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A monomeric PdII complex bearing a mixed carbocyclic/N-heterocyclic carbene ligand and two bromides was reacted with an excess of elemental iodine, which resulted in the surprising removal of one bromide ligand and dimerization of the mixed-carbene complex to form di-μ-bromido-bis­{[1-(cyclo­hepta-2,4,6-trien-2-yl-1-yl­idene-κC1)-3-(2,6-diiso­propyl­phen­yl)imidazol-2-yl­idene]palladium(II)} bis­(penta­iodide) di­chloro­methane monosolvate, [Pd2Br2(C22H24N2)2](I5)2·CH2Cl2. The dimeric complex features a slightly distorted square-planar core of two PdII centres bridged by two bromide ligands, which lie in the same plane as the seven- and five-membered rings of the bidentate carbene ligand. The counter-ions in the single crystal were found to be penta­iodide monoanions featuring their typical V-shape, whereas for the bulk material, a mixture of Br/I inter­halides is proposed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229617016412/ov3101sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229617016412/ov3101Isup2.hkl
Contains datablock I

cdx

Chemdraw file https://doi.org/10.1107/S2053229617016412/ov3101Isup3.cdx
Supplementary material

CCDC reference: 1573887

Computing details top

Data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b) and shelXle (Hübschle et al., 2011); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009), enCIFer (Allen et al., 2004) and publCIF (Westrip, 2010).

Di-µ-bromido-bis{[1-(cyclohepta-2,4,6-trien-2-yl-1-ylidene-κC1)-3-(2,6-diisopropylphenyl)imidazol-4-in-2-ylidene]palladium(II)} bis(pentaiodide) dichloromethane monosolvate top
Crystal data top
[Pd2Br2(C22H24N2)2](I5)2·CH2Cl2Z = 1
Mr = 2359.39F(000) = 1074
Triclinic, P1Dx = 2.555 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.1277 (10) ÅCell parameters from 9279 reflections
b = 13.5001 (16) Åθ = 2.4–28.3°
c = 14.6344 (17) ŵ = 7.05 mm1
α = 113.316 (3)°T = 100 K
β = 103.239 (3)°Fragment, red-black
γ = 100.711 (3)°0.30 × 0.23 × 0.11 mm
V = 1533.0 (3) Å3
Data collection top
Bruker Photon CMOS
diffractometer
7307 independent reflections
Radiation source: IMS microsource6600 reflections with I > 2σ(I)
Helios optic monochromatorRint = 0.032
Detector resolution: 16 pixels mm-1θmax = 27.9°, θmin = 2.4°
phi– and ω–rotation scansh = 1212
Absorption correction: multi-scan
(SADABS2014; Bruker, 2014)
k = 1717
Tmin = 0.508, Tmax = 0.746l = 1919
52411 measured reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.023H-atom parameters constrained
wR(F2) = 0.051 w = 1/[σ2(Fo2) + (0.0125P)2 + 5.9696P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
7307 reflectionsΔρmax = 2.73 e Å3
284 parametersΔρmin = 1.50 e Å3
Special details top

Experimental. Diffractometer operator C. Jandl, scanspeed 5 s per frame, dx 50 mm, 2914 frames measured in 12 data sets, phi-scans with delta_phi = 0.5, omega-scans with delta_omega = 0.5, shutterless mode

