Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807058291/lh2561sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807058291/lh2561Isup2.hkl |
CCDC reference: 672707
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.003 Å
- Disorder in solvent or counterion
- R factor = 0.026
- wR factor = 0.058
- Data-to-parameter ratio = 25.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 40.00 Perc.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 4
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Crystals of (dcpm)PdCl2 (dcpm = bis(dicyclohexylphosphino)methane) were obtained from a methylene chloride/diethyl ether solution of (dcpm)PdC2O4 which was exposed to fluorescent lighting for seven days in an attempt to crystallize the latter. The 31P{1H} NMR spectrum of the material remaining after selection of the crystal for x-ray diffraction exhibits a single resonance at -33.3 p.p.m. and no visible carbonyl resonance in the 13C{1H} NMR spectrum.The same -33.3 p.p.m. resonance is observed after treatment of an authentic sample of (dcpm)PdC2O4 with HCl suggesting that the prolonged exposure of (dcpm)PdC2O4 to the chlorinated solvent and light generated sufficient HCl to convert the (dcpm)PdC2O4 to (dcpm)PdCl2. Additional evidence for this proposal comes from the observation of a small peak at -33.3 p.p.m. in the 31P{1H} NMR spectrum of the product initially obtained in the synthesis of (dcpm)PdC2O4 by ligand displacement from (tmeda)PdC2O4 (tmeda = N,N',N",N"'-tetramethylethylenediamine) with dcpm in methylene chloride with stirring over three days. 1H NMR (CD2Cl2): δ 1.2–2.4 (m, 44 H, Cy), 2.85 (t, JPH = 10 Hz, 2 H, PCH2P). 31P{1H} NMR (CD2Cl2): δ -33.3. 13C{1H} NMR (CD2Cl2): δ 19.37 (t, JPC = 21 Hz, PCH2P), 26.18 (s, Cy), 27.13 (t, JPC = 6 Hz Cy), 27.42 (t, JPC = 7 Hz Cy), 28.70 (s, Cy), 29.52 (s, Cy), 35.94 (t, JPC = 10 Hz, –CHP–).
H-atoms were placed in calculated positions (C—H = 0.99 - 1.00 Å) and included as riding contributions with isotropic displacement parameters 1.2 times those of the attached carbon atoms. The solvent dichloromethane molecule is disordered over two sites having one chlorine (Cl3) in common in a 5755 (15):4245 (15) ratio of refined occupancies. Refinement was completed with the disordered model constrained to have C—Cl distances of 1.72 (1) Å.
Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: APEX2 (Bruker, 2007); software used to prepare material for publication: APEX2 (Bruker, 2007).
Fig. 1. The molecular structure with displacement ellipsoids drawn at the 50% probability level and H-atoms are represented by spheres of arbitrary radius. The dichloromethane solvent is not shown. |
