metal-organic compounds
Bis(di-2-pyridylamine-κ2N2,N2′)palladium(II) bis(thiocyanate)
aSchool of Applied Chemical Engineering, The Research Institute of Catalysis, Chonnam National University, Gwangju 500-757, Republic of Korea
*Correspondence e-mail: hakwang@chonnam.ac.kr
The PdII atom of the title salt, [Pd(C10H9N3)2](NCS)2, lies on a center of inversion and exists in a square-planar environment defined by the four pyridine N atoms derived from the two chelating di-2-pyridylamine (dpa) ligands. The chelate ring displays a boat conformation with a dihedral angle between the pyridine rings of 43.0 (1)°. Adjacent thiocyanate ions are linked to the cations by N—H⋯N hydrogen bonds.
Related literature
For the crystal structures of the related cationic PdII and PtII complexes, [Pd(dpa)2](X)2 (X = Cl, PF6 or NO3) and [Pt(dpa)2]Br2·H2O, see: Živković et al. (2007); Antonioli et al. (2008); Ha (2012a,b).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536812033958/ng5285sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812033958/ng5285Isup2.hkl
The title complex was obtained as a byproduct from the reaction of Na2PdCl4 (0.1462 g, 0.497 mmol) with KSCN (0.4688 g, 4.824 mmol) and di-2-pyridylamine (0.0877 g, 0.512 mmol) in MeOH (30 ml)/acetone (30 ml). After stirring of the reaction mixture for 24 h at room temperature, the formed precipitate was separated by filtration, washed with H2O and acetone, to give the main product as a pale red powder (0.1562 g). A small amount of the yellow byproduct was obtained from the mixture of filtrate and washing solution. Yellow crystals were obtained by slow evaporation from a CH3CN solution of the byproduct at room temperature.
Carbon-bound H atoms were positioned geometrically and allowed to ride on their respective parent atoms: C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C). Nitrogen-bound H atom was located from the difference Fourier map then allowed to ride on its parent atom in the final cycles of
with N—H = 0.92 Å and Uiso(H) = 1.5Ueq(N). The highest peak (1.10 e Å-3) and the deepest hole (-0.61 e Å-3) in the difference Fourier map are located 0.85 Å and 1.48 Å, respectively, from the atoms C1 and H1.Data collection: SMART (Bruker, 2000); cell
SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).[Pd(C10H9N3)2](NCS)2 | F(000) = 568 |
Mr = 564.96 | Dx = 1.694 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2711 reflections |
a = 7.7353 (9) Å | θ = 2.3–25.9° |
b = 17.478 (2) Å | µ = 1.06 mm−1 |
c = 8.3822 (10) Å | T = 200 K |
β = 102.137 (2)° | Block, yellow |
V = 1107.9 (2) Å3 | 0.16 × 0.09 × 0.09 mm |
Z = 2 |
Bruker SMART 1000 CCD diffractometer | 2172 independent reflections |
Radiation source: fine-focus sealed tube | 1552 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
ϕ and ω scans | θmax = 26.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −9→6 |
Tmin = 0.876, Tmax = 1.000 | k = −21→20 |
