metal-organic compounds
Di-μ-chlorido-bis({4-[bis(trimethylsilyl)amino]-6-chloro-2,2,8,8-tetramethyl-5,7-bis(trimethylsilyl)-3,5,7-triaza-4,6-diphospha-2,8-disilanon-3-en-4-ido-κ2P,P′}palladium(II)) diethyl ether disolvate
aLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
*Correspondence e-mail: uwe.rosenthal@catalysis.de
The title compound, [Pd2(C18H54Cl2N4P2Si6)2Cl2]·2C4H10O, features a dinuclear chloride-bridged palladium complex bearing two equivalents of the novel monoanionic mixed valent (λ3-P)—N—(λ5-P) ligand. A metal catalyzed coupling of two aminoiminophosphines and a shift of one chlorine from the metal to the phosphorus results in the (λ3-P)—N—(λ5-P) ligand. The molecule contains a planar bimetallic Pd2Cl2 core with a crystallographic centre of inversion at the mid-point of the Pd⋯Pd line. The Pd atoms are in a distorted square-planar arrangement, where the P/Pd/P and Cl/Pd/Cl planes are twisted with respect to each other by a dihedral angle of 7.57 (4)°. The P—Pd—P bite angle is 71.380 (18)°. Intramolecular C—H⋯Cl interactions are observed. In the crystal, the diethyl ether solvent molecule is disordered over two sites, with an occupancy ratio of 0.788 (5):0.212 (5).
Keywords: crystal structure; dinuclear palladium complex; chloride-bridged complex; metal catalyzed coupling; phosphorous ligand.
CCDC reference: 1486161
Structure description
Low-valent phosphorous compounds, such as aminoiminophosphines R2N—P=NR, are versatile ligands. Due to their unsaturated P=N double bond they can undergo [2 + 2] cycloaddition to yield the cyclodiphosphadiazanes (Niecke et al., 1976). In the presence of dichlorido(1,5-cyclooctadiene)palladium(II), two N—P=N molecules undergo a [2 + 1] cycloaddition which results in a kind of azadiphosphiridine or, respectively, a monoanionic six-electron-donor ligand (Scherer & Brück, 1987). In the course of coordination to dichlorido(1,5-cyclooctadiene)palladium(II), one chlorine is transferred from the metal centre to the PIII atom. As a consequence, two palladium cores dimerize by building a dinuclear chloride-bridged palladium complex with two equivalents of the monoanionic mixed-valent (λ3-P)—N—(λ5-P) ligand. The molecule contains a planar bimetallic Pd2Cl2 core with a crystallographic centre of inversion at the mid-point of Pd⋯Pd line (Fig. 1). The Pd—Cl bond lengths are 2.4296 (5) and 2.4815 (4) Å, which are similar to other dinuclear chloride-bridged palladium(II) complexes (average Pd—Cl = 2.432 Å for Pd—Cl—Pd > 85°; Orpen et al., 1989). Due to the large Pd⋯Pd distance of 3.521 Å there is no metal–metal interaction. The Pd atoms are in a distorted square-planar arrangement where the P1/Pd1/P2 and Cl1/Pd1/Cl1i planes [symmetry code: (i) −x + 1, −y + 1, −z + 1] are twisted with respect to each other by an angle of 7.57 (4)°. The mixed valent (λ3-P)—N—(λ5-P) ligand is remarkable, with the ability to form a four-membered metallacycle that is nearly planar, with a P2—N2—P1—Pd1 torsion angle of 6.45 (7)°. The different Pd—P distances are 2.1947 (5) (λ3-P—Pd) and 2.2294 (5) Å (λ5-P—Pd). Compared to a λ3-P–metal bond, the λ5-P–metal bond length is elongated. A longer λ5-P–metal bond compared to the λ3-P–metal bond length was also observed in a Pd complex bearing a mixed-valent (λ3-P)—N—(λ5-P) ligand (du Mont et al., 2009)
The P1—Pd1—P2 bite angle is 71.380 (18)°. For the (λ5-P)=N double bond (N3—P2), a value of 1.5346 (17) Å was observed. All other P—N bond distances range from 1.6519 (16) (P1—N1) to 1.7772 (16) Å (P2—N2). Compared to the calculated P—N single-bond distance (1.82 Å; Pyykkö, 2015) they are obviously shorter and display some multiple bonding character. The calculated P=N double bond length is 1.62 Å (Pyykkö, 2015). This might be explained by being a consequence of in the alternating P—N ligand backbone. Similar but mononuclear iron and platinum complexes with mixed-valent (λ3-P)—N—(λ5-P) ligands have been reported (du Mont et al., 2009; Jones et al., 2015). Intramolecular C—H⋯Cl interactions are observed (Table 1). The crystal of the title compound contains a diethyl ether solvent molecule which is disordered over two sites with an occupancy ratio of 0.788 (5):0.212 (5).
Synthesis and crystallization
A pale-yellow solution of 1.27 mmol of the aminoiminophosphine (TMS)2N—P= N(TMS) in 5 ml toluene was added dropwise to a bright-yellow suspension of 0.58 mmol dichlorido(1,5-cyclooctadiene)palladium(II) in 15 ml toluene. After stirring for 10 min at room temperature, the yellow solution became clear. It was stirred for another 12 h before the solvent was reduced in a vacuum. The resulting yellow solution was filtered. After adding diethyl ether, it was cooled to 233 K to obtain yellow crystals of the title compound that were suitable for X-ray analysis (yield 77%; m.p. decomposition above 347 K). Analysis calculated for C36H108Cl4N8P4Pd2Si12: C 29.44, H 7.41, N 7.63, P 8.43%; found: C 29.24, H 7.66, N 7.07, P 8.51%. 1H NMR (400 MHz, C6D6): δ 0.44 (s, 24H, 2 × TMS), 0.57 (s, 24H, 2 × TMS), 0.69 (s, 12H, TMS), 0.74 (s, 12H, TMS). 13C (100.6 MHz, C6D6): δ 3.8 (TMS), 5.7 (TMS), 6.3 (TMS), 7.5 (TMS). 31P (121 MHz, C6D6): δ −88.52 (s), −28.06 (br, s). 29Si (79.5 MHz, C6D6): δ 8.32 (2 × N-TMS), 11.34 (4 × N-TMS). MS CI (m/z) 1466 [M + 2]+, 1275 [C30H90N7P3Pd2Si10]+, 1158 [C27H81N6P3Pd2Si9 + 3H]+. IR ATR (cm−1) 2896.9 (w), 2957.2 (w).
