.3549 | 0.1416 | 0.047* | |
H8B | 0.3954 | 0.4474 | 0.1368 | 0.047* | |
C9 | 0.3170 (2) | 0.4485 (3) | 0.19724 (17) | 0.0293 (9) | |
C10 | 0.2895 (2) | 0.5295 (3) | 0.17559 (17) | 0.0319 (9) | |
C11 | 0.2326 (2) | 0.5708 (3) | 0.20403 (16) | 0.0286 (9) | |
H11 | 0.2149 | 0.6249 | 0.1895 | 0.034* | |
C12 | 0.2015 (2) | 0.5345 (3) | 0.25317 (17) | 0.0271 (9) | |
C13 | 0.2288 (2) | 0.4529 (3) | 0.27535 (16) | 0.0274 (9) | |
C14 | 0.2851 (2) | 0.4084 (3) | 0.24643 (17) | 0.0268 (9) | |
C15 | 0.1935 (2) | 0.4135 (3) | 0.32872 (17) | 0.0283 (9) | |
H15A | 0.1427 | 0.4060 | 0.3218 | 0.034* | |
H15B | 0.2136 | 0.3545 | 0.3368 | 0.034* | |
C16 | 0.6282 (2) | 0.2403 (3) | 0.2727 (2) | 0.0360 (10) | |
H16A | 0.6139 | 0.2050 | 0.3054 | 0.054* | |
H16B | 0.6624 | 0.2849 | 0.2846 | 0.054* | |
H16C | 0.6495 | 0.2014 | 0.2443 | 0.054* | |
C17 | 0.4378 (3) | 0.2303 (4) | 0.1237 (2) | 0.0464 (12) | |
H17A | 0.4664 | 0.1780 | 0.1154 | 0.070* | |
H17B | 0.4369 | 0.2692 | 0.0906 | 0.070* | |
H17C | 0.3901 | 0.2118 | 0.1330 | 0.070* | |
C18 | 0.4534 (2) | 0.5050 (3) | 0.25403 (19) | 0.0334 (10) | |
H18A | 0.4126 | 0.5021 | 0.2791 | 0.050* | |
H18B | 0.4408 | 0.5367 | 0.2194 | 0.050* | |
H18C | 0.4916 | 0.5363 | 0.2732 | 0.050* | |
C19 | 0.3112 (2) | 0.3161 (3) | 0.26521 (19) | 0.0320 (10) | |
H19A | 0.3529 | 0.3228 | 0.2889 | 0.048* | |
H19B | 0.3229 | 0.2807 | 0.2318 | 0.048* | |
H19C | 0.2743 | 0.2863 | 0.2868 | 0.048* | |
C20 | 0.3157 (3) | 0.5732 (4) | 0.12039 (19) | 0.0431 (12) | |
H20A | 0.3057 | 0.5341 | 0.0884 | 0.065* | |
H20B | 0.3663 | 0.5831 | 0.1229 | 0.065* | |
H20C | 0.2918 | 0.6299 | 0.1149 | 0.065* | |
C21 | 0.1385 (2) | 0.5844 (3) | 0.27893 (19) | 0.0325 (9) | |
H21A | 0.1548 | 0.6231 | 0.3095 | 0.049* | |
H21B | 0.1048 | 0.5416 | 0.2940 | 0.049* | |
H21C | 0.1159 | 0.6203 | 0.2496 | 0.049* | |
C22 | 0.6132 (2) | 0.3860 (3) | 0.42283 (18) | 0.0307 (9) | |
C23 | 0.6175 (2) | 0.4873 (3) | 0.43222 (19) | 0.0354 (10) | |
H23A | 0.6345 | 0.5159 | 0.3977 | 0.053* | |
H23B | 0.6497 | 0.4999 | 0.4634 | 0.053* | |
H23C | 0.5709 | 0.5102 | 0.4415 | 0.053* | |
C24 | 0.5848 (3) | 0.3393 (3) | 0.47687 (19) | 0.0397 (11) | |
H24A | 0.6192 | 0.3448 | 0.5074 | 0.060* | |
H24B | 0.5765 | 0.2766 | 0.4688 | 0.060* | |
H24C | 0.5408 | 0.3673 | 0.4885 | 0.060* | |
C25 | 0.6874 (2) | 0.3479 (4) | 0.4085 (2) | 0.0451 (13) | |
H25A | 0.7063 | 0.3785 | 0.3754 | 0.068* | |
