Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104002690/fg1730sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104002690/fg1730Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104002690/fg1730IIsup3.hkl |
CCDC references: 237906; 237907
For the preparation of (I), bpy was reacted with palladium acetate (Pd(CH3COOH)2) for 30 min at room temperature (molar ratio 2:3) in dimethylformamide (DMF), and then nad (equivalent to bpy) dissolved to DMF was added. This mixture was left to stand at room temperature, and red prismatic crystals appeared after a few days. Complex (II) was synthesized by a similar method, except that biq was used instead of bpy. Colorless prismatic crystals appeared after a few days.
For (I) and (II), all H atoms were located from difference Fourier maps and then placed at idealized positions and treated as riding, with C—H distances of 0.93 Å and Uiso(H) values equal to 1.2Ueq(C).
For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992); cell refinement: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992); data reduction: TEXSAN (Molecular Structure Corporation, 2000). Program(s) used to solve structure: SIR97 (Altomare et al., 1999) for (I); SHELXS97 (Scheldrick, 1997) for (II). For both compounds, program(s) used to refine structure: SHELXL97 (Scheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN (Molecular Structure Corporation, 2000).
[Pd(C10H6O2)(C10H8N2)] | F(000) = 840.0 |
Mr = 420.75 | Dx = 1.754 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 12.117 (2) Å | θ = 14.8–15.0° |
b = 8.239 (2) Å | µ = 1.18 mm−1 |
c = 16.857 (1) Å | T = 296 K |
β = 108.804 (8)° | Plate, red |
V = 1593.1 (5) Å3 | 0.50 × 0.20 × 0.20 mm |
Z = 4 |
Rigaku AFC-5R diffractometer | Rint = 0.014 |
ω–2θ scans | θmax = 27.5° |
Absorption correction: ψ scan (North, Phillips & Mathews, 1968) | h = 0→15 |
Tmin = 0.936, Tmax = 1.000 | k = 0→10 |
4095 measured reflections | l = −21→20 |
3658 independent reflections | 3 standard reflections every 150 reflections |
3090 reflections with I > 2σ(I) | intensity decay: 1.1% |
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.027 | w = 1/[σ2(Fo2) + (0.0381P)2 + 0.8904P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.078 | (Δ/σ)max = 0.001 |
S = 1.14 | Δρmax = 0.38 e Å−3 |
3658 reflections | Δρmin = −0.88 e Å−3 |
226 parameters |
[Pd(C10H6O2)(C10H8N2)] | V = 1593.1 (5) Å3 |
Mr = 420.75 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.117 (2) Å | µ = 1.18 mm−1 |
b = 8.239 (2) Å | T = 296 K |
c = 16.857 (1) Å | 0.50 × 0.20 × 0.20 mm |
β = 108.804 (8)° |
Rigaku AFC-5R diffractometer | 3090 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North, Phillips & Mathews, 1968) | Rint = 0.014 |
Tmin = 0.936, Tmax = 1.000 | 3 standard reflections every 150 reflections |
4095 measured reflections | intensity decay: 1.1% |
3658 independent reflections |
R[F2 > 2σ(F2)] = 0.027 | 226 parameters |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 1.14 | Δρmax = 0.38 e Å−3 |
3658 reflections | Δρmin = −0.88 e Å−3 |
Refinement. Refinement using reflections with F2 > −10.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
Pd1 | 0.49700 (2) | 0.23263 (2) | 0.47388 (1) | 0.03169 (8) | |
O1 | 0.6355 (2) | 0.3261 (3) | 0.4527 (1) | 0.0409 (4) | |
O2 | 0.5596 (2) | 0.3391 (3) | 0.5850 (1) | 0.0391 (4) | |
N1 | 0.4318 (2) | 0.1172 (3) | 0.3641 (1) | 0.0351 (5) | |
N2 | 0.3573 (2) | 0.1303 (3) | 0.4920 (1) | 0.0344 (5) | |
C2 | 0.3331 (2) | 0.0323 (3) | 0.3547 (2) | 0.0353 (5) | |
C3 | 0.2787 (3) | −0.0528 (4) | 0.2817 (2) | 0.0467 (7) | |
C4 | 0.3268 (3) | −0.0503 (4) | 0.2181 (2) | 0.0507 (8) | |
C5 | 0.4275 (3) | 0.0360 (4) | 0.2277 (2) | 0.0479 (7) | |
C6 | 0.4779 (3) | 0.1182 (4) | 0.3014 (2) | 0.0429 (6) | |
C12 | 0.2903 (2) | 0.0389 (3) | 0.4273 (2) | 0.0340 (5) | |
C13 | 0.1932 (3) | −0.0426 (4) | 0.4322 (2) | 0.0433 (6) | |
C14 | 0.1648 (3) | −0.0308 (4) | 0.5051 (2) | 0.0523 (8) | |
C15 | 0.2331 (3) | 0.0630 (5) | 0.5700 (2) | 0.0551 (8) | |
