Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802021281/lh6009sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802021281/lh6009Isup2.hkl |
CCDC reference: 202307
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.006 Å
- R factor = 0.032
- wR factor = 0.078
- Data-to-parameter ratio = 14.4
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
CELLV_02 Alert C The supplied cell volume s.u. differs from that calculated from the cell parameter s.u.'s by > 2 Calculated cell volume su = 4.22 Cell volume su given = 2.00
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
For the preparation of compound (I), p-phenylenediamine was combined with dpk in a 1:2 stoichiometric ratio in CH3CN/CH3CH2OH, followed by addition of PdCl2. The resulting solution was filtered and slow evaporation of the clear filtrate gave clear yellow crystals suitable for X-ray diffraction studies (yield: 0.07 g, 75%). Analysis calculated for C13H14Cl2N2O2Pd: C 38.43, H 3.48, N 6.90%; found: C 38.23, H 3.09, N 6.68%.
H atoms were included in caculated positions and allowed to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SHELXTL (Bruker, 1999); program(s) used to solve structure: SHELXL97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. A view of the structure of the title compound, showing 30% probability displacement ellipsoids. H atoms have been omitted for clarity. |
[PdCl2(C13H14N2O2)] | Z = 4 |
Mr = 407.56 | F(000) = 808 |
Monoclinic, P21/n | Dx = 1.801 Mg m−3 |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 9.8277 (1) Å | θ = 2.3–25.0° |
b = 12.0717 (3) Å | µ = 1.59 mm−1 |
c = 12.6885 (1) Å | T = 293 K |
β = 93.162 (2)° | Column, yellow |
V = 1503.03 (2) Å3 | 0.36 × 0.22 × 0.20 mm |
Siemens SMART CCD diffractometer | 2600 independent reflections |
Radiation source: fine-focus sealed tube | 2270 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→11 |
Tmin = 0.558, Tmax = 0.727 | k = −9→14 |
4510 measured reflections | l = −15→11 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 1.15 | w = 1/[σ2(Fo2) + (0.0225P)2 + 2.9262P] where P = (Fo2 + 2Fc2)/3 |
2600 reflections | (Δ/σ)max = 0.001 |
181 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.63 e Å−3 |
[PdCl2(C13H14N2O2)] | V = 1503.03 (2) Å3 |
Mr = 407.56 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.8277 (1) Å | µ = 1.59 mm−1 |
b = 12.0717 (3) Å | T = 293 K |
c = 12.6885 (1) Å | 0.36 × 0.22 × 0.20 mm |
β = 93.162 (2)° |
Siemens SMART CCD diffractometer | 2600 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2270 reflections with I > 2σ(I) |
Tmin = 0.558, Tmax = 0.727 | Rint = 0.019 |
4510 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 1.15 | Δρmax = 0.32 e Å−3 |