H25B | 0.6835 | 0.2844 | 0.4004 | 0.068* | |
H25C | 0.7187 | 0.3568 | 0.4408 | 0.068* | |
C26 | 0.1549 (2) | 0.4595 (3) | 0.43174 (16) | 0.0291 (9) | |
C27 | 0.0767 (2) | 0.4595 (4) | 0.4113 (2) | 0.0399 (11) | |
H27A | 0.0694 | 0.4103 | 0.3849 | 0.060* | |
H27B | 0.0664 | 0.5156 | 0.3922 | 0.060* | |
H27C | 0.0456 | 0.4526 | 0.4439 | 0.060* | |
C28 | 0.1667 (3) | 0.5402 (3) | 0.47139 (19) | 0.0390 (11) | |
H28A | 0.1391 | 0.5326 | 0.5059 | 0.058* | |
H28B | 0.1520 | 0.5945 | 0.4521 | 0.058* | |
H28C | 0.2165 | 0.5444 | 0.4811 | 0.058* | |
C29 | 0.1720 (3) | 0.3719 (3) | 0.4619 (2) | 0.0435 (12) | |
H29A | 0.2197 | 0.3744 | 0.4770 | 0.065* | |
H29B | 0.1684 | 0.3228 | 0.4350 | 0.065* | |
H29C | 0.1388 | 0.3626 | 0.4929 | 0.065* | |
Cl1 | 0.47124 (6) | 0.19910 (8) | 0.38347 (5) | 0.0417 (3) | |
Cl2 | 0.33518 (5) | 0.33643 (8) | 0.41655 (5) | 0.0344 (2) | |
Cl3 | 0.43593 (5) | 0.50561 (7) | 0.40657 (5) | 0.0319 (2) | |
Cl4 | 0.29904 (6) | 0.63889 (8) | 0.37556 (5) | 0.0365 (3) | |
N1 | 0.56226 (17) | 0.3624 (2) | 0.37331 (15) | 0.0285 (8) | |
H1 | 0.5749 | 0.3050 | 0.3637 | 0.034* | |
N2 | 0.20462 (17) | 0.4748 (2) | 0.37997 (14) | 0.0265 (7) | |
H2 | 0.1914 | 0.5301 | 0.3666 | 0.032* | |
Pd1 | 0.455757 (16) | 0.35125 (2) | 0.393763 (13) | 0.02669 (11) | |
Pd2 | 0.312726 (15) | 0.48875 (2) | 0.395103 (12) | 0.02541 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.029 (2) | 0.024 (2) | 0.037 (2) | −0.0035 (17) | 0.0036 (17) | −0.0001 (17) |
C2 | 0.0269 (19) | 0.025 (2) | 0.030 (2) | −0.0020 (17) | 0.0095 (16) | 0.0003 (16) |
C3 | 0.029 (2) | 0.027 (3) | 0.031 (2) | −0.0009 (17) | 0.0086 (17) | 0.0002 (17) |
C4 | 0.039 (2) | 0.023 (2) | 0.037 (2) | −0.0015 (18) | 0.0088 (19) | −0.0029 (18) |
C5 | 0.035 (2) | 0.027 (3) | 0.033 (2) | −0.0056 (18) | 0.0076 (17) | −0.0027 (18) |
C6 | 0.032 (2) | 0.032 (3) | 0.027 (2) | 0.0001 (17) | 0.0074 (16) | −0.0002 (17) |
C7 | 0.032 (2) | 0.022 (2) | 0.033 (2) | −0.0028 (17) | 0.0105 (17) | 0.0001 (17) |
C8 | 0.046 (3) | 0.045 (3) | 0.025 (2) | 0.011 (2) | 0.0036 (19) | −0.0042 (19) |
C9 | 0.034 (2) | 0.030 (3) | 0.024 (2) | 0.0003 (18) | −0.0033 (16) | −0.0045 (16) |
C10 | 0.040 (2) | 0.032 (3) | 0.025 (2) | −0.0011 (19) | −0.0018 (17) | 0.0014 (17) |
C11 | 0.038 (2) | 0.020 (2) | 0.027 (2) | 0.0018 (17) | −0.0049 (17) | 0.0009 (16) |
C12 | 0.0267 (19) | 0.027 (2) | 0.028 (2) | −0.0006 (16) | −0.0058 (16) | −0.0071 (17) |
