Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104010893/ta1448sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104010893/ta1448Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104010893/ta1448IIsup3.hkl |
CCDC references: 245845; 245846
The white powder obtained from the reaction of PdMe2{(py)2COH} with water in acetone in the presence of pyridazine (Canty et al., 1994) was dissolved in methanol-water (Ratio?) and a few drops of dilute nitric acid. Colourless crystals of (I) formed over several days, and these were found to be suitable for structural studies. An initial determination, executed with a single counter instrument at room temperature on a capillary-mounted specimen, did not convincingly locate all H atoms. A fragment of the same specimen was used for a second determination using a CCD instrument, as reported here.
The H atoms were located in difference Fourier maps and placed at idealized positions (C—H = 0.95 Å), with Uiso(H) = 1.25Ueq(C). The largest peaks in the difference maps were 0.87 Å from Pd (at 150 K) and at the site of the Pd (at 298 K).
Data collection: SMART (Siemens, 1995) for (I); CAD-4 Software (Enraf-Nonius, 1989) for (II). Cell refinement: SAINT (Siemens, 1995) for (I); CAD-4 Software for (II). Data reduction: SAINT for (I); CAD-4 Software for (II). For both compounds, program(s) used to solve structure: Xtal3.5 (Hall et al., 1995); program(s) used to refine structure: CRYLSQ in Xtal3.5; molecular graphics: Xtal3.5; software used to prepare material for publication: BONDLA and CIFIO in Xtal3.5.
[Pd(C16H13N3O)2](NO3)2 | F(000) = 768 |
Mr = 757.03 | Dx = 1.652 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -p 2ybc | Cell parameters from 4042 reflections |
a = 8.428 (1) Å | θ = 2.6–27.5° |
b = 10.284 (2) Å | µ = 0.68 mm−1 |
c = 17.669 (3) Å | T = 150 K |
β = 96.294 (2)° | Block, colourless |
V = 1522.2 (4) Å3 | 0.2 × 0.2 × 0.15 mm |
Z = 2 |
Siemens SMART CCD area-detector diffractometer | 3681 independent reflections |
Radiation source: sealed tube | 2726 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
ω scans | θmax = 28.1°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→11 |
Tmin = 0.73, Tmax = 0.93 | k = −13→13 |
17629 measured reflections | l = −23→23 |
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)] = 0.048 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.36 | w = 1/[σ2(F) + 0.54F2] |
2726 reflections | (Δ/σ)max = 0.001 |
223 parameters | Δρmax = 2.45 e Å−3 |
0 restraints | Δρmin = −0.88 e Å−3 |
0 constraints |
[Pd(C16H13N3O)2](NO3)2 | V = 1522.2 (4) Å3 |
Mr = 757.03 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.428 (1) Å | µ = 0.68 mm−1 |
b = 10.284 (2) Å | T = 150 K |
c = 17.669 (3) Å | 0.2 × 0.2 × 0.15 mm |
β = 96.294 (2)° |
Siemens SMART CCD area-detector diffractometer | 3681 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2726 reflections with I > 2σ(I) |