C16 | 0.3275 (3) | 0.1433 (4) | 0.5613 (2) | 0.0450 (7) | |
C17 | 0.6984 (2) | 0.4126 (3) | 0.5193 (2) | 0.0349 (5) | |
C18 | 0.7994 (3) | 0.4910 (4) | 0.5224 (2) | 0.0402 (6) | |
C19 | 0.8626 (2) | 0.5844 (3) | 0.5929 (2) | 0.0371 (6) | |
C20 | 0.9663 (3) | 0.6695 (4) | 0.5973 (2) | 0.0474 (7) | |
C21 | 1.0233 (3) | 0.7637 (4) | 0.6644 (2) | 0.0539 (8) | |
C22 | 0.9800 (3) | 0.7778 (4) | 0.7318 (2) | 0.0543 (8) | |
C23 | 0.8817 (3) | 0.6956 (4) | 0.7306 (2) | 0.0471 (7) | |
C24 | 0.8200 (2) | 0.5964 (3) | 0.6621 (2) | 0.0356 (6) | |
C25 | 0.7176 (3) | 0.5108 (3) | 0.6589 (2) | 0.0381 (6) | |
C26 | 0.6565 (2) | 0.4206 (3) | 0.5903 (2) | 0.0339 (5) | |
H3 | 0.2106 | −0.1108 | 0.2757 | 0.0560* | |
H4 | 0.2914 | −0.1069 | 0.1687 | 0.0608* | |
H5 | 0.4608 | 0.0388 | 0.1851 | 0.0575* | |
H6 | 0.5461 | 0.1764 | 0.3083 | 0.0515* | |
H13 | 0.1479 | −0.1044 | 0.3875 | 0.0520* | |
H14 | 0.1004 | −0.0855 | 0.5102 | 0.0627* | |
H15 | 0.2152 | 0.0718 | 0.6195 | 0.0661* | |
H16 | 0.3721 | 0.2085 | 0.6050 | 0.0539* | |
H18 | 0.8271 | 0.4828 | 0.4772 | 0.0483* | |
H20 | 0.9962 | 0.6605 | 0.5531 | 0.0568* | |
H21 | 1.0908 | 0.8186 | 0.6654 | 0.0647* | |
H22 | 1.0183 | 0.8432 | 0.7774 | 0.0651* | |
H23 | 0.8544 | 0.7051 | 0.7760 | 0.0566* | |
H25 | 0.6907 | 0.5159 | 0.7047 | 0.0457* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.0341 (1) | 0.0339 (1) | 0.0272 (1) | 0.00362 (8) | 0.01012 (8) | 0.00112 (7) |
O1 | 0.043 (1) | 0.047 (1) | 0.036 (1) | −0.0028 (9) | 0.0176 (9) | −0.0045 (9) |
O2 | 0.036 (1) | 0.047 (1) | 0.037 (1) | −0.0050 (9) | 0.0143 (8) | −0.0032 (9) |
N1 | 0.040 (1) | 0.036 (1) | 0.031 (1) | 0.005 (1) | 0.0129 (9) | 0.0030 (9) |
N2 | 0.038 (1) | 0.034 (1) | 0.032 (1) | 0.0074 (9) | 0.0126 (9) | 0.0026 (9) |
C2 | 0.038 (1) | 0.037 (1) | 0.031 (1) | 0.007 (1) | 0.012 (1) | 0.003 (1) |
C3 | 0.046 (2) | 0.054 (2) | 0.038 (2) | −0.003 (1) | 0.011 (1) | −0.008 (1) |
C4 | 0.058 (2) | 0.061 (2) | 0.031 (1) | 0.008 (2) | 0.011 (1) | −0.008 (1) |
C5 | 0.059 (2) | 0.055 (2) | 0.034 (1) | 0.012 (2) | 0.022 (1) | 0.003 (1) |
C6 | 0.048 (2) | 0.045 (2) | 0.042 (2) | 0.003 (1) | 0.023 (1) | 0.004 (1) |
C12 | 0.036 (1) | 0.035 (1) | 0.032 (1) | 0.007 (1) | 0.011 (1) | 0.004 (1) |
C13 | 0.040 (2) | 0.044 (2) | 0.047 (2) | 0.000 (1) | 0.016 (1) | 0.001 (1) |
C14 | 0.047 (2) | 0.057 (2) | 0.060 (2) | −0.002 (1) | 0.029 (2) | 0.006 (2) |
C15 | 0.064 (2) | 0.069 (2) | 0.043 (2) | 0.005 (2) | 0.033 (2) | 0.003 (2) |
C16 | 0.053 (2) | 0.052 (2) | 0.033 (1) | 0.005 (1) | 0.017 (1) | −0.003 (1) |
C17 | 0.037 (1) | 0.034 (1) | 0.034 (1) | 0.007 (1) | 0.012 (1) | 0.003 (1) |
C18 | 0.041 (2) | 0.042 (2) | 0.042 (1) | 0.005 (1) | 0.020 (1) | 0.003 (1) |
C19 | 0.033 (1) | 0.035 (1) | 0.042 (1) | 0.006 (1) | 0.011 (1) | 0.007 (1) |
C20 | 0.036 (1) | 0.049 (2) | 0.056 (2) | 0.002 (1) | 0.013 (1) | 0.009 (1) |
C21 | 0.039 (2) | 0.052 (2) | 0.062 (2) | −0.005 (1) | 0.005 (2) | 0.011 (2) |
C22 | 0.050 (2) | 0.050 (2) | 0.049 (2) | −0.007 (1) | −0.002 (2) | 0.001 (1) |
C23 | 0.051 (2) | 0.048 (2) | 0.036 (1) | 0.000 (1) | 0.006 (1) | 0.001 (1) |
C24 | 0.036 (1) | 0.032 (1) | 0.035 (1) | 0.004 (1) | 0.005 (1) | 0.005 (1) |
C25 | 0.043 (1) | 0.042 (1) | 0.031 (1) | 0.002 (1) | 0.013 (1) | 0.001 (1) |
C26 | 0.034 (1) | 0.033 (1) | 0.035 (1) | 0.006 (1) | 0.012 (1) | 0.004 (1) |
Pd1—O1 | 1.981 (3) | C14—C15 | 1.377 (4) |
Pd1—O2 | 1.984 (2) | C14—H14 | 0.93 |
Pd1—N1 | 2.003 (2) | C15—C16 | 1.370 (6) |
Pd1—N2 | 2.001 (3) | C15—H15 | 0.93 |
O1—C17 | 1.341 (3) | C16—H16 | 0.93 |
O2—C26 | 1.330 (4) | C17—C18 | 1.370 (4) |
N1—C2 | 1.350 (4) | C17—C26 | 1.444 (5) |
N1—C6 | 1.345 (4) | C18—C19 | 1.416 (4) |
N2—C12 | 1.358 (3) | C18—H18 | 0.93 |
N2—C16 | 1.334 (4) | C19—C20 | 1.420 (4) |
C2—C3 | 1.385 (4) | C19—C24 | 1.423 (5) |
C2—C12 | 1.476 (5) | C20—C21 | 1.362 (4) |
C3—C4 | 1.376 (6) | C20—H20 | 0.93 |
C3—H3 | 0.93 | C21—C22 | 1.401 (6) |
C4—C5 | 1.376 (5) | C21—H21 | 0.93 |
C4—H4 | 0.93 | C22—C23 | 1.365 (5) |