Refinement
Crystal data, data collection and structure . The diethyl ether molecule is disordered over two sites with refined occupancies 0.788 (5):0.212 (5). DFIX and DANG instructions were used to improve the geometry of the disordered solvent molecule. Additionally, the anisotropic displacement parameters of O1A and O1B were restrained to be equal (SIMU). Atoms C19A, C19B C20A, C20B, C21A, C21B, C22A and C22B were refined isotropically. A SIMU instruction was also applied for these atoms.
details are summarized in Table 2Structural data
CCDC reference: 1486161
10.1107/S241431461600986X/is4009sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S241431461600986X/is4009Isup2.hkl
Data collection: APEX2 (Bruker, 2014); cell
SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).[Pd2(C18H54Cl2N4P2Si6)2Cl2]·2C4H10O | Z = 1 |
Mr = 1617.10 | F(000) = 852 |
Triclinic, P1 | Dx = 1.314 Mg m−3 |
a = 12.7331 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.9694 (3) Å | Cell parameters from 9897 reflections |
c = 14.6354 (3) Å | θ = 2.5–29.0° |
α = 104.1592 (6)° | µ = 0.86 mm−1 |
β = 101.3576 (6)° | T = 150 K |
γ = 112.6871 (6)° | Prism, yellow |
V = 2044.32 (8) Å3 | 0.42 × 0.40 × 0.18 mm |
Bruker APEXII CCD diffractometer | 9871 independent reflections |
Radiation source: fine-focus sealed tube | 8984 reflections with I > 2σ(I) |
Detector resolution: 8.3333 pixels mm-1 | Rint = 0.021 |
φ and ω scans | θmax = 28.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −16→16 |
Tmin = 0.77, Tmax = 0.86 | k = −17→17 |
40794 measured reflections | l = −19→19 |
Refinement on F2 | 29 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.076 | w = 1/[σ2(Fo2) + (0.0355P)2 + 2.0017P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
9871 reflections | Δρmax = 0.95 e Å−3 |
367 parameters | Δρmin = −0.92 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.6444 (3) | 0.1775 (4) | 0.2536 (4) | 0.0864 (14) | |
H1A | 0.6442 | 0.1971 | 0.3226 | 0.130* | |
H1B | 0.7235 | 0.1847 | 0.2523 | 0.130* | |
H1C | 0.5825 | 0.0954 | 0.2142 | 0.130* | |
C2 | 0.6250 (3) | 0.2550 (3) | 0.0734 (2) | 0.0517 (7) | |
H2A | 0.5583 | 0.1781 | 0.0276 | 0.078* | |
H2B | 0.7017 | 0.2535 | 0.0751 | 0.078* | |
H2C | 0.6217 | 0.3190 | 0.0506 | 0.078* | |
C3 | 0.7322 (2) | 0.4325 (3) | 0.2872 (2) | 0.0539 (7) | |
H3A | 0.7625 | 0.4829 | 0.2489 | 0.081* | |
H3B | 0.7983 | 0.4239 | 0.3262 | 0.081* | |
H3C | 0.6988 | 0.4697 | 0.3323 | 0.081* | |
C4 | 0.1995 (2) | 0.0972 (2) | 0.1565 (2) | 0.0443 (6) | |
H4A | 0.1965 | 0.1676 | 0.1972 | 0.066* | |
H4B | 0.1485 | 0.0265 | 0.1687 | 0.066* | |
H4C | 0.1705 | 0.0858 | 0.0859 | 0.066* | |
C5 | 0.3946 (2) | 0.1077 (2) | 0.3154 (2) | 0.0433 (6) | |
H5A | 0.4650 | 0.0928 | 0.3264 | 0.065* | |
H5B | 0.3262 | 0.0417 | 0.3191 | 0.065* | |
H5C | 0.4128 | 0.1826 | 0.3666 | 0.065* | |
C6 | 0.3559 (3) | −0.0021 (3) | 0.0910 (2) | 0.0583 (8) | |
H6A | 0.3386 | 0.0099 | 0.0272 | 0.087* | |
H6B | 0.2941 | −0.0795 | 0.0855 | 0.087* | |
H6C | 0.4351 | −0.0006 | 0.1080 | 0.087* | |
C7 | 0.0637 (2) | 0.2099 (2) | −0.0030 (2) | 0.0447 (6) | |
