Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102004602/gd1195sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102004602/gd1195Isup2.hkl |
CCDC reference: 187906
To a solution of PdCl2 (17 mg, 0.1 mmol) in concentrated aqueous ammonium hydroxide (5 ml), a mixture of 3-(2-fluorophenyl)-1-(4-nitrophenyl)triazene (50 g, 0.2 mmol) in tetrahydrofuran (30 ml) and concentrated aqueous ammonium hydroxide (1 ml) was slowly added under continuous stirring. After stirring for 1 h at room temperature, pyridine (1 ml) was added to the deep-red reaction mixture, which was then stirred for a further 24 h. Red prism-shaped crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of the solvent mixture at room temperature (yield: 45 mg, 60%; m.p. 525–529 K).
Data collection: CAD-4 EXPRESS (Enraf Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Fig. 1. A perspective view of the molecule of (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity. |
[Pd(C5H5N)2(C12H8FN4O2)2] | Z = 1 |
Mr = 783.07 | F(000) = 396 |
Triclinic, P1 | Dx = 1.567 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.941 (2) Å | Cell parameters from 25 reflections |
b = 9.732 (2) Å | θ = 2.6–25.1° |
c = 10.9449 (10) Å | µ = 0.63 mm−1 |
α = 110.058 (14)° | T = 293 K |
β = 93.437 (13)° | Prism, red |
γ = 109.012 (19)° | 0.20 × 0.13 × 0.07 mm |
V = 829.9 (3) Å3 |
Enraf Nonius TurboCAD-4 diffractometer | Rint = 0.032 |
non–profiled ω/2θ scans | θmax = 25.1°, θmin = 2.7° |
Absorption correction: ψ-scan (North et al., 1968) | h = 0→10 |
Tmin = 0.885, Tmax = 0.958 | k = −11→10 |
3149 measured reflections | l = −13→13 |
2947 independent reflections | 3 standard reflections every 120 min |
2446 reflections with I > 2σ(I) | intensity decay: 1% |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0476P)2 where P = (Fo2 + 2Fc2)/3 |
2947 reflections | (Δ/σ)max < 0.001 |
232 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.98 e Å−3 |
[Pd(C5H5N)2(C12H8FN4O2)2] | γ = 109.012 (19)° |
Mr = 783.07 | V = 829.9 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.941 (2) Å | Mo Kα radiation |
b = 9.732 (2) Å | µ = 0.63 mm−1 |
c = 10.9449 (10) Å | T = 293 K |
α = 110.058 (14)° | 0.20 × 0.13 × 0.07 mm |
β = 93.437 (13)° |
Enraf Nonius TurboCAD-4 diffractometer | 2446 reflections with I > 2σ(I) |
Absorption correction: ψ-scan (North et al., 1968) | Rint = 0.032 |
Tmin = 0.885, Tmax = 0.958 | 3 standard reflections every 120 min |
3149 measured reflections | intensity decay: 1% |
2947 independent reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.48 e Å−3 |
2947 reflections | Δρmin = −0.98 e Å−3 |
