trans-Bis[1-(2-benzamido­eth­yl)-3-(2,4,6-trimethyl­phen­yl)imidazol-2-yl­idene]dichloridopalladium(II)

Warsink, S.; Roodt, A.

doi:10.1107/S1600536812031868

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Pages m1075-m1076

https://doi.org/10.1107/S1600536812031868

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trans-Bis[1-(2-benzamidoethyl)-3-(2,4,6-trimethylphenyl)imidazol-2-ylidene]dichloridopalladium(II)

Stefan Warsink ^a ^* and Andreas Roodt ^a

^aDepartment of Chemistry, University of the Free State, PO Box 339, Bloemfontein, South Africa
^*Correspondence e-mail: 2011009426@ufs4life.ac.za

(Received 10 July 2012; accepted 12 July 2012; online 18 July 2012)

In the title compound, [PdCl₂(C₂₁H₂₃N₃O)₂], the Pd^II atom is located on an inversion centre and is coordinated in a slightly distorted square-planar environment by the chloride and N-heterocyclic carbene (NHC) ligands in mutual trans positions. There are several hydrogen-bonding interactions, the most significant of which is a hydrogen bond between the amide moiety of the NHC and the chloride ligand. These hydrogen-bond interactions form a three-dimensional network.

Related literature

For a review on N-heterocyclic carbenes (NHCs) and their coordination chemistry, see: Hahn & Jahnke (2008 ). For seminal papers on NHC structure and coordination chemistry, see: Arduengo et al. (1991 ); Wang & Lin (1998 ). For Pd(NHC) complexes, see, for example: Meij et al. (2005 ); Warsink et al. (2009 , 2010 ); Fu et al. (2010 ).

Experimental

Crystal data

[PdCl₂(C₂₁H₂₃N₃O)₂]
M_r = 844.15
Monoclinic, P 2₁ /c
a = 12.594 (4) Å
b = 11.736 (4) Å
c = 14.403 (4) Å
β = 113.3098 (10)°
V = 1955.0 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.66 mm⁻¹
T = 100 K
0.73 × 0.58 × 0.25 mm

Data collection

Bruker X8 APEXII KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.640, T_max = 0.849
28432 measured reflections
4845 independent reflections
4441 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.055
S = 1.03
4845 reflections
248 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

C01—Pd1	2.0335 (14)
Cl1—Pd1	2.3188 (6)

C01—Pd1—Cl1	87.55 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1⋯Cl1ⁱ	0.797 (19)	2.549 (19)	3.3181 (15)	162.6 (17)
C09—H09⋯O1ⁱⁱ	0.95	2.49	3.386 (2)	157
C10—H10⋯O1ⁱⁱⁱ	0.95	2.44	3.201 (2)	137
C19—H19C⋯Cl1	0.98	2.81	3.772 (2)	167
C21—H21B⋯Cl1ⁱ	0.98	2.78	3.567 (2)	137
Symmetry codes: (i) -x+2, -y, -z+2; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: Mercury (Macrae et al., 2008 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812031868/wm2660sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812031868/wm2660Isup2.hkl

checkCIF report

Comment top

Palladium complexes bearing NHC ligands are well documented in literature (Hahn & Jahnke, 2008), even before the first free NHC was crystallographically characterized (Arduengo et al., 1991). As part of our focus on ligand manipulation for palladium complexes (Meij et al., 2005), we concentrated on the development of complexes bearing NHC ligands. NHCs are well-known for being very good σ-donors, but because of the empty p-orbital on the carbene carbon, complexes with high electron density are not necessarily destabilized by the presence of an NHC (Warsink et al., 2010). Several examples exist where an NHC is present on an electron-rich palladium(0) atom (Warsink et al., 2009), or where more than one NHC is present on palladium(II) (Fu et al., 2010).

With the addition of two NHCs to palladium(II), two possible isomers can result. Both have been prepared, with reaction conditions normally favouring the kinetic trans-product. The cis-product can be obtained by performing the reaction under thermodynamic control. When this type of complex is prepared from the silver(I) NHC complex (Wang & Lin, 1998), transfer of the carbene ligand usually takes place in minutes, even when two NHC moieties are transferred. The precipitation of the silver salt ensures the reaction goes to completion.

