metal-organic compounds
(Nitrato-κO)(2,2′:6′,2′′-terpyridine-κ3N,N′,N′′)palladium(II) nitrate
aChonnam National University, School of Chemical Engineering, Research Institute of Catalysis, Gwangju, Republic of Korea
*Correspondence e-mail: hakwang@chonnam.ac.kr
The title complex, [Pd(NO3)(C15H11N3)]NO3, comprises a cationic PdII complex and a nitrate anion. In the complex, the PdII cation is four-coordinated in a distorted square-planar coordination geometry defined by the three N atoms of the tridentate 2,2′:6′,2′′-terpyridine ligand and one O atom from the NO3− anion. In the crystal, the complex molecules are stacked in columns along the a axis being connected by π–π stacking [closest inter-centroid separation between pyridyl rings = 3.878 (3) Å]. The connections between columns and anions to sustain a three-dimensional architecture are C—H⋯O hydrogen bonds.
Keywords: crystal structure; palladium(II) complex; square-planar structure; 2,2′:6′,2′′-terpyridine; tridentate ligand; nitrate salt.
CCDC reference: 2058389
Structure description
With reference to the title complex, [Pd(terpy)(NO3)](NO3) (terpy = 2,2′:6′,2"-terpyridine), the crystal structures of related PdII complexes [Pd(terpy)(pyridine)](ClO4)2 (Bugarčić et al., 2004), [Pd(terpy)(NO3)](NTf2) [NTf2 = bis(trifluoromethylsulfonyl)amide anion; Illner et al., 2009) and [Pd2(terpy)2(NO3)]2(PF6)6·CH3CN (Mei et al., 2007) have been determined previously.
The title complex comprises a cationic PdII complex [Pd(terpy)(NO3)]+ and an NO3− anion (Fig. 1). In the complex, the central PdII cation is four-coordinated in a distorted square-planar coordination geometry defined by the pyridyl N1, N2 and N3 atoms derived from the tridentate terpy ligand and the O1 atom from the nitrato ligand. The tight N—Pd—N chelating angles of <N1—Pd1—N2 = 81.26 (17)° and <N2—Pd1—N8 = 81.03 (16)° contribute to the distortion of the square-plane. The Pd—N [1.917 (4) to 2.030 (4) Å] and Pd—O [2.028 (3) Å] bond lengths are close. The pyridine rings of the terpy ligand are located approximately parallel to the least-squares plane of the PdN3O unit [maximum deviation = 0.023 (2) Å], with dihedral angles of 1.4 (2)° (ring N1/C1–C5), 3.1 (2)° (ring N2/C6–C10) and 3.0 (2)° (ring N3/C11–C15). In the crystal (Fig. 2), the complex molecules are stacked in columns along the a axis. Within the columns, numerous intermolecular π–π interactions between adjacent pyridine rings are present. For Cg1 (the centroid of ring N2/C6–C10) and Cg2i [the centroid of ring N3/C11–C15; symmetry code: (i) x + 1, y, z], the centroid-centroid distance is 3.878 (3) Å and the dihedral angle between the ring planes is 3.2 (3)° (Spek, 2020). The complex cations and anions form intermolecular C—H⋯O hydrogen bonds (Table 1) to stabilize the three-dimensional packing.