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

Refinement. Refinement on F2 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 F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > 2sigma(F2) is used only for calculating -R-factor-obs 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) top
xyzUiso*/Ueq
I10.44928 (4)0.25761 (2)0.06905 (2)0.0395 (1)
I20.60969 (3)0.44761 (2)0.12738 (2)0.0206 (1)
I30.78107 (3)0.65254 (2)0.34424 (2)0.0258 (1)
I41.01616 (3)0.77990 (2)0.28338 (2)0.0172 (1)
I51.24828 (3)0.88864 (2)0.22710 (2)0.0301 (1)
Pd10.11011 (3)0.55326 (2)0.42718 (2)0.0090 (1)
Br10.10563 (4)0.38340 (3)0.38730 (2)0.0147 (1)
N10.3288 (3)0.6709 (2)0.3662 (2)0.0100 (7)
N20.3908 (3)0.7745 (2)0.5334 (2)0.0109 (7)
C10.1140 (4)0.5052 (3)0.2793 (2)0.0114 (8)
C20.0006 (4)0.4089 (3)0.1942 (3)0.0174 (9)
C30.0183 (4)0.3600 (3)0.0868 (3)0.0245 (10)
C40.0744 (5)0.3922 (3)0.0347 (3)0.0243 (11)
C50.2056 (4)0.4854 (3)0.0771 (3)0.0220 (10)
C60.2776 (4)0.5693 (3)0.1810 (3)0.0179 (10)
C70.2362 (4)0.5775 (3)0.2690 (2)0.0117 (8)
C80.2889 (4)0.6775 (2)0.4529 (2)0.0104 (8)
C90.4543 (4)0.7658 (3)0.3941 (3)0.0153 (9)
C100.4934 (4)0.8298 (3)0.4986 (3)0.0157 (9)
C110.4024 (4)0.8159 (2)0.6438 (2)0.0116 (8)
C120.5089 (4)0.7873 (3)0.7060 (3)0.0150 (9)
C130.5148 (4)0.8252 (3)0.8111 (3)0.0193 (10)
C140.4203 (4)0.8890 (3)0.8500 (3)0.0206 (9)
C150.3177 (4)0.9171 (3)0.7849 (3)0.0182 (9)
C160.3048 (4)0.8798 (3)0.6789 (3)0.0134 (8)
C170.6100 (4)0.7153 (3)0.6635 (3)0.0210 (11)
C180.7813 (5)0.7642 (4)0.7382 (4)0.0347 (14)
C190.5403 (5)0.5932 (3)0.6415 (3)0.0266 (11)
C200.1888 (4)0.9061 (3)0.6058 (3)0.0162 (9)
C210.2672 (5)1.0178 (3)0.6075 (3)0.0237 (11)
C220.0363 (4)0.9086 (3)0.6307 (3)0.0261 (11)
H20.076700.370000.212400.0210*
H30.108400.294900.043100.0290*
H40.043800.344300.039000.0290*
H50.254100.493600.028500.0260*
H60.366200.628600.193600.0220*
H90.502500.782000.348400.0180*
H100.575700.899800.541200.0190*
H130.584700.807000.856400.0230*
H140.425600.913700.921500.0250*
H150.255500.962400.813100.0220*
H170.610600.714600.595000.0250*
H18A0.845600.721000.704300.0520*
H18B0.785200.759100.803600.0520*
H18C0.823100.843800.754500.0520*
H19A0.429900.563400.594800.0400*
H19B0.544700.590900.708200.0400*
H19C0.601300.546800.607500.0400*
H200.160200.844300.532400.0190*