C5—C6 | 1.373 (4) | C22—H22 | 0.93 |
C5—H5 | 0.93 | C23—C24 | 1.416 (4) |
C6—H6 | 0.93 | C23—H23 | 0.93 |
C12—C13 | 1.380 (5) | C24—C25 | 1.413 (4) |
C13—C14 | 1.382 (5) | C25—C26 | 1.373 (4) |
C13—H13 | 0.93 | C25—H25 | 0.93 |
Pd1···C26i | 3.391 (2) | N2···C19i | 3.495 (3) |
Pd1···C12ii | 3.414 (2) | N2···C24i | 3.583 (3) |
Pd1···N2ii | 3.425 (2) | C2···C23i | 3.385 (4) |
Pd1···C25i | 3.534 (3) | C2···C24i | 3.541 (4) |
O1···C4iii | 3.222 (4) | C3···C23i | 3.496 (5) |
O1···C13ii | 3.306 (4) | C3···C21v | 3.544 (4) |
O1···C14ii | 3.342 (4) | C6···C16ii | 3.470 (4) |
O1···C5iii | 3.365 (4) | C12···C24i | 3.433 (4) |
O1···O2i | 3.554 (3) | C12···C23i | 3.555 (4) |
O1···C12ii | 3.574 (4) | C12···C19i | 3.574 (4) |
O2···C2ii | 3.352 (3) | C13···C17ii | 3.316 (4) |
O2···C3ii | 3.408 (4) | C13···C21i | 3.473 (4) |
O2···C5iv | 3.448 (5) | C13···C20i | 3.579 (5) |
N1···C16ii | 3.511 (4) | C14···C20i | 3.549 (4) |
N1···C25i | 3.517 (4) | C16···C18i | 3.469 (4) |
N1···N2ii | 3.546 (3) | ||
O1—Pd1—O2 | 84.84 (9) | C15—C14—H14 | 120.4 |
O1—Pd1—N1 | 97.06 (9) | C14—C15—C16 | 119.7 (3) |
O1—Pd1—N2 | 177.54 (9) | C14—C15—H15 | 120.2 |
O2—Pd1—N1 | 177.58 (10) | C16—C15—H15 | 120.2 |
O2—Pd1—N2 | 97.29 (9) | N2—C16—C15 | 121.8 (3) |
N1—Pd1—N2 | 80.78 (9) | N2—C16—H16 | 119.2 |
Pd1—O1—C17 | 110.0 (2) | C15—C16—H16 | 119.1 |
Pd1—O2—C26 | 110.3 (2) | O1—C17—C18 | 122.8 (3) |
Pd1—N1—C2 | 115.2 (2) | O1—C17—C26 | 117.5 (2) |
Pd1—N1—C6 | 125.7 (2) | C18—C17—C26 | 119.7 (3) |
C2—N1—C6 | 119.2 (2) | C17—C18—C19 | 121.5 (3) |
Pd1—N2—C12 | 115.3 (2) | C17—C18—H18 | 119.3 |
Pd1—N2—C16 | 125.5 (2) | C19—C18—H18 | 119.2 |
C12—N2—C16 | 119.2 (3) | C18—C19—C20 | 122.8 (3) |
N1—C2—C3 | 121.1 (3) | C18—C19—C24 | 119.0 (3) |
N1—C2—C12 | 114.7 (2) | C20—C19—C24 | 118.1 (3) |
C3—C2—C12 | 124.2 (3) | C19—C20—C21 | 121.9 (4) |
C2—C3—C4 | 119.0 (3) | C19—C20—H20 | 119.0 |
C2—C3—H3 | 120.5 | C21—C20—H20 | 119.1 |
C4—C3—H3 | 120.4 | C20—C21—C22 | 119.9 (3) |
C3—C4—C5 | 119.9 (3) | C20—C21—H21 | 120.0 |
C3—C4—H4 | 120.1 | C22—C21—H21 | 120.1 |
C5—C4—H4 | 120.0 | C21—C22—C23 | 120.0 (3) |
C4—C5—C6 | 118.7 (4) | C21—C22—H22 | 120.0 |
C4—C5—H5 | 120.7 | C23—C22—H22 | 120.0 |
C6—C5—H5 | 120.6 | C22—C23—C24 | 121.8 (3) |
N1—C6—C5 | 122.1 (3) | C22—C23—H23 | 119.1 |
N1—C6—H6 | 118.8 | C24—C23—H23 | 119.0 |
C5—C6—H6 | 119.1 | C19—C24—C23 | 118.2 (3) |
N2—C12—C2 | 114.0 (2) | C19—C24—C25 | 118.7 (3) |
N2—C12—C13 | 121.5 (3) | C23—C24—C25 | 123.1 (3) |
C2—C12—C13 | 124.5 (3) | C24—C25—C26 | 122.1 (3) |
C12—C13—C14 | 118.7 (3) | C24—C25—H25 | 118.9 |
C12—C13—H13 | 120.7 | C26—C25—H25 | 119.0 |
C14—C13—H13 | 120.6 | O2—C26—C17 | 117.4 (2) |
C13—C14—C15 | 119.2 (3) | O2—C26—C25 | 123.7 (3) |
C13—C14—H14 | 120.4 | C17—C26—C25 | 119.0 (3) |
Pd1—O1—C17—C18 | 179.8 (2) | N2—C16—C15—C14 | −1.6 (5) |
Pd1—O1—C17—C26 | 0.3 (3) | C2—N1—C6—C5 | 0.3 (4) |
Pd1—O2—C26—C17 | −2.0 (3) | C2—C3—C4—C5 | 0.0 (5) |
Pd1—O2—C26—C25 | 177.9 (2) | C2—C12—N2—C16 | −179.3 (2) |
Pd1—N1—C2—C3 | 179.8 (2) | C2—C12—C13—C14 | 177.7 (3) |
Pd1—N1—C2—C12 | −0.1 (3) | C3—C2—N1—C6 | −0.2 (4) |
Pd1—N1—C6—C5 | −179.8 (2) | C3—C2—C12—C13 | 2.0 (4) |
Pd1—N2—C12—C2 | −0.2 (3) | C3—C4—C5—C6 | 0.0 (5) |
Pd1—N2—C12—C13 | 178.1 (2) | C4—C3—C2—C12 | −179.9 (3) |
Pd1—N2—C16—C15 | −176.9 (3) | C6—N1—C2—C12 | 179.8 (2) |
O1—Pd1—O2—C26 | 1.7 (2) | C12—N2—C16—C15 | 2.0 (4) |
O1—Pd1—N1—C2 | 178.8 (2) | C12—C13—C14—C15 | 0.8 (5) |
O1—Pd1—N1—C6 | −1.1 (3) | C13—C12—N2—C16 | −1.0 (4) |
O1—C17—C18—C19 | 178.6 (3) | C13—C14—C15—C16 | 0.2 (5) |
O1—C17—C26—O2 | 1.2 (3) | C17—C18—C19—C20 | −178.8 (3) |
O1—C17—C26—C25 | −178.7 (2) | C17—C18—C19—C24 | 0.2 (4) |
O2—Pd1—O1—C17 | −1.1 (2) | C17—C26—C25—C24 | 0.2 (4) |
O2—Pd1—N2—C12 | −178.4 (2) | C18—C17—C26—C25 | 1.7 (4) |
O2—Pd1—N2—C16 | 0.6 (3) | C18—C19—C20—C21 | 177.4 (3) |
O2—C26—C17—C18 | −178.4 (3) | C18—C19—C24—C23 | −177.5 (3) |
O2—C26—C25—C24 | −179.7 (2) | C18—C19—C24—C25 | 1.7 (4) |
N1—Pd1—O1—C17 | −179.6 (2) | C19—C18—C17—C26 | −1.9 (4) |