6810 measured reflections | l = −10→10 |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0333P)2 + 0.3195P] where P = (Fo2 + 2Fc2)/3 |
2172 reflections | (Δ/σ)max < 0.001 |
151 parameters | Δρmax = 1.10 e Å−3 |
0 restraints | Δρmin = −0.61 e Å−3 |
[Pd(C10H9N3)2](NCS)2 | V = 1107.9 (2) Å3 |
Mr = 564.96 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.7353 (9) Å | µ = 1.06 mm−1 |
b = 17.478 (2) Å | T = 200 K |
c = 8.3822 (10) Å | 0.16 × 0.09 × 0.09 mm |
β = 102.137 (2)° |
Bruker SMART 1000 CCD diffractometer | 2172 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1552 reflections with I > 2σ(I) |
Tmin = 0.876, Tmax = 1.000 | Rint = 0.046 |
6810 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.07 | Δρmax = 1.10 e Å−3 |
2172 reflections | Δρmin = −0.61 e Å−3 |
151 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. 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 | 0.5000 | 0.0000 | 0.5000 | 0.02072 (15) | |
N1 | 0.6536 (4) | 0.08760 (17) | 0.6087 (4) | 0.0216 (7) | |
N2 | 0.4264 (4) | 0.12533 (17) | 0.7419 (4) | 0.0240 (8) | |
H2N | 0.3803 | 0.1669 | 0.7859 | 0.036* | |
N3 | 0.4123 (4) | −0.00805 (17) | 0.7101 (4) | 0.0199 (7) | |
C1 | 0.8191 (5) | 0.0992 (2) | 0.5843 (5) | 0.0274 (9) | |
H1 | 0.8688 | 0.0616 | 0.5253 | 0.033* | |
C2 | 0.9181 (5) | 0.1620 (2) | 0.6399 (5) | 0.0319 (10) | |
H2 | 1.0339 | 0.1681 | 0.6204 | 0.038* | |
C3 | 0.8453 (6) | 0.2168 (2) | 0.7258 (5) | 0.0329 (11) | |
H3 | 0.9097 | 0.2619 | 0.7633 | 0.039* | |
C4 | 0.6808 (5) | 0.2056 (2) | 0.7562 (5) | 0.0283 (10) | |
H4 | 0.6303 | 0.2427 | 0.8155 | 0.034* | |
C5 | 0.5868 (5) | 0.1392 (2) | 0.6995 (4) | 0.0223 (9) | |
C6 | 0.3700 (5) | 0.0553 (2) | 0.7841 (4) | 0.0207 (9) | |
C7 | 0.2737 (5) | 0.0502 (2) | 0.9079 (5) | 0.0283 (10) | |
H7 | 0.2371 | 0.0954 | 0.9545 | 0.034* | |
C8 | 0.2331 (5) | −0.0194 (2) | 0.9605 (5) | 0.0303 (11) | |
H8 | 0.1663 | −0.0234 | 1.0432 | 0.036* | |
C9 | 0.2900 (5) | −0.0854 (2) | 0.8927 (5) | 0.0293 (10) | |
H9 | 0.2673 | −0.1346 | 0.9315 | 0.035* | |
C10 | 0.3784 (5) | −0.0773 (2) | 0.7701 (5) | 0.0247 (9) | |
H10 | 0.4184 | −0.1220 | 0.7244 | 0.030* | |
S1 | 0.15609 (16) | 0.10410 (7) | 0.31675 (16) | 0.0421 (3) | |
N4 | 0.3250 (5) | 0.2438 (2) | 0.4024 (5) | 0.0511 (11) | |
C11 | 0.2561 (6) | 0.1855 (3) | 0.3654 (5) | 0.0326 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.0234 (3) | 0.0179 (2) | 0.0213 (2) | −0.00227 (18) | 0.00572 (16) | −0.00236 (19) |
N1 | 0.0248 (19) | 0.0182 (18) | 0.0214 (18) | −0.0019 (13) | 0.0037 (14) | −0.0016 (14) |
N2 | 0.0285 (19) | 0.0178 (18) | 0.0275 (19) | 0.0043 (14) | 0.0099 (15) | −0.0034 (14) |
N3 | 0.0189 (17) | 0.0213 (18) | 0.0186 (16) | −0.0031 (13) | 0.0023 (13) | −0.0019 (14) |
C1 | 0.019 (2) | 0.025 (2) | 0.040 (3) | 0.0017 (17) | 0.0094 (18) | 0.0015 (19) |
C2 | 0.024 (2) | 0.040 (3) | 0.031 (2) | −0.0078 (19) | 0.0037 (19) | 0.003 (2) |
C3 | 0.038 (3) | 0.023 (2) | 0.034 (3) | −0.0071 (19) | −0.001 (2) | 0.0007 (19) |