Tmin = 0.73, Tmax = 0.93 | Rint = 0.045 |
17629 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.36 | Δρmax = 2.45 e Å−3 |
2726 reflections | Δρmin = −0.88 e Å−3 |
223 parameters |
x | y | z | Uiso*/Ueq | ||
Pd | 0.50000 | 0.50000 | 0.50000 | 0.02062 (19) | |
C10 | 0.2922 (4) | 0.7445 (4) | 0.5132 (2) | 0.0236 (17) | |
O10 | 0.1936 (3) | 0.8537 (3) | 0.51290 (16) | 0.0289 (13) | |
C1A | 0.2181 (4) | 0.6272 (4) | 0.5498 (2) | 0.0237 (17) | |
N2A | 0.2940 (4) | 0.5111 (3) | 0.54846 (17) | 0.0215 (13) | |
C3A | 0.2358 (5) | 0.4079 (4) | 0.5831 (2) | 0.0272 (18) | |
C4A | 0.1006 (5) | 0.4161 (4) | 0.6210 (2) | 0.030 (2) | |
C5A | 0.0203 (5) | 0.5332 (5) | 0.6212 (2) | 0.034 (2) | |
C6A | 0.0781 (5) | 0.6395 (4) | 0.5844 (2) | 0.0290 (19) | |
C1B | 0.3070 (4) | 0.7141 (4) | 0.4291 (2) | 0.0231 (16) | |
N2B | 0.3917 (4) | 0.6085 (3) | 0.41359 (18) | 0.0234 (14) | |
C3B | 0.4059 (5) | 0.5756 (4) | 0.3408 (2) | 0.0260 (18) | |
C4B | 0.3359 (5) | 0.6485 (4) | 0.2806 (2) | 0.0277 (18) | |
C5B | 0.2501 (5) | 0.7577 (4) | 0.2960 (2) | 0.0306 (19) | |
C6B | 0.2342 (5) | 0.7922 (4) | 0.3705 (2) | 0.0283 (19) | |
C1C | 0.4585 (4) | 0.7735 (4) | 0.5558 (2) | 0.0236 (17) | |
N2C | 0.4794 (4) | 0.7364 (3) | 0.62928 (18) | 0.0275 (16) | |
C3C | 0.6191 (5) | 0.7661 (4) | 0.6700 (2) | 0.030 (2) | |
C4C | 0.7412 (5) | 0.8314 (4) | 0.6391 (2) | 0.032 (2) | |
C5C | 0.7169 (5) | 0.8709 (4) | 0.5643 (2) | 0.0302 (19) | |
C6C | 0.5726 (5) | 0.8427 (4) | 0.5215 (2) | 0.0281 (18) | |
N | 0.1648 (4) | 1.0631 (3) | 0.6658 (2) | 0.0292 (17) | |
O1 | 0.2944 (4) | 1.0990 (4) | 0.6443 (2) | 0.049 (2) | |
O2 | 0.1009 (4) | 0.9601 (3) | 0.6384 (2) | 0.0418 (17) | |
O3 | 0.1023 (4) | 1.1251 (3) | 0.71392 (18) | 0.0408 (17) | |
H10 | 0.18197 | 0.88408 | 0.55884 | 0.04400* | |
H3C | 0.63432 | 0.72964 | 0.72112 | 0.02300* | |
H3A | 0.28794 | 0.32714 | 0.58159 | 0.04300* | |
H4A | 0.06360 | 0.34272 | 0.64633 | 0.02500* | |
H5A | −0.07366 | 0.54088 | 0.64595 | 0.02600* | |
H6A | 0.02337 | 0.71981 | 0.58301 | 0.03200* | |
H3B | 0.46551 | 0.50092 | 0.33058 | 0.02700* | |
H4B | 0.34644 | 0.62398 | 0.22980 | 0.01200* | |
H5B | 0.20227 | 0.80937 | 0.25519 | 0.04300* | |
H6B | 0.17503 | 0.86679 | 0.38145 | 0.02000* | |
H4C | 0.83914 | 0.84768 | 0.66837 | 0.03200* | |
H5C | 0.79840 | 0.91749 | 0.54277 | 0.05400* | |
H6C | 0.55228 | 0.86943 | 0.46996 | 0.03000* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd | 0.0230 (2) | 0.0190 (2) | 0.0196 (2) | 0.00086 (17) | 0.00143 (13) | 0.00056 (16) |
C10 | 0.0228 (17) | 0.0243 (18) | 0.0231 (17) | 0.0045 (14) | 0.0002 (13) | −0.0008 (14) |
O10 | 0.0318 (15) | 0.0272 (14) | 0.0273 (14) | 0.0094 (12) | 0.0010 (11) | 0.0012 (11) |
C1A | 0.0245 (17) | 0.0253 (18) | 0.0206 (17) | 0.0010 (15) | −0.0013 (13) | −0.0033 (14) |