Synthesis and crystallization
To a solution of Pd(NO3)2·2H2O (0.1320 g, 0.495 mmol) in acetone (30 ml) was added 2,2′:6′,2"-terpyridine (0.1179 g, 0.505 mmol) followed by stirring for 3 h at room temperature. The formed precipitate was separated by filtration, washed with acetone and dried at 323 K to give a light-yellow powder (0.2123 g). Yellow crystals of the product suitable for X-ray analysis were obtained by slow evaporation of its CH3NO2 solution at room temperature.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2
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Structural data
CCDC reference: 2058389
https://doi.org/10.1107/S2414314621000857/tk4067sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314621000857/tk4067Isup2.hkl
Data collection: APEX2 (Bruker, 2016); cell
SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2014/7 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2014/7 (Sheldrick, 2015b).[Pd(C15H11N3)(NO3)]NO3 | Dx = 1.948 Mg m−3 |
Mr = 463.69 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pna21 | Cell parameters from 9942 reflections |
a = 6.2190 (2) Å | θ = 2.4–27.7° |
b = 33.9728 (15) Å | µ = 1.22 mm−1 |
c = 7.4819 (3) Å | T = 223 K |
V = 1580.75 (11) Å3 | Plate, yellow |
Z = 4 | 0.21 × 0.14 × 0.06 mm |
F(000) = 920 |
PHOTON 100 CMOS detector diffractometer | 2745 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.084 |
φ and ω scans | θmax = 26.1°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | h = −7→7 |
Tmin = 0.688, Tmax = 0.745 | k = −41→42 |
41749 measured reflections | l = −9→9 |
3116 independent reflections |
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)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.048 | w = 1/[σ2(Fo2) + (0.0152P)2 + 0.8349P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
3116 reflections | Δρmax = 0.34 e Å−3 |
244 parameters | Δρmin = −0.43 e Å−3 |
1 restraint | Absolute structure: Flack x determined using 1141 quotients [(I+)-(I-)]/[(I+)+(I-)] Parsons et al. (2013). |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.006 (16) |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Hydrogen atoms on C atoms were positioned geometrically and allowed to ride on their respective parent atoms: C—H = 0.94 Å and Uiso(H) = 1.2Ueq(C). The Flack parameter = 0.006 (16) after the final cycles of refinement. |
x | y | z | Uiso*/Ueq | ||
Pd1 | 0.22807 (4) | 0.15784 (2) | 0.48682 (9) | 0.02233 (10) | |
O1 | 0.1702 (6) | 0.21529 (10) | 0.4313 (4) | 0.0343 (10) | |
O2 | 0.2291 (7) | 0.19950 (12) | 0.1521 (6) | 0.0463 (10) | |
O3 | 0.1758 (7) | 0.26017 (11) | 0.2256 (6) | 0.0540 (13) | |
N1 | 0.4977 (6) | 0.16769 (12) | 0.6321 (6) | 0.0261 (10) | |
N2 | 0.2920 (6) | 0.10452 (11) | 0.5520 (5) | 0.0220 (9) | |