The geometric parameters of the title compound, [PdCl₂(C₂₁H₂₃N₃O)₂], (I), show that the complex is square-planar, with bond lengths between palladium and its ligands being in the expected range. The Pd²⁺ cation lies on an inversion centre, generating half of the molecule by symmetry. The C1—Pd1—Cl1 angle is 87.55 (4) °, slightly distorting the geometry of the complex. The NHC is twisted out of the coordination plane to alleviate the steric bulk induced by the mesityl-substituent; the dihedral angle between the carbene core and the coordination plane is 72.37 (13) °.

There are several hydrogen bonding interactions, both inter- and intramolecular. The most significant of these is a hydrogen bond between the amide H atoms and the chlorido ligands (Table 2)

Related literature top

For a review on N-heterocyclic carbenes (NHCs) and their coordination chemistry, see: Hahn & Jahnke (2008). For seminal papers on NHC structure and coordination chemistry, see: Arduengo et al. (1991); Wang & Lin (1998). For Pd(NHC) complexes, see, for example: Meij et al. (2005); Warsink et al. (2009, 2010); Fu et al. (2010).

Experimental top

To a dichloromethane solution of chlorido[(1-(2-benzamido)-ethylene-3-mesityl)-imidazol-2-ylidene]silver(I) (0.175 g, 0.36 mmol) was added 0.5 equivalent of dichlorido bis(acetonitrile)palladium(II). The resulting orange solution changed to a suspension in 5 minutes time. This suspension was filtered over a celite pad and the pale yellow solution was concentrated to give the product as a pale orange solid in a yield of 98% (150 mg). ¹H NMR (300 MHz, CDCl₃): δ 7.75 (d, ³J(HH) = 7.4 Hz, 4H, o-Ph—H), 7.45 (t, ³J(HH) = 7.3 Hz, 2H, p-Ph—H), 7.35 (dt, ³J(HH) = 7.4 Hz, ³J(HH) = 7.3 Hz, 4H, m-Ph—H), 7.08 (broad t, ³J(HH) = 5.9 Hz, 2H, NH), 6.93 (s, 4H, Mes-H), 6.89 (d, ³J(HH) = 1.6 Hz, 2H, CH), 6.69 (d, ³J(HH) = 1.6 Hz, 2H, CH), 4.41 (t, ³J(HH) = 5.6 Hz, 4H, NCH₂), 4.02 (dt, ³J(HH) = 5.6 Hz, ³J(HH) = 5.9 Hz, 4H, NHCH₂), 2.31 (s, 6H, p-Mes-CH₃), 2.09 (s, 12H, o-Mes-CH₃). Colourless crystals were obtained by vapour diffusion of diethyl ether into a concentrated dichloromethane solution.

Structure description top

There are several hydrogen bonding interactions, both inter- and intramolecular. The most significant of these is a hydrogen bond between the amide H atoms and the chlorido ligands (Table 2)

For a review on N-heterocyclic carbenes (NHCs) and their coordination chemistry, see: Hahn & Jahnke (2008). For seminal papers on NHC structure and coordination chemistry, see: Arduengo et al. (1991); Wang & Lin (1998). For Pd(NHC) complexes, see, for example: Meij et al. (2005); Warsink et al. (2009, 2010); Fu et al. (2010).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of compound (I) with displacement ellipsoids drawn at the 50% probability level. Hydrogen atoms have been omitted for clarity. [Symmetry code to generate symmetry-related atoms marked with ' : -x + 2, -y, -z + 2.]

trans-Bis[1-(2-benzamidoethyl)-3-(2,4,6-trimethylphenyl)imidazol- 2-ylidene]dichloridopalladium(II) top

Crystal data top

[PdCl₂(C₂₁H₂₃N₃O)₂]	F(000) = 872
M_r = 844.15	D_x = 1.434 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9963 reflections
a = 12.594 (4) Å	θ = 2.5–28.3°
b = 11.736 (4) Å	µ = 0.66 mm⁻¹
c = 14.403 (4) Å	T = 100 K
β = 113.3098 (10)°	Plate, colourless
V = 1955.0 (10) Å³	0.73 × 0.58 × 0.25 mm
Z = 2