N2A | 0.0245 (14) | 0.0208 (15) | 0.0191 (13) | −0.0016 (13) | 0.0019 (11) | −0.0012 (12) |
C3A | 0.0271 (19) | 0.0233 (18) | 0.031 (2) | −0.0029 (15) | 0.0017 (15) | 0.0026 (15) |
C4A | 0.034 (2) | 0.032 (2) | 0.0246 (19) | −0.0081 (17) | 0.0030 (16) | 0.0032 (16) |
C5A | 0.027 (2) | 0.045 (3) | 0.030 (2) | −0.0043 (17) | 0.0055 (16) | −0.0060 (17) |
C6A | 0.028 (2) | 0.031 (2) | 0.027 (2) | 0.0025 (16) | 0.0006 (15) | −0.0038 (16) |
C1B | 0.0245 (18) | 0.0204 (17) | 0.0240 (17) | −0.0013 (14) | 0.0005 (14) | 0.0017 (14) |
N2B | 0.0237 (15) | 0.0227 (16) | 0.0231 (15) | −0.0011 (12) | 0.0004 (12) | 0.0012 (12) |
C3B | 0.030 (2) | 0.0256 (19) | 0.0220 (17) | −0.0027 (15) | 0.0023 (14) | −0.0020 (14) |
C4B | 0.029 (2) | 0.032 (2) | 0.0211 (17) | −0.0068 (16) | −0.0001 (14) | −0.0010 (15) |
C5B | 0.032 (2) | 0.032 (2) | 0.0260 (19) | −0.0046 (17) | −0.0052 (15) | 0.0062 (16) |
C6B | 0.0258 (19) | 0.030 (2) | 0.028 (2) | 0.0027 (16) | −0.0021 (15) | 0.0000 (16) |
C1C | 0.0253 (18) | 0.0212 (18) | 0.0236 (17) | 0.0033 (14) | −0.0006 (14) | −0.0021 (14) |
N2C | 0.0290 (17) | 0.0289 (17) | 0.0239 (16) | −0.0006 (14) | 0.0002 (13) | 0.0001 (13) |
C3C | 0.031 (2) | 0.032 (2) | 0.026 (2) | 0.0012 (17) | −0.0010 (16) | −0.0012 (16) |
C4C | 0.027 (2) | 0.033 (2) | 0.035 (2) | −0.0017 (17) | −0.0056 (16) | −0.0020 (18) |
C5C | 0.031 (2) | 0.0221 (18) | 0.037 (2) | −0.0037 (16) | 0.0036 (16) | 0.0015 (16) |
C6C | 0.036 (2) | 0.0228 (18) | 0.0252 (18) | −0.0001 (16) | 0.0017 (16) | 0.0037 (15) |
N | 0.0322 (17) | 0.0250 (18) | 0.0306 (18) | 0.0056 (14) | 0.0041 (14) | 0.0051 (14) |
O1 | 0.049 (2) | 0.045 (2) | 0.057 (2) | −0.0066 (16) | 0.0178 (17) | 0.0039 (17) |
O2 | 0.0446 (19) | 0.0373 (17) | 0.0427 (19) | −0.0046 (15) | 0.0013 (15) | −0.0119 (14) |
O3 | 0.0442 (18) | 0.0429 (19) | 0.0345 (16) | 0.0104 (15) | 0.0006 (14) | −0.0086 (14) |
Pd—N2A | 2.022 (3) | N2B—C3B | 1.347 (5) |
Pd—N2B | 2.026 (3) | C3B—C4B | 1.381 (5) |
Pd—N2A | 2.022 (3) | C3B—H3B | 0.946 |
Pd—N2B | 2.026 (3) | C4B—C5B | 1.378 (6) |
C10—O10 | 1.396 (5) | C4B—H4B | 0.946 |
C10—C1A | 1.534 (6) | C5B—C6B | 1.384 (6) |
C10—C1B | 1.538 (5) | C5B—H5B | 0.949 |
C10—C1C | 1.545 (5) | C6B—H6B | 0.947 |
O10—H10 | 0.885 | C1C—N2C | 1.345 (5) |
C1A—N2A | 1.355 (5) | C1C—C6C | 1.389 (6) |
C1A—C6A | 1.394 (6) | N2C—C3C | 1.346 (5) |
N2A—C3A | 1.345 (5) | C3C—C4C | 1.390 (6) |
C3A—C4A | 1.386 (6) | C3C—H3C | 0.973 |
C3A—H3A | 0.941 | C4C—C5C | 1.377 (6) |
C4A—C5A | 1.382 (6) | C4C—H4C | 0.939 |
C4A—H4A | 0.947 | C5C—C6C | 1.391 (6) |
C5A—C6A | 1.387 (6) | C5C—H5C | 0.950 |
C5A—H5A | 0.949 | C6C—H6C | 0.948 |
C6A—H6A | 0.945 | N—O1 | 1.250 (5) |
C1B—N2B | 1.345 (5) | N—O2 | 1.261 (5) |
C1B—C6B | 1.397 (5) | N—O3 | 1.227 (5) |
N2A—Pd—N2B | 87.20 (12) | Pd—N2B—C1B | 119.8 (3) |
N2A—Pd—N2A | 180.0000 | Pd—N2B—C3B | 120.1 (3) |
N2A—Pd—N2B | 92.80 (12) | C1B—N2B—C3B | 120.1 (3) |