2600 reflections | Δρmin = −0.63 e Å−3 |
181 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. The structure was solved by direct methods and successive Fourier difference syntheses. 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 | 0.18888 (3) | 0.07957 (2) | 0.73840 (2) | 0.03211 (11) | |
Cl2 | −0.03247 (11) | 0.11059 (11) | 0.67829 (10) | 0.0508 (3) | |
Cl1 | 0.11749 (13) | 0.01755 (9) | 0.89699 (9) | 0.0501 (3) | |
O1 | 0.5394 (3) | 0.3071 (2) | 0.7049 (2) | 0.0411 (7) | |
H1A | 0.5128 | 0.3654 | 0.6777 | 0.062* | |
N2 | 0.2575 (3) | 0.1355 (3) | 0.6002 (3) | 0.0335 (7) | |
C7 | 0.3650 (4) | 0.2062 (3) | 0.6023 (3) | 0.0340 (9) | |
C6 | 0.4293 (4) | 0.2342 (3) | 0.7110 (3) | 0.0338 (9) | |
C11 | 0.2024 (4) | 0.1023 (4) | 0.5067 (3) | 0.0405 (10) | |
H11A | 0.1285 | 0.0541 | 0.5053 | 0.049* | |
C1 | 0.4288 (5) | −0.0453 (4) | 0.8291 (4) | 0.0455 (11) | |
H1B | 0.3632 | −0.0983 | 0.8425 | 0.055* | |
C4 | 0.6216 (4) | 0.1076 (4) | 0.7854 (4) | 0.0454 (11) | |
H4A | 0.6864 | 0.1596 | 0.7678 | 0.055* | |
C5 | 0.4846 (4) | 0.1269 (3) | 0.7626 (3) | 0.0349 (9) | |
C3 | 0.6610 (5) | 0.0093 (4) | 0.8351 (4) | 0.0556 (13) | |
H3A | 0.7524 | −0.0042 | 0.8536 | 0.067* | |
C2 | 0.5638 (5) | −0.0674 (4) | 0.8563 (4) | 0.0586 (14) | |
H2A | 0.5886 | −0.1340 | 0.8888 | 0.070* | |
N1 | 0.3898 (3) | 0.0507 (3) | 0.7840 (3) | 0.0365 (8) | |
C10 | 0.2511 (5) | 0.1370 (4) | 0.4127 (4) | 0.0483 (11) | |
H10A | 0.2112 | 0.1122 | 0.3488 | 0.058* | |
C8 | 0.4161 (4) | 0.2443 (4) | 0.5110 (3) | 0.0389 (10) | |
H8A | 0.4887 | 0.2939 | 0.5137 | 0.047* | |
C9 | 0.3596 (5) | 0.2088 (4) | 0.4144 (4) | 0.0484 (11) | |
H9A | 0.3945 | 0.2332 | 0.3518 | 0.058* | |
O2 | 0.3243 (2) | 0.2797 (2) | 0.7691 (2) | 0.0316 (6) | |
C12 | 0.3637 (4) | 0.3085 (4) | 0.8775 (3) | 0.0420 (10) | |
H12A | 0.4154 | 0.3770 | 0.8798 | 0.050* | |
H12B | 0.4200 | 0.2505 | 0.9099 | 0.050* | |
C13 | 0.2364 (5) | 0.3219 (4) | 0.9348 (4) | 0.0549 (13) | |
H13A | 0.2593 | 0.3409 | 1.0071 | 0.082* | |
H13B | 0.1862 | 0.2537 | 0.9320 | 0.082* | |
H13C | 0.1818 | 0.3797 | 0.9023 | 0.082* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.03223 (18) | 0.02898 (18) | 0.03556 (18) | −0.00490 (13) | 0.00571 (12) | −0.00013 (13) |
Cl2 | 0.0313 (5) | 0.0600 (7) | 0.0611 (7) | −0.0023 (5) | 0.0034 (5) | −0.0073 (6) |
Cl1 | 0.0674 (7) | 0.0406 (6) | 0.0444 (6) | −0.0085 (5) | 0.0217 (5) | 0.0015 (5) |
O1 | 0.0307 (14) | 0.0368 (16) | 0.0555 (18) | −0.0056 (12) | 0.0011 (13) | 0.0013 (14) |
N2 | 0.0301 (17) | 0.0330 (18) | 0.0376 (19) | −0.0016 (14) | 0.0029 (14) | 0.0003 (15) |
