Tetra­carbonyldi-μ-chlorido-di­chlorido­bis­(η5-cyclo­penta­dien­yl)diirondigallium(2 Fe—Ga)

Harakas, G.N.; Demmin, M.E.

doi:10.1107/S241431462200832X

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 7| Part 8| August 2022| x220832

https://doi.org/10.1107/S241431462200832X

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Tetracarbonyldi-μ-chlorido-dichloridobis(η⁵-cyclopentadienyl)diirondigallium(2 Fe—Ga)

George N. Harakas ^a ^* and Mary Elizabeth Demmin ^a

^aPO Box 6949, Radford University, Radford, Virginia 24142, USA
^*Correspondence e-mail: gharakas@radford.edu

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 19 August 2022; accepted 20 August 2022; online 26 August 2022)

The title compound, [Fe₂Ga₂(C₅H₅)₂Cl₄(CO)₄], has an iron–gallium bond distance of 2.3028 (3) Å. The gallium atoms are connected by two bridging chlorine atoms, each gallium also has one terminal chlorine. The molecule has an inversion center located between the gallium atoms. The cyclopentadienyl ligand is disordered over two sites with an occupancy of 0.57 (2) for the major occupied site.

Keywords: crystal structure; iron; gallium.

CCDC reference: 2202575

Structure description

Digallium(II) dichloride has been used in the synthesis of two gallium–ruthenium metal clusters (Harakas & Whittlesey, 1997 ). The reaction of Ga₂Cl₄·1,4 dioxane with [CpFe(CO)₂]₂ in toluene, followed by work-up with a THF, diethyl ether and pentane solution resulted in the isolation of η⁵-CpFeGaCl₂L, L = 1,4-dioxane or THF (Linti et al., 2001 ). The reaction of GaCl₃ and K[CpFe(CO)₂] in toluene produced [{CpFe(CO)₂}(Ga(Cl·GaCl₃)(μ-Cl)]₂ (Borovik et al., 1999 ). In the absence of ether solvents, the reaction of Ga₂Cl₄ with [CpFe(CO)₂]₂ in toluene produced the title compound, which is a dimeric analog to the compounds isolated by Linti et al. (2001).

The Fe1—Ga1 bond distance of 2.3028 (3) Å in the title compound (Fig. 1) is similar to the 2.317 and 2.316 Å distances found for the etherate compounds (Linti et al., 2001) but longer than the 2.286 Å value in [{CpFe(CO)₂}(Ga(Cl·GaCl₃)(μ-Cl)]₂ (Borovik et al., 1999). The gallium–gallium distance of 3.4603 (3) Å is much greater than 2.406 Å for Ga₂Cl₄·2 (1,4-dioxane) (Beamish et al., 1979 ), indicating there are no metal–metal bonding interactions between the gallium atoms.

Figure 1
The title compound with 50% displacement ellipsoids. The H atoms and the minor occupied sites of the disordered atoms have been omitted for clarity. Unlabeled atoms are generated by an inversion center.

Synthesis and crystallization

All manipulations were conducted using inert atmosphere techniques. A stock solution of Ga₂Cl₄ was produced by the reaction of Ga (5.496 g, 78.83 mmol) with GaCl₃ (5.01 g, 28.4 mmol) in 150 ml of toluene. The mixture was heated to reflux for 24 h then cooled to 25°C. In a 150 ml Schlenk flask, [CpFe(CO)₂]₂ (1.107 g, 3.128 mmol) in 25 ml of toluene was combined with 25 ml of the Ga₂Cl₄ stock solution. The reaction flask was refluxed for 1 h. The mixture was cooled to room temperature, and the solution was decanted away from the residue into a new Schlenk flask. Crystals suitable for X-ray analysis formed after 24 h at 25°C. A single crystal was coated with NVH oil and mounted on a MiTeGen loop under a stream of argon gas then cooled to −75°C for data collection.

Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 1. The cyclopentadienyl rings were modeled for disorder with two offset ring orientations (C1A—C5A and C1B—C5B) at 0.57 (2):0.43 (2) occupancy, respectively.