N2B—Pd—N2A | 92.80 (12) | N2B—C3B—C4B | 121.6 (4) |
N2B—Pd—N2B | 180.0000 | N2B—C3B—H3B | 119.4 |
N2A—Pd—N2B | 87.20 (12) | C4B—C3B—H3B | 119.0 |
O10—C10—C1A | 111.4 (3) | C3B—C4B—C5B | 118.7 (4) |
O10—C10—C1B | 105.7 (3) | C3B—C4B—H4B | 120.6 |
O10—C10—C1C | 110.8 (3) | C5B—C4B—H4B | 120.7 |
C1A—C10—C1B | 109.1 (3) | C4B—C5B—C6B | 120.2 (4) |
C1A—C10—C1C | 109.6 (3) | C4B—C5B—H5B | 119.6 |
C1B—C10—C1C | 110.2 (3) | C6B—C5B—H5B | 120.1 |
C10—O10—H10 | 113.9 | C1B—C6B—C5B | 118.5 (4) |
C10—C1A—N2A | 118.1 (3) | C1B—C6B—H6B | 120.8 |
C10—C1A—C6A | 121.1 (4) | C5B—C6B—H6B | 120.7 |
N2A—C1A—C6A | 120.8 (4) | C10—C1C—N2C | 115.5 (3) |
Pd—N2A—C1A | 119.1 (3) | C10—C1C—C6C | 121.3 (3) |
Pd—N2A—C3A | 121.4 (3) | N2C—C1C—C6C | 122.9 (3) |
C1A—N2A—C3A | 119.4 (3) | C1C—N2C—C3C | 117.8 (4) |
N2A—C3A—C4A | 122.1 (4) | N2C—C3C—C4C | 122.8 (4) |
N2A—C3A—H3A | 119.3 | N2C—C3C—H3C | 115.3 |
C4A—C3A—H3A | 118.6 | C4C—C3C—H3C | 121.5 |
C3A—C4A—C5A | 118.9 (4) | C3C—C4C—C5C | 118.8 (4) |
C3A—C4A—H4A | 120.7 | C3C—C4C—H4C | 120.9 |
C5A—C4A—H4A | 120.4 | C5C—C4C—H4C | 120.4 |
C4A—C5A—C6A | 119.3 (4) | C4C—C5C—C6C | 119.4 (4) |
C4A—C5A—H5A | 120.5 | C4C—C5C—H5C | 119.7 |
C6A—C5A—H5A | 120.3 | C6C—C5C—H5C | 121.0 |
C1A—C6A—C5A | 119.4 (4) | C1C—C6C—C5C | 118.4 (4) |
C1A—C6A—H6A | 120.2 | C1C—C6C—H6C | 120.5 |
C5A—C6A—H6A | 120.4 | C5C—C6C—H6C | 121.1 |
C10—C1B—N2B | 117.5 (3) | O1—N—O2 | 118.8 (4) |
C10—C1B—C6B | 121.6 (3) | O1—N—O3 | 120.9 (4) |
N2B—C1B—C6B | 120.9 (4) | O2—N—O3 | 120.3 (4) |
N2B—Pd—N2A—C1A | −44.5 (3) | C1A—C10—C1B—N2B | −57.4 (4) |
N2A—Pd—N2B—C1B | 45.5 (3) | C10—C1A—N2A—Pd | 0.7 (4) |
C1B—C10—C1A—N2A | 58.3 (4) | C10—C1B—N2B—Pd | −2.0 (4) |
[Pd(C16H13N3O)2](NO3)2 | F(000) = 768 |
Mr = 757.03 | Dx = 1.626 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -p 2ybc | Cell parameters from 6 reflections |
a = 8.430 (3) Å | θ = 12.2–16.3° |
b = 10.431 (4) Å | µ = 0.67 mm−1 |
c = 17.67 (2) Å | T = 298 K |
β = 95.54 (6)° | Block, colourless |
V = 1546.5 (19) Å3 | 0.25 × 0.22 × 0.19 mm |
Z = 2 |
Enraf-Nonius CAD-4 diffractometer | 2323 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.086 |
Graphite monochromator | θmax = 30.0°, θmin = 2.3° |
2θ–ω scans | h = 0→10 |
Absorption correction: gaussian ABSORB in Xtal3.5 (Hall et al., 1995) | k = 0→14 |
Tmin = 0.85, Tmax = 0.88 | l = −24→24 |
4422 measured reflections | 8 standard reflections every 60 min |
4414 independent reflections | intensity decay: none |
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)] = 0.056 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.145 | H-atom parameters constrained |
S = 1.59 | w = 1/[σ2(F) + 0.84F2] |
2323 reflections | (Δ/σ)max = 0.001 |
223 parameters | Δρmax = 1.38 e Å−3 |
0 restraints | Δρmin = −0.79 e Å−3 |
0 constraints |
[Pd(C16H13N3O)2](NO3)2 | V = 1546.5 (19) Å3 |
Mr = 757.03 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.430 (3) Å | µ = 0.67 mm−1 |