H21A0.362801.013400.588400.0350*
H21B0.295801.080300.678500.0350*
H21C0.193201.031000.556800.0350*
H22A0.039100.916000.576000.0390*
H22B0.059000.973300.699500.0390*
H22C0.009400.838100.632700.0390*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.0519 (2)0.0320 (1)0.0260 (1)0.0014 (1)0.0128 (1)0.0103 (1)
I20.0217 (1)0.0253 (1)0.0241 (1)0.0102 (1)0.0132 (1)0.0158 (1)
I30.0282 (1)0.0254 (1)0.0270 (1)0.0111 (1)0.0116 (1)0.0125 (1)
I40.0208 (1)0.0156 (1)0.0129 (1)0.0091 (1)0.0021 (1)0.0047 (1)
I50.0271 (1)0.0315 (1)0.0237 (1)0.0003 (1)0.0020 (1)0.0128 (1)
Pd10.0120 (1)0.0078 (1)0.0084 (1)0.0023 (1)0.0055 (1)0.0041 (1)
Br10.0206 (2)0.0097 (1)0.0094 (1)0.0020 (1)0.0071 (1)0.0020 (1)
N10.0117 (12)0.0112 (12)0.0104 (12)0.0043 (10)0.0061 (10)0.0064 (10)
N20.0118 (12)0.0108 (12)0.0129 (13)0.0017 (10)0.0052 (10)0.0084 (10)
C10.0142 (15)0.0133 (14)0.0115 (14)0.0081 (12)0.0058 (12)0.0078 (12)
C20.0169 (16)0.0214 (16)0.0135 (16)0.0033 (13)0.0044 (13)0.0091 (13)
C30.0237 (19)0.0264 (19)0.0129 (16)0.0010 (15)0.0024 (14)0.0041 (14)
C40.029 (2)0.032 (2)0.0109 (16)0.0116 (16)0.0075 (14)0.0076 (15)
C50.0272 (19)0.0322 (19)0.0147 (16)0.0130 (16)0.0128 (15)0.0138 (15)
C60.0208 (17)0.0222 (17)0.0180 (17)0.0087 (14)0.0123 (14)0.0120 (14)
C70.0122 (14)0.0144 (14)0.0125 (14)0.0078 (12)0.0058 (12)0.0075 (12)
C80.0124 (14)0.0105 (14)0.0134 (14)0.0063 (11)0.0063 (12)0.0081 (12)
C90.0175 (16)0.0150 (15)0.0191 (16)0.0035 (12)0.0100 (13)0.0118 (13)
C100.0161 (16)0.0135 (15)0.0190 (16)0.0021 (12)0.0079 (13)0.0089 (13)
C110.0141 (15)0.0077 (13)0.0099 (14)0.0009 (11)0.0034 (12)0.0033 (11)
C120.0143 (15)0.0152 (15)0.0158 (16)0.0022 (12)0.0037 (13)0.0093 (13)
C130.0191 (17)0.0224 (17)0.0140 (16)0.0027 (14)0.0015 (13)0.0099 (14)
C140.0249 (18)0.0183 (16)0.0100 (15)0.0010 (14)0.0039 (14)0.0028 (13)
C150.0243 (18)0.0116 (14)0.0165 (16)0.0048 (13)0.0094 (14)0.0033 (13)
C160.0155 (15)0.0074 (13)0.0137 (15)0.0003 (11)0.0032 (12)0.0040 (12)
C170.0241 (18)0.0295 (19)0.0226 (18)0.0157 (15)0.0126 (15)0.0186 (16)
C180.021 (2)0.036 (2)0.052 (3)0.0127 (17)0.0126 (19)0.023 (2)
C190.029 (2)0.0251 (19)0.029 (2)0.0134 (16)0.0139 (17)0.0112 (16)
C200.0179 (16)0.0103 (14)0.0200 (17)0.0045 (12)0.0062 (13)0.0065 (13)
C210.0256 (19)0.0215 (17)0.031 (2)0.0079 (15)0.0095 (16)0.0185 (16)