N3 | −0.0259 (6) | 0.13077 (12) | 0.3685 (5) | 0.0214 (9) | |
N4 | 0.1927 (7) | 0.22538 (14) | 0.2626 (7) | 0.0364 (12) | |
C1 | 0.5913 (9) | 0.20210 (16) | 0.6668 (8) | 0.0344 (13) | |
H1 | 0.5322 | 0.2252 | 0.6180 | 0.041* | |
C2 | 0.7726 (9) | 0.2048 (2) | 0.7722 (8) | 0.0450 (16) | |
H2 | 0.8307 | 0.2295 | 0.8015 | 0.054* | |
C3 | 0.8672 (9) | 0.17072 (19) | 0.8340 (8) | 0.0415 (15) | |
H3 | 0.9939 | 0.1719 | 0.9023 | 0.050* | |
C4 | 0.7740 (9) | 0.13467 (19) | 0.7944 (8) | 0.0323 (13) | |
H4 | 0.8378 | 0.1112 | 0.8343 | 0.039* | |
C5 | 0.5864 (9) | 0.13370 (17) | 0.6959 (7) | 0.0232 (12) | |
C6 | 0.4710 (8) | 0.09759 (15) | 0.6481 (6) | 0.0232 (11) | |
C7 | 0.5267 (8) | 0.05923 (15) | 0.6877 (7) | 0.0293 (13) | |
H7 | 0.6493 | 0.0536 | 0.7566 | 0.035* | |
C8 | 0.3979 (8) | 0.02930 (15) | 0.6235 (7) | 0.0308 (13) | |
H8 | 0.4354 | 0.0031 | 0.6481 | 0.037* | |
C9 | 0.2163 (7) | 0.03682 (14) | 0.5247 (7) | 0.0282 (16) | |
H9 | 0.1295 | 0.0161 | 0.4828 | 0.034* | |
C10 | 0.1642 (6) | 0.07567 (11) | 0.4881 (12) | 0.0219 (8) | |
C11 | −0.0190 (8) | 0.09089 (14) | 0.3876 (7) | 0.0222 (11) | |
C12 | −0.1803 (8) | 0.06726 (16) | 0.3173 (7) | 0.0285 (12) | |
H12 | −0.1745 | 0.0398 | 0.3300 | 0.034* | |
C13 | −0.3493 (8) | 0.08484 (17) | 0.2285 (7) | 0.0302 (13) | |
H13 | −0.4597 | 0.0694 | 0.1793 | 0.036* | |
C14 | −0.3552 (9) | 0.12527 (18) | 0.2122 (8) | 0.0266 (14) | |
H14 | −0.4706 | 0.1376 | 0.1535 | 0.032* | |
C15 | −0.1895 (8) | 0.14736 (16) | 0.2831 (8) | 0.0269 (12) | |
H15 | −0.1927 | 0.1749 | 0.2705 | 0.032* | |
O4 | 0.1900 (5) | 0.09192 (10) | 1.0047 (10) | 0.0396 (10) | |
O5 | 0.2336 (6) | 0.03043 (12) | 1.0689 (6) | 0.0505 (11) | |
O6 | −0.0235 (6) | 0.04770 (11) | 0.8974 (5) | 0.0425 (10) | |
N5 | 0.1345 (5) | 0.05686 (11) | 0.9909 (9) | 0.0287 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.02599 (16) | 0.01582 (15) | 0.02517 (16) | 0.00131 (14) | −0.0033 (4) | −0.0007 (3) |
O1 | 0.049 (2) | 0.0166 (18) | 0.037 (3) | 0.0048 (15) | −0.0099 (16) | 0.0013 (15) |
O2 | 0.064 (3) | 0.036 (2) | 0.040 (2) | −0.010 (2) | −0.010 (2) | 0.000 (2) |
O3 | 0.059 (3) | 0.020 (2) | 0.083 (3) | −0.003 (2) | −0.020 (2) | 0.021 (2) |
N1 | 0.030 (2) | 0.025 (3) | 0.023 (2) | −0.0059 (18) | −0.0040 (19) | −0.0003 (19) |
N2 | 0.0229 (19) | 0.019 (2) | 0.024 (2) | 0.0028 (17) | 0.0051 (17) | 0.0003 (16) |
N3 | 0.025 (2) | 0.019 (2) | 0.020 (2) | −0.0004 (17) | 0.0018 (18) | −0.0021 (19) |
N4 | 0.030 (2) | 0.026 (3) | 0.054 (3) | −0.007 (2) | −0.016 (2) | 0.011 (3) |
C1 | 0.042 (3) | 0.024 (3) | 0.037 (3) | −0.002 (3) | −0.004 (3) | 0.000 (3) |
C2 | 0.051 (4) | 0.047 (4) | 0.038 (3) | −0.021 (3) | −0.008 (3) | −0.002 (3) |
C3 | 0.035 (3) | 0.063 (4) | 0.027 (3) | −0.014 (3) | −0.009 (3) | 0.003 (3) |
C4 | 0.029 (3) | 0.044 (4) | 0.025 (3) | 0.003 (3) | 0.001 (3) | 0.006 (3) |