b = 10.431 (4) Å | T = 298 K |
c = 17.67 (2) Å | 0.25 × 0.22 × 0.19 mm |
β = 95.54 (6)° |
Enraf-Nonius CAD-4 diffractometer | 2323 reflections with I > 2σ(I) |
Absorption correction: gaussian ABSORB in Xtal3.5 (Hall et al., 1995) | Rint = 0.086 |
Tmin = 0.85, Tmax = 0.88 | 8 standard reflections every 60 min |
4422 measured reflections | intensity decay: none |
4414 independent reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.145 | H-atom parameters constrained |
S = 1.59 | Δρmax = 1.38 e Å−3 |
2323 reflections | Δρmin = −0.79 e Å−3 |
223 parameters |
x | y | z | Uiso*/Ueq | ||
Pd | 0.50000 | 0.50000 | 0.50000 | 0.0303 (3) | |
C10 | 0.2979 (7) | 0.7427 (6) | 0.5144 (4) | 0.033 (3) | |
O10 | 0.1991 (6) | 0.8516 (5) | 0.5151 (3) | 0.049 (3) | |
C1A | 0.2212 (7) | 0.6292 (7) | 0.5514 (4) | 0.034 (3) | |
N2A | 0.2939 (6) | 0.5152 (6) | 0.5489 (3) | 0.033 (2) | |
C3A | 0.2320 (8) | 0.4123 (7) | 0.5828 (4) | 0.043 (4) | |
C4A | 0.0965 (10) | 0.4221 (9) | 0.6207 (5) | 0.054 (5) | |
C5A | 0.0213 (10) | 0.5376 (9) | 0.6217 (5) | 0.059 (5) | |
C6A | 0.0830 (9) | 0.6427 (8) | 0.5869 (4) | 0.048 (4) | |
C1B | 0.3122 (8) | 0.7132 (6) | 0.4310 (4) | 0.036 (3) | |
N2B | 0.3956 (6) | 0.6079 (5) | 0.4152 (3) | 0.036 (3) | |
C3B | 0.4078 (9) | 0.5762 (7) | 0.3418 (4) | 0.042 (3) | |
C4B | 0.3390 (9) | 0.6490 (8) | 0.2832 (4) | 0.048 (4) | |
C5B | 0.2542 (10) | 0.7569 (8) | 0.2994 (4) | 0.053 (4) | |
C6B | 0.2407 (9) | 0.7886 (8) | 0.3736 (5) | 0.048 (4) | |
C1C | 0.4620 (8) | 0.7718 (6) | 0.5565 (4) | 0.035 (3) | |
N2C | 0.4824 (7) | 0.7335 (6) | 0.6289 (3) | 0.045 (3) | |
C3C | 0.6206 (10) | 0.7644 (8) | 0.6689 (4) | 0.052 (4) | |
C4C | 0.7414 (10) | 0.8315 (9) | 0.6383 (5) | 0.054 (5) | |
C5C | 0.7188 (9) | 0.8705 (8) | 0.5639 (5) | 0.053 (4) | |
C6C | 0.5766 (9) | 0.8407 (7) | 0.5221 (4) | 0.043 (3) | |
N | 0.8347 (8) | 0.5602 (7) | 0.8367 (4) | 0.049 (3) | |
O1 | 0.7087 (12) | 0.5856 (13) | 0.8598 (6) | 0.134 (8) | |
O2 | 0.9012 (11) | 0.4627 (7) | 0.8588 (6) | 0.100 (6) | |
O3 | 0.8904 (10) | 0.6298 (9) | 0.7905 (4) | 0.096 (5) | |
H10 | 0.21410 | 0.87720 | 0.56660 | 0.08000* | |
H3A | 0.28257 | 0.32937 | 0.57846 | 0.05300* | |
H4A | 0.05820 | 0.34883 | 0.64828 | 0.06600* | |
H5A | −0.07682 | 0.54481 | 0.64516 | 0.07700* | |
H6A | 0.03156 | 0.72697 | 0.58926 | 0.06100* | |
H3B | 0.46828 | 0.50105 | 0.33041 | 0.05400* | |
H4B | 0.34693 | 0.62321 | 0.23079 | 0.06000* | |
H5B | 0.20741 | 0.80872 | 0.25700 | 0.06600* | |
H6B | 0.17843 | 0.86330 | 0.38620 | 0.05900* | |
H3C | 0.63752 | 0.73717 | 0.72182 | 0.06500* | |
H4C | 0.83754 | 0.85195 | 0.66895 | 0.06400* | |
H5C | 0.80156 | 0.91733 | 0.54127 | 0.06600* | |
H6C | 0.55788 | 0.86722 | 0.46981 | 0.05500* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd | 0.0312 (3) | 0.0316 (3) | 0.0288 (3) | 0.0024 (4) | 0.00716 (18) | 0.0011 (4) |