N1—Pd1—N2—C12 | 0.1 (2) | C19—C20—C21—C22 | 0.3 (5) |
N1—Pd1—N2—C16 | 179.1 (3) | C19—C24—C23—C22 | −0.4 (4) |
N1—C2—C3—C4 | 0.1 (4) | C19—C24—C25—C26 | −1.9 (4) |
N1—C2—C12—N2 | 0.2 (3) | C20—C19—C24—C23 | 1.5 (4) |
N1—C2—C12—C13 | −178.0 (3) | C20—C19—C24—C25 | −179.3 (2) |
N1—C6—C5—C4 | −0.2 (5) | C20—C21—C22—C23 | 0.8 (5) |
N2—Pd1—O2—C26 | −179.6 (2) | C21—C20—C19—C24 | −1.5 (4) |
N2—Pd1—N1—C2 | 0.0 (2) | C21—C22—C23—C24 | −0.8 (5) |
N2—Pd1—N1—C6 | −179.9 (3) | C22—C23—C24—C25 | −179.6 (3) |
N2—C12—C2—C3 | −179.7 (3) | C23—C24—C25—C26 | 177.3 (3) |
N2—C12—C13—C14 | −0.4 (4) | C23—C24—C25—C26 | 177.3 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) −x+1, y+1/2, −z+1/2; (iv) x, −y+1/2, z+1/2; (v) x−1, −y+1/2, z−1/2. |
[Pd(C10H6O2)(C18H12N2)] | F(000) = 1048.0 |
Mr = 520.86 | Dx = 1.638 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2yn | Cell parameters from 18 reflections |
a = 9.859 (5) Å | θ = 10.6–13.2° |
b = 19.67 (1) Å | µ = 0.91 mm−1 |
c = 10.922 (5) Å | T = 296 K |
β = 94.33 (4)° | Prism, colorless |
V = 2112.0 (18) Å3 | 0.20 × 0.20 × 0.20 mm |
Z = 4 |
Rigaku AFC-5R diffractometer | Rint = 0.044 |
ω–2θ scans | θmax = 27.5° |
Absorption correction: ψ scan (North et al., 1968) | h = 0→12 |
Tmin = 0.917, Tmax = 0.998 | k = 0→25 |
5278 measured reflections | l = −14→14 |
4849 independent reflections | 3 standard reflections every 150 reflections |
2647 reflections with I > 2σ(I) | intensity decay: 0.2% |
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.044 | w = 1/[σ2(Fo2) + (0.0556P)2 + ] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.135 | (Δ/σ)max = 0.001 |
S = 0.98 | Δρmax = 1.14 e Å−3 |
4849 reflections | Δρmin = −0.67 e Å−3 |
298 parameters |
[Pd(C10H6O2)(C18H12N2)] | V = 2112.0 (18) Å3 |
Mr = 520.86 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.859 (5) Å | µ = 0.91 mm−1 |
b = 19.67 (1) Å | T = 296 K |
c = 10.922 (5) Å | 0.20 × 0.20 × 0.20 mm |
β = 94.33 (4)° |
Rigaku AFC-5R diffractometer | 2647 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.044 |
Tmin = 0.917, Tmax = 0.998 | 3 standard reflections every 150 reflections |
5278 measured reflections | intensity decay: 0.2% |
4849 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | 298 parameters |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 0.98 | Δρmax = 1.14 e Å−3 |
4849 reflections | Δρmin = −0.67 e Å−3 |
Refinement. Refinement using reflections with F2 > −10.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
Pd1 | 0.78287 (4) | 0.01197 (2) | 0.97950 (4) | 0.0382 (1) | |
O1 | 0.8559 (4) | 0.0125 (2) | 1.1546 (3) | 0.0477 (9) | |
O2 | 0.8948 (4) | 0.0951 (2) | 0.9690 (3) | 0.0470 (9) | |
N1 | 0.6515 (4) | −0.0677 (2) | 0.9880 (4) | 0.041 (1) | |
N2 | 0.6829 (4) | 0.0194 (2) | 0.8098 (4) | 0.0392 (10) | |
C2 | 0.5462 (5) | −0.0632 (3) | 0.9026 (5) | 0.043 (1) | |
C3 | 0.4356 (6) | −0.1075 (3) | 0.8990 (6) | 0.050 (1) | |
C4 | 0.4335 (7) | −0.1577 (3) | 0.9848 (6) | 0.060 (2) | |
C5 | 0.5433 (6) | −0.1664 (3) | 1.0712 (6) | 0.050 (1) | |
C6 | 0.5491 (7) | −0.2198 (3) | 1.1587 (6) | 0.061 (2) | |
C7 | 0.6585 (8) | −0.2287 (3) | 1.2369 (6) | 0.062 (2) | |
C8 | 0.7701 (7) | −0.1841 (3) | 1.2367 (6) | 0.061 (2) | |
C9 | 0.7683 (6) | −0.1302 (3) | 1.1557 (5) | 0.049 (1) | |
C10 | 0.6547 (6) | −0.1204 (3) | 1.0717 (5) | 0.045 (1) | |
C12 | 0.5607 (5) | −0.0102 (3) | 0.8078 (5) | 0.042 (1) | |
C13 | 0.4546 (6) | 0.0050 (3) | 0.7189 (6) | 0.052 (1) | |
C14 | 0.4794 (6) | 0.0484 (3) | 0.6264 (6) | 0.056 (2) | |
C15 | 0.6118 (6) | 0.0745 (3) | 0.6175 (5) | 0.048 (1) | |
C16 | 0.6471 (7) | 0.1131 (3) | 0.5143 (5) | 0.056 (2) | |
C17 | 0.7770 (8) | 0.1333 (3) | 0.5052 (6) | 0.062 (2) | |
C18 | 0.8772 (6) | 0.1182 (3) | 0.6002 (6) | 0.056 (2) | |
C19 | 0.8466 (6) | 0.0829 (3) | 0.7031 (5) | 0.045 (1) | |
C20 | 0.7135 (5) | 0.0597 (3) | 0.7119 (5) | 0.042 (1) | |
C21 | 0.9487 (5) | 0.0619 (3) | 1.1745 (5) | 0.038 (1) | |
C22 | 1.0208 (6) | 0.0713 (3) | 1.2843 (5) | 0.043 (1) | |
C23 | 1.1226 (5) | 0.1221 (3) | 1.3005 (5) | 0.040 (1) | |
