Bis[2,6-bis­(dipiperidin-1-ylphosphanyl­oxy)­phen­yl]bromidopalladium(II)

Bolliger, J.L.; Blacque, O.; Frech, C.M.

doi:10.1107/S1600536807059405

Bis[2,6-bis(dipiperidin-1-ylphosphanyloxy)phenyl]bromidopalladium(II)

J. L. Bolliger, O. Blacque and C. M. Frech

The title compound, [PdBr(C₂₆H₄₃N₄O₂P₂)], a so-called palladium pincer complex, is a very efficient catalyst for the Suzuki cross-coupling reaction. The Pd atom exhibits a distorted square-planar coordination, typical for Pd^II complexes.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807059405/su2024sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807059405/su2024Isup2.hkl Contains datablock I

CCDC reference: 672710

checkCIF report

Key indicators

Single-crystal X-ray study
T = 183 K
Mean (C-C) = 0.005 Å
R factor = 0.024
wR factor = 0.065
Data-to-parameter ratio = 15.4

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .......       0.94

Author Response: The data completeness of about 94% is a low value very often encountered for triclinic systems with our type of IPDS diffractometer. The very good quality of the crystal structure led us to give up the idea to collect an additional data set after remounting the crystal...


Alert level C
REFLT03_ALERT_3_C  Reflection count < 95% complete
           From the CIF: _diffrn_reflns_theta_max           25.00
           From the CIF: _diffrn_reflns_theta_full          25.00
           From the CIF: _reflns_number_total               4989
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         5329
           Completeness (_total/calc)             93.62%
PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low ....       0.94
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.47 Ratio
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Pd1    -   Br1     ..       6.36 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Pd1    -   P1      ..       6.95 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C8
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C24

   1 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

In a recent article, we reported a new concept for the synthesis of aminophosphine-based pincer complexes of palladium with the general formula of [Pd(Cl){C₆H₃(XP(piperidinyl)₂)₂}] (X = NH or O), which were formed by facile activation of C—H and P—N bonds (Bolliger et al., 2007). These complexes proved to be extremely efficient catalysts for the Suzuki–Miyaura cross-coupling reaction (Miyaura et al., 1979) and led to very high conversion rates and quantitative yields in extremely short reaction times and with very low catalyst loadings. The analogous bromo complex [Pd(Br){C₆H₃(OP(piperidinyl)₂)₂}] (I), which was found to be formed in the catalytic cycle, was independently prepared and the X-ray structure is presented here.

The crystal structure of (I) consists of discrete molecules with no intermolecular short contacts. The palladium atom presents a distorted square planar coordination with Br, C1, P1 and P2 as donor atoms. The main distortion affects the angle P—Pd—P of the mutually trans phosphorus atoms (160.31 (3)°) and is a consequence of the two five-membered rings which impose strains to the coordination sphere. The Pd—Br bond length of 2.5066 (7) Å is very similar to values found in the literature for the [Pd(Br){C₆H₃(XPR₂)₂}] compounds: 2.495 (1) Å, X = CH₂, R = Ph (Bachechi, 2003) and 2.514 (2) Å, X = CH₂, R = Cy (Cross et al., 1995). The Pd—P bond distances of 2.2808 (7) and 2.2891 (7) Å fall in the typical range observed for compounds with the [Pd{C₆H₃(XPR₂)₂}] moiety.

Related literature top

For related literature, see: Bolliger et al. (2007); Miyaura et al. (1979); Bachechi (2003); Cross et al. (1995).

Experimental top

To an orange suspension of 0.709 g (1.89 mmol) of [Pd(Br)₂(cod)] (cod=cycloocta-1,5-diene) in 15 ml of tetrahydrofurane, 1.077 g (3.80 mmol, 2.01 equiv.) of P(NC₅H₁₀)₃ (dissolved in 10 ml of tetrahydrofurane) was added and stirred for 5 minutes at room temperature, which quantitatively yielded the dibromo-(bis(1,1',1''-(phosphinetriyl)tripiperidine))palladium [Pd(Br)₂{P(NC₅H₁₀)₃}₂] complex. To a toluene solution (10 ml) of 262.8 mg (0.32 mmol) of [Pd(Br)₂{P(NC₅H₁₀)₃}₂], 36.0 mg (0.33 mmol, 1.01 equiv.) of resorcinol was added. The reaction mixture was placed in an oil bath and heated up to 80°C for 15 minutes, during which the solution decolorized. The solvent was removed under reduced pressure, and the solid was extracted with 20 ml of diethyl ether. After removal of the solvent in vacuo, 161.5 mg (0.24 mmol, 74%) of [Pd(Br){C₆H₃(OP(piperidinyl)₂)₂}] (I) was obtained as colorless powder.

