


Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S160053681301088X/is5266sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S160053681301088X/is5266Isup2.hkl |
![]() | MDL mol file https://doi.org/10.1107/S160053681301088X/is5266Isup4.mol |
CCDC reference: 954209
Key indicators
- Single-crystal X-ray study
- T = 200 K
- Mean
(C-C) = 0.007 Å
- Disorder in solvent or counterion
- R factor = 0.025
- wR factor = 0.062
- Data-to-parameter ratio = 14.6
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT417_ALERT_2_B Short Inter D-H..H-D H21G .. H30G .. 2.04 Ang. PLAT910_ALERT_3_B Missing # of FCF Reflections Below Th(Min) ..... 12
Alert level C PLAT041_ALERT_1_C Calc. and Reported SumFormula Strings Differ ? PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms .. ? PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.23 PLAT417_ALERT_2_C Short Inter D-H..H-D H6 .. H28G .. 2.12 Ang. PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of . 46 A 3 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 13 PLAT915_ALERT_3_C Low Friedel Pair Coverage ...................... 64 Perc. PLAT976_ALERT_2_C Negative Residual Density at 0.79A from O32 . -0.55 eA-3
Alert level G PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 63 PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF ? PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............ 16 PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings Differ ? PLAT045_ALERT_1_G Calculated and Reported Z Differ by ............ 0.50 Ratio PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Pd8 -- S7 .. 6.8 su PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Pd8 -- S8 .. 5.2 su PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Pd8 -- N8 .. 5.8 su PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ................... 8 Perc. PLAT791_ALERT_4_G Note: The Model has Chirality at C2 (Verify) S PLAT791_ALERT_4_G Note: The Model has Chirality at C7 (Verify) S PLAT791_ALERT_4_G Note: The Model has Chirality at C12 (Verify) S PLAT791_ALERT_4_G Note: The Model has Chirality at C17 (Verify) S PLAT791_ALERT_4_G Note: The Model has Chirality at C22 (Verify) S PLAT791_ALERT_4_G Note: The Model has Chirality at C27 (Verify) S PLAT791_ALERT_4_G Note: The Model has Chirality at C32 (Verify) S PLAT791_ALERT_4_G Note: The Model has Chirality at C37 (Verify) S PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 67 PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 33
0 ALERT level A = Most likely a serious problem - resolve or explain 2 ALERT level B = A potentially serious problem, consider carefully 8 ALERT level C = Check. Ensure it is not caused by an omission or oversight 19 ALERT level G = General information/check it is not something unexpected 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 9 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 11 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
To an orange suspension containing 100 mg (0.08 mmol) of [Pd4(D-Hpen)4Cl4].7H2O in water (10 ml) was added an aqueous K2CO3 (0.2 M, 1 ml). From the resulting orange solution, a yellow crystalline powder of (I) was immediately precipitated, which was collected by filtration. Yield: 43 mg (46%). 1H NMR in DMSO-d6 (500 MHz): δ 5.84 (dd, J = 11.1, 7.5 Hz, 1H, NH2), 4.95 (d, J = 11.2 Hz, 1H, NH2), 3.15 (d, J = 7.6 Hz, 1H, CH), 1.64 (s, 3H, CH3), 1.64 (s, 3H, CH3). IR (KBr): 1610 cm-1 (νCO for COO-). Single-crystals of (I) suitable for X-ray analysis were obtained by recrystallization of the powder from a small amount of ethanol/water (1:1).
H atoms bound to C and N atoms were placed at calculated positions [C—H = 0.98 (CH3), 0.99 (CH2) or 1.00 Å (CH) and N—H = 0.92 Å (NH2)] and refined as riding with Uiso(H) = 1.2Ueq(C,N) for CH and NH2, and 1.5Ueq(C) for CH3. One and a half water molecules were disordered, and these molecules were refined with occupancies of 0.5. H atoms of water molecules were placed so as to form reasonable hydrogen bonding. All H atoms bound to O atoms were refined with restrained geometric and displacement parameters [O—H = 0.85 (2) Å, H···H = 1.38 (2) Å and Uiso(H) = 1.2Ueq(O)]. In addition, one H atom (H32F) was refined with an additional intermolecular H···O distance restraint so as to form reasonable hydrogen bonding. Reflections of (-6 14 -9), (-13 2 1), (-12 -3 0) and (-12 2 14) were removed to improve the data quality.
D-Penicillamine (C5H11NSO2, D—H2pen), which is a sulfur-containing amino acid, has been known as a unique multidentate chiral ligand that has three kinds of coordination sites, amine N, carboxylate O, and thiolate S atoms (Igashira-Kamiyama & Konno, 2011). Recently, we found that an S-bridged cyclic tetranuclear PdII complex with D-pen, [Pd4Cl4(D-Hpen)4].7H2O, gradually converts to an S-bridged cyclic trinuclear PdII structure in [Pd3(D-pen)3].4.5H2O (II), by treating with K2CO3 in water (Yoshinari et al., 2009). We assumed that some intermediate species exists in this reaction because not only the nuclearity of the complex (PdII4 versus. PdII3) but also the coordination mode of D-pen (κ2N,S:κS versus. κ2N,S:κ2S,O) are required to be changed for this structural conversion. In the course of our trials to find an intermediate species, we were able to isolate crystals (I), the composition of which is different from those of [Pd4Cl4(D-Hpen)4].7H2O and [Pd3(D-pen)3].4.5H2O, and its structure was determined by single-crystal X-ray crystallography. Herein we report that crystal (I) thus obtained has a new cyclic tetranuclear PdII structure in [PdII4(D-pen)4].9.75H2O, which forms an intriguing supramolecular dimer structure.
The asymmetric unit of (I) contains two tetranuclear PdII molecules, [Pd4(D-pen)4], and nineteen and a half solvated water molecules (Figure 1). The two tetranuclear molecules are essentially the same as each other, comprising of four square-planar PdII atoms and four D-pen ligands. Each D-pen ligand bridges two PdII centers in a κ2N,S:κ2S,O coordination mode, while each PdII atom is coordinated by two D-pen ligands in N,S- and S,O- chelating modes, forming a crown-type eight-membered Pd4S4 metallacycle. Note that amine and carboxy groups cover one face of the metallacycle, while thiolate and methyl groups cover another face in (I). It has been shown that similar hydrophilic and hydrophobic surfaces are formed in the S-bridged metallacycle structure in (II).
The Pd—S distances and S—Pd—S angles in (I) [Pd—S = 2.2261 (11)–2.2968 (10) Å, S—Pd—S = 89.76 (4)–93.65 (4)°] are similar to those in (II) [Pd—S = 2.2427 (15)–2.2934 (15) Å, S—Pd—S = 90.08 (6)–92.66 (6)°]. However, the Pd—S—Pd angles in (I) [96.90 (4)–102.42 (4)°] are closer to the ideal tetrahedral angle of 109.5° compared with those in (II) [Pd—S—Pd = 82.89 (5)–91.65 (6)°], while the trans angles around PdII atoms in (I) [167.45 (12)–172.13 (8)°] are slightly smaller than those in (II) [170.41 (13)–176.67 (16)°]. This implies that the distortion around S atoms is larger but the distortion around Pd atoms is smaller in (I), compared with those in (II).
The most remarkable structural feature in (I) is the construction of a cylindrical supramolecular structure, in which two cyclic tetranuclear molecules face to each other to form eight intermolecular N—H···O hydrogen bonds [N···O = 2.917 (4)–3.278 (5) Å] (Figure 2). None of solvent molecules are accommodated in the cylinder despite the presence of a void space with a diameter of ca 4 Å. All of the water molecules are participated in the formation of O—H···O and/or N—H···O hydrogen bonds with neighboring water molecules and/or tetranuclear molecules [O···O = 2.650 (5)–3.135 (9) Å, N···O = 2.886 (5)–3.326 (5) Å], completing three dimensional structure in (I) (Table 1).
For background to this class of compound, see: Igashira-Kamiyama & Konno (2011). For related structures, see: Yoshinari et al. (2009).
