



Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536812043036/su2513sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536812043036/su2513Isup2.hkl |
CCDC reference: 909742
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean
(C-C) = 0.011 Å
- Disorder in solvent or counterion
- R factor = 0.052
- wR factor = 0.147
- Data-to-parameter ratio = 10.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT088_ALERT_3_C Poor Data / Parameter Ratio .................... 9.97 PLAT234_ALERT_4_C Large Hirshfeld Difference P1 -- F1' .. 0.19 Ang. PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C4 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C10 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C11 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N3 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C3 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C6 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C9 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors of P1 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors of P2 PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds ............... 0.0106 Ang PLAT906_ALERT_3_C Large K value in the Analysis of Variance ...... 2.956 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 17 PLAT976_ALERT_2_C Negative Residual Density at 0.76A from N4 . -0.40 eA-3
Alert level G PLAT003_ALERT_2_G Number of Uiso or Uij Restrained Atom Sites .... 24 PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF .... ? PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............ 4 PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings Differ ? PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large. 9.90 PLAT231_ALERT_4_G Hirshfeld Test (Solvent) P1 -- F6' .. 5.5 su PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ................... 86 Perc. PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms .... ! PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 144 PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 53
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 15 ALERT level C = Check. Ensure it is not caused by an omission or oversight 10 ALERT level G = General information/check it is not something unexpected 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 10 ALERT type 2 Indicator that the structure model may be wrong or deficient 5 ALERT type 3 Indicator that the structure quality may be low 6 ALERT type 4 Improvement, methodology, query or suggestion 3 ALERT type 5 Informative message, check
Pd(bpy)(PF6)2 [bpy = 2,2'-bipyridine] was prepared by adding solid AgPF6 to an acetonitrile suspension of Pd(bpy)Cl2 (0.050 g, 0.15 mmol). After being stirred for 2 h, the mixture was filtered to remove AgCl. Isonicotinamide (0.037 g, 0.30 mmol) was added to the Pd(bpy)(PF6)2 solution and the solution was heated at 323 K for 3 h. Crystals were obtained by vapour diffusion of diethyl ether over an acetonitrile solution of the title complex [0.083 g, 85% yield; M.pt: 513 K (dec.), 523 K (melting)].