[PdCl2(C25H46P2)]·CH2Cl2 | F(000) = 1392.1 |
Mr = 670.78 | Dx = 1.438 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 9765 reflections |
a = 10.6978 (4) Å | θ = 2.3–29.3° |
b = 20.2154 (7) Å | µ = 1.06 mm−1 |
c = 15.0333 (5) Å | T = 100 K |
β = 107.641 (1)° | Block, colourless |
V = 3098.2 (2) Å3 | 0.19 × 0.15 × 0.11 mm |
Z = 4 |
Bruker SMART APEX CCD area-detector diffractometer | 7832 independent reflections |
Radiation source: fine-focus sealed tube | 6992 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ϕ and ω scans | θmax = 28.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | h = −14→14 |
Tmin = 0.803, Tmax = 0.894 | k = −27→27 |
54228 measured reflections | l = −19→20 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.058 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0171P)2 + 3.7026P] where P = (Fo2 + 2Fc2)/3 |
7832 reflections | (Δ/σ)max = 0.001 |
305 parameters | Δρmax = 1.11 e Å−3 |
4 restraints | Δρmin = −1.05 e Å−3 |
[PdCl2(C25H46P2)]·CH2Cl2 | V = 3098.2 (2) Å3 |
Mr = 670.78 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.6978 (4) Å | µ = 1.06 mm−1 |
b = 20.2154 (7) Å | T = 100 K |
c = 15.0333 (5) Å | 0.19 × 0.15 × 0.11 mm |
β = 107.641 (1)° |
Bruker SMART APEX CCD area-detector diffractometer | 7832 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | 6992 reflections with I > 2σ(I) |
Tmin = 0.803, Tmax = 0.894 | Rint = 0.033 |
54228 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 4 restraints |
wR(F2) = 0.058 | H-atom parameters constrained |
S = 1.04 | Δρmax = 1.11 e Å−3 |
7832 reflections | Δρmin = −1.05 e Å−3 |
305 parameters |
Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5 °. in omega, colllected at phi = 0.00, 90.00 and 180.00 °. and 2 sets of 800 frames, each of width 0.45 ° in phi, collected at omega = -30.00 and 210.00 °. The scan time was 10 sec/frame. |
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. H-atoms were placed in calculated positions (C—H = 0.99 - 1.00 Å) and included as riding contributions with isotropic displacement parameters 1.2 times those of the attached carbon atoms. The solvent dichloromethane molecule is disordered over two sites having one chlorine (Cl3) in common in a 58:42 ratio. Refinement was completed with the disordered model constrained to have C—Cl distances of 1.72 (1) Å. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Pd1 | 0.448118 (12) | 0.231722 (6) | 0.766483 (9) | 0.01362 (4) | |
Cl1 | 0.28057 (4) | 0.23668 (2) | 0.62016 (3) | 0.01973 (9) | |
Cl2 | 0.60824 (4) | 0.18028 (2) | 0.70938 (3) | 0.02113 (9) | |