Data collection: PROCESS-AUTO (Rigaku, 2000); cell refinement: PROCESS-AUTO (Rigaku, 2000); data reduction: PROCESS-AUTO (Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Yadokari-XG 2009 (Kabuto et al., 2009); software used to prepare material for publication: Yadokari-XG 2009 (Kabuto et al., 2009).
[Pd4(C5H9NO2S)4]·9.75H2O | Z = 2 |
Mr = 1190.03 | F(000) = 1187 |
Triclinic, P1 | Dx = 1.912 Mg m−3 |
Hall symbol: P 1 | Mo Kα radiation, λ = 0.71075 Å |
a = 12.4517 (3) Å | Cell parameters from 20017 reflections |
b = 13.2680 (4) Å | θ = 3.1–27.5° |
c = 15.1666 (11) Å | µ = 1.98 mm−1 |
α = 113.527 (8)° | T = 200 K |
β = 98.425 (7)° | Platelet, yellow |
γ = 108.557 (8)° | 0.25 × 0.10 × 0.03 mm |
V = 2067.3 (3) Å3 |
Rigaku R-AXIS RAPID diffractometer | 15410 independent reflections |
Radiation source: fine-focus sealed tube | 15064 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
Detector resolution: 10.000 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω scans | h = −16→14 |
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995) | k = −16→17 |
Tmin = 0.730, Tmax = 0.916 | l = −19→19 |
20447 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)] = 0.025 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.062 | w = 1/[σ2(Fo2) + (0.0317P)2 + 0.9989P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
15410 reflections | Δρmax = 1.52 e Å−3 |
1052 parameters | Δρmin = −0.68 e Å−3 |
67 restraints | Absolute structure: Flack (1983), 6026 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.024 (13) |
[Pd4(C5H9NO2S)4]·9.75H2O | γ = 108.557 (8)° |
Mr = 1190.03 | V = 2067.3 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 12.4517 (3) Å | Mo Kα radiation |
b = 13.2680 (4) Å | µ = 1.98 mm−1 |
c = 15.1666 (11) Å | T = 200 K |
α = 113.527 (8)° | 0.25 × 0.10 × 0.03 mm |
β = 98.425 (7)° |
Rigaku R-AXIS RAPID diffractometer | 15410 independent reflections |
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995) | 15064 reflections with I > 2σ(I) |
Tmin = 0.730, Tmax = 0.916 | Rint = 0.027 |
20447 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.062 | Δρmax = 1.52 e Å−3 |
S = 1.08 | Δρmin = −0.68 e Å−3 |
15410 reflections | Absolute structure: Flack (1983), 6026 Friedel pairs |
1052 parameters | Absolute structure parameter: −0.024 (13) |
67 restraints |
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 | Occ. (<1) | |
Pd1 | 0.56254 (2) | 0.15412 (2) | −0.01146 (2) | 0.01755 (6) | |
Pd2 | 0.41117 (2) | 0.20457 (2) | 0.15893 (2) | 0.01745 (6) | |
Pd3 | 0.65618 (3) | 0.29031 (2) | 0.35747 (2) | 0.01965 (7) | |
Pd4 | 0.80963 (2) | 0.23751 (2) | 0.19018 (2) | 0.01745 (6) | |
Pd5 | 0.38317 (2) | 0.68823 (2) | −0.09373 (2) | 0.01653 (6) | |
Pd6 | 0.64056 (2) | 0.76363 (2) | 0.08388 (2) | 0.01663 (6) | |
Pd7 | 0.52043 (2) | 0.81899 (2) | 0.27928 (2) | 0.01811 (6) | |
Pd8 | 0.26082 (2) | 0.75142 (2) | 0.10469 (2) | 0.01650 (6) | |
S1 | 0.48748 (9) | 0.28612 (8) | 0.06247 (7) | 0.02000 (19) | |
S2 | 0.53843 (9) | 0.36787 (8) | 0.30163 (7) | 0.01988 (19) | |
S3 | 0.80787 (9) | 0.39725 (8) | 0.32436 (7) | 0.02019 (19) | |
S4 | 0.75113 (9) | 0.30047 (8) | 0.08309 (7) | 0.01972 (19) | |
S5 | 0.49291 (8) | 0.59918 (8) | −0.05455 (7) | 0.01876 (19) | |
S6 | 0.58784 (9) | 0.68416 (9) | 0.18395 (7) | 0.01953 (19) | |
S7 | 0.33138 (8) | 0.67908 (8) | 0.20419 (7) | 0.01933 (19) | |
S8 | 0.23872 (8) | 0.59553 (8) | −0.04008 (7) | 0.01813 (18) | |
O1 | 0.2813 (2) | 0.0429 (2) | 0.0384 (2) | 0.0231 (6) | |
O2 | 0.1159 (3) | 0.0122 (3) | −0.0646 (2) | 0.0332 (7) | |
O3 | 0.5311 (3) | 0.1763 (3) | 0.3917 (3) | 0.0332 (7) | |
O4 | 0.4366 (4) | 0.2102 (4) | 0.5046 (3) | 0.0484 (10) | |
O5 | 0.8676 (3) | 0.1593 (3) | 0.2715 (2) | 0.0272 (6) | |
O6 | 1.0310 (3) | 0.2146 (4) | 0.3895 (3) | 0.0510 (11) | |
O7 | 0.6082 (2) | 0.0152 (2) | −0.0941 (2) | 0.0231 (6) | |
O8 | 0.7179 (3) | −0.0477 (3) | −0.1856 (2) | 0.0299 (7) | |
O9 | 0.7102 (3) | 0.8570 (2) | 0.0075 (2) | 0.0238 (6) | |
O10 | 0.8157 (3) | 0.8105 (3) | −0.0954 (2) | 0.0333 (7) | |
O11 | 0.6842 (3) | 0.9670 (3) | 0.3624 (2) | 0.0282 (7) | |
O12 | 0.8575 (3) | 1.0212 (4) | 0.4671 (3) | 0.0553 (11) | |
O13 | 0.2651 (3) | 0.9032 (3) | 0.2224 (2) | 0.0260 (6) | |
O14 | 0.2040 (3) | 0.9751 (3) | 0.3530 (3) | 0.0410 (9) | |
O15 | 0.2990 (2) | 0.7811 (3) | −0.1378 (2) | 0.0229 (6) | |
O16 | 0.1355 (3) | 0.7755 (3) | −0.2233 (2) | 0.0275 (6) | |
N1 | 0.3900 (3) | 0.0411 (3) | −0.1125 (2) | 0.0203 (7) | |
H1 | 0.3935 | 0.0211 | −0.1772 | 0.024* | |
H1A | 0.3649 | −0.0292 | −0.1079 | 0.024* | |
N2 | 0.3325 (3) | 0.1506 (3) | 0.2542 (3) | 0.0240 (7) | |
H2 | 0.2517 | 0.1275 | 0.2301 | 0.029* | |
H2A | 0.3433 | 0.0831 | 0.2484 | 0.029* | |
N3 | 0.7798 (3) | 0.2570 (4) | 0.4357 (3) | 0.0296 (8) | |
H3 | 0.7763 | 0.2823 | 0.5008 | 0.036* | |
H3A | 0.7565 | 0.1748 | 0.4061 | 0.036* | |
N4 | 0.8342 (3) | 0.1127 (3) | 0.0675 (2) | 0.0203 (7) | |
H4 | 0.9089 | 0.1160 | 0.0887 | 0.024* | |
H4A | 0.7797 | 0.0369 | 0.0506 | 0.024* | |
N5 | 0.5071 (3) | 0.7408 (3) | −0.1641 (2) | 0.0194 (7) | |
H5 | 0.4659 | 0.7140 | −0.2303 | 0.023* | |
H5A | 0.5420 | 0.8239 | −0.1330 | 0.023* | |
N6 | 0.7913 (3) | 0.8925 (3) | 0.2088 (2) | 0.0236 (7) | |
H6 | 0.8574 | 0.8985 | 0.1874 | 0.028* | |
H6A | 0.7870 | 0.9660 | 0.2301 | 0.028* | |
N7 | 0.4558 (3) | 0.9259 (3) | 0.3788 (2) | 0.0208 (7) | |
H7 | 0.4972 | 0.9475 | 0.4436 | 0.025* | |
H7A | 0.4733 | 0.9957 | 0.3737 | 0.025* | |
N8 | 0.1709 (3) | 0.7980 (3) | 0.0124 (2) | 0.0210 (7) | |
H8 | 0.1111 | 0.8127 | 0.0370 | 0.025* | |
H8A | 0.2232 | 0.8698 | 0.0195 | 0.025* | |
C1 | 0.3559 (4) | 0.2285 (4) | −0.0483 (3) | 0.0234 (8) | |
C2 | 0.2972 (4) | 0.0906 (4) | −0.0983 (3) | 0.0209 (8) | |
H2B | 0.2414 | 0.0600 | −0.1668 | 0.025* | |
C3 | 0.2244 (4) | 0.0447 (4) | −0.0382 (3) | 0.0229 (8) | |
C4 | 0.4041 (5) | 0.2698 (4) | −0.1216 (3) | 0.0317 (10) | |
H4C | 0.3372 | 0.2462 | −0.1794 | 0.047* | |
H4D | 0.4570 | 0.2316 | −0.1458 | 0.047* | |
H4E | 0.4487 | 0.3578 | −0.0863 | 0.047* | |
C5 | 0.2723 (4) | 0.2883 (4) | −0.0111 (4) | 0.0348 (10) | |
H5C | 0.3125 | 0.3756 | 0.0137 | 0.052* | |
H5D | 0.2521 | 0.2734 | 0.0439 | 0.052* | |
H5E | 0.1992 | 0.2540 | −0.0672 | 0.052* | |
C6 | 0.4359 (4) | 0.3684 (4) | 0.3796 (3) | 0.0265 (9) | |
C7 | 0.3745 (4) | 0.2393 (4) | 0.3644 (3) | 0.0218 (8) | |
H7B | 0.3023 | 0.2338 | 0.3869 | 0.026* | |
C8 | 0.4521 (4) | 0.2079 (4) | 0.4268 (3) | 0.0258 (9) | |
C9 | 0.3439 (5) | 0.4063 (5) | 0.3404 (4) | 0.0391 (12) | |
H9C | 0.2943 | 0.4180 | 0.3849 | 0.059* | |
H9D | 0.2932 | 0.3432 | 0.2716 | 0.059* | |
H9E | 0.3849 | 0.4821 | 0.3394 | 0.059* | |
C10 | 0.5084 (5) | 0.4600 (4) | 0.4895 (4) | 0.0350 (11) | |
H10C | 0.5444 | 0.5407 | 0.4955 | 0.052* | |
H10D | 0.5716 | 0.4383 | 0.5120 | 0.052* | |
H10E | 0.4561 | 0.4600 | 0.5319 | 0.052* | |
C11 | 0.9312 (4) | 0.4296 (4) | 0.4314 (3) | 0.0254 (9) | |
C12 | 0.9076 (4) | 0.3144 (4) | 0.4416 (3) | 0.0249 (9) | |
H12B | 0.9589 | 0.3384 | 0.5101 | 0.030* | |
C13 | 0.9386 (4) | 0.2236 (4) | 0.3631 (3) | 0.0213 (8) | |
C14 | 0.9306 (5) | 0.5310 (5) | 0.5255 (4) | 0.0455 (13) | |
H14C | 1.0004 | 0.5587 | 0.5825 | 0.068* | |
H14D | 0.8576 | 0.5010 | 0.5419 | 0.068* | |
H14E | 0.9334 | 0.5983 | 0.5126 | 0.068* | |
C15 | 1.0490 (4) | 0.4763 (4) | 0.4098 (4) | 0.0375 (11) | |
H15C | 1.0545 | 0.5440 | 0.3965 | 0.056* | |
H15D | 1.0513 | 0.4111 | 0.3505 | 0.056* | |
H15E | 1.1163 | 0.5036 | 0.4687 | 0.056* | |
C16 | 0.8366 (3) | 0.2537 (3) | −0.0042 (3) | 0.0202 (8) | |
C17 | 0.8233 (3) | 0.1252 (4) | −0.0265 (3) | 0.0207 (8) | |
H17B | 0.8911 | 0.1137 | −0.0508 | 0.025* | |
C18 | 0.7080 (3) | 0.0242 (3) | −0.1089 (3) | 0.0200 (8) | |
C19 | 0.9684 (4) | 0.3435 (4) | 0.0515 (3) | 0.0288 (9) | |
H19C | 1.0158 | 0.3253 | 0.0060 | 0.043* | |
H19D | 0.9979 | 0.3364 | 0.1113 | 0.043* | |
H19E | 0.9753 | 0.4261 | 0.0726 | 0.043* | |
C20 | 0.7879 (4) | 0.2604 (4) | −0.0998 (3) | 0.0266 (9) | |
H20C | 0.7841 | 0.3388 | −0.0803 | 0.040* | |
H20D | 0.7078 | 0.1955 | −0.1387 | 0.040* | |
