Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046399/ng2311sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046399/ng2311Isup2.hkl |
CCDC reference: 663656
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.007 Å
- R factor = 0.039
- wR factor = 0.111
- Data-to-parameter ratio = 18.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.10 PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.84 Ratio PLAT480_ALERT_4_C Long H...A H-Bond Reported H19 .. BR3 .. 2.95 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H31 .. BR1 .. 2.99 Ang. PLAT731_ALERT_1_C Bond Calc 1.49(2), Rep 1.488(9) ...... 2.22 su-Ra O5 -C33 1.555 1.555 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 C H4 O
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 13
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 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 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Common examples of the class of Pd—P-bonded compounds represented by the title compound have phosphinate and phosphane hydroxide ligands with a hydrogen-bond interaction between the oxo and hydroxo groups; see: Gebauer et al. (1992, 1995); Pryjomska et al. (2006). [Please revise Fig. 1 with atom label numbers inline, not subscript]
The title compound was obtained unintentionally as the product of a Suzuki coupling reaction of diphenylnaphtolphosphane and bis(3,5,7-tribromotropolonato)palladium(II) in methanol (10 ml) solution. On evaporation of the solvent; crystals suitable for X-Ray crystallography was obtained.
H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 and 0.98 Å and with Uiso(H) = 1.2 times Ueq(C aromatic) and Uiso(H) = 1.2 times Ueq(C methyl). The final difference Fourier map had a large peak near Pd.
In the current paper the title compound, (I), is presented as an example of a by-product formed during the catalytic cycle. It should be noted that both a diphenylphosphanito and a diphenylmethoxyphosphane, Fig. 1, was formed from the initial starting diphenylnaphtolphosphane. In either case, the diphenylnaphtolphosphane moiety decomposed and in the one instance a Suzuki coupling occurred to form the diphenylmethoxyphosphane derivative. This product is in contrast to the more readily observed hydroxyl derivative.
The Pd—O and Pd—P bond distances only differ slightly, Table 1. This relative similarity in bond distances (Pd—P) might be due to the hydrogen bonding observed between the methanol solvate and the diphenylphosphaneoxide oxygen atom, Table 2. The P—O(Me) and P?O bond distances are significantly different indicating the bond order in which the oxygen atoms bond with the phosphorous atom.
Weak intra- and intermolecular interactions is observed in the solid state, see Table 2. The role of the bromo-atoms on the solid state arrangement can be observed from the intermolecular distances between Br3···Br7 [1 - x, 1 - y, 1 - z] and Br5···Pd [1 - x, 1 - y, 1 - z] in the order of 3.729 (1) and 3.717 (1) Å, respectively. This interaction is further enhanced through π–π stacking of the cycloheptatriene rings systems of the bromo moieties with an interplanar distance of 3.496 (8) Å and a centroid-to-centroid distance of 3.507 (1) Å. The ordering of the solid state can be observed as stacking along the a axis, see Figure 2.
