The twinned crystal structure of di­iodo­bis­(tri­phenyl­phosphine)palladium(II) di­chloro­methane disolvate at 173 K

metal-organic papers

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2(C18H15P)2]2CH2Cl2 doi:10.1107/S1600536806013262 Acta Cryst.(2006). E62, m1056–m1058 Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

The twinned crystal structure of

diiodobis(tri-phenylphosphine)palladium(II) dichloromethane

disolvate at 173 K

Thomas Theissmannaand Michael Bolteb*

a

Institut fu¨r Organische Chemie, J. W. Goethe-Universita¨t Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany, andb_Institut

fu¨r Anorganische Chemie, J. W. Goethe-Universita¨t Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany

Correspondence e-mail: bolte@chemie.uni-frankfurt.de

Key indicators

Single-crystal X-ray study T= 173 K

Mean(C–C) = 0.015 A˚ Rfactor = 0.047 wRfactor = 0.148

Data-to-parameter ratio = 18.8

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

Received 10 April 2006 Accepted 11 April 2006

#2006 International Union of Crystallography

All rights reserved

The structure of the title compound, [PdI2(C18H15P)2]

-2CH2Cl2, has previously been reported by Debaerdemaeker,

Kutoglu, Schmid & Weber [Acta Cryst. (1973), B29, 1283– 1288] at room temperature. We report the structure determi-nation of this compound from a twinned crystal at 173 (2) K. The Pd atom is located on a centre of inversion and has square-planar coordination geometry.

Comment

While attempting to synthesize (R)-2,20 -bis(methoxymeth-oxy)-3,30-diphenanthren-9-yl[1,10]binaphthalenyl by a Suzuki coupling reaction (see scheme), we instead obtained crystals of the title compound, (I). The structure of (I) has previously been reported by Debaerdemaekeret al.(1973). The structure was determined using data collected from a yellow needle at room temperature, but the coordinates of the H atoms were not reported. We obtained dark-red block-shaped crystals of (I) which appeared to be twinned. However, after applying the appropriate twin law, satisfactory refinement was possible and our results are of higher precision than that previously reported.

calcu-lated bond lengths and angles are higher overall. The final residual indices for the title compound are lower, with R1=

0.047 compared with 0.081 in the original determination. The Pd atom is located on a centre of inversion. It is coordinated by two I and two P atoms in a square-planar fashion. The C—P—C angles are significantly smaller than the C—P—Pd angles. The crystal structure of (I) was discussed extensively by Debaerdemaekeret al.(1973) and those details agree with the title structure.

Experimental

A mixture of (R)-3,30_-diiodo-2,20_{-bis(methoxmethoxy)-1,1}0

-binaph-thalenyl (3.0 g, 5 mmol), Ba(OH)28H2O (7.90 g, 25 mmol, 5

equiva-lents) and 9-phenanthrenyl boronic acid (3.30 g, 15 mmol, 3 equivalents) was dissolved in dioxan–H2O (3:1v/v, 120 ml). The

solution was degassed, followed by addition of Pd(PPh3)4(0.55 g,

0.5 mmol, 10 mol%). The reaction mixture was heated to 383 K for 48 h. After cooling, the dioxan was evaporated and the residue was extracted with CH2Cl2(370 ml). The organic layer was dried over

MgSO4and the solvent was removed under reduced pressure. The

crude product was purified by column chromatography (SiO2) with

hexane–ethyl acetate as eluent. For further purification, the isolated product was recrystallized from CH2Cl2–hexane (1:10) (yield 2.50 g,

72%), and crystals of I2Pd(PPh3)2were isolated as a by-product.

Crystal data

[PdI2(C18H15P)2]2CH2Cl2

Mr= 1054.59

Monoclinic,P2₁=c a= 11.8422 (6) A˚

b= 20.3802 (7) A˚

c= 8.2420 (4) A˚

= 95.364 (4) V= 1980.47 (15) A˚3

Z= 2

Dx= 1.768 Mg m 3

MoKradiation

= 2.40 mm1

T= 173 (2) K Block, dark red 0.320.300.28 mm

Data collection

Stoe IPDS-II two-circle diffractometer

!scans

Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)

Tmin= 0.513,Tmax= 0.553

(expected range = 0.474–0.510) 43265 measured reflections 4044 independent reflections 3868 reflections withI> 2(I)

Rint= 0.074 max= 26.5

Refinement

Refinement onF2

R[F2_{> 2(F}2_{)] = 0.047}

wR(F2_{) = 0.148}

S= 1.37 4044 reflections 215 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0112P)2

+ 25.7032P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001 max= 1.36 e A˚

3 min=1.20 e A˚

3

Table 1

Selected geometric parameters (A˚ ,_).