Colorless crystals of the title compound (I) were obtained by slow evaporation of the solvent from a saturated diethyl ether solution at room temperature within three weeks.

³¹P{¹H}-NMR (C₆D₆; δ, p.p.m.): 147.6 (s, P(NC₅H₁₀)₂).

¹H NMR (C₆D₆; δ,p.p.m.): 6.96 (t, ³J_HH = 8.0 Hz, 1H, Ar_para), 6.63 (d, ³J_HH = 8.0 Hz, 2H, Ar_meta), 3.27 (m, 16H, NCH₂), 1.41 (m, 16H, NCH₂CH₂),1.27 (m, 8H, NCH₂CH₂CH₂).

¹³C{¹H} NMR (C₆D₆; δ, p.p.m.): 160.9 (vt, J_PC = 10.2 Hz, ArOP), 129.3 (s, Ar_para), 126.9 (unresolved t, Ar_ipso), 106.4 (vt, J_PC = 8.4 Hz, Ar_meta), 46.7 (vt, ²J_PC = ⁴J_PC = 4.1, NCH₂), 26.6 (s, NCH₂CH₂), 24.9 (s, NCH₂CH₂CH₂). The assignmentof the ¹H and ¹³C{¹H} NMR signals was confirmed by COSY and ¹³C{¹H}DEPT experiments.

Elemental Analysis: Calc. for C₂₆H₄₃BrN₄O₂P₂Pd: C, 45.13; H, 6.26; N, 8.10. Found: C, 45.08; H, 6.35; N, 8.13.

Computing details top

Data collection: IPDS Software (Stoe & Cie, 1999); cell refinement: IPDS Software (Stoe & Cie, 1999); data reduction: IPDS Software (Stoe & Cie, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and SHELXL97 (Sheldrick, 1997).

Figures top

Fig. 1. The molecular structure of (I) with the atom-labeling scheme (30% probability displacement ellipsoids).

Bis[2,6-bis(dipiperidin-1-ylphosphanyloxy)phenyl]bromidopalladium(II) top

Crystal data top

[PdBr(C₂₆H₄₃N₄O₂P₂)]	Z = 2
M_r = 691.9	F(000) = 708
Triclinic, P1	D_x = 1.522 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.8843 (15) Å	Cell parameters from 8000 reflections
b = 12.3457 (19) Å	θ = 3.1–30.2°
c = 13.815 (2) Å	µ = 2.07 mm⁻¹
α = 76.635 (18)°	T = 183 K
β = 70.676 (17)°	Plate, colourless
γ = 73.847 (17)°	0.33 × 0.32 × 0.12 mm
V = 1510.0 (4) Å³

Data collection top

Stoe IPDS diffractometer	4431 reflections with I > 2σ(I)
ϕ oscillation scans	R_int = 0.056
Absorption correction: numerical (Coppens et al., 1965)	θ_max = 25°, θ_min = 3.1°
T_min = 0.568, T_max = 0.797	h = −11→11
19696 measured reflections	k = −14→14
4989 independent reflections	l = −16→16

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.024	w = 1/[σ²(F_o²) + (0.0407P)² + 0.1788P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.065	(Δ/σ)_max = 0.001
S = 1.02	Δρ_max = 0.71 e Å⁻³
4989 reflections	Δρ_min = −0.37 e Å⁻³
325 parameters

Crystal data top

[PdBr(C₂₆H₄₃N₄O₂P₂)]	γ = 73.847 (17)°
M_r = 691.9	V = 1510.0 (4) Å³
Triclinic, P1	Z = 2
a = 9.8843 (15) Å	Mo Kα radiation
b = 12.3457 (19) Å	µ = 2.07 mm⁻¹
c = 13.815 (2) Å	T = 183 K
α = 76.635 (18)°	0.33 × 0.32 × 0.12 mm
β = 70.676 (17)°