P1 | 0.32599 (4) | 0.28077 (2) | 0.84313 (3) | 0.01365 (8) | |
P2 | 0.57527 (4) | 0.24148 (2) | 0.91426 (3) | 0.01433 (9) | |
C1 | 0.19916 (16) | 0.23196 (8) | 0.87199 (12) | 0.0150 (3) | |
H1 | 0.1687 | 0.2579 | 0.9182 | 0.018* | |
C2 | 0.25493 (17) | 0.16610 (9) | 0.91832 (13) | 0.0183 (3) | |
H2A | 0.2875 | 0.1396 | 0.8746 | 0.022* | |
H2B | 0.3298 | 0.1749 | 0.9747 | 0.022* | |
C3 | 0.14985 (19) | 0.12702 (9) | 0.94548 (13) | 0.0224 (4) | |
H3A | 0.1868 | 0.0842 | 0.9731 | 0.027* | |
H3B | 0.1226 | 0.1520 | 0.9932 | 0.027* | |
C4 | 0.03056 (19) | 0.11457 (10) | 0.86100 (14) | 0.0247 (4) | |
H4A | −0.0379 | 0.0914 | 0.8811 | 0.030* | |
H4B | 0.0558 | 0.0858 | 0.8159 | 0.030* | |
C5 | −0.02433 (18) | 0.17960 (10) | 0.81380 (14) | 0.0232 (4) | |
H5A | −0.0584 | 0.2061 | 0.8568 | 0.028* | |
H5B | −0.0985 | 0.1702 | 0.7572 | 0.028* | |
C6 | 0.07970 (17) | 0.21976 (10) | 0.78645 (13) | 0.0203 (4) | |
H6A | 0.0420 | 0.2627 | 0.7595 | 0.024* | |
H6B | 0.1073 | 0.1955 | 0.7384 | 0.024* | |
C7 | 0.25300 (17) | 0.35974 (9) | 0.79393 (12) | 0.0175 (3) | |
H7 | 0.1803 | 0.3496 | 0.7358 | 0.021* | |
C8 | 0.35254 (19) | 0.40298 (10) | 0.76581 (14) | 0.0237 (4) | |
H8A | 0.3830 | 0.3795 | 0.7184 | 0.028* | |
H8B | 0.4296 | 0.4109 | 0.8211 | 0.028* | |
C9 | 0.2918 (2) | 0.46947 (10) | 0.72597 (15) | 0.0300 (4) | |
H9A | 0.3599 | 0.4975 | 0.7126 | 0.036* | |
H9B | 0.2217 | 0.4618 | 0.6665 | 0.036* | |
C10 | 0.2346 (2) | 0.50554 (10) | 0.79358 (15) | 0.0291 (4) | |
H10A | 0.1930 | 0.5472 | 0.7647 | 0.035* | |
H10B | 0.3059 | 0.5169 | 0.8510 | 0.035* | |
C11 | 0.1332 (2) | 0.46278 (10) | 0.81885 (16) | 0.0293 (4) | |
H11A | 0.0582 | 0.4547 | 0.7623 | 0.035* | |
H11B | 0.1000 | 0.4865 | 0.8647 | 0.035* | |
C12 | 0.19240 (19) | 0.39641 (9) | 0.86022 (14) | 0.0222 (4) | |
H12A | 0.1231 | 0.3686 | 0.8723 | 0.027* | |
H12B | 0.2608 | 0.4042 | 0.9205 | 0.027* | |
C13 | 0.45996 (16) | 0.29384 (8) | 0.95274 (11) | 0.0147 (3) | |
H13A | 0.4399 | 0.2761 | 1.0083 | 0.018* | |
H13B | 0.4883 | 0.3406 | 0.9629 | 0.018* | |
C14 | 0.60524 (17) | 0.16181 (9) | 0.97685 (12) | 0.0168 (3) | |
H14 | 0.5288 | 0.1331 | 0.9448 | 0.020* | |
C15 | 0.7263 (2) | 0.12752 (9) | 0.96282 (13) | 0.0231 (4) | |
H15A | 0.7189 | 0.1268 | 0.8956 | 0.028* | |
H15B | 0.8064 | 0.1526 | 0.9960 | 0.028* | |
C16 | 0.7371 (2) | 0.05674 (10) | 1.00019 (14) | 0.0300 (5) | |
H16A | 0.8185 | 0.0363 | 0.9947 | 0.036* | |
H16B | 0.6619 | 0.0305 | 0.9619 | 0.036* | |
C17 | 0.7388 (2) | 0.05499 (11) | 1.10233 (14) | 0.0320 (5) | |
H17A | 0.7388 | 0.0084 | 1.1227 | 0.038* | |
H17B | 0.8201 | 0.0762 | 1.1418 | 0.038* | |
C18 | 0.6198 (2) | 0.09083 (9) | 1.11558 (13) | 0.0243 (4) | |