C24 | 1.2024 (6) | 0.1333 (3) | 1.4123 (6) | 0.052 (1) | |
C25 | 1.2995 (7) | 0.1836 (4) | 1.4239 (6) | 0.061 (2) | |
C26 | 1.3220 (6) | 0.2250 (4) | 1.3249 (6) | 0.063 (2) | |
C27 | 1.2484 (7) | 0.2162 (3) | 1.2165 (6) | 0.056 (2) | |
C28 | 1.1450 (5) | 0.1658 (3) | 1.1986 (5) | 0.042 (1) | |
C29 | 1.0638 (6) | 0.1576 (3) | 1.0871 (5) | 0.043 (1) | |
C30 | 0.9708 (5) | 0.1066 (3) | 1.0743 (5) | 0.039 (1) | |
H3 | 0.3641 | −0.1028 | 0.8389 | 0.0596* | |
H4 | 0.3582 | −0.1861 | 0.9855 | 0.0716* | |
H6 | 0.4753 | −0.2491 | 1.1619 | 0.0738* | |
H7 | 0.6611 | −0.2648 | 1.2920 | 0.0747* | |
H8 | 0.8456 | −0.1910 | 1.2916 | 0.0731* | |
H9 | 0.8420 | −0.1006 | 1.1563 | 0.0593* | |
H13 | 0.3689 | −0.0141 | 0.7234 | 0.0624* | |
H14 | 0.4094 | 0.0608 | 0.5691 | 0.0666* | |
H16 | 0.5806 | 0.1244 | 0.4528 | 0.0671* | |
H17 | 0.8004 | 0.1571 | 0.4365 | 0.0739* | |
H18 | 0.9662 | 0.1324 | 0.5930 | 0.0677* | |
H19 | 0.9134 | 0.0744 | 0.7660 | 0.0538* | |
H22 | 1.0030 | 0.0438 | 1.3503 | 0.0515* | |
H24 | 1.1885 | 0.1060 | 1.4796 | 0.0621* | |
H25 | 1.3501 | 0.1897 | 1.4983 | 0.0733* | |
H26 | 1.3877 | 0.2589 | 1.3330 | 0.0756* | |
H27 | 1.2663 | 0.2441 | 1.1509 | 0.0675* | |
H29 | 1.0742 | 0.1873 | 1.0223 | 0.0514* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.0375 (2) | 0.0372 (2) | 0.0399 (2) | −0.0015 (2) | 0.0021 (2) | −0.0010 (2) |
O1 | 0.053 (2) | 0.045 (2) | 0.044 (2) | −0.009 (2) | −0.003 (2) | 0.001 (2) |
O2 | 0.052 (2) | 0.049 (2) | 0.039 (2) | −0.012 (2) | −0.005 (2) | 0.002 (2) |
N1 | 0.043 (2) | 0.039 (3) | 0.042 (3) | −0.001 (2) | 0.004 (2) | −0.006 (2) |
N2 | 0.041 (2) | 0.038 (2) | 0.039 (2) | 0.007 (2) | 0.003 (2) | −0.003 (2) |
C2 | 0.037 (3) | 0.044 (3) | 0.048 (3) | 0.006 (2) | 0.001 (2) | −0.015 (2) |
C3 | 0.036 (3) | 0.052 (4) | 0.060 (4) | −0.002 (3) | −0.002 (3) | −0.012 (3) |
C4 | 0.051 (4) | 0.049 (4) | 0.081 (5) | −0.020 (3) | 0.017 (3) | −0.008 (3) |
C5 | 0.053 (4) | 0.041 (3) | 0.056 (4) | −0.007 (3) | 0.011 (3) | −0.005 (3) |
C6 | 0.077 (5) | 0.038 (3) | 0.072 (4) | −0.015 (3) | 0.021 (4) | −0.001 (3) |
C7 | 0.088 (5) | 0.051 (4) | 0.050 (4) | −0.011 (4) | 0.015 (4) | 0.012 (3) |
C8 | 0.073 (4) | 0.052 (4) | 0.056 (4) | −0.001 (3) | −0.005 (3) | 0.003 (3) |
C9 | 0.052 (3) | 0.045 (3) | 0.051 (3) | −0.008 (3) | 0.002 (3) | −0.004 (3) |
C10 | 0.052 (3) | 0.037 (3) | 0.049 (3) | 0.000 (3) | 0.017 (3) | −0.005 (3) |
C12 | 0.042 (3) | 0.042 (3) | 0.044 (3) | 0.002 (2) | 0.004 (2) | −0.012 (3) |
C13 | 0.045 (3) | 0.059 (4) | 0.052 (3) | 0.002 (3) | 0.000 (3) | −0.010 (3) |
C14 | 0.046 (3) | 0.072 (4) | 0.046 (4) | 0.009 (3) | −0.009 (3) | −0.002 (3) |
C15 | 0.051 (3) | 0.046 (3) | 0.047 (3) | 0.005 (3) | −0.001 (3) | −0.002 (3) |
C16 | 0.070 (4) | 0.062 (4) | 0.036 (3) | 0.009 (3) | 0.001 (3) | 0.002 (3) |
C17 | 0.086 (5) | 0.054 (4) | 0.046 (4) | 0.000 (4) | 0.013 (4) | 0.014 (3) |
C18 | 0.058 (4) | 0.062 (4) | 0.051 (4) | −0.007 (3) | 0.016 (3) | 0.004 (3) |
C19 | 0.047 (3) | 0.048 (3) | 0.041 (3) | 0.002 (3) | 0.007 (2) | −0.006 (3) |
C20 | 0.048 (3) | 0.040 (3) | 0.038 (3) | 0.006 (2) | 0.006 (2) | −0.005 (2) |
C21 | 0.035 (3) | 0.034 (3) | 0.045 (3) | 0.005 (2) | 0.003 (2) | −0.002 (2) |
C22 | 0.053 (3) | 0.041 (3) | 0.036 (3) | 0.004 (3) | 0.008 (2) | 0.004 (2) |
C23 | 0.045 (3) | 0.033 (3) | 0.040 (3) | 0.007 (2) | 0.001 (2) | −0.005 (2) |
C24 | 0.047 (3) | 0.056 (4) | 0.051 (4) | 0.004 (3) | −0.008 (3) | −0.002 (3) |
C25 | 0.058 (4) | 0.071 (5) | 0.052 (4) | −0.005 (3) | −0.010 (3) | −0.009 (3) |
C26 | 0.047 (4) | 0.074 (5) | 0.066 (4) | −0.017 (3) | −0.005 (3) | −0.012 (4) |
C27 | 0.059 (4) | 0.053 (4) | 0.057 (4) | −0.010 (3) | 0.005 (3) | −0.003 (3) |
C28 | 0.039 (3) | 0.042 (3) | 0.045 (3) | 0.003 (2) | 0.004 (2) | −0.011 (2) |
C29 | 0.048 (3) | 0.039 (3) | 0.042 (3) | 0.001 (2) | 0.004 (3) | 0.005 (2) |
C30 | 0.039 (3) | 0.039 (3) | 0.039 (3) | 0.003 (2) | 0.004 (2) | −0.003 (2) |
Pd1—O1 | 1.992 (4) | C14—C15 | 1.412 (8) |
Pd1—O2 | 1.982 (4) | C14—H14 | 0.93 |
