Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112047452/fg3281sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112047452/fg3281Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112047452/fg3281IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112047452/fg3281IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112047452/fg3281IVsup5.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112047452/fg3281IIIsup6.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112047452/fg3281IVsup7.cml |
CCDC references: 915099; 915100; 915101; 915102
To prepare the compounds under study, we used NiCl2.6H2O (p.a.) and a 40% water solution of PdCl2 from Lachema. The solvents [ethanol (96%) and N,N'-dimethylformamide (DMF) (p.a.)] were also obtained from Lachema, while 5-chloroquinolin-8-ol (95%) was obtained from Sigma–Aldrich, ethylenediamine (99%) was obtained from Alfa Aesar and hydrochloride acid (35%) was obtained from ITES. All chemicals were used as received.
For the preparation of (HClQ)2[PdCl4], (I), an ethanolic solution (25 ml) of ClQ (48 mg, 0.270 mmol) was mixed with an ethanolic solution (5 ml) of PdCl2 (0.1 ml of 40% water solution of PdCl2; 24 mg of PdCl2, 0.135 mmol). Three drops of concentrated hydrochloride acid were then added to the solution, while mixing continuously. The prepared solution was then heated to boiling point (~353 K). Afterwards, the solution was allowed to cool to room temperature and after 7 d, orange prisms of (I) were filtered off and dried on air.
For the preparation of [NH2(CH3)2][PdCl3], (II), ClQ (48 mg, 0.270 mmol) was dissolved in ethanol (25 ml). An ethanolic solution (5 ml) of PdCl2 (0.1 ml of 40% water solution of PdCl2; 24 mg of PdCl2, 0.135 mmol) was then added. Three drops of concentrated hydrochloride acid were added to form an orange solution. After 15 d at room temperature an orange microcrystalline powder was filtered off and dried in air. Afterwards, the product was recrystallized in a mixture of of ethanol (25 ml) and DMF (2 ml). After several days, red–brown needle-like crystals of (II) were filtered off and dried in air.
For the preparation of (NH3CH2CH2NH3)(ClQ)2, (III), ClQ (38 mg, 0.22 mmol) was dissolved in ethanol (25 ml) and three drops of ethylenediamine were added. The light-yellow color of the solution changed to yellow–green. Subsequently, a water solution (2 ml) of NiCl2.6H2O (25 mg, 0.11 mmol) was added to the solution of ClQ, while mixing continuously. After 10 d at room temperature, yellow prisms of (III) were filtered off and dried in air.
For the preparation of (HClQ)Cl, (IV), ClQ (38 mg, 0.22 mmol) was dissolved in ethanol (20 ml) and this solution was mixed with a water solution (2 ml) of NiCl2.6H2O (25 mg, 0.11 mmol). Three drops of concentrated hydrochloride acid were then added to the solution, while mixing continuously. The dark-green solution set aside for crystallization at room temperature and after 15 d, light-yellow plates of (IV) were filtered off and dried in air.
The aromatic H atoms in all structures, as well as the methyl H atoms in (II), were placed in calculated positions and refined riding on their parent C atoms with C—H = 0.93 and 0.96 Å, respectively. Amine [for (II) and (III)], hydroxy and pyridinium [for (I) and (IV)] H atoms, as well as methylene H atoms in (III), were found in difference maps.
For all compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
(C9H7ClNO)2[PdCl4] | F(000) = 1200 |
Mr = 609.41 | Dx = 1.977 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4110 reflections |
a = 7.2339 (2) Å | θ = 3.0–29.1° |
b = 21.7998 (8) Å | µ = 1.71 mm−1 |
c = 13.0306 (4) Å | T = 183 K |
β = 94.903 (3)° | Prism, orange |
V = 2047.37 (11) Å3 | 0.29 × 0.14 × 0.05 mm |
Z = 4 |
Oxford Diffraction Xcalibur (Sapphire2, large Be window) diffractometer | 4226 independent reflections |
Radiation source: fine-focus sealed tube | 3467 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
Detector resolution: 8.3438 pixels mm-1 | θmax = 26.5°, θmin = 3.0° |
ω scans | h = −6→9 |
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)] | k = −25→27 |
Tmin = 0.816, Tmax = 0.939 | l = −16→14 |
8968 measured reflections |
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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.054 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0171P)2 + 0.0183P] where P = (Fo2 + 2Fc2)/3 |
4226 reflections | (Δ/σ)max = 0.001 |
278 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.45 e Å−3 |
(C9H7ClNO)2[PdCl4] | V = 2047.37 (11) Å3 |
Mr = 609.41 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.2339 (2) Å | µ = 1.71 mm−1 |
b = 21.7998 (8) Å | T = 183 K |
c = 13.0306 (4) Å | 0.29 × 0.14 × 0.05 mm |
β = 94.903 (3)° |
Oxford Diffraction Xcalibur (Sapphire2, large Be window) diffractometer | 4226 independent reflections |
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)] | 3467 reflections with I > 2σ(I) |
Tmin = 0.816, Tmax = 0.939 | Rint = 0.025 |
8968 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.054 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.44 e Å−3 |
4226 reflections | Δρmin = −0.45 e Å−3 |
278 parameters |
