Di-μ2-chlorido-bis­[chlorido(η5-2,3,4,5-tetra­methyl-1-propyl­cyclo­penta­dien­yl)iridium(III)]

Merola, J.S.; Morris, D.; De Weerd, N.

doi:10.1107/S1600536813005072

metal-organic compounds

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Volume 69| Part 3| March 2013| Page m176

doi:10.1107/S1600536813005072

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Di-μ₂-chlorido-bis[chlorido(η⁵-2,3,4,5-tetramethyl-1-propylcyclopentadienyl)iridium(III)]

Joseph S. Merola,^a ^* David Morris ^a and Nicholas De Weerd ^a

^aDepartment of Chemistry 0212, Virginia Tech, Blacksburg, VA 24061, USA
^*Correspondence e-mail: jmerola@vt.edu

(Received 10 February 2013; accepted 21 February 2013; online 28 February 2013)

The asymmetric unit of the title complex, [Ir₂Cl₄(C₁₂H₁₉)₂], a versatile starting material for the preparation of uniquely substituted pentaalkylcyclopentadienyl–iridium complexes, consists of an iridium(III) atom, a substituted cyclopentadienyl ligand and two chlorine ligands. The full dimer is generated by an inversion center. In the dimer, the two Ir^III atoms and two bridging Cl atoms form a perfectly planar ring. The two Ir^III atoms and the two terminal Cl atoms also form a rigorous plane that is orthogonal [89.48 (3)°] to the Ir₂Cl₂ ring. The plane of the cyclopentadienyl ligand forms a dihedral angle of 54.06 (7)° with respect to the Ir₂Cl₂ ring.

Related literature

For the structure of the analogous pentamethylcyclopentadienyl compound (CCDC 508943), see: Churchill & Julius (1977 ). For the structure of the 1-phenyl-2,3,4,5-tetramethylcyclopentadienyl complex (CCDC 802289), see: Liu et al. (2011 ).

Experimental

Crystal data

[Ir₂Cl₄(C₁₂H₁₉)₂]
M_r = 852.74
Monoclinic, P 2₁ /c
a = 8.84367 (12) Å
b = 8.83900 (12) Å
c = 17.2662 (2) Å
β = 103.6737 (14)°
V = 1311.43 (3) Å³
Z = 2
Mo Kα radiation
μ = 10.56 mm⁻¹
T = 100 K
0.26 × 0.12 × 0.05 mm

Data collection

Agilent Xcalibur (Eos, Gemini ultra) diffractometer
Absorption correction: Gaussian (CrysAlis PRO; Agilent, 2011 ) T_min = 0.225, T_max = 0.647
20544 measured reflections
4440 independent reflections
3968 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.019
wR(F²) = 0.040
S = 1.06
4440 reflections
141 parameters
H-atom parameters constrained
Δρ_max = 1.02 e Å⁻³
Δρ_min = −1.18 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813005072/pk2466sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813005072/pk2466Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813005072/pk2466Isup3.cml

checkCIF report

Comment top

Di-µ₂-chlorido-bis[chlorido(η⁵-2,3,4,5-tetramethyl-1-propylcyclopentadienyl)iridium(III)] is a useful starting material for half-sandwich complexes of iridium. Compared with the pentamethycylopentadienyl variety, complexes of the propyl-tetramethyl complexes are more soluble in organic solvents. Structurally, the core of the title compound is superimposable with the parent pentamethylcyclopentadiene complex.

The unit-cell dimensions for the pentamethylcyclopentadienyl compound (Churchill, et al. (1977) are quite similar with the exception of the c axis being 1.5 A longer due to the longer chain on the cyclopentadienyl ligand.

Related literature top

For the structure of the analogous pentamethylcyclopentadienyl compound (CCDC 508943), see: Churchill et al. (1977). For the structure of the 1-phenyl-2,3,4,5-tetramethylcyclopentadienyl complex (CCDC 802289), see: Liu et al. (2011).

Experimental top

Iridium(III)chloride hydrate was purchased from Pressure Chemical Company. 1-Propyl-2,3,4,5-tetramethyl cyclopentadiene was purchased from Sigma-Aldrich. The iridium(III)chloride hydrate (1.00 g, 2.84 mmol) was dissolved in 100 ml methanol. 1-Propyl-2,3,4,5-tetramethyl cyclopentadiene (0.70 g,4.25 mmol) was added and the mixture refluxed under nitrogen for 48 hrs. The methanol was removed under vacuum, the solid dissolved in dichloromethane and precipitated with diethylether to yield crystals of the title material. A suitable single-crystal was chosen from those that formed.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

Fig. 1. Thermal ellipsoid plot of the title compound. Ellipsoids are displayed at the 50% probability level. The entire molecule is generated by the inversion center and atoms related by inversion [-x, 2-y, 1-z] are labelled with (') after the atom designator. Only carbon atoms for one asymmetric unit are labelled.