C10 | 0.031 (3) | 0.030 (3) | 0.038 (3) | 0.004 (2) | 0.001 (2) | −0.001 (2) |
O10 | 0.052 (3) | 0.045 (3) | 0.050 (3) | 0.022 (2) | 0.000 (2) | −0.001 (2) |
C1A | 0.027 (3) | 0.044 (4) | 0.031 (3) | 0.004 (3) | 0.004 (2) | −0.002 (3) |
N2A | 0.033 (2) | 0.031 (3) | 0.037 (2) | −0.002 (2) | 0.0066 (17) | −0.002 (2) |
C3A | 0.039 (4) | 0.042 (4) | 0.049 (4) | −0.009 (3) | 0.007 (3) | −0.005 (3) |
C4A | 0.045 (4) | 0.060 (5) | 0.057 (5) | −0.013 (4) | 0.010 (4) | 0.003 (4) |
C5A | 0.039 (4) | 0.075 (6) | 0.063 (5) | −0.010 (4) | 0.015 (3) | −0.011 (4) |
C6A | 0.038 (4) | 0.058 (5) | 0.049 (4) | 0.005 (3) | 0.009 (3) | −0.006 (4) |
C1B | 0.034 (3) | 0.032 (3) | 0.041 (3) | 0.002 (2) | 0.003 (3) | −0.002 (3) |
N2B | 0.037 (3) | 0.041 (3) | 0.031 (2) | −0.006 (2) | 0.005 (2) | −0.003 (2) |
C3B | 0.049 (4) | 0.046 (4) | 0.033 (3) | −0.002 (3) | 0.007 (3) | −0.003 (3) |
C4B | 0.050 (4) | 0.059 (5) | 0.036 (3) | −0.011 (4) | 0.006 (3) | 0.001 (3) |
C5B | 0.058 (5) | 0.060 (5) | 0.040 (4) | 0.000 (4) | −0.001 (3) | 0.012 (3) |
C6B | 0.045 (4) | 0.050 (5) | 0.049 (4) | 0.005 (3) | −0.002 (3) | 0.012 (4) |
C1C | 0.039 (3) | 0.027 (3) | 0.039 (3) | 0.005 (2) | 0.004 (3) | −0.002 (2) |
N2C | 0.045 (3) | 0.055 (4) | 0.034 (3) | 0.001 (3) | 0.002 (2) | −0.002 (3) |
C3C | 0.050 (4) | 0.060 (5) | 0.045 (4) | −0.001 (4) | 0.001 (3) | −0.006 (4) |
C4C | 0.047 (4) | 0.052 (5) | 0.061 (5) | −0.005 (4) | −0.003 (4) | −0.014 (4) |
C5C | 0.045 (4) | 0.044 (4) | 0.072 (5) | −0.009 (3) | 0.012 (4) | −0.002 (4) |
C6C | 0.048 (4) | 0.039 (4) | 0.042 (4) | −0.008 (3) | 0.007 (3) | 0.002 (3) |
N | 0.054 (4) | 0.048 (4) | 0.046 (3) | −0.008 (3) | 0.006 (3) | −0.003 (3) |
O1 | 0.101 (7) | 0.191 (11) | 0.118 (7) | 0.004 (7) | 0.056 (6) | −0.053 (8) |
O2 | 0.110 (7) | 0.066 (5) | 0.118 (7) | 0.023 (4) | −0.018 (5) | 0.014 (4) |
O3 | 0.108 (6) | 0.103 (6) | 0.075 (4) | −0.043 (5) | −0.002 (4) | 0.031 (4) |
Pd—N2A | 2.020 (5) | N2B—C3B | 1.351 (9) |
Pd—N2B | 2.008 (5) | C3B—C4B | 1.367 (10) |
Pd—N2A | 2.020 (5) | C3B—H3B | 0.967 |
Pd—N2B | 2.008 (5) | C4B—C5B | 1.379 (12) |
C10—O10 | 1.409 (8) | C4B—H4B | 0.972 |
C10—C1A | 1.527 (9) | C5B—C6B | 1.367 (12) |
C10—C1B | 1.521 (9) | C5B—H5B | 0.976 |
C10—C1C | 1.536 (8) | C6B—H6B | 0.977 |
O10—H10 | 0.944 | C1C—N2C | 1.335 (9) |
C1A—N2A | 1.341 (9) | C1C—C6C | 1.390 (10) |
C1A—C6A | 1.382 (10) | N2C—C3C | 1.342 (10) |
N2A—C3A | 1.357 (10) | C3C—C4C | 1.388 (12) |
C3A—C4A | 1.382 (12) | C3C—H3C | 0.974 |
C3A—H3A | 0.970 | C4C—C5C | 1.371 (13) |
C4A—C5A | 1.362 (13) | C4C—H4C | 0.955 |
C4A—H4A | 0.979 | C5C—C6C | 1.381 (11) |
C5A—C6A | 1.382 (13) | C5C—H5C | 0.969 |
C5A—H5A | 0.963 | C6C—H6C | 0.963 |
C6A—H6A | 0.983 | N—O1 | 1.204 (13) |
C1B—N2B | 1.348 (9) | N—O2 | 1.208 (11) |
C1B—C6B | 1.375 (10) | N—O3 | 1.220 (11) |
N2A—Pd—N2B | 86.7 (2) | Pd—N2B—C1B | 120.1 (4) |