H18A | 0.6259 | 0.0907 | 1.1826 | 0.029* | |
H18B | 0.5389 | 0.0669 | 1.0811 | 0.029* | |
C19 | 0.61176 (19) | 0.16234 (9) | 1.08058 (12) | 0.0195 (4) | |
H19A | 0.6898 | 0.1874 | 1.1174 | 0.023* | |
H19B | 0.5327 | 0.1841 | 1.0881 | 0.023* | |
C20 | 0.73094 (17) | 0.28521 (9) | 0.93334 (12) | 0.0173 (3) | |
H20 | 0.7951 | 0.2521 | 0.9237 | 0.021* | |
C21 | 0.71984 (19) | 0.33969 (10) | 0.86050 (13) | 0.0220 (4) | |
H21A | 0.6856 | 0.3207 | 0.7970 | 0.026* | |
H21B | 0.6576 | 0.3740 | 0.8676 | 0.026* | |
C22 | 0.8540 (2) | 0.37096 (10) | 0.87262 (14) | 0.0259 (4) | |
H22A | 0.8448 | 0.4071 | 0.8267 | 0.031* | |
H22B | 0.9139 | 0.3373 | 0.8603 | 0.031* | |
C23 | 0.91271 (19) | 0.39850 (10) | 0.97123 (14) | 0.0250 (4) | |
H23A | 1.0013 | 0.4164 | 0.9780 | 0.030* | |
H23B | 0.8573 | 0.4353 | 0.9813 | 0.030* | |
C24 | 0.92213 (19) | 0.34531 (11) | 1.04445 (14) | 0.0281 (4) | |
H24A | 0.9543 | 0.3654 | 1.1074 | 0.034* | |
H24B | 0.9864 | 0.3114 | 1.0394 | 0.034* | |
C25 | 0.78904 (19) | 0.31208 (11) | 1.03284 (13) | 0.0251 (4) | |
H25A | 0.8004 | 0.2753 | 1.0781 | 0.030* | |
H25B | 0.7278 | 0.3446 | 1.0461 | 0.030* | |
Cl3 | 0.39612 (6) | 0.01216 (3) | 0.56653 (4) | 0.03819 (13) | |
C26 | 0.3451 (16) | 0.0691 (4) | 0.6368 (9) | 0.0492 (10) | 0.5755 (15) |
H26A | 0.4232 | 0.0816 | 0.6890 | 0.059* | 0.5755 (15) |
H26B | 0.3149 | 0.1095 | 0.5992 | 0.059* | 0.5755 (15) |
Cl4 | 0.22199 (18) | 0.04556 (6) | 0.68461 (10) | 0.0584 (3) | 0.5755 (15) |
C26A | 0.350 (2) | 0.0762 (5) | 0.6273 (12) | 0.0492 (10) | 0.4245 (15) |
H26C | 0.4206 | 0.1097 | 0.6459 | 0.059* | 0.4245 (15) |
H26D | 0.2695 | 0.0979 | 0.5873 | 0.059* | 0.4245 (15) |
Cl4A | 0.3214 (3) | 0.04277 (8) | 0.72482 (14) | 0.0584 (3) | 0.4245 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.01279 (6) | 0.01723 (7) | 0.01114 (6) | 0.00052 (5) | 0.00407 (5) | 0.00010 (4) |
Cl1 | 0.0177 (2) | 0.0280 (2) | 0.01247 (18) | 0.00222 (16) | 0.00295 (15) | 0.00058 (15) |
Cl2 | 0.0178 (2) | 0.0288 (2) | 0.0184 (2) | 0.00419 (16) | 0.00797 (16) | −0.00154 (16) |
P1 | 0.0119 (2) | 0.0162 (2) | 0.01268 (19) | 0.00027 (15) | 0.00344 (16) | 0.00006 (15) |
P2 | 0.0127 (2) | 0.0175 (2) | 0.01261 (19) | 0.00122 (16) | 0.00358 (16) | 0.00073 (15) |
C1 | 0.0129 (8) | 0.0169 (8) | 0.0163 (8) | −0.0011 (6) | 0.0059 (6) | −0.0009 (6) |
C2 | 0.0169 (8) | 0.0174 (8) | 0.0208 (9) | −0.0003 (6) | 0.0058 (7) | 0.0001 (6) |
C3 | 0.0238 (9) | 0.0188 (9) | 0.0259 (10) | −0.0035 (7) | 0.0093 (8) | −0.0001 (7) |
C4 | 0.0233 (10) | 0.0229 (9) | 0.0302 (10) | −0.0073 (7) | 0.0117 (8) | −0.0055 (8) |
C5 | 0.0136 (8) | 0.0283 (10) | 0.0276 (10) | −0.0037 (7) | 0.0060 (7) | −0.0033 (8) |
