Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103004578/gg1159sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103004578/gg1159Isup2.hkl |
CCDC reference: 211731
2,2'-Bipyridylamine (171 mg, 1.0 mmol) was dissolved in dichloromethane (5 ml) and added to [PdBr2(SMe2)2] (395 mg, 1.0 mmol) in acetonitrile (5 ml) in a Schlenk vessel. After 3 d at room temperature, orange crystals separated from the solution, and these were used directly for X-ray analysis.
Crystal decay was monitored by repeating 50 initial frames at the end of data collection and analysing the duplicate reflections, and was found to be negligible. H atoms were treated as riding atoms, with C—H = 0.93 and N—H = 0.86 Å.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL.
[PdBr2(C10H9N3)] | F(000) = 824 |
Mr = 437.42 | Dx = 2.369 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P2yn | Cell parameters from 3136 reflections |
a = 10.3274 (8) Å | θ = 2.5–28.3° |
b = 9.6764 (7) Å | µ = 8.00 mm−1 |
c = 12.3385 (10) Å | T = 294 K |
β = 95.880 (2)° | Block, orange |
V = 1226.52 (16) Å3 | 0.32 × 0.30 × 0.26 mm |
Z = 4 |
CCD area detector diffractometer | 3047 independent reflections |
Radiation source: fine-focus sealed tube | 2561 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ϕ and ω scans | θmax = 28.3°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS, Bruker, 1997) | h = −13→8 |
Tmin = 0.840, Tmax = 1.000 | k = −12→12 |
9229 measured reflections | l = −16→16 |
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) = 0.093 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0496P)2 + 1.2599P] where P = (Fo2 + 2Fc2)/3 |
3047 reflections | (Δ/σ)max = 0.001 |
145 parameters | Δρmax = 1.21 e Å−3 |
0 restraints | Δρmin = −0.83 e Å−3 |
[PdBr2(C10H9N3)] | V = 1226.52 (16) Å3 |
Mr = 437.42 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.3274 (8) Å | µ = 8.00 mm−1 |
b = 9.6764 (7) Å | T = 294 K |
c = 12.3385 (10) Å | 0.32 × 0.30 × 0.26 mm |
β = 95.880 (2)° |
CCD area detector diffractometer | 3047 independent reflections |
Absorption correction: multi-scan (SADABS, Bruker, 1997) | 2561 reflections with I > 2σ(I) |
Tmin = 0.840, Tmax = 1.000 | Rint = 0.030 |
9229 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.03 | Δρmax = 1.21 e Å−3 |
3047 reflections | Δρmin = −0.83 e Å−3 |
145 parameters |
Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 20 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was −35°. Coverage of the unique set is over 99% complete. |
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 | ||
Pd1 | 0.41999 (3) | 0.25568 (3) | 0.74512 (2) | 0.03152 (10) | |
Br1 | 0.44054 (5) | 0.29502 (6) | 0.55421 (4) | 0.05536 (16) | |