C5 | 0.026 (3) | 0.026 (3) | 0.018 (3) | 0.000 (2) | 0.000 (2) | 0.003 (2) |
C6 | 0.025 (3) | 0.027 (3) | 0.018 (3) | 0.003 (2) | 0.003 (2) | 0.005 (2) |
C7 | 0.027 (3) | 0.029 (3) | 0.031 (3) | 0.003 (2) | 0.002 (2) | 0.009 (3) |
C8 | 0.034 (3) | 0.020 (3) | 0.039 (3) | 0.008 (2) | 0.007 (3) | 0.012 (2) |
C9 | 0.029 (2) | 0.019 (2) | 0.037 (5) | −0.0034 (19) | 0.008 (2) | 0.000 (2) |
C10 | 0.0234 (19) | 0.018 (2) | 0.024 (2) | 0.0004 (15) | 0.000 (5) | −0.001 (4) |
C11 | 0.026 (3) | 0.018 (3) | 0.022 (3) | 0.002 (2) | 0.006 (2) | 0.000 (2) |
C12 | 0.028 (3) | 0.024 (3) | 0.033 (3) | −0.006 (2) | 0.007 (2) | −0.004 (2) |
C13 | 0.024 (3) | 0.037 (4) | 0.030 (3) | −0.004 (2) | 0.003 (2) | −0.009 (3) |
C14 | 0.021 (3) | 0.034 (4) | 0.024 (4) | 0.006 (3) | 0.004 (3) | 0.001 (3) |
C15 | 0.029 (3) | 0.024 (3) | 0.027 (3) | 0.007 (2) | 0.003 (3) | −0.002 (2) |
O4 | 0.0415 (17) | 0.0291 (18) | 0.048 (3) | −0.0045 (14) | −0.002 (3) | −0.003 (3) |
O5 | 0.041 (2) | 0.042 (3) | 0.068 (3) | 0.011 (2) | −0.020 (2) | 0.013 (2) |
O6 | 0.039 (2) | 0.039 (2) | 0.050 (2) | −0.0026 (18) | −0.0192 (19) | 0.002 (2) |
N5 | 0.0249 (17) | 0.035 (2) | 0.027 (2) | 0.0011 (16) | 0.004 (4) | −0.007 (4) |
Pd1—N2 | 1.917 (4) | C5—C6 | 1.466 (8) |
Pd1—N1 | 2.026 (4) | C6—C7 | 1.381 (7) |
Pd1—O1 | 2.028 (3) | C7—C8 | 1.380 (7) |
Pd1—N3 | 2.030 (4) | C7—H7 | 0.9400 |
O1—N4 | 1.315 (6) | C8—C9 | 1.374 (7) |
O2—N4 | 1.228 (6) | C8—H8 | 0.9400 |
O3—N4 | 1.218 (6) | C9—C10 | 1.386 (6) |
N1—C1 | 1.332 (6) | C9—H9 | 0.9400 |
N1—C5 | 1.366 (7) | C10—C11 | 1.460 (7) |
N2—C6 | 1.346 (6) | C11—C12 | 1.388 (7) |
N2—C10 | 1.349 (6) | C12—C13 | 1.379 (7) |
N3—C15 | 1.328 (6) | C12—H12 | 0.9400 |
N3—C11 | 1.363 (6) | C13—C14 | 1.379 (8) |
C1—C2 | 1.379 (7) | C13—H13 | 0.9400 |
C1—H1 | 0.9400 | C14—C15 | 1.381 (8) |
C2—C3 | 1.379 (9) | C14—H14 | 0.9400 |
C2—H2 | 0.9400 | C15—H15 | 0.9400 |
C3—C4 | 1.387 (8) | O4—N5 | 1.245 (5) |
C3—H3 | 0.9400 | O5—N5 | 1.236 (6) |
C4—C5 | 1.380 (7) | O6—N5 | 1.245 (5) |
C4—H4 | 0.9400 | ||
N2—Pd1—N1 | 81.26 (17) | N2—C6—C7 | 119.1 (5) |
N2—Pd1—O1 | 176.54 (15) | N2—C6—C5 | 112.9 (4) |
N1—Pd1—O1 | 95.62 (15) | C7—C6—C5 | 128.0 (5) |
N2—Pd1—N3 | 81.03 (16) | C8—C7—C6 | 118.4 (5) |
N1—Pd1—N3 | 162.23 (16) | C8—C7—H7 | 120.8 |
O1—Pd1—N3 | 102.04 (15) | C6—C7—H7 | 120.8 |
N4—O1—Pd1 | 115.4 (3) | C9—C8—C7 | 121.8 (5) |
C1—N1—C5 | 119.8 (5) | C9—C8—H8 | 119.1 |
C1—N1—Pd1 | 127.7 (4) | C7—C8—H8 | 119.1 |
C5—N1—Pd1 | 112.5 (4) | C8—C9—C10 | 118.4 (5) |
C6—N2—C10 | 123.3 (4) | C8—C9—H9 | 120.8 |
C6—N2—Pd1 | 118.2 (3) | C10—C9—H9 | 120.8 |
C10—N2—Pd1 | 118.3 (3) | N2—C10—C9 | 118.9 (5) |
C15—N3—C11 | 119.8 (4) | N2—C10—C11 | 112.6 (4) |
C15—N3—Pd1 | 127.9 (3) | C9—C10—C11 | 128.4 (4) |
C11—N3—Pd1 | 112.4 (3) | N3—C11—C12 | 120.8 (5) |