Pd1—N1 | 2.039 (4) | C15—C16 | 1.424 (9) |
Pd1—N2 | 2.037 (4) | C15—C20 | 1.413 (8) |
O1—C21 | 1.341 (6) | C16—C17 | 1.35 (1) |
O2—C30 | 1.344 (6) | C16—H16 | 0.93 |
N1—C2 | 1.345 (7) | C17—C18 | 1.409 (9) |
N1—C10 | 1.381 (7) | C17—H17 | 0.93 |
N2—C12 | 1.337 (7) | C18—C19 | 1.375 (9) |
N2—C20 | 1.383 (7) | C18—H18 | 0.93 |
C2—C3 | 1.395 (8) | C19—C20 | 1.399 (8) |
C2—C12 | 1.484 (8) | C19—H19 | 0.93 |
C3—C4 | 1.362 (9) | C21—C22 | 1.360 (7) |
C3—H3 | 0.93 | C21—C30 | 1.432 (8) |
C4—C5 | 1.392 (9) | C22—C23 | 1.416 (8) |
C4—H4 | 0.93 | C22—H22 | 0.93 |
C5—C6 | 1.418 (9) | C23—C24 | 1.420 (8) |
C5—C10 | 1.424 (8) | C23—C28 | 1.437 (8) |
C6—C7 | 1.335 (10) | C24—C25 | 1.375 (9) |
C6—H6 | 0.93 | C24—H24 | 0.93 |
C7—C8 | 1.407 (10) | C25—C26 | 1.385 (10) |
C7—H7 | 0.93 | C25—H25 | 0.93 |
C8—C9 | 1.380 (9) | C26—C27 | 1.352 (9) |
C8—H8 | 0.93 | C26—H26 | 0.93 |
C9—C10 | 1.406 (8) | C27—C28 | 1.426 (8) |
C9—H9 | 0.93 | C27—H27 | 0.93 |
C12—C13 | 1.405 (8) | C28—C29 | 1.414 (7) |
C13—C14 | 1.359 (9) | C29—C30 | 1.360 (7) |
C13—H13 | 0.93 | C29—H29 | 0.93 |
Pd1···C3i | 3.219 (6) | C2···C2i | 3.44 (1) |
Pd1···C30ii | 3.449 (5) | C6···C28iii | 3.407 (9) |
Pd1···C21ii | 3.552 (5) | C6···C27iii | 3.557 (10) |
O1···C3i | 3.442 (7) | C6···C23iii | 3.586 (8) |
O1···C13i | 3.470 (7) | C9···C29ii | 3.275 (8) |
O1···O2ii | 3.584 (6) | C10···C13i | 3.451 (8) |
O2···C4i | 3.534 (8) | C10···C29ii | 3.461 (8) |
N1···C29ii | 3.467 (7) | C13···C16iv | 3.536 (9) |
N1···C2i | 3.493 (7) | C14···C14iv | 3.40 (1) |
N1···C12i | 3.523 (7) | C19···C22ii | 3.302 (8) |
N1···C28ii | 3.538 (7) | ||
O1—Pd1—O2 | 83.6 (2) | C15—C14—H14 | 120.0 |
O1—Pd1—N1 | 98.4 (2) | C14—C15—C16 | 122.1 (5) |
O1—Pd1—N2 | 171.1 (2) | C14—C15—C20 | 118.8 (5) |
O2—Pd1—N1 | 174.4 (2) | C16—C15—C20 | 119.0 (5) |
O2—Pd1—N2 | 97.0 (2) | C15—C16—C17 | 120.2 (6) |
N1—Pd1—N2 | 80.3 (2) | C15—C16—H16 | 119.9 |
Pd1—O1—C21 | 110.6 (3) | C17—C16—H16 | 119.9 |
Pd1—O2—C30 | 111.4 (3) | C16—C17—C18 | 120.0 (6) |
Pd1—N1—C2 | 112.2 (3) | C16—C17—H17 | 120.0 |
Pd1—N1—C10 | 128.6 (3) | C18—C17—H17 | 120.0 |
C2—N1—C10 | 119.0 (5) | C17—C18—C19 | 121.6 (6) |
Pd1—N2—C12 | 110.9 (3) | C17—C18—H18 | 119.2 |
Pd1—N2—C20 | 128.8 (3) | C19—C18—H18 | 119.2 |
C12—N2—C20 | 119.0 (4) | C18—C19—C20 | 119.0 (5) |
N1—C2—C3 | 122.7 (5) | C18—C19—H19 | 120.5 |
N1—C2—C12 | 114.8 (5) | C20—C19—H19 | 120.5 |
C3—C2—C12 | 122.4 (5) | N2—C20—C15 | 119.9 (5) |
C2—C3—C4 | 119.1 (5) | N2—C20—C19 | 120.0 (5) |
C2—C3—H3 | 120.5 | C15—C20—C19 | 120.1 (5) |
C4—C3—H3 | 120.5 | O1—C21—C22 | 123.1 (5) |
C3—C4—C5 | 120.3 (6) | O1—C21—C30 | 117.5 (4) |
C3—C4—H4 | 119.8 | C22—C21—C30 | 119.4 (5) |
C5—C4—H4 | 119.8 | C21—C22—C23 | 121.6 (5) |
C4—C5—C6 | 122.6 (6) | C21—C22—H22 | 119.2 |
C4—C5—C10 | 118.9 (5) | C23—C22—H22 | 119.2 |
C6—C5—C10 | 118.5 (5) | C22—C23—C24 | 124.0 (5) |
C5—C6—C7 | 121.1 (6) | C22—C23—C28 | 118.3 (5) |
C5—C6—H6 | 119.4 | C24—C23—C28 | 117.7 (5) |
C7—C6—H6 | 119.4 | C23—C24—C25 | 121.9 (6) |
C6—C7—C8 | 120.8 (6) | C23—C24—H24 | 119.1 |
C6—C7—H7 | 119.6 | C25—C24—H24 | 119.0 |
C8—C7—H7 | 119.6 | C24—C25—C26 | 120.2 (6) |
C7—C8—C9 | 120.5 (6) | C24—C25—H25 | 119.9 |
C7—C8—H8 | 119.7 | C26—C25—H25 | 119.9 |
C9—C8—H8 | 119.7 | C25—C26—C27 | 120.1 (6) |
C8—C9—C10 | 119.6 (6) | C25—C26—H26 | 120.0 |
C8—C9—H9 | 120.2 | C27—C26—H26 | 120.0 |
C10—C9—H9 | 120.2 | C26—C27—C28 | 122.7 (6) |
N1—C10—C5 | 119.8 (5) | C26—C27—H27 | 118.6 |
N1—C10—C9 | 120.8 (5) | C28—C27—H27 | 118.6 |
C5—C10—C9 | 119.4 (5) | C23—C28—C27 | 117.4 (5) |
N2—C12—C2 | 115.4 (4) | C23—C28—C29 | 119.2 (5) |
N2—C12—C13 | 122.8 (5) | C27—C28—C29 | 123.4 (5) |
C2—C12—C13 | 121.8 (5) | C28—C29—C30 | 120.4 (5) |
C12—C13—C14 | 118.8 (5) | C28—C29—H29 | 119.8 |
C12—C13—H13 | 120.6 | C30—C29—H29 | 119.8 |
C14—C13—H13 | 120.6 | O2—C30—C21 | 116.4 (4) |
C13—C14—C15 | 120.0 (5) | O2—C30—C29 | 122.7 (5) |
C13—C14—H14 | 120.0 | C21—C30—C29 | 120.9 (5) |
Pd1—O1—C21—C22 | −176.0 (4) | C3—C2—C12—C13 | 9.6 (9) |