Experimental. Absorption correction: CrysAlisPro, Oxford Diffraction Ltd., Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) |
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. 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 | 0.75083 (3) | 0.373726 (10) | 0.726874 (15) | 0.01454 (7) | |
Cl11 | 0.54189 (9) | 0.39239 (3) | 0.84992 (5) | 0.01980 (16) | |
Cl12 | 0.50724 (9) | 0.35196 (4) | 0.60614 (5) | 0.02160 (17) | |
Cl13 | 0.95767 (9) | 0.35740 (4) | 0.60553 (5) | 0.02442 (18) | |
Cl14 | 0.99715 (9) | 0.39547 (3) | 0.84913 (5) | 0.01880 (16) | |
Cl1 | 0.17959 (10) | 0.03163 (4) | 0.86297 (5) | 0.02952 (19) | |
Cl2 | 0.69473 (10) | 0.27089 (4) | 1.35240 (5) | 0.02894 (19) | |
C11 | 0.2368 (3) | 0.26863 (14) | 0.7750 (2) | 0.0223 (7) | |
H11 | 0.2376 | 0.3122 | 0.7756 | 0.027* | |
C12 | 0.1760 (4) | 0.23623 (15) | 0.8578 (2) | 0.0237 (7) | |
H12 | 0.1315 | 0.2577 | 0.9142 | 0.028* | |
C13 | 0.1804 (3) | 0.17353 (15) | 0.8578 (2) | 0.0210 (7) | |
H13 | 0.1442 | 0.1515 | 0.9157 | 0.025* | |
C14 | 0.2386 (3) | 0.14131 (13) | 0.77204 (19) | 0.0159 (6) | |
C15 | 0.2430 (3) | 0.07639 (14) | 0.76228 (19) | 0.0178 (6) | |
C16 | 0.2955 (3) | 0.04908 (14) | 0.6748 (2) | 0.0205 (6) | |
H16 | 0.2962 | 0.0056 | 0.6697 | 0.025* | |
C17 | 0.3485 (4) | 0.08484 (14) | 0.5928 (2) | 0.0208 (7) | |
H17 | 0.3836 | 0.0652 | 0.5323 | 0.025* | |
C18 | 0.3503 (4) | 0.14737 (14) | 0.59847 (19) | 0.0169 (6) | |
C19 | 0.2943 (3) | 0.17595 (13) | 0.68860 (19) | 0.0150 (6) | |
C21 | 0.7259 (3) | 0.51346 (15) | 1.3182 (2) | 0.0229 (7) | |
H21 | 0.7229 | 0.5565 | 1.3289 | 0.027* | |
C22 | 0.6796 (4) | 0.47335 (15) | 1.3948 (2) | 0.0239 (7) | |
H22 | 0.6431 | 0.4890 | 1.4580 | 0.029* | |
C23 | 0.6866 (3) | 0.41175 (15) | 1.3794 (2) | 0.0205 (7) | |
H23 | 0.6573 | 0.3847 | 1.4328 | 0.025* | |
C24 | 0.7367 (3) | 0.38742 (13) | 1.28509 (19) | 0.0150 (6) | |
C25 | 0.7454 (3) | 0.32436 (14) | 1.26052 (19) | 0.0177 (6) | |
C26 | 0.7947 (3) | 0.30549 (14) | 1.1662 (2) | 0.0196 (6) | |
H26 | 0.8014 | 0.2629 | 1.1513 | 0.023* | |
C27 | 0.8353 (4) | 0.34874 (13) | 1.0913 (2) | 0.0183 (6) | |
H27 | 0.8686 | 0.3350 | 1.0262 | 0.022* | |
C28 | 0.8278 (4) | 0.41018 (14) | 1.11068 (19) | 0.0164 (6) | |
C29 | 0.7794 (3) | 0.42975 (13) | 1.20898 (18) | 0.0138 (6) | |
O1 | 0.3999 (3) | 0.18659 (11) | 0.52533 (17) | 0.0248 (5) | |
O2 | 0.8623 (3) | 0.45605 (10) | 1.04542 (16) | 0.0239 (5) | |
N1 | 0.2934 (3) | 0.23839 (12) | 0.69567 (18) | 0.0189 (6) | |
N2 | 0.7743 (3) | 0.49082 (12) | 1.22992 (18) | 0.0175 (5) | |
H2O1 | 0.433 (4) | 0.1710 (16) | 0.489 (2) | 0.022 (11)* | |
H1O2 | 0.885 (4) | 0.4432 (15) | 0.999 (2) | 0.022 (10)* | |
H1N2 | 0.806 (4) | 0.5160 (16) | 1.189 (2) | 0.046 (11)* | |
H1N1 | 0.337 (4) | 0.2587 (16) | 0.650 (2) | 0.041 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.01750 (12) | 0.01365 (12) | 0.01301 (11) | −0.00059 (10) | 0.00440 (7) | −0.00018 (9) |
Cl11 | 0.0220 (4) | 0.0212 (4) | 0.0173 (3) | 0.0000 (3) | 0.0082 (3) | −0.0005 (3) |
Cl12 | 0.0219 (4) | 0.0267 (4) | 0.0163 (3) | −0.0038 (3) | 0.0022 (3) | −0.0003 (3) |
Cl13 | 0.0223 (4) | 0.0350 (5) | 0.0170 (3) | 0.0011 (4) | 0.0073 (3) | −0.0025 (3) |
Cl14 | 0.0198 (4) | 0.0209 (4) | 0.0160 (3) | −0.0019 (3) | 0.0036 (2) | −0.0031 (3) |
Cl1 | 0.0275 (4) | 0.0322 (5) | 0.0286 (4) | −0.0044 (4) | 0.0008 (3) | 0.0132 (3) |
Cl2 | 0.0282 (4) | 0.0255 (5) | 0.0328 (4) | −0.0051 (4) | 0.0010 (3) | 0.0128 (3) |
C11 | 0.0168 (15) | 0.0178 (17) | 0.0314 (17) | 0.0033 (14) | −0.0029 (12) | −0.0114 (14) |
C12 | 0.0139 (15) | 0.034 (2) | 0.0234 (16) | −0.0007 (15) | 0.0014 (11) | −0.0144 (14) |
C13 | 0.0136 (15) | 0.032 (2) | 0.0174 (15) | −0.0033 (15) | −0.0001 (11) | −0.0052 (13) |
C14 | 0.0107 (14) | 0.0203 (17) | 0.0161 (14) | −0.0007 (13) | −0.0024 (10) | −0.0003 (12) |
C15 | 0.0121 (14) | 0.0201 (17) | 0.0206 (15) | −0.0026 (13) | −0.0021 (10) | 0.0045 (13) |
C16 | 0.0168 (15) | 0.0156 (17) | 0.0282 (16) | 0.0023 (13) | −0.0038 (12) | −0.0001 (13) |
C17 | 0.0196 (15) | 0.0222 (18) | 0.0204 (15) | 0.0023 (14) | 0.0008 (11) | −0.0030 (13) |
C18 | 0.0160 (15) | 0.0184 (17) | 0.0159 (14) | 0.0024 (13) | −0.0006 (11) | 0.0010 (12) |
C19 | 0.0105 (14) | 0.0156 (16) | 0.0181 (14) | 0.0006 (13) | −0.0031 (10) | −0.0010 (12) |
C21 | 0.0187 (16) | 0.0221 (18) | 0.0271 (16) | 0.0041 (14) | −0.0026 (12) | −0.0097 (14) |
C22 | 0.0168 (16) | 0.038 (2) | 0.0170 (15) | 0.0018 (15) | 0.0017 (11) | −0.0079 (14) |
C23 | 0.0129 (15) | 0.032 (2) | 0.0161 (15) | −0.0032 (14) | −0.0005 (11) | 0.0018 (13) |
C24 | 0.0108 (14) | 0.0182 (17) | 0.0157 (14) | −0.0013 (13) | −0.0013 (10) | 0.0003 (12) |
C25 | 0.0146 (15) | 0.0172 (17) | 0.0209 (15) | −0.0055 (13) | −0.0018 (11) | 0.0088 (12) |
C26 | 0.0172 (15) | 0.0149 (17) | 0.0259 (16) | −0.0013 (13) | −0.0020 (11) | −0.0027 (12) |
C27 | 0.0196 (15) | 0.0185 (17) | 0.0166 (14) | 0.0011 (14) | 0.0008 (11) | −0.0030 (12) |
C28 | 0.0159 (15) | 0.0194 (17) | 0.0139 (14) | −0.0014 (13) | 0.0012 (10) | 0.0007 (12) |
C29 | 0.0123 (14) | 0.0142 (16) | 0.0144 (14) | 0.0005 (13) | −0.0023 (10) | −0.0006 (11) |
O1 | 0.0361 (14) | 0.0216 (14) | 0.0175 (12) | 0.0045 (11) | 0.0072 (10) | 0.0009 (10) |
O2 | 0.0389 (13) | 0.0203 (13) | 0.0135 (11) | −0.0006 (11) | 0.0084 (9) | 0.0003 (10) |