Table 1
Experimental details

Crystal data
Chemical formula	[Fe₂Ga₂(C₅H₅)₂Cl₄(CO)₄]
M_r	635.16
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	198
a, b, c (Å)	8.3567 (3), 7.0331 (2), 16.5792 (6)
β (°)	91.218 (1)
V (Å³)	974.20 (6)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	4.76
Crystal size (mm)	0.24 × 0.22 × 0.12

Data collection
Diffractometer	Bruker D8 Quest Eco, Photon II 7
Absorption correction	Multi-scan (Krause et al., 2015 )
T_min, T_max	0.36, 0.60
No. of measured, independent and observed [I > 2σ(I)] reflections	100078, 7242, 5892
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.962

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.086, 1.21
No. of reflections	7242
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.93, −0.99
Computer programs: APEX3 and SAINT (Bruker, 2019 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), and ShelXle (Hübschle et al., 2011 ).

Structural data

CCDC reference: 2202575

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S241431462200832X/bt4125sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431462200832X/bt4125Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2019); cell refinement: SAINT (Bruker, 2019); data reduction: SAINT (Bruker, 2019); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ShelXle (Hübschle et al., 2011).

Tetracarbonyldi-µ-chlorido-dichloridobis(η⁵-cyclopentadienyl)diirondigallium(2 Fe—Ga) top

Crystal data top

[Fe₂Ga₂(C₅H₅)₂Cl₄(CO)₄]	F(000) = 616
M_r = 635.16	D_x = 2.165 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.3567 (3) Å	Cell parameters from 9746 reflections
b = 7.0331 (2) Å	θ = 2.9–42.0°
c = 16.5792 (6) Å	µ = 4.76 mm⁻¹
β = 91.218 (1)°	T = 198 K
V = 974.20 (6) Å³	Cube, orange
Z = 2	0.24 × 0.22 × 0.12 mm

Data collection top

Bruker D8 Quest Eco, Photon II 7 diffractometer	5892 reflections with I > 2σ(I)
Detector resolution: 7.3910 pixels mm^-1	R_int = 0.041
phi and ω scans	θ_max = 43.1°, θ_min = 2.5°
Absorption correction: multi-scan (Krause et al., 2015)	h = −15→16
T_min = 0.36, T_max = 0.60	k = −13→13
100078 measured reflections	l = −29→31
7242 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.086	w = 1/[σ²(F_o²) + (0.0255P)² + 0.9013P] where P = (F_o² + 2F_c²)/3
S = 1.21	(Δ/σ)_max = 0.001
7242 reflections	Δρ_max = 0.93 e Å⁻³
164 parameters	Δρ_min = −0.99 e Å⁻³