C6 | 0.0151 (8) | 0.0260 (9) | 0.0185 (9) | −0.0020 (7) | 0.0032 (7) | −0.0010 (7) |
C7 | 0.0155 (8) | 0.0176 (8) | 0.0177 (8) | 0.0011 (6) | 0.0024 (7) | 0.0023 (6) |
C8 | 0.0232 (10) | 0.0227 (9) | 0.0268 (10) | 0.0001 (7) | 0.0099 (8) | 0.0062 (7) |
C9 | 0.0315 (11) | 0.0263 (10) | 0.0304 (11) | −0.0001 (8) | 0.0066 (9) | 0.0112 (8) |
C10 | 0.0264 (10) | 0.0190 (9) | 0.0371 (11) | 0.0027 (8) | 0.0025 (9) | 0.0082 (8) |
C11 | 0.0220 (10) | 0.0201 (9) | 0.0449 (13) | 0.0049 (7) | 0.0087 (9) | 0.0034 (8) |
C12 | 0.0192 (9) | 0.0196 (9) | 0.0300 (10) | 0.0019 (7) | 0.0107 (8) | 0.0015 (7) |
C13 | 0.0129 (8) | 0.0157 (8) | 0.0151 (8) | 0.0006 (6) | 0.0039 (6) | −0.0014 (6) |
C14 | 0.0174 (8) | 0.0173 (8) | 0.0156 (8) | 0.0023 (6) | 0.0047 (7) | 0.0021 (6) |
C15 | 0.0274 (10) | 0.0239 (9) | 0.0205 (9) | 0.0095 (7) | 0.0109 (8) | 0.0041 (7) |
C16 | 0.0436 (13) | 0.0243 (10) | 0.0266 (10) | 0.0147 (9) | 0.0172 (9) | 0.0045 (8) |
C17 | 0.0474 (13) | 0.0262 (10) | 0.0242 (10) | 0.0160 (9) | 0.0137 (9) | 0.0083 (8) |
C18 | 0.0362 (11) | 0.0212 (9) | 0.0174 (9) | 0.0039 (8) | 0.0109 (8) | 0.0021 (7) |
C19 | 0.0226 (9) | 0.0205 (9) | 0.0160 (8) | 0.0032 (7) | 0.0070 (7) | 0.0009 (6) |
C20 | 0.0119 (8) | 0.0218 (9) | 0.0184 (8) | 0.0009 (6) | 0.0048 (7) | 0.0016 (6) |
C21 | 0.0213 (9) | 0.0251 (9) | 0.0177 (9) | −0.0048 (7) | 0.0034 (7) | 0.0022 (7) |
C22 | 0.0259 (10) | 0.0312 (11) | 0.0226 (9) | −0.0083 (8) | 0.0104 (8) | 0.0006 (8) |
C23 | 0.0187 (9) | 0.0304 (10) | 0.0243 (10) | −0.0052 (8) | 0.0042 (8) | 0.0015 (8) |
C24 | 0.0172 (9) | 0.0378 (12) | 0.0246 (10) | −0.0061 (8) | −0.0007 (8) | 0.0042 (8) |
C25 | 0.0200 (9) | 0.0364 (11) | 0.0161 (9) | −0.0070 (8) | 0.0015 (7) | 0.0035 (8) |
Cl3 | 0.0340 (3) | 0.0310 (3) | 0.0464 (3) | 0.0093 (2) | 0.0075 (2) | 0.0033 (2) |
C26 | 0.053 (2) | 0.0254 (19) | 0.078 (3) | −0.0104 (18) | 0.0321 (18) | −0.0084 (19) |
Cl4 | 0.1019 (10) | 0.0379 (4) | 0.0566 (7) | −0.0043 (7) | 0.0557 (7) | 0.0007 (5) |
C26A | 0.053 (2) | 0.0254 (19) | 0.078 (3) | −0.0104 (18) | 0.0321 (18) | −0.0084 (19) |
Cl4A | 0.1019 (10) | 0.0379 (4) | 0.0566 (7) | −0.0043 (7) | 0.0557 (7) | 0.0007 (5) |
Pd1—P1 | 2.2205 (4) | C13—H13A | 0.9900 |
Pd1—P2 | 2.2345 (5) | C13—H13B | 0.9900 |
Pd1—Cl2 | 2.3756 (4) | C14—C15 | 1.539 (2) |
Pd1—Cl1 | 2.3815 (4) | C14—C19 | 1.540 (2) |
P1—C7 | 1.8316 (18) | C14—H14 | 1.0000 |
P1—C1 | 1.8330 (17) | C15—C16 | 1.529 (3) |
P1—C13 | 1.8459 (17) | C15—H15A | 0.9900 |
P2—C20 | 1.8297 (18) | C15—H15B | 0.9900 |
P2—C14 | 1.8435 (18) | C16—C17 | 1.531 (3) |
P2—C13 | 1.8464 (17) | C16—H16A | 0.9900 |
C1—C6 | 1.534 (2) | C16—H16B | 0.9900 |