Data collection top

Stoe IPDS diffractometer	4989 independent reflections
Absorption correction: numerical (Coppens et al., 1965)	4431 reflections with I > 2σ(I)
T_min = 0.568, T_max = 0.797	R_int = 0.056
19696 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.065	H-atom parameters constrained
S = 1.02	Δρ_max = 0.71 e Å⁻³
4989 reflections	Δρ_min = −0.37 e Å⁻³
325 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Pd1	0.595039 (18)	0.296726 (15)	0.253679 (13)	0.02177 (7)
Br1	0.37214 (3)	0.32621 (3)	0.40672 (2)	0.03958 (9)
P1	0.59392 (7)	0.11866 (5)	0.23383 (5)	0.02443 (14)
P2	0.67472 (7)	0.45960 (5)	0.23525 (4)	0.02443 (14)
C1	0.7721 (3)	0.2712 (2)	0.13281 (17)	0.0232 (5)
C2	0.8616 (3)	0.3495 (2)	0.09128 (18)	0.0266 (5)
C3	0.9860 (3)	0.3337 (2)	0.0074 (2)	0.0332 (6)
H3	1.0454	0.3866	−0.0178	0.043*
C4	1.0193 (3)	0.2369 (2)	−0.0377 (2)	0.0344 (6)
H4	1.1021	0.2252	−0.0943	0.045*
C5	0.9317 (3)	0.1564 (2)	−0.00032 (19)	0.0302 (5)
H5	0.9542	0.0922	−0.0319	0.039*
C6	0.8106 (3)	0.1747 (2)	0.08503 (17)	0.0238 (5)
O1	0.72162 (19)	0.09514 (15)	0.12318 (13)	0.0288 (4)
O2	0.8238 (2)	0.44822 (15)	0.13463 (13)	0.0334 (4)
N1	0.4599 (2)	0.07942 (19)	0.21028 (15)	0.0307 (5)
C7	0.4193 (3)	0.1359 (3)	0.1142 (2)	0.0449 (8)
H7A	0.5074	0.1394	0.0565	0.058*
H7B	0.364	0.2133	0.1218	0.058*
C8	0.3280 (4)	0.0702 (5)	0.0927 (3)	0.0780 (14)
H8A	0.3862	−0.0054	0.0807	0.101*
H8B	0.3	0.1085	0.0302	0.101*
C9	0.1899 (4)	0.0598 (4)	0.1828 (3)	0.0644 (11)
H9A	0.1253	0.1345	0.1897	0.084*
H9B	0.1377	0.0115	0.1695	0.084*
C10	0.2330 (4)	0.0087 (3)	0.2823 (3)	0.0585 (9)
H10A	0.145	0.0094	0.3406	0.076*
H10B	0.2853	−0.0701	0.2787	0.076*
C11	0.3273 (4)	0.0728 (4)	0.2992 (2)	0.0551 (9)
H11A	0.2714	0.1494	0.3099	0.072*
H11B	0.3565	0.0357	0.3614	0.072*
N2	0.6376 (2)	0.01734 (18)	0.32605 (16)	0.0306 (5)
C12	0.6752 (3)	0.0430 (3)	0.41152 (19)	0.0321 (6)
H12A	0.6247	0.0029	0.4768	0.042*
H12B	0.6422	0.1242	0.4145	0.042*
C13	0.8394 (3)	0.0077 (2)	0.3971 (2)	0.0340 (6)
H13A	0.8605	0.0202	0.4569	0.044*
H13B	0.8892	0.0544	0.3362	0.044*
C14	0.8968 (3)	−0.1179 (3)	0.3840 (2)	0.0432 (7)
H14A	1.0029	−0.1373	0.3691	0.056*
H14B	0.8563	−0.1652	0.4481	0.056*
C15	0.8537 (4)	−0.1412 (3)	0.2961 (3)	0.0448 (7)
H15A	0.8843	−0.2222	0.2921	0.058*
H15B	0.904	−0.1009	0.2308	0.058*
C16	0.6882 (3)	−0.1029 (2)	0.3126 (2)	0.0424 (7)
H16A	0.6644	−0.1136	0.2533	0.055*
H16B	0.6382	−0.1493	0.3736	0.055*
N3	0.5935 (3)	0.59172 (19)	0.19468 (17)	0.0358 (5)
C17	0.5694 (4)	0.6169 (3)	0.0915 (2)	0.0574 (9)
H17A	0.6409	0.5631	0.0482	0.075*
H17B	0.5839	0.6929	0.0591	0.075*
C18	0.4161 (5)	0.6095 (4)	0.0985 (3)	0.0741 (13)
H18A	0.4058	0.5311	0.1227	0.096*
H18B	0.4016	0.6318	0.0299	0.096*
C19	0.2992 (4)	0.6858 (4)	0.1717 (3)	0.0727 (12)
H19A	0.3011	0.7651	0.1433	0.095*
H19B	0.2029	0.6746	0.1786	0.095*
C20	0.3262 (4)	0.6582 (3)	0.2774 (3)	0.0606 (9)
H20A	0.3103	0.5825	0.3099	0.079*
H20B	0.2571	0.7124	0.3213	0.079*
C21	0.4819 (4)	0.6631 (3)	0.2676 (2)	0.0458 (7)
H21A	0.4924	0.7416	0.2448	0.06*
H21B	0.4988	0.6387	0.3354	0.06*
N4	0.7223 (2)	0.47366 (18)	0.33326 (16)	0.0297 (5)
C22	0.7178 (3)	0.3868 (2)	0.4260 (2)	0.0388 (7)
H22A	0.6579	0.3358	0.4275	0.05*
H22B	0.6726	0.4235	0.4874	0.05*