Data collection top

Bruker X8 APEXII KappaCCD diffractometer	4845 independent reflections
Radiation source: sealed tube	4441 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
φ and ω scans	θ_max = 28.3°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −15→16
T_min = 0.640, T_max = 0.849	k = −15→15
28432 measured reflections	l = −19→19

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.055	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0252P)² + 1.206P] where P = (F_o² + 2F_c²)/3
4845 reflections	(Δ/σ)_max = 0.001
248 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³
0 constraints

Crystal data top

[PdCl₂(C₂₁H₂₃N₃O)₂]	V = 1955.0 (10) Å³
M_r = 844.15	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.594 (4) Å	µ = 0.66 mm⁻¹
b = 11.736 (4) Å	T = 100 K
c = 14.403 (4) Å	0.73 × 0.58 × 0.25 mm
β = 113.3098 (10)°

Data collection top

Bruker X8 APEXII KappaCCD diffractometer	4845 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	4441 reflections with I > 2σ(I)
T_min = 0.640, T_max = 0.849	R_int = 0.025
28432 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	0 restraints
wR(F²) = 0.055	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.37 e Å⁻³
4845 reflections	Δρ_min = −0.43 e Å⁻³
248 parameters

Special details top

Experimental. The intensity data was collected on a Bruker X8 ApexII 4 K Kappa CCD diffractometer using an exposure time of 5 s/frame. A total of 1386 frames was collected with a frame width of 0.5° covering up to θ = 28.31° with 99.7% completeness accomplished.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