H7A | 0.0499 | 0.1267 | −0.0250 | 0.067* | |
H7B | 0.0159 | 0.2226 | −0.0564 | 0.067* | |
H7C | 0.0397 | 0.2270 | 0.0564 | 0.067* | |
C8 | 0.2971 (3) | 0.2308 (3) | −0.04103 (17) | 0.0472 (7) | |
H8A | 0.3813 | 0.2862 | −0.0280 | 0.071* | |
H8B | 0.2536 | 0.1990 | −0.1127 | 0.071* | |
H8C | 0.2936 | 0.1648 | −0.0183 | 0.071* | |
C9 | 0.2465 (2) | 0.4447 (2) | −0.00733 (17) | 0.0392 (5) | |
H9A | 0.2120 | 0.4890 | 0.0302 | 0.059* | |
H9B | 0.2056 | 0.4191 | −0.0789 | 0.059* | |
H9C | 0.3325 | 0.4963 | 0.0085 | 0.059* | |
C10 | −0.0606 (2) | 0.1388 (2) | 0.2237 (2) | 0.0481 (6) | |
H10A | −0.1082 | 0.1654 | 0.1831 | 0.072* | |
H10B | −0.1109 | 0.0892 | 0.2544 | 0.072* | |
H10C | −0.0320 | 0.0919 | 0.1815 | 0.072* | |
C11 | 0.0147 (3) | 0.3501 (3) | 0.4110 (2) | 0.0465 (6) | |
H11A | 0.0827 | 0.4211 | 0.4631 | 0.070* | |
H11B | −0.0296 | 0.2958 | 0.4416 | 0.070* | |
H11C | −0.0392 | 0.3741 | 0.3741 | 0.070* | |
C12 | 0.1624 (3) | 0.2200 (3) | 0.3995 (2) | 0.0469 (6) | |
H12A | 0.1869 | 0.1699 | 0.3557 | 0.070* | |
H12B | 0.1138 | 0.1734 | 0.4327 | 0.070* | |
H12C | 0.2342 | 0.2892 | 0.4497 | 0.070* | |
C13 | 0.4009 (2) | 0.8176 (2) | 0.39408 (18) | 0.0376 (5) | |
H13A | 0.3302 | 0.8261 | 0.3640 | 0.056* | |
H13B | 0.4730 | 0.8947 | 0.4175 | 0.056* | |
H13C | 0.3907 | 0.7914 | 0.4505 | 0.056* | |
C14 | 0.55987 (19) | 0.70951 (19) | 0.36919 (19) | 0.0343 (5) | |
H14A | 0.5512 | 0.6912 | 0.4292 | 0.051* | |
H14B | 0.6264 | 0.7896 | 0.3883 | 0.051* | |
H14C | 0.5768 | 0.6506 | 0.3269 | 0.051* | |
C15 | 0.4489 (2) | 0.7538 (2) | 0.1936 (2) | 0.0420 (6) | |
H15A | 0.4773 | 0.7035 | 0.1548 | 0.063* | |
H15B | 0.5109 | 0.8373 | 0.2200 | 0.063* | |
H15C | 0.3750 | 0.7466 | 0.1507 | 0.063* | |
C16 | 0.1596 (2) | 0.6979 (2) | 0.1776 (2) | 0.0449 (6) | |
H16A | 0.2305 | 0.7723 | 0.2221 | 0.067* | |
H16B | 0.0875 | 0.7100 | 0.1711 | 0.067* | |
H16C | 0.1687 | 0.6744 | 0.1119 | 0.067* | |
C17 | 0.1115 (2) | 0.6141 (2) | 0.3497 (2) | 0.0405 (5) | |
H17A | 0.1503 | 0.5863 | 0.3961 | 0.061* | |
H17B | 0.0243 | 0.5749 | 0.3365 | 0.061* | |
H17C | 0.1426 | 0.7009 | 0.3792 | 0.061* | |
C18 | 0.0096 (2) | 0.4459 (2) | 0.1325 (2) | 0.0436 (6) | |
H18A | 0.0295 | 0.4246 | 0.0715 | 0.065* | |
H18B | −0.0568 | 0.4665 | 0.1189 | 0.065* | |
H18C | −0.0145 | 0.3779 | 0.1554 | 0.065* | |
Cl1 | 0.39377 (4) | 0.54640 (5) | 0.51614 (3) | 0.02502 (10) | |
Cl2 | 0.54536 (5) | 0.48760 (5) | 0.15850 (4) | 0.03183 (11) | |
N1 | 0.46063 (15) | 0.26090 (15) | 0.19051 (12) | 0.0242 (3) | |
N2 | 0.30091 (14) | 0.36004 (14) | 0.15804 (12) | 0.0208 (3) | |
N3 | 0.14924 (14) | 0.36071 (15) | 0.26758 (13) | 0.0252 (3) | |
N4 | 0.28301 (14) | 0.56547 (14) | 0.25223 (12) | 0.0210 (3) | |
P1 | 0.43459 (4) | 0.37814 (4) | 0.21907 (3) | 0.01973 (10) | |
P2 | 0.27309 (4) | 0.43630 (4) | 0.26184 (3) | 0.01800 (9) | |
Pd1 | 0.43737 (2) | 0.45924 (2) | 0.37046 (2) | 0.01843 (5) | |
Si1 | 0.61214 (6) | 0.28225 (6) | 0.20011 (5) | 0.03514 (14) | |
Si2 | 0.35607 (6) | 0.11934 (5) | 0.19020 (5) | 0.03079 (13) | |
Si3 | 0.22635 (6) | 0.31142 (5) | 0.02732 (4) | 0.02928 (13) | |