C7 | 0.029 (2) | 0.030 (2) | 0.042 (2) | 0.0039 (16) | 0.0043 (17) | 0.0028 (18) |
C6 | 0.0249 (19) | 0.032 (2) | 0.045 (2) | −0.0039 (16) | 0.0048 (17) | −0.0036 (18) |
C11 | 0.036 (2) | 0.042 (2) | 0.043 (2) | −0.0021 (19) | −0.0022 (18) | 0.001 (2) |
C1 | 0.052 (3) | 0.034 (2) | 0.050 (3) | 0.000 (2) | 0.000 (2) | 0.006 (2) |
C4 | 0.034 (2) | 0.045 (3) | 0.057 (3) | 0.002 (2) | −0.003 (2) | −0.005 (2) |
C5 | 0.036 (2) | 0.032 (2) | 0.037 (2) | 0.0010 (17) | 0.0027 (17) | −0.0050 (17) |
C3 | 0.048 (3) | 0.052 (3) | 0.065 (3) | 0.016 (2) | −0.010 (2) | −0.006 (3) |
C2 | 0.066 (3) | 0.045 (3) | 0.064 (3) | 0.019 (3) | −0.007 (3) | 0.005 (2) |
N1 | 0.0426 (19) | 0.0325 (19) | 0.0348 (19) | 0.0052 (15) | 0.0048 (15) | 0.0006 (15) |
C10 | 0.043 (2) | 0.063 (3) | 0.038 (2) | 0.004 (2) | −0.0017 (19) | −0.002 (2) |
C8 | 0.037 (2) | 0.038 (2) | 0.044 (2) | 0.0002 (18) | 0.0116 (19) | 0.0088 (19) |
C9 | 0.048 (3) | 0.059 (3) | 0.039 (2) | 0.005 (2) | 0.010 (2) | 0.013 (2) |
O2 | 0.0275 (13) | 0.0335 (15) | 0.0340 (14) | 0.0011 (11) | 0.0031 (11) | −0.0026 (12) |
C12 | 0.045 (2) | 0.040 (2) | 0.041 (2) | −0.002 (2) | −0.0026 (19) | −0.0038 (19) |
C13 | 0.061 (3) | 0.054 (3) | 0.051 (3) | −0.009 (3) | 0.019 (2) | −0.013 (2) |
Pd1—N2 | 2.029 (3) | C4—C3 | 1.389 (7) |
Pd1—N1 | 2.057 (3) | C4—H4A | 0.9300 |
Pd1—Cl1 | 2.2929 (11) | C5—N1 | 1.348 (5) |
Pd1—Cl2 | 2.2959 (11) | C3—C2 | 1.368 (7) |
O1—C6 | 1.400 (4) | C3—H3A | 0.9300 |
O1—H1A | 0.8200 | C2—H2A | 0.9300 |
N2—C11 | 1.337 (5) | C10—C9 | 1.374 (6) |
N2—C7 | 1.357 (5) | C10—H10A | 0.9300 |
C7—C8 | 1.369 (6) | C8—C9 | 1.386 (6) |
C7—C6 | 1.523 (6) | C8—H8A | 0.9300 |
C6—O2 | 1.412 (4) | C9—H9A | 0.9300 |
C6—C5 | 1.537 (6) | O2—C12 | 1.451 (5) |
C11—C10 | 1.376 (6) | C12—C13 | 1.490 (6) |
C11—H11A | 0.9300 | C12—H12A | 0.9700 |
C1—N1 | 1.339 (5) | C12—H12B | 0.9700 |
C1—C2 | 1.378 (7) | C13—H13A | 0.9600 |
C1—H1B | 0.9300 | C13—H13B | 0.9600 |
C4—C5 | 1.380 (6) | C13—H13C | 0.9600 |
N2—Pd1—N1 | 86.56 (13) | C2—C3—C4 | 119.2 (4) |
N2—Pd1—Cl1 | 178.32 (10) | C2—C3—H3A | 120.4 |
N1—Pd1—Cl1 | 91.91 (10) | C4—C3—H3A | 120.4 |
N2—Pd1—Cl2 | 90.71 (9) | C3—C2—C1 | 119.5 (5) |
N1—Pd1—Cl2 | 176.93 (10) | C3—C2—H2A | 120.2 |
Cl1—Pd1—Cl2 | 90.84 (5) | C1—C2—H2A | 120.2 |
C6—O1—H1A | 109.5 | C1—N1—C5 | 119.5 (4) |
C11—N2—C7 | 118.9 (4) | C1—N1—Pd1 | 121.0 (3) |
C11—N2—Pd1 | 122.0 (3) | C5—N1—Pd1 | 119.4 (3) |
C7—N2—Pd1 | 119.1 (3) | C9—C10—C11 | 119.0 (4) |
N2—C7—C8 | 121.1 (4) | C9—C10—H10A | 120.5 |
N2—C7—C6 | 116.2 (3) | C11—C10—H10A | 120.5 |
C8—C7—C6 | 122.6 (4) | C7—C8—C9 | 119.8 (4) |
O1—C6—O2 | 112.0 (3) | C7—C8—H8A | 120.1 |
O1—C6—C7 | 111.9 (3) | C9—C8—H8A | 120.1 |
O2—C6—C7 | 106.2 (3) | C10—C9—C8 | 118.8 (4) |