H20E | 0.8408 | 0.2513 | −0.1415 | 0.040* | |
C21 | 0.5636 (4) | 0.5795 (3) | −0.1569 (3) | 0.0206 (8) | |
C22 | 0.6039 (3) | 0.6977 (4) | −0.1639 (3) | 0.0197 (8) | |
H22B | 0.6204 | 0.6801 | −0.2298 | 0.024* | |
C23 | 0.7192 (4) | 0.7945 (4) | −0.0790 (3) | 0.0220 (8) | |
C24 | 0.4685 (4) | 0.4759 (4) | −0.2548 (3) | 0.0304 (10) | |
H24C | 0.5037 | 0.4590 | −0.3099 | 0.046* | |
H24D | 0.4034 | 0.4984 | −0.2712 | 0.046* | |
H24E | 0.4372 | 0.4037 | −0.2464 | 0.046* | |
C25 | 0.6677 (4) | 0.5470 (4) | −0.1301 (4) | 0.0303 (10) | |
H25C | 0.6361 | 0.4668 | −0.1345 | 0.045* | |
H25D | 0.7201 | 0.6070 | −0.0610 | 0.045* | |
H25E | 0.7132 | 0.5466 | −0.1776 | 0.045* | |
C26 | 0.7410 (4) | 0.7371 (4) | 0.2672 (3) | 0.0253 (9) | |
C27 | 0.8110 (4) | 0.8710 (4) | 0.2986 (3) | 0.0215 (8) | |
H27B | 0.8978 | 0.8908 | 0.3235 | 0.026* | |
C28 | 0.7823 (4) | 0.9590 (4) | 0.3831 (3) | 0.0262 (9) | |
C29 | 0.7994 (4) | 0.6606 (5) | 0.2034 (4) | 0.0359 (11) | |
H29C | 0.8081 | 0.6779 | 0.1471 | 0.054* | |
H29D | 0.7489 | 0.5746 | 0.1766 | 0.054* | |
H29E | 0.8781 | 0.6808 | 0.2461 | 0.054* | |
C30 | 0.7311 (5) | 0.7148 (5) | 0.3579 (4) | 0.0364 (11) | |
H30C | 0.8112 | 0.7447 | 0.4037 | 0.055* | |
H30D | 0.6888 | 0.6279 | 0.3339 | 0.055* | |
H30E | 0.6870 | 0.7573 | 0.3941 | 0.055* | |
C31 | 0.2743 (4) | 0.7331 (4) | 0.3133 (3) | 0.0211 (8) | |
C32 | 0.3264 (4) | 0.8728 (4) | 0.3654 (3) | 0.0190 (8) | |
H32B | 0.3172 | 0.9012 | 0.4345 | 0.023* | |
C33 | 0.2592 (4) | 0.9188 (3) | 0.3094 (3) | 0.0210 (8) | |
C34 | 0.3183 (4) | 0.6923 (4) | 0.3870 (3) | 0.0283 (9) | |
H34C | 0.2912 | 0.7207 | 0.4461 | 0.042* | |
H34D | 0.4057 | 0.7261 | 0.4088 | 0.042* | |
H34E | 0.2861 | 0.6038 | 0.3532 | 0.042* | |
C35 | 0.1378 (4) | 0.6754 (4) | 0.2741 (3) | 0.0266 (9) | |
H35C | 0.1088 | 0.5872 | 0.2401 | 0.040* | |
H35D | 0.1105 | 0.7010 | 0.2260 | 0.040* | |
H35E | 0.1067 | 0.7011 | 0.3311 | 0.040* | |
C36 | 0.1010 (3) | 0.5834 (3) | −0.1193 (3) | 0.0211 (8) | |
C37 | 0.1163 (3) | 0.7115 (3) | −0.0981 (3) | 0.0174 (7) | |
H37B | 0.0347 | 0.7079 | −0.1193 | 0.021* | |
C38 | 0.1877 (3) | 0.7582 (3) | −0.1584 (3) | 0.0176 (7) | |
C39 | −0.0021 (4) | 0.5281 (4) | −0.0858 (4) | 0.0327 (10) | |
H39C | −0.0772 | 0.5156 | −0.1285 | 0.049* | |
H39D | 0.0108 | 0.5827 | −0.0150 | 0.049* | |
H39E | −0.0059 | 0.4503 | −0.0926 | 0.049* | |
C40 | 0.0796 (4) | 0.4998 (4) | −0.2302 (3) | 0.0306 (10) | |
H40C | 0.0787 | 0.4226 | −0.2379 | 0.046* | |
H40D | 0.1437 | 0.5373 | −0.2526 | 0.046* | |
H40E | 0.0027 | 0.4857 | −0.2714 | 0.046* | |
O17 | 0.2360 (3) | 0.7792 (3) | 0.6258 (3) | 0.0368 (8) | |
H17F | 0.295 (4) | 0.846 (3) | 0.647 (3) | 0.044* | |
H17G | 0.213 (4) | 0.779 (4) | 0.676 (3) | 0.044* | |
O18 | 0.3581 (3) | 0.6315 (3) | 0.6191 (3) | 0.0376 (8) | |
H18F | 0.323 (4) | 0.677 (4) | 0.632 (4) | 0.045* | |
H18G | 0.422 (3) | 0.665 (4) | 0.609 (4) | 0.045* | |
O19 | 0.9512 (3) | 0.0057 (3) | 0.7877 (3) | 0.0372 (8) | |
H19F | 0.881 (2) | −0.021 (5) | 0.792 (4) | 0.045* | |
H19G | 0.997 (3) | −0.010 (5) | 0.823 (4) | 0.045* | |
O20 | 0.5778 (3) | 0.7806 (3) | 0.6202 (2) | 0.0372 (8) | |
H20F | 0.635 (3) | 0.768 (5) | 0.601 (3) | 0.045* | |
H20G | 0.603 (4) | 0.826 (4) | 0.6846 (16) | 0.045* | |
O21 | 0.7559 (3) | 0.7161 (4) | 0.5734 (3) | 0.0460 (9) | |
H21F | 0.782 (4) | 0.694 (5) | 0.615 (4) | 0.055* | |
H21G | 0.818 (3) | 0.772 (4) | 0.576 (4) | 0.055* | |
O22 | 0.8781 (3) | 0.6974 (4) | 0.7329 (3) | 0.0414 (9) | |
H22F | 0.859 (4) | 0.728 (5) | 0.786 (3) | 0.050* | |
H22G | 0.947 (3) | 0.749 (4) | 0.742 (4) | 0.050* | |
O23 | 0.5672 (3) | 0.9673 (3) | 0.5820 (3) | 0.0363 (8) | |
H23F | 0.563 (4) | 0.904 (3) | 0.585 (4) | 0.044* | |
H23G | 0.641 (2) | 1.013 (4) | 0.600 (4) | 0.044* | |
O24 | 0.0002 (3) | 0.2202 (4) | 0.7741 (3) | 0.0449 (9) | |
H24F | −0.012 (5) | 0.157 (4) | 0.779 (5) | 0.054* | |
H24G | 0.060 (4) | 0.235 (5) | 0.753 (4) | 0.054* | |
O25 | 0.7894 (3) | 0.1475 (3) | 0.6288 (3) | 0.0416 (8) | |
H25F | 0.858 (3) | 0.178 (5) | 0.674 (3) | 0.050* | |
H25G | 0.802 (4) | 0.116 (5) | 0.572 (2) | 0.050* | |
O26 | 0.4061 (3) | 0.0111 (3) | 0.6861 (3) | 0.0386 (8) | |
H26F | 0.464 (3) | 0.007 (5) | 0.663 (4) | 0.046* | |
H26G | 0.362 (4) | 0.026 (5) | 0.649 (4) | 0.046* | |
O27 | 0.0682 (3) | 0.0366 (3) | 0.2512 (2) | 0.0374 (8) | |
H27F | 0.040 (4) | 0.077 (4) | 0.293 (3) | 0.045* | |
H27G | 0.115 (4) | 0.018 (5) | 0.282 (3) | 0.045* | |
O28 | 0.9639 (3) | 0.8198 (4) | 0.0690 (3) | 0.0405 (8) | |
H28F | 0.930 (5) | 0.835 (5) | 0.028 (3) | 0.049* | |
H28G | 0.996 (5) | 0.875 (4) | 0.1274 (18) | 0.049* | |
O29 | 0.0768 (3) | 0.1372 (4) | 0.1199 (3) | 0.0439 (9) | |
H29F | 0.078 (6) | 0.096 (4) | 0.059 (2) | 0.053* | |
H29G | 0.069 (6) | 0.091 (4) | 0.147 (4) | 0.053* | |
O30 | 0.9422 (4) | 0.9185 (4) | 0.5849 (3) | 0.0563 (11) | |
H30F | 0.961 (6) | 0.983 (3) | 0.578 (4) | 0.068* | |
H30G | 0.954 (6) | 0.940 (5) | 0.6485 (19) | 0.068* | |
O31 | 0.2735 (4) | 0.0901 (4) | 0.5859 (3) | 0.0523 (10) | |
H31F | 0.213 (4) | 0.025 (4) | 0.549 (4) | 0.063* | |
H31G | 0.315 (5) | 0.109 (5) | 0.550 (4) | 0.063* | |
O32 | 0.1683 (6) | 0.2489 (5) | 0.6778 (5) | 0.094 (2) | |
H32F | 0.144 (4) | 0.263 (5) | 0.626 (4) | 0.113* | |
H32G | 0.202 (8) | 0.202 (7) | 0.651 (6) | 0.113* | |
O33 | 0.0993 (5) | 0.8375 (5) | 0.4988 (4) | 0.0651 (13) | |
H33F | 0.111 (6) | 0.797 (6) | 0.530 (5) | 0.078* | |
H33G | 0.056 (6) | 0.871 (6) | 0.529 (5) | 0.078* | |
O34 | 0.2066 (5) | 0.3892 (5) | 0.5768 (4) | 0.0731 (15) | |
H34F | 0.267 (4) | 0.450 (5) | 0.587 (5) | 0.088* | |
H34G | 0.164 (5) | 0.353 (6) | 0.514 (2) | 0.088* | |
O35A | 0.6203 (8) | 0.2636 (7) | 0.6738 (6) | 0.0473 (18) | 0.50 |
H35F | 0.673 (8) | 0.236 (11) | 0.662 (8) | 0.057* | 0.50 |
H35G | 0.562 (7) | 0.227 (10) | 0.620 (5) | 0.057* | 0.50 |
O35B | 0.7105 (7) | 0.3189 (8) | 0.6173 (6) | 0.0428 (18) | 0.50 |
H35H | 0.645 (5) | 0.323 (10) | 0.613 (9) | 0.051* | 0.50 |
H35I | 0.710 (9) | 0.258 (7) | 0.622 (10) | 0.051* | 0.50 |
O36A | 0.7793 (9) | 0.4317 (7) | 0.6403 (6) | 0.060 (3) | 0.50 |
H36F | 0.790 (12) | 0.506 (4) | 0.669 (10) | 0.072* | 0.50 |
H36G | 0.736 (12) | 0.395 (9) | 0.666 (10) | 0.072* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.01898 (15) | 0.01577 (14) | 0.01867 (14) | 0.00661 (11) | 0.00782 (11) | 0.00872 (11) |
Pd2 | 0.01978 (15) | 0.01643 (14) | 0.01862 (14) | 0.00832 (11) | 0.00777 (11) | 0.00939 (11) |
Pd3 | 0.02208 (15) | 0.02032 (15) | 0.02266 (15) | 0.01175 (12) | 0.01158 (12) | 0.01195 (12) |
Pd4 | 0.01941 (15) | 0.01653 (14) | 0.01521 (13) | 0.00718 (11) | 0.00666 (10) | 0.00626 (11) |
Pd5 | 0.01712 (14) | 0.01635 (13) | 0.01776 (13) | 0.00712 (11) | 0.00635 (10) | 0.00918 (11) |
Pd6 | 0.01805 (14) | 0.01675 (13) | 0.01560 (13) | 0.00801 (11) | 0.00604 (10) | 0.00728 (11) |
Pd7 | 0.02024 (15) | 0.01885 (14) | 0.01730 (14) | 0.01009 (11) | 0.00649 (11) | 0.00875 (12) |
Pd8 | 0.02006 (14) | 0.01697 (14) | 0.01576 (13) | 0.00908 (11) | 0.00712 (10) | 0.00920 (11) |
S1 | 0.0235 (5) | 0.0168 (4) | 0.0221 (5) | 0.0086 (4) | 0.0102 (4) | 0.0104 (4) |
S2 | 0.0233 (5) | 0.0166 (4) | 0.0219 (4) | 0.0090 (4) | 0.0090 (4) | 0.0098 (4) |
S3 | 0.0230 (5) | 0.0175 (4) | 0.0194 (4) | 0.0084 (4) | 0.0091 (4) | 0.0074 (4) |
S4 | 0.0221 (5) | 0.0164 (4) | 0.0191 (4) | 0.0065 (4) | 0.0075 (3) | 0.0078 (4) |
S5 | 0.0205 (5) | 0.0167 (4) | 0.0191 (4) | 0.0081 (3) | 0.0059 (3) | 0.0082 (4) |
S6 | 0.0226 (5) | 0.0199 (4) | 0.0191 (4) | 0.0102 (4) | 0.0081 (3) | 0.0103 (4) |
S7 | 0.0225 (5) | 0.0186 (4) | 0.0198 (4) | 0.0110 (4) | 0.0076 (3) | 0.0095 (4) |
S8 | 0.0210 (5) | 0.0170 (4) | 0.0194 (4) | 0.0082 (4) | 0.0083 (3) | 0.0104 (4) |
O1 | 0.0247 (15) | 0.0210 (14) | 0.0206 (14) | 0.0049 (11) | 0.0053 (11) | 0.0114 (12) |
O2 | 0.0210 (15) | 0.050 (2) | 0.0358 (17) | 0.0146 (14) | 0.0108 (12) | 0.0262 (16) |
O3 | 0.0333 (17) | 0.0367 (17) | 0.057 (2) | 0.0233 (14) | 0.0292 (15) | 0.0353 (16) |