O3—N4—O2 | 123.9 (5) | N3—C11—C10 | 115.5 (4) |
O3—N4—O1 | 117.5 (5) | C12—C11—C10 | 123.7 (4) |
O2—N4—O1 | 118.6 (4) | C13—C12—C11 | 118.9 (5) |
N1—C1—C2 | 121.9 (6) | C13—C12—H12 | 120.6 |
N1—C1—H1 | 119.1 | C11—C12—H12 | 120.6 |
C2—C1—H1 | 119.1 | C12—C13—C14 | 119.6 (5) |
C1—C2—C3 | 118.9 (6) | C12—C13—H13 | 120.2 |
C1—C2—H2 | 120.5 | C14—C13—H13 | 120.2 |
C3—C2—H2 | 120.5 | C13—C14—C15 | 119.1 (5) |
C2—C3—C4 | 119.5 (5) | C13—C14—H14 | 120.4 |
C2—C3—H3 | 120.3 | C15—C14—H14 | 120.4 |
C4—C3—H3 | 120.3 | N3—C15—C14 | 121.8 (5) |
C5—C4—C3 | 119.2 (6) | N3—C15—H15 | 119.1 |
C5—C4—H4 | 120.4 | C14—C15—H15 | 119.1 |
C3—C4—H4 | 120.4 | O5—N5—O4 | 121.2 (5) |
N1—C5—C4 | 120.5 (5) | O5—N5—O6 | 118.5 (4) |
N1—C5—C6 | 115.1 (5) | O4—N5—O6 | 120.3 (5) |
C4—C5—C6 | 124.3 (5) | ||
Pd1—O1—N4—O3 | −174.4 (3) | C6—C7—C8—C9 | −0.9 (8) |
Pd1—O1—N4—O2 | 5.6 (6) | C7—C8—C9—C10 | 0.6 (8) |
C5—N1—C1—C2 | −2.6 (8) | C6—N2—C10—C9 | 1.0 (9) |
Pd1—N1—C1—C2 | 178.2 (4) | Pd1—N2—C10—C9 | 175.9 (5) |
N1—C1—C2—C3 | 4.2 (9) | C6—N2—C10—C11 | −179.7 (4) |
C1—C2—C3—C4 | −2.4 (9) | Pd1—N2—C10—C11 | −4.8 (7) |
C2—C3—C4—C5 | −0.9 (8) | C8—C9—C10—N2 | −0.6 (9) |
C1—N1—C5—C4 | −0.8 (8) | C8—C9—C10—C11 | −179.7 (6) |
Pd1—N1—C5—C4 | 178.5 (4) | C15—N3—C11—C12 | 0.5 (7) |
C1—N1—C5—C6 | −179.4 (5) | Pd1—N3—C11—C12 | 179.3 (4) |
Pd1—N1—C5—C6 | −0.2 (5) | C15—N3—C11—C10 | −178.3 (5) |
C3—C4—C5—N1 | 2.5 (8) | Pd1—N3—C11—C10 | 0.5 (6) |
C3—C4—C5—C6 | −179.0 (5) | N2—C10—C11—N3 | 2.6 (8) |
C10—N2—C6—C7 | −1.4 (8) | C9—C10—C11—N3 | −178.2 (6) |
Pd1—N2—C6—C7 | −176.3 (4) | N2—C10—C11—C12 | −176.1 (5) |
C10—N2—C6—C5 | 177.7 (5) | C9—C10—C11—C12 | 3.0 (11) |
Pd1—N2—C6—C5 | 2.8 (5) | N3—C11—C12—C13 | −0.4 (8) |
N1—C5—C6—N2 | −1.6 (6) | C10—C11—C12—C13 | 178.3 (5) |
C4—C5—C6—N2 | 179.8 (5) | C11—C12—C13—C14 | −0.3 (8) |
N1—C5—C6—C7 | 177.4 (5) | C12—C13—C14—C15 | 1.0 (8) |
C4—C5—C6—C7 | −1.2 (8) | C11—N3—C15—C14 | 0.1 (8) |
N2—C6—C7—C8 | 1.3 (7) | Pd1—N3—C15—C14 | −178.4 (4) |
C5—C6—C7—C8 | −177.7 (5) | C13—C14—C15—N3 | −0.9 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O2i | 0.94 | 2.55 | 3.419 (7) | 153 |
C4—H4···O6ii | 0.94 | 2.37 | 3.303 (7) | 172 |
C7—H7···O6ii | 0.94 | 2.30 | 3.231 (6) | 171 |
C8—H8···O5iii | 0.94 | 2.43 | 3.088 (6) | 127 |
C9—H9···O6iv | 0.94 | 2.35 | 3.254 (6) | 160 |
C13—H13···O5v | 0.94 | 2.46 | 3.402 (7) | 176 |
C15—H15···O3vi | 0.94 | 2.38 | 3.280 (7) | 161 |
Symmetry codes: (i) x+1, y, z+1; (ii) x+1, y, z; (iii) −x+1, −y, z−1/2; (iv) −x, −y, z−1/2; (v) x−1, y, z−1; (vi) x−1/2, −y+1/2, z. |
Acknowledgements
The author thanks the KBSI, Seoul Center, for the X-ray data collection.
Funding information
This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (grant No. 2018R1D1A1B07050550).
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