(Diphenyl­methoxy­phosphane-κP)(diphenyl­phosphanito-κP)(3,5,7-tribromo­tropolonato-κ²O,O′)palladium(II) methanol solvate

The title compound, [Pd(C₇H₂Br₃)(C₁₂H₁₀OP)(C₁₃H₁₃OP)]·CH₃OH, the by-product of an attempted Suzuki-coupling reaction, has two different diphenyl­phosphane groups bonded to Pd and is the first structural example of a metal complex having a diphenyl­phosphanite anion [–P(O)Ph₂] and a diphenyl­methoxy­phosphane mol­ecule (MeOPPh₂) coordinated to the same metal centre. Mol­ecules are linked by hydrogen bonds, Br...Br inter­actions [3.729 (1) Å] and π–π stacking inter­actions parallel to the a axis [inter­planar distance 3.496 (8) Å and centroid-to-centroid distance 3.507 (1) Å].

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](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

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S1. Comment

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.

Related literature

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]

S2. Experimental

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.

S3. Refinement

H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 and 0.98 Å and with U_iso(H) = 1.2 times U_eq(C aromatic) and U_iso(H) = 1.2 times U_eq(C methyl). The final difference Fourier map had a large peak near Pd.

Computing details

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).

Figures

	Fig. 1. Representation of the title compound (I), showing the numbering scheme and displacement ellipsoids (50% probability). For the carbon rings, first digit refers to ring number, second digit to atom in the ring. Hydrogen atoms omitted for clarity.
	Fig. 2. Fraction of the unit cell showing the stacking pattern [symmetry codes: (a) x, -y, z - 1/2; (b) -x, -y, -z].

(Diphenylmethoxyphosphane-κP)(diphenylphosphanito-κP)(3,5,7- tribromotropolonato-κ²O,O')palladium(II) methanol solvate

Crystal data

[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) Å^3

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0572P)^2 + 2.8917P] where P = (Fo^2 + 2Fc^2)/3
7543 reflections	(Δ/σ)max = 0.001
399 parameters	Δρmax = 1.92 e Å^−3
13 restraints	Δρmin = −0.91 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

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···O5^i	0.95	2.56	3.435 (9)	154
C31—H31···Br1^ii	0.95	2.99	3.920 (6)	168

Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z.