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

	x	y	z	U_iso*/U_eq
C01	0.93466 (11)	0.12682 (11)	0.89676 (9)	0.0151 (2)
C02	0.83145 (13)	0.21976 (12)	0.75160 (10)	0.0225 (3)
H02	0.7778	0.2338	0.6844	0.027*
C03	0.90016 (13)	0.29692 (13)	0.81658 (10)	0.0237 (3)
H03	0.905	0.3758	0.8041	0.028*
C04	0.79774 (13)	0.00921 (12)	0.75366 (10)	0.0195 (3)
H04A	0.855	−0.0393	0.7411	0.023*
H04B	0.7351	0.0269	0.6874	0.023*
C05	0.74689 (12)	−0.05763 (12)	0.81778 (10)	0.0204 (3)
H05A	0.687	−0.1103	0.7731	0.025*
H05B	0.8089	−0.1045	0.8673	0.025*
C06	0.60980 (12)	0.08742 (13)	0.82388 (10)	0.0207 (3)
C07	0.57994 (12)	0.16735 (13)	0.89085 (10)	0.0204 (3)
C08	0.54646 (13)	0.27752 (14)	0.85645 (11)	0.0269 (3)
H08	0.5419	0.2997	0.7915	0.032*
C09	0.51965 (15)	0.35543 (15)	0.91642 (13)	0.0336 (4)
H09	0.4984	0.4312	0.8932	0.04*
C10	0.52404 (14)	0.32240 (17)	1.01020 (12)	0.0345 (4)
H10	0.5057	0.3756	1.0513	0.041*
C11	0.55517 (13)	0.21202 (16)	1.04414 (11)	0.0305 (4)
H11	0.5565	0.1894	1.1079	0.037*
C12	0.58435 (12)	0.13441 (14)	0.98548 (10)	0.0240 (3)
H12	0.6072	0.0592	1.0096	0.029*
C13	1.04514 (12)	0.29318 (11)	0.99505 (9)	0.0169 (2)
C14	1.16210 (12)	0.29244 (11)	1.01144 (10)	0.0189 (3)
C15	1.23975 (12)	0.34349 (12)	1.09968 (11)	0.0205 (3)
H15	1.3197	0.3448	1.1123	0.025*
C16	1.20260 (12)	0.39272 (12)	1.16990 (10)	0.0201 (3)
C17	1.08462 (12)	0.39442 (11)	1.14869 (10)	0.0191 (3)
H17	1.0589	0.4282	1.1961	0.023*
C18	1.00316 (12)	0.34792 (11)	1.05991 (10)	0.0175 (3)
C19	1.20317 (13)	0.23864 (13)	0.93643 (11)	0.0254 (3)
H19A	1.2861	0.253	0.9574	0.038*
H19B	1.1608	0.2717	0.8693	0.038*
H19C	1.1893	0.1563	0.9339	0.038*
C20	1.28891 (13)	0.44417 (14)	1.26630 (11)	0.0269 (3)
H20A	1.2478	0.4878	1.2998	0.04*
H20B	1.3412	0.4948	1.2503	0.04*
H20C	1.3337	0.3833	1.3113	0.04*
C21	0.87535 (12)	0.36035 (12)	1.03310 (10)	0.0212 (3)
H21A	0.863	0.3995	1.0881	0.032*
H21B	0.8395	0.2847	1.023	0.032*
H21C	0.8404	0.4049	0.9708	0.032*
N1	0.85384 (10)	0.11576 (10)	0.80130 (8)	0.0165 (2)
N2	0.96271 (10)	0.23883 (9)	0.90550 (8)	0.0167 (2)
N3	0.69588 (11)	0.01305 (10)	0.87193 (9)	0.0197 (2)
O1	0.55957 (10)	0.09075 (10)	0.73122 (7)	0.0289 (2)
Cl1	1.09679 (3)	−0.06511 (3)	0.90286 (2)	0.01787 (7)
Pd1	1	0	1	0.01239 (4)
H1	0.7338 (16)	0.0244 (15)	0.9304 (15)	0.023 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C01	0.0188 (6)	0.0141 (6)	0.0136 (5)	0.0012 (5)	0.0077 (5)	−0.0003 (4)
C02	0.0312 (7)	0.0195 (7)	0.0146 (6)	0.0054 (6)	0.0068 (5)	0.0044 (5)
C03	0.0368 (8)	0.0166 (7)	0.0163 (6)	0.0037 (6)	0.0091 (6)	0.0055 (5)
C04	0.0233 (7)	0.0188 (7)	0.0146 (6)	−0.0007 (5)	0.0056 (5)	−0.0040 (5)
C05	0.0229 (7)	0.0169 (7)	0.0188 (6)	−0.0006 (5)	0.0053 (5)	−0.0006 (5)
C06	0.0210 (6)	0.0232 (7)	0.0164 (6)	−0.0015 (5)	0.0058 (5)	0.0010 (5)
C07	0.0175 (6)	0.0260 (7)	0.0143 (6)	−0.0009 (5)	0.0029 (5)	−0.0015 (5)
C08	0.0288 (7)	0.0270 (8)	0.0209 (7)	0.0035 (6)	0.0055 (6)	0.0021 (6)
C09	0.0346 (9)	0.0270 (8)	0.0303 (8)	0.0060 (7)	0.0034 (7)	−0.0040 (6)
C10	0.0276 (8)	0.0436 (10)	0.0253 (8)	0.0059 (7)	0.0029 (6)	−0.0146 (7)
C11	0.0251 (7)	0.0485 (10)	0.0155 (6)	0.0039 (7)	0.0054 (6)	−0.0040 (6)
C12	0.0212 (7)	0.0320 (8)	0.0164 (6)	0.0010 (6)	0.0048 (5)	0.0016 (6)
C13	0.0239 (6)	0.0110 (6)	0.0149 (6)	−0.0006 (5)	0.0068 (5)	0.0015 (4)
C14	0.0256 (7)	0.0125 (6)	0.0211 (6)	−0.0006 (5)	0.0119 (5)	0.0004 (5)
C15	0.0229 (7)	0.0150 (6)	0.0240 (7)	−0.0004 (5)	0.0097 (5)	0.0008 (5)
C16	0.0261 (7)	0.0132 (6)	0.0190 (6)	−0.0010 (5)	0.0069 (5)	0.0008 (5)
C17	0.0275 (7)	0.0134 (6)	0.0176 (6)	−0.0003 (5)	0.0104 (5)	−0.0006 (5)
C18	0.0247 (7)	0.0117 (6)	0.0172 (6)	−0.0001 (5)	0.0093 (5)	0.0024 (5)
C19	0.0301 (8)	0.0236 (7)	0.0284 (7)	−0.0035 (6)	0.0179 (6)	−0.0049 (6)
C20	0.0275 (7)	0.0265 (8)	0.0233 (7)	−0.0030 (6)	0.0064 (6)	−0.0053 (6)
C21	0.0248 (7)	0.0190 (7)	0.0211 (6)	0.0023 (5)	0.0106 (5)	0.0006 (5)
N1	0.0216 (5)	0.0157 (5)	0.0122 (5)	0.0019 (4)	0.0066 (4)	0.0005 (4)
N2	0.0233 (6)	0.0131 (5)	0.0135 (5)	0.0010 (4)	0.0071 (4)	0.0018 (4)
N3	0.0208 (6)	0.0233 (6)	0.0130 (5)	0.0001 (5)	0.0045 (5)	0.0008 (4)
O1	0.0297 (6)	0.0383 (6)	0.0134 (4)	0.0082 (5)	0.0029 (4)	−0.0008 (4)
Cl1	0.02339 (15)	0.01741 (15)	0.01444 (13)	0.00286 (12)	0.00921 (11)	−0.00015 (11)
Pd1	0.01673 (7)	0.01039 (7)	0.00985 (7)	0.00060 (5)	0.00504 (5)	0.00040 (4)