O4 | 0.057 (2) | 0.083 (3) | 0.037 (2) | 0.045 (2) | 0.0266 (17) | 0.041 (2) |
O5 | 0.0362 (17) | 0.0256 (15) | 0.0163 (13) | 0.0162 (13) | 0.0044 (11) | 0.0057 (12) |
O6 | 0.042 (2) | 0.056 (2) | 0.0342 (19) | 0.0325 (18) | −0.0008 (15) | −0.0023 (17) |
O7 | 0.0176 (13) | 0.0153 (13) | 0.0292 (15) | 0.0049 (10) | 0.0078 (11) | 0.0054 (11) |
O8 | 0.0266 (15) | 0.0299 (16) | 0.0197 (14) | 0.0110 (13) | 0.0062 (11) | 0.0004 (12) |
O9 | 0.0273 (15) | 0.0221 (14) | 0.0219 (14) | 0.0072 (11) | 0.0127 (11) | 0.0111 (12) |
O10 | 0.0231 (16) | 0.0492 (19) | 0.0283 (16) | 0.0150 (14) | 0.0128 (12) | 0.0174 (15) |
O11 | 0.0262 (15) | 0.0218 (14) | 0.0311 (16) | 0.0112 (12) | 0.0068 (12) | 0.0075 (13) |
O12 | 0.040 (2) | 0.072 (3) | 0.0229 (17) | 0.0284 (19) | −0.0025 (14) | −0.0044 (18) |
O13 | 0.0420 (18) | 0.0267 (15) | 0.0194 (14) | 0.0219 (14) | 0.0109 (12) | 0.0138 (12) |
O14 | 0.062 (2) | 0.064 (2) | 0.0338 (18) | 0.055 (2) | 0.0265 (16) | 0.0299 (17) |
O15 | 0.0225 (14) | 0.0262 (15) | 0.0283 (15) | 0.0109 (12) | 0.0103 (11) | 0.0191 (12) |
O16 | 0.0275 (16) | 0.0426 (18) | 0.0295 (15) | 0.0192 (13) | 0.0126 (12) | 0.0278 (14) |
N1 | 0.0219 (17) | 0.0180 (16) | 0.0216 (16) | 0.0065 (13) | 0.0098 (13) | 0.0104 (13) |
N2 | 0.0240 (18) | 0.0231 (17) | 0.0253 (17) | 0.0060 (14) | 0.0113 (14) | 0.0135 (15) |
N3 | 0.038 (2) | 0.043 (2) | 0.034 (2) | 0.0275 (18) | 0.0237 (16) | 0.0291 (18) |
N4 | 0.0210 (16) | 0.0196 (16) | 0.0208 (16) | 0.0101 (13) | 0.0092 (13) | 0.0080 (13) |
N5 | 0.0165 (15) | 0.0218 (16) | 0.0188 (15) | 0.0073 (13) | 0.0074 (12) | 0.0087 (13) |
N6 | 0.0226 (17) | 0.0241 (17) | 0.0196 (16) | 0.0041 (13) | 0.0060 (13) | 0.0109 (14) |
N7 | 0.0251 (17) | 0.0187 (16) | 0.0194 (16) | 0.0102 (13) | 0.0054 (13) | 0.0096 (13) |
N8 | 0.0234 (17) | 0.0212 (16) | 0.0224 (16) | 0.0105 (13) | 0.0120 (13) | 0.0113 (14) |
C1 | 0.029 (2) | 0.022 (2) | 0.024 (2) | 0.0120 (16) | 0.0071 (16) | 0.0146 (17) |
C2 | 0.025 (2) | 0.027 (2) | 0.0171 (18) | 0.0140 (16) | 0.0090 (15) | 0.0131 (16) |
C3 | 0.023 (2) | 0.022 (2) | 0.0225 (19) | 0.0092 (16) | 0.0086 (15) | 0.0095 (16) |
C4 | 0.051 (3) | 0.023 (2) | 0.029 (2) | 0.015 (2) | 0.0132 (19) | 0.0197 (18) |
C5 | 0.039 (3) | 0.033 (2) | 0.042 (3) | 0.024 (2) | 0.014 (2) | 0.020 (2) |
C6 | 0.031 (2) | 0.023 (2) | 0.029 (2) | 0.0149 (18) | 0.0151 (17) | 0.0095 (17) |
C7 | 0.0203 (19) | 0.023 (2) | 0.0229 (19) | 0.0114 (16) | 0.0115 (15) | 0.0083 (16) |
C8 | 0.025 (2) | 0.021 (2) | 0.031 (2) | 0.0094 (16) | 0.0098 (17) | 0.0129 (17) |
C9 | 0.041 (3) | 0.044 (3) | 0.058 (3) | 0.033 (2) | 0.030 (2) | 0.032 (3) |
C10 | 0.047 (3) | 0.027 (2) | 0.030 (2) | 0.015 (2) | 0.021 (2) | 0.0093 (19) |
C11 | 0.025 (2) | 0.022 (2) | 0.0207 (19) | 0.0097 (16) | 0.0010 (15) | 0.0043 (16) |
C12 | 0.024 (2) | 0.033 (2) | 0.0173 (19) | 0.0167 (18) | 0.0050 (15) | 0.0083 (17) |
C13 | 0.0222 (19) | 0.0197 (19) | 0.0174 (18) | 0.0094 (15) | 0.0030 (14) | 0.0053 (15) |
C14 | 0.064 (4) | 0.033 (3) | 0.024 (2) | 0.028 (3) | 0.002 (2) | −0.002 (2) |
C15 | 0.024 (2) | 0.036 (3) | 0.043 (3) | 0.0050 (19) | 0.0066 (19) | 0.017 (2) |
C16 | 0.0216 (19) | 0.0176 (18) | 0.0190 (18) | 0.0039 (15) | 0.0084 (14) | 0.0091 (15) |
C17 | 0.0177 (19) | 0.0222 (19) | 0.0198 (19) | 0.0048 (15) | 0.0080 (14) | 0.0099 (16) |
C18 | 0.0191 (19) | 0.0199 (18) | 0.0218 (19) | 0.0088 (15) | 0.0060 (14) | 0.0102 (16) |
C19 | 0.021 (2) | 0.027 (2) | 0.028 (2) | 0.0012 (16) | 0.0053 (16) | 0.0099 (18) |
C20 | 0.030 (2) | 0.027 (2) | 0.023 (2) | 0.0080 (18) | 0.0112 (17) | 0.0152 (18) |
C21 | 0.024 (2) | 0.0187 (18) | 0.0196 (18) | 0.0116 (16) | 0.0088 (15) | 0.0073 (15) |
C22 | 0.0201 (19) | 0.0228 (19) | 0.0169 (18) | 0.0093 (15) | 0.0081 (14) | 0.0090 (16) |
C23 | 0.027 (2) | 0.0194 (19) | 0.0212 (19) | 0.0105 (16) | 0.0061 (15) | 0.0103 (16) |
C24 | 0.040 (3) | 0.020 (2) | 0.022 (2) | 0.0063 (18) | 0.0077 (18) | 0.0076 (17) |
C25 | 0.035 (2) | 0.036 (2) | 0.036 (2) | 0.026 (2) | 0.0180 (19) | 0.021 (2) |
C26 | 0.026 (2) | 0.027 (2) | 0.025 (2) | 0.0132 (17) | 0.0029 (16) | 0.0146 (18) |
C27 | 0.0210 (19) | 0.0220 (19) | 0.0197 (18) | 0.0094 (16) | 0.0053 (14) | 0.0083 (16) |
C28 | 0.027 (2) | 0.024 (2) | 0.023 (2) | 0.0088 (17) | 0.0052 (16) | 0.0087 (17) |
C29 | 0.032 (2) | 0.038 (3) | 0.045 (3) | 0.025 (2) | 0.010 (2) | 0.020 (2) |
C30 | 0.042 (3) | 0.037 (3) | 0.037 (3) | 0.016 (2) | 0.007 (2) | 0.026 (2) |
C31 | 0.026 (2) | 0.0209 (19) | 0.0189 (18) | 0.0138 (16) | 0.0083 (15) | 0.0080 (15) |
C32 | 0.025 (2) | 0.0220 (19) | 0.0166 (17) | 0.0142 (16) | 0.0104 (14) | 0.0110 (15) |
C33 | 0.026 (2) | 0.0161 (18) | 0.0185 (18) | 0.0102 (15) | 0.0037 (15) | 0.0063 (15) |
C34 | 0.036 (2) | 0.031 (2) | 0.030 (2) | 0.0193 (19) | 0.0162 (18) | 0.0196 (19) |
C35 | 0.028 (2) | 0.030 (2) | 0.031 (2) | 0.0139 (18) | 0.0149 (17) | 0.0183 (19) |
C36 | 0.022 (2) | 0.0158 (18) | 0.0212 (19) | 0.0032 (15) | 0.0026 (15) | 0.0094 (16) |
C37 | 0.0155 (18) | 0.0196 (18) | 0.0205 (18) | 0.0055 (14) | 0.0063 (14) | 0.0139 (16) |
C38 | 0.0199 (19) | 0.0171 (17) | 0.0180 (17) | 0.0086 (14) | 0.0080 (14) | 0.0088 (15) |
C39 | 0.025 (2) | 0.032 (2) | 0.036 (2) | 0.0030 (18) | 0.0062 (18) | 0.020 (2) |
C40 | 0.037 (3) | 0.024 (2) | 0.020 (2) | 0.0036 (18) | 0.0021 (17) | 0.0098 (18) |
O17 | 0.040 (2) | 0.0383 (19) | 0.0361 (18) | 0.0147 (15) | 0.0203 (15) | 0.0197 (16) |
O18 | 0.040 (2) | 0.0367 (19) | 0.0373 (19) | 0.0171 (15) | 0.0110 (15) | 0.0177 (16) |
O19 | 0.0335 (18) | 0.051 (2) | 0.0362 (19) | 0.0196 (16) | 0.0129 (15) | 0.0269 (17) |
O20 | 0.0357 (19) | 0.0325 (18) | 0.0287 (17) | 0.0126 (15) | 0.0022 (13) | 0.0051 (14) |
O21 | 0.047 (2) | 0.057 (2) | 0.040 (2) | 0.0277 (18) | 0.0133 (17) | 0.0246 (19) |
O22 | 0.0326 (18) | 0.060 (2) | 0.0297 (17) | 0.0237 (17) | 0.0130 (14) | 0.0149 (17) |
O23 | 0.0358 (18) | 0.044 (2) | 0.0336 (17) | 0.0187 (15) | 0.0064 (14) | 0.0221 (16) |
O24 | 0.037 (2) | 0.048 (2) | 0.062 (3) | 0.0216 (18) | 0.0201 (18) | 0.032 (2) |
O25 | 0.047 (2) | 0.043 (2) | 0.0327 (18) | 0.0220 (17) | 0.0151 (15) | 0.0127 (17) |
O26 | 0.043 (2) | 0.050 (2) | 0.039 (2) | 0.0259 (18) | 0.0221 (16) | 0.0283 (18) |
O27 | 0.050 (2) | 0.051 (2) | 0.0245 (15) | 0.0407 (17) | 0.0119 (14) | 0.0145 (15) |
O28 | 0.0282 (18) | 0.056 (2) | 0.0349 (19) | 0.0183 (16) | 0.0068 (14) | 0.0201 (18) |
O29 | 0.0353 (19) | 0.059 (2) | 0.047 (2) | 0.0236 (18) | 0.0222 (17) | 0.0268 (19) |
O30 | 0.061 (3) | 0.067 (3) | 0.041 (2) | 0.033 (2) | 0.0171 (19) | 0.020 (2) |
O31 | 0.071 (3) | 0.071 (3) | 0.043 (2) | 0.046 (2) | 0.032 (2) | 0.036 (2) |
O32 | 0.113 (5) | 0.093 (4) | 0.161 (6) | 0.074 (4) | 0.103 (4) | 0.093 (4) |
O33 | 0.072 (3) | 0.087 (4) | 0.055 (3) | 0.046 (3) | 0.028 (2) | 0.038 (3) |
O34 | 0.068 (3) | 0.063 (3) | 0.055 (3) | −0.001 (2) | −0.010 (2) | 0.030 (3) |
O35A | 0.053 (5) | 0.046 (4) | 0.045 (4) | 0.025 (4) | 0.012 (3) | 0.022 (4) |
O35B | 0.055 (5) | 0.051 (5) | 0.031 (4) | 0.026 (4) | 0.017 (3) | 0.023 (3) |
O36A | 0.096 (7) | 0.037 (4) | 0.045 (5) | 0.017 (5) | 0.049 (5) | 0.017 (4) |
Pd1—O7 | 2.079 (3) | C12—C13 | 1.518 (5) |
Pd1—N1 | 2.089 (3) | C12—H12B | 1.0000 |
Pd1—S1 | 2.2315 (10) | C14—H14C | 0.9800 |
Pd1—S4 | 2.2867 (10) | C14—H14D | 0.9800 |
Pd2—O1 | 2.086 (3) | C14—H14E | 0.9800 |
Pd2—N2 | 2.087 (3) | C15—H15C | 0.9800 |
Pd2—S2 | 2.2261 (11) | C15—H15D | 0.9800 |
Pd2—S1 | 2.2871 (10) | C15—H15E | 0.9800 |
Pd3—N3 | 2.070 (4) | C16—C20 | 1.536 (6) |
Pd3—O3 | 2.085 (3) | C16—C19 | 1.540 (5) |
Pd3—S3 | 2.2302 (10) | C16—C17 | 1.547 (6) |
Pd3—S2 | 2.2843 (11) | C17—C18 | 1.527 (5) |
Pd4—N4 | 2.080 (3) | C17—H17B | 1.0000 |
Pd4—O5 | 2.088 (3) | C19—H19C | 0.9800 |
Pd4—S4 | 2.2338 (11) | C19—H19D | 0.9800 |
Pd4—S3 | 2.2876 (10) | C19—H19E | 0.9800 |
Pd5—O15 | 2.082 (3) | C20—H20C | 0.9800 |
Pd5—N5 | 2.097 (3) | C20—H20D | 0.9800 |
Pd5—S5 | 2.2285 (11) | C20—H20E | 0.9800 |
Pd5—S8 | 2.2869 (9) | C21—C24 | 1.522 (5) |
Pd6—N6 | 2.089 (3) | C21—C22 | 1.539 (6) |
Pd6—O9 | 2.095 (3) | C21—C25 | 1.541 (6) |