N1 | 0.0178 (13) | 0.0165 (15) | 0.0222 (14) | −0.0026 (12) | 0.0010 (10) | −0.0006 (11) |
N2 | 0.0192 (13) | 0.0136 (14) | 0.0197 (13) | 0.0009 (12) | 0.0013 (10) | −0.0001 (11) |
Pd1—Cl13 | 2.2956 (6) | C19—N1 | 1.364 (4) |
Pd1—Cl12 | 2.3089 (7) | C21—N2 | 1.325 (3) |
Pd1—Cl11 | 2.3313 (6) | C21—C22 | 1.389 (4) |
Pd1—Cl14 | 2.3350 (7) | C21—H21 | 0.9500 |
Cl1—C15 | 1.728 (3) | C22—C23 | 1.359 (4) |
Cl2—C25 | 1.733 (3) | C22—H22 | 0.9500 |
C11—N1 | 1.320 (3) | C23—C24 | 1.414 (4) |
C11—C12 | 1.392 (4) | C23—H23 | 0.9500 |
C11—H11 | 0.9500 | C24—C29 | 1.408 (4) |
C12—C13 | 1.367 (4) | C24—C25 | 1.414 (4) |
C12—H12 | 0.9500 | C25—C26 | 1.372 (4) |
C13—C14 | 1.414 (4) | C26—C27 | 1.406 (4) |
C13—H13 | 0.9500 | C26—H26 | 0.9500 |
C14—C19 | 1.411 (4) | C27—C28 | 1.365 (4) |
C14—C15 | 1.421 (4) | C27—H27 | 0.9500 |
C15—C16 | 1.368 (4) | C28—O2 | 1.350 (3) |
C16—C17 | 1.403 (4) | C28—C29 | 1.422 (3) |
C16—H16 | 0.9500 | C29—N2 | 1.360 (4) |
C17—C18 | 1.365 (4) | O1—H2O1 | 0.65 (3) |
C17—H17 | 0.9500 | O2—H1O2 | 0.69 (3) |
C18—O1 | 1.352 (3) | N1—H1N1 | 0.82 (3) |
C18—C19 | 1.419 (4) | N2—H1N2 | 0.82 (3) |
Cl13—Pd1—Cl12 | 90.19 (2) | N2—C21—H21 | 120.4 |
Cl13—Pd1—Cl11 | 178.86 (3) | C22—C21—H21 | 120.4 |
Cl12—Pd1—Cl11 | 90.15 (2) | C23—C22—C21 | 120.1 (3) |
Cl13—Pd1—Cl14 | 89.83 (2) | C23—C22—H22 | 119.9 |
Cl12—Pd1—Cl14 | 179.85 (3) | C21—C22—H22 | 119.9 |
Cl11—Pd1—Cl14 | 89.84 (2) | C22—C23—C24 | 120.9 (3) |
N1—C11—C12 | 119.6 (3) | C22—C23—H23 | 119.5 |
N1—C11—H11 | 120.2 | C24—C23—H23 | 119.5 |
C12—C11—H11 | 120.2 | C29—C24—C23 | 117.0 (3) |
C13—C12—C11 | 119.9 (3) | C29—C24—C25 | 117.4 (2) |
C13—C12—H12 | 120.1 | C23—C24—C25 | 125.5 (3) |
C11—C12—H12 | 120.1 | C26—C25—C24 | 120.9 (3) |
C12—C13—C14 | 120.3 (3) | C26—C25—Cl2 | 120.3 (2) |
C12—C13—H13 | 119.8 | C24—C25—Cl2 | 118.8 (2) |
C14—C13—H13 | 119.8 | C25—C26—C27 | 120.4 (3) |
C19—C14—C13 | 117.9 (3) | C25—C26—H26 | 119.8 |
C19—C14—C15 | 117.0 (2) | C27—C26—H26 | 119.8 |
C13—C14—C15 | 125.1 (3) | C28—C27—C26 | 121.1 (3) |
C16—C15—C14 | 121.2 (3) | C28—C27—H27 | 119.5 |
C16—C15—Cl1 | 119.8 (2) | C26—C27—H27 | 119.5 |
C14—C15—Cl1 | 119.0 (2) | O2—C28—C27 | 126.7 (2) |
C15—C16—C17 | 120.4 (3) | O2—C28—C29 | 114.7 (3) |
C15—C16—H16 | 119.8 | C27—C28—C29 | 118.5 (3) |
C17—C16—H16 | 119.8 | N2—C29—C24 | 119.2 (2) |
C18—C17—C16 | 121.0 (3) | N2—C29—C28 | 119.2 (3) |
C18—C17—H17 | 119.5 | C24—C29—C28 | 121.6 (3) |
C16—C17—H17 | 119.5 | C18—O1—H2O1 | 109 (3) |
O1—C18—C17 | 126.5 (3) | C28—O2—H1O2 | 108 (3) |
O1—C18—C19 | 114.7 (3) | C11—N1—C19 | 123.7 (3) |
C17—C18—C19 | 118.8 (3) | C11—N1—H1N1 | 117 (2) |
N1—C19—C14 | 118.6 (3) | C19—N1—H1N1 | 119 (2) |
N1—C19—C18 | 119.8 (3) | C21—N2—C29 | 123.5 (3) |
C14—C19—C18 | 121.6 (3) | C21—N2—H1N2 | 116 (2) |
N2—C21—C22 | 119.1 (3) | C29—N2—H1N2 | 121 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H2O1···Cl11i | 0.65 (3) | 2.46 (3) | 3.106 (2) | 177 (4) |
O2—H1O2···Cl14 | 0.69 (3) | 2.42 (3) | 3.109 (2) | 174 (3) |
N2—H1N2···Cl14ii | 0.82 (3) | 2.47 (3) | 3.199 (3) | 149 (3) |
N1—H1N1···Cl12 | 0.82 (3) | 2.47 (3) | 3.192 (3) | 147 (3) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+2, −y+1, −z+2. |
(C2H8N)[PdCl3] | F(000) = 496 |
Mr = 258.84 | Dx = 2.341 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 545 reflections |
a = 7.7896 (7) Å | θ = 3.1–28.9° |
b = 13.2070 (11) Å | µ = 3.51 mm−1 |
c = 7.1410 (6) Å | T = 293 K |
β = 91.359 (7)° | Needle, red-brown |
V = 734.44 (11) Å3 | 0.97 × 0.19 × 0.18 mm |
Z = 4 |
Oxford Diffraction Xcalibur (Sapphire2, large Be window) diffractometer | 762 independent reflections |
Radiation source: fine-focus sealed tube | 629 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
Detector resolution: 8.3438 pixels mm-1 | θmax = 26.5°, θmin = 3.1° |
ω scans | h = −5→9 |
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)] | k = −16→15 |
Tmin = 0.214, Tmax = 0.603 | l = −8→8 |
1387 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.027 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.064 | w = 1/[σ2(Fo2) + (0.0291P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
762 reflections | Δρmax = 0.67 e Å−3 |
40 parameters | Δρmin = −0.68 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0188 (9) |
(C2H8N)[PdCl3] | V = 734.44 (11) Å3 |
Mr = 258.84 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 7.7896 (7) Å | µ = 3.51 mm−1 |
b = 13.2070 (11) Å | T = 293 K |
c = 7.1410 (6) Å | 0.97 × 0.19 × 0.18 mm |
β = 91.359 (7)° |
Oxford Diffraction Xcalibur (Sapphire2, large Be window) diffractometer | 762 independent reflections |
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)] | 629 reflections with I > 2σ(I) |
Tmin = 0.214, Tmax = 0.603 | Rint = 0.020 |
1387 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.67 e Å−3 |
762 reflections | Δρmin = −0.68 e Å−3 |
40 parameters |
Experimental. Absorption correction: CrysAlisPro, Oxford Diffraction Ltd., Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) |
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. 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 | 0.5000 | 0.5000 | 0.5000 | 0.0227 (2) | |
Cl1 | 0.5000 | 0.61090 (11) | 0.7500 | 0.0329 (4) | |
Cl2 | 0.74937 (14) | 0.42723 (9) | 0.61492 (15) | 0.0378 (3) | |
C1 | 0.9193 (6) | 0.3120 (4) | 0.1009 (6) | 0.0421 (11) | |