232 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. Mean-plane data from final SHELXL refinement run:- Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 6.5788 (0.0158) x + 3.8984 (0.0231) y - 3.3162 (0.0235) z = 0.1283 (0.0069) * -0.0063 (0.0032) N31 * 0.0021 (0.0036) C32 * 0.0063 (0.0041) C33 * -0.0103 (0.0047) C34 * 0.0060 (0.0050) C35 * 0.0022 (0.0042) C36 Rms deviation of fitted atoms = 0.0062 - 2.5738 (0.0306) x + 6.1420 (0.0622) y - 9.9713 (0.0186) z = 0.0511 (0.0630) Angle to previous plane (with approximate e.s.d.) = 80.07 (0.34) * 0.0000 (0.0000) O1 * 0.0000 (0.0000) N1 * 0.0000 (0.0000) O2 Rms deviation of fitted atoms = 0.0000 - 2.8753 (0.0153) x + 6.4731 (0.0127) y - 9.7250 (0.0096) z = 0.1027 (0.0074) Angle to previous plane (with approximate e.s.d.) = 3.02 (0.63) * 0.0094 (0.0029) C11 * -0.0050 (0.0030) C12 * -0.0041 (0.0031) C13 * 0.0088 (0.0030) C14 * -0.0042 (0.0030) C15 * -0.0049 (0.0030) C16 Rms deviation of fitted atoms = 0.0064 3.4817 (0.0480) x - 6.5938 (0.0167) y + 9.3862 (0.0255) z = 0.0001 (0.0138) Angle to previous plane (with approximate e.s.d.) = 4.18 (0.42) * 0.0000 (0.0000) N11 * 0.0000 (0.0000) N12 * 0.0000 (0.0000) N13 Rms deviation of fitted atoms = 0.0000 5.5096 (0.0100) x - 5.6656 (0.0161) y + 8.1117 (0.0112) z = 0.4652 (0.0096) Angle to previous plane (with approximate e.s.d.) = 16.75 (0.48) * 0.0023 (0.0035) C21 * -0.0068 (0.0041) C22 * -0.0010 (0.0039) C23 * -0.0008 (0.0038) C24 * 0.0057 (0.0042) C25 * -0.0041 (0.0037) C26 * 0.0047 (0.0028) F Rms deviation of fitted atoms = 0.0042 - 1.8669 (0.0145) x + 7.5101 (0.0113) y + 3.4136 (0.0185) z = 0.0000 (0.0000) Angle to previous plane (with approximate e.s.d.) = 89.99 (0.13) * 0.0000 (0.0000) N11 * 0.0000 (0.0000) N31 * 0.0000 (0.0000) N11_$1 * 0.0000 (0.0000) N31_$1 0.0000 (0.0000) Pd Rms deviation of fitted atoms = 0.0000 - 1.8669 (0.0145) x + 7.5101 (0.0113) y + 3.4136 (0.0185) z = 0.0000 (0.0000) Angle to previous plane (with approximate e.s.d.) = 0.00 (0.30) * 0.0000 (0.0000) N11 * 0.0000 (0.0000) N31 * 0.0000 (0.0000) N11_$1 * 0.0000 (0.0000) N31_$1 Rms deviation of fitted atoms = 0.0000 6.5788 (0.0158) x + 3.8984 (0.0231) y - 3.3162 (0.0235) z = 0.1283 (0.0069) Angle to previous plane (with approximate e.s.d.) = 69.46 (0.17) * -0.0063 (0.0032) N31 * 0.0021 (0.0036) C32 * 0.0063 (0.0041) C33 * -0.0103 (0.0047) C34 * 0.0060 (0.0050) C35 * 0.0022 (0.0042) C36 Rms deviation of fitted atoms = 0.0062 1.8669 (0.0145) x - 7.5101 (0.0114) y - 3.4136 (0.0186) z = 0.0000 (0.0000) Angle to previous plane (with approximate e.s.d.) = 69.46 (0.17) * 0.0000 (0.0000) N11 * 0.0000 (0.0000) Pd * 0.0000 (0.0000) N31_$1 Rms deviation of fitted atoms = 0.0000 |