C23	0.8690 (4)	0.3190 (3)	0.4275 (3)	0.0586 (9)
H23A	0.9121	0.2775	0.3689	0.076*
H23B	0.8633	0.264	0.4907	0.076*
C24	0.9645 (4)	0.3990 (4)	0.4220 (4)	0.0800 (14)
H24A	1.0637	0.3558	0.4189	0.104*
H24B	0.9263	0.4347	0.4841	0.104*
C25	0.9672 (4)	0.4908 (4)	0.3267 (3)	0.0702 (11)
H25A	1.0222	0.5443	0.3275	0.091*
H25B	1.0167	0.4557	0.2645	0.091*
C26	0.8136 (3)	0.5542 (3)	0.3239 (2)	0.0428 (7)
H26A	0.769	0.5986	0.3805	0.056*
H26B	0.8181	0.6065	0.2592	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.01969 (10)	0.02554 (12)	0.01935 (10)	−0.00848 (8)	−0.00401 (7)	−0.00008 (7)
Br1	0.02724 (14)	0.04573 (19)	0.03679 (16)	−0.01067 (13)	0.00621 (11)	−0.00854 (12)
P1	0.0256 (3)	0.0282 (3)	0.0210 (3)	−0.0126 (3)	−0.0072 (2)	0.0025 (2)
P2	0.0274 (3)	0.0246 (3)	0.0212 (3)	−0.0093 (3)	−0.0055 (2)	−0.0010 (2)
C1	0.0224 (11)	0.0271 (13)	0.0203 (11)	−0.0068 (10)	−0.0082 (9)	0.0003 (9)
C2	0.0281 (12)	0.0269 (13)	0.0241 (12)	−0.0088 (11)	−0.0062 (10)	−0.0008 (10)
C3	0.0313 (13)	0.0365 (15)	0.0299 (13)	−0.0170 (12)	−0.0014 (11)	−0.0006 (11)
C4	0.0280 (13)	0.0405 (16)	0.0271 (13)	−0.0089 (13)	0.0012 (10)	−0.0024 (11)
C5	0.0341 (13)	0.0303 (14)	0.0234 (12)	−0.0066 (12)	−0.0052 (10)	−0.0039 (10)
C6	0.0251 (11)	0.0252 (13)	0.0201 (11)	−0.0079 (10)	−0.0077 (9)	0.0032 (9)
O1	0.0328 (9)	0.0291 (10)	0.0252 (8)	−0.0143 (8)	−0.0041 (7)	−0.0026 (7)
O2	0.0353 (10)	0.0318 (10)	0.0307 (9)	−0.0190 (9)	0.0050 (8)	−0.0073 (7)
N1	0.0331 (11)	0.0415 (13)	0.0233 (10)	−0.0206 (10)	−0.0130 (9)	0.0060 (9)
C7	0.0425 (16)	0.066 (2)	0.0253 (14)	−0.0202 (15)	−0.0163 (12)	0.0139 (13)
C8	0.062 (2)	0.148 (4)	0.0414 (19)	−0.045 (3)	−0.0186 (17)	−0.015 (2)
C9	0.0439 (18)	0.113 (3)	0.0499 (19)	−0.034 (2)	−0.0188 (15)	−0.010 (2)
C10	0.0436 (17)	0.080 (3)	0.057 (2)	−0.0337 (19)	−0.0175 (16)	0.0076 (18)
C11	0.0447 (17)	0.100 (3)	0.0267 (15)	−0.0359 (19)	−0.0106 (13)	0.0033 (15)
N2	0.0343 (11)	0.0334 (12)	0.0278 (11)	−0.0147 (10)	−0.0152 (9)	0.0068 (9)
C12	0.0277 (12)	0.0469 (16)	0.0203 (12)	−0.0093 (12)	−0.0078 (10)	0.0002 (10)
C13	0.0291 (13)	0.0451 (17)	0.0317 (13)	−0.0132 (13)	−0.0128 (11)	−0.0009 (11)
C14	0.0326 (14)	0.0423 (18)	0.0515 (18)	−0.0083 (14)	−0.0169 (13)	0.0062 (14)
C15	0.0546 (18)	0.0266 (15)	0.0528 (18)	−0.0091 (15)	−0.0173 (15)	−0.0020 (13)
C16	0.0568 (18)	0.0317 (15)	0.0480 (17)	−0.0222 (15)	−0.0279 (15)	0.0106 (12)
N3	0.0479 (13)	0.0310 (13)	0.0253 (11)	−0.0048 (11)	−0.0132 (10)	0.0012 (9)
C17	0.086 (3)	0.052 (2)	0.0294 (16)	−0.0068 (19)	−0.0281 (17)	0.0096 (14)
C18	0.110 (3)	0.064 (2)	0.069 (3)	−0.012 (3)	−0.068 (3)	0.004 (2)
C19	0.064 (2)	0.064 (3)	0.092 (3)	−0.007 (2)	−0.050 (2)	0.017 (2)
C20	0.0463 (18)	0.053 (2)	0.066 (2)	0.0032 (18)	−0.0169 (17)	0.0070 (18)
C21	0.0547 (18)	0.0347 (17)	0.0434 (17)	0.0031 (15)	−0.0182 (15)	−0.0063 (13)
N4	0.0347 (11)	0.0320 (12)	0.0272 (10)	−0.0135 (10)	−0.0127 (9)	−0.0001 (9)
C22	0.0485 (16)	0.0446 (17)	0.0303 (14)	−0.0199 (14)	−0.0188 (13)	0.0043 (12)
C23	0.064 (2)	0.047 (2)	0.072 (2)	−0.0073 (18)	−0.044 (2)	0.0058 (17)
C24	0.057 (2)	0.092 (3)	0.106 (3)	−0.024 (2)	−0.055 (2)	0.013 (3)
C25	0.045 (2)	0.095 (3)	0.085 (3)	−0.038 (2)	−0.0196 (19)	−0.013 (2)
C26	0.0592 (19)	0.0417 (17)	0.0395 (15)	−0.0290 (16)	−0.0175 (14)	−0.0022 (12)