H1A | 0.8692 | 0.3557 | 0.0071 | 0.063* | |
H1B | 0.8314 | 0.2704 | 0.1530 | 0.063* | |
H1C | 1.0044 | 0.2698 | 0.0452 | 0.063* | |
N1 | 1.0000 | 0.3736 (4) | 0.2500 | 0.0349 (13) | |
H1N1 | 0.919 (8) | 0.406 (4) | 0.303 (9) | 0.09 (2)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.0241 (3) | 0.0254 (3) | 0.0185 (3) | 0.0004 (2) | 0.00107 (17) | 0.00164 (16) |
Cl1 | 0.0471 (10) | 0.0294 (8) | 0.0224 (7) | 0.000 | 0.0011 (6) | 0.000 |
Cl2 | 0.0324 (6) | 0.0441 (7) | 0.0365 (6) | 0.0103 (6) | −0.0051 (4) | −0.0005 (5) |
C1 | 0.038 (3) | 0.044 (3) | 0.043 (3) | −0.006 (2) | −0.007 (2) | −0.006 (2) |
N1 | 0.035 (3) | 0.032 (3) | 0.037 (3) | 0.000 | −0.005 (3) | 0.000 |
Pd1—Cl2i | 2.3010 (10) | C1—H1A | 0.9600 |
Pd1—Cl2 | 2.3010 (10) | C1—H1B | 0.9600 |
Pd1—Cl1 | 2.3092 (9) | C1—H1C | 0.9600 |
Pd1—Cl1i | 2.3092 (9) | N1—C1iii | 1.469 (5) |
Cl1—Pd1ii | 2.3092 (9) | N1—H1N1 | 0.86 (5) |
C1—N1 | 1.469 (5) | ||
Cl2i—Pd1—Cl2 | 180.0 | N1—C1—H1B | 109.5 |
Cl2i—Pd1—Cl1 | 89.73 (3) | H1A—C1—H1B | 109.5 |
Cl2—Pd1—Cl1 | 90.27 (3) | N1—C1—H1C | 109.5 |
Cl2i—Pd1—Cl1i | 90.27 (3) | H1A—C1—H1C | 109.5 |
Cl2—Pd1—Cl1i | 89.73 (3) | H1B—C1—H1C | 109.5 |
Cl1—Pd1—Cl1i | 180.0 | C1—N1—C1iii | 112.8 (5) |
Pd1—Cl1—Pd1ii | 101.27 (6) | C1—N1—H1N1 | 107 (5) |
N1—C1—H1A | 109.5 | C1iii—N1—H1N1 | 105 (5) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y, −z+3/2; (iii) −x+2, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···Cl2 | 0.86 (5) | 2.63 (6) | 3.3684 (16) | 145 (6) |
N1—H1N1···Cl2iv | 0.86 (5) | 2.88 (6) | 3.402 (5) | 121 (5) |
Symmetry code: (iv) x, −y+1, z−1/2. |
C2H10N22+·2C9H5ClNO− | F(000) = 436 |
Mr = 419.30 | Dx = 1.480 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3109 reflections |
a = 15.8369 (5) Å | θ = 3.2–29.5° |
b = 6.8335 (3) Å | µ = 0.37 mm−1 |
c = 8.7459 (4) Å | T = 183 K |
β = 96.087 (3)° | Prism, yellow |
V = 941.16 (7) Å3 | 0.32 × 0.30 × 0.18 mm |
Z = 2 |
Oxford Diffraction Xcalibur (Sapphire2, large Be window) diffractometer | 1953 independent reflections |
Radiation source: fine-focus sealed tube | 1610 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
Detector resolution: 8.3438 pixels mm-1 | θmax = 26.5°, θmin = 3.3° |
ω scans | h = −19→19 |
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)] | k = −8→8 |
Tmin = 0.106, Tmax = 0.241 | l = −10→10 |
6777 measured reflections |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0437P)2 + 0.3861P] where P = (Fo2 + 2Fc2)/3 |
1953 reflections | (Δ/σ)max < 0.001 |
147 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C2H10N22+·2C9H5ClNO− | V = 941.16 (7) Å3 |
Mr = 419.30 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.8369 (5) Å | µ = 0.37 mm−1 |
b = 6.8335 (3) Å | T = 183 K |
c = 8.7459 (4) Å | 0.32 × 0.30 × 0.18 mm |
β = 96.087 (3)° |
Oxford Diffraction Xcalibur (Sapphire2, large Be window) diffractometer | 1953 independent reflections |
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)] | 1610 reflections with I > 2σ(I) |
Tmin = 0.106, Tmax = 0.241 | Rint = 0.025 |
6777 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.39 e Å−3 |
1953 reflections | Δρmin = −0.19 e Å−3 |
147 parameters |
Experimental. Absorption correction: CrysAlisPro, Oxford Diffraction Ltd., Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) |
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. 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 | ||
Cl1 | 0.05358 (3) | 0.72953 (8) | 0.71628 (6) | 0.03992 (18) | |
C1 | 0.24967 (11) | 0.1971 (3) | 0.4904 (2) | 0.0265 (4) | |
H1 | 0.2705 | 0.0842 | 0.4434 | 0.032* | |
C2 | 0.16153 (11) | 0.2106 (3) | 0.4988 (2) | 0.0281 (4) | |
H2 | 0.1244 | 0.1098 | 0.4581 | 0.034* | |
C3 | 0.13066 (10) | 0.3702 (3) | 0.5661 (2) | 0.0271 (4) | |
H3 | 0.0714 | 0.3818 | 0.5733 | 0.032* | |
C4 | 0.18667 (10) | 0.5197 (2) | 0.62566 (18) | 0.0209 (4) | |
C5 | 0.16087 (10) | 0.6923 (3) | 0.6970 (2) | 0.0249 (4) | |
C6 | 0.21846 (11) | 0.8303 (3) | 0.75126 (19) | 0.0248 (4) | |
H6 | 0.1998 | 0.9451 | 0.7989 | 0.030* | |
C7 | 0.30545 (10) | 0.8038 (2) | 0.73709 (19) | 0.0224 (4) | |
H7 | 0.3444 | 0.9017 | 0.7765 | 0.027* | |
C8 | 0.33615 (10) | 0.6403 (2) | 0.66789 (17) | 0.0188 (3) | |
C9 | 0.27492 (9) | 0.4934 (2) | 0.61074 (18) | 0.0189 (3) | |
C11 | 0.53688 (10) | 0.5689 (2) | 0.9921 (2) | 0.0208 (4) | |
O1 | 0.41795 (6) | 0.61455 (16) | 0.65317 (12) | 0.0202 (3) | |
N1 | 0.30504 (8) | 0.3310 (2) | 0.54356 (16) | 0.0219 (3) | |
N2 | 0.50427 (9) | 0.7520 (2) | 0.91811 (17) | 0.0183 (3) | |
H11B | 0.5767 (11) | 0.512 (3) | 0.925 (2) | 0.024 (5)* | |
H2N2 | 0.4685 (12) | 0.801 (3) | 0.980 (2) | 0.020 (5)* | |
H11A | 0.5664 (11) | 0.601 (3) | 1.092 (2) | 0.023 (5)* | |
H1N2 | 0.4779 (14) | 0.722 (3) | 0.825 (3) | 0.036 (6)* | |
H3N2 | 0.5461 (14) | 0.839 (3) | 0.907 (2) | 0.037 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0186 (2) | 0.0518 (3) | 0.0505 (3) | 0.0073 (2) | 0.0087 (2) | −0.0129 (2) |
C1 | 0.0265 (9) | 0.0261 (9) | 0.0266 (9) | 0.0013 (7) | 0.0019 (7) | −0.0035 (7) |
C2 | 0.0240 (8) | 0.0300 (10) | 0.0295 (10) | −0.0046 (7) | 0.0000 (7) | −0.0025 (8) |
C3 | 0.0183 (8) | 0.0350 (10) | 0.0278 (9) | −0.0022 (7) | 0.0021 (7) | 0.0024 (8) |
C4 | 0.0201 (8) | 0.0257 (9) | 0.0169 (8) | 0.0015 (7) | 0.0021 (6) | 0.0031 (7) |