Common examples of the class of Pd—P-bonded compounds represented by the title compound have phosphinate and phosphane hydroxide ligands with a hydrogen-bond interaction between the oxo and hydroxo groups; see: Gebauer et al. (1992, 1995); Pryjomska et al. (2006). [Please revise Fig. 1 with atom label numbers inline, not subscript]
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004) and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[Pd(C7H2Br3)(C12H10OP)(C13H13OP)]·CH4O | Z = 2 |
Mr = 913.63 | F(000) = 896 |
Triclinic, P1 | Dx = 1.839 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.125 (3) Å | Cell parameters from 5022 reflections |
b = 11.326 (4) Å | θ = 2.4–27.7° |
c = 17.137 (3) Å | µ = 4.33 mm−1 |
α = 87.652 (8)° | T = 100 K |
β = 78.285 (7)° | Plate, yellow |
γ = 72.121 (8)° | 0.19 × 0.14 × 0.04 mm |
V = 1650.0 (8) Å3 |
Bruker APEXII area-detector diffractometer | 7543 independent reflections |
Radiation source: fine-focus sealed tube | 6131 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
Detector resolution: 512 pixels mm-1 | θmax = 27.5°, θmin = 1.2° |
φ and ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | k = −14→14 |
Tmin = 0.493, Tmax = 0.846 | l = −22→22 |
33856 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0572P)2 + 2.8917P] where P = (Fo2 + 2Fc2)/3 |
7543 reflections | (Δ/σ)max = 0.001 |
399 parameters | Δρmax = 1.92 e Å−3 |
13 restraints | Δρmin = −0.91 e Å−3 |
[Pd(C7H2Br3)(C12H10OP)(C13H13OP)]·CH4O | γ = 72.121 (8)° |
Mr = 913.63 | V = 1650.0 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.125 (3) Å | Mo Kα radiation |
b = 11.326 (4) Å | µ = 4.33 mm−1 |
c = 17.137 (3) Å | T = 100 K |
α = 87.652 (8)° | 0.19 × 0.14 × 0.04 mm |
β = 78.285 (7)° |
Bruker APEXII area-detector diffractometer | 7543 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 6131 reflections with I > 2σ(I) |
Tmin = 0.493, Tmax = 0.846 | Rint = 0.041 |
33856 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 13 restraints |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.09 | Δρmax = 1.92 e Å−3 |
7543 reflections | Δρmin = −0.91 e Å−3 |
399 parameters |
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. The solvent molecule in the asymmetric unit were were identified from the difference Fourier map. Refinement of the MeOH moiety was done with the DFIX command to place the C and O atoms at an idealized distance from each other and the ISOR command was used to attempt to restrain the C atom within a certain range. |
x | y | z | Uiso*/Ueq | ||
Pd | 0.79443 (4) | 0.29918 (3) | 0.25916 (2) | 0.01933 (9) | |
Br1 | 0.35292 (5) | 0.69319 (4) | 0.31393 (3) | 0.02862 (12) | |
Br2 | 0.05373 (5) | 0.55669 (4) | 0.59648 (3) | 0.02661 (12) | |
Br3 | 0.57021 (5) | 0.15579 (4) | 0.51586 (3) | 0.02441 (11) | |