Geometric parameters (Å, º) top

Pd1—C1	1.988 (2)	C13—H13A	0.9700
Pd1—P1	2.2808 (7)	C13—H13B	0.9700
Pd1—P2	2.2891 (7)	C14—C15	1.521 (4)
Pd1—Br1	2.5066 (7)	C14—H14A	0.9700
P1—N2	1.643 (2)	C14—H14B	0.9700
P1—O1	1.6549 (19)	C15—C16	1.524 (4)
P1—N1	1.6762 (18)	C15—H15A	0.9700
P2—N4	1.631 (2)	C15—H15B	0.9700
P2—O2	1.6563 (19)	C16—H16A	0.9700
P2—N3	1.663 (2)	C16—H16B	0.9700
C1—C2	1.388 (3)	N3—C21	1.464 (4)
C1—C6	1.395 (3)	N3—C17	1.471 (3)
C2—O2	1.386 (3)	C17—C18	1.514 (6)
C2—C3	1.386 (4)	C17—H17A	0.9700
C3—C4	1.384 (4)	C17—H17B	0.9700
C3—H3	0.9300	C18—C19	1.519 (6)
C4—C5	1.397 (4)	C18—H18A	0.9700
C4—H4	0.9300	C18—H18B	0.9700
C5—C6	1.383 (4)	C19—C20	1.516 (5)
C5—H5	0.9300	C19—H19A	0.9700
C6—O1	1.397 (3)	C19—H19B	0.9700
N1—C7	1.476 (3)	C20—C21	1.517 (5)
N1—C11	1.478 (4)	C20—H20A	0.9700
C7—C8	1.502 (5)	C20—H20B	0.9700
C7—H7A	0.9700	C21—H21A	0.9700
C7—H7B	0.9700	C21—H21B	0.9700
C8—C9	1.526 (5)	N4—C22	1.465 (3)
C8—H8A	0.9700	N4—C26	1.477 (3)
C8—H8B	0.9700	C22—C23	1.500 (4)
C9—C10	1.519 (5)	C22—H22A	0.9700
C9—H9A	0.9700	C22—H22B	0.9700
C9—H9B	0.9700	C23—C24	1.520 (5)
C10—C11	1.479 (4)	C23—H23A	0.9700
C10—H10A	0.9700	C23—H23B	0.9700
C10—H10B	0.9700	C24—C25	1.524 (6)
C11—H11A	0.9700	C24—H24A	0.9700
C11—H11B	0.9700	C24—H24B	0.9700
N2—C16	1.464 (4)	C25—C26	1.511 (5)
N2—C12	1.470 (3)	C25—H25A	0.9700
C12—C13	1.515 (3)	C25—H25B	0.9700
C12—H12A	0.9700	C26—H26A	0.9700
C12—H12B	0.9700	C26—H26B	0.9700
C13—C14	1.527 (4)