C5 | 0.0178 (8) | 0.0347 (10) | 0.0226 (9) | 0.0059 (7) | 0.0049 (6) | 0.0011 (7) |
C6 | 0.0272 (9) | 0.0268 (9) | 0.0210 (9) | 0.0075 (7) | 0.0054 (7) | −0.0023 (7) |
C7 | 0.0231 (8) | 0.0235 (9) | 0.0206 (8) | 0.0000 (7) | 0.0015 (7) | −0.0023 (7) |
C8 | 0.0193 (8) | 0.0225 (8) | 0.0148 (8) | 0.0012 (6) | 0.0024 (6) | 0.0033 (6) |
C9 | 0.0186 (8) | 0.0227 (8) | 0.0156 (8) | 0.0028 (6) | 0.0025 (6) | 0.0023 (6) |
C11 | 0.0175 (8) | 0.0217 (8) | 0.0234 (9) | −0.0008 (7) | 0.0031 (7) | −0.0003 (7) |
O1 | 0.0164 (5) | 0.0256 (6) | 0.0189 (6) | 0.0006 (4) | 0.0037 (4) | 0.0004 (5) |
N1 | 0.0210 (7) | 0.0225 (7) | 0.0222 (7) | 0.0019 (6) | 0.0020 (6) | −0.0012 (6) |
N2 | 0.0180 (7) | 0.0201 (7) | 0.0173 (7) | −0.0021 (6) | 0.0044 (6) | −0.0009 (6) |
Cl1—C5 | 1.7437 (17) | C7—C8 | 1.383 (2) |
C1—N1 | 1.317 (2) | C7—H7 | 0.9500 |
C1—C2 | 1.409 (2) | C8—O1 | 1.3272 (18) |
C1—H1 | 0.9500 | C8—C9 | 1.447 (2) |
C2—C3 | 1.355 (3) | C9—N1 | 1.365 (2) |
C2—H2 | 0.9500 | C11—N2 | 1.477 (2) |
C3—C4 | 1.416 (2) | C11—C11i | 1.518 (3) |
C3—H3 | 0.9500 | C11—H11B | 0.983 (19) |
C4—C5 | 1.414 (2) | C11—H11A | 0.974 (18) |
C4—C9 | 1.429 (2) | N2—H2N2 | 0.89 (2) |
C5—C6 | 1.362 (3) | N2—H1N2 | 0.90 (2) |
C6—C7 | 1.408 (2) | N2—H3N2 | 0.90 (2) |
C6—H6 | 0.9500 | ||
N1—C1—C2 | 124.21 (16) | C6—C7—H7 | 118.8 |
N1—C1—H1 | 117.9 | O1—C8—C7 | 122.80 (14) |
C2—C1—H1 | 117.9 | O1—C8—C9 | 119.96 (14) |
C3—C2—C1 | 118.73 (16) | C7—C8—C9 | 117.23 (14) |
C3—C2—H2 | 120.6 | N1—C9—C4 | 122.10 (14) |
C1—C2—H2 | 120.6 | N1—C9—C8 | 117.43 (14) |
C2—C3—C4 | 119.99 (16) | C4—C9—C8 | 120.47 (15) |
C2—C3—H3 | 120.0 | N2—C11—C11i | 109.19 (16) |
C4—C3—H3 | 120.0 | N2—C11—H11B | 107.0 (11) |
C5—C4—C3 | 124.40 (15) | C11i—C11—H11B | 110.9 (11) |
C5—C4—C9 | 118.45 (15) | N2—C11—H11A | 108.4 (11) |
C3—C4—C9 | 117.15 (15) | C11i—C11—H11A | 110.9 (11) |
C6—C5—C4 | 121.12 (15) | H11B—C11—H11A | 110.3 (14) |
C6—C5—Cl1 | 119.26 (14) | C1—N1—C9 | 117.81 (14) |
C4—C5—Cl1 | 119.63 (13) | C11—N2—H2N2 | 105.8 (12) |
C5—C6—C7 | 120.38 (16) | C11—N2—H1N2 | 107.9 (13) |
C5—C6—H6 | 119.8 | H2N2—N2—H1N2 | 111.8 (18) |
C7—C6—H6 | 119.8 | C11—N2—H3N2 | 112.2 (13) |
C8—C7—C6 | 122.35 (15) | H2N2—N2—H3N2 | 110.0 (18) |
C8—C7—H7 | 118.8 | H1N2—N2—H3N2 | 109.2 (18) |
Symmetry code: (i) −x+1, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N2···O1ii | 0.89 (2) | 1.88 (2) | 2.7427 (18) | 163.6 (16) |
N2—H1N2···O1 | 0.90 (2) | 1.84 (2) | 2.7292 (18) | 168.7 (19) |
N2—H3N2···O1iii | 0.90 (2) | 2.05 (2) | 2.8646 (18) | 149.0 (18) |
N2—H3N2···N1iii | 0.90 (2) | 2.35 (2) | 3.051 (2) | 134.3 (17) |
Symmetry codes: (ii) x, −y+3/2, z+1/2; (iii) −x+1, y+1/2, −z+3/2. |
C9H7ClNO·Cl | Z = 2 |
Mr = 216.06 | F(000) = 220 |
Triclinic, P1 | Dx = 1.614 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.3980 (4) Å | Cell parameters from 2895 reflections |
b = 7.6612 (5) Å | θ = 3.2–29.2° |
c = 8.4536 (4) Å | µ = 0.68 mm−1 |
α = 72.400 (5)° | T = 183 K |
β = 76.797 (5)° | Plate, light yellow |
γ = 84.615 (5)° | 0.64 × 0.42 × 0.12 mm |
V = 444.47 (4) Å3 |
Oxford Diffraction Xcalibur (Sapphire2, large Be window) diffractometer | 1836 independent reflections |
Radiation source: fine-focus sealed tube | 1508 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
Detector resolution: 8.3438 pixels mm-1 | θmax = 26.5°, θmin = 3.2° |
ω scans | h = −9→9 |
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)] | k = −9→9 |
Tmin = 0.775, Tmax = 0.935 | l = −10→10 |
5950 measured reflections |
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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.073 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0338P)2 + 0.2637P] where P = (Fo2 + 2Fc2)/3 |
1836 reflections | (Δ/σ)max < 0.001 |
126 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C9H7ClNO·Cl | γ = 84.615 (5)° |
Mr = 216.06 | V = 444.47 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.3980 (4) Å | Mo Kα radiation |
b = 7.6612 (5) Å | µ = 0.68 mm−1 |
c = 8.4536 (4) Å | T = 183 K |
α = 72.400 (5)° | 0.64 × 0.42 × 0.12 mm |
β = 76.797 (5)° |
Oxford Diffraction Xcalibur (Sapphire2, large Be window) diffractometer | 1836 independent reflections |
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)] | 1508 reflections with I > 2σ(I) |
Tmin = 0.775, Tmax = 0.935 | Rint = 0.023 |
5950 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.073 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | Δρmax = 0.28 e Å−3 |
1836 reflections | Δρmin = −0.20 e Å−3 |
126 parameters |
Experimental. Absorption correction: CrysAlisPro, Oxford Diffraction Ltd., Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) |
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. 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 | ||
Cl1 | −0.27168 (7) | 1.08850 (7) | 0.23024 (6) | 0.03076 (15) | |
Cl2 | 0.68520 (6) | 0.63769 (6) | 0.14647 (5) | 0.02654 (14) | |
C1 | −0.1109 (3) | 0.5638 (3) | 0.7615 (2) | 0.0243 (4) | |
H1 | −0.1134 | 0.4755 | 0.8687 | 0.029* | |
C2 | −0.2760 (3) | 0.6490 (3) | 0.7208 (2) | 0.0264 (4) | |
H2 | −0.3910 | 0.6173 | 0.7985 | 0.032* | |
C3 | −0.2706 (3) | 0.7787 (3) | 0.5677 (2) | 0.0235 (4) | |
H3 | −0.3827 | 0.8373 | 0.5396 | 0.028* | |