Pd1—P1 2.340 (2) Pd1—I1 2.6009 (6) P1—C31 1.823 (9)

P1—C21 1.826 (9) P1—C11 1.834 (9)

P1i

—Pd1—I1 92.70 (5) P1—Pd1—I1 87.30 (5) C31—P1—C21 107.7 (4) C31—P1—C11 103.1 (4)

C21—P1—C11 102.1 (4) C31—P1—Pd1 111.5 (3) C21—P1—Pd1 112.5 (3) C11—P1—Pd1 118.9 (3)

Symmetry code: (i)xþ1;yþ1;zþ1.

Having encountered problems during the determination of the unit-cell parameters of several crystals of (I), all of which looked of good quality, the unit cell was eventually determined using approxi-mately two thirds of the inital reflections. The same cell in a different orientation was obtained for the remaining third of the reflections, indicating that the crystals were twinned. However, the structure could be solved, but anisotropic refinement converged with wR2=

0.261 andR1= 0.125 using all data. At this point, the anisotropic

displacement parameters appeared strange and high residual peaks showed up in difference electron-densitity maps (highest peak 5.64 e A˚3_{and deepest hole3.17 e A˚}3_{). The twin law (1 0 0.268/}

0 1 0/0 0 1) was obtained using the programTWINLAW(Bolte, 2004). The file containing the reflection data was then modified using the programHKLF5(Bolte, 2004), using a distance of 0.015 A˚1as the maximum distance for overlap of two reflections of the different domains. This treatment provided ultimate success (R1 dropped

below 0.1) and all H atoms could now be located in a difference Fourier map. They were refined with fixed individual isotropic displacement parameters [Uiso(H) = 1.2Ueq(C)] using a riding model,

with C—H(aromatic) = 0.95 A˚ or C—H(methylene) = 0.99 A˚. The twin ratio refined to 0.316 (2)/0.684 (2). The highest peak in the final difference map is located 1.48 A˚ from atom C32 and the deepest hole 1.22 A˚ from C11.

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement:

X-AREA; data reduction: X-AREA; program(s) used to solve structure:SHELXS97(Sheldrick, 1990); program(s) used to refine structure:SHELXL97(Sheldrick, 1997); molecular graphics:XPin

SHELXTL-Plus(Sheldrick, 1991); software used to prepare material for publication:SHELXL97andPLATON(Spek, 2003).

References

Blessing, R. H. (1995).Acta Cryst.A51, 33–38. Bolte, M. (2004).J. Appl. Cryst.37, 162–165.

Debaerdemaeker, T., Kutoglu, A., Schmid, G. & Weber, L. (1973).Acta Cryst.

B29, 1283–1288.

metal-organic papers

Acta Cryst.(2006). E62, m1056–m1058 Theissmann and Bolte _[PdI

2(C18H15P)2]2CH2Cl2

m1057

Figure 1

A perspective view of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The CH2Cl2solvent molecule and all H atoms have been omitted for

Sheldrick, G. M. (1990).Acta Cryst.A46, 467–473.

Sheldrick, G. M. (1991). SHELXTL-Plus. Release 4.1. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997).SHELXL97. University of Go¨ttingen, Germany. Spek, A. L. (2003).J. Appl. Cryst.36, 7–13.

Stoe & Cie (2001).X-AREA. Stoe & Cie, Darmstadt, Germany.

metal-organic papers

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Acta Cryst. (2006). E62, m1056–m1058

supporting information

Acta Cryst. (2006). E62, m1056–m1058 [https://doi.org/10.1107/S1600536806013262]

The twinned crystal structure of diiodobis(triphenylphosphine)palladium(II)

di-chloromethane disolvate at 173

K

Thomas Theissmann and Michael Bolte

diiodobis(triphenylphosphine)palladium(II) dichloromethane disolvate

Crystal data

[PdI2(C18H15P)2]·2CH2Cl2

Mr = 1054.59

Monoclinic, P21/c

Hall symbol: -P 2ybc

a = 11.8422 (6) Å

b = 20.3802 (7) Å

c = 8.2420 (4) Å

β = 95.364 (4)°

V = 1980.47 (15) Å3

Z = 2

F(000) = 1024

Dx = 1.768 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 43265 reflections

θ = 2.0–26.7°

µ = 2.41 mm−1

T = 173 K Block, dark red 0.32 × 0.30 × 0.28 mm

Data collection

Stoe IPDS-II two-circle diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

Absorption correction: multi-scan

(MULABS; Spek, 2003; Blessing, 1995)

Tmin = 0.513, Tmax = 0.553

43265 measured reflections 4044 independent reflections 3868 reflections with I > 2σ(I)

Rint = 0.074

θmax = 26.5°, θmin = 2.0°

h = −14→14

k = −25→25

l = −8→10

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.047}

wR(F2_{) = 0.148}

S = 1.37 4044 reflections 215 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2_(F

o2) + (0.0112P)2 + 25.7032P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 1.36 e Å−3

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Acta Cryst. (2006). E62, m1056–m1058 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 F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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.