Pd1—O1—C21—C30 | 4.3 (5) | C3—C4—C5—C6 | −176.9 (6) |
Pd1—O2—C30—C21 | −5.3 (6) | C3—C4—C5—C10 | 2.8 (9) |
Pd1—O2—C30—C29 | 174.9 (4) | C4—C3—C2—C12 | 175.8 (6) |
Pd1—N1—C2—C3 | −172.7 (4) | C4—C5—C6—C7 | 177.0 (7) |
Pd1—N1—C2—C12 | 11.0 (6) | C4—C5—C10—C9 | −177.7 (6) |
Pd1—N1—C10—C5 | 171.9 (4) | C5—C6—C7—C8 | 1 (1) |
Pd1—N1—C10—C9 | −9.8 (8) | C5—C10—C9—C8 | −0.3 (9) |
Pd1—N2—C12—C2 | −23.6 (6) | C6—C5—C10—C9 | 2.0 (9) |
Pd1—N2—C12—C13 | 159.2 (5) | C6—C7—C8—C9 | 0 (1) |
Pd1—N2—C20—C15 | −159.8 (4) | C7—C6—C5—C10 | −2.7 (10) |
Pd1—N2—C20—C19 | 23.5 (7) | C7—C8—C9—C10 | −0.8 (10) |
O1—Pd1—O2—C30 | 6.0 (3) | C10—N1—C2—C12 | −172.7 (5) |
O1—Pd1—N1—C2 | 152.7 (4) | C12—N2—C20—C15 | 6.3 (7) |
O1—Pd1—N1—C10 | −23.1 (5) | C12—N2—C20—C19 | −170.4 (5) |
O1—C21—C22—C23 | 177.0 (5) | C12—C13—C14—C15 | 3.3 (9) |
O1—C21—C30—O2 | 0.7 (7) | C13—C12—N2—C20 | −9.1 (8) |
O1—C21—C30—C29 | −179.6 (5) | C13—C14—C15—C16 | 171.9 (6) |
O2—Pd1—O1—C21 | −5.5 (3) | C13—C14—C15—C20 | −5.8 (9) |
O2—Pd1—N2—C12 | −152.3 (4) | C14—C15—C16—C17 | −175.5 (6) |
O2—Pd1—N2—C20 | 14.7 (5) | C14—C15—C20—C19 | 177.7 (5) |
O2—C30—C21—C22 | −179.0 (5) | C15—C16—C17—C18 | −2.2 (10) |
O2—C30—C29—C28 | −177.6 (5) | C15—C20—C19—C18 | −1.9 (8) |
N1—Pd1—O1—C21 | 179.7 (3) | C16—C15—C20—C19 | −0.1 (8) |
N1—Pd1—N2—C12 | 22.8 (4) | C16—C17—C18—C19 | 0.2 (10) |
N1—Pd1—N2—C20 | −170.2 (5) | C17—C16—C15—C20 | 2.2 (9) |
N1—C2—C3—C4 | −0.2 (9) | C17—C18—C19—C20 | 1.9 (9) |
N1—C2—C12—N2 | 8.6 (7) | C21—C22—C23—C24 | −178.9 (5) |
N1—C2—C12—C13 | −174.2 (5) | C21—C22—C23—C28 | 2.4 (8) |
N1—C10—C5—C4 | 0.6 (9) | C21—C30—C29—C28 | 2.7 (8) |
N1—C10—C5—C6 | −179.6 (5) | C22—C21—C30—C29 | 0.8 (8) |
N1—C10—C9—C8 | −178.6 (6) | C22—C23—C24—C25 | −179.5 (6) |
N2—Pd1—O2—C30 | 177.0 (3) | C22—C23—C28—C27 | −179.6 (5) |
N2—Pd1—N1—C2 | −18.3 (4) | C22—C23—C28—C29 | 1.0 (8) |
N2—Pd1—N1—C10 | 165.8 (5) | C23—C22—C21—C30 | −3.3 (8) |
N2—C12—C2—C3 | −167.6 (5) | C23—C24—C25—C26 | 0.0 (10) |
N2—C12—C13—C14 | 4.4 (9) | C23—C28—C27—C26 | −1.7 (9) |
N2—C20—C15—C14 | 1.0 (8) | C23—C28—C29—C30 | −3.6 (8) |
N2—C20—C15—C16 | −176.7 (5) | C24—C23—C28—C27 | 1.6 (8) |
N2—C20—C19—C18 | 174.8 (5) | C24—C23—C28—C29 | −177.7 (5) |
C2—N1—C10—C5 | −3.7 (8) | C24—C25—C26—C27 | 0 (1) |
C2—N1—C10—C9 | 174.6 (5) | C25—C24—C23—C28 | −0.9 (9) |
C2—C3—C4—C5 | −3.0 (9) | C25—C26—C27—C28 | 0 (1) |
C2—C12—N2—C20 | 168.0 (5) | C26—C27—C28—C29 | 177.7 (6) |
C2—C12—C13—C14 | −172.6 (6) | C27—C28—C29—C30 | 177.1 (5) |
C3—C2—N1—C10 | 3.6 (8) | C27—C28—C29—C30 | 177.1 (5) |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+2, −y, −z+2; (iii) −x+3/2, y−1/2, −z+5/2; (iv) −x+1, −y, −z+1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Pd(C10H6O2)(C10H8N2)] | [Pd(C10H6O2)(C18H12N2)] |
Mr | 420.75 | 520.86 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/n |
Temperature (K) | 296 | 296 |
a, b, c (Å) | 12.117 (2), 8.239 (2), 16.857 (1) | 9.859 (5), 19.67 (1), 10.922 (5) |
β (°) | 108.804 (8) | 94.33 (4) |
V (Å3) | 1593.1 (5) | 2112.0 (18) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.18 | 0.91 |
Crystal size (mm) | 0.50 × 0.20 × 0.20 | 0.20 × 0.20 × 0.20 |
Data collection | ||
Diffractometer | Rigaku AFC-5R diffractometer | Rigaku AFC-5R diffractometer |
Absorption correction | ψ scan (North, Phillips & Mathews, 1968) | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.936, 1.000 | 0.917, 0.998 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4095, 3658, 3090 | 5278, 4849, 2647 |
Rint | 0.014 | 0.044 |
(sin θ/λ)max (Å−1) | 0.650 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.078, 1.14 | 0.044, 0.135, 0.98 |
No. of reflections | 3658 | 4849 |
No. of parameters | 226 | 298 |
No. of restraints | ? | ? |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.88 | 1.14, −0.67 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992), TEXSAN (Molecular Structure Corporation, 2000), SIR97 (Altomare et al., 1999), SHELXS97 (Scheldrick, 1997), SHELXL97 (Scheldrick, 1997), ORTEPII (Johnson, 1976).