Special details top

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

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ga1	0.85697 (2)	0.66995 (2)	0.47616 (2)	0.01798 (4)
Fe1	0.69410 (2)	0.68540 (3)	0.36255 (2)	0.01656 (4)
Cl1	0.86625 (6)	0.86249 (6)	0.57979 (3)	0.02919 (8)
Cl2	0.86216 (4)	0.37209 (6)	0.54493 (3)	0.02429 (7)
O1	0.50545 (19)	0.3758 (2)	0.42638 (10)	0.0335 (3)
O2	0.9025 (2)	0.4232 (3)	0.28009 (11)	0.0501 (5)
C1	0.58075 (19)	0.4990 (2)	0.40250 (10)	0.0221 (3)
C2	0.8235 (2)	0.5277 (3)	0.31382 (11)	0.0281 (3)
C1A	0.6807 (11)	0.9801 (13)	0.3870 (7)	0.0346 (17)	0.57 (2)
H1A	0.725236	1.046554	0.435902	0.041000*	0.57 (2)
C2A	0.5295 (13)	0.9041 (14)	0.3781 (7)	0.0381 (18)	0.57 (2)
H2A	0.445268	0.906758	0.420085	0.046000*	0.57 (2)
C3A	0.5114 (15)	0.8261 (14)	0.3027 (10)	0.057 (4)	0.57 (2)
H3A	0.411632	0.767194	0.279609	0.068000*	0.57 (2)
C4A	0.653 (2)	0.8541 (18)	0.2625 (4)	0.056 (3)	0.57 (2)
H4A	0.673376	0.817989	0.205359	0.067000*	0.57 (2)
C5A	0.7600 (10)	0.9482 (15)	0.3150 (7)	0.043 (2)	0.57 (2)
H5A	0.871108	0.989832	0.302262	0.052000*	0.57 (2)
C1B	0.627 (4)	0.956 (3)	0.3914 (8)	0.077 (6)	0.43 (2)
H1B	0.628153	1.011381	0.447019	0.092000*	0.43 (2)
C2B	0.4986 (19)	0.865 (3)	0.3545 (15)	0.064 (6)	0.43 (2)
H2B	0.392019	0.842282	0.379064	0.076000*	0.43 (2)
C3B	0.540 (2)	0.8158 (16)	0.2786 (11)	0.050 (4)	0.43 (2)
H3B	0.471033	0.750474	0.237288	0.060000*	0.43 (2)
C4B	0.7000 (17)	0.878 (2)	0.2685 (9)	0.043 (3)	0.43 (2)
H4B	0.763455	0.864982	0.218325	0.052000*	0.43 (2)
C5B	0.7506 (15)	0.9653 (16)	0.3384 (12)	0.052 (4)	0.43 (2)
H5B	0.856690	1.027701	0.348301	0.062000*	0.43 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ga1	0.01699 (6)	0.01791 (7)	0.01880 (7)	0.00328 (5)	−0.00553 (5)	0.00044 (5)
Fe1	0.01504 (7)	0.01978 (9)	0.01474 (8)	0.00420 (6)	−0.00213 (6)	0.00057 (6)
Cl1	0.0355 (2)	0.02587 (18)	0.02603 (18)	0.00044 (15)	−0.00416 (15)	−0.00649 (14)
Cl2	0.01591 (12)	0.02142 (15)	0.03549 (19)	0.00060 (11)	−0.00080 (12)	0.01075 (14)
O1	0.0346 (7)	0.0321 (7)	0.0339 (7)	−0.0102 (6)	0.0019 (5)	−0.0029 (6)
O2	0.0548 (11)	0.0556 (11)	0.0403 (9)	0.0282 (9)	0.0118 (8)	−0.0069 (8)
C1	0.0212 (6)	0.0243 (6)	0.0206 (6)	0.0006 (5)	−0.0028 (5)	−0.0032 (5)
C2	0.0291 (7)	0.0332 (8)	0.0219 (7)	0.0095 (6)	0.0018 (6)	−0.0005 (6)
C1A	0.048 (3)	0.0189 (15)	0.036 (4)	0.005 (2)	−0.022 (3)	−0.0042 (17)
C2A	0.036 (4)	0.027 (3)	0.052 (4)	0.016 (2)	0.017 (3)	0.003 (2)
C3A	0.047 (4)	0.036 (3)	0.085 (9)	0.018 (3)	−0.051 (5)	−0.012 (4)
C4A	0.101 (9)	0.051 (6)	0.017 (2)	0.043 (6)	−0.009 (4)	0.006 (2)
C5A	0.036 (3)	0.033 (4)	0.062 (4)	0.008 (2)	0.020 (3)	0.026 (3)
C1B	0.154 (18)	0.049 (9)	0.026 (3)	0.066 (10)	−0.003 (9)	−0.003 (5)
C2B	0.033 (5)	0.051 (9)	0.108 (15)	0.025 (5)	0.031 (8)	0.050 (8)
C3B	0.067 (8)	0.023 (3)	0.058 (7)	−0.013 (4)	−0.048 (6)	0.017 (4)
C4B	0.050 (5)	0.030 (3)	0.051 (7)	0.011 (3)	0.029 (5)	0.019 (4)
C5B	0.042 (6)	0.022 (2)	0.089 (9)	−0.006 (3)	−0.045 (6)	0.001 (5)

Geometric parameters (Å, º) top

Ga1—Cl1	2.1877 (5)	Fe1—C5A	2.088 (8)
Ga1—Fe1	2.3028 (3)	Fe1—C1A	2.116 (9)
Ga1—Cl2	2.3850 (4)	O1—C1	1.146 (2)
Ga1—Cl2ⁱ	2.3987 (4)	O2—C2	1.142 (2)
Fe1—C1	1.7555 (17)	C1A—C2A	1.377 (11)
Fe1—C2	1.7578 (18)	C1A—C5A	1.397 (13)
Fe1—C1B	2.045 (12)	C2A—C3A	1.372 (13)
Fe1—C3A	2.057 (8)	C3A—C4A	1.382 (16)
Fe1—C4A	2.062 (8)	C4A—C5A	1.401 (13)
Fe1—C5B	2.066 (11)	C1B—C5B	1.37 (2)
Fe1—C2B	2.068 (11)	C1B—C2B	1.38 (2)
Fe1—C4B	2.069 (11)	C2B—C3B	1.36 (2)
Fe1—C2A	2.083 (9)	C3B—C4B	1.417 (17)
Fe1—C3B	2.086 (11)	C4B—C5B	1.369 (16)