Si4 | 0.07178 (5) | 0.27242 (5) | 0.32387 (5) | 0.02940 (13) | |
Si5 | 0.41760 (5) | 0.70410 (5) | 0.29902 (4) | 0.02496 (11) | |
Si6 | 0.14410 (5) | 0.57669 (5) | 0.23102 (5) | 0.02895 (13) | |
O1A | 0.9440 (2) | 0.1275 (2) | 0.5576 (2) | 0.0579 (8) | 0.788 (5) |
C19A | 1.1344 (4) | 0.2281 (5) | 0.6796 (4) | 0.0839 (14)* | 0.788 (5) |
H19A | 1.1836 | 0.2323 | 0.7423 | 0.126* | 0.788 (5) |
H19B | 1.1707 | 0.2137 | 0.6277 | 0.126* | 0.788 (5) |
H19C | 1.1303 | 0.3037 | 0.6889 | 0.126* | 0.788 (5) |
C20A | 1.0105 (4) | 0.1284 (5) | 0.6491 (3) | 0.0791 (13)* | 0.788 (5) |
H20A | 1.0131 | 0.0513 | 0.6394 | 0.095* | 0.788 (5) |
H20B | 0.9726 | 0.1418 | 0.7008 | 0.095* | 0.788 (5) |
C21A | 0.8231 (3) | 0.0430 (4) | 0.5182 (3) | 0.0676 (11)* | 0.788 (5) |
H21A | 0.7833 | 0.0527 | 0.5691 | 0.081* | 0.788 (5) |
H21B | 0.8173 | −0.0383 | 0.5007 | 0.081* | 0.788 (5) |
C22A | 0.7602 (5) | 0.0556 (5) | 0.4282 (3) | 0.0604 (11)* | 0.788 (5) |
H22A | 0.6756 | −0.0048 | 0.4022 | 0.091* | 0.788 (5) |
H22B | 0.7647 | 0.1355 | 0.4456 | 0.091* | 0.788 (5) |
H22C | 0.7986 | 0.0446 | 0.3772 | 0.091* | 0.788 (5) |
O1B | 0.8894 (7) | 0.1045 (8) | 0.6139 (6) | 0.050 (2) | 0.212 (5) |
C19B | 1.0964 (9) | 0.2188 (16) | 0.7046 (13) | 0.080 (2)* | 0.212 (5) |
H19D | 1.1774 | 0.2298 | 0.7061 | 0.121* | 0.212 (5) |
H19E | 1.0905 | 0.2919 | 0.7045 | 0.121* | 0.212 (5) |
H19F | 1.0809 | 0.2016 | 0.7635 | 0.121* | 0.212 (5) |
C20B | 1.0053 (8) | 0.1165 (16) | 0.6123 (12) | 0.0791 (18)* | 0.212 (5) |
H20C | 1.0200 | 0.1327 | 0.5521 | 0.095* | 0.212 (5) |
H20D | 1.0104 | 0.0420 | 0.6115 | 0.095* | 0.212 (5) |
C21B | 0.7957 (10) | 0.0114 (9) | 0.5278 (9) | 0.0730 (17)* | 0.212 (5) |
H21C | 0.7248 | −0.0318 | 0.5462 | 0.088* | 0.212 (5) |
H21D | 0.8233 | −0.0463 | 0.4977 | 0.088* | 0.212 (5) |
C22B | 0.7628 (16) | 0.0660 (17) | 0.4551 (9) | 0.060 (2)* | 0.212 (5) |
H22D | 0.6982 | 0.0030 | 0.3951 | 0.090* | 0.212 (5) |
H22E | 0.7352 | 0.1226 | 0.4854 | 0.090* | 0.212 (5) |
H22F | 0.8334 | 0.1081 | 0.4371 | 0.090* | 0.212 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.059 (2) | 0.121 (3) | 0.156 (4) | 0.070 (2) | 0.059 (2) | 0.106 (3) |
C2 | 0.0638 (18) | 0.0589 (17) | 0.0496 (16) | 0.0372 (15) | 0.0389 (14) | 0.0152 (13) |
C3 | 0.0295 (12) | 0.083 (2) | 0.0448 (15) | 0.0278 (14) | 0.0115 (11) | 0.0131 (15) |
C4 | 0.0347 (12) | 0.0253 (11) | 0.0618 (17) | 0.0086 (10) | 0.0045 (11) | 0.0146 (11) |
C5 | 0.0484 (15) | 0.0459 (14) | 0.0460 (15) | 0.0238 (12) | 0.0179 (12) | 0.0272 (12) |
C6 | 0.089 (2) | 0.0374 (14) | 0.0527 (17) | 0.0402 (16) | 0.0212 (16) | 0.0061 (12) |
C7 | 0.0362 (13) | 0.0378 (13) | 0.0383 (13) | 0.0137 (11) | −0.0122 (10) | 0.0029 (10) |
C8 | 0.0655 (18) | 0.0591 (16) | 0.0202 (11) | 0.0409 (15) | 0.0076 (11) | 0.0038 (11) |
C9 | 0.0516 (14) | 0.0488 (14) | 0.0251 (11) | 0.0294 (12) | 0.0094 (10) | 0.0176 (10) |
C10 | 0.0288 (12) | 0.0385 (13) | 0.0619 (18) | 0.0034 (10) | 0.0159 (12) | 0.0125 (12) |
C11 | 0.0463 (15) | 0.0494 (15) | 0.0564 (17) | 0.0237 (12) | 0.0319 (13) | 0.0240 (13) |
C12 | 0.0488 (15) | 0.0506 (15) | 0.0573 (17) | 0.0263 (13) | 0.0209 (13) | 0.0361 (14) |