C13 | 0.030 (2) | 0.028 (2) | 0.0247 (19) | −0.0050 (17) | −0.0073 (16) | −0.0009 (16) |
C14 | 0.031 (2) | 0.022 (2) | 0.028 (2) | 0.0027 (17) | −0.0051 (16) | −0.0025 (16) |
C15 | 0.0285 (19) | 0.027 (2) | 0.030 (2) | −0.0012 (17) | −0.0032 (16) | −0.0023 (17) |
C16 | 0.034 (2) | 0.027 (3) | 0.047 (3) | 0.0050 (19) | 0.0043 (19) | −0.002 (2) |
C17 | 0.055 (3) | 0.042 (3) | 0.041 (3) | 0.002 (2) | 0.000 (2) | −0.012 (2) |
C18 | 0.036 (2) | 0.027 (3) | 0.037 (2) | 0.0058 (18) | −0.0002 (19) | −0.0044 (18) |
C19 | 0.033 (2) | 0.027 (3) | 0.036 (2) | 0.0016 (18) | 0.0012 (17) | −0.0034 (18) |
C20 | 0.062 (3) | 0.042 (3) | 0.025 (2) | 0.003 (2) | 0.006 (2) | 0.002 (2) |
C21 | 0.033 (2) | 0.027 (3) | 0.037 (2) | −0.0006 (18) | −0.0013 (18) | 0.0038 (18) |
C22 | 0.0252 (19) | 0.029 (3) | 0.038 (2) | −0.0021 (17) | −0.0070 (17) | −0.0061 (18) |
C23 | 0.035 (2) | 0.032 (3) | 0.039 (2) | −0.0034 (19) | −0.0075 (19) | −0.0055 (19) |
C24 | 0.043 (3) | 0.034 (3) | 0.043 (3) | −0.003 (2) | −0.014 (2) | 0.001 (2) |
C25 | 0.031 (2) | 0.039 (3) | 0.065 (3) | 0.006 (2) | −0.009 (2) | −0.014 (2) |
C26 | 0.030 (2) | 0.033 (3) | 0.024 (2) | −0.0016 (18) | 0.0053 (16) | 0.0028 (17) |
C27 | 0.027 (2) | 0.051 (3) | 0.042 (2) | −0.004 (2) | 0.0018 (18) | −0.002 (2) |
C28 | 0.045 (3) | 0.044 (3) | 0.028 (2) | −0.003 (2) | 0.0036 (19) | −0.005 (2) |
C29 | 0.048 (3) | 0.040 (3) | 0.043 (3) | 0.005 (2) | 0.016 (2) | 0.011 (2) |
Cl1 | 0.0401 (6) | 0.0243 (6) | 0.0607 (7) | −0.0071 (5) | −0.0001 (5) | −0.0003 (5) |
Cl2 | 0.0273 (5) | 0.0312 (6) | 0.0447 (6) | −0.0032 (4) | 0.0012 (4) | 0.0070 (5) |
Cl3 | 0.0251 (5) | 0.0291 (6) | 0.0414 (6) | −0.0036 (4) | 0.0009 (4) | −0.0043 (4) |
Cl4 | 0.0377 (5) | 0.0265 (6) | 0.0453 (6) | −0.0051 (4) | −0.0040 (5) | 0.0035 (4) |
N1 | 0.0280 (17) | 0.024 (2) | 0.0331 (17) | −0.0002 (14) | −0.0008 (14) | −0.0036 (14) |
N2 | 0.0269 (17) | 0.025 (2) | 0.0275 (17) | −0.0028 (14) | 0.0029 (14) | 0.0017 (14) |
Pd1 | 0.02492 (17) | 0.0251 (2) | 0.03005 (17) | −0.00315 (12) | −0.00053 (12) | 0.00089 (13) |
Pd2 | 0.02467 (17) | 0.0255 (2) | 0.02605 (17) | −0.00274 (12) | −0.00058 (12) | 0.00051 (12) |
C1—N1 | 1.505 (5) | C19—H19C | 0.9600 |
C1—C2 | 1.523 (6) | C20—H20A | 0.9600 |
C1—H1A | 0.9700 | C20—H20B | 0.9600 |
C1—H1B | 0.9700 | C20—H20C | 0.9600 |
C2—C3 | 1.410 (6) | C21—H21A | 0.9600 |
C2—C7 | 1.418 (6) | C21—H21B | 0.9600 |
C3—C4 | 1.384 (6) | C21—H21C | 0.9600 |