Pd6—S6 | 2.2306 (10) | C22—C23 | 1.527 (5) |
Pd6—S5 | 2.2819 (10) | C22—H22B | 1.0000 |
Pd7—N7 | 2.076 (3) | C24—H24C | 0.9800 |
Pd7—O11 | 2.080 (3) | C24—H24D | 0.9800 |
Pd7—S7 | 2.2427 (10) | C24—H24E | 0.9800 |
Pd7—S6 | 2.2894 (10) | C25—H25C | 0.9800 |
Pd8—N8 | 2.065 (3) | C25—H25D | 0.9800 |
Pd8—O13 | 2.068 (3) | C25—H25E | 0.9800 |
Pd8—S8 | 2.2382 (10) | C26—C30 | 1.532 (6) |
Pd8—S7 | 2.2968 (10) | C26—C27 | 1.536 (6) |
S1—C1 | 1.861 (4) | C26—C29 | 1.544 (6) |
S2—C6 | 1.863 (4) | C27—C28 | 1.529 (6) |
S3—C11 | 1.863 (4) | C27—H27B | 1.0000 |
S4—C16 | 1.856 (4) | C29—H29C | 0.9800 |
S5—C21 | 1.864 (4) | C29—H29D | 0.9800 |
S6—C26 | 1.860 (4) | C29—H29E | 0.9800 |
S7—C31 | 1.865 (4) | C30—H30C | 0.9800 |
S8—C36 | 1.864 (4) | C30—H30D | 0.9800 |
O1—C3 | 1.282 (5) | C30—H30E | 0.9800 |
O2—C3 | 1.226 (5) | C31—C34 | 1.528 (6) |
O3—C8 | 1.291 (5) | C31—C35 | 1.529 (6) |
O4—C8 | 1.214 (5) | C31—C32 | 1.548 (5) |
O5—C13 | 1.285 (5) | C32—C33 | 1.525 (6) |
O6—C13 | 1.221 (5) | C32—H32B | 1.0000 |
O7—C18 | 1.273 (5) | C34—H34C | 0.9800 |
O8—C18 | 1.228 (5) | C34—H34D | 0.9800 |
O9—C23 | 1.286 (5) | C34—H34E | 0.9800 |
O10—C23 | 1.233 (5) | C35—H35C | 0.9800 |
O11—C28 | 1.263 (5) | C35—H35D | 0.9800 |
O12—C28 | 1.225 (5) | C35—H35E | 0.9800 |
O13—C33 | 1.269 (5) | C36—C40 | 1.524 (6) |
O14—C33 | 1.238 (5) | C36—C39 | 1.527 (6) |
O15—C38 | 1.280 (5) | C36—C37 | 1.538 (5) |
O16—C38 | 1.238 (5) | C37—C38 | 1.533 (5) |
N1—C2 | 1.502 (5) | C37—H37B | 1.0000 |
N1—H1 | 0.9200 | C39—H39C | 0.9800 |
N1—H1A | 0.9200 | C39—H39D | 0.9800 |
N2—C7 | 1.494 (5) | C39—H39E | 0.9800 |
N2—H2 | 0.9200 | C40—H40C | 0.9800 |
N2—H2A | 0.9200 | C40—H40D | 0.9800 |
N3—C12 | 1.501 (6) | C40—H40E | 0.9800 |
N3—H3 | 0.9200 | O17—H17F | 0.847 (19) |
N3—H3A | 0.9200 | O17—H17G | 0.856 (19) |
N4—C17 | 1.491 (5) | O18—H18F | 0.841 (19) |
N4—H4 | 0.9200 | O18—H18G | 0.852 (19) |
N4—H4A | 0.9200 | O19—H19F | 0.851 (19) |
N5—C22 | 1.490 (5) | O19—H19G | 0.854 (19) |
N5—H5 | 0.9200 | O20—H20F | 0.845 (19) |
N5—H5A | 0.9200 | O20—H20G | 0.858 (19) |
N6—C27 | 1.501 (5) | O21—H21F | 0.863 (19) |
N6—H6 | 0.9200 | O21—H21G | 0.869 (19) |
N6—H6A | 0.9200 | O22—H22F | 0.854 (19) |
N7—C32 | 1.484 (5) | O22—H22G | 0.859 (19) |
N7—H7 | 0.9200 | O23—H23F | 0.851 (19) |
N7—H7A | 0.9200 | O23—H23G | 0.854 (19) |
N8—C37 | 1.491 (5) | O24—H24F | 0.849 (19) |
N8—H8 | 0.9200 | O24—H24G | 0.851 (19) |
N8—H8A | 0.9200 | O25—H25F | 0.865 (19) |
C1—C2 | 1.529 (6) | O25—H25G | 0.852 (19) |
C1—C4 | 1.539 (6) | O26—H26F | 0.860 (19) |
C1—C5 | 1.541 (6) | O26—H26G | 0.851 (19) |
C2—C3 | 1.535 (5) | O27—H27F | 0.847 (19) |
C2—H2B | 1.0000 | O27—H27G | 0.844 (19) |
C4—H4C | 0.9800 | O28—H28F | 0.822 (19) |
C4—H4D | 0.9800 | O28—H28G | 0.821 (19) |
C4—H4E | 0.9800 | O29—H29F | 0.868 (19) |
C5—H5C | 0.9800 | O29—H29G | 0.854 (19) |
C5—H5D | 0.9800 | O30—H30F | 0.861 (19) |
C5—H5E | 0.9800 | O30—H30G | 0.864 (19) |
C6—C10 | 1.521 (6) | O31—H31F | 0.839 (19) |
C6—C9 | 1.525 (7) | O31—H31G | 0.858 (19) |
C6—C7 | 1.540 (6) | O32—H32F | 0.917 (19) |
C7—C8 | 1.518 (6) | O32—H32G | 0.86 (2) |
C7—H7B | 1.0000 | O33—H33F | 0.875 (19) |
C9—H9C | 0.9800 | O33—H33G | 0.87 (2) |
C9—H9D | 0.9800 | O34—H34F | 0.85 (2) |
C9—H9E | 0.9800 | O34—H34G | 0.86 (2) |
C10—H10C | 0.9800 | O35A—H35F | 0.85 (2) |
C10—H10D | 0.9800 | O35A—H35G | 0.85 (2) |
C10—H10E | 0.9800 | O35B—H35H | 0.83 (2) |
C11—C14 | 1.524 (6) | O35B—H35I | 0.84 (2) |
C11—C12 | 1.537 (6) | O36A—H36F | 0.85 (2) |
C11—C15 | 1.539 (6) | O36A—H36G | 0.85 (2) |
O7—Pd1—N1 | 85.63 (12) | C14—C11—C15 | 108.8 (4) |
O7—Pd1—S1 | 171.94 (8) | C12—C11—C15 | 113.5 (4) |
N1—Pd1—S1 | 86.31 (9) | C14—C11—S3 | 106.2 (3) |
O7—Pd1—S4 | 98.20 (8) | C12—C11—S3 | 109.0 (3) |
N1—Pd1—S4 | 168.53 (10) | C15—C11—S3 | 107.6 (3) |
S1—Pd1—S4 | 89.76 (4) | N3—C12—C13 | 110.1 (3) |
O1—Pd2—N2 | 86.93 (12) | N3—C12—C11 | 110.2 (3) |
O1—Pd2—S2 | 171.92 (8) | C13—C12—C11 | 112.9 (4) |
N2—Pd2—S2 | 85.00 (10) | N3—C12—H12B | 107.8 |
O1—Pd2—S1 | 96.38 (8) | C13—C12—H12B | 107.8 |
N2—Pd2—S1 | 171.42 (11) | C11—C12—H12B | 107.8 |
S2—Pd2—S1 | 91.67 (4) | O6—C13—O5 | 122.2 (4) |
N3—Pd3—O3 | 85.09 (14) | O6—C13—C12 | 118.4 (4) |
N3—Pd3—S3 | 86.53 (10) | O5—C13—C12 | 119.4 (4) |
O3—Pd3—S3 | 170.89 (9) | C11—C14—H14C | 109.5 |
N3—Pd3—S2 | 167.45 (12) | C11—C14—H14D | 109.5 |
O3—Pd3—S2 | 98.63 (9) | H14C—C14—H14D | 109.5 |
S3—Pd3—S2 | 90.31 (4) | C11—C14—H14E | 109.5 |
N4—Pd4—O5 | 85.91 (12) | H14C—C14—H14E | 109.5 |
N4—Pd4—S4 | 85.40 (10) | H14D—C14—H14E | 109.5 |
O5—Pd4—S4 | 171.31 (8) | C11—C15—H15C | 109.5 |
N4—Pd4—S3 | 170.89 (9) | C11—C15—H15D | 109.5 |
O5—Pd4—S3 | 97.34 (8) | H15C—C15—H15D | 109.5 |
S4—Pd4—S3 | 91.28 (4) | C11—C15—H15E | 109.5 |
O15—Pd5—N5 | 86.31 (12) | H15C—C15—H15E | 109.5 |
O15—Pd5—S5 | 172.13 (8) | H15D—C15—H15E | 109.5 |
N5—Pd5—S5 | 85.87 (10) | C20—C16—C19 | 111.0 (3) |
O15—Pd5—S8 | 97.94 (8) | C20—C16—C17 | 112.9 (3) |
N5—Pd5—S8 | 169.40 (9) | C19—C16—C17 | 109.6 (4) |
S5—Pd5—S8 | 89.92 (4) | C20—C16—S4 | 107.7 (3) |
N6—Pd6—O9 | 86.45 (12) | C19—C16—S4 | 107.0 (3) |
N6—Pd6—S6 | 85.64 (10) | C17—C16—S4 | 108.5 (3) |
O9—Pd6—S6 | 172.08 (8) | N4—C17—C18 | 109.7 (3) |
N6—Pd6—S5 | 169.28 (11) | N4—C17—C16 | 111.1 (3) |
O9—Pd6—S5 | 96.66 (8) | C18—C17—C16 | 114.0 (4) |
S6—Pd6—S5 | 91.20 (4) | N4—C17—H17B | 107.2 |
N7—Pd7—O11 | 84.28 (12) | C18—C17—H17B | 107.2 |
N7—Pd7—S7 | 86.56 (9) | C16—C17—H17B | 107.2 |
O11—Pd7—S7 | 170.76 (9) | O8—C18—O7 | 123.4 (4) |
N7—Pd7—S6 | 170.75 (10) | O8—C18—C17 | 117.0 (4) |
O11—Pd7—S6 | 98.17 (9) | O7—C18—C17 | 119.6 (3) |
S7—Pd7—S6 | 91.07 (4) | C16—C19—H19C | 109.5 |
N8—Pd8—O13 | 84.85 (12) | C16—C19—H19D | 109.5 |
N8—Pd8—S8 | 85.18 (9) | H19C—C19—H19D | 109.5 |
O13—Pd8—S8 | 170.03 (9) | C16—C19—H19E | 109.5 |
N8—Pd8—S7 | 170.92 (9) | H19C—C19—H19E | 109.5 |
O13—Pd8—S7 | 96.17 (8) | H19D—C19—H19E | 109.5 |
S8—Pd8—S7 | 93.65 (4) | C16—C20—H20C | 109.5 |
C1—S1—Pd1 | 97.60 (14) | C16—C20—H20D | 109.5 |
C1—S1—Pd2 | 104.04 (13) | H20C—C20—H20D | 109.5 |
Pd1—S1—Pd2 | 97.42 (4) | C16—C20—H20E | 109.5 |
C6—S2—Pd2 | 97.34 (14) | H20C—C20—H20E | 109.5 |
C6—S2—Pd3 | 102.37 (15) | H20D—C20—H20E | 109.5 |
Pd2—S2—Pd3 | 100.53 (4) | C24—C21—C22 | 110.5 (3) |
C11—S3—Pd3 | 97.93 (14) | C24—C21—C25 | 110.5 (4) |
C11—S3—Pd4 | 103.18 (14) | C22—C21—C25 | 113.1 (3) |
Pd3—S3—Pd4 | 96.90 (4) | C24—C21—S5 | 106.9 (3) |
C16—S4—Pd4 | 98.06 (14) | C22—C21—S5 | 108.0 (3) |
C16—S4—Pd1 | 101.06 (12) | C25—C21—S5 | 107.6 (3) |
Pd4—S4—Pd1 | 102.42 (4) | N5—C22—C23 | 111.5 (3) |
C21—S5—Pd5 | 98.24 (13) | N5—C22—C21 | 110.6 (3) |
C21—S5—Pd6 | 102.92 (12) | C23—C22—C21 | 111.3 (3) |
Pd5—S5—Pd6 | 99.24 (4) | N5—C22—H22B | 107.8 |
C26—S6—Pd6 | 97.13 (14) | C23—C22—H22B | 107.8 |
C26—S6—Pd7 | 103.20 (14) | C21—C22—H22B | 107.8 |
Pd6—S6—Pd7 | 99.03 (4) | O10—C23—O9 | 122.8 (4) |
C31—S7—Pd7 | 97.98 (13) | O10—C23—C22 | 119.7 (4) |
C31—S7—Pd8 | 102.32 (14) | O9—C23—C22 | 117.5 (4) |
Pd7—S7—Pd8 | 99.57 (4) | C21—C24—H24C | 109.5 |
C36—S8—Pd8 | 97.79 (13) | C21—C24—H24D | 109.5 |
C36—S8—Pd5 | 102.08 (13) | H24C—C24—H24D | 109.5 |
Pd8—S8—Pd5 | 101.17 (4) | C21—C24—H24E | 109.5 |
C3—O1—Pd2 | 119.2 (3) | H24C—C24—H24E | 109.5 |
C8—O3—Pd3 | 119.8 (3) | H24D—C24—H24E | 109.5 |
C13—O5—Pd4 | 121.7 (3) | C21—C25—H25C | 109.5 |
C18—O7—Pd1 | 127.7 (2) | C21—C25—H25D | 109.5 |
C23—O9—Pd6 | 117.0 (2) | H25C—C25—H25D | 109.5 |
C28—O11—Pd7 | 124.1 (3) | C21—C25—H25E | 109.5 |
C33—O13—Pd8 | 127.9 (3) | H25C—C25—H25E | 109.5 |
C38—O15—Pd5 | 127.3 (2) | H25D—C25—H25E | 109.5 |
C2—N1—Pd1 | 116.6 (2) | C30—C26—C27 | 112.9 (4) |
C2—N1—H1 | 108.1 | C30—C26—C29 | 110.1 (4) |
Pd1—N1—H1 | 108.1 | C27—C26—C29 | 109.9 (4) |
C2—N1—H1A | 108.1 | C30—C26—S6 | 108.5 (3) |
Pd1—N1—H1A | 108.1 | C27—C26—S6 | 108.7 (3) |
H1—N1—H1A | 107.3 | C29—C26—S6 | 106.6 (3) |
C7—N2—Pd2 | 118.2 (2) | N6—C27—C28 | 108.8 (3) |
C7—N2—H2 | 107.8 | N6—C27—C26 | 110.5 (3) |
Pd2—N2—H2 | 107.8 | C28—C27—C26 | 114.7 (3) |
C7—N2—H2A | 107.8 | N6—C27—H27B | 107.5 |