Pd1—O1 | 1.981 (3) | Pd1—N1 | 2.003 (2) |
Pd1—O2 | 1.984 (2) | Pd1—N2 | 2.001 (3) |
O1—Pd1—O2 | 84.84 (9) | O2—Pd1—N1 | 177.58 (10) |
O1—Pd1—N1 | 97.06 (9) | O2—Pd1—N2 | 97.29 (9) |
O1—Pd1—N2 | 177.54 (9) | N1—Pd1—N2 | 80.78 (9) |
Pd1—O1 | 1.992 (4) | Pd1—N1 | 2.039 (4) |
Pd1—O2 | 1.982 (4) | Pd1—N2 | 2.037 (4) |
O1—Pd1—O2 | 83.6 (2) | O2—Pd1—N1 | 174.4 (2) |
O1—Pd1—N1 | 98.4 (2) | O2—Pd1—N2 | 97.0 (2) |
O1—Pd1—N2 | 171.1 (2) | N1—Pd1—N2 | 80.3 (2) |
Recently, the palladium complex [Pd(bpy)(cbdca)] (where bpy is 2,2'-bipyridine and cbdca is the 1,1-cyclobutanedicarboxylate ligand), with a cis-square-planar coordination geometry, has been shown to have better cytotoxic activity than cisplatin, cis-diamminedichloroplatinum(II), against P388 lymphocytic leukemia cells (Mansuri-Torshizi et al., 2001).
The planar aromatic ligands interact with DNA, which is the principal target in the chemotherapy of tumors (Neidle et al., 1987; Cusumano & Giannetto, 1997; Shehata, 2001). In the present study, we have prepared two cis-coordinated ternary complexes of PdII, with the aromatic ligands bpy, 2,2'-biquinoline (biq) and 2,3-naphthalenediol (nad), namely the title complexes [Pd(bpy)(nad)], (I), and [Pd(biq)(nad)], (II), and determined their structures. The same complexes have previously been synthesized by a different method for electrochemical studies into their use as photosensitizers in inorganic photochemistry (Kamath et al., 1989). Structures have been determined for complexes of nad with Si (Holmes et al., 1985; Strohmann et al., 1991; Tacke et al., 1991; Sperlich et al., 1993; Tacke et al., 1993), Fe (Jü stel et al., 1999), Ge (Tacke et al., 1994), Rb (Yang et al., 1997), Mo (El-Hendawy et al., 1989; Mondal et al., 1988; Kang et al., 1989) and Sb (Holmes et al., 1987). The present study is the first determination of the crystal structures of Pd complexes with nad.
The central Pd atom of each complex has the same distorted cis-square-planer coordination geometry, involving the two N atoms of the heterocycle and the two O atoms of the dianion of the nad ligand (Figs. 1 and 2). The overall structure of (I) is essentially planar. Atom C14 of the bpy ligand ?shows the maximum deviation from the mean molecular plane [0.085 (3) Å].
In contrast, the overall structure of (II) is not planar; the dihedral angle between the biq and Pd(nad) planes is 148.73 (7)°. In the square-planar coordination, atoms Pd1, N1, N2, O1 and O2 deviate by 0.0055 (1), −0.135 (3), −0.073 (3), −0.093 (3) and −0.167 (3) Å, respectively, from the plane through these five atoms, while the Pd(nad) moiety, including the square-planar coordination plane, is mostly planar, the maximum deviation from the plane being that of atom C26 [0.139 (7) Å]. The biq molecule is bowed to relieve intramolecular overcrowding between the biq moieties (C9/H9 and C19/H19) and nad atoms (O1 and O2). The H9···O1 and H19···O2 separations are 2.23 and 2.28 Å, respectively. As a result, the angle between the two quinoline ring planes is 19.9 (1) °.
Selected bond lengths and bond angles in (I), (II) are listed in Tables 2 and 3. The Pd—O bond lengths in (I) and (II) are similar, but the Pd—N distances in (I) are slightly shorter than those in (II). These values may be compared with those reported for [Pd(NH3)2(cbdca)] (III; Barnham et al., 1994), [Pd(en)(cbdca)] (IV; en is ethylenediamine; Tercero et al., 2003) and [Pd(cat)(phen)] (V; cat is cathecholate and phen is 1,10-phenanthloline; Okabe et al., 2003), since the central Pd atoms of all of these compounds have the same distorted cis-square-planar coordination geometry, with the formula [Pd(NN)(OO)]. The Pd—N bonds of (I) are slightly shorter than those in (III)–(IV) [2.020 (7)–2.030 (2) Å] and are nearly the same as those in (V) [2.003 (2)–2.019 (2) Å]. The Pd—N distances in (II) are slightly longer than those in (III)–(V). The Pd—O bond lengths in (I) and (II) are also slightly shorter than those in (III)–(IV) [2.005 (2)–2.017 (6) Å] and nearly the same as those in (V) [1.981 (2)–1.989 (2) Å]. It thus appears that the coordination bonds in (I) are stronger than those in (III)–(IV) or nearly identical to those in (V). The Pd—N bonds in (II) are the weakest of all, possibly as a result of intramolecular steric hindrance between the O atoms of the dianion of the nad molecule and the H atoms attached to atoms C9 and C19 of the biq molecule, as noted above.
The O—Pd—O angles in the five-membered rings in (I) and (II) are small compared with those observed in the six-membered rings in (III) and (IV) [90.9–92.69 (7)°], and slightly smaller than that reported for the five-membered ring in (V) [85.09 (7) °]. The N—Pd—N angles in (I) and (II) are also smaller than those in (IV) [84.15 (8) ° for en] and in (III) [95.0° for NH3—Pd—NH3], and slightly smaller than that in (V) [81.69 (8) ° for cat].
The crystal structure of (I) is stabilized by centrosymmetric stacking interactions between molecules at (1 − x,-y,1 − z), (x,y,z), (1 − x,1 − y,1 − z), (x,1 + y,z) etc., as shown in Fig. 3, the shortest separations being between atoms Pd1 and C26 [at (1 − x,1 − y,1 − z); 3.391 (2) Å], and between atoms Pd1 and C12 [at (1 − x,-y,1 − z); 3.414 (2) Å]. The crystal structure of (II) exhibits interactions between inversion-related molecules, as shown in Fig. 4, the shortest separations being between atoms Pd1 and C3 [at (1 − x,-y,1 − z); 3.219 (6) Å], and between atoms Pd1 and C30 [at (2 − x,-y,1 − z); 3.449 (5) Å]. These stacks are then connected by C—H···π arene interactions [H6.·Cg1 = 2.50 Å, C6···Cg1 = 3.431 Å and C6—H6···Cg1 = 176°; Cg1 is the centroid of the C23–C28 ring at (3/2 − x,-1/2 + y,5/2 − z)].