C13 | 0.0409 (13) | 0.0274 (11) | 0.0372 (13) | 0.0159 (10) | 0.0079 (10) | 0.0028 (9) |
C14 | 0.0248 (10) | 0.0249 (10) | 0.0442 (13) | 0.0077 (8) | 0.0057 (9) | 0.0082 (9) |
C15 | 0.0477 (14) | 0.0385 (13) | 0.0419 (14) | 0.0144 (11) | 0.0189 (11) | 0.0231 (11) |
C16 | 0.0480 (15) | 0.0469 (14) | 0.0500 (15) | 0.0319 (12) | 0.0073 (12) | 0.0238 (12) |
C17 | 0.0391 (13) | 0.0427 (13) | 0.0527 (15) | 0.0274 (11) | 0.0226 (11) | 0.0175 (11) |
C18 | 0.0288 (11) | 0.0446 (14) | 0.0500 (15) | 0.0193 (11) | −0.0045 (10) | 0.0144 (12) |
Cl1 | 0.0260 (2) | 0.0423 (3) | 0.01267 (19) | 0.0246 (2) | 0.00442 (16) | 0.00584 (18) |
Cl2 | 0.0334 (3) | 0.0344 (3) | 0.0361 (3) | 0.0172 (2) | 0.0200 (2) | 0.0163 (2) |
N1 | 0.0291 (8) | 0.0277 (8) | 0.0219 (8) | 0.0191 (7) | 0.0090 (7) | 0.0081 (7) |
N2 | 0.0214 (7) | 0.0216 (7) | 0.0175 (7) | 0.0115 (6) | 0.0028 (6) | 0.0040 (6) |
N3 | 0.0187 (8) | 0.0297 (9) | 0.0283 (9) | 0.0109 (7) | 0.0066 (7) | 0.0130 (7) |
N4 | 0.0220 (8) | 0.0217 (7) | 0.0210 (8) | 0.0122 (6) | 0.0050 (6) | 0.0082 (6) |
P1 | 0.0209 (2) | 0.0231 (2) | 0.0164 (2) | 0.01211 (19) | 0.00553 (17) | 0.00576 (18) |
P2 | 0.0167 (2) | 0.0206 (2) | 0.0167 (2) | 0.00981 (18) | 0.00340 (17) | 0.00615 (17) |
Pd1 | 0.01793 (7) | 0.02364 (8) | 0.01437 (7) | 0.01211 (6) | 0.00337 (5) | 0.00495 (5) |
Si1 | 0.0382 (3) | 0.0500 (4) | 0.0408 (4) | 0.0334 (3) | 0.0227 (3) | 0.0243 (3) |
Si2 | 0.0376 (3) | 0.0239 (3) | 0.0316 (3) | 0.0180 (3) | 0.0078 (3) | 0.0071 (2) |
Si3 | 0.0357 (3) | 0.0322 (3) | 0.0163 (3) | 0.0189 (3) | 0.0001 (2) | 0.0037 (2) |
Si4 | 0.0228 (3) | 0.0302 (3) | 0.0377 (3) | 0.0109 (2) | 0.0124 (2) | 0.0161 (3) |
Si5 | 0.0267 (3) | 0.0214 (3) | 0.0260 (3) | 0.0107 (2) | 0.0076 (2) | 0.0083 (2) |
Si6 | 0.0261 (3) | 0.0314 (3) | 0.0330 (3) | 0.0189 (2) | 0.0044 (2) | 0.0118 (2) |
O1A | 0.0549 (16) | 0.0586 (16) | 0.0620 (18) | 0.0237 (13) | 0.0201 (13) | 0.0273 (13) |
O1B | 0.058 (5) | 0.046 (4) | 0.053 (5) | 0.027 (4) | 0.027 (4) | 0.017 (4) |
C1—Si1 | 1.858 (3) | C15—H15C | 0.9800 |
C1—H1A | 0.9800 | C16—Si6 | 1.882 (3) |
C1—H1B | 0.9800 | C16—H16A | 0.9800 |
C1—H1C | 0.9800 | C16—H16B | 0.9800 |
C2—Si1 | 1.853 (3) | C16—H16C | 0.9800 |
C2—H2A | 0.9800 | C17—Si6 | 1.858 (3) |
C2—H2B | 0.9800 | C17—H17A | 0.9800 |
C2—H2C | 0.9800 | C17—H17B | 0.9800 |
C3—Si1 | 1.865 (3) | C17—H17C | 0.9800 |
C3—H3A | 0.9800 | C18—Si6 | 1.865 (3) |
C3—H3B | 0.9800 | C18—H18A | 0.9800 |
C3—H3C | 0.9800 | C18—H18B | 0.9800 |
C4—Si2 | 1.844 (3) | C18—H18C | 0.9800 |
C4—H4A | 0.9800 | Cl1—Pd1 | 2.4296 (5) |
C4—H4B | 0.9800 | Cl1—Pd1i | 2.4815 (4) |
C4—H4C | 0.9800 | Cl2—P1 | 2.0867 (7) |
C5—Si2 | 1.860 (3) | N1—P1 | 1.6519 (16) |
C5—H5A | 0.9800 | N1—Si2 | 1.8032 (19) |
C5—H5B | 0.9800 | N1—Si1 | 1.8112 (18) |
C5—H5C | 0.9800 | N2—P1 | 1.6556 (16) |
C6—Si2 | 1.862 (3) | N2—P2 | 1.7772 (16) |
C6—H6A | 0.9800 | N2—Si3 | 1.7865 (17) |
C6—H6B | 0.9800 | N3—P2 | 1.5346 (17) |
C6—H6C | 0.9800 | N3—Si4 | 1.6950 (18) |
C7—Si3 | 1.862 (3) | N4—P2 | 1.6736 (16) |
C7—H7A | 0.9800 | N4—Si5 | 1.7881 (17) |
C7—H7B | 0.9800 | N4—Si6 | 1.8029 (16) |