x | y | z | Uiso*/Ueq | ||
Pd | 0.000 | 0.000 | 0.000 | 0.03118 (18) | |
F | −0.0045 (4) | −0.4695 (3) | −0.2670 (3) | 0.0730 (9) | |
O1 | 0.7974 (5) | 0.7313 (5) | 0.2395 (4) | 0.0874 (14) | |
O2 | 0.6004 (6) | 0.7853 (5) | 0.3236 (4) | 0.0850 (14) | |
N11 | 0.2269 (4) | 0.0717 (4) | −0.0337 (3) | 0.0349 (8) | |
N12 | 0.2805 (4) | −0.0246 (4) | −0.1213 (3) | 0.0366 (8) | |
N13 | 0.1707 (4) | −0.1625 (4) | −0.1775 (4) | 0.0389 (9) | |
N31 | −0.0860 (4) | 0.0475 (4) | −0.1515 (4) | 0.0376 (9) | |
N1 | 0.6557 (6) | 0.6932 (5) | 0.2526 (5) | 0.0602 (13) | |
C11 | 0.3410 (5) | 0.2240 (5) | 0.0368 (4) | 0.0324 (9) | |
C12 | 0.5022 (5) | 0.2731 (5) | 0.0232 (4) | 0.0417 (11) | |
H12 | 0.5403 | 0.2024 | −0.034 | 0.05* | |
C13 | 0.6041 (5) | 0.4257 (6) | 0.0946 (5) | 0.0468 (12) | |
H13 | 0.7113 | 0.4585 | 0.0856 | 0.056* | |
C14 | 0.5481 (5) | 0.5299 (5) | 0.1792 (4) | 0.0424 (12) | |
C15 | 0.3905 (5) | 0.4829 (5) | 0.1959 (4) | 0.0411 (11) | |
H15 | 0.3541 | 0.5539 | 0.2547 | 0.049* | |
C16 | 0.2877 (5) | 0.3310 (5) | 0.1252 (4) | 0.0394 (11) | |
H16 | 0.1813 | 0.299 | 0.1364 | 0.047* | |
C21 | 0.2191 (5) | −0.2668 (5) | −0.2775 (4) | 0.0392 (10) | |
C22 | 0.1233 (6) | −0.4242 (5) | −0.3235 (5) | 0.0460 (11) | |
C23 | 0.1531 (7) | −0.5372 (6) | −0.4220 (5) | 0.0558 (13) | |
H23 | 0.0864 | −0.6425 | −0.4497 | 0.067* | |
C24 | 0.2826 (7) | −0.4936 (7) | −0.4795 (5) | 0.0639 (15) | |
H24 | 0.304 | −0.5693 | −0.5474 | 0.077* | |
C25 | 0.3818 (7) | −0.3368 (7) | −0.4366 (5) | 0.0659 (16) | |
H25 | 0.4707 | −0.3074 | −0.475 | 0.079* | |
C26 | 0.3495 (6) | −0.2239 (6) | −0.3369 (5) | 0.0552 (13) | |
H26 | 0.4156 | −0.1184 | −0.3095 | 0.066* | |
C32 | −0.0961 (6) | −0.0402 (6) | −0.2772 (5) | 0.0537 (13) | |
H32 | −0.0571 | −0.1213 | −0.2962 | 0.064* | |
C33 | −0.1621 (7) | −0.0153 (7) | −0.3802 (6) | 0.0714 (17) | |
H33 | −0.1666 | −0.0782 | −0.4673 | 0.086* | |
C34 | −0.2202 (8) | 0.1002 (10) | −0.3545 (8) | 0.092 (2) | |
H34 | −0.268 | 0.1169 | −0.4232 | 0.11* | |
C35 | −0.2076 (9) | 0.1931 (10) | −0.2253 (8) | 0.097 (2) | |
H35 | −0.2444 | 0.2759 | −0.205 | 0.117* | |
C36 | −0.1400 (7) | 0.1632 (7) | −0.1252 (6) | 0.0684 (17) | |
H36 | −0.1325 | 0.2261 | −0.0374 | 0.082* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd | 0.0271 (3) | 0.0297 (3) | 0.0361 (3) | 0.0078 (2) | 0.0078 (2) | 0.0142 (2) |
F | 0.073 (2) | 0.0492 (17) | 0.083 (2) | 0.0122 (15) | 0.0313 (18) | 0.0169 (16) |
O1 | 0.053 (3) | 0.075 (3) | 0.102 (3) | −0.023 (2) | −0.015 (2) | 0.045 (3) |
O2 | 0.102 (4) | 0.048 (2) | 0.063 (3) | −0.005 (2) | −0.003 (2) | 0.006 (2) |