C3—C16 | 1.516 (6) | C22—C23 | 1.517 (6) |
C4—C5 | 1.383 (6) | C22—C24 | 1.527 (6) |
C4—H4 | 0.9300 | C22—N1 | 1.533 (5) |
C5—C6 | 1.407 (6) | C22—C25 | 1.535 (6) |
C5—C17 | 1.513 (6) | C23—H23A | 0.9600 |
C6—C7 | 1.407 (6) | C23—H23B | 0.9600 |
C6—C8 | 1.520 (6) | C23—H23C | 0.9600 |
C7—C18 | 1.513 (6) | C24—H24A | 0.9600 |
C8—C9 | 1.525 (6) | C24—H24B | 0.9600 |
C8—H8A | 0.9700 | C24—H24C | 0.9600 |
C8—H8B | 0.9700 | C25—H25A | 0.9600 |
C9—C10 | 1.397 (6) | C25—H25B | 0.9600 |
C9—C14 | 1.418 (6) | C25—H25C | 0.9600 |
C10—C11 | 1.394 (6) | C26—C29 | 1.508 (6) |
C10—C20 | 1.516 (6) | C26—C28 | 1.523 (6) |
C11—C12 | 1.388 (6) | C26—N2 | 1.536 (5) |
C11—H11 | 0.9300 | C26—C27 | 1.538 (6) |
C12—C13 | 1.409 (6) | C27—H27A | 0.9600 |
C12—C21 | 1.514 (6) | C27—H27B | 0.9600 |
C13—C14 | 1.412 (6) | C27—H27C | 0.9600 |
C13—C15 | 1.520 (6) | C28—H28A | 0.9600 |
C14—C19 | 1.514 (6) | C28—H28B | 0.9600 |
C15—N2 | 1.510 (5) | C28—H28C | 0.9600 |
C15—H15A | 0.9700 | C29—H29A | 0.9600 |
C15—H15B | 0.9700 | C29—H29B | 0.9600 |
C16—H16A | 0.9600 | C29—H29C | 0.9600 |
C16—H16B | 0.9600 | Cl1—Pd1 | 2.2825 (12) |
C16—H16C | 0.9600 | Cl2—Pd1 | 2.3283 (10) |
C17—H17A | 0.9600 | Cl2—Pd2 | 2.3460 (12) |
C17—H17B | 0.9600 | Cl3—Pd1 | 2.3329 (11) |
C17—H17C | 0.9600 | Cl3—Pd2 | 2.3347 (10) |
C18—H18A | 0.9600 | Cl4—Pd2 | 2.2818 (12) |
C18—H18B | 0.9600 | N1—Pd1 | 2.056 (3) |
C18—H18C | 0.9600 | N1—H1 | 0.9100 |
C19—H19A | 0.9600 | N2—Pd2 | 2.064 (3) |
C19—H19B | 0.9600 | N2—H2 | 0.9100 |
N1—C1—C2 | 111.6 (3) | H20A—C20—H20C | 109.5 |
N1—C1—H1A | 109.3 | H20B—C20—H20C | 109.5 |
C2—C1—H1A | 109.3 | C12—C21—H21A | 109.5 |
N1—C1—H1B | 109.3 | C12—C21—H21B | 109.5 |
C2—C1—H1B | 109.3 | H21A—C21—H21B | 109.5 |
H1A—C1—H1B | 108.0 | C12—C21—H21C | 109.5 |
C3—C2—C7 | 119.5 (4) | H21A—C21—H21C | 109.5 |
C3—C2—C1 | 118.2 (4) | H21B—C21—H21C | 109.5 |
C7—C2—C1 | 122.2 (4) | C23—C22—C24 | 110.3 (4) |
C4—C3—C2 | 118.6 (4) | C23—C22—N1 | 111.4 (3) |
C4—C3—C16 | 118.0 (4) | C24—C22—N1 | 107.2 (3) |
C2—C3—C16 | 123.5 (4) | C23—C22—C25 | 110.3 (4) |
C5—C4—C3 | 123.4 (4) | C24—C22—C25 | 109.1 (4) |
C5—C4—H4 | 118.3 | N1—C22—C25 | 108.5 (3) |
C3—C4—H4 | 118.3 | C22—C23—H23A | 109.5 |
C4—C5—C6 | 118.4 (4) | C22—C23—H23B | 109.5 |
C4—C5—C17 | 118.7 (4) | H23A—C23—H23B | 109.5 |
C6—C5—C17 | 122.9 (4) | C22—C23—H23C | 109.5 |
C7—C6—C5 | 120.1 (4) | H23A—C23—H23C | 109.5 |
C7—C6—C8 | 121.5 (4) | H23B—C23—H23C | 109.5 |