C7—H7C | 0.9800 | P1—Pd1 | 2.1947 (5) |
C8—Si3 | 1.864 (3) | P2—Pd1 | 2.2294 (5) |
C8—H8A | 0.9800 | Pd1—Cl1i | 2.4815 (4) |
C8—H8B | 0.9800 | O1A—C21A | 1.394 (3) |
C8—H8C | 0.9800 | O1A—C20A | 1.430 (3) |
C9—Si3 | 1.857 (2) | C19A—C20A | 1.492 (4) |
C9—H9A | 0.9800 | C19A—H19A | 0.9800 |
C9—H9B | 0.9800 | C19A—H19B | 0.9800 |
C9—H9C | 0.9800 | C19A—H19C | 0.9800 |
C10—Si4 | 1.877 (3) | C20A—H20A | 0.9900 |
C10—H10A | 0.9800 | C20A—H20B | 0.9900 |
C10—H10B | 0.9800 | C21A—C22A | 1.482 (3) |
C10—H10C | 0.9800 | C21A—H21A | 0.9900 |
C11—Si4 | 1.863 (3) | C21A—H21B | 0.9900 |
C11—H11A | 0.9800 | C22A—H22A | 0.9800 |
C11—H11B | 0.9800 | C22A—H22B | 0.9800 |
C11—H11C | 0.9800 | C22A—H22C | 0.9800 |
C12—Si4 | 1.868 (3) | O1B—C21B | 1.422 (4) |
C12—H12A | 0.9800 | O1B—C20B | 1.429 (4) |
C12—H12B | 0.9800 | C19B—C20B | 1.500 (4) |
C12—H12C | 0.9800 | C19B—H19D | 0.9800 |
C13—Si5 | 1.872 (2) | C19B—H19E | 0.9800 |
C13—H13A | 0.9800 | C19B—H19F | 0.9800 |
C13—H13B | 0.9800 | C20B—H20C | 0.9900 |
C13—H13C | 0.9800 | C20B—H20D | 0.9900 |
C14—Si5 | 1.864 (2) | C21B—C22B | 1.494 (4) |
C14—H14A | 0.9800 | C21B—H21C | 0.9900 |
C14—H14B | 0.9800 | C21B—H21D | 0.9900 |
C14—H14C | 0.9800 | C22B—H22D | 0.9800 |
C15—Si5 | 1.867 (2) | C22B—H22E | 0.9800 |
C15—H15A | 0.9800 | C22B—H22F | 0.9800 |
C15—H15B | 0.9800 | ||
Si1—C1—H1A | 109.5 | P2—N3—Si4 | 146.58 (11) |
Si1—C1—H1B | 109.5 | P2—N4—Si5 | 125.76 (9) |
H1A—C1—H1B | 109.5 | P2—N4—Si6 | 115.33 (9) |
Si1—C1—H1C | 109.5 | Si5—N4—Si6 | 115.66 (9) |
H1A—C1—H1C | 109.5 | N1—P1—N2 | 116.97 (8) |
H1B—C1—H1C | 109.5 | N1—P1—Cl2 | 101.47 (7) |
Si1—C2—H2A | 109.5 | N2—P1—Cl2 | 101.22 (6) |
Si1—C2—H2B | 109.5 | N1—P1—Pd1 | 120.46 (6) |
H2A—C2—H2B | 109.5 | N2—P1—Pd1 | 97.69 (6) |
Si1—C2—H2C | 109.5 | Cl2—P1—Pd1 | 118.18 (3) |
H2A—C2—H2C | 109.5 | N1—P1—P2 | 140.56 (7) |
H2B—C2—H2C | 109.5 | Cl2—P1—P2 | 114.75 (3) |
Si1—C3—H3A | 109.5 | Pd1—P1—P2 | 54.935 (15) |
Si1—C3—H3B | 109.5 | N3—P2—N4 | 110.53 (9) |
H3A—C3—H3B | 109.5 | N3—P2—N2 | 111.64 (9) |
Si1—C3—H3C | 109.5 | N4—P2—N2 | 108.49 (8) |
H3A—C3—H3C | 109.5 | N3—P2—Pd1 | 118.85 (7) |
H3B—C3—H3C | 109.5 | N4—P2—Pd1 | 112.87 (6) |
Si2—C4—H4A | 109.5 | N2—P2—Pd1 | 92.90 (5) |
Si2—C4—H4B | 109.5 | N3—P2—P1 | 131.03 (7) |
H4A—C4—H4B | 109.5 | N4—P2—P1 | 116.17 (6) |
Si2—C4—H4C | 109.5 | Pd1—P2—P1 | 53.685 (15) |
H4A—C4—H4C | 109.5 | P1—Pd1—P2 | 71.380 (18) |
H4B—C4—H4C | 109.5 | P1—Pd1—Cl1 | 165.791 (17) |
Si2—C5—H5A | 109.5 | P2—Pd1—Cl1 | 94.413 (16) |
Si2—C5—H5B | 109.5 | P1—Pd1—Cl1i | 105.637 (16) |
H5A—C5—H5B | 109.5 | P2—Pd1—Cl1i | 171.920 (18) |
Si2—C5—H5C | 109.5 | Cl1—Pd1—Cl1i | 88.411 (15) |
H5A—C5—H5C | 109.5 | N1—Si1—C2 | 108.05 (12) |
H5B—C5—H5C | 109.5 | N1—Si1—C1 | 110.50 (12) |
Si2—C6—H6A | 109.5 | C2—Si1—C1 | 110.16 (18) |
Si2—C6—H6B | 109.5 | N1—Si1—C3 | 114.01 (10) |
H6A—C6—H6B | 109.5 | C2—Si1—C3 | 110.42 (14) |
Si2—C6—H6C | 109.5 | C1—Si1—C3 | 103.65 (19) |
H6A—C6—H6C | 109.5 | N1—Si2—C4 | 112.48 (10) |
H6B—C6—H6C | 109.5 | N1—Si2—C5 | 110.76 (10) |
Si3—C7—H7A | 109.5 | C4—Si2—C5 | 107.33 (13) |
Si3—C7—H7B | 109.5 | N1—Si2—C6 | 108.33 (12) |