Ni and C-bound H-atoms were placed in calculated positions (N—H = 0.88 Å and C—H 0.95 Å) and were included in the refinement in the riding model approximation, with Uiso(H) = 1.2Uequiv(carrier atom). Both PF6 anions are disordered over two positions in respect of the F atoms only. The occupancy was assumed to be 1:1 as it could not be refined. The anisotropic displacement parameters of the F atoms were restrained to be nearly isotropic. Two reflections, i.e. (2 0 18) and (0 6 15), were omitted from the final refinement owing to poor agreement.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).
[Pd(C10H8N2)(C6H6NO2)2](PF6)2 | F(000) = 3152 |
Mr = 796.78 | Dx = 1.900 Mg m−3 |
Monoclinic, C2/c | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -C 2yc | Cell parameters from 4302 reflections |
a = 22.5920 (14) Å | θ = 3.8–68.1° |
b = 13.8299 (8) Å | µ = 7.55 mm−1 |
c = 17.9092 (12) Å | T = 100 K |
β = 95.269 (8)° | Rod, colourless |
V = 5572.0 (6) Å3 | 0.46 × 0.16 × 0.15 mm |
Z = 8 |
Bruker APEX CCD diffractometer | 5182 independent reflections |
Radiation source: fine-focus sealed tube | 3944 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.072 |
ϕ and ω scans | θmax = 69.8°, θmin = 3.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | h = −26→26 |
Tmin = 0.126, Tmax = 0.401 | k = −16→16 |
30116 measured reflections | l = −21→18 |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0879P)2 + 9.8993P] where P = (Fo2 + 2Fc2)/3 |
5182 reflections | (Δ/σ)max = 0.001 |
520 parameters | Δρmax = 0.67 e Å−3 |
144 restraints | Δρmin = −0.78 e Å−3 |
[Pd(C10H8N2)(C6H6NO2)2](PF6)2 | V = 5572.0 (6) Å3 |
Mr = 796.78 | Z = 8 |
Monoclinic, C2/c | Cu Kα radiation |
a = 22.5920 (14) Å | µ = 7.55 mm−1 |
b = 13.8299 (8) Å | T = 100 K |
c = 17.9092 (12) Å | 0.46 × 0.16 × 0.15 mm |
β = 95.269 (8)° |
Bruker APEX CCD diffractometer | 5182 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | 3944 reflections with I > 2σ(I) |
Tmin = 0.126, Tmax = 0.401 | Rint = 0.072 |
30116 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 144 restraints |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.67 e Å−3 |
5182 reflections | Δρmin = −0.78 e Å−3 |
520 parameters |
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 | Occ. (<1) | |
Pd | 0.667091 (18) | 0.53803 (3) | 0.62000 (2) | 0.03743 (15) | |
P1 | 0.70718 (7) | 0.64260 (15) | 0.84670 (11) | 0.0532 (4) | |
P2 | 0.57543 (8) | 0.73478 (13) | 0.41320 (11) | 0.0519 (4) | |
F1 | 0.7509 (5) | 0.6745 (11) | 0.7858 (7) | 0.086 (3) | 0.50 |
F2 | 0.7240 (7) | 0.7410 (9) | 0.8898 (9) | 0.118 (4) | 0.50 |
F3 | 0.6661 (5) | 0.6128 (12) | 0.9038 (7) | 0.093 (4) | 0.50 |
F4 | 0.6999 (6) | 0.5423 (8) | 0.8021 (6) | 0.084 (3) | 0.50 |
F5 | 0.6557 (5) | 0.6892 (10) | 0.7948 (8) | 0.087 (4) | 0.50 |
F6 | 0.7629 (4) | 0.5972 (6) | 0.8934 (6) | 0.052 (2) | 0.50 |
F7 | 0.5623 (7) | 0.6485 (8) | 0.4674 (6) | 0.088 (3) | 0.50 |
F8 | 0.5449 (7) | 0.8077 (15) | 0.4605 (11) | 0.081 (5) | 0.50 |
F9 | 0.5970 (6) | 0.8181 (7) | 0.3611 (7) | 0.077 (3) | 0.50 |
F10 | 0.6113 (4) | 0.6573 (8) | 0.3638 (6) | 0.052 (2) | 0.50 |
F11 | 0.6403 (4) | 0.7503 (9) | 0.4640 (6) | 0.078 (3) | 0.50 |
F12 | 0.5198 (4) | 0.7132 (10) | 0.3636 (7) | 0.087 (3) | 0.50 |
F1' | 0.7399 (10) | 0.5757 (17) | 0.7956 (11) | 0.160 (7) | 0.50 |