C1—C2 | 1.537 (2) | C17—C18 | 1.529 (3) |
C1—H1 | 1.0000 | C17—H17A | 0.9900 |
C2—C3 | 1.527 (2) | C17—H17B | 0.9900 |
C2—H2A | 0.9900 | C18—C19 | 1.532 (3) |
C2—H2B | 0.9900 | C18—H18A | 0.9900 |
C3—C4 | 1.524 (3) | C18—H18B | 0.9900 |
C3—H3A | 0.9900 | C19—H19A | 0.9900 |
C3—H3B | 0.9900 | C19—H19B | 0.9900 |
C4—C5 | 1.525 (3) | C20—C21 | 1.532 (2) |
C4—H4A | 0.9900 | C20—C25 | 1.535 (3) |
C4—H4B | 0.9900 | C20—H20 | 1.0000 |
C5—C6 | 1.531 (3) | C21—C22 | 1.527 (3) |
C5—H5A | 0.9900 | C21—H21A | 0.9900 |
C5—H5B | 0.9900 | C21—H21B | 0.9900 |
C6—H6A | 0.9900 | C22—C23 | 1.529 (3) |
C6—H6B | 0.9900 | C22—H22A | 0.9900 |
C7—C8 | 1.533 (2) | C22—H22B | 0.9900 |
C7—C12 | 1.535 (3) | C23—C24 | 1.520 (3) |
C7—H7 | 1.0000 | C23—H23A | 0.9900 |
C8—C9 | 1.533 (3) | C23—H23B | 0.9900 |
C8—H8A | 0.9900 | C24—C25 | 1.536 (3) |
C8—H8B | 0.9900 | C24—H24A | 0.9900 |
C9—C10 | 1.522 (3) | C24—H24B | 0.9900 |
C9—H9A | 0.9900 | C25—H25A | 0.9900 |
C9—H9B | 0.9900 | C25—H25B | 0.9900 |
C10—C11 | 1.523 (3) | Cl3—C26A | 1.740 (9) |
C10—H10A | 0.9900 | Cl3—C26 | 1.757 (6) |
C10—H10B | 0.9900 | C26—Cl4 | 1.747 (9) |
C11—C12 | 1.533 (3) | C26—H26A | 0.9900 |
C11—H11A | 0.9900 | C26—H26B | 0.9900 |
C11—H11B | 0.9900 | C26A—Cl4A | 1.724 (9) |
C12—H12A | 0.9900 | C26A—H26C | 0.9900 |
C12—H12B | 0.9900 | C26A—H26D | 0.9900 |
P1—Pd1—P2 | 73.816 (16) | P1—C13—P2 | 92.87 (8) |
P1—Pd1—Cl2 | 170.092 (17) | P1—C13—H13A | 113.1 |
P2—Pd1—Cl2 | 96.291 (16) | P2—C13—H13A | 113.1 |
P1—Pd1—Cl1 | 93.670 (16) | P1—C13—H13B | 113.1 |
P2—Pd1—Cl1 | 167.313 (16) | P2—C13—H13B | 113.1 |
Cl2—Pd1—Cl1 | 96.195 (16) | H13A—C13—H13B | 110.5 |
C7—P1—C1 | 108.02 (8) | C15—C14—C19 | 111.11 (14) |
C7—P1—C13 | 110.87 (8) | C15—C14—P2 | 110.30 (12) |
C1—P1—C13 | 107.22 (8) | C19—C14—P2 | 117.28 (12) |
C7—P1—Pd1 | 115.18 (6) | C15—C14—H14 | 105.8 |
C1—P1—Pd1 | 118.46 (6) | C19—C14—H14 | 105.8 |
C13—P1—Pd1 | 96.16 (5) | P2—C14—H14 | 105.8 |
C20—P2—C14 | 109.44 (8) | C16—C15—C14 | 110.13 (16) |
C20—P2—C13 | 109.67 (8) | C16—C15—H15A | 109.6 |
C14—P2—C13 | 111.74 (8) | C14—C15—H15A | 109.6 |
C20—P2—Pd1 | 116.70 (6) | C16—C15—H15B | 109.6 |
C14—P2—Pd1 | 112.93 (6) | C14—C15—H15B | 109.6 |
C13—P2—Pd1 | 95.67 (5) | H15A—C15—H15B | 108.1 |
C6—C1—C2 | 110.56 (14) | C15—C16—C17 | 111.53 (17) |
C6—C1—P1 | 112.12 (12) | C15—C16—H16A | 109.3 |
C2—C1—P1 | 111.10 (12) | C17—C16—H16A | 109.3 |
C6—C1—H1 | 107.6 | C15—C16—H16B | 109.3 |
C2—C1—H1 | 107.6 | C17—C16—H16B | 109.3 |
P1—C1—H1 | 107.6 | H16A—C16—H16B | 108.0 |
C3—C2—C1 | 110.67 (15) | C18—C17—C16 | 111.26 (17) |
C3—C2—H2A | 109.5 | C18—C17—H17A | 109.4 |
C1—C2—H2A | 109.5 | C16—C17—H17A | 109.4 |