Pd2—N2—H2A | 107.8 | C28—C27—H27B | 107.5 |
H2—N2—H2A | 107.1 | C26—C27—H27B | 107.5 |
C12—N3—Pd3 | 117.4 (3) | O12—C28—O11 | 123.1 (4) |
C12—N3—H3 | 108.0 | O12—C28—C27 | 118.1 (4) |
Pd3—N3—H3 | 108.0 | O11—C28—C27 | 118.7 (4) |
C12—N3—H3A | 108.0 | C26—C29—H29C | 109.5 |
Pd3—N3—H3A | 108.0 | C26—C29—H29D | 109.5 |
H3—N3—H3A | 107.2 | H29C—C29—H29D | 109.5 |
C17—N4—Pd4 | 118.0 (3) | C26—C29—H29E | 109.5 |
C17—N4—H4 | 107.8 | H29C—C29—H29E | 109.5 |
Pd4—N4—H4 | 107.8 | H29D—C29—H29E | 109.5 |
C17—N4—H4A | 107.8 | C26—C30—H30C | 109.5 |
Pd4—N4—H4A | 107.8 | C26—C30—H30D | 109.5 |
H4—N4—H4A | 107.1 | H30C—C30—H30D | 109.5 |
C22—N5—Pd5 | 116.9 (2) | C26—C30—H30E | 109.5 |
C22—N5—H5 | 108.1 | H30C—C30—H30E | 109.5 |
Pd5—N5—H5 | 108.1 | H30D—C30—H30E | 109.5 |
C22—N5—H5A | 108.1 | C34—C31—C35 | 110.1 (3) |
Pd5—N5—H5A | 108.1 | C34—C31—C32 | 109.8 (3) |
H5—N5—H5A | 107.3 | C35—C31—C32 | 112.2 (3) |
C27—N6—Pd6 | 117.2 (2) | C34—C31—S7 | 107.3 (3) |
C27—N6—H6 | 108.0 | C35—C31—S7 | 108.7 (3) |
Pd6—N6—H6 | 108.0 | C32—C31—S7 | 108.6 (3) |
C27—N6—H6A | 108.0 | N7—C32—C33 | 110.7 (3) |
Pd6—N6—H6A | 108.0 | N7—C32—C31 | 111.4 (3) |
H6—N6—H6A | 107.2 | C33—C32—C31 | 112.4 (3) |
C32—N7—Pd7 | 117.2 (2) | N7—C32—H32B | 107.4 |
C32—N7—H7 | 108.0 | C33—C32—H32B | 107.4 |
Pd7—N7—H7 | 108.0 | C31—C32—H32B | 107.4 |
C32—N7—H7A | 108.0 | O14—C33—O13 | 122.0 (4) |
Pd7—N7—H7A | 108.0 | O14—C33—C32 | 118.1 (4) |
H7—N7—H7A | 107.2 | O13—C33—C32 | 119.8 (4) |
C37—N8—Pd8 | 118.7 (2) | C31—C34—H34C | 109.5 |
C37—N8—H8 | 107.6 | C31—C34—H34D | 109.5 |
Pd8—N8—H8 | 107.6 | H34C—C34—H34D | 109.5 |
C37—N8—H8A | 107.6 | C31—C34—H34E | 109.5 |
Pd8—N8—H8A | 107.6 | H34C—C34—H34E | 109.5 |
H8—N8—H8A | 107.1 | H34D—C34—H34E | 109.5 |
C2—C1—C4 | 110.4 (3) | C31—C35—H35C | 109.5 |
C2—C1—C5 | 113.6 (4) | C31—C35—H35D | 109.5 |
C4—C1—C5 | 109.2 (4) | H35C—C35—H35D | 109.5 |
C2—C1—S1 | 108.8 (3) | C31—C35—H35E | 109.5 |
C4—C1—S1 | 106.4 (3) | H35C—C35—H35E | 109.5 |
C5—C1—S1 | 108.2 (3) | H35D—C35—H35E | 109.5 |
N1—C2—C1 | 110.1 (3) | C40—C36—C39 | 109.5 (3) |
N1—C2—C3 | 110.5 (3) | C40—C36—C37 | 113.2 (3) |
C1—C2—C3 | 112.4 (3) | C39—C36—C37 | 109.8 (4) |
N1—C2—H2B | 107.9 | C40—C36—S8 | 109.0 (3) |
C1—C2—H2B | 107.9 | C39—C36—S8 | 106.9 (3) |
C3—C2—H2B | 107.9 | C37—C36—S8 | 108.3 (3) |
O2—C3—O1 | 123.1 (4) | N8—C37—C38 | 110.4 (3) |
O2—C3—C2 | 119.4 (4) | N8—C37—C36 | 110.9 (3) |
O1—C3—C2 | 117.6 (4) | C38—C37—C36 | 113.3 (3) |
C1—C4—H4C | 109.5 | N8—C37—H37B | 107.3 |
C1—C4—H4D | 109.5 | C38—C37—H37B | 107.3 |
H4C—C4—H4D | 109.5 | C36—C37—H37B | 107.3 |
C1—C4—H4E | 109.5 | O16—C38—O15 | 122.7 (3) |
H4C—C4—H4E | 109.5 | O16—C38—C37 | 118.2 (3) |
H4D—C4—H4E | 109.5 | O15—C38—C37 | 119.1 (3) |
C1—C5—H5C | 109.5 | C36—C39—H39C | 109.5 |
C1—C5—H5D | 109.5 | C36—C39—H39D | 109.5 |
H5C—C5—H5D | 109.5 | H39C—C39—H39D | 109.5 |
C1—C5—H5E | 109.5 | C36—C39—H39E | 109.5 |
H5C—C5—H5E | 109.5 | H39C—C39—H39E | 109.5 |
H5D—C5—H5E | 109.5 | H39D—C39—H39E | 109.5 |
C10—C6—C9 | 110.3 (4) | C36—C40—H40C | 109.5 |
C10—C6—C7 | 112.6 (4) | C36—C40—H40D | 109.5 |
C9—C6—C7 | 110.4 (4) | H40C—C40—H40D | 109.5 |
C10—C6—S2 | 108.4 (3) | C36—C40—H40E | 109.5 |
C9—C6—S2 | 106.8 (3) | H40C—C40—H40E | 109.5 |
C7—C6—S2 | 108.2 (3) | H40D—C40—H40E | 109.5 |
N2—C7—C8 | 111.4 (3) | H17F—O17—H17G | 108 (3) |
N2—C7—C6 | 109.7 (3) | H18F—O18—H18G | 109 (3) |
C8—C7—C6 | 113.4 (3) | H19F—O19—H19G | 110 (3) |
N2—C7—H7B | 107.3 | H20F—O20—H20G | 108 (3) |
C8—C7—H7B | 107.3 | H21F—O21—H21G | 105 (3) |
C6—C7—H7B | 107.3 | H22F—O22—H22G | 107 (3) |
O4—C8—O3 | 122.7 (4) | H23F—O23—H23G | 107 (3) |
O4—C8—C7 | 120.2 (4) | H24F—O24—H24G | 108 (3) |
O3—C8—C7 | 117.0 (4) | H25F—O25—H25G | 105 (3) |
C6—C9—H9C | 109.5 | H26F—O26—H26G | 107 (3) |
C6—C9—H9D | 109.5 | H27F—O27—H27G | 109 (3) |
H9C—C9—H9D | 109.5 | H28F—O28—H28G | 116 (3) |
C6—C9—H9E | 109.5 | H29F—O29—H29G | 106 (3) |
H9C—C9—H9E | 109.5 | H30F—O30—H30G | 108 (3) |
H9D—C9—H9E | 109.5 | H31F—O31—H31G | 110 (3) |
C6—C10—H10C | 109.5 | H32F—O32—H32G | 101 (3) |
C6—C10—H10D | 109.5 | H33F—O33—H33G | 103 (3) |
H10C—C10—H10D | 109.5 | H34F—O34—H34G | 108 (3) |
C6—C10—H10E | 109.5 | H35F—O35A—H35G | 109 (3) |
H10C—C10—H10E | 109.5 | H35H—O35B—H35I | 113 (4) |
H10D—C10—H10E | 109.5 | H36F—O36A—H36G | 109 (3) |
C14—C11—C12 | 111.5 (4) | ||
N1—Pd1—S1—C1 | −23.21 (16) | Pd2—N2—C7—C8 | −105.8 (3) |
S4—Pd1—S1—C1 | 146.02 (13) | Pd2—N2—C7—C6 | 20.7 (4) |
N1—Pd1—S1—Pd2 | 82.11 (9) | C10—C6—C7—N2 | −165.2 (4) |
S4—Pd1—S1—Pd2 | −108.66 (4) | C9—C6—C7—N2 | 71.1 (4) |
O1—Pd2—S1—C1 | 33.51 (16) | S2—C6—C7—N2 | −45.5 (4) |
S2—Pd2—S1—C1 | −145.78 (14) | C10—C6—C7—C8 | −39.9 (5) |
O1—Pd2—S1—Pd1 | −66.29 (9) | C9—C6—C7—C8 | −163.7 (4) |
S2—Pd2—S1—Pd1 | 114.43 (4) | S2—C6—C7—C8 | 79.8 (4) |
N2—Pd2—S2—C6 | −27.85 (19) | Pd3—O3—C8—O4 | −126.5 (4) |
S1—Pd2—S2—C6 | 144.23 (15) | Pd3—O3—C8—C7 | 55.4 (5) |
N2—Pd2—S2—Pd3 | 76.25 (11) | N2—C7—C8—O4 | −134.5 (4) |
S1—Pd2—S2—Pd3 | −111.67 (4) | C6—C7—C8—O4 | 101.2 (5) |
N3—Pd3—S2—C6 | −74.5 (5) | N2—C7—C8—O3 | 43.7 (5) |
O3—Pd3—S2—C6 | 31.90 (17) | C6—C7—C8—O3 | −80.7 (5) |
S3—Pd3—S2—C6 | −149.81 (14) | Pd3—S3—C11—C14 | −77.6 (3) |
N3—Pd3—S2—Pd2 | −174.5 (4) | Pd4—S3—C11—C14 | −176.7 (3) |
O3—Pd3—S2—Pd2 | −68.11 (10) | Pd3—S3—C11—C12 | 42.6 (3) |
S3—Pd3—S2—Pd2 | 110.18 (4) | Pd4—S3—C11—C12 | −56.4 (3) |
N3—Pd3—S3—C11 | −22.52 (17) | Pd3—S3—C11—C15 | 166.0 (3) |
S2—Pd3—S3—C11 | 145.32 (14) | Pd4—S3—C11—C15 | 67.0 (3) |
N3—Pd3—S3—Pd4 | 81.89 (11) | Pd3—N3—C12—C13 | −99.3 (4) |
S2—Pd3—S3—Pd4 | −110.27 (4) | Pd3—N3—C12—C11 | 25.9 (4) |
O5—Pd4—S3—C11 | 31.59 (17) | C14—C11—C12—N3 | 71.2 (4) |
S4—Pd4—S3—C11 | −147.27 (15) | C15—C11—C12—N3 | −165.5 (3) |
O5—Pd4—S3—Pd3 | −68.27 (9) | S3—C11—C12—N3 | −45.7 (4) |
S4—Pd4—S3—Pd3 | 112.87 (4) | C14—C11—C12—C13 | −165.2 (4) |
N4—Pd4—S4—C16 | −26.63 (15) | C15—C11—C12—C13 | −41.9 (5) |
S3—Pd4—S4—C16 | 144.88 (12) | S3—C11—C12—C13 | 77.9 (4) |
N4—Pd4—S4—Pd1 | 76.65 (10) | Pd4—O5—C13—O6 | −127.5 (4) |
S3—Pd4—S4—Pd1 | −111.85 (4) | Pd4—O5—C13—C12 | 52.3 (5) |
O7—Pd1—S4—C16 | 29.29 (16) | N3—C12—C13—O6 | −133.1 (4) |
N1—Pd1—S4—C16 | −79.6 (5) | C11—C12—C13—O6 | 103.3 (5) |
S1—Pd1—S4—C16 | −149.39 (14) | N3—C12—C13—O5 | 47.2 (5) |
O7—Pd1—S4—Pd4 | −71.63 (9) | C11—C12—C13—O5 | −76.4 (5) |
N1—Pd1—S4—Pd4 | 179.5 (5) | Pd4—S4—C16—C20 | 166.7 (2) |
S1—Pd1—S4—Pd4 | 109.69 (4) | Pd1—S4—C16—C20 | 62.3 (3) |
N5—Pd5—S5—C21 | −23.67 (15) | Pd4—S4—C16—C19 | −74.0 (3) |
S8—Pd5—S5—C21 | 146.60 (12) | Pd1—S4—C16—C19 | −178.4 (3) |
N5—Pd5—S5—Pd6 | 80.95 (9) | Pd4—S4—C16—C17 | 44.2 (3) |
S8—Pd5—S5—Pd6 | −108.78 (4) | Pd1—S4—C16—C17 | −60.3 (3) |
N6—Pd6—S5—C21 | −70.4 (5) | Pd4—N4—C17—C18 | −108.1 (3) |
O9—Pd6—S5—C21 | 35.97 (16) | Pd4—N4—C17—C16 | 18.9 (4) |
S6—Pd6—S5—C21 | −143.07 (14) | C20—C16—C17—N4 | −161.8 (3) |
N6—Pd6—S5—Pd5 | −171.1 (5) | C19—C16—C17—N4 | 73.9 (4) |
O9—Pd6—S5—Pd5 | −64.77 (9) | S4—C16—C17—N4 | −42.5 (4) |
S6—Pd6—S5—Pd5 | 116.19 (4) | C20—C16—C17—C18 | −37.2 (5) |
N6—Pd6—S6—C26 | −27.51 (18) | C19—C16—C17—C18 | −161.4 (3) |
S5—Pd6—S6—C26 | 142.24 (14) | S4—C16—C17—C18 | 82.1 (3) |
N6—Pd6—S6—Pd7 | 77.14 (11) | Pd1—O7—C18—O8 | −149.9 (3) |
S5—Pd6—S6—Pd7 | −113.11 (4) | Pd1—O7—C18—C17 | 33.2 (5) |
O11—Pd7—S6—C26 | 28.82 (17) | N4—C17—C18—O8 | −116.7 (4) |
S7—Pd7—S6—C26 | −151.02 (15) | C16—C17—C18—O8 | 117.9 (4) |
O11—Pd7—S6—Pd6 | −70.75 (10) | N4—C17—C18—O7 | 60.4 (5) |
S7—Pd7—S6—Pd6 | 109.40 (4) | C16—C17—C18—O7 | −65.0 (5) |
N7—Pd7—S7—C31 | −22.31 (16) | Pd5—S5—C21—C24 | −74.9 (3) |
S6—Pd7—S7—C31 | 148.75 (14) | Pd6—S5—C21—C24 | −176.4 (3) |
N7—Pd7—S7—Pd8 | 81.70 (10) | Pd5—S5—C21—C22 | 44.1 (3) |
S6—Pd7—S7—Pd8 | −107.25 (4) | Pd6—S5—C21—C22 | −57.4 (3) |
O13—Pd8—S7—C31 | 30.71 (16) | Pd5—S5—C21—C25 | 166.4 (3) |
S8—Pd8—S7—C31 | −147.56 (13) | Pd6—S5—C21—C25 | 64.9 (3) |
O13—Pd8—S7—Pd7 | −69.71 (9) | Pd5—N5—C22—C23 | −98.2 (3) |
S8—Pd8—S7—Pd7 | 112.02 (4) | Pd5—N5—C22—C21 | 26.2 (4) |
N8—Pd8—S8—C36 | −26.71 (15) | C24—C21—C22—N5 | 69.7 (4) |