C4 | −0.1003 (2) | 0.8267 (2) | 0.4509 (2) | 0.0194 (4) | |
C5 | −0.0790 (3) | 0.9595 (2) | 0.2901 (2) | 0.0217 (4) | |
C6 | 0.0904 (3) | 0.9914 (3) | 0.1827 (2) | 0.0232 (4) | |
H6 | 0.1010 | 1.0813 | 0.0755 | 0.028* | |
C7 | 0.2500 (3) | 0.8925 (3) | 0.2289 (2) | 0.0233 (4) | |
H7 | 0.3665 | 0.9149 | 0.1515 | 0.028* | |
C8 | 0.2395 (2) | 0.7643 (2) | 0.3842 (2) | 0.0200 (4) | |
C9 | 0.0626 (2) | 0.7324 (2) | 0.4967 (2) | 0.0180 (4) | |
O1 | 0.38214 (19) | 0.66338 (19) | 0.44309 (17) | 0.0259 (3) | |
N1 | 0.0496 (2) | 0.6050 (2) | 0.65167 (18) | 0.0202 (3) | |
H1O1 | 0.466 (3) | 0.661 (3) | 0.366 (3) | 0.043 (7)* | |
H1N1 | 0.155 (3) | 0.538 (3) | 0.689 (3) | 0.048 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0274 (3) | 0.0355 (3) | 0.0313 (3) | 0.0103 (2) | −0.0104 (2) | −0.0127 (2) |
Cl2 | 0.0241 (3) | 0.0285 (3) | 0.0207 (2) | 0.00215 (19) | 0.00148 (17) | −0.00325 (18) |
C1 | 0.0267 (10) | 0.0240 (9) | 0.0211 (9) | −0.0051 (8) | 0.0013 (7) | −0.0084 (8) |
C2 | 0.0206 (10) | 0.0325 (11) | 0.0263 (10) | −0.0063 (8) | 0.0031 (8) | −0.0129 (8) |
C3 | 0.0178 (9) | 0.0297 (10) | 0.0268 (10) | −0.0016 (8) | −0.0025 (7) | −0.0151 (8) |
C4 | 0.0186 (9) | 0.0228 (9) | 0.0209 (9) | −0.0001 (7) | −0.0035 (7) | −0.0131 (7) |
C5 | 0.0213 (9) | 0.0237 (9) | 0.0242 (9) | 0.0030 (8) | −0.0071 (7) | −0.0121 (8) |
C6 | 0.0274 (10) | 0.0235 (9) | 0.0193 (9) | −0.0022 (8) | −0.0049 (7) | −0.0068 (7) |
C7 | 0.0194 (9) | 0.0287 (10) | 0.0213 (9) | −0.0048 (8) | 0.0015 (7) | −0.0093 (8) |
C8 | 0.0170 (9) | 0.0243 (9) | 0.0207 (9) | 0.0004 (7) | −0.0025 (7) | −0.0110 (7) |
C9 | 0.0196 (9) | 0.0180 (9) | 0.0187 (8) | −0.0015 (7) | −0.0023 (7) | −0.0094 (7) |
O1 | 0.0164 (7) | 0.0364 (8) | 0.0222 (7) | 0.0041 (6) | −0.0006 (6) | −0.0084 (6) |
N1 | 0.0204 (8) | 0.0209 (8) | 0.0199 (8) | 0.0007 (6) | −0.0026 (6) | −0.0085 (6) |
Cl1—C5 | 1.7398 (18) | C5—C6 | 1.364 (3) |
C1—N1 | 1.327 (2) | C6—C7 | 1.409 (3) |
C1—C2 | 1.394 (3) | C6—H6 | 0.9500 |
C1—H1 | 0.9500 | C7—C8 | 1.372 (3) |
C2—C3 | 1.367 (3) | C7—H7 | 0.9500 |
C2—H2 | 0.9500 | C8—O1 | 1.347 (2) |
C3—C4 | 1.413 (2) | C8—C9 | 1.424 (2) |
C3—H3 | 0.9500 | C9—N1 | 1.366 (2) |
C4—C9 | 1.416 (2) | O1—H1O1 | 0.79 (2) |
C4—C5 | 1.415 (3) | N1—H1N1 | 0.95 (3) |
N1—C1—C2 | 120.46 (17) | C5—C6—H6 | 119.6 |
N1—C1—H1 | 119.8 | C7—C6—H6 | 119.6 |
C2—C1—H1 | 119.8 | C8—C7—C6 | 120.90 (17) |
C3—C2—C1 | 119.33 (17) | C8—C7—H7 | 119.5 |
C3—C2—H2 | 120.3 | C6—C7—H7 | 119.5 |
C1—C2—H2 | 120.3 | O1—C8—C7 | 126.23 (16) |
C2—C3—C4 | 120.84 (18) | O1—C8—C9 | 115.51 (16) |
C2—C3—H3 | 119.6 | C7—C8—C9 | 118.26 (16) |
C4—C3—H3 | 119.6 | N1—C9—C4 | 119.21 (16) |
C3—C4—C9 | 117.52 (16) | N1—C9—C8 | 119.03 (16) |
C3—C4—C5 | 125.40 (17) | C4—C9—C8 | 121.75 (16) |
C9—C4—C5 | 117.06 (16) | C8—O1—H1O1 | 109.9 (18) |
C6—C5—C4 | 121.27 (17) | C1—N1—C9 | 122.60 (16) |
C6—C5—Cl1 | 119.26 (14) | C1—N1—H1N1 | 114.6 (15) |
C4—C5—Cl1 | 119.45 (14) | C9—N1—H1N1 | 122.8 (15) |
C5—C6—C7 | 120.72 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O1···Cl2 | 0.79 (2) | 2.21 (3) | 3.0001 (14) | 174 (2) |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | (C9H7ClNO)2[PdCl4] | (C2H8N)[PdCl3] | C2H10N22+·2C9H5ClNO− | C9H7ClNO·Cl |
Mr | 609.41 | 258.84 | 419.30 | 216.06 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, C2/c | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 183 | 293 | 183 | 183 |
a, b, c (Å) | 7.2339 (2), 21.7998 (8), 13.0306 (4) | 7.7896 (7), 13.2070 (11), 7.1410 (6) | 15.8369 (5), 6.8335 (3), 8.7459 (4) | 7.3980 (4), 7.6612 (5), 8.4536 (4) |
α, β, γ (°) | 90, 94.903 (3), 90 | 90, 91.359 (7), 90 | 90, 96.087 (3), 90 | 72.400 (5), 76.797 (5), 84.615 (5) |
V (Å3) | 2047.37 (11) | 734.44 (11) | 941.16 (7) | 444.47 (4) |
Z | 4 | 4 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 1.71 | 3.51 | 0.37 | 0.68 |
Crystal size (mm) | 0.29 × 0.14 × 0.05 | 0.97 × 0.19 × 0.18 | 0.32 × 0.30 × 0.18 | 0.64 × 0.42 × 0.12 |
Data collection | ||||
Diffractometer | Oxford Diffraction Xcalibur (Sapphire2, large Be window) diffractometer | Oxford Diffraction Xcalibur (Sapphire2, large Be window) diffractometer | Oxford Diffraction Xcalibur (Sapphire2, large Be window) diffractometer | Oxford Diffraction Xcalibur (Sapphire2, large Be window) diffractometer |
Absorption correction | Analytical [CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)] | Analytical [CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)] | Analytical [CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)] | Analytical [CrysAlis PRO (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)] |
Tmin, Tmax | 0.816, 0.939 | 0.214, 0.603 | 0.106, 0.241 | 0.775, 0.935 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8968, 4226, 3467 | 1387, 762, 629 | 6777, 1953, 1610 | 5950, 1836, 1508 |
Rint | 0.025 | 0.020 | 0.025 | 0.023 |
(sin θ/λ)max (Å−1) | 0.628 | 0.628 | 0.628 | 0.628 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.054, 1.06 | 0.027, 0.064, 1.07 | 0.037, 0.093, 1.04 | 0.029, 0.073, 0.94 |
No. of reflections | 4226 | 762 | 1953 | 1836 |
No. of parameters | 278 | 40 | 147 | 126 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.44, −0.45 | 0.67, −0.68 | 0.39, −0.19 | 0.28, −0.20 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2001).
