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The palladium center of the title compound, [PdBr2(C10H9N3)], has a slightly distorted square-planar conformation, with the Pd atom bonded to the two pyridine N atoms of the di-2-pyridyl­amine moiety and to two Br atoms. The Pd—Br and Pd—N bond lengths are 2.4168 (6)/2.4201 (5) and 2.036 (3)/2.042 (3) Å, respectively.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103004578/gg1159sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103004578/gg1159Isup2.hkl
Contains datablock I

CCDC reference: 211731

Comment top

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.

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing displacement ellipsoids at the 50% probability level.
[Figure 2] Fig. 2. The three-dimensional packing framework of (I), viewed down the b axis, showing intermolecular contacts.
Dibromo-[N,N-di(pyrid-2-yl)amine]-palladium(II) top
Crystal data top
[PdBr2(C10H9N3)]F(000) = 824
Mr = 437.42Dx = 2.369 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ynCell parameters from 3136 reflections
a = 10.3274 (8) Åθ = 2.5–28.3°
b = 9.6764 (7) ŵ = 8.00 mm1
c = 12.3385 (10) ÅT = 294 K
β = 95.880 (2)°Block, orange
V = 1226.52 (16) Å30.32 × 0.30 × 0.26 mm
Z = 4
Data collection top
CCD area detector
diffractometer
3047 independent reflections
Radiation source: fine-focus sealed tube2561 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
ϕ and ω scansθmax = 28.3°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS, Bruker, 1997)
h = 138
Tmin = 0.840, Tmax = 1.000k = 1212
9229 measured reflectionsl = 1616
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093H-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 parametersΔρmax = 1.21 e Å3
0 restraintsΔρmin = 0.83 e Å3
Crystal data top
[PdBr2(C10H9N3)]V = 1226.52 (16) Å3
Mr = 437.42Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.3274 (8) ŵ = 8.00 mm1
b = 9.6764 (7) ÅT = 294 K
c = 12.3385 (10) Å0.32 × 0.30 × 0.26 mm
β = 95.880 (2)°
Data collection top
CCD area detector
diffractometer
3047 independent reflections
Absorption correction: multi-scan
(SADABS, Bruker, 1997)
2561 reflections with I > 2σ(I)
Tmin = 0.840, Tmax = 1.000Rint = 0.030
9229 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.093H-atom parameters constrained
S = 1.03Δρmax = 1.21 e Å3
3047 reflectionsΔρmin = 0.83 e Å3
145 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pd10.41999 (3)0.25568 (3)0.74512 (2)0.03152 (10)
Br10.44054 (5)0.29502 (6)0.55421 (4)0.05536 (16)
Br20.28505 (5)0.05654 (5)0.69534 (4)0.05413 (15)
N10.5465 (3)0.4133 (3)0.7881 (3)0.0325 (7)
N20.4150 (3)0.2174 (3)0.9069 (3)0.0332 (7)
N30.6348 (3)0.2825 (4)0.9389 (3)0.0387 (8)
H30.70840.24640.96260.046*
C10.5495 (4)0.5274 (4)0.7263 (3)0.0383 (9)
H10.48210.54260.67170.046*
C20.6484 (5)0.6225 (5)0.7408 (4)0.0456 (10)
H20.64770.70130.69760.055*
C30.7487 (5)0.5983 (5)0.8208 (4)0.0477 (11)
H3A0.81920.65850.82970.057*
C40.7446 (4)0.4853 (5)0.8877 (3)0.0421 (9)
H40.81060.46940.94340.050*
C50.6392 (3)0.3947 (4)0.8704 (3)0.0321 (7)
C60.5247 (4)0.2213 (4)0.9738 (3)0.0336 (8)
C70.5339 (5)0.1616 (4)1.0772 (3)0.0403 (9)
H70.61240.16161.12160.048*
C80.4249 (5)0.1029 (5)1.1119 (3)0.0451 (10)
H80.42920.05981.17950.054*
C90.3097 (5)0.1078 (5)1.0470 (4)0.0465 (10)
H90.23430.07211.07160.056*
C100.3059 (4)0.1655 (5)0.9452 (4)0.0434 (10)
H100.22710.16930.90140.052*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.02235 (16)0.04018 (18)0.03017 (16)0.00304 (11)0.00630 (11)0.00477 (11)
Br10.0473 (3)0.0789 (4)0.0370 (2)0.0159 (2)0.00988 (19)0.0078 (2)
Br20.0544 (3)0.0596 (3)0.0451 (3)0.0220 (2)0.0109 (2)0.0040 (2)
N10.0262 (15)0.0342 (16)0.0362 (16)0.0005 (12)0.0018 (13)0.0031 (13)
N20.0278 (16)0.0361 (16)0.0350 (17)0.0024 (12)0.0003 (13)0.0023 (13)
N30.0247 (16)0.0496 (19)0.0394 (18)0.0011 (14)0.0084 (14)0.0087 (15)
C10.036 (2)0.042 (2)0.037 (2)0.0019 (17)0.0015 (16)0.0025 (16)
C20.056 (3)0.039 (2)0.044 (2)0.0072 (19)0.012 (2)0.0021 (18)
C30.043 (2)0.053 (3)0.047 (2)0.016 (2)0.007 (2)0.009 (2)
C40.035 (2)0.051 (2)0.040 (2)0.0110 (18)0.0027 (17)0.0039 (18)
C50.0245 (17)0.0406 (19)0.0303 (17)0.0006 (15)0.0009 (14)0.0034 (15)
C60.032 (2)0.0351 (19)0.0327 (19)0.0020 (15)0.0004 (15)0.0019 (14)
C70.051 (3)0.041 (2)0.0282 (18)0.0022 (18)0.0026 (17)0.0006 (16)
C80.060 (3)0.046 (2)0.0299 (19)0.000 (2)0.0084 (19)0.0025 (17)
C90.047 (3)0.047 (2)0.049 (2)0.009 (2)0.019 (2)0.0002 (19)
C100.033 (2)0.052 (2)0.046 (2)0.0020 (18)0.0075 (18)0.0011 (19)
Geometric parameters (Å, º) top
Pd1—Br12.4168 (6)N3—C61.389 (5)
Pd1—Br22.4201 (5)C1—C21.373 (6)
Pd1—N12.042 (3)C2—C31.376 (7)
Pd1—N22.036 (3)C3—C41.373 (7)
N1—C11.345 (5)C4—C51.396 (5)
N1—C51.335 (5)C6—C71.395 (5)
N2—C61.332 (5)C7—C81.368 (6)
N2—C101.362 (5)C8—C91.365 (7)
N3—C51.380 (5)C9—C101.371 (6)
Br1—Pd1—Br289.07 (2)C1—C2—C3118.3 (4)
N1—Pd1—N287.79 (13)C2—C3—C4120.0 (4)
N1—Pd1—Br191.01 (9)C3—C4—C5118.7 (4)
N2—Pd1—Br1176.17 (9)N1—C5—N3120.4 (3)
N1—Pd1—Br2175.38 (9)N1—C5—C4121.3 (4)
N2—Pd1—Br291.83 (9)N3—C5—C4118.4 (4)
C1—N1—Pd1121.2 (3)N2—C6—N3119.4 (3)
C5—N1—Pd1119.2 (3)N2—C6—C7122.0 (4)
C1—N1—C5119.0 (3)N3—C6—C7118.6 (4)
C6—N2—Pd1119.8 (3)C6—C7—C8118.4 (4)
C10—N2—Pd1120.8 (3)C7—C8—C9119.9 (4)
C6—N2—C10118.4 (4)C8—C9—C10119.5 (4)
C5—N3—C6127.2 (3)N2—C10—C9121.4 (4)
N1—C1—C2122.5 (4)
N2—Pd1—N1—C540.5 (3)C6—N3—C5—N135.6 (6)
Br1—Pd1—N1—C5135.8 (3)C6—N3—C5—C4146.2 (4)
N2—Pd1—N1—C1148.6 (3)C3—C4—C5—N12.7 (6)
Br1—Pd1—N1—C135.0 (3)C3—C4—C5—N3179.1 (4)
N1—Pd1—N2—C642.1 (3)C10—N2—C6—N3175.6 (4)
Br2—Pd1—N2—C6133.3 (3)Pd1—N2—C6—N315.2 (5)
N1—Pd1—N2—C10148.9 (3)C10—N2—C6—C76.6 (6)
Br2—Pd1—N2—C1035.7 (3)Pd1—N2—C6—C7162.7 (3)
C5—N1—C1—C23.6 (6)C5—N3—C6—N234.0 (6)
Pd1—N1—C1—C2167.2 (3)C5—N3—C6—C7148.0 (4)
N1—C1—C2—C30.9 (7)N2—C6—C7—C83.0 (6)
C1—C2—C3—C43.6 (7)N3—C6—C7—C8179.2 (4)
C2—C3—C4—C51.8 (7)C6—C7—C8—C92.1 (6)
C1—N1—C5—N3176.5 (4)C7—C8—C9—C103.2 (7)
Pd1—N1—C5—N312.5 (5)C6—N2—C10—C95.4 (6)
C1—N1—C5—C45.4 (6)Pd1—N2—C10—C9163.8 (3)
Pd1—N1—C5—C4165.6 (3)C8—C9—C10—N20.5 (7)