Br2 | 0.28505 (5) | 0.05654 (5) | 0.69534 (4) | 0.05413 (15) | |
N1 | 0.5465 (3) | 0.4133 (3) | 0.7881 (3) | 0.0325 (7) | |
N2 | 0.4150 (3) | 0.2174 (3) | 0.9069 (3) | 0.0332 (7) | |
N3 | 0.6348 (3) | 0.2825 (4) | 0.9389 (3) | 0.0387 (8) | |
H3 | 0.7084 | 0.2464 | 0.9626 | 0.046* | |
C1 | 0.5495 (4) | 0.5274 (4) | 0.7263 (3) | 0.0383 (9) | |
H1 | 0.4821 | 0.5426 | 0.6717 | 0.046* | |
C2 | 0.6484 (5) | 0.6225 (5) | 0.7408 (4) | 0.0456 (10) | |
H2 | 0.6477 | 0.7013 | 0.6976 | 0.055* | |
C3 | 0.7487 (5) | 0.5983 (5) | 0.8208 (4) | 0.0477 (11) | |
H3A | 0.8192 | 0.6585 | 0.8297 | 0.057* | |
C4 | 0.7446 (4) | 0.4853 (5) | 0.8877 (3) | 0.0421 (9) | |
H4 | 0.8106 | 0.4694 | 0.9434 | 0.050* | |
C5 | 0.6392 (3) | 0.3947 (4) | 0.8704 (3) | 0.0321 (7) | |
C6 | 0.5247 (4) | 0.2213 (4) | 0.9738 (3) | 0.0336 (8) | |
C7 | 0.5339 (5) | 0.1616 (4) | 1.0772 (3) | 0.0403 (9) | |
H7 | 0.6124 | 0.1616 | 1.1216 | 0.048* | |
C8 | 0.4249 (5) | 0.1029 (5) | 1.1119 (3) | 0.0451 (10) | |
H8 | 0.4292 | 0.0598 | 1.1795 | 0.054* | |
C9 | 0.3097 (5) | 0.1078 (5) | 1.0470 (4) | 0.0465 (10) | |
H9 | 0.2343 | 0.0721 | 1.0716 | 0.056* | |
C10 | 0.3059 (4) | 0.1655 (5) | 0.9452 (4) | 0.0434 (10) | |
H10 | 0.2271 | 0.1693 | 0.9014 | 0.052* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.02235 (16) | 0.04018 (18) | 0.03017 (16) | −0.00304 (11) | −0.00630 (11) | 0.00477 (11) |
Br1 | 0.0473 (3) | 0.0789 (4) | 0.0370 (2) | −0.0159 (2) | −0.00988 (19) | 0.0078 (2) |
Br2 | 0.0544 (3) | 0.0596 (3) | 0.0451 (3) | −0.0220 (2) | −0.0109 (2) | 0.0040 (2) |
N1 | 0.0262 (15) | 0.0342 (16) | 0.0362 (16) | −0.0005 (12) | −0.0018 (13) | 0.0031 (13) |
N2 | 0.0278 (16) | 0.0361 (16) | 0.0350 (17) | −0.0024 (12) | −0.0003 (13) | 0.0023 (13) |
N3 | 0.0247 (16) | 0.0496 (19) | 0.0394 (18) | −0.0011 (14) | −0.0084 (14) | 0.0087 (15) |
C1 | 0.036 (2) | 0.042 (2) | 0.037 (2) | 0.0019 (17) | 0.0015 (16) | 0.0025 (16) |
C2 | 0.056 (3) | 0.039 (2) | 0.044 (2) | −0.0072 (19) | 0.012 (2) | 0.0021 (18) |
C3 | 0.043 (2) | 0.053 (3) | 0.047 (2) | −0.016 (2) | 0.007 (2) | −0.009 (2) |
C4 | 0.035 (2) | 0.051 (2) | 0.040 (2) | −0.0110 (18) | −0.0027 (17) | −0.0039 (18) |
C5 | 0.0245 (17) | 0.0406 (19) | 0.0303 (17) | −0.0006 (15) | −0.0009 (14) | −0.0034 (15) |
C6 | 0.032 (2) | 0.0351 (19) | 0.0327 (19) | 0.0020 (15) | −0.0004 (15) | 0.0019 (14) |
C7 | 0.051 (3) | 0.041 (2) | 0.0282 (18) | 0.0022 (18) | −0.0026 (17) | 0.0006 (16) |
C8 | 0.060 (3) | 0.046 (2) | 0.0299 (19) | 0.000 (2) | 0.0084 (19) | 0.0025 (17) |
C9 | 0.047 (3) | 0.047 (2) | 0.049 (2) | −0.009 (2) | 0.019 (2) | 0.0002 (19) |
C10 | 0.033 (2) | 0.052 (2) | 0.046 (2) | −0.0020 (18) | 0.0075 (18) | −0.0011 (19) |
Pd1—Br1 | 2.4168 (6) | N3—C6 | 1.389 (5) |