Pd1—Cl13 | 2.2956 (6) | C11—N1 | 1.320 (3) |
Pd1—Cl12 | 2.3089 (7) | C18—O1 | 1.352 (3) |
Pd1—Cl11 | 2.3313 (6) | C19—N1 | 1.364 (4) |
Pd1—Cl14 | 2.3350 (7) | C21—N2 | 1.325 (3) |
Cl1—C15 | 1.728 (3) | C28—O2 | 1.350 (3) |
Cl2—C25 | 1.733 (3) | C29—N2 | 1.360 (4) |
Cl13—Pd1—Cl12 | 90.19 (2) | Cl13—Pd1—Cl14 | 89.83 (2) |
Cl13—Pd1—Cl11 | 178.86 (3) | Cl12—Pd1—Cl14 | 179.85 (3) |
Cl12—Pd1—Cl11 | 90.15 (2) | Cl11—Pd1—Cl14 | 89.84 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H2O1···Cl11i | 0.65 (3) | 2.46 (3) | 3.106 (2) | 177 (4) |
O2—H1O2···Cl14 | 0.69 (3) | 2.42 (3) | 3.109 (2) | 174 (3) |
N2—H1N2···Cl14ii | 0.82 (3) | 2.47 (3) | 3.199 (3) | 149 (3) |
N1—H1N1···Cl12 | 0.82 (3) | 2.47 (3) | 3.192 (3) | 147 (3) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+2, −y+1, −z+2. |
Pd1—Cl2i | 2.3010 (10) | Pd1—Cl1i | 2.3092 (9) |
Pd1—Cl2 | 2.3010 (10) | Cl1—Pd1ii | 2.3092 (9) |
Pd1—Cl1 | 2.3092 (9) | ||
Cl2i—Pd1—Cl2 | 180.0 | Cl2—Pd1—Cl1i | 89.73 (3) |
Cl2i—Pd1—Cl1 | 89.73 (3) | Cl1—Pd1—Cl1i | 180.0 |
Cl2—Pd1—Cl1 | 90.27 (3) | Pd1—Cl1—Pd1ii | 101.27 (6) |
Cl2i—Pd1—Cl1i | 90.27 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···Cl2 | 0.86 (5) | 2.63 (6) | 3.3684 (16) | 145 (6) |
N1—H1N1···Cl2iii | 0.86 (5) | 2.88 (6) | 3.402 (5) | 121 (5) |
Symmetry code: (iii) x, −y+1, z−1/2. |
Cl1—C5 | 1.7437 (17) | C8—O1 | 1.3272 (18) |
C1—N1 | 1.317 (2) | C9—N1 | 1.365 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N2···O1i | 0.89 (2) | 1.88 (2) | 2.7427 (18) | 163.6 (16) |
N2—H1N2···O1 | 0.90 (2) | 1.84 (2) | 2.7292 (18) | 168.7 (19) |
N2—H3N2···O1ii | 0.90 (2) | 2.05 (2) | 2.8646 (18) | 149.0 (18) |
N2—H3N2···N1ii | 0.90 (2) | 2.35 (2) | 3.051 (2) | 134.3 (17) |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+1, y+1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O1···Cl2 | 0.79 (2) | 2.21 (3) | 3.0001 (14) | 174 (2) |
With the development of anticancer agents containing platinum, such as cisplatin or carboplatin, there is also an interest in the preparation of other transition metal complexes that can serve as anticancer drugs. Palladium, as a metal very analogous to platinum, forms complexes which are also promising agents for the development of new anticancer drugs.
In general, PdII complexes containing chelating ligands exhibit antiproliferative activity against the Sarcoma 180 tumor (Fricker, 1994). Due to the significant difference in reactivity of palladium and platinum complexes towards DNA, it has been suggested that PdII complexes might circumvent resistance to cisplatin-derived drugs in some tumor cell lines (Farrell, 1989; Shi et al., 2010). On the other hand, the activity of anticancer agent might be enhanced by the coordination of organic drugs with known biological activities to transition metals. A perfect example of this strategy was reported on trans-palladium(II) complexes with chloroquine, which has been used as an antimalarial (Miller, 1954) and anti-inflammatory drug (Ferrante et al., 1986). It has been shown that its coordination to the PdII atom resulted in an increased antitumor activity against four cancer cell lines comparing to chloroquine itself (Navarro et al., 2006).
Other examples of biologically active substances are 5-chloroquinolin-8-ol (ClQ) and halogenated derivatives of quinolin-8-ol (XQ), which were recently investigated for anticancer activity with positive results (Jiang et al., 2011). Promising anticancer activity of PdII complexes with different ligands mentioned above, as well as the activity of ClQ, motivated us to prepare square-planar complexes containing the [Pd(ClQ)Cl2]- anion. For the sake of comparison, we also tried to prepare analogous NiII complexes. Our initial efforts resulted in the preparation of two ionic complexes containing PdII atoms, viz. (HClQ)2[PdCl4], (I), and [NH2(CH3)2][PdCl3], (II), and two ionic compounds comprising only protonated and deprotonated ions of the ClQ ligand, viz. (NH3CH2CH2NH3)(ClQ)2, (III), and (HClQ)Cl, (IV). The structure of (II) is already known (Raper et al., 1997), therefore we report here the preparation of (I)–(IV) and the crystal structures of (I), (III) and (IV), while the structure of (II) is only compared with the structure of (I).
The structures of compounds (I) and (II) contain PdII atoms which are coordinated in a square-planar manner by four chloride ligands. However, in (I), there is an isolated [PdCl4]2- anion, while in (II) PdII atoms are bridged by a pair of trans-coordinated Cl- ligands, forming an infinite chain. Six types of [PdCl4]2- anion units were found in the Cambridge Structural Database (Allen, 2002). [PdCl4]2- occurs most frequently as an isolated anion (101 hits), as in (I). In other structures containing [PdCl4]2-, PdII atoms are bridged in different modes and different chain-like or polynuclear compounds are formed. The most popular bridging mode (34 hits) is by pair of cis-coordinated Cl- ligands bridging two PdII atoms which have two other terminal Cl- ligands and thus binuclear [Pd2Cl6]2- units are formed. There is also one compound of similar composition, however this contains two pairs of cis-coordinated Cl- ligands bridging three PdII atoms, giving a trinuclear [Pd3Cl8]2- complex (Schwarz et al., 2002). On the other hand, there are two structures with a pair of trans-coordinated bridging Cl- ligands, as in (II) (Raper et al., 1997; Yang et al., 2006). Another unusual bridging mode (2 hits) is reported by Hosokawa et al. (1994, 1998), where three chloride ligands act as bridging atoms. Finally, the last type of bridging mode contains four bridging chloride ligands and different types of chains or polynuclear complexes are formed (23 hits).