Di-µ₂-chlorido-bis[chlorido(η⁵-2,3,4,5-tetramethyl-1-propylcyclopentadienyl)iridium(III)] top

Crystal data top

[Ir₂Cl₄(C₁₂H₁₉)₂]	F(000) = 808
M_r = 852.74	D_x = 2.159 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.7107 Å
a = 8.84367 (12) Å	Cell parameters from 11826 reflections
b = 8.83900 (12) Å	θ = 3.6–32.4°
c = 17.2662 (2) Å	µ = 10.56 mm⁻¹
β = 103.6737 (14)°	T = 100 K
V = 1311.43 (3) Å³	Irregular, red
Z = 2	0.26 × 0.12 × 0.05 mm

Data collection top

Agilent Xcalibur (Eos, Gemini ultra) diffractometer	4440 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3968 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
Detector resolution: 16.0122 pixels mm^-1	θ_max = 32.5°, θ_min = 3.7°
ω scans	h = −13→13
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2011)	k = −13→13
T_min = 0.225, T_max = 0.647	l = −25→25
20544 measured reflections

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)] = 0.019	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.040	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0107P)² + 0.0112P] where P = (F_o² + 2F_c²)/3
4440 reflections	(Δ/σ)_max = 0.003
141 parameters	Δρ_max = 1.02 e Å⁻³
0 restraints	Δρ_min = −1.18 e Å⁻³

Crystal data top

[Ir₂Cl₄(C₁₂H₁₉)₂]	V = 1311.43 (3) Å³
M_r = 852.74	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.84367 (12) Å	µ = 10.56 mm⁻¹
b = 8.83900 (12) Å	T = 100 K
c = 17.2662 (2) Å	0.26 × 0.12 × 0.05 mm
β = 103.6737 (14)°

Data collection top

Agilent Xcalibur (Eos, Gemini ultra) diffractometer	4440 independent reflections
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2011)	3968 reflections with I > 2σ(I)
T_min = 0.225, T_max = 0.647	R_int = 0.043
20544 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.019	0 restraints
wR(F²) = 0.040	H-atom parameters constrained
S = 1.06	Δρ_max = 1.02 e Å⁻³
4440 reflections	Δρ_min = −1.18 e Å⁻³
141 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.