Pd1—Br2 | 2.4201 (5) | C1—C2 | 1.373 (6) |
Pd1—N1 | 2.042 (3) | C2—C3 | 1.376 (7) |
Pd1—N2 | 2.036 (3) | C3—C4 | 1.373 (7) |
N1—C1 | 1.345 (5) | C4—C5 | 1.396 (5) |
N1—C5 | 1.335 (5) | C6—C7 | 1.395 (5) |
N2—C6 | 1.332 (5) | C7—C8 | 1.368 (6) |
N2—C10 | 1.362 (5) | C8—C9 | 1.365 (7) |
N3—C5 | 1.380 (5) | C9—C10 | 1.371 (6) |
Br1—Pd1—Br2 | 89.07 (2) | C1—C2—C3 | 118.3 (4) |
N1—Pd1—N2 | 87.79 (13) | C2—C3—C4 | 120.0 (4) |
N1—Pd1—Br1 | 91.01 (9) | C3—C4—C5 | 118.7 (4) |
N2—Pd1—Br1 | 176.17 (9) | N1—C5—N3 | 120.4 (3) |
N1—Pd1—Br2 | 175.38 (9) | N1—C5—C4 | 121.3 (4) |
N2—Pd1—Br2 | 91.83 (9) | N3—C5—C4 | 118.4 (4) |
C1—N1—Pd1 | 121.2 (3) | N2—C6—N3 | 119.4 (3) |
C5—N1—Pd1 | 119.2 (3) | N2—C6—C7 | 122.0 (4) |
C1—N1—C5 | 119.0 (3) | N3—C6—C7 | 118.6 (4) |
C6—N2—Pd1 | 119.8 (3) | C6—C7—C8 | 118.4 (4) |
C10—N2—Pd1 | 120.8 (3) | C7—C8—C9 | 119.9 (4) |
C6—N2—C10 | 118.4 (4) | C8—C9—C10 | 119.5 (4) |
C5—N3—C6 | 127.2 (3) | N2—C10—C9 | 121.4 (4) |
N1—C1—C2 | 122.5 (4) | ||
N2—Pd1—N1—C5 | 40.5 (3) | C6—N3—C5—N1 | −35.6 (6) |
Br1—Pd1—N1—C5 | −135.8 (3) | C6—N3—C5—C4 | 146.2 (4) |
N2—Pd1—N1—C1 | −148.6 (3) | C3—C4—C5—N1 | 2.7 (6) |
Br1—Pd1—N1—C1 | 35.0 (3) | C3—C4—C5—N3 | −179.1 (4) |
N1—Pd1—N2—C6 | −42.1 (3) | C10—N2—C6—N3 | −175.6 (4) |
Br2—Pd1—N2—C6 | 133.3 (3) | Pd1—N2—C6—N3 | 15.2 (5) |
N1—Pd1—N2—C10 | 148.9 (3) | C10—N2—C6—C7 | 6.6 (6) |
Br2—Pd1—N2—C10 | −35.7 (3) | Pd1—N2—C6—C7 | −162.7 (3) |
C5—N1—C1—C2 | 3.6 (6) | C5—N3—C6—N2 | 34.0 (6) |
Pd1—N1—C1—C2 | −167.2 (3) | C5—N3—C6—C7 | −148.0 (4) |
N1—C1—C2—C3 | 0.9 (7) | N2—C6—C7—C8 | −3.0 (6) |
C1—C2—C3—C4 | −3.6 (7) | N3—C6—C7—C8 | 179.2 (4) |
C2—C3—C4—C5 | 1.8 (7) | C6—C7—C8—C9 | −2.1 (6) |
C1—N1—C5—N3 | 176.5 (4) | C7—C8—C9—C10 | 3.2 (7) |
Pd1—N1—C5—N3 | −12.5 (5) | C6—N2—C10—C9 | −5.4 (6) |
C1—N1—C5—C4 | −5.4 (6) | Pd1—N2—C10—C9 | 163.8 (3) |
Pd1—N1—C5—C4 | 165.6 (3) | C8—C9—C10—N2 | 0.5 (7) |
Experimental details
Crystal data | |
Chemical formula | [PdBr2(C10H9N3)] |
Mr | 437.42 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 294 |
a, b, c (Å) | 10.3274 (8), 9.6764 (7), 12.3385 (10) |
β (°) | 95.880 (2) |
V (Å3) | 1226.52 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 8.00 |
Crystal size (mm) | 0.32 × 0.30 × 0.26 |
Data collection | |
Diffractometer | CCD area detector diffractometer |
Absorption correction | Multi-scan (SADABS, Bruker, 1997) |
Tmin, Tmax | 0.840, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9229, 3047, 2561 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.093, 1.03 |
No. of reflections | 3047 |
No. of parameters | 145 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.21, −0.83 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997) and PLATON (Spek, 2003), SHELXTL.