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

x y z Uiso*/Ueq

Pd1 0.5000 0.5000 0.5000 0.0179 (2)

I1 0.61286 (5) 0.39141 (3) 0.47747 (8) 0.02967 (18)

P1 0.36134 (18) 0.43787 (10) 0.6144 (3) 0.0192 (4)

C11 0.2503 (7) 0.4805 (4) 0.7140 (12) 0.0253 (19)

C12 0.2500 (9) 0.4838 (5) 0.8822 (13) 0.032 (2)

H12 0.3078 0.4622 0.9499 0.038*

C13 0.1657 (10) 0.5185 (6) 0.9528 (15) 0.043 (3)

H13 0.1674 0.5215 1.0680 0.051*

C14 0.0799 (9) 0.5485 (6) 0.8551 (16) 0.044 (3)

H14 0.0222 0.5720 0.9031 0.052*

C15 0.0775 (9) 0.5444 (6) 0.6864 (17) 0.045 (3)

H15 0.0179 0.5648 0.6195 0.054*

C16 0.1617 (8) 0.5108 (5) 0.6156 (14) 0.033 (2)

H16 0.1597 0.5081 0.5003 0.040*

C21 0.2785 (7) 0.3875 (4) 0.4635 (11) 0.0231 (18)

C22 0.1838 (8) 0.3533 (4) 0.5056 (12) 0.028 (2)

H22 0.1637 0.3556 0.6143 0.034*

C23 0.1183 (9) 0.3160 (5) 0.3920 (14) 0.037 (2)

H23 0.0548 0.2922 0.4228 0.044*

C24 0.1471 (9) 0.3140 (5) 0.2316 (14) 0.037 (2)

H24 0.1024 0.2888 0.1528 0.045*

C25 0.2388 (9) 0.3479 (5) 0.1862 (13) 0.036 (2)

H25 0.2572 0.3462 0.0766 0.044*

C26 0.3061 (8) 0.3853 (5) 0.3025 (12) 0.029 (2)

H26 0.3698 0.4089 0.2714 0.035*

C31 0.4239 (7) 0.3834 (4) 0.7736 (11) 0.0205 (17)

C32 0.5071 (8) 0.4101 (5) 0.8858 (11) 0.0270 (19)

H32 0.5281 0.4548 0.8758 0.032*

C33 0.5598 (8) 0.3724 (5) 1.0118 (12) 0.032 (2)

H33 0.6143 0.3913 1.0901 0.038*

C34 0.5306 (8) 0.3059 (5) 1.0203 (13) 0.034 (2)

H34 0.5656 0.2793 1.1052 0.040*

C35 0.4507 (9) 0.2786 (5) 0.9052 (13) 0.033 (2)

H35 0.4331 0.2332 0.9099 0.039*

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Acta Cryst. (2006). E62, m1056–m1058

H36 0.3418 0.2982 0.7088 0.029*

C1 0.8212 (10) 0.3169 (7) 0.829 (2) 0.064 (4)

H1A 0.7552 0.3384 0.7683 0.077*

H1B 0.8179 0.3265 0.9464 0.077*

Cl1 0.8113 (3) 0.2321 (2) 0.7992 (7) 0.0814 (13)

Cl2 0.9452 (3) 0.3500 (2) 0.7662 (6) 0.0732 (11)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Pd1 0.0170 (4) 0.0151 (4) 0.0221 (4) −0.0002 (3) 0.0036 (4) 0.0013 (3)

I1 0.0305 (3) 0.0214 (3) 0.0385 (3) 0.0045 (2) 0.0109 (3) 0.0026 (2)

P1 0.0183 (10) 0.0173 (10) 0.0225 (11) −0.0016 (8) 0.0041 (8) 0.0012 (8)

C11 0.018 (4) 0.020 (4) 0.038 (5) 0.000 (3) 0.004 (4) −0.004 (4)

C12 0.035 (5) 0.028 (5) 0.034 (5) −0.006 (4) 0.010 (4) −0.003 (4)

