The allyl complex di-μ-chloro-bis­{[(1,2,3-η)-4-oxo-5,5-di­methyl-1-(ethoxy­carbonyl)­hexenyl]palladium(II)}

The title compound, di-μ-chloro-bis{[(2,3,4-η)-ethyl 6,6-di­methyl-5-oxohept-2-enoato]­palladium(II)}, [Pd₂Cl₂(C₁₁­H₁₇­O₃)₂], is a binuclear chloro-bridged palladium allyl complex that was obtained serendipitously From the reaction of 6,6-di­methyl-2-hepten-4-ynoate with Na₂PdCl₄ in water-containing alcohol. The allyl group is substituted with an ester and a tert-butyl­carboxy group. The dimeric mol­ecules link via C—H...O contacts into a two-dimensional network parallel to the bc plane.

Computing details

Data collection: Locally modified CAD-4 Software (Enraf-Nonius, 1989); cell refinement: SET4 (de Boer & Duisenberg, 1984); data reduction: HELENA (Spek, 1997); program(s) used to solve structure: DIRDIF99 (Beurskens et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2000); software used to prepare material for publication: PLATON.

Bis(µ₂-chloro)-bis-[1,2,3,3-(4-oxo-6,6-dimethyl-1-ethoxycarbonyl)- hexenyl]-palladium (II)

Crystal data

[Pd2(C11H17O3)2Cl2]	Z = 1
Mr = 678.23	F(000) = 340
Triclinic, P1	Least Squares Treatment of 25 SET4 setting angles.
Hall symbol: -P 1	Dx = 1.734 Mg m^−3
a = 6.6157 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.654 (4) Å	Cell parameters from 25 reflections
c = 10.748 (4) Å	θ = 9.6–14.0°
α = 101.96 (3)°	µ = 1.62 mm^−1
β = 90.13 (3)°	T = 150 K
γ = 104.29 (3)°	Plate, orange
V = 649.7 (4) Å^3	0.50 × 0.42 × 0.13 mm

Data collection

CAD4T diffractometer	2903 reflections with I > 2σ(I)
Radiation source: Rotating Anode	Rint = 0.034
Graphite monochromator	θmax = 27.5°, θmin = 1.9°
ω–scan	h = −8→8
Absorption correction: analytical (De Meulenaer & Tompa, 1965)	k = −12→12
Tmin = 0.549, Tmax = 0.805	l = −13→13
6309 measured reflections	3 standard reflections every 60 min
2994 independent reflections	intensity decay: 3%