Experimental details

Crystal data
Chemical formula[PdBr2(C10H9N3)]
Mr437.42
Crystal system, space groupMonoclinic, P21/n
Temperature (K)294
a, b, c (Å)10.3274 (8), 9.6764 (7), 12.3385 (10)
β (°) 95.880 (2)
V3)1226.52 (16)
Z4
Radiation typeMo Kα
µ (mm1)8.00
Crystal size (mm)0.32 × 0.30 × 0.26
Data collection
DiffractometerCCD area detector
diffractometer
Absorption correctionMulti-scan
(SADABS, Bruker, 1997)
Tmin, Tmax0.840, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
9229, 3047, 2561
Rint0.030
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.093, 1.03
No. of reflections3047
No. of parameters145
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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.

Selected geometric parameters (Å, º) top
Pd1—Br12.4168 (6)N1—C51.335 (5)
Pd1—Br22.4201 (5)N2—C61.332 (5)
Pd1—N12.042 (3)N2—C101.362 (5)
Pd1—N22.036 (3)N3—C51.380 (5)
N1—C11.345 (5)N3—C61.389 (5)
Br1—Pd1—Br289.07 (2)C5—N1—Pd1119.2 (3)
N1—Pd1—N287.79 (13)C1—N1—C5119.0 (3)
N1—Pd1—Br191.01 (9)C6—N2—Pd1119.8 (3)
N2—Pd1—Br1176.17 (9)C10—N2—Pd1120.8 (3)
N1—Pd1—Br2175.38 (9)C6—N2—C10118.4 (4)
N2—Pd1—Br291.83 (9)C5—N3—C6127.2 (3)
C1—N1—Pd1121.2 (3)
Br1—Pd1—N1—C135.0 (3)Pd1—N1—C5—N312.5 (5)
Br2—Pd1—N2—C1035.7 (3)Pd1—N2—C6—N315.2 (5)
 

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