C3—C2—H2B | 109.5 | C18—C17—H17B | 109.4 |
C1—C2—H2B | 109.5 | C16—C17—H17B | 109.4 |
H2A—C2—H2B | 108.1 | H17A—C17—H17B | 108.0 |
C4—C3—C2 | 111.16 (16) | C17—C18—C19 | 111.40 (17) |
C4—C3—H3A | 109.4 | C17—C18—H18A | 109.3 |
C2—C3—H3A | 109.4 | C19—C18—H18A | 109.3 |
C4—C3—H3B | 109.4 | C17—C18—H18B | 109.3 |
C2—C3—H3B | 109.4 | C19—C18—H18B | 109.3 |
H3A—C3—H3B | 108.0 | H18A—C18—H18B | 108.0 |
C3—C4—C5 | 110.65 (16) | C18—C19—C14 | 108.78 (15) |
C3—C4—H4A | 109.5 | C18—C19—H19A | 109.9 |
C5—C4—H4A | 109.5 | C14—C19—H19A | 109.9 |
C3—C4—H4B | 109.5 | C18—C19—H19B | 109.9 |
C5—C4—H4B | 109.5 | C14—C19—H19B | 109.9 |
H4A—C4—H4B | 108.1 | H19A—C19—H19B | 108.3 |
C4—C5—C6 | 111.93 (15) | C21—C20—C25 | 111.28 (15) |
C4—C5—H5A | 109.2 | C21—C20—P2 | 111.44 (12) |
C6—C5—H5A | 109.2 | C25—C20—P2 | 113.85 (12) |
C4—C5—H5B | 109.2 | C21—C20—H20 | 106.6 |
C6—C5—H5B | 109.2 | C25—C20—H20 | 106.6 |
H5A—C5—H5B | 107.9 | P2—C20—H20 | 106.6 |
C5—C6—C1 | 110.42 (15) | C22—C21—C20 | 110.22 (15) |
C5—C6—H6A | 109.6 | C22—C21—H21A | 109.6 |
C1—C6—H6A | 109.6 | C20—C21—H21A | 109.6 |
C5—C6—H6B | 109.6 | C22—C21—H21B | 109.6 |
C1—C6—H6B | 109.6 | C20—C21—H21B | 109.6 |
H6A—C6—H6B | 108.1 | H21A—C21—H21B | 108.1 |
C8—C7—C12 | 111.66 (15) | C21—C22—C23 | 111.20 (16) |
C8—C7—P1 | 111.21 (12) | C21—C22—H22A | 109.4 |
C12—C7—P1 | 111.78 (12) | C23—C22—H22A | 109.4 |
C8—C7—H7 | 107.3 | C21—C22—H22B | 109.4 |
C12—C7—H7 | 107.3 | C23—C22—H22B | 109.4 |
P1—C7—H7 | 107.3 | H22A—C22—H22B | 108.0 |
C7—C8—C9 | 111.12 (16) | C24—C23—C22 | 111.22 (17) |
C7—C8—H8A | 109.4 | C24—C23—H23A | 109.4 |
C9—C8—H8A | 109.4 | C22—C23—H23A | 109.4 |
C7—C8—H8B | 109.4 | C24—C23—H23B | 109.4 |
C9—C8—H8B | 109.4 | C22—C23—H23B | 109.4 |
H8A—C8—H8B | 108.0 | H23A—C23—H23B | 108.0 |
C10—C9—C8 | 111.56 (17) | C23—C24—C25 | 111.80 (16) |
C10—C9—H9A | 109.3 | C23—C24—H24A | 109.3 |
C8—C9—H9A | 109.3 | C25—C24—H24A | 109.3 |
C10—C9—H9B | 109.3 | C23—C24—H24B | 109.3 |
C8—C9—H9B | 109.3 | C25—C24—H24B | 109.3 |
H9A—C9—H9B | 108.0 | H24A—C24—H24B | 107.9 |
C9—C10—C11 | 110.84 (18) | C20—C25—C24 | 110.69 (16) |
C9—C10—H10A | 109.5 | C20—C25—H25A | 109.5 |
C11—C10—H10A | 109.5 | C24—C25—H25A | 109.5 |
C9—C10—H10B | 109.5 | C20—C25—H25B | 109.5 |
C11—C10—H10B | 109.5 | C24—C25—H25B | 109.5 |
H10A—C10—H10B | 108.1 | H25A—C25—H25B | 108.1 |
C10—C11—C12 | 111.10 (16) | Cl4—C26—Cl3 | 118.6 (6) |
C10—C11—H11A | 109.4 | Cl4—C26—H26A | 107.7 |
C12—C11—H11A | 109.4 | Cl3—C26—H26A | 107.7 |
C10—C11—H11B | 109.4 | Cl4—C26—H26B | 107.7 |
C12—C11—H11B | 109.4 | Cl3—C26—H26B | 107.7 |
H11A—C11—H11B | 108.0 | H26A—C26—H26B | 107.1 |