C1—Pd1—P1	80.14 (7)	H13A—C13—H13B	108.1
C1—Pd1—P2	80.63 (7)	C15—C14—C13	110.3 (2)
P1—Pd1—P2	160.31 (3)	C15—C14—H14A	109.6
C1—Pd1—Br1	179.28 (7)	C13—C14—H14A	109.6
P1—Pd1—Br1	99.20 (3)	C15—C14—H14B	109.6
P2—Pd1—Br1	100.00 (3)	C13—C14—H14B	109.6
N2—P1—O1	108.07 (11)	H14A—C14—H14B	108.1
N2—P1—N1	103.23 (10)	C14—C15—C16	111.1 (3)
O1—P1—N1	97.66 (10)	C14—C15—H15A	109.4
N2—P1—Pd1	113.99 (8)	C16—C15—H15A	109.4
O1—P1—Pd1	104.72 (6)	C14—C15—H15B	109.4
N1—P1—Pd1	126.94 (9)	C16—C15—H15B	109.4
N4—P2—O2	107.57 (10)	H15A—C15—H15B	108.0
N4—P2—N3	103.59 (11)	N2—C16—C15	110.5 (2)
O2—P2—N3	97.15 (11)	N2—C16—H16A	109.5
N4—P2—Pd1	115.52 (8)	C15—C16—H16A	109.5
O2—P2—Pd1	103.76 (7)	N2—C16—H16B	109.5
N3—P2—Pd1	126.50 (8)	C15—C16—H16B	109.5
C2—C1—C6	117.1 (2)	H16A—C16—H16B	108.1
C2—C1—Pd1	121.52 (19)	C21—N3—C17	112.6 (2)
C6—C1—Pd1	121.40 (16)	C21—N3—P2	121.29 (18)
O2—C2—C3	118.6 (2)	C17—N3—P2	118.4 (2)
O2—C2—C1	118.6 (2)	N3—C17—C18	111.5 (3)
C3—C2—C1	122.8 (2)	N3—C17—H17A	109.3
C4—C3—C2	118.0 (2)	C18—C17—H17A	109.3
C4—C3—H3	121.0	N3—C17—H17B	109.3
C2—C3—H3	121.0	C18—C17—H17B	109.3
C3—C4—C5	121.6 (2)	H17A—C17—H17B	108.0
C3—C4—H4	119.2	C17—C18—C19	111.7 (3)
C5—C4—H4	119.2	C17—C18—H18A	109.3
C6—C5—C4	118.1 (2)	C19—C18—H18A	109.3
C6—C5—H5	120.9	C17—C18—H18B	109.3
C4—C5—H5	120.9	C19—C18—H18B	109.3
C5—C6—C1	122.4 (2)	H18A—C18—H18B	107.9
C5—C6—O1	118.8 (2)	C20—C19—C18	110.2 (3)
C1—C6—O1	118.8 (2)	C20—C19—H19A	109.6
C6—O1—P1	113.66 (15)	C18—C19—H19A	109.6
C2—O2—P2	115.47 (14)	C20—C19—H19B	109.6
C7—N1—C11	110.7 (2)	C18—C19—H19B	109.6
C7—N1—P1	117.55 (17)	H19A—C19—H19B	108.1
C11—N1—P1	115.22 (17)	C19—C20—C21	110.7 (3)
N1—C7—C8	109.6 (3)	C19—C20—H20A	109.5
N1—C7—H7A	109.8	C21—C20—H20A	109.5
C8—C7—H7A	109.8	C19—C20—H20B	109.5
N1—C7—H7B	109.8	C21—C20—H20B	109.5
C8—C7—H7B	109.8	H20A—C20—H20B	108.1
H7A—C7—H7B	108.2	N3—C21—C20	113.2 (3)
C7—C8—C9	111.6 (3)	N3—C21—H21A	108.9
C7—C8—H8A	109.3	C20—C21—H21A	108.9
C9—C8—H8A	109.3	N3—C21—H21B	108.9
C7—C8—H8B	109.3	C20—C21—H21B	108.9
C9—C8—H8B	109.3	H21A—C21—H21B	107.8
H8A—C8—H8B	108.0	C22—N4—C26	112.93 (19)
C10—C9—C8	109.3 (3)	C22—N4—P2	122.37 (16)
C10—C9—H9A	109.8	C26—N4—P2	122.27 (17)
C8—C9—H9A	109.8	N4—C22—C23	111.4 (3)
C10—C9—H9B	109.8	N4—C22—H22A	109.3
C8—C9—H9B	109.8	C23—C22—H22A	109.3
H9A—C9—H9B	108.3	N4—C22—H22B	109.3
C11—C10—C9	111.5 (3)	C23—C22—H22B	109.3
C11—C10—H10A	109.3	H22A—C22—H22B	108.0
C9—C10—H10A	109.3	C22—C23—C24	109.5 (3)
C11—C10—H10B	109.3	C22—C23—H23A	109.8
C9—C10—H10B	109.3	C24—C23—H23A	109.8
H10A—C10—H10B	108.0	C22—C23—H23B	109.8
N1—C11—C10	111.8 (3)	C24—C23—H23B	109.8
N1—C11—H11A	109.3	H23A—C23—H23B	108.2
C10—C11—H11A	109.3	C23—C24—C25	110.7 (3)
N1—C11—H11B	109.3	C23—C24—H24A	109.5
C10—C11—H11B	109.3	C25—C24—H24A	109.5
H11A—C11—H11B	107.9	C23—C24—H24B	109.5
C16—N2—C12	113.5 (2)	C25—C24—H24B	109.5
C16—N2—P1	122.31 (18)	H24A—C24—H24B	108.1
C12—N2—P1	121.26 (18)	C26—C25—C24	111.3 (3)
N2—C12—C13	111.1 (2)	C26—C25—H25A	109.4
N2—C12—H12A	109.4	C24—C25—H25A	109.4
C13—C12—H12A	109.4	C26—C25—H25B	109.4
N2—C12—H12B	109.4	C24—C25—H25B	109.4
C13—C12—H12B	109.4	H25A—C25—H25B	108.0
H12A—C12—H12B	108.0	N4—C26—C25	110.7 (3)
C12—C13—C14	110.7 (2)	N4—C26—H26A	109.5
C12—C13—H13A	109.5	C25—C26—H26A	109.5
C14—C13—H13A	109.5	N4—C26—H26B	109.5
C12—C13—H13B	109.5	C25—C26—H26B	109.5
C14—C13—H13B	109.5	H26A—C26—H26B	108.1