N11 | 0.0295 (19) | 0.0360 (19) | 0.041 (2) | 0.0126 (16) | 0.0117 (16) | 0.0159 (17) |
N12 | 0.036 (2) | 0.043 (2) | 0.035 (2) | 0.0169 (18) | 0.0096 (17) | 0.0177 (17) |
N13 | 0.040 (2) | 0.039 (2) | 0.038 (2) | 0.0164 (18) | 0.0103 (17) | 0.0133 (17) |
N31 | 0.0263 (19) | 0.045 (2) | 0.049 (2) | 0.0129 (17) | 0.0095 (17) | 0.0266 (19) |
N1 | 0.062 (3) | 0.050 (3) | 0.049 (3) | −0.009 (2) | −0.019 (2) | 0.028 (2) |
C11 | 0.032 (2) | 0.036 (2) | 0.032 (2) | 0.0091 (19) | 0.0055 (18) | 0.0193 (19) |
C12 | 0.035 (3) | 0.050 (3) | 0.042 (3) | 0.014 (2) | 0.008 (2) | 0.022 (2) |
C13 | 0.027 (2) | 0.064 (3) | 0.050 (3) | 0.005 (2) | 0.002 (2) | 0.034 (3) |
C14 | 0.039 (3) | 0.038 (2) | 0.040 (3) | −0.005 (2) | −0.005 (2) | 0.023 (2) |
C15 | 0.046 (3) | 0.036 (2) | 0.039 (3) | 0.012 (2) | 0.004 (2) | 0.016 (2) |
C16 | 0.032 (2) | 0.037 (2) | 0.046 (3) | 0.005 (2) | 0.007 (2) | 0.019 (2) |
C21 | 0.042 (3) | 0.048 (3) | 0.032 (2) | 0.021 (2) | 0.006 (2) | 0.016 (2) |
C22 | 0.049 (3) | 0.049 (3) | 0.044 (3) | 0.022 (2) | 0.011 (2) | 0.020 (2) |
C23 | 0.069 (4) | 0.052 (3) | 0.047 (3) | 0.033 (3) | 0.006 (3) | 0.012 (2) |
C24 | 0.081 (4) | 0.070 (4) | 0.047 (3) | 0.049 (3) | 0.013 (3) | 0.010 (3) |
C25 | 0.065 (4) | 0.088 (4) | 0.050 (3) | 0.037 (3) | 0.027 (3) | 0.022 (3) |
C26 | 0.056 (3) | 0.058 (3) | 0.049 (3) | 0.020 (3) | 0.019 (3) | 0.017 (3) |
C32 | 0.056 (3) | 0.048 (3) | 0.049 (3) | 0.014 (2) | −0.006 (3) | 0.016 (2) |
C33 | 0.063 (4) | 0.079 (4) | 0.062 (4) | 0.009 (3) | −0.015 (3) | 0.036 (3) |
C34 | 0.071 (4) | 0.154 (7) | 0.096 (6) | 0.046 (5) | 0.016 (4) | 0.098 (6) |
C35 | 0.116 (6) | 0.143 (7) | 0.123 (6) | 0.098 (6) | 0.058 (5) | 0.103 (6) |
C36 | 0.090 (4) | 0.095 (4) | 0.074 (4) | 0.070 (4) | 0.043 (3) | 0.059 (4) |
Pd—N11 | 2.021 (3) | C15—C16 | 1.369 (6) |
Pd—N11i | 2.021 (3) | C15—H15 | 0.93 |
Pd—N31 | 2.039 (3) | C16—H16 | 0.93 |
Pd—N31i | 2.039 (3) | C21—C22 | 1.378 (6) |
Pd—N13 | 2.903 (4) | C21—C26 | 1.384 (6) |
F—C22 | 1.353 (5) | C22—C23 | 1.362 (7) |
O1—N1 | 1.231 (6) | C23—C24 | 1.366 (7) |
O2—N1 | 1.229 (6) | C23—H23 | 0.93 |
N11—N12 | 1.325 (5) | C24—C25 | 1.383 (8) |
N11—C11 | 1.403 (5) | C24—H24 | 0.93 |
N12—N13 | 1.283 (5) | C25—C26 | 1.380 (7) |
N13—C21 | 1.413 (5) | C25—H25 | 0.93 |
N31—C36 | 1.317 (6) | C26—H26 | 0.93 |
N31—C32 | 1.326 (6) | C32—C33 | 1.370 (7) |
N1—C14 | 1.460 (6) | C32—H32 | 0.93 |
C11—C16 | 1.391 (6) | C33—C34 | 1.339 (9) |
C11—C12 | 1.397 (6) | C33—H33 | 0.93 |
C12—C13 | 1.373 (6) | C34—C35 | 1.366 (10) |
C12—H12 | 0.93 | C34—H34 | 0.93 |
C13—C14 | 1.371 (7) | C35—C36 | 1.380 (8) |
C13—H13 | 0.93 | C35—H35 | 0.93 |
C14—C15 | 1.377 (6) | C36—H36 | 0.93 |