P1 | 0.97836 (13) | 0.11498 (10) | 0.24798 (7) | 0.0202 (2) | |
P2 | 0.92127 (13) | 0.35250 (10) | 0.14639 (7) | 0.0224 (2) | |
O1 | 0.6711 (3) | 0.2547 (3) | 0.36606 (19) | 0.0240 (6) | |
O2 | 0.6024 (3) | 0.4642 (3) | 0.29453 (18) | 0.0236 (6) | |
O3 | 1.1000 (3) | 0.0763 (3) | 0.17293 (19) | 0.0255 (7) | |
O4 | 0.8531 (4) | 0.4997 (3) | 0.1320 (2) | 0.0294 (7) | |
O5 | 1.3757 (8) | −0.1108 (7) | 0.1698 (5) | 0.109 (2) | |
H5 | 1.2994 | −0.0506 | 0.1907 | 0.164* | |
C1 | 0.5507 (5) | 0.3391 (4) | 0.4014 (3) | 0.0205 (9) | |
C2 | 0.5083 (5) | 0.4569 (4) | 0.3591 (3) | 0.0198 (8) | |
C3 | 0.3716 (5) | 0.5589 (3) | 0.3854 (3) | 0.0199 (8) | |
C4 | 0.2530 (5) | 0.5765 (4) | 0.4518 (3) | 0.0224 (9) | |
H4 | 0.1712 | 0.6531 | 0.4550 | 0.027* | |
C5 | 0.2366 (5) | 0.4976 (4) | 0.5147 (3) | 0.0216 (9) | |
C6 | 0.3344 (5) | 0.3816 (4) | 0.5269 (3) | 0.0220 (9) | |
H6 | 0.3041 | 0.3436 | 0.5753 | 0.026* | |
C7 | 0.4715 (5) | 0.3140 (4) | 0.4769 (3) | 0.0196 (8) | |
C8 | 0.8745 (5) | −0.0001 (4) | 0.2719 (3) | 0.0228 (9) | |
C9 | 0.9531 (5) | −0.1131 (4) | 0.2999 (3) | 0.0257 (9) | |
H9 | 1.0514 | −0.1237 | 0.3145 | 0.031* | |
C10 | 0.8907 (6) | −0.2109 (4) | 0.3071 (3) | 0.0292 (10) | |
H10 | 0.9466 | −0.2885 | 0.3258 | 0.035* | |
C11 | 0.7459 (6) | −0.1955 (5) | 0.2870 (3) | 0.0329 (11) | |
H11 | 0.7038 | −0.2630 | 0.2905 | 0.039* | |
C12 | 0.6649 (6) | −0.0832 (5) | 0.2620 (3) | 0.0367 (12) | |
H12 | 0.5641 | −0.0717 | 0.2502 | 0.044* | |
C13 | 0.7280 (5) | 0.0145 (5) | 0.2537 (3) | 0.0321 (11) | |
H13 | 0.6709 | 0.0920 | 0.2354 | 0.038* | |
C14 | 1.0716 (5) | 0.1175 (4) | 0.3310 (3) | 0.0222 (9) | |
C15 | 1.2223 (5) | 0.1309 (4) | 0.3165 (3) | 0.0254 (9) | |
H15 | 1.2759 | 0.1347 | 0.2632 | 0.030* | |
C16 | 1.2936 (5) | 0.1386 (4) | 0.3793 (3) | 0.0286 (10) | |
H16 | 1.3966 | 0.1461 | 0.3691 | 0.034* | |
C17 | 1.2151 (5) | 0.1353 (4) | 0.4570 (3) | 0.0261 (10) | |
H17 | 1.2636 | 0.1415 | 0.5001 | 0.031* | |
C18 | 1.0648 (5) | 0.1230 (4) | 0.4721 (3) | 0.0256 (9) | |
H18 | 1.0110 | 0.1205 | 0.5255 | 0.031* | |
C19 | 0.9936 (5) | 0.1143 (4) | 0.4091 (3) | 0.0228 (9) | |
H19 | 0.8909 | 0.1061 | 0.4196 | 0.027* | |
C20 | 0.6949 (6) | 0.5537 (5) | 0.1206 (3) | 0.0340 (11) | |
H20A | 0.6740 | 0.6432 | 0.1132 | 0.051* | |
H20B | 0.6214 | 0.5392 | 0.1675 | 0.051* | |
H20C | 0.6811 | 0.5157 | 0.0734 | 0.051* | |
C21 | 0.9153 (5) | 0.2799 (4) | 0.0560 (3) | 0.0267 (10) | |
C22 | 0.8548 (6) | 0.1815 (4) | 0.0572 (3) | 0.0305 (10) | |
H22 | 0.8160 | 0.1496 | 0.1065 | 0.037* | |
C23 | 0.8513 (7) | 0.1303 (5) | −0.0138 (3) | 0.0376 (12) | |
H23 | 0.8115 | 0.0620 | −0.0133 | 0.045* | |
C24 | 0.9044 (8) | 0.1771 (5) | −0.0842 (3) | 0.0484 (15) | |
H24 | 0.8996 | 0.1421 | −0.1327 | 0.058* | |
C25 | 0.9657 (8) | 0.2754 (5) | −0.0864 (3) | 0.0516 (16) | |
H25 | 1.0032 | 0.3074 | −0.1360 | 0.062* | |
C26 | 0.9716 (7) | 0.3266 (5) | −0.0155 (3) | 0.0404 (13) | |
H26 | 1.0142 | 0.3934 | −0.0161 | 0.048* | |
C27 | 1.1224 (5) | 0.3462 (4) | 0.1445 (3) | 0.0290 (10) | |