C4 | 0.035 (3) | 0.019 (2) | 0.029 (2) | −0.0023 (17) | 0.0043 (19) | −0.0002 (18) |
C5 | 0.024 (2) | 0.021 (2) | 0.019 (2) | 0.0034 (16) | −0.0014 (16) | 0.0011 (17) |
C6 | 0.019 (2) | 0.024 (2) | 0.017 (2) | 0.0009 (16) | 0.0000 (16) | −0.0010 (17) |
C7 | 0.025 (2) | 0.034 (3) | 0.026 (2) | 0.0012 (18) | 0.0031 (18) | −0.0058 (19) |
C8 | 0.021 (2) | 0.049 (3) | 0.022 (2) | −0.0057 (18) | 0.0057 (17) | 0.0035 (19) |
C9 | 0.028 (2) | 0.030 (2) | 0.026 (2) | −0.0100 (18) | −0.0002 (18) | 0.0047 (19) |
C10 | 0.025 (2) | 0.024 (2) | 0.024 (2) | −0.0045 (17) | 0.0036 (18) | 0.0033 (18) |
S1 | 0.0391 (7) | 0.0371 (7) | 0.0512 (8) | 0.0015 (5) | 0.0122 (6) | −0.0057 (6) |
N4 | 0.053 (3) | 0.041 (3) | 0.060 (3) | −0.011 (2) | 0.013 (2) | 0.018 (2) |
C11 | 0.029 (3) | 0.039 (3) | 0.031 (3) | 0.008 (2) | 0.010 (2) | 0.013 (2) |
Pd1—N3 | 2.021 (3) | C3—C4 | 1.363 (5) |
Pd1—N3i | 2.021 (3) | C3—H3 | 0.9500 |
Pd1—N1 | 2.032 (3) | C4—C5 | 1.399 (5) |
Pd1—N1i | 2.032 (3) | C4—H4 | 0.9500 |
N1—C5 | 1.350 (5) | C6—C7 | 1.402 (5) |
N1—C1 | 1.354 (5) | C7—C8 | 1.355 (6) |
N2—C6 | 1.371 (5) | C7—H7 | 0.9500 |
N2—C5 | 1.382 (5) | C8—C9 | 1.396 (6) |
N2—H2N | 0.9200 | C8—H8 | 0.9500 |
N3—C6 | 1.342 (5) | C9—C10 | 1.356 (5) |
N3—C10 | 1.358 (5) | C9—H9 | 0.9500 |
C1—C2 | 1.364 (5) | C10—H10 | 0.9500 |
C1—H1 | 0.9500 | S1—C11 | 1.630 (5) |
C2—C3 | 1.387 (6) | N4—C11 | 1.161 (5) |
C2—H2 | 0.9500 | ||
N3—Pd1—N3i | 180.0 | C2—C3—H3 | 120.2 |
N3—Pd1—N1 | 86.18 (12) | C3—C4—C5 | 119.6 (4) |
N3i—Pd1—N1 | 93.82 (12) | C3—C4—H4 | 120.2 |
N3—Pd1—N1i | 93.82 (12) | C5—C4—H4 | 120.2 |
N3i—Pd1—N1i | 86.18 (12) | N1—C5—N2 | 119.9 (3) |
N1—Pd1—N1i | 180.00 (11) | N1—C5—C4 | 120.8 (4) |
C5—N1—C1 | 118.1 (3) | N2—C5—C4 | 119.2 (3) |
C5—N1—Pd1 | 119.9 (3) | N3—C6—N2 | 119.7 (3) |
C1—N1—Pd1 | 121.8 (3) | N3—C6—C7 | 120.6 (4) |
C6—N2—C5 | 125.0 (3) | N2—C6—C7 | 119.6 (4) |
C6—N2—H2N | 115.5 | C8—C7—C6 | 119.6 (4) |
C5—N2—H2N | 114.2 | C8—C7—H7 | 120.2 |
C6—N3—C10 | 118.6 (3) | C6—C7—H7 | 120.2 |
C6—N3—Pd1 | 120.3 (2) | C7—C8—C9 | 119.6 (4) |
C10—N3—Pd1 | 120.8 (3) | C7—C8—H8 | 120.2 |
N1—C1—C2 | 123.3 (4) | C9—C8—H8 | 120.2 |
N1—C1—H1 | 118.3 | C10—C9—C8 | 118.4 (4) |
C2—C1—H1 | 118.3 | C10—C9—H9 | 120.8 |
C1—C2—C3 | 118.2 (4) | C8—C9—H9 | 120.8 |
C1—C2—H2 | 120.9 | C9—C10—N3 | 122.7 (4) |
C3—C2—H2 | 120.9 | C9—C10—H10 | 118.6 |
C4—C3—C2 | 119.7 (4) | N3—C10—H10 | 118.6 |
C4—C3—H3 | 120.2 | N4—C11—S1 | 178.6 (4) |
N3—Pd1—N1—C5 | −41.3 (3) | C6—N2—C5—N1 | 38.3 (5) |
N3i—Pd1—N1—C5 | 138.7 (3) | C6—N2—C5—C4 | −139.6 (4) |
N3—Pd1—N1—C1 | 143.2 (3) | C3—C4—C5—N1 | −3.0 (6) |
N3i—Pd1—N1—C1 | −36.8 (3) | C3—C4—C5—N2 | 174.9 (3) |
N1—Pd1—N3—C6 | 44.1 (3) | C10—N3—C6—N2 | 170.2 (3) |
N1i—Pd1—N3—C6 | −135.9 (3) | Pd1—N3—C6—N2 | −16.2 (4) |
N1—Pd1—N3—C10 | −142.4 (3) | C10—N3—C6—C7 | −7.7 (5) |
N1i—Pd1—N3—C10 | 37.6 (3) | Pd1—N3—C6—C7 | 165.9 (3) |
C5—N1—C1—C2 | −3.3 (6) | C5—N2—C6—N3 | −35.6 (5) |
Pd1—N1—C1—C2 | 172.3 (3) | C5—N2—C6—C7 | 142.3 (4) |