C1—Pd1—P1—N2	109.12 (11)	Pd1—P1—N1—C11	−73.1 (2)
P2—Pd1—P1—N2	96.51 (11)	C11—N1—C7—C8	−59.2 (4)
Br1—Pd1—P1—N2	−70.58 (9)	P1—N1—C7—C8	165.5 (3)
C1—Pd1—P1—O1	−8.77 (9)	N1—C7—C8—C9	57.9 (4)
P2—Pd1—P1—O1	−21.39 (10)	C7—C8—C9—C10	−54.5 (5)
Br1—Pd1—P1—O1	171.52 (6)	C8—C9—C10—C11	53.1 (5)
C1—Pd1—P1—N1	−120.48 (11)	C7—N1—C11—C10	59.2 (4)
P2—Pd1—P1—N1	−133.10 (10)	P1—N1—C11—C10	−164.4 (2)
Br1—Pd1—P1—N1	59.81 (9)	C9—C10—C11—N1	−56.2 (4)
C1—Pd1—P2—N4	−117.13 (11)	O1—P1—N2—C16	−44.3 (2)
P1—Pd1—P2—N4	−104.54 (11)	N1—P1—N2—C16	58.5 (2)
Br1—Pd1—P2—N4	62.52 (10)	Pd1—P1—N2—C16	−160.24 (17)
C1—Pd1—P2—O2	0.34 (9)	O1—P1—N2—C12	115.2 (2)
P1—Pd1—P2—O2	12.94 (10)	N1—P1—N2—C12	−142.08 (19)
Br1—Pd1—P2—O2	180.00 (7)	Pd1—P1—N2—C12	−0.8 (2)
C1—Pd1—P2—N3	110.24 (12)	C16—N2—C12—C13	56.8 (3)
P1—Pd1—P2—N3	122.84 (12)	P1—N2—C12—C13	−104.4 (2)
Br1—Pd1—P2—N3	−70.10 (11)	N2—C12—C13—C14	−54.9 (3)
P1—Pd1—C1—C2	−175.34 (19)	C12—C13—C14—C15	54.5 (3)
P2—Pd1—C1—C2	0.39 (17)	C13—C14—C15—C16	−54.8 (3)
P1—Pd1—C1—C6	5.65 (16)	C12—N2—C16—C15	−56.5 (3)
P2—Pd1—C1—C6	−178.63 (18)	P1—N2—C16—C15	104.4 (2)
C6—C1—C2—O2	177.85 (19)	C14—C15—C16—N2	55.2 (3)
Pd1—C1—C2—O2	−1.2 (3)	N4—P2—N3—C21	−47.9 (2)
C6—C1—C2—C3	−1.3 (3)	O2—P2—N3—C21	−158.0 (2)
Pd1—C1—C2—C3	179.68 (18)	Pd1—P2—N3—C21	89.0 (2)
O2—C2—C3—C4	−177.5 (2)	N4—P2—N3—C17	164.8 (2)
C1—C2—C3—C4	1.6 (4)	O2—P2—N3—C17	54.7 (2)
C2—C3—C4—C5	−0.4 (4)	Pd1—P2—N3—C17	−58.3 (3)
C3—C4—C5—C6	−1.0 (4)	C21—N3—C17—C18	−54.1 (4)
C4—C5—C6—C1	1.4 (3)	P2—N3—C17—C18	95.9 (3)
C4—C5—C6—O1	179.8 (2)	N3—C17—C18—C19	54.9 (4)
C2—C1—C6—C5	−0.3 (3)	C17—C18—C19—C20	−54.8 (4)
Pd1—C1—C6—C5	178.77 (17)	C18—C19—C20—C21	53.4 (4)
C2—C1—C6—O1	−178.70 (19)	C17—N3—C21—C20	54.1 (3)
Pd1—C1—C6—O1	0.4 (3)	P2—N3—C21—C20	−94.9 (3)
C5—C6—O1—P1	172.54 (17)	C19—C20—C21—N3	−53.7 (4)
C1—C6—O1—P1	−9.0 (2)	O2—P2—N4—C22	−113.9 (2)
N2—P1—O1—C6	−110.08 (16)	N3—P2—N4—C22	143.9 (2)
N1—P1—O1—C6	143.25 (16)	Pd1—P2—N4—C22	1.4 (3)
Pd1—P1—O1—C6	11.78 (15)	O2—P2—N4—C26	47.1 (2)
C3—C2—O2—P2	−179.37 (18)	N3—P2—N4—C26	−55.1 (2)
C1—C2—O2—P2	1.5 (3)	Pd1—P2—N4—C26	162.4 (2)
N4—P2—O2—C2	121.83 (17)	C26—N4—C22—C23	−58.1 (3)
N3—P2—O2—C2	−131.42 (17)	P2—N4—C22—C23	104.5 (3)
Pd1—P2—O2—C2	−1.04 (17)	N4—C22—C23—C24	57.4 (4)
N2—P1—N1—C7	−165.4 (2)	C22—C23—C24—C25	−55.9 (5)
O1—P1—N1—C7	−54.8 (2)	C23—C24—C25—C26	54.6 (5)
Pd1—P1—N1—C7	60.2 (2)	C22—N4—C26—C25	55.4 (3)
N2—P1—N1—C11	61.2 (2)	P2—N4—C26—C25	−107.3 (3)
O1—P1—N1—C11	171.9 (2)	C24—C25—C26—N4	−53.4 (4)