Geometric parameters (Å, º) top

C01—N2	1.3541 (18)	C11—H11	0.95
C01—N1	1.3548 (16)	C12—H12	0.95
C01—Pd1	2.0335 (14)	C13—C14	1.397 (2)
C02—C03	1.343 (2)	C13—C18	1.3985 (19)
C02—N1	1.3864 (18)	C13—N2	1.4451 (17)
C02—H02	0.95	C14—C15	1.395 (2)
C03—N2	1.3882 (17)	C14—C19	1.5085 (19)
C03—H03	0.95	C15—C16	1.396 (2)
C04—N1	1.4663 (18)	C15—H15	0.95
C04—C05	1.532 (2)	C16—C17	1.394 (2)
C04—H04A	0.99	C16—C20	1.510 (2)
C04—H04B	0.99	C17—C18	1.3955 (19)
C05—N3	1.4512 (19)	C17—H17	0.95
C05—H05A	0.99	C18—C21	1.506 (2)
C05—H05B	0.99	C19—H19A	0.98
C06—O1	1.2307 (17)	C19—H19B	0.98
C06—N3	1.3498 (19)	C19—H19C	0.98
C06—C07	1.496 (2)	C20—H20A	0.98
C07—C08	1.389 (2)	C20—H20B	0.98
C07—C12	1.3965 (19)	C20—H20C	0.98
C08—C09	1.388 (2)	C21—H21A	0.98
C08—H08	0.95	C21—H21B	0.98
C09—C10	1.385 (3)	C21—H21C	0.98
C09—H09	0.95	N3—H1	0.797 (19)
C10—C11	1.385 (3)	Cl1—Pd1	2.3188 (6)
C10—H10	0.95	Pd1—C01ⁱ	2.0335 (14)
C11—C12	1.387 (2)	Pd1—Cl1ⁱ	2.3188 (6)