S7—Pd8—S8—C36 | 144.26 (12) | C25—C21—C22—N5 | −165.8 (3) |
N8—Pd8—S8—Pd5 | 77.31 (10) | S5—C21—C22—N5 | −46.9 (4) |
S7—Pd8—S8—Pd5 | −111.73 (4) | C24—C21—C22—C23 | −165.7 (3) |
O15—Pd5—S8—C36 | 27.72 (15) | C25—C21—C22—C23 | −41.3 (4) |
N5—Pd5—S8—C36 | −85.4 (6) | S5—C21—C22—C23 | 77.6 (4) |
S5—Pd5—S8—C36 | −151.84 (13) | Pd6—O9—C23—O10 | −117.2 (4) |
O15—Pd5—S8—Pd8 | −72.85 (9) | Pd6—O9—C23—C22 | 63.4 (4) |
N5—Pd5—S8—Pd8 | 174.1 (5) | N5—C22—C23—O10 | −138.9 (4) |
S5—Pd5—S8—Pd8 | 107.59 (4) | C21—C22—C23—O10 | 97.1 (5) |
N2—Pd2—O1—C3 | 132.9 (3) | N5—C22—C23—O9 | 40.6 (5) |
S1—Pd2—O1—C3 | −39.1 (3) | C21—C22—C23—O9 | −83.4 (4) |
N3—Pd3—O3—C8 | 133.2 (4) | Pd6—S6—C26—C30 | 169.5 (3) |
S2—Pd3—O3—C8 | −34.8 (3) | Pd7—S6—C26—C30 | 68.4 (3) |
N4—Pd4—O5—C13 | 139.1 (3) | Pd6—S6—C26—C27 | 46.4 (3) |
S3—Pd4—O5—C13 | −32.4 (3) | Pd7—S6—C26—C27 | −54.6 (3) |
N1—Pd1—O7—C18 | 149.4 (3) | Pd6—S6—C26—C29 | −72.0 (3) |
S4—Pd1—O7—C18 | −19.7 (3) | Pd7—S6—C26—C29 | −173.0 (3) |
N6—Pd6—O9—C23 | 128.3 (3) | Pd6—N6—C27—C28 | −106.6 (3) |
S5—Pd6—O9—C23 | −41.4 (3) | Pd6—N6—C27—C26 | 20.1 (4) |
N7—Pd7—O11—C28 | 143.1 (3) | C30—C26—C27—N6 | −165.3 (4) |
S6—Pd7—O11—C28 | −27.9 (3) | C29—C26—C27—N6 | 71.4 (4) |
N8—Pd8—O13—C33 | 145.6 (4) | S6—C26—C27—N6 | −44.9 (4) |
S7—Pd8—O13—C33 | −25.3 (3) | C30—C26—C27—C28 | −42.0 (5) |
N5—Pd5—O15—C38 | 150.5 (3) | C29—C26—C27—C28 | −165.3 (4) |
S8—Pd5—O15—C38 | −19.8 (3) | S6—C26—C27—C28 | 78.4 (4) |
O7—Pd1—N1—C2 | −178.3 (3) | Pd7—O11—C28—O12 | −135.9 (4) |
S1—Pd1—N1—C2 | 1.9 (2) | Pd7—O11—C28—C27 | 46.5 (5) |
S4—Pd1—N1—C2 | −68.3 (6) | N6—C27—C28—O12 | −127.5 (5) |
O1—Pd2—N2—C7 | −171.9 (3) | C26—C27—C28—O12 | 108.3 (5) |
S2—Pd2—N2—C7 | 8.5 (3) | N6—C27—C28—O11 | 50.2 (5) |
O3—Pd3—N3—C12 | 178.3 (3) | C26—C27—C28—O11 | −74.0 (5) |
S3—Pd3—N3—C12 | 1.8 (3) | Pd7—S7—C31—C34 | −77.1 (3) |
S2—Pd3—N3—C12 | −73.8 (6) | Pd8—S7—C31—C34 | −178.8 (2) |
O5—Pd4—N4—C17 | −171.7 (3) | Pd7—S7—C31—C35 | 163.9 (3) |
S4—Pd4—N4—C17 | 8.5 (2) | Pd8—S7—C31—C35 | 62.2 (3) |
O15—Pd5—N5—C22 | −178.4 (3) | Pd7—S7—C31—C32 | 41.5 (3) |
S5—Pd5—N5—C22 | 2.5 (2) | Pd8—S7—C31—C32 | −60.2 (3) |
S8—Pd5—N5—C22 | −64.3 (6) | Pd7—N7—C32—C33 | −100.4 (3) |
O9—Pd6—N6—C27 | −171.9 (3) | Pd7—N7—C32—C31 | 25.4 (4) |
S6—Pd6—N6—C27 | 8.6 (3) | C34—C31—C32—N7 | 72.0 (4) |
S5—Pd6—N6—C27 | −64.6 (6) | C35—C31—C32—N7 | −165.2 (3) |
O11—Pd7—N7—C32 | −179.3 (3) | S7—C31—C32—N7 | −45.0 (4) |
S7—Pd7—N7—C32 | 2.0 (3) | C34—C31—C32—C33 | −163.1 (3) |
O13—Pd8—N8—C37 | −171.1 (3) | C35—C31—C32—C33 | −40.3 (4) |
S8—Pd8—N8—C37 | 8.7 (2) | S7—C31—C32—C33 | 79.9 (3) |
Pd1—S1—C1—C2 | 44.4 (3) | Pd8—O13—C33—O14 | −142.1 (4) |
Pd2—S1—C1—C2 | −55.3 (3) | Pd8—O13—C33—C32 | 40.9 (5) |
Pd1—S1—C1—C4 | −74.6 (3) | N7—C32—C33—O14 | −119.8 (4) |
Pd2—S1—C1—C4 | −174.3 (3) | C31—C32—C33—O14 | 115.0 (4) |
Pd1—S1—C1—C5 | 168.2 (3) | N7—C32—C33—O13 | 57.4 (5) |
Pd2—S1—C1—C5 | 68.5 (3) | C31—C32—C33—O13 | −67.9 (5) |
Pd1—N1—C2—C1 | 26.9 (4) | Pd8—S8—C36—C40 | 167.9 (2) |
Pd1—N1—C2—C3 | −97.9 (3) | Pd5—S8—C36—C40 | 64.6 (3) |
C4—C1—C2—N1 | 68.7 (4) | Pd8—S8—C36—C39 | −73.9 (3) |
C5—C1—C2—N1 | −168.2 (3) | Pd5—S8—C36—C39 | −177.1 (3) |
S1—C1—C2—N1 | −47.7 (4) | Pd8—S8—C36—C37 | 44.3 (3) |
C4—C1—C2—C3 | −167.6 (4) | Pd5—S8—C36—C37 | −58.9 (3) |
C5—C1—C2—C3 | −44.5 (5) | Pd8—N8—C37—C38 | −107.5 (3) |
S1—C1—C2—C3 | 76.0 (4) | Pd8—N8—C37—C36 | 18.9 (4) |
Pd2—O1—C3—O2 | −118.8 (4) | C40—C36—C37—N8 | −163.6 (3) |
Pd2—O1—C3—C2 | 60.9 (4) | C39—C36—C37—N8 | 73.8 (4) |
N1—C2—C3—O2 | −137.9 (4) | S8—C36—C37—N8 | −42.6 (4) |
C1—C2—C3—O2 | 98.6 (5) | C40—C36—C37—C38 | −38.7 (5) |
N1—C2—C3—O1 | 42.4 (5) | C39—C36—C37—C38 | −161.4 (3) |
C1—C2—C3—O1 | −81.1 (5) | S8—C36—C37—C38 | 82.3 (3) |
Pd2—S2—C6—C10 | 169.6 (3) | Pd5—O15—C38—O16 | −146.6 (3) |
Pd3—S2—C6—C10 | 67.1 (3) | Pd5—O15—C38—C37 | 35.6 (5) |
Pd2—S2—C6—C9 | −71.5 (3) | N8—C37—C38—O16 | −120.8 (4) |
Pd3—S2—C6—C9 | −174.1 (3) | C36—C37—C38—O16 | 114.1 (4) |
Pd2—S2—C6—C7 | 47.3 (3) | N8—C37—C38—O15 | 57.1 (5) |
Pd3—S2—C6—C7 | −55.3 (3) | C36—C37—C38—O15 | −68.0 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O26i | 0.92 | 2.06 | 2.963 (5) | 169 |
N1—H1A···O15ii | 0.92 | 2.21 | 3.109 (4) | 166 |
N2—H2···O27 | 0.92 | 2.35 | 3.139 (5) | 143 |
N2—H2A···O13ii | 0.92 | 2.11 | 2.928 (5) | 148 |
N3—H3···O35B | 0.92 | 2.01 | 2.889 (8) | 160 |
N3—H3···O36A | 0.92 | 2.23 | 3.045 (8) | 147 |
N3—H3A···O11ii | 0.92 | 2.37 | 3.278 (5) | 167 |
N4—H4···O29iii | 0.92 | 1.98 | 2.886 (5) | 170 |
N4—H4A···O9ii | 0.92 | 2.04 | 2.917 (4) | 160 |
N5—H5···O18i | 0.92 | 2.09 | 3.008 (5) | 172 |
N5—H5A···O7iv | 0.92 | 2.19 | 3.094 (4) | 167 |
N6—H6···O27v | 0.92 | 2.44 | 3.183 (5) | 138 |
N6—H6···O28 | 0.92 | 2.48 | 3.326 (5) | 153 |
N6—H6A···O5iv | 0.92 | 2.21 | 3.041 (5) | 151 |
N7—H7···O23 | 0.92 | 2.03 | 2.938 (5) | 170 |
N7—H7A···O3iv | 0.92 | 2.16 | 3.066 (5) | 169 |
N8—H8···O28vi | 0.92 | 1.98 | 2.896 (5) | 171 |
N8—H8A···O1iv | 0.92 | 2.06 | 2.930 (4) | 157 |
O17—H17F···O26iv | 0.85 (2) | 1.96 (2) | 2.798 (5) | 167 (6) |
O17—H17G···O16vii | 0.86 (2) | 1.93 (2) | 2.775 (4) | 170 (5) |
O18—H18F···O17 | 0.84 (2) | 2.00 (3) | 2.818 (5) | 165 (6) |
O18—H18G···O20 | 0.85 (2) | 1.98 (2) | 2.814 (5) | 165 (5) |
O19—H19F···O8vii | 0.85 (2) | 2.05 (2) | 2.892 (5) | 168 (5) |
O19—H19G···O2viii | 0.85 (2) | 1.94 (3) | 2.760 (5) | 160 (6) |
O20—H20F···O21 | 0.85 (2) | 1.88 (2) | 2.709 (5) | 167 (6) |
O20—H20G···O8ix | 0.86 (2) | 1.94 (3) | 2.742 (4) | 156 (5) |
O21—H21F···O22 | 0.86 (2) | 1.97 (3) | 2.805 (6) | 162 (5) |
O21—H21G···O30 | 0.87 (2) | 2.00 (2) | 2.857 (6) | 169 (6) |
O22—H22F···O10vii | 0.85 (2) | 1.95 (2) | 2.802 (5) | 174 (6) |
O22—H22G···O16viii | 0.86 (2) | 2.21 (4) | 2.915 (5) | 139 (6) |
O23—H23F···O20 | 0.85 (2) | 1.96 (2) | 2.796 (5) | 168 (5) |
O23—H23G···O25iv | 0.85 (2) | 1.96 (2) | 2.782 (5) | 162 (5) |
O24—H24F···O19vi | 0.85 (2) | 1.97 (2) | 2.814 (5) | 177 (6) |
O24—H24G···O32 | 0.85 (2) | 1.90 (2) | 2.736 (6) | 168 (6) |
O25—H25F···O24iii | 0.87 (2) | 1.91 (2) | 2.770 (6) | 170 (6) |
O25—H25G···O12ii | 0.85 (2) | 1.97 (3) | 2.788 (5) | 159 (5) |
O26—H26F···O23ii | 0.86 (2) | 1.95 (2) | 2.791 (5) | 167 (6) |
O26—H26G···O31 | 0.85 (2) | 1.95 (2) | 2.788 (6) | 169 (6) |
O27—H27F···O6vi | 0.85 (2) | 1.88 (3) | 2.687 (5) | 158 (5) |
O27—H27G···O14ii | 0.84 (2) | 1.81 (2) | 2.650 (5) | 175 (5) |
O28—H28F···O10 | 0.82 (2) | 2.02 (2) | 2.810 (5) | 161 (5) |
O28—H28G···O27v | 0.82 (2) | 2.00 (3) | 2.797 (5) | 164 (5) |
O29—H29F···O2 | 0.87 (2) | 1.98 (2) | 2.834 (5) | 168 (6) |
O29—H29G···O27 | 0.85 (2) | 1.98 (2) | 2.802 (5) | 160 (5) |
O30—H30F···O12 | 0.86 (2) | 2.28 (5) | 2.911 (7) | 130 (6) |
O30—H30G···O19iv | 0.86 (2) | 1.95 (3) | 2.791 (5) | 165 (6) |
O31—H31F···O33ii | 0.84 (2) | 2.17 (3) | 2.946 (8) | 154 (7) |
O31—H31G···O4 | 0.86 (2) | 2.08 (2) | 2.902 (6) | 161 (5) |
O32—H32F···O34 | 0.92 (2) | 2.07 (2) | 2.823 (7) | 139 (3) |
O32—H32G···O31 | 0.86 (2) | 1.98 (2) | 2.837 (7) | 178 (9) |
O33—H33F···O17 | 0.88 (2) | 2.11 (4) | 2.877 (6) | 146 (7) |
O33—H33G···O30vi | 0.87 (2) | 1.90 (2) | 2.766 (6) | 170 (7) |
O34—H34F···O18 | 0.85 (2) | 2.12 (4) | 2.906 (6) | 154 (8) |
O34—H34G···O6vi | 0.86 (2) | 2.02 (3) | 2.815 (6) | 154 (6) |
O35A—H35F···O25 | 0.85 (2) | 2.14 (3) | 2.986 (9) | 174 (13) |
O35A—H35G···O4 | 0.85 (2) | 2.05 (5) | 2.848 (9) | 157 (12) |
O35B—H35H···O4 | 0.83 (2) | 2.45 (8) | 3.135 (9) | 141 (10) |
O35B—H35I···O25 | 0.84 (2) | 2.03 (5) | 2.802 (10) | 152 (9) |
O36A—H36F···O22 | 0.85 (2) | 2.14 (5) | 2.949 (9) | 159 (12) |
O36A—H36G···O35A | 0.85 (2) | 1.93 (5) | 2.746 (12) | 158 (12) |
Symmetry codes: (i) x, y, z−1; (ii) x, y−1, z; (iii) x+1, y, z; (iv) x, y+1, z; (v) x+1, y+1, z; (vi) x−1, y, z; (vii) x, y, z+1; (viii) x+1, y, z+1; (ix) x, y+1, z+1. |
Experimental details
Crystal data | |
Chemical formula | [Pd4(C5H9NO2S)4]·9.75H2O |
Mr | 1190.03 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 200 |
a, b, c (Å) | 12.4517 (3), 13.2680 (4), 15.1666 (11) |