C28 | 1.2481 (6) | 0.2606 (5) | 0.0974 (4) | 0.0435 (14) | |
H28 | 1.2306 | 0.2047 | 0.0631 | 0.052* | |
C29 | 1.4008 (6) | 0.2571 (6) | 0.1008 (4) | 0.0552 (17) | |
H29 | 1.4879 | 0.1987 | 0.0686 | 0.066* | |
C30 | 1.4252 (7) | 0.3370 (6) | 0.1501 (4) | 0.0560 (17) | |
H30 | 1.5297 | 0.3339 | 0.1518 | 0.067* | |
C31 | 1.3020 (7) | 0.4221 (6) | 0.1976 (4) | 0.0453 (14) | |
H31 | 1.3212 | 0.4774 | 0.2317 | 0.054* | |
C32 | 1.1494 (6) | 0.4265 (5) | 0.1954 (3) | 0.0328 (11) | |
H32 | 1.0633 | 0.4843 | 0.2286 | 0.039* | |
C33 | 1.460 (3) | −0.071 (2) | 0.0948 (10) | 0.289 (12) | |
H33A | 1.4047 | 0.0150 | 0.0844 | 0.434* | |
H33B | 1.4650 | −0.1249 | 0.0504 | 0.434* | |
H33C | 1.5675 | −0.0775 | 0.1002 | 0.434* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd | 0.01660 (16) | 0.01855 (16) | 0.02193 (18) | −0.00428 (12) | −0.00401 (13) | 0.00306 (12) |
Br1 | 0.0284 (2) | 0.0192 (2) | 0.0348 (3) | −0.00220 (17) | −0.0076 (2) | 0.00673 (18) |
Br2 | 0.0233 (2) | 0.0228 (2) | 0.0304 (3) | −0.00586 (17) | 0.00139 (18) | −0.00407 (17) |
Br3 | 0.0233 (2) | 0.0216 (2) | 0.0265 (2) | −0.00448 (16) | −0.00538 (18) | 0.00626 (17) |
P1 | 0.0175 (5) | 0.0191 (5) | 0.0250 (6) | −0.0055 (4) | −0.0072 (4) | 0.0017 (4) |
P2 | 0.0193 (5) | 0.0220 (5) | 0.0258 (6) | −0.0083 (4) | −0.0019 (5) | 0.0016 (4) |
O1 | 0.0190 (15) | 0.0222 (15) | 0.0245 (16) | −0.0007 (12) | 0.0000 (12) | 0.0047 (12) |
O2 | 0.0202 (15) | 0.0210 (14) | 0.0268 (17) | −0.0029 (12) | −0.0046 (13) | 0.0053 (12) |
O3 | 0.0226 (16) | 0.0240 (15) | 0.0305 (18) | −0.0069 (12) | −0.0067 (13) | −0.0017 (13) |
O4 | 0.0295 (17) | 0.0222 (15) | 0.0352 (19) | −0.0089 (13) | −0.0025 (15) | 0.0026 (13) |
O5 | 0.082 (4) | 0.099 (5) | 0.135 (6) | −0.005 (3) | −0.031 (4) | 0.008 (4) |
C1 | 0.019 (2) | 0.0187 (19) | 0.026 (2) | −0.0058 (16) | −0.0092 (17) | 0.0024 (16) |
C2 | 0.018 (2) | 0.021 (2) | 0.024 (2) | −0.0087 (16) | −0.0070 (17) | 0.0011 (16) |
C3 | 0.022 (2) | 0.0127 (18) | 0.027 (2) | −0.0057 (15) | −0.0083 (18) | 0.0041 (16) |
C4 | 0.019 (2) | 0.019 (2) | 0.029 (2) | −0.0058 (16) | −0.0054 (18) | −0.0037 (17) |
C5 | 0.017 (2) | 0.024 (2) | 0.025 (2) | −0.0079 (16) | −0.0027 (17) | −0.0052 (17) |
C6 | 0.024 (2) | 0.023 (2) | 0.021 (2) | −0.0102 (17) | −0.0062 (18) | 0.0015 (17) |
C7 | 0.019 (2) | 0.0162 (18) | 0.025 (2) | −0.0045 (15) | −0.0087 (17) | 0.0042 (16) |
C8 | 0.022 (2) | 0.022 (2) | 0.025 (2) | −0.0072 (17) | −0.0034 (18) | −0.0029 (17) |
C9 | 0.022 (2) | 0.024 (2) | 0.030 (3) | −0.0060 (17) | −0.0029 (19) | −0.0011 (18) |
C10 | 0.034 (3) | 0.024 (2) | 0.030 (3) | −0.0102 (19) | −0.006 (2) | 0.0024 (19) |
C11 | 0.034 (3) | 0.040 (3) | 0.031 (3) | −0.023 (2) | −0.003 (2) | 0.001 (2) |
C12 | 0.026 (2) | 0.046 (3) | 0.043 (3) | −0.019 (2) | −0.007 (2) | 0.005 (2) |
C13 | 0.024 (2) | 0.033 (2) | 0.041 (3) | −0.0101 (19) | −0.007 (2) | 0.004 (2) |
C14 | 0.020 (2) | 0.0159 (18) | 0.031 (2) | −0.0030 (15) | −0.0105 (18) | 0.0004 (17) |
C15 | 0.021 (2) | 0.024 (2) | 0.031 (3) | −0.0063 (17) | −0.0060 (19) | −0.0037 (18) |
