(μ-Formato-κ2O:O′)bis­[dicarbon­yl(η5-cyclo­penta­dien­yl)iron(II)] tetra­fluoridoborate

M'thiruaine, C.M.; Friedrich, H.B.; Changamu, E.O.; Omondi, B.

doi:10.1107/S1600536811032764

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page m1252

doi:10.1107/S1600536811032764

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(μ-Formato-κ²O:O′)bis[dicarbonyl(η⁵-cyclopentadienyl)iron(II)] tetrafluoridoborate

Cyprian M. M'thiruaine,^a Holger B. Friedrich,^a Evans O. Changamu ^b and Bernard Omondi ^a ^*

^aSchool of Chemistry, University of KwaZulu-Natal, Westville Campus, Private Bag X54001, Durban 4000, South Africa, and ^bChemistry Department, Kenyatta University, PO Box 43844, Nairobi, Kenya
^*Correspondence e-mail: owaga@ukzn.ac.za

(Received 8 August 2011; accepted 12 August 2011; online 17 August 2011)

In the structure of the title compound [Fe₂(C₅H₅)₂(CHO₂)(CO)₄]BF₄, each Fe^II atom is coordinated in a pseudo-octahedral three-legged piano-stool fashion. The cyclopentadienyl ligand occupies three fac coordination sites while the two carbonyl ligands and formate O atom occupy the remaining three sites.

Related literature

For the synthesis of the title and other analogous compounds, see: Tso & Cutler (1985 , 1990 ). For mononuclear [Fe(κ¹-OCHO)(η⁵-C₅H₅)(CO)₂], see: Darensbourg, Day et al. (1981 ); Darensbourg, Fischer et al. (1981 ); Dombek & Angelici (1973 ). For related compounds, see: M'thiruaine, Friedrich, Changamu & Bala (2011 ); M'thiruaine, Friedrich, Changamu & Omondi (2011 ); Pinkes et al. (1997 ).

Experimental

Crystal data

[Fe₂(C₅H₅)₂(CHO₂)(CO)₄]BF₄
M_r = 485.75
Monoclinic, P 2₁ /c
a = 7.4964 (5) Å
b = 17.8845 (14) Å
c = 14.1931 (9) Å
β = 115.144 (3)°
V = 1722.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.76 mm⁻¹
T = 100 K
0.24 × 0.11 × 0.1 mm

Data collection

Bruker X8 APEXII 4K Kappa CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.678, T_max = 0.844
41366 measured reflections
4341 independent reflections
3784 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.069
S = 1.02
4341 reflections
253 parameters
11 restraints
H-atom parameters constrained
Δρ_max = 1.38 e Å⁻³
Δρ_min = −0.92 e Å⁻³

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus and XPREP (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811032764/ng5211sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811032764/ng5211Isup2.hkl

checkCIF report

Comment top

There has been a considerable interest in metalloformates and metallocarboxylates due to their potential application in the catalysis of water-gas shift reactions (Darensbourg, Day et al. 1981; Darensbourg, Fischer et al. 1981) and catalytic reduction of CO₂ (Tso & Cutler, 1985, 1990; Pinkes et al. 1997). In connection to this the neutral mononuclear formate complex [(η⁵-C₅H₅)Fe(CO)₂(η¹-OC(H)O)] has been prepared using different routes (Dombek & Angelici 1973; Darensbourg, Day et al. 1981; Tso & Cutler, 1985) and its molecular structure is well known (Darensbourg, Day et al. 1981; Darensbourg, Fischer et al. 1981). The cationic binuclear complex [{(η⁵-C₅H₅)Fe(CO)₂}₂(µ-OC(H)O)]PF₆ has been reported as the product of the reaction between the neutral mononuclear complex [(η⁵-C₅H₅)Fe(CO)₂(η¹-OC(H)O)] and [(η₅-C₅H₅)Fe(CO)₂(THF)]PF₆, and has been assumed to exist as a syn-syn isomer based on spectroscopic data (Tso & Cutler, 1985). The same authors have reported various formate bridged heterobimetallic complexes (Tso & Cutler, 1990) but none of their crystal structures are known.