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 > σ(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
Ir1	0.648925 (10)	0.848148 (9)	0.034000 (5)	0.00818 (3)
Cl1	0.61998 (8)	0.77491 (7)	−0.10212 (4)	0.01940 (13)
Cl2	0.36739 (7)	0.88743 (6)	0.00829 (4)	0.01276 (11)
C1	0.8565 (3)	0.8778 (3)	0.12571 (14)	0.0114 (4)
C2	0.8698 (3)	0.7453 (3)	0.07978 (14)	0.0107 (4)
C3	0.7466 (3)	0.6410 (2)	0.08763 (14)	0.0107 (4)
C4	0.6597 (3)	0.7121 (3)	0.13820 (14)	0.0111 (4)
C5	0.7257 (3)	0.8590 (3)	0.16167 (14)	0.0114 (4)
C6	0.9915 (3)	0.7111 (3)	0.03555 (16)	0.0169 (5)
H6A	0.9426	0.6665	−0.0163	0.025*
H6B	1.0669	0.6397	0.0664	0.025*
H6C	1.0449	0.8048	0.0274	0.025*
C7	0.7237 (3)	0.4861 (3)	0.05290 (15)	0.0164 (5)
H7A	0.6226	0.4468	0.0575	0.025*
H7B	0.8067	0.4195	0.0818	0.025*
H7C	0.7269	0.4901	−0.0034	0.025*
C8	0.5254 (3)	0.6462 (3)	0.16461 (16)	0.0158 (5)
H8A	0.4363	0.7149	0.1503	0.024*
H8B	0.5538	0.6318	0.2225	0.024*
H8C	0.4978	0.5483	0.1384	0.024*
C9	0.6723 (3)	0.9646 (3)	0.21693 (15)	0.0186 (5)
H9A	0.6986	1.0687	0.2055	0.028*
H9B	0.7237	0.9391	0.2721	0.028*
H9C	0.5593	0.9556	0.2095	0.028*
C10	0.9598 (3)	1.0150 (3)	0.13630 (15)	0.0162 (5)
H10A	0.8951	1.1073	0.1332	0.019*
H10B	1.0147	1.0192	0.0926	0.019*
C11	1.0796 (3)	1.0121 (3)	0.21638 (16)	0.0202 (5)
H11A	1.1392	1.1079	0.2231	0.024*
H11B	1.0244	1.0054	0.2599	0.024*
C12	1.1919 (3)	0.8801 (3)	0.22310 (19)	0.0268 (6)
H12A	1.2463	0.8856	0.1799	0.040*
H12B	1.1340	0.7848	0.2192	0.040*
H12C	1.2679	0.8847	0.2745	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ir1	0.00843 (5)	0.00775 (5)	0.00831 (4)	0.00059 (3)	0.00184 (3)	0.00011 (3)
Cl1	0.0274 (3)	0.0203 (3)	0.0095 (3)	0.0054 (3)	0.0024 (2)	−0.0022 (2)
Cl2	0.0094 (2)	0.0104 (2)	0.0176 (3)	−0.00074 (19)	0.0014 (2)	0.0035 (2)
C1	0.0090 (10)	0.0135 (11)	0.0104 (10)	0.0028 (8)	−0.0002 (8)	0.0016 (9)
C2	0.0084 (10)	0.0128 (11)	0.0103 (10)	0.0033 (8)	0.0011 (8)	0.0022 (9)
C3	0.0118 (11)	0.0103 (10)	0.0099 (10)	0.0025 (8)	0.0024 (9)	0.0019 (9)
C4	0.0132 (11)	0.0097 (10)	0.0100 (10)	0.0026 (9)	0.0018 (9)	0.0028 (9)
C5	0.0129 (11)	0.0125 (11)	0.0083 (10)	0.0014 (9)	0.0013 (9)	0.0003 (9)
C6	0.0133 (12)	0.0180 (12)	0.0203 (13)	0.0026 (10)	0.0060 (10)	0.0000 (10)
C7	0.0189 (13)	0.0112 (11)	0.0186 (12)	0.0007 (10)	0.0031 (10)	−0.0027 (10)
C8	0.0161 (12)	0.0173 (12)	0.0156 (12)	0.0009 (10)	0.0067 (10)	0.0040 (10)
C9	0.0239 (14)	0.0199 (13)	0.0119 (11)	0.0052 (11)	0.0042 (10)	−0.0027 (10)
C10	0.0156 (12)	0.0126 (11)	0.0184 (12)	−0.0018 (9)	−0.0002 (10)	−0.0015 (10)
C11	0.0184 (13)	0.0193 (13)	0.0198 (13)	−0.0030 (10)	−0.0016 (10)	−0.0023 (11)
C12	0.0211 (14)	0.0257 (15)	0.0280 (16)	0.0005 (12)	−0.0053 (12)	−0.0009 (12)

Geometric parameters (Å, º) top

Ir1—Cl1	2.3924 (6)	C6—H6B	0.9800
Ir1—Cl2	2.4483 (6)	C6—H6C	0.9800
Ir1—Cl2ⁱ	2.4427 (6)	C7—H7A	0.9800
Ir1—C1	2.138 (2)	C7—H7B	0.9800
Ir1—C2	2.130 (2)	C7—H7C	0.9800
Ir1—C3	2.139 (2)	C8—H8A	0.9800
Ir1—C4	2.148 (2)	C8—H8B	0.9800
Ir1—C5	2.150 (2)	C8—H8C	0.9800
Cl2—Ir1ⁱ	2.4427 (6)	C9—H9A	0.9800
C1—C2	1.434 (3)	C9—H9B	0.9800
C1—C5	1.446 (3)	C9—H9C	0.9800
C1—C10	1.504 (3)	C10—H10A	0.9900
C2—C3	1.458 (3)	C10—H10B	0.9900
C2—C6	1.490 (3)	C10—C11	1.530 (4)
C3—C4	1.437 (3)	C11—H11A	0.9900
C3—C7	1.489 (3)	C11—H11B	0.9900
C4—C5	1.442 (3)	C11—C12	1.519 (4)
C4—C8	1.488 (3)	C12—H12A	0.9800
C5—C9	1.490 (3)	C12—H12B	0.9800
C6—H6A	0.9800	C12—H12C	0.9800