C16 | 0.022 (2) | 0.030 (2) | 0.037 (3) | −0.0094 (18) | −0.012 (2) | −0.001 (2) |
C17 | 0.027 (2) | 0.021 (2) | 0.035 (3) | −0.0075 (17) | −0.017 (2) | 0.0042 (18) |
C18 | 0.031 (2) | 0.0168 (19) | 0.031 (3) | −0.0073 (17) | −0.012 (2) | 0.0045 (17) |
C19 | 0.020 (2) | 0.0189 (19) | 0.030 (2) | −0.0054 (16) | −0.0083 (18) | 0.0054 (17) |
C20 | 0.032 (3) | 0.031 (2) | 0.036 (3) | −0.006 (2) | −0.008 (2) | 0.013 (2) |
C21 | 0.030 (2) | 0.026 (2) | 0.024 (2) | −0.0110 (18) | 0.0017 (19) | −0.0039 (18) |
C22 | 0.035 (3) | 0.032 (2) | 0.031 (3) | −0.017 (2) | −0.012 (2) | 0.004 (2) |
C23 | 0.048 (3) | 0.035 (3) | 0.038 (3) | −0.017 (2) | −0.020 (3) | 0.002 (2) |
C24 | 0.080 (5) | 0.041 (3) | 0.028 (3) | −0.024 (3) | −0.012 (3) | −0.008 (2) |
C25 | 0.087 (5) | 0.044 (3) | 0.025 (3) | −0.029 (3) | 0.000 (3) | 0.001 (2) |
C26 | 0.062 (4) | 0.034 (3) | 0.027 (3) | −0.024 (3) | 0.003 (2) | −0.004 (2) |
C27 | 0.025 (2) | 0.029 (2) | 0.035 (3) | −0.0136 (19) | −0.002 (2) | 0.003 (2) |
C28 | 0.028 (3) | 0.042 (3) | 0.059 (4) | −0.014 (2) | 0.004 (3) | −0.012 (3) |
C29 | 0.022 (3) | 0.056 (4) | 0.081 (5) | −0.010 (3) | 0.003 (3) | −0.012 (3) |
C30 | 0.039 (3) | 0.049 (4) | 0.088 (5) | −0.028 (3) | −0.010 (3) | 0.003 (3) |
C31 | 0.046 (3) | 0.055 (3) | 0.050 (4) | −0.030 (3) | −0.020 (3) | 0.002 (3) |
C32 | 0.031 (3) | 0.041 (3) | 0.029 (3) | −0.015 (2) | −0.007 (2) | 0.003 (2) |
C33 | 0.295 (15) | 0.303 (15) | 0.274 (15) | −0.101 (10) | −0.053 (9) | 0.001 (9) |
Pd—O1 | 2.076 (3) | C14—C15 | 1.401 (6) |
Pd—O2 | 2.140 (3) | C15—C16 | 1.386 (6) |
Pd—P2 | 2.2055 (12) | C15—H15 | 0.9500 |
Pd—P1 | 2.2267 (12) | C16—C17 | 1.383 (7) |
Br1—C3 | 1.902 (4) | C16—H16 | 0.9500 |
Br2—C5 | 1.907 (4) | C17—C18 | 1.392 (6) |
Br3—C7 | 1.904 (4) | C17—H17 | 0.9500 |
P1—O3 | 1.499 (3) | C18—C19 | 1.389 (6) |
P1—C14 | 1.806 (4) | C18—H18 | 0.9500 |
P1—C8 | 1.823 (4) | C19—H19 | 0.9500 |
P2—O4 | 1.618 (3) | C20—H20A | 0.9800 |
P2—C21 | 1.801 (5) | C20—H20B | 0.9800 |
P2—C27 | 1.809 (5) | C20—H20C | 0.9800 |
O1—C1 | 1.273 (5) | C21—C26 | 1.380 (7) |
O2—C2 | 1.273 (5) | C21—C22 | 1.384 (6) |
O4—C20 | 1.435 (6) | C22—C23 | 1.378 (7) |
O5—C33 | 1.488 (9) | C22—H22 | 0.9500 |
O5—H5 | 0.8400 | C23—C24 | 1.357 (8) |
C1—C7 | 1.412 (6) | C23—H23 | 0.9500 |
C1—C2 | 1.475 (6) | C24—C25 | 1.387 (8) |
C2—C3 | 1.422 (6) | C24—H24 | 0.9500 |
C3—C4 | 1.376 (6) | C25—C26 | 1.385 (8) |
C4—C5 | 1.385 (6) | C25—H25 | 0.9500 |
C4—H4 | 0.9500 | C26—H26 | 0.9500 |
C5—C6 | 1.378 (6) | C27—C28 | 1.383 (7) |
C6—C7 | 1.384 (6) | C27—C32 | 1.393 (7) |
C6—H6 | 0.9500 | C28—C29 | 1.395 (8) |
C8—C9 | 1.381 (6) | C28—H28 | 0.9500 |
C8—C13 | 1.394 (6) | C29—C30 | 1.358 (9) |
C9—C10 | 1.384 (6) | C29—H29 | 0.9500 |
C9—H9 | 0.9500 | C30—C31 | 1.372 (9) |
C10—C11 | 1.391 (7) | C30—H30 | 0.9500 |
C10—H10 | 0.9500 | C31—C32 | 1.386 (7) |
C11—C12 | 1.362 (7) | C31—H31 | 0.9500 |
C11—H11 | 0.9500 | C32—H32 | 0.9500 |
C12—C13 | 1.386 (7) | C33—H33A | 0.9800 |
C12—H12 | 0.9500 | C33—H33B | 0.9800 |
C13—H13 | 0.9500 | C33—H33C | 0.9800 |
C14—C19 | 1.387 (6) | ||