F2' | 0.7296 (7) | 0.7305 (12) | 0.8075 (9) | 0.118 (5) | 0.50 |
F3' | 0.6705 (6) | 0.7100 (9) | 0.8982 (6) | 0.089 (3) | 0.50 |
F4' | 0.6788 (7) | 0.5562 (9) | 0.8956 (8) | 0.095 (4) | 0.50 |
F5' | 0.6495 (6) | 0.6323 (10) | 0.7903 (7) | 0.082 (3) | 0.50 |
F6' | 0.7612 (9) | 0.6409 (15) | 0.9077 (11) | 0.136 (7) | 0.50 |
F7' | 0.5639 (7) | 0.8201 (13) | 0.4737 (11) | 0.065 (4) | 0.50 |
F8' | 0.6250 (4) | 0.7947 (9) | 0.3815 (7) | 0.066 (3) | 0.50 |
F9' | 0.5184 (6) | 0.6781 (9) | 0.4411 (7) | 0.094 (3) | 0.50 |
F10' | 0.5814 (6) | 0.6529 (10) | 0.3528 (7) | 0.081 (3) | 0.50 |
F11' | 0.5277 (4) | 0.7880 (9) | 0.3518 (6) | 0.081 (3) | 0.50 |
F12' | 0.6163 (6) | 0.6839 (10) | 0.4707 (6) | 0.094 (3) | 0.50 |
O1 | 0.5848 (2) | 0.0479 (3) | 0.5984 (4) | 0.0706 (16) | |
O2 | 0.9674 (2) | 0.4298 (4) | 0.6755 (4) | 0.0730 (16) | |
N1 | 0.6458 (2) | 0.3976 (4) | 0.6254 (3) | 0.0426 (11) | |
N2 | 0.5616 (5) | 0.0829 (6) | 0.7123 (5) | 0.105 (3) | |
H1n | 0.5465 | 0.0249 | 0.7176 | 0.126* | |
H2n | 0.5616 | 0.1254 | 0.7488 | 0.126* | |
N3 | 0.7528 (2) | 0.4988 (4) | 0.6136 (3) | 0.0393 (11) | |
N4 | 0.9639 (3) | 0.4321 (6) | 0.5525 (5) | 0.086 (2) | |
H3n | 1.0022 | 0.4192 | 0.5553 | 0.103* | |
H4n | 0.9437 | 0.4393 | 0.5085 | 0.103* | |
N5 | 0.5835 (2) | 0.5845 (4) | 0.6278 (3) | 0.0459 (12) | |
N6 | 0.6826 (2) | 0.6815 (4) | 0.6218 (3) | 0.0407 (11) | |
C1 | 0.6372 (4) | 0.3601 (5) | 0.6929 (4) | 0.0602 (19) | |
H1 | 0.6435 | 0.3999 | 0.7361 | 0.072* | |
C2 | 0.6201 (4) | 0.2674 (5) | 0.7010 (4) | 0.0586 (18) | |
H2 | 0.6160 | 0.2428 | 0.7498 | 0.070* | |
C3 | 0.6084 (3) | 0.2081 (4) | 0.6399 (4) | 0.0455 (15) | |
C4 | 0.6180 (5) | 0.2470 (6) | 0.5720 (5) | 0.077 (3) | |
H4 | 0.6113 | 0.2087 | 0.5280 | 0.092* | |
C5 | 0.6369 (4) | 0.3400 (6) | 0.5663 (5) | 0.068 (2) | |
H5 | 0.6440 | 0.3644 | 0.5184 | 0.082* | |
C6 | 0.5854 (3) | 0.1070 (5) | 0.6467 (5) | 0.0577 (18) | |
C7 | 0.7775 (3) | 0.5003 (8) | 0.5506 (5) | 0.071 (2) | |
H7 | 0.7535 | 0.5146 | 0.5055 | 0.085* | |
C8 | 0.8376 (4) | 0.4816 (8) | 0.5470 (5) | 0.074 (3) | |
H8 | 0.8545 | 0.4856 | 0.5005 | 0.089* | |
C9 | 0.8717 (3) | 0.4578 (4) | 0.6095 (4) | 0.0468 (15) | |
C10 | 0.8457 (4) | 0.4501 (9) | 0.6735 (6) | 0.097 (4) | |
H10 | 0.8684 | 0.4304 | 0.7182 | 0.116* | |
C11 | 0.7862 (4) | 0.4707 (9) | 0.6746 (5) | 0.090 (3) | |
H11 | 0.7684 | 0.4646 | 0.7205 | 0.108* | |
C12 | 0.9376 (3) | 0.4405 (5) | 0.6127 (5) | 0.0546 (18) | |
C13 | 0.5341 (3) | 0.5284 (5) | 0.6259 (5) | 0.0560 (17) | |
H13 | 0.5372 | 0.4608 | 0.6179 | 0.067* | |
C14 | 0.4796 (3) | 0.5682 (6) | 0.6354 (5) | 0.068 (2) | |
H14 | 0.4451 | 0.5286 | 0.6333 | 0.081* | |
C15 | 0.4755 (3) | 0.6653 (6) | 0.6479 (6) | 0.082 (3) | |
H15 | 0.4384 | 0.6936 | 0.6560 | 0.098* | |
C16 | 0.5259 (3) | 0.7221 (6) | 0.6486 (5) | 0.068 (2) | |
H16 | 0.5236 | 0.7898 | 0.6569 | 0.082* | |
C17 | 0.5794 (3) | 0.6798 (5) | 0.6372 (4) | 0.0497 (16) | |
C18 | 0.6345 (3) | 0.7349 (5) | 0.6329 (4) | 0.0435 (14) | |
C19 | 0.6381 (3) | 0.8338 (5) | 0.6376 (4) | 0.0520 (16) | |
H19 | 0.6037 | 0.8706 | 0.6452 | 0.062* | |
C20 | 0.6913 (3) | 0.8800 (5) | 0.6313 (4) | 0.0558 (17) | |