C5—C6—C8 | 118.3 (4) | C22—C24—H24A | 109.5 |
C6—C7—C2 | 119.8 (4) | C22—C24—H24B | 109.5 |
C6—C7—C18 | 119.1 (4) | H24A—C24—H24B | 109.5 |
C2—C7—C18 | 121.1 (4) | C22—C24—H24C | 109.5 |
C6—C8—C9 | 121.9 (3) | H24A—C24—H24C | 109.5 |
C6—C8—H8A | 106.8 | H24B—C24—H24C | 109.5 |
C9—C8—H8A | 106.8 | C22—C25—H25A | 109.5 |
C6—C8—H8B | 106.8 | C22—C25—H25B | 109.5 |
C9—C8—H8B | 106.8 | H25A—C25—H25B | 109.5 |
H8A—C8—H8B | 106.7 | C22—C25—H25C | 109.5 |
C10—C9—C14 | 119.6 (4) | H25A—C25—H25C | 109.5 |
C10—C9—C8 | 118.0 (4) | H25B—C25—H25C | 109.5 |
C14—C9—C8 | 122.3 (4) | C29—C26—C28 | 111.3 (4) |
C11—C10—C9 | 119.2 (4) | C29—C26—N2 | 111.1 (3) |
C11—C10—C20 | 117.4 (4) | C28—C26—N2 | 105.6 (3) |
C9—C10—C20 | 123.4 (4) | C29—C26—C27 | 110.2 (4) |
C12—C11—C10 | 122.6 (4) | C28—C26—C27 | 109.0 (4) |
C12—C11—H11 | 118.7 | N2—C26—C27 | 109.6 (3) |
C10—C11—H11 | 118.7 | C26—C27—H27A | 109.5 |
C11—C12—C13 | 118.6 (4) | C26—C27—H27B | 109.5 |
C11—C12—C21 | 117.5 (4) | H27A—C27—H27B | 109.5 |
C13—C12—C21 | 123.8 (4) | C26—C27—H27C | 109.5 |
C12—C13—C14 | 119.8 (4) | H27A—C27—H27C | 109.5 |
C12—C13—C15 | 117.9 (4) | H27B—C27—H27C | 109.5 |
C14—C13—C15 | 122.2 (4) | C26—C28—H28A | 109.5 |
C13—C14—C9 | 120.1 (4) | C26—C28—H28B | 109.5 |
C13—C14—C19 | 121.6 (4) | H28A—C28—H28B | 109.5 |
C9—C14—C19 | 118.3 (4) | C26—C28—H28C | 109.5 |
N2—C15—C13 | 110.6 (3) | H28A—C28—H28C | 109.5 |
N2—C15—H15A | 109.5 | H28B—C28—H28C | 109.5 |
C13—C15—H15A | 109.5 | C26—C29—H29A | 109.5 |
N2—C15—H15B | 109.5 | C26—C29—H29B | 109.5 |
C13—C15—H15B | 109.5 | H29A—C29—H29B | 109.5 |
H15A—C15—H15B | 108.1 | C26—C29—H29C | 109.5 |
C3—C16—H16A | 109.5 | H29A—C29—H29C | 109.5 |
C3—C16—H16B | 109.5 | H29B—C29—H29C | 109.5 |
H16A—C16—H16B | 109.5 | Pd1—Cl2—Pd2 | 92.01 (4) |
C3—C16—H16C | 109.5 | Pd1—Cl3—Pd2 | 92.18 (4) |
H16A—C16—H16C | 109.5 | C1—N1—C22 | 115.6 (3) |
H16B—C16—H16C | 109.5 | C1—N1—Pd1 | 111.9 (2) |
C5—C17—H17A | 109.5 | C22—N1—Pd1 | 116.6 (3) |
C5—C17—H17B | 109.5 | C1—N1—H1 | 103.5 |
H17A—C17—H17B | 109.5 | C22—N1—H1 | 103.5 |
C5—C17—H17C | 109.5 | Pd1—N1—H1 | 103.5 |
H17A—C17—H17C | 109.5 | C15—N2—C26 | 116.3 (3) |
H17B—C17—H17C | 109.5 | C15—N2—Pd2 | 109.2 (2) |
C7—C18—H18A | 109.5 | C26—N2—Pd2 | 118.4 (2) |
C7—C18—H18B | 109.5 | C15—N2—H2 | 103.6 |
H18A—C18—H18B | 109.5 | C26—N2—H2 | 103.6 |
C7—C18—H18C | 109.5 | Pd2—N2—H2 | 103.6 |
H18A—C18—H18C | 109.5 | N1—Pd1—Cl1 | 86.11 (11) |