H7A—C7—H7B | 109.5 | C4—Si2—C6 | 105.24 (15) |
Si3—C7—H7C | 109.5 | C5—Si2—C6 | 112.64 (13) |
H7A—C7—H7C | 109.5 | N2—Si3—C9 | 108.72 (10) |
H7B—C7—H7C | 109.5 | N2—Si3—C7 | 109.53 (11) |
Si3—C8—H8A | 109.5 | C9—Si3—C7 | 110.83 (12) |
Si3—C8—H8B | 109.5 | N2—Si3—C8 | 108.61 (10) |
H8A—C8—H8B | 109.5 | C9—Si3—C8 | 109.09 (13) |
Si3—C8—H8C | 109.5 | C7—Si3—C8 | 110.02 (13) |
H8A—C8—H8C | 109.5 | N3—Si4—C11 | 112.26 (11) |
H8B—C8—H8C | 109.5 | N3—Si4—C12 | 113.80 (11) |
Si3—C9—H9A | 109.5 | C11—Si4—C12 | 105.73 (14) |
Si3—C9—H9B | 109.5 | N3—Si4—C10 | 107.63 (11) |
H9A—C9—H9B | 109.5 | C11—Si4—C10 | 108.40 (13) |
Si3—C9—H9C | 109.5 | C12—Si4—C10 | 108.88 (14) |
H9A—C9—H9C | 109.5 | N4—Si5—C14 | 118.23 (9) |
H9B—C9—H9C | 109.5 | N4—Si5—C15 | 109.61 (10) |
Si4—C10—H10A | 109.5 | C14—Si5—C15 | 105.73 (12) |
Si4—C10—H10B | 109.5 | N4—Si5—C13 | 109.35 (10) |
H10A—C10—H10B | 109.5 | C14—Si5—C13 | 101.96 (11) |
Si4—C10—H10C | 109.5 | C15—Si5—C13 | 111.74 (12) |
H10A—C10—H10C | 109.5 | N4—Si6—C17 | 110.54 (10) |
H10B—C10—H10C | 109.5 | N4—Si6—C18 | 116.19 (10) |
Si4—C11—H11A | 109.5 | C17—Si6—C18 | 110.40 (13) |
Si4—C11—H11B | 109.5 | N4—Si6—C16 | 108.40 (10) |
H11A—C11—H11B | 109.5 | C17—Si6—C16 | 109.50 (12) |
Si4—C11—H11C | 109.5 | C18—Si6—C16 | 101.29 (12) |
H11A—C11—H11C | 109.5 | C21A—O1A—C20A | 115.6 (3) |
H11B—C11—H11C | 109.5 | C20A—C19A—H19A | 109.5 |
Si4—C12—H12A | 109.5 | C20A—C19A—H19B | 109.5 |
Si4—C12—H12B | 109.5 | H19A—C19A—H19B | 109.5 |
H12A—C12—H12B | 109.5 | C20A—C19A—H19C | 109.5 |
Si4—C12—H12C | 109.5 | H19A—C19A—H19C | 109.5 |
H12A—C12—H12C | 109.5 | H19B—C19A—H19C | 109.5 |
H12B—C12—H12C | 109.5 | O1A—C20A—C19A | 106.5 (4) |
Si5—C13—H13A | 109.5 | O1A—C20A—H20A | 110.4 |
Si5—C13—H13B | 109.5 | C19A—C20A—H20A | 110.4 |
H13A—C13—H13B | 109.5 | O1A—C20A—H20B | 110.4 |
Si5—C13—H13C | 109.5 | C19A—C20A—H20B | 110.4 |
H13A—C13—H13C | 109.5 | H20A—C20A—H20B | 108.6 |
H13B—C13—H13C | 109.5 | O1A—C21A—C22A | 111.4 (4) |
Si5—C14—H14A | 109.5 | O1A—C21A—H21A | 109.4 |
Si5—C14—H14B | 109.5 | C22A—C21A—H21A | 109.4 |
H14A—C14—H14B | 109.5 | O1A—C21A—H21B | 109.4 |
Si5—C14—H14C | 109.5 | C22A—C21A—H21B | 109.4 |
H14A—C14—H14C | 109.5 | H21A—C21A—H21B | 108.0 |
H14B—C14—H14C | 109.5 | C21A—C22A—H22A | 109.5 |
Si5—C15—H15A | 109.5 | C21A—C22A—H22B | 109.5 |
Si5—C15—H15B | 109.5 | H22A—C22A—H22B | 109.5 |
H15A—C15—H15B | 109.5 | C21A—C22A—H22C | 109.5 |
Si5—C15—H15C | 109.5 | H22A—C22A—H22C | 109.5 |
H15A—C15—H15C | 109.5 | H22B—C22A—H22C | 109.5 |
H15B—C15—H15C | 109.5 | C21B—O1B—C20B | 111.9 (4) |
Si6—C16—H16A | 109.5 | C20B—C19B—H19D | 109.5 |
Si6—C16—H16B | 109.5 | C20B—C19B—H19E | 109.5 |
H16A—C16—H16B | 109.5 | H19D—C19B—H19E | 109.5 |
Si6—C16—H16C | 109.5 | C20B—C19B—H19F | 109.5 |
H16A—C16—H16C | 109.5 | H19D—C19B—H19F | 109.5 |
H16B—C16—H16C | 109.5 | H19E—C19B—H19F | 109.5 |
Si6—C17—H17A | 109.5 | O1B—C20B—C19B | 107.1 (4) |
Si6—C17—H17B | 109.5 | O1B—C20B—H20C | 110.3 |
H17A—C17—H17B | 109.5 | C19B—C20B—H20C | 110.3 |
Si6—C17—H17C | 109.5 | O1B—C20B—H20D | 110.3 |
H17A—C17—H17C | 109.5 | C19B—C20B—H20D | 110.3 |