N11—Pd—N11i | 180.0 (2) | C14—C15—H15 | 120.2 |
N11—Pd—N31 | 91.59 (14) | C15—C16—C11 | 120.6 (4) |
N11i—Pd—N31 | 88.41 (14) | C15—C16—H16 | 119.7 |
N11—Pd—N31i | 88.41 (14) | C11—C16—H16 | 119.7 |
N11i—Pd—N31i | 91.59 (14) | C22—C21—C26 | 117.5 (4) |
N31—Pd—N31i | 180.00 (16) | C22—C21—N13 | 116.7 (4) |
N11—Pd—N13 | 47.77 (12) | C26—C21—N13 | 125.8 (4) |
N11i—Pd—N13 | 132.23 (12) | F—C22—C23 | 118.2 (4) |
N31—Pd—N13 | 88.44 (12) | F—C22—C21 | 118.7 (4) |
N31i—Pd—N13 | 91.56 (12) | C23—C22—C21 | 123.0 (5) |
N12—N11—C11 | 115.1 (3) | C22—C23—C24 | 119.0 (5) |
N12—N11—Pd | 122.0 (3) | C22—C23—H23 | 120.5 |
C11—N11—Pd | 122.9 (3) | C24—C23—H23 | 120.5 |
N13—N12—N11 | 111.0 (3) | C23—C24—C25 | 119.9 (5) |
N12—N13—C21 | 113.0 (4) | C23—C24—H24 | 120 |
N12—N13—Pd | 79.2 (2) | C25—C24—H24 | 120 |
C21—N13—Pd | 167.3 (3) | C26—C25—C24 | 120.3 (5) |
C36—N31—C32 | 118.6 (4) | C26—C25—H25 | 119.9 |
C36—N31—Pd | 119.7 (4) | C24—C25—H25 | 119.9 |
C32—N31—Pd | 121.6 (3) | C25—C26—C21 | 120.3 (5) |
O2—N1—O1 | 123.4 (5) | C25—C26—H26 | 119.8 |
O2—N1—C14 | 118.5 (5) | C21—C26—H26 | 119.8 |
O1—N1—C14 | 118.1 (5) | N31—C32—C33 | 122.3 (5) |
C16—C11—C12 | 119.0 (4) | N31—C32—H32 | 118.9 |
C16—C11—N11 | 116.9 (4) | C33—C32—H32 | 118.9 |
C12—C11—N11 | 124.1 (4) | C34—C33—C32 | 119.6 (6) |
C13—C12—C11 | 119.9 (4) | C34—C33—H33 | 120.2 |
C13—C12—H12 | 120.1 | C32—C33—H33 | 120.2 |
C11—C12—H12 | 120.1 | C33—C34—C35 | 118.6 (6) |
C14—C13—C12 | 120.2 (4) | C33—C34—H34 | 120.7 |
C14—C13—H13 | 119.9 | C35—C34—H34 | 120.7 |
C12—C13—H13 | 119.9 | C34—C35—C36 | 119.6 (6) |
C13—C14—C15 | 120.8 (4) | C34—C35—H35 | 120.2 |
C13—C14—N1 | 120.0 (5) | C36—C35—H35 | 120.2 |
C15—C14—N1 | 119.2 (5) | N31—C36—C35 | 121.3 (6) |
C16—C15—C14 | 119.6 (4) | N31—C36—H36 | 119.3 |
C16—C15—H15 | 120.2 | C35—C36—H36 | 119.3 |
N31—Pd—N11—N12 | −86.4 (3) | O2—N1—C14—C13 | 177.1 (4) |
N31i—Pd—N11—N12 | 93.6 (3) | O1—N1—C14—C13 | −2.6 (6) |
N13—Pd—N11—N12 | 0.0 (3) | O2—N1—C14—C15 | −2.6 (7) |
N31—Pd—N11—C11 | 96.2 (3) | O1—N1—C14—C15 | 177.7 (4) |
N31i—Pd—N11—C11 | −83.8 (3) | C13—C14—C15—C16 | −1.2 (7) |
N13—Pd—N11—C11 | −177.3 (4) | N1—C14—C15—C16 | 178.5 (4) |
C11—N11—N12—N13 | 177.5 (3) | C14—C15—C16—C11 | −0.1 (7) |
Pd—N11—N12—N13 | 0.0 (5) | C12—C11—C16—C15 | 1.4 (6) |
N11—N12—N13—C21 | 176.3 (3) | N11—C11—C16—C15 | −178.6 (4) |
N11—N12—N13—Pd | 0.0 (3) | N12—N13—C21—C22 | 166.9 (4) |
N11—Pd—N13—N12 | 0.0 (2) | Pd—N13—C21—C22 | −29.7 (15) |
N11i—Pd—N13—N12 | 180.0 (2) | N12—N13—C21—C26 | −16.1 (6) |
N31—Pd—N13—N12 | 93.6 (2) | Pd—N13—C21—C26 | 147.3 (11) |
N31i—Pd—N13—N12 | −86.4 (2) | C26—C21—C22—F | 179.7 (4) |