Pd1—Br1 | 2.4168 (6) | N1—C5 | 1.335 (5) |
Pd1—Br2 | 2.4201 (5) | N2—C6 | 1.332 (5) |
Pd1—N1 | 2.042 (3) | N2—C10 | 1.362 (5) |
Pd1—N2 | 2.036 (3) | N3—C5 | 1.380 (5) |
N1—C1 | 1.345 (5) | N3—C6 | 1.389 (5) |
Br1—Pd1—Br2 | 89.07 (2) | C5—N1—Pd1 | 119.2 (3) |
N1—Pd1—N2 | 87.79 (13) | C1—N1—C5 | 119.0 (3) |
N1—Pd1—Br1 | 91.01 (9) | C6—N2—Pd1 | 119.8 (3) |
N2—Pd1—Br1 | 176.17 (9) | C10—N2—Pd1 | 120.8 (3) |
N1—Pd1—Br2 | 175.38 (9) | C6—N2—C10 | 118.4 (4) |
N2—Pd1—Br2 | 91.83 (9) | C5—N3—C6 | 127.2 (3) |
C1—N1—Pd1 | 121.2 (3) | ||
Br1—Pd1—N1—C1 | 35.0 (3) | Pd1—N1—C5—N3 | −12.5 (5) |
Br2—Pd1—N2—C10 | −35.7 (3) | Pd1—N2—C6—N3 | 15.2 (5) |
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Palladium-mediated reactions such as polymerization, C—C coupling reactions and aminations have attracted significant interest during recent years, as they represent versatile tools in synthetic chemistry and industrial catalysis (Miyaura & Suzuki, 1995). Recently, 2,2'-bipyridylamines have been obtained by sequential palladium-catalyzed aryl amination reactions starting from a primary amine (Buchmeiser & Wurst, 1999). Such compounds have three sites where coordination to a transition metal may occur: the two-pyridine moieties and the amine function. In contrast to the classical 2,2'-bipyridine-type ligand, six-membered rings are formed. The coordination chemistry of the simplest member of the bipyridylamine group, the 2,2'-bipyridylamine, has been described in detail for Cu (Thompson & Whitenew, 1984). However, compounds of palladium complexes are much rarer (Schareina et al., 2001). We report herein the crystal structure of a neutral mononuclear palladium(II) complex of 2,2'-bipyridylamine, [PdBr2(2-py)2NH], (I), with selective catalytic activity.
In compound (I) (Fig. 1), the coordination of the palladium center is slightly distorted square planar, ??with the N—Pd—N [87.79 (13)°] and Br—Pd—Br [89.07 (2)°] bond angles deviated slighted?? from the standard planar angle of 90°. However, in contrast to dipyridyldichloropalladium(II), [PdCl2(dipy)], in which the N—Pd—N bond angle is 80.1 (7)° (Canty et al., 1992), the geometry of the palladium atom in (I) is best described as square planar. The average Pd—N bond length of 2.039 (3) Å in (I) compares reasonably well with the corresponding distances in [PdCl2(2-py)2N(COCH3)] [mean = 2.040 (3) Å; Buchmeiser & Wurst, 1999] and [PdCl2(4-Me-2-py)2N(CH2Ph)] [mean = 2.022 (3) Å; Schareina et al., 2001]. The mean Pd—Br bond length of 2.4184 (6) Å in (I) is normal, and also compares well with those in other related compounds (Smeets et al., 1997).
The configuration around the sp2-hybridized amide-nitrogen atoms N3 is virtually distorted triangular, and consequently the C5—N3—C6 bond angle [127.2 (3) Å] deviates from the standard angle of 120°. The C5—N1—C1 and C6—N2—C10 angles [119.0 (3) Å and 118.4 (4)°, respectively] are very close to the angle of the standard six-membered planar ring. The deviations of the six-membered ring from an eclipsed conformation ??at the?? Pd1 and N3 atoms are 0.45 and 0.39 Å, respectively, in the same direction. This distortion can be explained by the Gillespie–Nyholm rules (Gillespie, 1992). The high selectivity of (I) results from its geometry, as indicated by the molecular packing shown in Fig. 2. There are weak C1AA—H1AA···Br1A [3.216 (3) Å] and N3AA—H3AA···Br1A(1/2 + x,1/2 − y,1/2 + z) [3.411 (3) Å] intermolecular interactions, and atom Pd1 is also involved in weaker interactions with the amine N atom. The separation between Pd1A and N3AA is 3.102 (3) Å, which indicates the presence of d-π stacking interactions.