O1—Pd—O2 | 75.61 (11) | C16—C15—C14 | 120.3 (4) |
O1—Pd—P2 | 178.23 (9) | C16—C15—H15 | 119.8 |
O2—Pd—P2 | 102.66 (9) | C14—C15—H15 | 119.8 |
O1—Pd—P1 | 92.64 (9) | C17—C16—C15 | 120.1 (4) |
O2—Pd—P1 | 168.03 (9) | C17—C16—H16 | 120.0 |
P2—Pd—P1 | 89.07 (5) | C15—C16—H16 | 120.0 |
O3—P1—C14 | 110.12 (19) | C16—C17—C18 | 120.0 (4) |
O3—P1—C8 | 109.78 (19) | C16—C17—H17 | 120.0 |
C14—P1—C8 | 105.7 (2) | C18—C17—H17 | 120.0 |
O3—P1—Pd | 120.99 (13) | C19—C18—C17 | 120.0 (4) |
C14—P1—Pd | 102.86 (14) | C19—C18—H18 | 120.0 |
C8—P1—Pd | 106.28 (15) | C17—C18—H18 | 120.0 |
O4—P2—C21 | 104.4 (2) | C14—C19—C18 | 120.4 (4) |
O4—P2—C27 | 97.64 (19) | C14—C19—H19 | 119.8 |
C21—P2—C27 | 108.3 (2) | C18—C19—H19 | 119.8 |
O4—P2—Pd | 111.14 (13) | O4—C20—H20A | 109.5 |
C21—P2—Pd | 117.19 (15) | O4—C20—H20B | 109.5 |
C27—P2—Pd | 115.78 (17) | H20A—C20—H20B | 109.5 |
C1—O1—Pd | 117.4 (3) | O4—C20—H20C | 109.5 |
C2—O2—Pd | 115.1 (3) | H20A—C20—H20C | 109.5 |
C20—O4—P2 | 120.7 (3) | H20B—C20—H20C | 109.5 |
C33—O5—H5 | 109.5 | C26—C21—C22 | 120.4 (4) |
O1—C1—C7 | 118.5 (4) | C26—C21—P2 | 117.7 (4) |
O1—C1—C2 | 115.8 (4) | C22—C21—P2 | 121.9 (4) |
C7—C1—C2 | 125.7 (4) | C23—C22—C21 | 119.5 (5) |
O2—C2—C3 | 119.6 (4) | C23—C22—H22 | 120.2 |
O2—C2—C1 | 115.9 (4) | C21—C22—H22 | 120.2 |
C3—C2—C1 | 124.5 (4) | C24—C23—C22 | 120.3 (5) |
C4—C3—C2 | 131.8 (4) | C24—C23—H23 | 119.9 |
C4—C3—Br1 | 115.6 (3) | C22—C23—H23 | 119.9 |
C2—C3—Br1 | 112.6 (3) | C23—C24—C25 | 120.9 (5) |
C3—C4—C5 | 128.8 (4) | C23—C24—H24 | 119.6 |
C3—C4—H4 | 115.6 | C25—C24—H24 | 119.6 |
C5—C4—H4 | 115.6 | C26—C25—C24 | 119.3 (5) |
C6—C5—C4 | 129.1 (4) | C26—C25—H25 | 120.3 |
C6—C5—Br2 | 114.9 (3) | C24—C25—H25 | 120.3 |
C4—C5—Br2 | 116.0 (3) | C21—C26—C25 | 119.6 (5) |
C5—C6—C7 | 127.7 (4) | C21—C26—H26 | 120.2 |
C5—C6—H6 | 116.1 | C25—C26—H26 | 120.2 |
C7—C6—H6 | 116.1 | C28—C27—C32 | 119.9 (5) |
C6—C7—C1 | 132.1 (4) | C28—C27—P2 | 122.0 (4) |
C6—C7—Br3 | 114.3 (3) | C32—C27—P2 | 118.1 (4) |
C1—C7—Br3 | 113.6 (3) | C27—C28—C29 | 119.3 (5) |
C9—C8—C13 | 118.4 (4) | C27—C28—H28 | 120.3 |
C9—C8—P1 | 118.2 (3) | C29—C28—H28 | 120.3 |
C13—C8—P1 | 122.9 (3) | C30—C29—C28 | 120.1 (6) |
C8—C9—C10 | 120.9 (4) | C30—C29—H29 | 119.9 |
C8—C9—H9 | 119.5 | C28—C29—H29 | 119.9 |
C10—C9—H9 | 119.5 | C29—C30—C31 | 121.4 (6) |
C9—C10—C11 | 119.9 (4) | C29—C30—H30 | 119.3 |
C9—C10—H10 | 120.1 | C31—C30—H30 | 119.3 |
C11—C10—H10 | 120.1 | C30—C31—C32 | 119.3 (5) |
C12—C11—C10 | 119.6 (4) | C30—C31—H31 | 120.3 |
C12—C11—H11 | 120.2 | C32—C31—H31 | 120.3 |
C10—C11—H11 | 120.2 | C31—C32—C27 | 119.9 (5) |
C11—C12—C13 | 120.6 (5) | C31—C32—H32 | 120.0 |
C11—C12—H12 | 119.7 | C27—C32—H32 | 120.0 |
C13—C12—H12 | 119.7 | O5—C33—H33A | 109.5 |
C12—C13—C8 | 120.5 (5) | O5—C33—H33B | 109.5 |
C12—C13—H13 | 119.8 | H33A—C33—H33B | 109.5 |
C8—C13—H13 | 119.8 | O5—C33—H33C | 109.5 |
C19—C14—C15 | 119.2 (4) | H33A—C33—H33C | 109.5 |
C19—C14—P1 | 121.4 (3) | H33B—C33—H33C | 109.5 |
C15—C14—P1 | 119.2 (4) | ||
O1—Pd—P1—O3 | 170.90 (17) | Pd—P1—C8—C13 | 33.4 (4) |