C11—C12—C7 | 111.31 (16) | Cl4A—C26A—Cl3 | 107.8 (6) |
C11—C12—H12A | 109.4 | Cl4A—C26A—H26C | 110.1 |
C7—C12—H12A | 109.4 | Cl3—C26A—H26C | 110.1 |
C11—C12—H12B | 109.4 | Cl4A—C26A—H26D | 110.1 |
C7—C12—H12B | 109.4 | Cl3—C26A—H26D | 110.1 |
H12A—C12—H12B | 108.0 | H26C—C26A—H26D | 108.5 |
Experimental details
Crystal data | |
Chemical formula | [PdCl2(C25H46P2)]·CH2Cl2 |
Mr | 670.78 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 10.6978 (4), 20.2154 (7), 15.0333 (5) |
β (°) | 107.641 (1) |
V (Å3) | 3098.2 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.06 |
Crystal size (mm) | 0.19 × 0.15 × 0.11 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2007) |
Tmin, Tmax | 0.803, 0.894 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 54228, 7832, 6992 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.671 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.058, 1.04 |
No. of reflections | 7832 |
No. of parameters | 305 |
No. of restraints | 4 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.11, −1.05 |
Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2006), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997).
Pd1—P1 | 2.2205 (4) | Pd1—Cl2 | 2.3756 (4) |
Pd1—P2 | 2.2345 (5) | Pd1—Cl1 | 2.3815 (4) |
P1—Pd1—P2 | 73.816 (16) | P1—Pd1—Cl1 | 93.670 (16) |
P1—Pd1—Cl2 | 170.092 (17) | P2—Pd1—Cl1 | 167.313 (16) |
P2—Pd1—Cl2 | 96.291 (16) | Cl2—Pd1—Cl1 | 96.195 (16) |
cis-Dichloro(bis(dicyclohexylphosphino)methanepalladium(II), (dcpm)PdCl2 (I), has received brief mention as an intermediate in the synthesis of (dcpm)PdI2 (Zhuravel et al., 2000) but appears not to have been fully characterized. The present sample was obtained following prolonged exposure of a dichloromethane/diethyl ether solution of oxalato(bis(dicyclohexylphosphino)methanepalladium(II) to light in an attempt to grow crystals of the latter. Complex (I) exhibits distorted square planar coordination about the metal, the major distortion being the P1—Pd1—P2 angle of 73.82 (2)° which is the consequence of the small bite angle of the dcpm ligand. Additionally there is a slight tetrahedral distortion from planarity as indicated by a dihedral angle of 2.26 (3)° between the PdP2 and PdCl2 planes. These two metrical parameters are essentially the same as seen in the only other structurally characterized palladium dcpm complex (dcpm)Pd(CH3)2 (Reid et al., 2001) where they are, respectively 73.34 and 2.69°. The Pd—P and Pd—Cl distances differ only slightly in each case and compare favorably with those in the related complexes (RCH(PPh2)2)PdCl2 (R = H (Palenik et al., 1975), CH3 (Lee et al., 1986), CN (Braun et al., 2007)).