H18B—C18—H18C | 109.5 | N1—Pd1—Cl2 | 179.19 (11) |
C14—C19—H19A | 109.5 | Cl1—Pd1—Cl2 | 93.09 (4) |
C14—C19—H19B | 109.5 | N1—Pd1—Cl3 | 96.02 (10) |
H19A—C19—H19B | 109.5 | Cl1—Pd1—Cl3 | 177.71 (4) |
C14—C19—H19C | 109.5 | Cl2—Pd1—Cl3 | 84.78 (4) |
H19A—C19—H19C | 109.5 | N2—Pd2—Cl4 | 87.33 (10) |
H19B—C19—H19C | 109.5 | N2—Pd2—Cl3 | 176.73 (9) |
C10—C20—H20A | 109.5 | Cl4—Pd2—Cl3 | 91.69 (4) |
C10—C20—H20B | 109.5 | N2—Pd2—Cl2 | 96.64 (10) |
H20A—C20—H20B | 109.5 | Cl4—Pd2—Cl2 | 176.02 (4) |
C10—C20—H20C | 109.5 | Cl3—Pd2—Cl2 | 84.35 (4) |
N1—C1—C2—C3 | −70.0 (4) | C12—C13—C14—C19 | −173.8 (4) |
N1—C1—C2—C7 | 112.9 (4) | C15—C13—C14—C19 | 3.2 (6) |
C7—C2—C3—C4 | −2.4 (6) | C10—C9—C14—C13 | −3.8 (6) |
C1—C2—C3—C4 | −179.5 (4) | C8—C9—C14—C13 | −179.5 (4) |
C7—C2—C3—C16 | 177.0 (4) | C10—C9—C14—C19 | 173.9 (4) |
C1—C2—C3—C16 | −0.1 (6) | C8—C9—C14—C19 | −1.9 (6) |
C2—C3—C4—C5 | −2.0 (6) | C12—C13—C15—N2 | −65.6 (4) |
C16—C3—C4—C5 | 178.6 (4) | C14—C13—C15—N2 | 117.3 (4) |
C3—C4—C5—C6 | 2.3 (6) | C2—C1—N1—C22 | 163.9 (3) |
C3—C4—C5—C17 | 179.7 (4) | C2—C1—N1—Pd1 | −59.3 (4) |
C4—C5—C6—C7 | 1.9 (6) | C23—C22—N1—C1 | 49.3 (5) |
C17—C5—C6—C7 | −175.4 (4) | C24—C22—N1—C1 | 170.1 (4) |
C4—C5—C6—C8 | 177.8 (4) | C25—C22—N1—C1 | −72.3 (5) |
C17—C5—C6—C8 | 0.5 (6) | C23—C22—N1—Pd1 | −85.4 (4) |
C5—C6—C7—C2 | −6.2 (6) | C24—C22—N1—Pd1 | 35.3 (4) |
C8—C6—C7—C2 | 178.0 (4) | C25—C22—N1—Pd1 | 153.0 (3) |
C5—C6—C7—C18 | 171.1 (4) | C13—C15—N2—C26 | 162.7 (3) |
C8—C6—C7—C18 | −4.6 (6) | C13—C15—N2—Pd2 | −60.0 (4) |
C3—C2—C7—C6 | 6.5 (6) | C29—C26—N2—C15 | 70.3 (5) |
C1—C2—C7—C6 | −176.5 (4) | C28—C26—N2—C15 | −168.9 (3) |
C3—C2—C7—C18 | −170.8 (4) | C27—C26—N2—C15 | −51.7 (5) |
C1—C2—C7—C18 | 6.2 (6) | C29—C26—N2—Pd2 | −63.0 (4) |
C7—C6—C8—C9 | −44.5 (6) | C28—C26—N2—Pd2 | 57.8 (4) |
C5—C6—C8—C9 | 139.7 (4) | C27—C26—N2—Pd2 | 175.0 (3) |
C6—C8—C9—C10 | 136.6 (5) | C1—N1—Pd1—Cl1 | 117.2 (3) |
C6—C8—C9—C14 | −47.6 (7) | C22—N1—Pd1—Cl1 | −106.5 (3) |
C14—C9—C10—C11 | 2.1 (6) | C1—N1—Pd1—Cl3 | −63.7 (3) |
C8—C9—C10—C11 | 178.0 (4) | C22—N1—Pd1—Cl3 | 72.6 (3) |
C14—C9—C10—C20 | −174.5 (4) | Pd2—Cl2—Pd1—Cl1 | −161.48 (4) |
C8—C9—C10—C20 | 1.4 (6) | Pd2—Cl2—Pd1—Cl3 | 19.38 (4) |
C9—C10—C11—C12 | −0.5 (6) | Pd2—Cl3—Pd1—N1 | 160.38 (10) |
C20—C10—C11—C12 | 176.4 (4) | Pd2—Cl3—Pd1—Cl2 | −19.48 (4) |
C10—C11—C12—C13 | 0.4 (6) | C15—N2—Pd2—Cl4 | 117.0 (2) |