Cl1—Ga1—Fe1	128.582 (16)	C2A—Fe1—C5A	64.8 (4)
Cl1—Ga1—Cl2	99.687 (18)	C1—Fe1—C1A	128.9 (3)
Fe1—Ga1—Cl2	115.906 (14)	C2—Fe1—C1A	137.9 (3)
Cl1—Ga1—Cl2ⁱ	99.924 (18)	C3A—Fe1—C1A	65.1 (3)
Fe1—Ga1—Cl2ⁱ	116.724 (14)	C4A—Fe1—C1A	65.3 (4)
Cl2—Ga1—Cl2ⁱ	87.338 (14)	C2A—Fe1—C1A	38.3 (3)
C1—Fe1—C2	92.53 (9)	C5A—Fe1—C1A	38.8 (4)
C1—Fe1—C1B	117.0 (9)	Ga1—Cl2—Ga1ⁱ	92.662 (14)
C2—Fe1—C1B	150.4 (9)	O1—C1—Fe1	178.04 (15)
C1—Fe1—C3A	98.1 (4)	O2—C2—Fe1	177.2 (2)
C2—Fe1—C3A	122.6 (5)	C2A—C1A—C5A	107.3 (8)
C1—Fe1—C4A	130.6 (5)	C2A—C1A—Fe1	69.6 (5)
C2—Fe1—C4A	95.0 (3)	C5A—C1A—Fe1	69.5 (5)
C3A—Fe1—C4A	39.2 (5)	C3A—C2A—C1A	109.6 (10)
C1—Fe1—C5B	155.8 (6)	C3A—C2A—Fe1	69.6 (5)
C2—Fe1—C5B	111.5 (6)	C1A—C2A—Fe1	72.1 (6)
C1B—Fe1—C5B	39.0 (6)	C2A—C3A—C4A	107.7 (9)
C1—Fe1—C2B	92.8 (4)	C2A—C3A—Fe1	71.7 (5)
C2—Fe1—C2B	148.1 (8)	C4A—C3A—Fe1	70.6 (5)
C1B—Fe1—C2B	39.2 (6)	C3A—C4A—C5A	108.1 (7)
C5B—Fe1—C2B	65.7 (5)	C3A—C4A—Fe1	70.2 (5)
C1—Fe1—C4B	142.8 (5)	C5A—C4A—Fe1	71.3 (4)
C2—Fe1—C4B	92.5 (4)	C1A—C5A—C4A	107.3 (6)
C1B—Fe1—C4B	64.9 (6)	C1A—C5A—Fe1	71.7 (5)
C5B—Fe1—C4B	38.7 (5)	C4A—C5A—Fe1	69.3 (5)
C2B—Fe1—C4B	65.3 (5)	C5B—C1B—C2B	109.0 (10)
C1—Fe1—C2A	98.2 (3)	C5B—C1B—Fe1	71.3 (7)
C2—Fe1—C2A	159.6 (3)	C2B—C1B—Fe1	71.3 (7)
C3A—Fe1—C2A	38.7 (4)	C3B—C2B—C1B	108.4 (12)
C4A—Fe1—C2A	64.9 (4)	C3B—C2B—Fe1	71.6 (7)
C1—Fe1—C3B	104.5 (4)	C1B—C2B—Fe1	69.5 (7)
C2—Fe1—C3B	110.3 (6)	C2B—C3B—C4B	107.0 (11)
C1B—Fe1—C3B	65.1 (5)	C2B—C3B—Fe1	70.2 (7)
C5B—Fe1—C3B	65.9 (4)	C4B—C3B—Fe1	69.4 (7)
C2B—Fe1—C3B	38.2 (6)	C5B—C4B—C3B	108.2 (10)
C4B—Fe1—C3B	39.9 (5)	C5B—C4B—Fe1	70.5 (7)
C1—Fe1—C5A	162.3 (2)	C3B—C4B—Fe1	70.7 (6)
C2—Fe1—C5A	102.4 (3)	C4B—C5B—C1B	107.4 (9)
C3A—Fe1—C5A	65.8 (4)	C4B—C5B—Fe1	70.8 (6)
C4A—Fe1—C5A	39.5 (4)	C1B—C5B—Fe1	69.7 (7)

Symmetry code: (i) −x+2, −y+1, −z+1.

References

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