C13 0.046 (6) 0.043 (6) 0.041 (6) −0.002 (5) 0.020 (5) −0.007 (5)

C14 0.032 (5) 0.037 (6) 0.064 (8) 0.002 (5) 0.014 (5) −0.007 (6)

C15 0.027 (5) 0.041 (6) 0.068 (8) 0.008 (5) 0.009 (5) −0.009 (6)

C16 0.025 (5) 0.033 (5) 0.041 (6) 0.004 (4) 0.001 (4) −0.001 (5)

C21 0.020 (4) 0.018 (4) 0.031 (5) 0.000 (3) 0.001 (4) −0.001 (4)

C22 0.027 (5) 0.026 (5) 0.032 (5) −0.004 (4) 0.004 (4) 0.000 (4)

C23 0.030 (5) 0.030 (5) 0.050 (6) −0.006 (4) −0.002 (5) 0.002 (5)

C24 0.036 (5) 0.028 (5) 0.045 (6) −0.002 (4) −0.012 (5) −0.012 (5)

C25 0.037 (6) 0.041 (6) 0.029 (5) 0.007 (5) −0.005 (4) −0.003 (5)

C26 0.030 (5) 0.031 (5) 0.028 (5) 0.001 (4) 0.006 (4) 0.002 (4)

C31 0.022 (4) 0.019 (4) 0.021 (4) 0.000 (3) 0.004 (3) 0.004 (3)

C32 0.025 (4) 0.026 (4) 0.029 (5) −0.007 (4) −0.002 (4) 0.001 (4)

C33 0.025 (5) 0.040 (5) 0.029 (5) −0.001 (4) −0.005 (4) 0.000 (4)

C34 0.032 (5) 0.039 (5) 0.030 (5) 0.009 (4) 0.005 (4) 0.012 (4)

C35 0.039 (5) 0.023 (4) 0.038 (5) 0.003 (4) 0.006 (4) 0.009 (4)

C36 0.023 (4) 0.020 (4) 0.030 (5) −0.004 (3) 0.005 (4) −0.001 (4)

C1 0.032 (6) 0.078 (10) 0.082 (11) 0.010 (6) 0.007 (7) 0.018 (9)

Cl1 0.057 (2) 0.072 (3) 0.111 (4) −0.0132 (18) −0.017 (2) 0.016 (3)

Cl2 0.063 (2) 0.074 (2) 0.088 (3) −0.0106 (19) 0.037 (2) −0.012 (2)

Geometric parameters (Å, º)

Pd1—P1i _{2.340 (2) C23—C24 1.397 (16)}

Pd1—P1 2.340 (2) C23—H23 0.9500

Pd1—I1 2.6009 (6) C24—C25 1.368 (15)

Pd1—I1i _{2.6009 (6) C24—H24 0.9500}

P1—C31 1.823 (9) C25—C26 1.412 (14)

P1—C21 1.826 (9) C25—H25 0.9500

P1—C11 1.834 (9) C26—H26 0.9500

C11—C12 1.388 (14) C31—C36 1.394 (12)

C11—C16 1.407 (13) C31—C32 1.397 (12)

C12—C13 1.394 (14) C32—C33 1.391 (13)

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Acta Cryst. (2006). E62, m1056–m1058

C13—C14 1.380 (17) C33—C34 1.403 (14)

C13—H13 0.9500 C33—H33 0.9500

C14—C15 1.391 (18) C34—C35 1.392 (15)

C14—H14 0.9500 C34—H34 0.9500

C15—C16 1.383 (14) C35—C36 1.367 (13)

C15—H15 0.9500 C35—H35 0.9500

C16—H16 0.9500 C36—H36 0.9500

C21—C22 1.391 (12) C1—Cl2 1.739 (14)

C21—C26 1.397 (13) C1—Cl1 1.748 (16)

C22—C23 1.385 (14) C1—H1A 0.9900

C22—H22 0.9500 C1—H1B 0.9900

P1i_{—Pd1—P1 180.0 C22—C23—C24 119.0 (10)}

P1i_{—Pd1—I1 92.70 (5) C22—C23—H23 120.5}

P1—Pd1—I1 87.30 (5) C24—C23—H23 120.5

P1i_—Pd1—I1i _{87.30 (5) C25—C24—C23 121.0 (10)}

P1—Pd1—I1i _{92.70 (5) C25—C24—H24 119.5}

I1—Pd1—I1i _{179.999 (1) C23—C24—H24 119.5}

C31—P1—C21 107.7 (4) C24—C25—C26 120.0 (10)