N2A—Pd—N2A | 180.0000 | Pd—N2B—C3B | 120.7 (5) |
N2A—Pd—N2B | 93.3 (2) | C1B—N2B—C3B | 119.2 (6) |
N2B—Pd—N2A | 93.3 (2) | N2B—C3B—C4B | 121.7 (7) |
N2B—Pd—N2B | 180.0000 | N2B—C3B—H3B | 119.2 |
N2A—Pd—N2B | 86.7 (2) | C4B—C3B—H3B | 119.1 |
O10—C10—C1A | 110.2 (5) | C3B—C4B—C5B | 119.0 (7) |
O10—C10—C1B | 106.0 (5) | C3B—C4B—H4B | 120.3 |
O10—C10—C1C | 110.0 (5) | C5B—C4B—H4B | 120.6 |
C1A—C10—C1B | 109.6 (5) | C4B—C5B—C6B | 119.4 (7) |
C1A—C10—C1C | 110.1 (5) | C4B—C5B—H5B | 118.1 |
C1B—C10—C1C | 110.9 (5) | C6B—C5B—H5B | 122.6 |
C10—O10—H10 | 102.3 | C1B—C6B—C5B | 119.8 (8) |
C10—C1A—N2A | 117.4 (5) | C1B—C6B—H6B | 119.7 |
C10—C1A—C6A | 121.8 (6) | C5B—C6B—H6B | 120.4 |
N2A—C1A—C6A | 120.9 (7) | C10—C1C—N2C | 115.6 (6) |
Pd—N2A—C1A | 119.9 (4) | C10—C1C—C6C | 121.5 (6) |
Pd—N2A—C3A | 120.6 (5) | N2C—C1C—C6C | 122.8 (6) |
C1A—N2A—C3A | 119.4 (6) | C1C—N2C—C3C | 117.3 (6) |
N2A—C3A—C4A | 121.7 (7) | N2C—C3C—C4C | 123.2 (7) |
N2A—C3A—H3A | 118.7 | N2C—C3C—H3C | 118.4 |
C4A—C3A—H3A | 119.6 | C4C—C3C—H3C | 118.4 |
C3A—C4A—C5A | 118.7 (8) | C3C—C4C—C5C | 119.0 (8) |
C3A—C4A—H4A | 120.7 | C3C—C4C—H4C | 120.4 |
C5A—C4A—H4A | 120.5 | C5C—C4C—H4C | 120.6 |
C4A—C5A—C6A | 120.0 (8) | C4C—C5C—C6C | 118.6 (8) |
C4A—C5A—H5A | 119.6 | C4C—C5C—H5C | 120.4 |
C6A—C5A—H5A | 120.3 | C6C—C5C—H5C | 121.0 |
C1A—C6A—C5A | 119.4 (8) | C1C—C6C—C5C | 119.1 (7) |
C1A—C6A—H6A | 120.3 | C1C—C6C—H6C | 120.7 |
C5A—C6A—H6A | 120.3 | C5C—C6C—H6C | 120.1 |
C10—C1B—N2B | 117.2 (5) | O1—N—O2 | 118.3 (9) |
C10—C1B—C6B | 121.8 (6) | O1—N—O3 | 120.3 (9) |
N2B—C1B—C6B | 120.9 (6) | O2—N—O3 | 121.4 (9) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Pd(C16H13N3O)2](NO3)2 | [Pd(C16H13N3O)2](NO3)2 |
Mr | 757.03 | 757.03 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 150 | 298 |
a, b, c (Å) | 8.428 (1), 10.284 (2), 17.669 (3) | 8.430 (3), 10.431 (4), 17.67 (2) |
β (°) | 96.294 (2) | 95.54 (6) |
V (Å3) | 1522.2 (4) | 1546.5 (19) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.68 | 0.67 |
Crystal size (mm) | 0.2 × 0.2 × 0.15 | 0.25 × 0.22 × 0.19 |
Data collection | ||
Diffractometer | Siemens SMART CCD area-detector diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Gaussian ABSORB in Xtal3.5 (Hall et al., 1995) |
Tmin, Tmax | 0.73, 0.93 | 0.85, 0.88 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17629, 3681, 2726 | 4422, 4414, 2323 |
Rint | 0.045 | 0.086 |
(sin θ/λ)max (Å−1) | 0.662 | 0.703 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.117, 1.36 | 0.056, 0.145, 1.59 |
No. of reflections | 2726 | 2323 |
No. of parameters | 223 | 223 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.45, −0.88 | 1.38, −0.79 |
Computer programs: SMART (Siemens, 1995), CAD-4 Software (Enraf-Nonius, 1989), SAINT (Siemens, 1995), CAD-4 Software, SAINT, Xtal3.5 (Hall et al., 1995), CRYLSQ in Xtal3.5, BONDLA and CIFIO in Xtal3.5.