N11—Pd—N13—C21 | −164.5 (13) | N13—C21—C22—F | −3.0 (6) |
N11i—Pd—N13—C21 | 15.5 (13) | C26—C21—C22—C23 | 1.0 (7) |
N31—Pd—N13—C21 | −70.9 (13) | N13—C21—C22—C23 | 178.3 (4) |
N31i—Pd—N13—C21 | 109.1 (13) | F—C22—C23—C24 | −179.4 (5) |
N11—Pd—N31—C36 | −112.1 (4) | C21—C22—C23—C24 | −0.7 (8) |
N11i—Pd—N31—C36 | 67.9 (4) | C22—C23—C24—C25 | 0.6 (8) |
N13—Pd—N31—C36 | −159.8 (4) | C23—C24—C25—C26 | −0.8 (8) |
N11—Pd—N31—C32 | 71.1 (4) | C24—C25—C26—C21 | 1.1 (8) |
N11i—Pd—N31—C32 | −108.9 (4) | C22—C21—C26—C25 | −1.2 (7) |
N13—Pd—N31—C32 | 23.4 (3) | N13—C21—C26—C25 | −178.1 (5) |
N12—N11—C11—C16 | 177.1 (3) | C36—N31—C32—C33 | −0.6 (7) |
Pd—N11—C11—C16 | −5.4 (5) | Pd—N31—C32—C33 | 176.2 (4) |
N12—N11—C11—C12 | −2.9 (6) | N31—C32—C33—C34 | −0.6 (9) |
Pd—N11—C11—C12 | 174.6 (3) | C32—C33—C34—C35 | 1.8 (10) |
C16—C11—C12—C13 | −1.4 (6) | C33—C34—C35—C36 | −1.8 (11) |
N11—C11—C12—C13 | 178.6 (4) | C32—N31—C36—C35 | 0.7 (8) |
C11—C12—C13—C14 | 0.1 (7) | Pd—N31—C36—C35 | −176.2 (5) |
C12—C13—C14—C15 | 1.2 (7) | C34—C35—C36—N31 | 0.5 (10) |
C12—C13—C14—N1 | −178.5 (4) |
Symmetry code: (i) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Pd(C5H5N)2(C12H8FN4O2)2] |
Mr | 783.07 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.941 (2), 9.732 (2), 10.9449 (10) |
α, β, γ (°) | 110.058 (14), 93.437 (13), 109.012 (19) |
V (Å3) | 829.9 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.63 |
Crystal size (mm) | 0.20 × 0.13 × 0.07 |
Data collection | |
Diffractometer | Enraf Nonius TurboCAD-4 diffractometer |
Absorption correction | ψ-scan (North et al., 1968) |
Tmin, Tmax | 0.885, 0.958 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3149, 2947, 2446 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.105, 1.07 |
No. of reflections | 2947 |
No. of parameters | 232 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.48, −0.98 |
Computer programs: CAD-4 EXPRESS (Enraf Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Pd—N11 | 2.021 (3) | N11—C11 | 1.403 (5) |
Pd—N31 | 2.039 (3) | N12—N13 | 1.283 (5) |
Pd—N13 | 2.903 (4) | N13—C21 | 1.413 (5) |
F—C22 | 1.353 (5) | N31—C36 | 1.317 (6) |
O1—N1 | 1.231 (6) | N31—C32 | 1.326 (6) |
O2—N1 | 1.229 (6) | N1—C14 | 1.460 (6) |
N11—N12 | 1.325 (5) | ||
N11—Pd—N11i | 180.0 (2) | N31—Pd—N31i | 180.00 (16) |
N11—Pd—N31 | 91.59 (14) | N13—N12—N11 | 111.0 (3) |
N11—Pd—N31i | 88.41 (14) |
Symmetry code: (i) −x, −y, −z. |