H20 | 0.6939 | 0.9485 | 0.6336 | 0.067* | |
C21 | 0.7415 (3) | 0.8240 (5) | 0.6214 (4) | 0.0545 (17) | |
H21 | 0.7791 | 0.8536 | 0.6178 | 0.065* | |
C22 | 0.7353 (3) | 0.7249 (5) | 0.6170 (4) | 0.0437 (14) | |
H22 | 0.7692 | 0.6863 | 0.6104 | 0.052* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd | 0.0313 (2) | 0.0397 (2) | 0.0422 (3) | −0.00218 (17) | 0.00854 (15) | 0.00002 (19) |
P1 | 0.0333 (8) | 0.0718 (11) | 0.0553 (11) | 0.0101 (7) | 0.0084 (7) | 0.0075 (9) |
P2 | 0.0489 (10) | 0.0513 (9) | 0.0566 (11) | −0.0045 (7) | 0.0104 (7) | −0.0003 (8) |
F1 | 0.052 (5) | 0.120 (8) | 0.085 (7) | −0.023 (5) | 0.009 (4) | 0.023 (6) |
F2 | 0.135 (8) | 0.078 (6) | 0.133 (9) | 0.028 (6) | −0.024 (7) | −0.028 (6) |
F3 | 0.074 (6) | 0.141 (9) | 0.069 (6) | 0.002 (6) | 0.034 (5) | 0.002 (7) |
F4 | 0.096 (7) | 0.077 (6) | 0.076 (6) | −0.036 (5) | −0.006 (5) | −0.024 (5) |
F5 | 0.057 (6) | 0.116 (8) | 0.085 (7) | 0.031 (6) | −0.007 (5) | 0.019 (7) |
F6 | 0.041 (4) | 0.042 (4) | 0.069 (5) | 0.010 (3) | −0.005 (3) | 0.002 (4) |
F7 | 0.118 (8) | 0.082 (6) | 0.067 (6) | −0.025 (6) | 0.027 (6) | 0.011 (5) |
F8 | 0.078 (9) | 0.091 (8) | 0.078 (8) | 0.009 (7) | 0.023 (7) | −0.031 (6) |
F9 | 0.119 (8) | 0.039 (4) | 0.074 (6) | −0.011 (5) | 0.022 (6) | 0.000 (4) |
F10 | 0.044 (4) | 0.055 (5) | 0.057 (5) | 0.008 (4) | 0.000 (4) | −0.001 (4) |
F11 | 0.057 (5) | 0.100 (7) | 0.076 (6) | −0.001 (5) | −0.006 (4) | −0.021 (5) |
F12 | 0.048 (5) | 0.112 (7) | 0.098 (7) | 0.010 (5) | −0.003 (5) | −0.015 (6) |
F1' | 0.158 (10) | 0.174 (11) | 0.155 (10) | 0.065 (9) | 0.050 (8) | −0.009 (8) |
F2' | 0.122 (9) | 0.118 (8) | 0.115 (9) | −0.037 (7) | 0.016 (7) | 0.042 (7) |
F3' | 0.118 (7) | 0.084 (6) | 0.068 (6) | 0.025 (6) | 0.020 (5) | −0.010 (5) |
F4' | 0.122 (8) | 0.068 (6) | 0.096 (8) | −0.010 (6) | 0.008 (6) | 0.018 (6) |
F5' | 0.075 (6) | 0.104 (7) | 0.066 (6) | −0.011 (6) | 0.001 (5) | 0.001 (6) |
F6' | 0.098 (9) | 0.172 (11) | 0.134 (10) | −0.014 (9) | −0.002 (7) | 0.031 (9) |
F7' | 0.063 (7) | 0.063 (6) | 0.071 (7) | −0.003 (5) | 0.016 (6) | −0.014 (5) |
F8' | 0.045 (5) | 0.081 (6) | 0.075 (6) | −0.013 (4) | 0.019 (4) | −0.019 (5) |
F9' | 0.091 (7) | 0.097 (7) | 0.095 (7) | −0.034 (6) | 0.018 (6) | 0.012 (6) |
F10' | 0.118 (8) | 0.064 (5) | 0.063 (6) | −0.011 (7) | 0.012 (7) | −0.002 (5) |
F11' | 0.049 (5) | 0.109 (7) | 0.083 (6) | 0.015 (5) | 0.002 (4) | 0.028 (5) |
F12' | 0.101 (7) | 0.107 (7) | 0.073 (6) | 0.040 (6) | 0.001 (5) | 0.009 (6) |
O1 | 0.058 (3) | 0.043 (3) | 0.115 (5) | −0.003 (2) | 0.031 (3) | −0.020 (3) |
O2 | 0.049 (3) | 0.063 (3) | 0.106 (5) | 0.008 (2) | 0.002 (3) | −0.007 (3) |
N1 | 0.031 (2) | 0.051 (3) | 0.047 (3) | 0.002 (2) | 0.012 (2) | −0.004 (2) |
N2 | 0.158 (9) | 0.066 (5) | 0.101 (7) | −0.041 (5) | 0.058 (6) | −0.016 (4) |
N3 | 0.035 (2) | 0.038 (2) | 0.046 (3) | 0.0011 (19) | 0.011 (2) | 0.001 (2) |
N4 | 0.051 (4) | 0.109 (6) | 0.101 (6) | 0.006 (4) | 0.025 (4) | −0.022 (5) |
N5 | 0.037 (3) | 0.047 (3) | 0.053 (3) | −0.006 (2) | 0.002 (2) | −0.001 (2) |
N6 | 0.025 (2) | 0.050 (3) | 0.047 (3) | −0.0016 (19) | 0.0054 (19) | 0.000 (2) |
C1 | 0.077 (5) | 0.053 (4) | 0.052 (5) | −0.016 (4) | 0.018 (4) | −0.011 (3) |