C220.0229 (19)0.0251 (19)0.038 (2)0.0108 (15)0.0123 (17)0.0191 (17)
Geometric parameters (Å, º) top
I1—I22.7975 (5)C16—C201.521 (6)
I2—I33.0561 (5)C17—C181.529 (6)
I3—I43.0117 (5)C17—C191.524 (6)
I4—I52.8147 (5)C20—C221.520 (5)
Pd1—Br12.4925 (6)C20—C211.532 (6)
Pd1—C12.010 (3)C2—H20.9500
Pd1—C81.954 (3)C3—H30.9500
Pd1—Br1i2.5160 (5)C4—H40.9500
N1—C81.373 (4)C5—H50.9500
N1—C91.395 (5)C6—H60.9500
N1—C71.400 (4)C9—H90.9500
N2—C81.339 (4)C10—H100.9500
N2—C101.398 (5)C13—H130.9500
N2—C111.456 (4)C14—H140.9500
C1—C71.417 (6)C15—H150.9500
C1—C21.393 (5)C17—H171.0000
C2—C31.396 (5)C18—H18C0.9800
C3—C41.381 (6)C18—H18A0.9800
C4—C51.373 (6)C18—H18B0.9800
C5—C61.389 (5)C19—H19B0.9800
C6—C71.393 (5)C19—H19C0.9800
C9—C101.342 (5)C19—H19A0.9800
C11—C121.391 (5)C20—H201.0000
C11—C161.395 (5)C21—H21A0.9800
C12—C171.517 (6)C21—H21B0.9800
C12—C131.400 (5)C21—H21C0.9800
C13—C141.387 (6)C22—H22B0.9800
C14—C151.392 (6)C22—H22C0.9800
C15—C161.396 (5)C22—H22A0.9800
I1—I2—I3178.729 (12)C1—C2—H2115.00
I2—I3—I497.863 (13)C3—C2—H2115.00
I3—I4—I5176.004 (11)C2—C3—H3115.00
Br1—Pd1—C197.19 (11)C4—C3—H3115.00
Br1—Pd1—C8175.06 (10)C5—C4—H4116.00
Br1—Pd1—Br1i83.488 (13)C3—C4—H4116.00
Br1i—Pd1—C899.34 (8)C4—C5—H5115.00
Br1i—Pd1—C1179.08 (12)C6—C5—H5115.00
C1—Pd1—C880.03 (14)C5—C6—H6116.00
Pd1—Br1—Pd1i96.513 (13)C7—C6—H6116.00
C7—N1—C9132.4 (3)N1—C9—H9127.00
C7—N1—C8116.9 (3)C10—C9—H9127.00
C8—N1—C9110.6 (3)N2—C10—H10126.00
C8—N2—C10110.8 (3)C9—C10—H10126.00
C8—N2—C11125.8 (3)C14—C13—H13120.00
C10—N2—C11123.3 (3)C12—C13—H13119.00
C2—C1—C7123.6 (3)C13—C14—H14120.00
Pd1—C1—C2121.2 (3)C15—C14—H14120.00
Pd1—C1—C7115.2 (2)C14—C15—H15119.00
C1—C2—C3130.8 (4)C16—C15—H15120.00
C2—C3—C4129.6 (4)C18—C17—H17108.00
C3—C4—C5127.5 (4)C19—C17—H17108.00
C4—C5—C6129.2 (4)C12—C17—H17108.00
C5—C6—C7128.2 (4)C17—C18—H18B110.00
C1—C7—C6131.0 (3)H18A—C18—H18C109.00
N1—C7—C6117.2 (3)C17—C18—H18C109.00
N1—C7—C1111.8 (3)H18A—C18—H18B109.00
Pd1—C8—N1116.1 (2)C17—C18—H18A109.00
Pd1—C8—N2139.0 (2)H18B—C18—H18C110.00
N1—C8—N2105.0 (3)C17—C19—H19C110.00
N1—C9—C10106.2 (3)H19A—C19—H19C110.00
N2—C10—C9107.5 (3)H19B—C19—H19C109.00
N2—C11—C16117.7 (3)H19A—C19—H19B109.00
N2—C11—C12117.3 (3)C17—C19—H19A109.00
C12—C11—C16125.0 (3)C17—C19—H19B109.00
C11—C12—C13116.3 (3)C22—C20—H20107.00
C11—C12—C17123.0 (3)C16—C20—H20107.00