H17B—C17—H17C | 109.5 | H20C—C20B—H20D | 108.5 |
Si6—C18—H18A | 109.5 | O1B—C21B—C22B | 108.3 (4) |
Si6—C18—H18B | 109.5 | O1B—C21B—H21C | 110.0 |
H18A—C18—H18B | 109.5 | C22B—C21B—H21C | 110.0 |
Si6—C18—H18C | 109.5 | O1B—C21B—H21D | 110.0 |
H18A—C18—H18C | 109.5 | C22B—C21B—H21D | 110.0 |
H18B—C18—H18C | 109.5 | H21C—C21B—H21D | 108.4 |
Pd1—Cl1—Pd1i | 91.589 (15) | C21B—C22B—H22D | 109.5 |
P1—N1—Si2 | 120.40 (10) | C21B—C22B—H22E | 109.5 |
P1—N1—Si1 | 119.78 (10) | H22D—C22B—H22E | 109.5 |
Si2—N1—Si1 | 116.70 (9) | C21B—C22B—H22F | 109.5 |
P1—N2—P2 | 97.45 (8) | H22D—C22B—H22F | 109.5 |
P1—N2—Si3 | 130.40 (10) | H22E—C22B—H22F | 109.5 |
P2—N2—Si3 | 130.69 (9) | ||
Si2—N1—P1—N2 | −51.67 (14) | P1—N1—Si1—C1 | 139.3 (2) |
Si1—N1—P1—N2 | 148.97 (10) | Si2—N1—Si1—C1 | −20.8 (2) |
Si2—N1—P1—Cl2 | −160.70 (9) | P1—N1—Si1—C3 | 23.00 (17) |
Si1—N1—P1—Cl2 | 39.95 (11) | Si2—N1—Si1—C3 | −137.10 (13) |
Si2—N1—P1—Pd1 | 66.59 (12) | P1—N1—Si2—C4 | 30.84 (16) |
Si1—N1—P1—Pd1 | −92.77 (11) | Si1—N1—Si2—C4 | −169.18 (13) |
Si2—N1—P1—P2 | −3.89 (17) | P1—N1—Si2—C5 | −89.26 (14) |
Si1—N1—P1—P2 | −163.24 (5) | Si1—N1—Si2—C5 | 70.71 (14) |
P2—N2—P1—N1 | 136.44 (8) | P1—N1—Si2—C6 | 146.73 (14) |
Si3—N2—P1—N1 | −56.48 (15) | Si1—N1—Si2—C6 | −53.29 (15) |
P2—N2—P1—Cl2 | −114.39 (6) | P1—N2—Si3—C9 | −99.16 (15) |
Si3—N2—P1—Cl2 | 52.69 (13) | P2—N2—Si3—C9 | 63.83 (16) |
P2—N2—P1—Pd1 | 6.45 (7) | P1—N2—Si3—C7 | 139.60 (14) |
Si3—N2—P1—Pd1 | 173.53 (11) | P2—N2—Si3—C7 | −57.41 (16) |
Si3—N2—P1—P2 | 167.07 (18) | P1—N2—Si3—C8 | 19.42 (18) |
Si4—N3—P2—N4 | −136.4 (2) | P2—N2—Si3—C8 | −177.58 (14) |
Si4—N3—P2—N2 | 102.7 (2) | P2—N3—Si4—C11 | 105.7 (2) |
Si4—N3—P2—Pd1 | −3.6 (3) | P2—N3—Si4—C12 | −14.4 (3) |
Si4—N3—P2—P1 | 61.8 (3) | P2—N3—Si4—C10 | −135.1 (2) |
Si5—N4—P2—N3 | 149.26 (11) | P2—N4—Si5—C14 | −2.46 (17) |
Si6—N4—P2—N3 | −9.39 (13) | Si6—N4—Si5—C14 | 156.13 (11) |
Si5—N4—P2—N2 | −88.03 (12) | P2—N4—Si5—C15 | 118.75 (14) |
Si6—N4—P2—N2 | 113.32 (10) | Si6—N4—Si5—C15 | −82.67 (13) |
Si5—N4—P2—Pd1 | 13.45 (13) | P2—N4—Si5—C13 | −118.43 (13) |
Si6—N4—P2—Pd1 | −145.20 (7) | Si6—N4—Si5—C13 | 40.16 (13) |
Si5—N4—P2—P1 | −45.96 (13) | P2—N4—Si6—C17 | 80.04 (13) |
Si6—N4—P2—P1 | 155.39 (7) | Si5—N4—Si6—C17 | −80.83 (13) |
P1—N2—P2—N3 | −128.98 (9) | P2—N4—Si6—C18 | −46.76 (15) |
Si3—N2—P2—N3 | 64.00 (15) | Si5—N4—Si6—C18 | 152.37 (12) |
P1—N2—P2—N4 | 108.99 (9) | P2—N4—Si6—C16 | −159.94 (12) |
Si3—N2—P2—N4 | −58.03 (14) | Si5—N4—Si6—C16 | 39.19 (14) |
P1—N2—P2—Pd1 | −6.30 (7) | C21A—O1A—C20A—C19A | −177.5 (4) |
Si3—N2—P2—Pd1 | −173.32 (11) | C20A—O1A—C21A—C22A | 175.5 (4) |
Si3—N2—P2—P1 | −167.02 (18) | C21B—O1B—C20B—C19B | 178.5 (15) |
P1—N1—Si1—C2 | −100.16 (14) | C20B—O1B—C21B—C22B | −98.0 (17) |
Si2—N1—Si1—C2 | 99.74 (14) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3C···Cl1i | 0.98 | 2.72 | 3.564 (3) | 144 |
C14—H14C···Cl2 | 0.98 | 2.67 | 3.585 (2) | 156 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Acknowledgements
The publication of this article was funded by the Open Access Fund of the Leibniz Association.
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