α, β, γ (°) | 113.527 (8), 98.425 (7), 108.557 (8) |
V (Å3) | 2067.3 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.98 |
Crystal size (mm) | 0.25 × 0.10 × 0.03 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID |
Absorption correction | Multi-scan (ABSCOR; Rigaku, 1995) |
Tmin, Tmax | 0.730, 0.916 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20447, 15410, 15064 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.062, 1.08 |
No. of reflections | 15410 |
No. of parameters | 1052 |
No. of restraints | 67 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.52, −0.68 |
Absolute structure | Flack (1983), 6026 Friedel pairs |
Absolute structure parameter | −0.024 (13) |
Computer programs: PROCESS-AUTO (Rigaku, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Yadokari-XG 2009 (Kabuto et al., 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O26i | 0.92 | 2.06 | 2.963 (5) | 169 |
N1—H1A···O15ii | 0.92 | 2.21 | 3.109 (4) | 166 |
N2—H2···O27 | 0.92 | 2.35 | 3.139 (5) | 143 |
N2—H2A···O13ii | 0.92 | 2.11 | 2.928 (5) | 148 |
N3—H3···O35B | 0.92 | 2.01 | 2.889 (8) | 160 |
N3—H3···O36A | 0.92 | 2.23 | 3.045 (8) | 147 |
N3—H3A···O11ii | 0.92 | 2.37 | 3.278 (5) | 167 |
N4—H4···O29iii | 0.92 | 1.98 | 2.886 (5) | 170 |
N4—H4A···O9ii | 0.92 | 2.04 | 2.917 (4) | 160 |
N5—H5···O18i | 0.92 | 2.09 | 3.008 (5) | 172 |
N5—H5A···O7iv | 0.92 | 2.19 | 3.094 (4) | 167 |
N6—H6···O27v | 0.92 | 2.44 | 3.183 (5) | 138 |
N6—H6···O28 | 0.92 | 2.48 | 3.326 (5) | 153 |
N6—H6A···O5iv | 0.92 | 2.21 | 3.041 (5) | 151 |
N7—H7···O23 | 0.92 | 2.03 | 2.938 (5) | 170 |
N7—H7A···O3iv | 0.92 | 2.16 | 3.066 (5) | 169 |
N8—H8···O28vi | 0.92 | 1.98 | 2.896 (5) | 171 |
N8—H8A···O1iv | 0.92 | 2.06 | 2.930 (4) | 157 |
O17—H17F···O26iv | 0.847 (19) | 1.96 (2) | 2.798 (5) | 167 (6) |
O17—H17G···O16vii | 0.856 (19) | 1.93 (2) | 2.775 (4) | 170 (5) |
O18—H18F···O17 | 0.841 (19) | 2.00 (3) | 2.818 (5) | 165 (6) |
O18—H18G···O20 | 0.852 (19) | 1.98 (2) | 2.814 (5) | 165 (5) |
O19—H19F···O8vii | 0.851 (19) | 2.05 (2) | 2.892 (5) | 168 (5) |
O19—H19G···O2viii | 0.854 (19) | 1.94 (3) | 2.760 (5) | 160 (6) |
O20—H20F···O21 | 0.845 (19) | 1.88 (2) | 2.709 (5) | 167 (6) |
O20—H20G···O8ix | 0.858 (19) | 1.94 (3) | 2.742 (4) | 156 (5) |
O21—H21F···O22 | 0.863 (19) | 1.97 (3) | 2.805 (6) | 162 (5) |
O21—H21G···O30 | 0.869 (19) | 2.00 (2) | 2.857 (6) | 169 (6) |
O22—H22F···O10vii | 0.854 (19) | 1.95 (2) | 2.802 (5) | 174 (6) |
O22—H22G···O16viii | 0.859 (19) | 2.21 (4) | 2.915 (5) | 139 (6) |
O23—H23F···O20 | 0.851 (19) | 1.96 (2) | 2.796 (5) | 168 (5) |
O23—H23G···O25iv | 0.854 (19) | 1.96 (2) | 2.782 (5) | 162 (5) |
O24—H24F···O19vi | 0.849 (19) | 1.97 (2) | 2.814 (5) | 177 (6) |
O24—H24G···O32 | 0.851 (19) | 1.90 (2) | 2.736 (6) | 168 (6) |
O25—H25F···O24iii | 0.865 (19) | 1.91 (2) | 2.770 (6) | 170 (6) |
O25—H25G···O12ii | 0.852 (19) | 1.97 (3) | 2.788 (5) | 159 (5) |
O26—H26F···O23ii | 0.860 (19) | 1.95 (2) | 2.791 (5) | 167 (6) |
O26—H26G···O31 | 0.851 (19) | 1.95 (2) | 2.788 (6) | 169 (6) |
O27—H27F···O6vi | 0.847 (19) | 1.88 (3) | 2.687 (5) | 158 (5) |
O27—H27G···O14ii | 0.844 (19) | 1.81 (2) | 2.650 (5) | 175 (5) |
O28—H28F···O10 | 0.822 (19) | 2.02 (2) | 2.810 (5) | 161 (5) |
O28—H28G···O27v | 0.821 (19) | 2.00 (3) | 2.797 (5) | 164 (5) |
O29—H29F···O2 | 0.868 (19) | 1.98 (2) | 2.834 (5) | 168 (6) |
O29—H29G···O27 | 0.854 (19) | 1.98 (2) | 2.802 (5) | 160 (5) |
O30—H30F···O12 | 0.861 (19) | 2.28 (5) | 2.911 (7) | 130 (6) |
O30—H30G···O19iv | 0.864 (19) | 1.95 (3) | 2.791 (5) | 165 (6) |
O31—H31F···O33ii | 0.839 (19) | 2.17 (3) | 2.946 (8) | 154 (7) |
O31—H31G···O4 | 0.858 (19) | 2.08 (2) | 2.902 (6) | 161 (5) |
O32—H32F···O34 | 0.917 (19) | 2.07 (2) | 2.823 (7) | 139 (3) |
O32—H32G···O31 | 0.86 (2) | 1.98 (2) | 2.837 (7) | 178 (9) |
O33—H33F···O17 | 0.875 (19) | 2.11 (4) | 2.877 (6) | 146 (7) |
O33—H33G···O30vi | 0.87 (2) | 1.90 (2) | 2.766 (6) | 170 (7) |
O34—H34F···O18 | 0.85 (2) | 2.12 (4) | 2.906 (6) | 154 (8) |
O34—H34G···O6vi | 0.86 (2) | 2.02 (3) | 2.815 (6) | 154 (6) |
O35A—H35F···O25 | 0.85 (2) | 2.14 (3) | 2.986 (9) | 174 (13) |
O35A—H35G···O4 | 0.85 (2) | 2.05 (5) | 2.848 (9) | 157 (12) |
O35B—H35H···O4 | 0.83 (2) | 2.45 (8) | 3.135 (9) | 141 (10) |
O35B—H35I···O25 | 0.84 (2) | 2.03 (5) | 2.802 (10) | 152 (9) |
O36A—H36F···O22 | 0.85 (2) | 2.14 (5) | 2.949 (9) | 159 (12) |
O36A—H36G···O35A | 0.85 (2) | 1.93 (5) | 2.746 (12) | 158 (12) |
Symmetry codes: (i) x, y, z−1; (ii) x, y−1, z; (iii) x+1, y, z; (iv) x, y+1, z; (v) x+1, y+1, z; (vi) x−1, y, z; (vii) x, y, z+1; (viii) x+1, y, z+1; (ix) x, y+1, z+1. |
D-Penicillamine (C5H11NSO2, D—H2pen), which is a sulfur-containing amino acid, has been known as a unique multidentate chiral ligand that has three kinds of coordination sites, amine N, carboxylate O, and thiolate S atoms (Igashira-Kamiyama & Konno, 2011). Recently, we found that an S-bridged cyclic tetranuclear PdII complex with D-pen, [Pd4Cl4(D-Hpen)4].7H2O, gradually converts to an S-bridged cyclic trinuclear PdII structure in [Pd3(D-pen)3].4.5H2O (II), by treating with K2CO3 in water (Yoshinari et al., 2009). We assumed that some intermediate species exists in this reaction because not only the nuclearity of the complex (PdII4 versus. PdII3) but also the coordination mode of D-pen (κ2N,S:κS versus. κ2N,S:κ2S,O) are required to be changed for this structural conversion. In the course of our trials to find an intermediate species, we were able to isolate crystals (I), the composition of which is different from those of [Pd4Cl4(D-Hpen)4].7H2O and [Pd3(D-pen)3].4.5H2O, and its structure was determined by single-crystal X-ray crystallography. Herein we report that crystal (I) thus obtained has a new cyclic tetranuclear PdII structure in [PdII4(D-pen)4].9.75H2O, which forms an intriguing supramolecular dimer structure.
The asymmetric unit of (I) contains two tetranuclear PdII molecules, [Pd4(D-pen)4], and nineteen and a half solvated water molecules (Figure 1). The two tetranuclear molecules are essentially the same as each other, comprising of four square-planar PdII atoms and four D-pen ligands. Each D-pen ligand bridges two PdII centers in a κ2N,S:κ2S,O coordination mode, while each PdII atom is coordinated by two D-pen ligands in N,S- and S,O- chelating modes, forming a crown-type eight-membered Pd4S4 metallacycle. Note that amine and carboxy groups cover one face of the metallacycle, while thiolate and methyl groups cover another face in (I). It has been shown that similar hydrophilic and hydrophobic surfaces are formed in the S-bridged metallacycle structure in (II).
The Pd—S distances and S—Pd—S angles in (I) [Pd—S = 2.2261 (11)–2.2968 (10) Å, S—Pd—S = 89.76 (4)–93.65 (4)°] are similar to those in (II) [Pd—S = 2.2427 (15)–2.2934 (15) Å, S—Pd—S = 90.08 (6)–92.66 (6)°]. However, the Pd—S—Pd angles in (I) [96.90 (4)–102.42 (4)°] are closer to the ideal tetrahedral angle of 109.5° compared with those in (II) [Pd—S—Pd = 82.89 (5)–91.65 (6)°], while the trans angles around PdII atoms in (I) [167.45 (12)–172.13 (8)°] are slightly smaller than those in (II) [170.41 (13)–176.67 (16)°]. This implies that the distortion around S atoms is larger but the distortion around Pd atoms is smaller in (I), compared with those in (II).
The most remarkable structural feature in (I) is the construction of a cylindrical supramolecular structure, in which two cyclic tetranuclear molecules face to each other to form eight intermolecular N—H···O hydrogen bonds [N···O = 2.917 (4)–3.278 (5) Å] (Figure 2). None of solvent molecules are accommodated in the cylinder despite the presence of a void space with a diameter of ca 4 Å. All of the water molecules are participated in the formation of O—H···O and/or N—H···O hydrogen bonds with neighboring water molecules and/or tetranuclear molecules [O···O = 2.650 (5)–3.135 (9) Å, N···O = 2.886 (5)–3.326 (5) Å], completing three dimensional structure in (I) (Table 1).