Refinement

Refinement on F^2	161 parameters
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.018	w = 1/[σ^2(Fo^2) + (0.0134P)^2 + 0.225P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.044	(Δ/σ)max < 0.002
S = 1.12	Δρmax = 0.45 e Å^−3
2994 reflections	Δρmin = −0.68 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F^{2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F}2, conventional R-factors R are based on F, with F set to zero for negative F^{2. The observed criterion of F}2 > σ(F^{2) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F}2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Pd1	0.09560 (2)	1.03703 (1)	0.36047 (1)	0.0190 (1)
Cl1	0.09406 (8)	0.85197 (4)	0.47707 (4)	0.0299 (1)
O1	−0.2290 (2)	1.17828 (14)	0.18198 (15)	0.0346 (4)
O2	−0.0129 (2)	1.38560 (13)	0.29216 (14)	0.0339 (4)
O3	0.0620 (2)	0.73743 (15)	0.11137 (15)	0.0377 (4)
C1	−0.0609 (3)	1.24567 (17)	0.23201 (17)	0.0254 (4)
C2	0.1227 (3)	1.18370 (18)	0.23709 (17)	0.0241 (4)
C3	0.1127 (3)	1.04112 (17)	0.16695 (15)	0.0219 (4)
C4	0.2662 (3)	0.97428 (18)	0.19883 (16)	0.0227 (4)
C5	0.2334 (2)	0.81170 (17)	0.15246 (16)	0.0232 (4)
C6	0.4227 (3)	0.74894 (18)	0.15565 (16)	0.0245 (4)
C7	0.5484 (3)	0.8076 (2)	0.28382 (19)	0.0377 (6)
C8	0.5590 (3)	0.79659 (19)	0.04958 (17)	0.0274 (4)
C9	0.3500 (3)	0.5822 (2)	0.1306 (2)	0.0392 (6)
C10	−0.1768 (3)	1.4613 (2)	0.2914 (2)	0.0437 (7)
C11	−0.3061 (4)	1.4465 (3)	0.3992 (3)	0.0587 (9)
H2	0.259 (4)	1.248 (3)	0.259 (2)	0.046 (7)*
H3	−0.012 (4)	0.987 (2)	0.120 (2)	0.025 (5)*
H4	0.397 (4)	1.032 (2)	0.220 (2)	0.030 (5)*
H7A	0.60000	0.91420	0.29770	0.0570*
H7B	0.66710	0.76360	0.28320	0.0570*
H7C	0.45870	0.78260	0.35240	0.0570*
H8A	0.60350	0.90370	0.06630	0.0410*
H8B	0.47850	0.75960	−0.03240	0.0410*
H8C	0.68220	0.75700	0.04690	0.0410*
H9A	0.47180	0.54090	0.12150	0.0590*
H9B	0.26030	0.54580	0.05210	0.0590*
H9C	0.27140	0.55290	0.20210	0.0590*
H10A	−0.26490	1.42030	0.21130	0.0530*
H10B	−0.11340	1.56630	0.29460	0.0530*
H11A	−0.37200	1.34280	0.39480	0.0880*
H11B	−0.41450	1.49940	0.39690	0.0880*
H11C	−0.21920	1.48750	0.47850	0.0880*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.0222 (1)	0.0175 (1)	0.0186 (1)	0.0070 (1)	0.0014 (1)	0.0046 (1)
Cl1	0.0489 (3)	0.0253 (2)	0.0240 (2)	0.0218 (2)	0.0111 (2)	0.0092 (2)
O1	0.0302 (7)	0.0286 (6)	0.0463 (8)	0.0097 (5)	−0.0093 (6)	0.0083 (6)
O2	0.0301 (6)	0.0204 (5)	0.0518 (8)	0.0066 (5)	−0.0010 (6)	0.0086 (5)
O3	0.0219 (6)	0.0327 (6)	0.0526 (9)	0.0076 (5)	−0.0032 (6)	−0.0051 (6)
C1	0.0279 (8)	0.0209 (7)	0.0302 (8)	0.0060 (6)	0.0013 (7)	0.0118 (6)
C2	0.0215 (7)	0.0238 (7)	0.0296 (8)	0.0049 (6)	0.0026 (6)	0.0127 (6)
C3	0.0218 (7)	0.0269 (7)	0.0193 (7)	0.0060 (6)	0.0059 (6)	0.0101 (6)
C4	0.0180 (7)	0.0256 (7)	0.0241 (7)	0.0052 (6)	0.0047 (6)	0.0049 (6)
C5	0.0193 (7)	0.0261 (7)	0.0239 (7)	0.0068 (6)	0.0045 (6)	0.0037 (6)
C6	0.0204 (7)	0.0260 (7)	0.0288 (8)	0.0083 (6)	0.0041 (6)	0.0070 (6)
C7	0.0342 (10)	0.0532 (11)	0.0311 (9)	0.0222 (9)	−0.0023 (8)	0.0077 (8)
C8	0.0199 (7)	0.0319 (8)	0.0308 (8)	0.0080 (6)	0.0046 (6)	0.0056 (7)
C9	0.0338 (9)	0.0273 (8)	0.0604 (13)	0.0119 (7)	0.0110 (9)	0.0128 (9)
C10	0.0414 (11)	0.0263 (8)	0.0662 (14)	0.0155 (8)	−0.0035 (10)	0.0077 (9)
C11	0.0480 (14)	0.0668 (16)	0.0653 (16)	0.0260 (12)	0.0008 (12)	0.0092 (13)

Geometric parameters (Å, º)