N2—C01—N1	104.54 (11)	C13—C14—C19	121.28 (12)
N2—C01—Pd1	128.86 (10)	C14—C15—C16	121.50 (14)
N1—C01—Pd1	126.59 (10)	C14—C15—H15	119.3
C03—C02—N1	106.89 (12)	C16—C15—H15	119.3
C03—C02—H02	126.6	C17—C16—C15	118.74 (13)
N1—C02—H02	126.6	C17—C16—C20	120.87 (13)
C02—C03—N2	106.60 (13)	C15—C16—C20	120.39 (13)
C02—C03—H03	126.7	C16—C17—C18	121.92 (13)
N2—C03—H03	126.7	C16—C17—H17	119
N1—C04—C05	113.17 (11)	C18—C17—H17	119
N1—C04—H04A	108.9	C17—C18—C13	117.17 (13)
C05—C04—H04A	108.9	C17—C18—C21	121.37 (12)
N1—C04—H04B	108.9	C13—C18—C21	121.42 (12)
C05—C04—H04B	108.9	C14—C19—H19A	109.5
H04A—C04—H04B	107.8	C14—C19—H19B	109.5
N3—C05—C04	114.26 (12)	H19A—C19—H19B	109.5
N3—C05—H05A	108.7	C14—C19—H19C	109.5
C04—C05—H05A	108.7	H19A—C19—H19C	109.5
N3—C05—H05B	108.7	H19B—C19—H19C	109.5
C04—C05—H05B	108.7	C16—C20—H20A	109.5
H05A—C05—H05B	107.6	C16—C20—H20B	109.5
O1—C06—N3	122.72 (14)	H20A—C20—H20B	109.5
O1—C06—C07	121.78 (13)	C16—C20—H20C	109.5
N3—C06—C07	115.50 (12)	H20A—C20—H20C	109.5
C08—C07—C12	119.67 (14)	H20B—C20—H20C	109.5
C08—C07—C06	118.15 (13)	C18—C21—H21A	109.5
C12—C07—C06	122.18 (14)	C18—C21—H21B	109.5
C09—C08—C07	120.36 (15)	H21A—C21—H21B	109.5
C09—C08—H08	119.8	C18—C21—H21C	109.5
C07—C08—H08	119.8	H21A—C21—H21C	109.5
C10—C09—C08	119.78 (16)	H21B—C21—H21C	109.5
C10—C09—H09	120.1	C01—N1—C02	110.93 (12)
C08—C09—H09	120.1	C01—N1—C04	125.88 (11)
C09—C10—C11	120.16 (15)	C02—N1—C04	123.18 (11)
C09—C10—H10	119.9	C01—N2—C03	111.05 (11)
C11—C10—H10	119.9	C01—N2—C13	125.47 (11)
C10—C11—C12	120.35 (15)	C03—N2—C13	123.48 (12)
C10—C11—H11	119.8	C06—N3—C05	122.04 (12)
C12—C11—H11	119.8	C06—N3—H1	117.2 (13)
C11—C12—C07	119.66 (15)	C05—N3—H1	117.1 (13)
C11—C12—H12	120.2	C01ⁱ—Pd1—C01	180
C07—C12—H12	120.2	C01ⁱ—Pd1—Cl1	92.45 (4)
C14—C13—C18	122.83 (12)	C01—Pd1—Cl1	87.55 (4)
C14—C13—N2	119.03 (12)	C01ⁱ—Pd1—Cl1ⁱ	87.55 (4)
C18—C13—N2	118.10 (12)	C01—Pd1—Cl1ⁱ	92.45 (4)
C15—C14—C13	117.61 (12)	Cl1—Pd1—Cl1ⁱ	180
C15—C14—C19	121.11 (13)