Pd—N2A | 2.022 (3) | Pd—N2B | 2.026 (3) |
N2A—Pd—N2B | 87.20 (12) | ||
N2B—Pd—N2A—C1A | −44.5 (3) | C1A—C10—C1B—N2B | −57.4 (4) |
N2A—Pd—N2B—C1B | 45.5 (3) | C10—C1A—N2A—Pd | 0.7 (4) |
C1B—C10—C1A—N2A | 58.3 (4) | C10—C1B—N2B—Pd | −2.0 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O10—H10···O2 | 0.89 | 1.81 | 2.666 (5) | 163 |
Potentially tridentate `tripodal' ligands, such as (py)3CH (py is pyridin-2-yl), (pz)3CH (pz is pyrazol-1-yl) and [(pz)3BH]−, when coordinated to palladium(II) in the complexes [Pd{(py)3CH—N,N'}2](NO3)2, [Pd{(pz)3CH—N,N'}2](BF4)2 (both isomorphous) and [Pd{(pz)3BH—N,N'}2], may interact as bidentate ligands to give square-planar coordination for the metal atom (Canty et al., 1986). We have isolated a similar complex, the title compound, (I), with stoichiometry [Pd{(py)3COH}2(NO3)2], incorporating a ligand with added potential for interaction, and have examined its structure in a search for possible additional interaction at the Pd atom and elsewhere. We report here the X-ray analysis results for (I) at 150 and 298 K. \sch
Complex (I) crystallizes in space group P21/c, with similar cell dimensions to the earlier complexes. This is surprising, in view of the substitution of the methanic H atom by the polar hydroxyl group. The present complex thus provides a third member of this series of isomorphous complexes, in which the metal atom lies on a crystallographic inversion centre, with one half of the formula unit (half of the complex cation and a single nitrate ion) comprising the asymmetric unit of the structure (Figs. 1 and 2). The hydroxylic H atom and atom N2C aside, the cation symmetry is a good approximation to 2/m, Pd—N being effectively equivalent [2.022 (3) and 2.026 (3) Å at 150 K], with the chelate angle within the six-membered `boat' (atoms Pd and C1O Altered from C0 - Please check at the prows) being 87.2 (1)°. The torsion angles are given in Table 1. Geometries are generally harmonious with those found in the pair of isomorphous counterparts, with the uncoordinated ring shielding the Pd atom from the approach of other moieties. The hydroxyl group at the cation periphery interacts with the nitrate anion (Table 2), perhaps surprisingly since the uncoordinated pyridine offers, presumably, a more basic site.
As noted below, the present study was preceded by a room-temperature study on the same specimen. It is of interest to note, in comparing the two determinations, that, for all cation non-H atoms, all Ueq (Å2) are less than 0.054 (3) at 298 K and less than 0.033 (3) at 150 K. For the nitrate ion, however, the Ueq values at 298 K are all greater than 0.101 (3), decreasing much more dramatically to be less than 0.049 (2) at 150 K. It is interesting to find that, at 150 K, the longest N—O distance in the anion, N—O2, is 1.261 (5) Å, perhaps consequent on the interaction with the hydroxyl H atom. The interplanar dihedral angles at 150 K (298 K) are rings A/B 56.9 (1) [58.1 (2)], A/C 75.0 (1) [76.8 (3)] and B/C 81.7 (1) [83.2 (2)]°. The deviations of the Pd atom from the planes of rings A and B are 0.097 (5) and 0.039 (5) Å [0.092 (10) and 0.012 (9) Å]. Rings A, B and C form dihedral angles of 42.1 (1) [43.0 (2)], 45.3 (1) [44.9 (2)] and 42.2 (1) [44.1 (2)°] with the coordination plane.