C2 | 0.073 (5) | 0.048 (4) | 0.055 (5) | −0.013 (3) | 0.007 (3) | 0.001 (3) |
C3 | 0.037 (3) | 0.033 (3) | 0.066 (5) | 0.004 (2) | 0.007 (3) | −0.006 (3) |
C4 | 0.114 (8) | 0.058 (4) | 0.061 (6) | −0.015 (5) | 0.019 (5) | −0.023 (4) |
C5 | 0.099 (6) | 0.060 (4) | 0.049 (5) | −0.024 (4) | 0.022 (4) | −0.008 (3) |
C6 | 0.051 (4) | 0.048 (4) | 0.075 (5) | 0.004 (3) | 0.010 (3) | −0.009 (4) |
C7 | 0.045 (4) | 0.122 (7) | 0.047 (5) | 0.019 (4) | 0.013 (3) | −0.005 (4) |
C8 | 0.053 (4) | 0.123 (8) | 0.049 (5) | 0.027 (5) | 0.017 (3) | −0.008 (4) |
C9 | 0.038 (3) | 0.037 (3) | 0.066 (4) | −0.005 (2) | 0.009 (3) | −0.009 (3) |
C10 | 0.047 (5) | 0.170 (12) | 0.074 (6) | 0.026 (6) | 0.010 (4) | 0.037 (7) |
C11 | 0.047 (5) | 0.167 (11) | 0.059 (6) | 0.007 (5) | 0.018 (4) | 0.035 (6) |
C12 | 0.044 (4) | 0.042 (3) | 0.078 (5) | −0.001 (3) | 0.009 (3) | −0.010 (3) |
C13 | 0.036 (3) | 0.056 (4) | 0.075 (5) | −0.008 (3) | 0.001 (3) | 0.005 (3) |
C14 | 0.040 (4) | 0.066 (5) | 0.098 (7) | −0.006 (3) | 0.010 (4) | −0.004 (4) |
C15 | 0.039 (4) | 0.069 (5) | 0.139 (9) | 0.006 (4) | 0.020 (4) | −0.005 (5) |
C16 | 0.038 (4) | 0.059 (4) | 0.111 (7) | 0.007 (3) | 0.016 (4) | 0.000 (4) |
C17 | 0.032 (3) | 0.058 (4) | 0.060 (4) | −0.004 (3) | 0.009 (3) | 0.006 (3) |
C18 | 0.033 (3) | 0.047 (3) | 0.051 (4) | −0.003 (2) | 0.006 (2) | −0.002 (3) |
C19 | 0.041 (3) | 0.042 (3) | 0.073 (5) | 0.003 (3) | 0.004 (3) | −0.008 (3) |
C20 | 0.050 (4) | 0.042 (3) | 0.075 (5) | −0.003 (3) | 0.004 (3) | −0.005 (3) |
C21 | 0.043 (4) | 0.049 (4) | 0.071 (5) | −0.010 (3) | 0.005 (3) | −0.003 (3) |
C22 | 0.034 (3) | 0.045 (3) | 0.052 (4) | 0.000 (2) | 0.003 (2) | 0.002 (3) |
Pd—N1 | 2.005 (5) | N5—C17 | 1.332 (9) |
Pd—N3 | 2.024 (5) | N5—C13 | 1.357 (8) |
Pd—N5 | 2.013 (5) | N6—C22 | 1.343 (7) |
Pd—N6 | 2.014 (5) | N6—C18 | 1.346 (8) |
P1—F3 | 1.501 (11) | C1—C2 | 1.351 (10) |
P1—F2' | 1.514 (13) | C1—H1 | 0.9500 |
P1—F1' | 1.538 (16) | C2—C3 | 1.374 (10) |
P1—F5 | 1.561 (11) | C2—H2 | 0.9500 |
P1—F6' | 1.562 (19) | C3—C4 | 1.365 (11) |
P1—F6 | 1.577 (9) | C3—C6 | 1.501 (9) |
P1—F5' | 1.580 (13) | C4—C5 | 1.362 (11) |
P1—F2 | 1.593 (13) | C4—H4 | 0.9500 |
P1—F3' | 1.596 (10) | C5—H5 | 0.9500 |
P1—F1 | 1.599 (11) | C7—C8 | 1.391 (10) |
P1—F4 | 1.602 (10) | C7—H7 | 0.9500 |
P1—F4' | 1.646 (12) | C8—C9 | 1.340 (11) |
P2—F12' | 1.494 (11) | C8—H8 | 0.9500 |
P2—F12 | 1.500 (10) | C9—C10 | 1.339 (12) |
P2—F8 | 1.522 (19) | C9—C12 | 1.504 (9) |
P2—F8' | 1.542 (11) | C10—C11 | 1.376 (12) |
P2—F10' | 1.580 (13) | C10—H10 | 0.9500 |
P2—F7 | 1.583 (10) | C11—H11 | 0.9500 |
P2—F9 | 1.587 (11) | C13—C14 | 1.373 (10) |
P2—F9' | 1.626 (11) | C13—H13 | 0.9500 |
P2—F7' | 1.639 (19) | C14—C15 | 1.366 (12) |
P2—F11' | 1.642 (10) | C14—H14 | 0.9500 |
P2—F10 | 1.650 (11) | C15—C16 | 1.382 (11) |
P2—F11 | 1.667 (10) | C15—H15 | 0.9500 |
O1—C6 | 1.189 (9) | C16—C17 | 1.374 (9) |
O2—C12 | 1.266 (10) | C16—H16 | 0.9500 |
N1—C5 | 1.325 (9) | C17—C18 | 1.467 (8) |
N1—C1 | 1.345 (9) | C18—C19 | 1.372 (9) |
N2—C6 | 1.376 (11) | C19—C20 | 1.375 (9) |
N2—H1n | 0.8800 | C19—H19 | 0.9500 |
N2—H2n | 0.8800 | C20—C21 | 1.398 (10) |
N3—C7 | 1.303 (9) | C20—H20 | 0.9500 |