O2—Pd—P1—O3 | −178.3 (4) | C13—C8—C9—C10 | 2.3 (7) |
P2—Pd—P1—O3 | −9.57 (15) | P1—C8—C9—C10 | −169.7 (4) |
O1—Pd—P1—C14 | −65.82 (17) | C8—C9—C10—C11 | −0.9 (7) |
O2—Pd—P1—C14 | −55.0 (4) | C9—C10—C11—C12 | −1.6 (8) |
P2—Pd—P1—C14 | 113.71 (15) | C10—C11—C12—C13 | 2.5 (8) |
O1—Pd—P1—C8 | 44.99 (18) | C11—C12—C13—C8 | −1.0 (8) |
O2—Pd—P1—C8 | 55.8 (4) | C9—C8—C13—C12 | −1.4 (7) |
P2—Pd—P1—C8 | −135.49 (16) | P1—C8—C13—C12 | 170.2 (4) |
O2—Pd—P2—O4 | 9.33 (17) | O3—P1—C14—C19 | −160.9 (3) |
P1—Pd—P2—O4 | −168.29 (14) | C8—P1—C14—C19 | −42.4 (4) |
O2—Pd—P2—C21 | −110.6 (2) | Pd—P1—C14—C19 | 68.8 (3) |
P1—Pd—P2—C21 | 71.77 (18) | O3—P1—C14—C15 | 23.2 (4) |
O2—Pd—P2—C27 | 119.52 (19) | C8—P1—C14—C15 | 141.7 (3) |
P1—Pd—P2—C27 | −58.09 (18) | Pd—P1—C14—C15 | −107.1 (3) |
O2—Pd—O1—C1 | −1.4 (3) | C19—C14—C15—C16 | 1.1 (6) |
P1—Pd—O1—C1 | 176.3 (3) | P1—C14—C15—C16 | 177.2 (3) |
O1—Pd—O2—C2 | −1.1 (3) | C14—C15—C16—C17 | −1.2 (7) |
P2—Pd—O2—C2 | 179.3 (3) | C15—C16—C17—C18 | 0.7 (6) |
P1—Pd—O2—C2 | −12.3 (6) | C16—C17—C18—C19 | −0.2 (6) |
C21—P2—O4—C20 | 62.7 (4) | C15—C14—C19—C18 | −0.6 (6) |
C27—P2—O4—C20 | 174.0 (4) | P1—C14—C19—C18 | −176.6 (3) |
Pd—P2—O4—C20 | −64.6 (4) | C17—C18—C19—C14 | 0.2 (6) |
Pd—O1—C1—C7 | −175.5 (3) | O4—P2—C21—C26 | 46.2 (5) |
Pd—O1—C1—C2 | 3.4 (5) | C27—P2—C21—C26 | −57.1 (5) |
Pd—O2—C2—C3 | −176.2 (3) | Pd—P2—C21—C26 | 169.6 (4) |
Pd—O2—C2—C1 | 3.2 (4) | O4—P2—C21—C22 | −133.0 (4) |
O1—C1—C2—O2 | −4.4 (6) | C27—P2—C21—C22 | 123.7 (4) |
C7—C1—C2—O2 | 174.4 (4) | Pd—P2—C21—C22 | −9.5 (5) |
O1—C1—C2—C3 | 174.9 (4) | C26—C21—C22—C23 | 0.1 (8) |
C7—C1—C2—C3 | −6.3 (7) | P2—C21—C22—C23 | 179.2 (4) |
O2—C2—C3—C4 | −179.3 (4) | C21—C22—C23—C24 | −1.0 (8) |
C1—C2—C3—C4 | 1.4 (7) | C22—C23—C24—C25 | 1.2 (10) |
O2—C2—C3—Br1 | 1.0 (5) | C23—C24—C25—C26 | −0.3 (10) |
C1—C2—C3—Br1 | −178.3 (3) | C22—C21—C26—C25 | 0.8 (9) |
C2—C3—C4—C5 | 2.1 (8) | P2—C21—C26—C25 | −178.4 (5) |
Br1—C3—C4—C5 | −178.3 (4) | C24—C25—C26—C21 | −0.6 (10) |
C3—C4—C5—C6 | 0.0 (8) | O4—P2—C27—C28 | −129.7 (5) |
C3—C4—C5—Br2 | 179.8 (4) | C21—P2—C27—C28 | −21.7 (5) |
C4—C5—C6—C7 | −2.4 (8) | Pd—P2—C27—C28 | 112.3 (4) |
Br2—C5—C6—C7 | 177.7 (4) | O4—P2—C27—C32 | 53.5 (4) |
C5—C6—C7—C1 | −0.8 (8) | C21—P2—C27—C32 | 161.6 (4) |
C5—C6—C7—Br3 | −179.2 (4) | Pd—P2—C27—C32 | −64.4 (4) |
O1—C1—C7—C6 | −175.0 (4) | C32—C27—C28—C29 | −0.9 (9) |
C2—C1—C7—C6 | 6.2 (7) | P2—C27—C28—C29 | −177.5 (5) |
O1—C1—C7—Br3 | 3.3 (5) | C27—C28—C29—C30 | 0.1 (10) |
C2—C1—C7—Br3 | −175.5 (3) | C28—C29—C30—C31 | 0.2 (11) |
O3—P1—C8—C9 | 72.5 (4) | C29—C30—C31—C32 | 0.1 (10) |
C14—P1—C8—C9 | −46.2 (4) | C30—C31—C32—C27 | −0.9 (8) |
Pd—P1—C8—C9 | −155.0 (3) | C28—C27—C32—C31 | 1.2 (8) |
O3—P1—C8—C13 | −99.1 (4) | P2—C27—C32—C31 | 178.0 (4) |
C14—P1—C8—C13 | 142.2 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19···Br3 | 0.95 | 2.95 | 3.818 (5) | 152 |
O5—H5···O3 | 0.84 | 2.01 | 2.740 (7) | 144 |
C20—H20B···O2 | 0.98 | 2.30 | 3.143 (6) | 144 |
C12—H12···O5i | 0.95 | 2.56 | 3.435 (9) | 154 |