O1—C6—C5 | 107.3 (3) | C10—C9—H9A | 120.6 |
O2—C6—C5 | 110.9 (3) | C8—C9—H9A | 120.6 |
C7—C6—C5 | 108.5 (3) | C6—O2—C12 | 115.1 (3) |
N2—C11—C10 | 122.3 (4) | O2—C12—C13 | 107.6 (3) |
N2—C11—H11A | 118.8 | O2—C12—H12A | 110.2 |
C10—C11—H11A | 118.8 | C13—C12—H12A | 110.2 |
N1—C1—C2 | 121.6 (4) | O2—C12—H12B | 110.2 |
N1—C1—H1B | 119.2 | C13—C12—H12B | 110.2 |
C2—C1—H1B | 119.2 | H12A—C12—H12B | 108.5 |
C5—C4—C3 | 119.0 (4) | C12—C13—H13A | 109.5 |
C5—C4—H4A | 120.5 | C12—C13—H13B | 109.5 |
C3—C4—H4A | 120.5 | H13A—C13—H13B | 109.5 |
N1—C5—C4 | 121.2 (4) | C12—C13—H13C | 109.5 |
N1—C5—C6 | 115.4 (3) | H13A—C13—H13C | 109.5 |
C4—C5—C6 | 123.3 (4) | H13B—C13—H13C | 109.5 |
Experimental details
Crystal data | |
Chemical formula | [PdCl2(C13H14N2O2)] |
Mr | 407.56 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 9.8277 (1), 12.0717 (3), 12.6885 (1) |
β (°) | 93.162 (2) |
V (Å3) | 1503.03 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.59 |
Crystal size (mm) | 0.36 × 0.22 × 0.20 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.558, 0.727 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4510, 2600, 2270 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.078, 1.15 |
No. of reflections | 2600 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.63 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), SHELXTL (Bruker, 1999), SHELXL97 (Sheldrick, 1997), SHELXTL.
Pd1—N2 | 2.029 (3) | Pd1—Cl1 | 2.2929 (11) |
Pd1—N1 | 2.057 (3) | Pd1—Cl2 | 2.2959 (11) |
N2—Pd1—N1 | 86.56 (13) | N1—Pd1—Cl2 | 176.93 (10) |
N2—Pd1—Cl1 | 178.32 (10) | Cl1—Pd1—Cl2 | 90.84 (5) |
N1—Pd1—Cl1 | 91.91 (10) | C11—N2—Pd1 | 122.0 (3) |
N2—Pd1—Cl2 | 90.71 (9) | C7—N2—Pd1 | 119.1 (3) |
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The condensation products formed when metal complexes of di-2-pyridine ketone (dpk) are reacted with some nucleophiles, includung water, have been reported previously (Annibale et al., 1981; Sommerer et al., 1997). Herein we report the structure of the title compound, (I), which is formed via the reaction of dpk with PdCl2 in CH3CN/CH3CH2OH. In (I), the N1—Pd—N2 angle is narrower than the ideal value (for square-planar coordination) of 90° [86.56 (13)°]. This angle is also narrower than that observed in [Pd{dpk-(OH)2}]Cl2 and [Pd(2,2'-dipyridyl)]Cl2, where the N—Pd—N angles are 87.1 (2)(Annibale et al., 1981) and 80.5 (4)° (Beer et al., 1997), respectively. The N2—Pd—Cl2 and Cl1—Pd—Cl2 angles of 90.71 (9) and 90.84 (5), respectively, are closer to the ideal value of 90°; this indicates that the coordination geometry of the Pd atom is square planar with a slight tetrahedral distortion.