N3—C11 | 1.329 (10) | C21—C22 | 1.380 (9) |
N4—C12 | 1.282 (10) | C21—H21 | 0.9500 |
N4—H3n | 0.8800 | C22—H22 | 0.9500 |
N4—H4n | 0.8800 | ||
N1—Pd—N5 | 94.3 (2) | C11—N3—Pd | 120.4 (5) |
N1—Pd—N6 | 174.40 (19) | C12—N4—H3n | 120.0 |
N5—Pd—N6 | 81.2 (2) | C12—N4—H4n | 120.0 |
N1—Pd—N3 | 88.8 (2) | H3n—N4—H4n | 120.0 |
N5—Pd—N3 | 176.8 (2) | C17—N5—C13 | 120.2 (6) |
N6—Pd—N3 | 95.66 (19) | C17—N5—Pd | 113.6 (4) |
F2'—P1—F1' | 90.4 (10) | C13—N5—Pd | 126.2 (5) |
F3—P1—F5 | 92.6 (8) | C22—N6—C18 | 119.8 (6) |
F3—P1—F6' | 90.7 (9) | C22—N6—Pd | 126.4 (4) |
F2'—P1—F6' | 93.6 (10) | C18—N6—Pd | 113.7 (4) |
F1'—P1—F6' | 91.1 (11) | N1—C1—C2 | 121.9 (7) |
F5—P1—F6' | 156.2 (10) | N1—C1—H1 | 119.0 |
F3—P1—F6 | 92.5 (7) | C2—C1—H1 | 119.0 |
F5—P1—F6 | 174.9 (7) | C1—C2—C3 | 121.1 (7) |
F2'—P1—F5' | 93.9 (8) | C1—C2—H2 | 119.4 |
F1'—P1—F5' | 88.8 (10) | C3—C2—H2 | 119.4 |
F6'—P1—F5' | 172.5 (9) | C4—C3—C2 | 116.1 (6) |
F3—P1—F2 | 92.3 (9) | C4—C3—C6 | 121.7 (7) |
F5—P1—F2 | 93.9 (8) | C2—C3—C6 | 122.2 (7) |
F6—P1—F2 | 86.6 (6) | C5—C4—C3 | 121.0 (7) |
F2'—P1—F3' | 90.8 (9) | C5—C4—H4 | 119.5 |
F1'—P1—F3' | 177.4 (11) | C3—C4—H4 | 119.5 |
F6'—P1—F3' | 91.1 (9) | N1—C5—C4 | 122.3 (8) |
F5'—P1—F3' | 88.9 (7) | N1—C5—H5 | 118.9 |
F3—P1—F1 | 179.9 (10) | C4—C5—H5 | 118.9 |
F5—P1—F1 | 87.4 (7) | O1—C6—N2 | 118.3 (7) |
F6—P1—F1 | 87.6 (6) | O1—C6—C3 | 124.2 (7) |
F2—P1—F1 | 87.7 (8) | N2—C6—C3 | 117.4 (7) |
F3—P1—F4 | 93.5 (8) | N3—C7—C8 | 122.3 (8) |
F5—P1—F4 | 91.3 (7) | N3—C7—H7 | 118.9 |
F6—P1—F4 | 87.8 (6) | C8—C7—H7 | 118.9 |
F2—P1—F4 | 172.1 (8) | C9—C8—C7 | 119.8 (7) |
F1—P1—F4 | 86.6 (7) | C9—C8—H8 | 120.1 |
F2'—P1—F4' | 173.2 (9) | C7—C8—H8 | 120.1 |
F1'—P1—F4' | 96.4 (11) | C10—C9—C8 | 118.1 (7) |
F6'—P1—F4' | 86.3 (9) | C10—C9—C12 | 117.8 (7) |
F5'—P1—F4' | 86.3 (7) | C8—C9—C12 | 124.1 (7) |
F3'—P1—F4' | 82.4 (7) | C9—C10—C11 | 120.1 (8) |
F12—P2—F8 | 93.7 (8) | C9—C10—H10 | 120.0 |
F12'—P2—F8' | 94.8 (8) | C11—C10—H10 | 120.0 |
F12'—P2—F10' | 92.7 (7) | N3—C11—C10 | 122.1 (8) |
F8'—P2—F10' | 91.3 (6) | N3—C11—H11 | 119.0 |
F12—P2—F7 | 91.1 (7) | C10—C11—H11 | 119.0 |
F8—P2—F7 | 92.2 (10) | O2—C12—N4 | 119.1 (8) |
F12—P2—F9 | 94.7 (7) | O2—C12—C9 | 119.7 (7) |
F8—P2—F9 | 91.4 (9) | N4—C12—C9 | 121.1 (8) |
F10'—P2—F9 | 93.9 (6) | N5—C13—C14 | 120.8 (7) |
F7—P2—F9 | 172.9 (8) | N5—C13—H13 | 119.6 |
F12'—P2—F9' | 91.1 (8) | C14—C13—H13 | 119.6 |
F8'—P2—F9' | 174.1 (7) | C15—C14—C13 | 119.2 (7) |
F10'—P2—F9' | 89.1 (7) | C15—C14—H14 | 120.4 |
F12'—P2—F7' | 90.6 (8) | C13—C14—H14 | 120.4 |
F8'—P2—F7' | 91.2 (7) | C14—C15—C16 | 119.5 (7) |
F10'—P2—F7' | 175.7 (8) | C14—C15—H15 | 120.2 |
F9'—P2—F7' | 88.0 (7) | C16—C15—H15 | 120.2 |
F12'—P2—F11' | 177.2 (7) | C17—C16—C15 | 119.4 (8) |
F8'—P2—F11' | 88.1 (6) | C17—C16—H16 | 120.3 |
F10'—P2—F11' | 87.4 (7) | C15—C16—H16 | 120.3 |
F9'—P2—F11' | 86.0 (6) | N5—C17—C16 | 120.8 (6) |
F7'—P2—F11' | 89.2 (8) | N5—C17—C18 | 116.0 (6) |
F12—P2—F10 | 88.8 (5) | C16—C17—C18 | 123.2 (7) |
F8—P2—F10 | 177.5 (7) | N6—C18—C19 | 120.8 (6) |
F7—P2—F10 | 88.1 (6) | N6—C18—C17 | 115.1 (6) |
F9—P2—F10 | 88.0 (6) | C19—C18—C17 | 124.1 (6) |