Pd1—Cl1	2.3836 (11)	C2—H2	0.96 (3)
Pd1—C2	2.109 (2)	C3—H3	0.94 (2)
Pd1—C3	2.0913 (18)	C4—H4	0.91 (2)
Pd1—C4	2.138 (2)	C7—H7A	0.9801
Pd1—Cl1^i	2.3811 (11)	C7—H7B	0.9801
O1—C1	1.202 (2)	C7—H7C	0.9791
O2—C1	1.330 (2)	C8—H8A	0.9801
O2—C10	1.450 (2)	C8—H8B	0.9804
O3—C5	1.208 (2)	C8—H8C	0.9801
C1—C2	1.486 (3)	C9—H9A	0.9801
C2—C3	1.411 (2)	C9—H9B	0.9795
C3—C4	1.407 (3)	C9—H9C	0.9799
C4—C5	1.505 (2)	C10—H10A	0.9900
C5—C6	1.523 (3)	C10—H10B	0.9901
C6—C7	1.533 (3)	C11—H11A	0.9795
C6—C8	1.530 (3)	C11—H11B	0.9806
C6—C9	1.527 (3)	C11—H11C	0.9794
C10—C11	1.452 (4)
Cl1—Pd1—C2	171.29 (6)	C3—C2—H2	116.8 (16)
Cl1—Pd1—C3	133.15 (6)	Pd1—C3—H3	111.9 (13)
Cl1—Pd1—C4	102.46 (6)	C2—C3—H3	118.7 (14)
Cl1—Pd1—Cl1^i	88.91 (3)	C4—C3—H3	122.1 (13)
C2—Pd1—C3	39.26 (7)	Pd1—C4—H4	103.4 (14)
C2—Pd1—C4	68.83 (8)	C3—C4—H4	117.3 (14)
Cl1^i—Pd1—C2	99.80 (6)	C5—C4—H4	119.8 (14)
C3—Pd1—C4	38.84 (8)	C6—C7—H7A	109.47
Cl1^i—Pd1—C3	131.63 (6)	C6—C7—H7B	109.46
Cl1^i—Pd1—C4	168.60 (6)	C6—C7—H7C	109.49
Pd1—Cl1—Pd1^i	91.09 (3)	H7A—C7—H7B	109.42
C1—O2—C10	116.07 (15)	H7A—C7—H7C	109.48
O1—C1—O2	125.06 (18)	H7B—C7—H7C	109.52
O1—C1—C2	124.74 (16)	C6—C8—H8A	109.48
O2—C1—C2	110.19 (16)	C6—C8—H8B	109.47
Pd1—C2—C1	114.03 (13)	C6—C8—H8C	109.44
Pd1—C2—C3	69.68 (10)	H8A—C8—H8B	109.43
C1—C2—C3	119.38 (17)	H8A—C8—H8C	109.50
Pd1—C3—C2	71.06 (10)	H8B—C8—H8C	109.51
Pd1—C3—C4	72.36 (10)	C6—C9—H9A	109.47
C2—C3—C4	116.82 (16)	C6—C9—H9B	109.46
Pd1—C4—C3	68.80 (10)	C6—C9—H9C	109.49
Pd1—C4—C5	114.79 (12)	H9A—C9—H9B	109.44
C3—C4—C5	119.00 (16)	H9A—C9—H9C	109.47
O3—C5—C4	119.46 (15)	H9B—C9—H9C	109.50
O3—C5—C6	122.83 (16)	O2—C10—H10A	109.38
C4—C5—C6	117.67 (14)	O2—C10—H10B	109.44
C5—C6—C7	111.61 (15)	C11—C10—H10A	109.39
C5—C6—C8	106.47 (15)	C11—C10—H10B	109.44
C5—C6—C9	109.27 (16)	H10A—C10—H10B	108.07
C7—C6—C8	109.39 (16)	C10—C11—H11A	109.49
C7—C6—C9	109.77 (15)	C10—C11—H11B	109.40
C8—C6—C9	110.27 (15)	C10—C11—H11C	109.45
O2—C10—C11	111.07 (18)	H11A—C11—H11B	109.46
Pd1—C2—H2	104.0 (15)	H11A—C11—H11C	109.55
C1—C2—H2	119.7 (17)	H11B—C11—H11C	109.49
C3—Pd1—Cl1—Pd1^i	−153.24 (8)	C1—C2—C3—C4	−164.67 (16)
C4—Pd1—Cl1—Pd1^i	179.17 (5)	C2—C3—C4—Pd1	57.15 (14)
Cl1^i—Pd1—Cl1—Pd1^i	0.00 (3)	C2—C3—C4—C5	164.56 (16)
Cl1—Pd1—Cl1^i—Pd1^i	−0.02 (3)	Pd1—C3—C4—C5	107.41 (15)
C2—Pd1—Cl1^i—Pd1^i	−179.93 (6)	Pd1—C4—C5—O3	63.9 (2)
C3—Pd1—Cl1^i—Pd1^i	153.93 (7)	C3—C4—C5—O3	−14.6 (3)
C10—O2—C1—O1	−2.5 (3)	C3—C4—C5—C6	163.37 (16)
C1—O2—C10—C11	89.0 (2)	Pd1—C4—C5—C6	−118.13 (15)
C10—O2—C1—C2	178.28 (15)	O3—C5—C6—C9	−13.3 (2)
O2—C1—C2—Pd1	107.66 (15)	C4—C5—C6—C7	47.2 (2)
O1—C1—C2—C3	7.8 (3)	C4—C5—C6—C9	168.83 (15)
O1—C1—C2—Pd1	−71.5 (2)	O3—C5—C6—C8	105.8 (2)
O2—C1—C2—C3	−173.02 (16)	C4—C5—C6—C8	−72.09 (18)
Pd1—C2—C3—C4	−57.82 (14)	O3—C5—C6—C7	−134.89 (18)
C1—C2—C3—Pd1	−106.85 (16)

Symmetry code: (i) −x, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O1^ii	0.98	2.558	3.392 (3)	142.9
C9—H9C···O2^iii	0.98	2.498	3.394 (3)	151.9

Symmetry codes: (ii) −x, −y+2, −z; (iii) x, y−1, z.