C31—H31···Br1ii | 0.95 | 2.99 | 3.920 (6) | 168 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Pd(C7H2Br3)(C12H10OP)(C13H13OP)]·CH4O |
Mr | 913.63 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 9.125 (3), 11.326 (4), 17.137 (3) |
α, β, γ (°) | 87.652 (8), 78.285 (7), 72.121 (8) |
V (Å3) | 1650.0 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 4.33 |
Crystal size (mm) | 0.19 × 0.14 × 0.04 |
Data collection | |
Diffractometer | Bruker APEXII area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.493, 0.846 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 33856, 7543, 6131 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.111, 1.09 |
No. of reflections | 7543 |
No. of parameters | 399 |
No. of restraints | 13 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.92, −0.91 |
Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2004) and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg & Putz, 2006).
Pd—O1 | 2.076 (3) | Pd—P2 | 2.2055 (12) |
Pd—O2 | 2.140 (3) | Pd—P1 | 2.2267 (12) |
O1—Pd—O2 | 75.61 (11) | O1—Pd—P1 | 92.64 (9) |
O1—Pd—P2 | 178.23 (9) | O2—Pd—P1 | 168.03 (9) |
O2—Pd—P2 | 102.66 (9) | P2—Pd—P1 | 89.07 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19···Br3 | 0.95 | 2.95 | 3.818 (5) | 152.4 |
O5—H5···O3 | 0.84 | 2.01 | 2.740 (7) | 144.4 |
C20—H20B···O2 | 0.98 | 2.30 | 3.143 (6) | 144.1 |
C12—H12···O5i | 0.95 | 2.56 | 3.435 (9) | 153.9 |
C31—H31···Br1ii | 0.95 | 2.99 | 3.920 (6) | 167.5 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
In the current paper the title compound, (I), is presented as an example of a by-product formed during the catalytic cycle. It should be noted that both a diphenylphosphanito and a diphenylmethoxyphosphane, Fig. 1, was formed from the initial starting diphenylnaphtolphosphane. In either case, the diphenylnaphtolphosphane moiety decomposed and in the one instance a Suzuki coupling occurred to form the diphenylmethoxyphosphane derivative. This product is in contrast to the more readily observed hydroxyl derivative.
The Pd—O and Pd—P bond distances only differ slightly, Table 1. This relative similarity in bond distances (Pd—P) might be due to the hydrogen bonding observed between the methanol solvate and the diphenylphosphaneoxide oxygen atom, Table 2. The P—O(Me) and P?O bond distances are significantly different indicating the bond order in which the oxygen atoms bond with the phosphorous atom.
Weak intra- and intermolecular interactions is observed in the solid state, see Table 2. The role of the bromo-atoms on the solid state arrangement can be observed from the intermolecular distances between Br3···Br7 [1 - x, 1 - y, 1 - z] and Br5···Pd [1 - x, 1 - y, 1 - z] in the order of 3.729 (1) and 3.717 (1) Å, respectively. This interaction is further enhanced through π–π stacking of the cycloheptatriene rings systems of the bromo moieties with an interplanar distance of 3.496 (8) Å and a centroid-to-centroid distance of 3.507 (1) Å. The ordering of the solid state can be observed as stacking along the a axis, see Figure 2.