Thus, the structure of (I) belongs to the most frequently observed form of the [PdCl4]2- unit, i.e. as an isolated [PdCl4]2- anion, and its negative charge is balanced by two protonated molecules of ClQ (HClQ+) (Fig. 1).
Both HClQ+ cations are themselves planar [the largest deviation from the mean planes of the aromatic rings of the HClQ+ is 0.039 (3) Å for atom C12 and 0.019 (3) Å for atom N2]. The C—C and C—N(O) bond lengths within the pyridine and benzene rings have expected values compared with previously published compounds containing the ClQ molecule (Ng, 2009; García-Granda & Gómez-Beltrán, 1986), as well as complexes containing other halogen-substituted 8-HQ molecules (Di Vaira et al., 2004; García-Granda & Gómez-Beltrán, 1986; García-Granda et al., 1987; Kappaun et al., 2006; Potočňák & Vranec, 2012; Vranec & Potočňák, 2011; Vranec et al., 2012). The C—Cl bond lengths are close to the values for corresponding single bonds in aromatic rings (García-Granda & Gómez-Beltrán, 1986; García-Granda et al., 1987; Gniewek et al., 2006; Kappaun et al., 2006; Ng, 2009; Potočňák & Vranec, 2012; Vranec & Potočňák, 2011; Vranec et al., 2012). The Pd—Cl distances in the complex anion are also similar to previously reported compounds containing the [PdCl4]2- anion (Suyun et al., 2011; Carvalho et al., 2010). A distorted square-planar geometry around the PdII atom is confirmed by the Cl—Pd—Cl angles given in Table 1, where other selected bond lengths and angles are also summarized.
Except for ionic forces, the structure of (I) is also stabilized by a system of hydrogen bonds. Hydroxy and pyridinium H atoms from both HClQ+ cations are interconnected by Cl- atoms of the [PdCl4]2- anion and a wave-like plane parallel to (001) is formed (Fig. 2). Data characterizing all four hydrogen bonds are given in Table 2.
There are also π–π interactions in the structure of (I), which occur between the phenolic parts of both HClQ+ cations (Fig. 3). Data characterizing these interactions are consistent with the literature data on π–π interactions (Janiak, 2000). Dihedral angles between the planes of adjacent HClQ+ molecules are 3.65 and 3.88° for HClQ+(1) and HClQ+(2i), and HClQ+(1) and HClQ+(2ii) molecules, respectively, and the distances between the corresponding centroids of the phenolic parts are Cg1···Cg2i = 3.711 (1) and Cg1···Cg2ii = 3.576 (1) Å [symmetry codes: (i) x-1, -y+1/2, z-1/2; (ii) x, -y+1/2, z-1/2]. The angles between the benzene-ring normals and the Cg1···Cg2i and Cg1···Cg2ii centroid vectors are 22.97 and 20.22°, respectively.
In the structure of (II), the environment of the PdII atom is similar to that in (I) (Fig. 4). Nevertheless, as stated above, in this case, the [PdCl4]2- anion is part of a rarely occurring negatively charged [–µ2Cl–PdCl2–]n chain running along the c axis in which two PdII atoms are bridged by trans-coordinated Cl- ligands (Fig. 5). The negative charge of the repeating [PdCl3]- unit is balanced by the presence of a dimethylammonium cation.
Although the Cl- ligands have different bonding modes, the Pd–Cl bond lengths are still very similar (Table 3) and are close to those observed in (I); the same is also true for the Cl—Pd—Cl angles. The structure of the dimethylammonium cation exhibits normal features, both for bond lengths and for bond angles, confirming the sp3-hybridization of the C and N atoms (Raper et al., 1997; Melen et al., 2011).
The structure of (II) is also stabilized by a system of hydrogen bonds, which involve both amino H atoms and atom Cl2 of the [PdCl4]2- unit (Fig. 6). Due to these two hydrogen bonds, the cations and anions are linked to form a plane parallel to (010). Data characterizing hydrogen bonds for (II) are given in Table 4.
The structure of (III) consists of ethylenediammonium cations and ClQ- anions containing deprotonated hydroxy groups (Fig. 7). On the other hand, the structure of (IV) is formed by a protonated HClQ+ molecule, where the H atom is on the N atom of the ClQ molecule; the positive charge of the cation is compensated by the presence of a chloride anion (Fig. 8). To the best of our knowledge, compound (III) represents the first example of a structure with an isolated ClQ- anion, while (I) and (IV) are the second and third examples of structures with isolated HClQ+ cations (Allen, 2002).
The protonated and deprotonated ClQ molecules in (III) and (IV) are themselves planar [the largest deviation from the mean plane of the whole ClQ molecule is 0.005 (1) Å for atom N1 in (III) and 0.028 (2) Å for atom C5 in (IV)]. The C—C and C—N(O) bond lengths within the pyridine and benzene rings, as well as the C—Cl bond lengths, have values close to those for a previously published analogous (HClQ)NO3 compound (Ng, 2009), as well as for complexes containing other halogen-substituted 8-HQ molecules (Di Vaira et al., 2004; García-Granda & Gómez-Beltrán, 1986; García-Granda et al., 1987; Gniewek et al., 2006; Kappaun et al., 2006; Potočňák & Vranec, 2012; Vranec & Potočňák, 2011; Vranec et al., 2012). Selected bond lengths and angles for (III) and (IV) are given in Tables 5 and 6, respectively.
Except the ionic forces, the structures of both (III) and (IV) are stabilized by hydrogen bonds. All ammonium H atoms in (III) are involved in hydrogen bonding. One of them, H3N2, interacts with atoms O1ii and N1ii of the ClQ- anion, while other two H atoms, H1N2 and H2N2, interact with only one O atom, O1 and O1i, respectively [symmetry codes: (i) x, -y+3/2, z+1/2; (ii) -x+1, y+1/2, -z+3/2]. Due to these hydrogen bonds, a layered structure parallel to (100) is formed. Each layer comprises three planes, viz. a plane of ethylenediammonium cations surrounded by two planes of ClQ- anions with Cl1 atoms at the outer side of these two planes. These triple-plane layers are held together by weak London forces and Cl atoms in neighboring layers arrange themselves a zipper-like fashion with an interlayer Cl···Cliv distance of 3.888 (1) Å [symmetry codes: (iv) -x, y+1/2, -z+3/2; (v) -x, y-1/2, -z+3/2] (Fig 9). Data characterizing hydrogen bonds in (III) are summarized in Table 7.
Two hydrogen bonds were observed in the structure of (IV). One of them occurs between the chloride anion and the hydroxy H atom of the HClQ+ cation, while the second hydrogen bond occurs between the chloride anion and a pyridinium H atom of the HClQ+ cation and thus an R42(14) motif is formed (Bernstein et al., 1995). Data characterizing hydrogen bonds in (IV) are summarized in Table 8. There were also π–π interactions in the structure of (IV) between a pair of coplanar adjacent cations. The distance between parallel mean planes of the HClQ+ cations is 3.40 Å and the distance between the centroids of the pyridine and phenol parts of HClQ+ is 3.613 (1) Å. The angle between the benzene or pyridine ring normal and the centroids vector of 19.64°, as well as previously mentioned distances, are consistent with the literature data on π–π interactions (Janiak, 2000). Due to these interactions, the hydrogen-bonded motifs in (IV) are linked together and an infinite stair-like chain is formed (Fig. 10).