C13—C12—C17120.6 (4)C21—C20—H20108.00
C12—C13—C14121.0 (4)C20—C21—H21B109.00
C13—C14—C15120.4 (4)H21A—C21—H21C110.00
C14—C15—C16121.0 (4)C20—C21—H21C109.00
C15—C16—C20121.6 (4)H21A—C21—H21B109.00
C11—C16—C20122.1 (3)C20—C21—H21A109.00
C11—C16—C15116.3 (3)H21B—C21—H21C109.00
C12—C17—C18111.9 (3)C20—C22—H22C109.00
C12—C17—C19111.1 (3)H22A—C22—H22C109.00
C18—C17—C19110.2 (4)H22B—C22—H22C109.00
C21—C20—C22110.6 (4)H22A—C22—H22B109.00
C16—C20—C21110.5 (3)C20—C22—H22A110.00
C16—C20—C22113.0 (3)C20—C22—H22B109.00
C1—Pd1—Br1—Pd1i179.38 (11)Pd1—C1—C7—N11.3 (4)
Br1i—Pd1—Br1—Pd1i0.00 (4)Pd1—C1—C7—C6177.8 (4)
Br1—Pd1—C1—C27.2 (3)C2—C1—C7—N1177.1 (4)
Br1—Pd1—C1—C7174.4 (3)C2—C1—C7—C63.9 (7)
C8—Pd1—C1—C2177.0 (4)C1—C2—C3—C42.2 (8)
C8—Pd1—C1—C71.5 (3)C2—C3—C4—C53.6 (8)
C1—Pd1—C8—N11.3 (3)C3—C4—C5—C60.2 (8)
C1—Pd1—C8—N2177.5 (4)C4—C5—C6—C72.1 (8)
Br1i—Pd1—C8—N1179.4 (2)C5—C6—C7—N1179.7 (4)
Br1i—Pd1—C8—N21.8 (4)C5—C6—C7—C10.7 (8)
Br1—Pd1—Br1i—Pd1i0.00 (4)N1—C9—C10—N20.7 (4)
C8—Pd1—Br1i—Pd1i175.91 (10)N2—C11—C12—C13178.2 (3)
C8—N1—C7—C10.2 (5)N2—C11—C12—C170.5 (5)
C8—N1—C7—C6179.0 (3)C16—C11—C12—C130.9 (6)
C9—N1—C7—C1176.1 (4)C16—C11—C12—C17178.6 (4)
C9—N1—C7—C64.7 (6)N2—C11—C16—C15179.3 (3)
C7—N1—C8—Pd11.0 (4)N2—C11—C16—C200.2 (5)
C7—N1—C8—N2178.2 (3)C12—C11—C16—C150.2 (6)
C9—N1—C8—Pd1178.1 (2)C12—C11—C16—C20178.9 (4)
C9—N1—C8—N21.1 (4)C11—C12—C13—C140.9 (6)
C7—N1—C9—C10177.6 (4)C17—C12—C13—C14178.6 (4)
C8—N1—C9—C101.1 (4)C11—C12—C17—C18135.5 (4)
C10—N2—C8—Pd1178.3 (3)C11—C12—C17—C19100.8 (4)
C10—N2—C8—N10.6 (4)C13—C12—C17—C1846.9 (6)
C11—N2—C8—Pd15.1 (6)C13—C12—C17—C1976.8 (5)
C11—N2—C8—N1176.1 (3)C12—C13—C14—C150.3 (6)
C8—N2—C10—C90.1 (4)C13—C14—C15—C161.5 (6)
C11—N2—C10—C9176.8 (3)C14—C15—C16—C111.4 (6)
C8—N2—C11—C1292.3 (4)C14—C15—C16—C20177.7 (4)
C8—N2—C11—C1686.9 (4)C11—C16—C20—C2190.6 (5)
C10—N2—C11—C1284.0 (4)C11—C16—C20—C22144.8 (4)
C10—N2—C11—C1696.9 (4)C15—C16—C20—C2190.3 (5)
Pd1—C1—C2—C3179.4 (4)C15—C16—C20—C2234.3 (6)
C7—C1—C2—C32.4 (7)
Symmetry code: (i) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···Br10.952.573.308 (4)135
C17—H17···N21.002.422.885 (5)108
C20—H20···N21.002.462.881 (5)105
C4—H4···I4ii0.953.154.088 (4)170
C5—H5···I2ii0.953.124.062 (5)171
Symmetry code: (ii) x+1, y+1, z.
 

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