Experimental details

Crystal data
Chemical formula	[PdBr(C₂₆H₄₃N₄O₂P₂)]
M_r	691.9
Crystal system, space group	Triclinic, P1
Temperature (K)	183
a, b, c (Å)	9.8843 (15), 12.3457 (19), 13.815 (2)
α, β, γ (°)	76.635 (18), 70.676 (17), 73.847 (17)
V (Å³)	1510.0 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.07
Crystal size (mm)	0.33 × 0.32 × 0.12

Data collection
Diffractometer	Stoe IPDS diffractometer
Absorption correction	Numerical (Coppens et al., 1965)
T_min, T_max	0.568, 0.797
No. of measured, independent and observed [I > 2σ(I)] reflections	19696, 4989, 4431
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.065, 1.02
No. of reflections	4989
No. of parameters	325
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.71, −0.37

Computer programs: IPDS Software (Stoe & Cie, 1999), SHELXS97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and SHELXL97 (Sheldrick, 1997).

Selected geometric parameters (Å, º) top

Pd1—C1	1.988 (2)	P1—N1	1.6762 (18)
Pd1—P1	2.2808 (7)	P2—N4	1.631 (2)
Pd1—P2	2.2891 (7)	P2—O2	1.6563 (19)
Pd1—Br1	2.5066 (7)	P2—N3	1.663 (2)
P1—N2	1.643 (2)	C2—O2	1.386 (3)
P1—O1	1.6549 (19)	C6—O1	1.397 (3)

C1—Pd1—P1	80.14 (7)	P1—Pd1—Br1	99.20 (3)
C1—Pd1—P2	80.63 (7)	P2—Pd1—Br1	100.00 (3)
P1—Pd1—P2	160.31 (3)	O1—P1—Pd1	104.72 (6)
C1—Pd1—Br1	179.28 (7)	O2—P2—Pd1	103.76 (7)

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Bis[2,6-bis­(dipiperidin-1-ylphosphanyl­oxy)­phen­yl]bromidopalladium(II)

Supporting information

Key indicators

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Bis[2,6-bis(dipiperidin-1-ylphosphanyloxy)phenyl]bromidopalladium(II)