Cl1—Ir1—Cl2ⁱ	88.87 (2)	C5—C4—C8	124.5 (2)
Cl1—Ir1—Cl2	89.55 (2)	C8—C4—Ir1	126.53 (17)
Cl2ⁱ—Ir1—Cl2	79.89 (2)	C1—C5—Ir1	69.86 (13)
C1—Ir1—Cl1	129.38 (7)	C1—C5—C9	127.6 (2)
C1—Ir1—Cl2ⁱ	94.81 (6)	C4—C5—Ir1	70.30 (13)
C1—Ir1—Cl2	140.82 (6)	C4—C5—C1	107.1 (2)
C1—Ir1—C3	66.19 (9)	C4—C5—C9	125.2 (2)
C1—Ir1—C4	65.65 (9)	C9—C5—Ir1	127.85 (17)
C1—Ir1—C5	39.40 (9)	C2—C6—H6A	109.5
C2—Ir1—Cl1	97.18 (6)	C2—C6—H6B	109.5
C2—Ir1—Cl2ⁱ	120.22 (6)	C2—C6—H6C	109.5
C2—Ir1—Cl2	158.74 (6)	H6A—C6—H6B	109.5
C2—Ir1—C1	39.28 (9)	H6A—C6—H6C	109.5
C2—Ir1—C3	39.94 (9)	H6B—C6—H6C	109.5
C2—Ir1—C4	66.10 (9)	C3—C7—H7A	109.5
C2—Ir1—C5	66.35 (9)	C3—C7—H7B	109.5
C3—Ir1—Cl1	97.59 (6)	C3—C7—H7C	109.5
C3—Ir1—Cl2ⁱ	159.63 (7)	H7A—C7—H7B	109.5
C3—Ir1—Cl2	119.28 (7)	H7A—C7—H7C	109.5
C3—Ir1—C4	39.16 (8)	H7B—C7—H7C	109.5
C3—Ir1—C5	66.24 (9)	C4—C8—H8A	109.5
C4—Ir1—Cl1	130.14 (6)	C4—C8—H8B	109.5
C4—Ir1—Cl2	94.21 (6)	C4—C8—H8C	109.5
C4—Ir1—Cl2ⁱ	140.73 (6)	H8A—C8—H8B	109.5
C4—Ir1—C5	39.22 (9)	H8A—C8—H8C	109.5
C5—Ir1—Cl1	162.53 (6)	H8B—C8—H8C	109.5
C5—Ir1—Cl2	103.93 (7)	C5—C9—H9A	109.5
C5—Ir1—Cl2ⁱ	104.23 (6)	C5—C9—H9B	109.5
Ir1ⁱ—Cl2—Ir1	100.11 (2)	C5—C9—H9C	109.5
C2—C1—Ir1	70.05 (13)	H9A—C9—H9B	109.5
C2—C1—C5	108.8 (2)	H9A—C9—H9C	109.5
C2—C1—C10	126.8 (2)	H9B—C9—H9C	109.5
C5—C1—Ir1	70.74 (13)	C1—C10—H10A	109.3
C5—C1—C10	124.4 (2)	C1—C10—H10B	109.3
C10—C1—Ir1	125.42 (17)	C1—C10—C11	111.5 (2)
C1—C2—Ir1	70.67 (13)	H10A—C10—H10B	108.0
C1—C2—C3	107.7 (2)	C11—C10—H10A	109.3
C1—C2—C6	127.8 (2)	C11—C10—H10B	109.3
C3—C2—Ir1	70.38 (13)	C10—C11—H11A	109.1
C3—C2—C6	124.4 (2)	C10—C11—H11B	109.1
C6—C2—Ir1	127.32 (17)	H11A—C11—H11B	107.8
C2—C3—Ir1	69.68 (12)	C12—C11—C10	112.5 (2)
C2—C3—C7	125.3 (2)	C12—C11—H11A	109.1
C4—C3—Ir1	70.73 (13)	C12—C11—H11B	109.1
C4—C3—C2	107.4 (2)	C11—C12—H12A	109.5
C4—C3—C7	127.3 (2)	C11—C12—H12B	109.5
C7—C3—Ir1	127.59 (17)	C11—C12—H12C	109.5
C3—C4—Ir1	70.12 (13)	H12A—C12—H12B	109.5
C3—C4—C5	109.0 (2)	H12A—C12—H12C	109.5
C3—C4—C8	126.5 (2)	H12B—C12—H12C	109.5
C5—C4—Ir1	70.48 (13)

Symmetry code: (i) −x+1, −y+2, −z.

Experimental details

Crystal data
Chemical formula	[Ir₂Cl₄(C₁₂H₁₉)₂]
M_r	852.74
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	8.84367 (12), 8.83900 (12), 17.2662 (2)
β (°)	103.6737 (14)
V (Å³)	1311.43 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	10.56
Crystal size (mm)	0.26 × 0.12 × 0.05

Data collection
Diffractometer	Agilent Xcalibur (Eos, Gemini ultra) diffractometer
Absorption correction	Gaussian (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.225, 0.647
No. of measured, independent and observed [I > 2σ(I)] reflections	20544, 4440, 3968
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.755

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.040, 1.06
No. of reflections	4440
No. of parameters	141
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.02, −1.18

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Acknowledgements

We thank the National Science Foundation for funds (grant CHE-01311288) for the purchase of the Oxford Diffraction Xcalibur2 single-crystal diffractometer.

References

Agilent (2011). CrysAlis PRO. Agilent Technologies UK Ltd, Yarnton, England. Google Scholar
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