N1—C02—C03—N2	−0.59 (16)	C14—C13—C18—C21	171.86 (12)
N1—C04—C05—N3	37.27 (16)	N2—C13—C18—C21	−5.84 (19)
O1—C06—C07—C08	−34.5 (2)	N2—C01—N1—C02	−0.38 (15)
N3—C06—C07—C08	144.81 (14)	Pd1—C01—N1—C02	−178.84 (10)
O1—C06—C07—C12	145.30 (15)	N2—C01—N1—C04	178.29 (12)
N3—C06—C07—C12	−35.44 (19)	Pd1—C01—N1—C04	−0.18 (19)
C12—C07—C08—C09	1.3 (2)	C03—C02—N1—C01	0.62 (16)
C06—C07—C08—C09	−178.98 (14)	C03—C02—N1—C04	−178.08 (13)
C07—C08—C09—C10	−1.3 (2)	C05—C04—N1—C01	51.09 (18)
C08—C09—C10—C11	0.1 (3)	C05—C04—N1—C02	−130.40 (14)
C09—C10—C11—C12	1.3 (2)	N1—C01—N2—C03	0.00 (15)
C10—C11—C12—C07	−1.3 (2)	Pd1—C01—N2—C03	178.42 (10)
C08—C07—C12—C11	0.1 (2)	N1—C01—N2—C13	179.11 (12)
C06—C07—C12—C11	−179.70 (13)	Pd1—C01—N2—C13	−2.47 (19)
C18—C13—C14—C15	3.7 (2)	C02—C03—N2—C01	0.38 (17)
N2—C13—C14—C15	−178.65 (12)	C02—C03—N2—C13	−178.75 (13)
C18—C13—C14—C19	−176.21 (13)	C14—C13—N2—C01	85.73 (17)
N2—C13—C14—C19	1.47 (19)	C18—C13—N2—C01	−96.48 (16)
C13—C14—C15—C16	0.6 (2)	C14—C13—N2—C03	−95.26 (16)
C19—C14—C15—C16	−179.50 (13)	C18—C13—N2—C03	82.53 (17)
C14—C15—C16—C17	−2.6 (2)	O1—C06—N3—C05	9.0 (2)
C14—C15—C16—C20	178.11 (13)	C07—C06—N3—C05	−170.29 (12)
C15—C16—C17—C18	0.4 (2)	C04—C05—N3—C06	57.45 (18)
C20—C16—C17—C18	179.69 (13)	N2—C01—Pd1—Cl1	−106.64 (12)
C16—C17—C18—C13	3.61 (19)	N1—C01—Pd1—Cl1	71.46 (11)
C16—C17—C18—C21	−173.97 (13)	N2—C01—Pd1—Cl1ⁱ	73.36 (12)
C14—C13—C18—C17	−5.72 (19)	N1—C01—Pd1—Cl1ⁱ	−108.54 (11)
N2—C13—C18—C17	176.58 (11)

Symmetry code: (i) −x+2, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···Cl1ⁱ	0.797 (19)	2.549 (19)	3.3181 (15)	162.6 (17)
C09—H09···O1ⁱⁱ	0.95	2.49	3.386 (2)	157
C10—H10···O1ⁱⁱⁱ	0.95	2.44	3.201 (2)	137
C19—H19C···Cl1	0.98	2.81	3.772 (2)	167
C21—H21B···Cl1ⁱ	0.98	2.78	3.567 (2)	137

Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+1, y+1/2, −z+3/2; (iii) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[PdCl₂(C₂₁H₂₃N₃O)₂]
M_r	844.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	12.594 (4), 11.736 (4), 14.403 (4)
β (°)	113.3098 (10)
V (Å³)	1955.0 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.66
Crystal size (mm)	0.73 × 0.58 × 0.25

Data collection
Diffractometer	Bruker X8 APEXII KappaCCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.640, 0.849
No. of measured, independent and observed [I > 2σ(I)] reflections	28432, 4845, 4441
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.055, 1.03
No. of reflections	4845
No. of parameters	248
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.43

Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2008), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

C01—Pd1	2.0335 (14)	Cl1—Pd1	2.3188 (6)

C01—Pd1—Cl1	87.55 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···Cl1ⁱ	0.797 (19)	2.549 (19)	3.3181 (15)	162.6 (17)
C09—H09···O1ⁱⁱ	0.95	2.49	3.386 (2)	156.5
C10—H10···O1ⁱⁱⁱ	0.95	2.44	3.201 (2)	137.4
C19—H19C···Cl1	0.98	2.81	3.772 (2)	166.9
C21—H21B···Cl1ⁱ	0.98	2.78	3.567 (2)	137.3

Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+1, y+1/2, −z+3/2; (iii) x, −y+1/2, z+1/2.

Acknowledgements

Mr Theuns Muller is kindly acknowledged for collection of the diffraction data. The authors thank SASOL, the South African NRF and THRIP, the University of the Free State Research Fund and the UFS Materials and Nanosciences Strategic Research Cluster initiative for financial support. The views expressed do not necessarily represent those of the NRF.

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
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Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
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Volume 68| Part 8| August 2012| Pages m1075-m1076

https://doi.org/10.1107/S1600536812031868

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

trans-Bis[1-(2-benzamido­eth­yl)-3-(2,4,6-tri­methyl­phen­yl)imidazol-2-yl­­idene]di­chloridopalladium(II)

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

trans-Bis[1-(2-benzamidoethyl)-3-(2,4,6-trimethylphenyl)imidazol-2-ylidene]dichloridopalladium(II)