F12—P2—F11 | 174.5 (6) | C18—C19—C20 | 120.4 (6) |
F8—P2—F11 | 91.8 (7) | C18—C19—H19 | 119.8 |
F7—P2—F11 | 88.1 (7) | C20—C19—H19 | 119.8 |
F9—P2—F11 | 85.7 (7) | C19—C20—C21 | 118.6 (6) |
F10—P2—F11 | 85.8 (5) | C19—C20—H20 | 120.7 |
C5—N1—C1 | 117.5 (6) | C21—C20—H20 | 120.7 |
C5—N1—Pd | 124.3 (5) | C22—C21—C20 | 118.6 (6) |
C1—N1—Pd | 118.2 (4) | C22—C21—H21 | 120.7 |
C6—N2—H1n | 120.0 | C20—C21—H21 | 120.7 |
C6—N2—H2n | 120.0 | N6—C22—C21 | 121.8 (6) |
H1n—N2—H2n | 120.0 | N6—C22—H22 | 119.1 |
C7—N3—C11 | 117.4 (6) | C21—C22—H22 | 119.1 |
C7—N3—Pd | 122.2 (5) | ||
N5—Pd—N1—C5 | 99.2 (6) | C8—C9—C10—C11 | −2.9 (16) |
N3—Pd—N1—C5 | −81.7 (6) | C12—C9—C10—C11 | 176.3 (10) |
N5—Pd—N1—C1 | −77.7 (5) | C7—N3—C11—C10 | 4.4 (16) |
N3—Pd—N1—C1 | 101.4 (5) | Pd—N3—C11—C10 | −175.3 (9) |
N1—Pd—N3—C7 | 103.1 (7) | C9—C10—C11—N3 | −0.2 (19) |
N6—Pd—N3—C7 | −80.3 (7) | C10—C9—C12—O2 | −7.7 (11) |
N1—Pd—N3—C11 | −77.2 (7) | C8—C9—C12—O2 | 171.5 (8) |
N6—Pd—N3—C11 | 99.4 (7) | C10—C9—C12—N4 | 169.4 (9) |
N1—Pd—N5—C17 | 170.8 (5) | C8—C9—C12—N4 | −11.5 (12) |
N6—Pd—N5—C17 | −5.9 (5) | C17—N5—C13—C14 | −1.6 (12) |
N1—Pd—N5—C13 | −7.8 (6) | Pd—N5—C13—C14 | 176.9 (6) |
N6—Pd—N5—C13 | 175.6 (6) | N5—C13—C14—C15 | −0.9 (14) |
N5—Pd—N6—C22 | −178.6 (6) | C13—C14—C15—C16 | 1.8 (16) |
N3—Pd—N6—C22 | 2.1 (6) | C14—C15—C16—C17 | −0.4 (15) |
N5—Pd—N6—C18 | 4.9 (5) | C13—N5—C17—C16 | 3.0 (11) |
N3—Pd—N6—C18 | −174.4 (5) | Pd—N5—C17—C16 | −175.6 (6) |
C5—N1—C1—C2 | −0.3 (12) | C13—N5—C17—C18 | −175.6 (6) |
Pd—N1—C1—C2 | 176.9 (6) | Pd—N5—C17—C18 | 5.8 (8) |
N1—C1—C2—C3 | −2.4 (13) | C15—C16—C17—N5 | −2.0 (13) |
C1—C2—C3—C4 | 3.0 (12) | C15—C16—C17—C18 | 176.5 (8) |
C1—C2—C3—C6 | −175.9 (7) | C22—N6—C18—C19 | 1.5 (10) |
C2—C3—C4—C5 | −1.2 (13) | Pd—N6—C18—C19 | 178.2 (5) |
C6—C3—C4—C5 | 177.7 (8) | C22—N6—C18—C17 | −180.0 (6) |
C1—N1—C5—C4 | 2.1 (13) | Pd—N6—C18—C17 | −3.3 (7) |
Pd—N1—C5—C4 | −174.8 (8) | N5—C17—C18—N6 | −1.7 (9) |
C3—C4—C5—N1 | −1.4 (16) | C16—C17—C18—N6 | 179.7 (7) |
C4—C3—C6—O1 | 15.2 (12) | N5—C17—C18—C19 | 176.7 (7) |
C2—C3—C6—O1 | −166.0 (8) | C16—C17—C18—C19 | −1.8 (12) |
C4—C3—C6—N2 | −162.3 (9) | N6—C18—C19—C20 | −0.2 (11) |
C2—C3—C6—N2 | 16.6 (11) | C17—C18—C19—C20 | −178.6 (7) |
C11—N3—C7—C8 | −5.4 (14) | C18—C19—C20—C21 | −1.1 (12) |
Pd—N3—C7—C8 | 174.2 (8) | C19—C20—C21—C22 | 1.1 (12) |
N3—C7—C8—C9 | 2.4 (16) | C18—N6—C22—C21 | −1.5 (10) |
C7—C8—C9—C10 | 2.0 (14) | Pd—N6—C22—C21 | −177.7 (5) |
C7—C8—C9—C12 | −177.2 (8) | C20—C21—C22—N6 | 0.1 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N···O2i | 0.88 | 2.29 | 3.031 (11) | 142 |
N2—H1N···O2ii | 0.88 | 2.37 | 3.032 (11) | 132 |
N2—H2N···F9iii | 0.88 | 2.24 | 3.037 (15) | 151 |
N2—H2N···F11′iii | 0.88 | 2.38 | 3.220 (14) | 159 |
N4—H3N···F7′iv | 0.88 | 2.52 | 3.175 (19) | 132 |
N4—H3N···F8iv | 0.88 | 2.55 | 3.10 (2) | 121 |
N4—H4N···O1v | 0.88 | 1.97 | 2.836 (11) | 168 |
Symmetry codes: (i) x−1/2, y−1/2, z; (ii) −x+3/2, y−1/2, −z+3/2; (iii) x, −y+1, z+1/2; (iv) x+1/2, y−1/2, z; (v) −x+3/2, −y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Pd(C10H8N2)(C6H6NO2)2](PF6)2 |
Mr | 796.78 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 100 |