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Although palladium(II) complexes with nitrogen coordination spheres involving catenated 1,3-diaryl-substituted triazenido ligands, ArNNNAr-, have been investigated over the last few decades, the structures of such compounds continues to attract interest (Moore & Robinson, 1986; Peregudov et al., 1998; Cao et al., 2000). In this work, we report the synthesis and structural characterization of the title complex, (I), a centrosymmetric mononuclear PdII complex with an asymmetric disubstituted 1,3-diaryltriazenido ion and pyridine as ligands. \sch
In the molecule of the monomeric complex, (I), with site symmetry 1, the square-planar coordinated Pd2+ ion is situated on an inversion centre, with two 3-(2-fluorophenyl)-1-(4-nitrophenyl)triazenido ions, FC6H4N═ N—NC6H4NO2-, and two pyridine molecules coordinated trans to each other (Fig. 1).
The deviation observed in (I) from the normal N—N and Car—N bonds makes evident the delocalization of the π electrons on the N11—N12═N13 group towards the terminal aryl substituents. The N12═N13 bond [1.283 (5) Å] is longer than the characteristic value for such a double bond (1.24 Å), whereas N11—N12 [1.325 (5) Å] is shorter than the characteristic value for a single bond (1.44 Å) (International Tables for X-Ray Crystallography, 1985), and both N11—C11 [1.403 (5) Å] and N13—C21 [1.413 (5) Å] are shorter than expected for a Car—N single bond. The Pd—N11 bond distance of 2.021 (3) Å is close to the sum of the covalent radii of 2.08 Å (Sheldrick, 1997) and corresponds to a covalent single bond. These values are in good agreement with the distances found in the related compound trans-[Pd(RN1—N2═N3R)Cl(PPh3)2] (R is p-toluene?; N2═N3 1.286, N1—N2 1.336 and Pd—N1 2.033 Å; Moore & Robinson, 1986; Bombieri et al., 1975, 1976; Brown & Ibers, 1976).
Due to the delocalization of the π electrons over the nitro group and the C11—C16 phenyl ring, towards the N11—N12═N13 chain, this part of the triazenido ligand is nearly planar [interplanar angles O1/N1/O2/C11—C16 3.0 (6)° and C11—C16/N11—N12═N13 4.2 (4)°]. On the other hand, the C21—C26 ring makes an angle of 16.8 (5)° with the plane defined by the N11—N12═N13 group, which accounts for the significant deviation from planarity of the whole 1,3-diaryltriazenido ligand. The C11—C16 phenyl ring and the 2-fluorophenyl substituent are almost planar (r.m.s. deviations 0.0064 and 0.0042 Å, respectively).
The pyridine ring (N31—C36) is planar to within experimental accuracy (r.m.s. deviation 0.0062 Å), making a dihedral angle of 69.5 (2)° with the N11—Pd—N31i moiety [symmetry code: (i) -x, -y, -z]. The Pd—N31 bond distance of 2.039 (3) Å is shorter than the sum of the covalent radii (2.08 Å; Sheldrick, 1997) and may be compared with the value found in the compound [Pd(py)4](I3)2 (Pd—Npy 2.014 Å; Tebbe et al., 1996).