C10—C11—C12—C21 | −178.0 (4) | C26—N2—Pd2—Cl4 | −106.7 (3) |
C11—C12—C13—C14 | −2.1 (6) | C15—N2—Pd2—Cl2 | −63.1 (2) |
C21—C12—C13—C14 | 176.3 (4) | C26—N2—Pd2—Cl2 | 73.1 (3) |
C11—C12—C13—C15 | −179.3 (3) | Pd1—Cl3—Pd2—Cl4 | −161.03 (4) |
C21—C12—C13—C15 | −0.9 (6) | Pd1—Cl3—Pd2—Cl2 | 19.34 (4) |
C12—C13—C14—C9 | 3.8 (6) | Pd1—Cl2—Pd2—N2 | 157.49 (10) |
C15—C13—C14—C9 | −179.2 (4) | Pd1—Cl2—Pd2—Cl3 | −19.38 (4) |
Experimental details
Crystal data | |
Chemical formula | [Pd2Cl4(C29H46N2)] |
Mr | 777.28 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 173 |
a, b, c (Å) | 18.7173 (11), 14.7968 (8), 23.1967 (18) |
V (Å3) | 6424.5 (7) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.47 |
Crystal size (mm) | 0.22 × 0.19 × 0.16 |
Data collection | |
Diffractometer | Stoe IPDS |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 47318, 6218, 4450 |
Rint | 0.106 |
(sin θ/λ)max (Å−1) | 0.615 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.105, 0.92 |
No. of reflections | 6218 |
No. of parameters | 346 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.83, −1.24 |
Computer programs: EXPOSE in IPDS Software (Stoe & Cie, 2000), CELL in IPDS Software (Stoe & Cie, 2000), INTEGRATE in IPDS Software (Stoe & Cie, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997).
The title compound [PdCl(µ-Cl) (NHtBu—CH2-2,4,6-C6HMe3—CH2-2,4,6-C6HMe3—CH2—NHtBu)]2 (1) is prepared from N,N'-{3,3'-methylenebis(2,4,6-trimethyl-3,1-phenylene)}bis(methylene)bis (2-methylpropan-2-amine) (Chahen et al., 2007) and 2 eq. of [PdCl2(C6H5CN)2]. The molecular structure of 1 shows the palladium atoms to be surrounded by a terminal chloro ligand, a nitrogen atom of the bidentate amine ligand, NHtBu—CH2-2,4,6-C6HMe3—CH2-2,4,6-C6HMe3—CH2—NHtBu, and two bridging chloro ligands. Each Pd atom and the four atoms comprising its square-planar coordination sphere are planar with a mean deviation of the fitted atoms of 0.009Å for Pd1 and 0.03Å for Pd2. The angle between these two planes is 152.67 (3)°. The intramolecular Pd—Pd distance of 3.3625 (5) Å is slightly longer then those observed for the pyrazolyl analogues [3.2004 (6) to 3.2569 (6) Å] (Guzei et al., 2003).
A characteristic helical conformation of the diphenyl methane moiety (Barnes et al., 1981), which occurs as enantiomeric pairs, is observed in the bis-amine ligand. The two C6HMe3 planes are inclined at an angle of 74.9 (1)° to each other.