C31—P1—C11 103.1 (4) C24—C25—H25 120.0

C21—P1—C11 102.1 (4) C26—C25—H25 120.0

C31—P1—Pd1 111.5 (3) C21—C26—C25 119.6 (9)

C21—P1—Pd1 112.5 (3) C21—C26—H26 120.2

C11—P1—Pd1 118.9 (3) C25—C26—H26 120.2

C12—C11—C16 118.9 (9) C36—C31—C32 118.7 (8)

C12—C11—P1 122.6 (8) C36—C31—P1 124.2 (7)

C16—C11—P1 118.5 (8) C32—C31—P1 117.0 (6)

C11—C12—C13 120.6 (10) C33—C32—C31 121.3 (9)

C11—C12—H12 119.7 C33—C32—H32 119.4

C13—C12—H12 119.7 C31—C32—H32 119.4

C14—C13—C12 119.9 (11) C32—C33—C34 118.3 (9)

C14—C13—H13 120.0 C32—C33—H33 120.8

C12—C13—H13 120.0 C34—C33—H33 120.8

C13—C14—C15 120.1 (10) C35—C34—C33 120.5 (9)

C13—C14—H14 119.9 C35—C34—H34 119.7

C15—C14—H14 119.9 C33—C34—H34 119.7

C16—C15—C14 120.3 (11) C36—C35—C34 120.1 (9)

C16—C15—H15 119.9 C36—C35—H35 120.0

C14—C15—H15 119.9 C34—C35—H35 120.0

C15—C16—C11 120.1 (11) C35—C36—C31 121.0 (9)

C15—C16—H16 119.9 C35—C36—H36 119.5

C11—C16—H16 119.9 C31—C36—H36 119.5

C22—C21—C26 119.1 (9) Cl2—C1—Cl1 112.9 (8)

C22—C21—P1 120.4 (7) Cl2—C1—H1A 109.0

C26—C21—P1 120.4 (7) Cl1—C1—H1A 109.0

C23—C22—C21 121.3 (10) Cl2—C1—H1B 109.0

C23—C22—H22 119.3 Cl1—C1—H1B 109.0

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Acta Cryst. (2006). E62, m1056–m1058

I1—Pd1—P1—C31 47.6 (3) C11—P1—C21—C26 133.0 (8)

I1i_{—Pd1—P1—C31 −132.4 (3) Pd1—P1—C21—C26 4.4 (8)}

I1—Pd1—P1—C21 −73.5 (3) C26—C21—C22—C23 1.7 (14)

I1i_{—Pd1—P1—C21 106.5 (3) P1—C21—C22—C23 178.5 (8)}

I1—Pd1—P1—C11 167.3 (4) C21—C22—C23—C24 −1.3 (15)

I1i_{—Pd1—P1—C11 −12.7 (4) C22—C23—C24—C25 0.4 (16)}

C31—P1—C11—C12 19.5 (9) C23—C24—C25—C26 0.3 (16)

C21—P1—C11—C12 131.2 (8) C22—C21—C26—C25 −1.0 (14)

Pd1—P1—C11—C12 −104.4 (8) P1—C21—C26—C25 −177.8 (7)

C31—P1—C11—C16 −160.1 (7) C24—C25—C26—C21 0.1 (15)

C21—P1—C11—C16 −48.4 (8) C21—P1—C31—C36 −8.4 (9)

Pd1—P1—C11—C16 76.0 (8) C11—P1—C31—C36 99.1 (8)

C16—C11—C12—C13 −2.4 (15) Pd1—P1—C31—C36 −132.2 (7)

P1—C11—C12—C13 178.0 (8) C21—P1—C31—C32 168.7 (7)

C11—C12—C13—C14 1.8 (16) C11—P1—C31—C32 −83.9 (7)

C12—C13—C14—C15 −0.2 (17) Pd1—P1—C31—C32 44.8 (8)

C13—C14—C15—C16 −0.6 (18) C36—C31—C32—C33 −2.8 (14)

C14—C15—C16—C11 −0.1 (17) P1—C31—C32—C33 180.0 (7)

C12—C11—C16—C15 1.5 (15) C31—C32—C33—C34 2.4 (15)

P1—C11—C16—C15 −178.8 (8) C32—C33—C34—C35 −0.1 (15)

C31—P1—C21—C22 64.4 (8) C33—C34—C35—C36 −1.9 (15)

C11—P1—C21—C22 −43.7 (8) C34—C35—C36—C31 1.5 (15)

Pd1—P1—C21—C22 −172.4 (6) C32—C31—C36—C35 0.8 (13)

C31—P1—C21—C26 −118.8 (8) P1—C31—C36—C35 177.8 (7)