N1—C1—C2—C3 | 0.0 (6) | N3—C6—C7—C8 | 4.4 (5) |
C1—C2—C3—C4 | 1.9 (6) | N2—C6—C7—C8 | −173.5 (3) |
C2—C3—C4—C5 | −0.4 (6) | C6—C7—C8—C9 | 1.0 (6) |
C1—N1—C5—N2 | −173.1 (3) | C7—C8—C9—C10 | −2.8 (6) |
Pd1—N1—C5—N2 | 11.2 (5) | C8—C9—C10—N3 | −0.6 (6) |
C1—N1—C5—C4 | 4.7 (5) | C6—N3—C10—C9 | 5.9 (5) |
Pd1—N1—C5—C4 | −170.9 (3) | Pd1—N3—C10—C9 | −167.7 (3) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···N4ii | 0.92 | 1.94 | 2.846 (5) | 170 |
Symmetry code: (ii) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Pd(C10H9N3)2](NCS)2 |
Mr | 564.96 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 200 |
a, b, c (Å) | 7.7353 (9), 17.478 (2), 8.3822 (10) |
β (°) | 102.137 (2) |
V (Å3) | 1107.9 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.06 |
Crystal size (mm) | 0.16 × 0.09 × 0.09 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.876, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6810, 2172, 1552 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.088, 1.07 |
No. of reflections | 2172 |
No. of parameters | 151 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.10, −0.61 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···N4i | 0.92 | 1.94 | 2.846 (5) | 169.8 |
Symmetry code: (i) x, −y+1/2, z+1/2. |
Acknowledgements
This work was supported by the Priority Research Centers Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2011–0030747).
References
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Crystal structures of the related cationic PdII and PtII complexes, such as [Pd(dpa)2](X)2 (dpa = di-2-pyridylamine, C10H9N3; X = Cl, PF6 or NO3) (Živković et al., 2007; Antonioli et al., 2008; Ha, 2012a) and [Pt(dpa)2]Br2.H2O (Ha, 2012b), have been investigated previously.
The asymmetric unit of the title compound, [Pd(dpa)2](SCN)2, contains one half of a cationic PdII complex and one SCN- anion (Fig. 1). In the complex, the PdII ion is four-coordinated in a distorted square-planar environment by the four pyridine N atoms derived from the two chelating dpa ligands. The PdII ion is located on an inversion centre, and thus the PdN4 unit is exactly planar. The dpa ligands display a boat conformation with a dihedral angle between the least-squares planes of the two pyridine rings of 43.0 (1)°. The nearly planar pyridine rings [maximum deviation = 0.039 (2) Å] are considerably inclined to the PdN4 unit, making dihedral angles of 40.1 (2)° and 42.5 (1)°. The two Pd—N bond lengths are nearly equivalent [Pd—N: 2.021 (3) and 2.032 (3) Å] (Table 1). The SCN- anion is almost linear (Table 1), and two anions are linked to the cationic complex by intermolecular N—H···N hydrogen bonds between the N atom of the anions and the N—H group of the cation (Fig. 2 and Table 2). The complex molecules are stacked into columns along the a axis. In the columns, several intermolecular π-π interactions between the pyridine rings are present, the shortest ring centroid-centroid distance being 3.436 (2) Å.