a, b, c (Å) | 22.5920 (14), 13.8299 (8), 17.9092 (12) |
β (°) | 95.269 (8) |
V (Å3) | 5572.0 (6) |
Z | 8 |
Radiation type | Cu Kα |
µ (mm−1) | 7.55 |
Crystal size (mm) | 0.46 × 0.16 × 0.15 |
Data collection | |
Diffractometer | Bruker APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2007) |
Tmin, Tmax | 0.126, 0.401 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 30116, 5182, 3944 |
Rint | 0.072 |
(sin θ/λ)max (Å−1) | 0.609 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.147, 1.01 |
No. of reflections | 5182 |
No. of parameters | 520 |
No. of restraints | 144 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.67, −0.78 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N···O2i | 0.88 | 2.29 | 3.031 (11) | 142 |
N2—H1N···O2ii | 0.88 | 2.37 | 3.032 (11) | 132 |
N2—H2N···F9iii | 0.88 | 2.24 | 3.037 (15) | 151 |
N2—H2N···F11'iii | 0.88 | 2.38 | 3.220 (14) | 159 |
N4—H3N···F7'iv | 0.88 | 2.52 | 3.175 (19) | 132 |
N4—H3N···F8iv | 0.88 | 2.55 | 3.10 (2) | 121 |
N4—H4N···O1v | 0.88 | 1.97 | 2.836 (11) | 168 |
Symmetry codes: (i) x−1/2, y−1/2, z; (ii) −x+3/2, y−1/2, −z+3/2; (iii) x, −y+1, z+1/2; (iv) x+1/2, y−1/2, z; (v) −x+3/2, −y+1/2, −z+1. |
Carboxamides have been used for the synthesis of supramolecular structures due to their ability to hydrogen bond as shown by Sun et al. (2011) and Moncol et al. (2007). With that in mind we sought to crystallize palladium(II) complexes with 4-pyridinecarboxamide ligands, similar to those created by Galstyan et al., (2011), Fujimura et al. (2004) and Qin et al. (2001). The title compound can be synthesized by the reaction of the 2,2'-bipyridine palladium(II) metal centre with the 4-pyridinecarboxamide ligand or by the palladium-catalyzed hydration of the 2,2'-bipyridine palladium(II) 4-cyanopyridine analog complex in a similar reaction to the one reported by Sanchez et al. (2000).
The complex cation of the title compound, Fig. 1, features a square planar palladium(II) centre with a cis disposition of the N-bound 4-pyridinecarboxamide ligands. No systematic trends are evident in the Pd—N bond lengths (Table 1). The 4-pyridinecarboxamide ligands are almost orthogonal to each other, the dihedral angle being 85.7 (5)°, and to the PdN4 plane with dihedral angles of 79.3 (3) [N1-ligand] and 78.7 (3)°; a similar situation was found in the BF4- analogue (Qin et al., 2001). Each of the amide groups lies out of the plane of the pyridyl ring to which it is connected as seen in the C2—C3—C6—O1 and C8—C9—C12—O2 torsion angles of -166.0 (8) and 171.5 (8)°, respectively. The 2,2'-bipyridine ring is almost planar the dihedral angle between the pyridyl rings being 4.7 (4)°. The amide-O atoms lie to opposite sides of the PdN4 plane.
A detailed analysis of the crystal packing is not possible owing to the disorder in the two PF6- anions. However, the most notable feature of the crystal packing is a supramolecular chain orientated approximately along [3 1 0] arising from centrosymmetric 16-membered {···HNCO}4 synthons constructed by four interacting amide groups (Fig. 2 and Table 2). A three-dimensional architecture arises from additional amide-H···O, F interactions (Table 2).