The title compound (I) was obtained in high yields from the reaction of formic acid with two equivalents of the diethyl ether complex [(η⁵-C₅H₅)Fe(CO)₂(O(CH₂CH₃)₂)]BF₄. This is a part of our study on the reactions of the diethyl ether complex with electron pair donor ligands (M'thiruaine, Friedrich, Changamu & Bala, 2011; M'thiruaine, Friedrich, Changamu & Omondi, 2011). The crystallizes with one discrete molecular cation and one counter anion in the assymetric unit. Each Fe atom is coordinated in a pseudo-octahedral three-legged piano stool fashion in which the iron metal capped with cyclopentadienyl occupies three coordination sites while the two carbonyl ligands and formate oxygen occupy the other three coordination sites (Fig. 1). The Fe—O bond lengths of 1.9844 (13) and 1.9686 (13) Å are close to the 1.957 (2)Å reported for the neutral mononuclear complex [(η⁵-C₅H₅)Fe(CO)₂(η¹-OC(H)O)] (Darensbourg, Day et al. 1981). The two O—C bonds of the formate group (–OC(H)O–) are identical, with the bond distances being equal to 1.256 (2) and 1.258 (2) Å, which is close to 1.277 (3)Å and 1.208 (4) found for coordinated and uncoordinated O—C of the formate moiety in the complex [(η⁵-C₅H₅)Fe(CO)₂(η¹-OC(H)O)], respectively. The identical bond lengths of the two C—O bonds of bridging formate indicate electron delocalization between the two oxygen atoms of the formate moiety. Thus the structure shown in Fig. 1 is an overall structure of two resonance structures: [Fp—O=C(H)O—Fp]⁺ and [Fp—O-(H)C=O—Fp]⁺. This greatly contributes to the stability of the title compound in both solution and solid state. The Fp moieties are oriented in the solid state so as to adopt a syn-anti isomer structure contrary to the assumption made by Tso & Cutler (1985).

Related literature top

For the synthesis of the title and other analogous compounds, see: Tso & Cutler (1985, 1990). For mononuclear [Fe(η¹-OCHO)(η⁵-C₅H₅)(CO)₂], see: Darensbourg, Day et al. (1981); Darensbourg, Fischer et al. (1981); Dombek & Angelici (1973). For the synthesis and other preparative applications of the ether complex Fe(η¹-O(CH₂CH₃)₂)(η⁵-C₅H₅)(CO)₂BF₄, see: M'thiruaine, Friedrich, Changamu & Bala (2011); M'thiruaine, Friedrich, Changamu & Omondi, 2011); Pinkes et al. (1997).

Experimental top

The compound was synthesized as described below and its spectroscopic data is in good agreement with data reported for the PF₆^- salt.

To a solution of [(η⁵-C₅H₅)Fe(CO)₂(O(CH₂CH₃)₂)]BF₄ (0.560 g, 1.66 mmol) in CH₂Cl₂ (10 ml), 98% formic acid (0.030 ml, 0.796 mmol) was added and the mixture stirred at room temperature for 5 h after which diethyl ether was added to precipitate the formate compound as a light red solid. The mixture was allowed to stand for 30 min and then the mother liquor was syringed off and the residue washed with (2 x 5 ml) diethyl to give 0.70 g (87% yield) of the light red solid. Anal. Calc. for C₁₅H₁₁BF₄Fe₂O₆: C, 37.09; H, 2.28% Found: C, 36.53; H, 2.57%. ¹H NMR (400 MHz, acetone-d₆): δ 5.46 (s, 10H, Cp), 7.18 (s, 1H, OCHO). ¹³C NMR (400 MHz, acetone-d₆): δ 86.88 (Cp) 212.23 (CO). IR (solid state): ν(CO) 2057, 2039, 1985 cm^-1, v(OCO) 1562 cm^-1. M.p 109–110 °C.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus and XPREP (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. View of (I) (50% probability displacement ellipsoids) with H atoms omited for clarity.

(µ-Formato-κ²O:O')bis[dicarbonyl(η⁵- cyclopentadienyl)iron(II)] tetrafluoridoborate top

Crystal data top

[Fe₂(C₅H₅)₂(CHO₂)(CO)₄]BF₄	F(000) = 968
M_r = 485.75	D_x = 1.873 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 42124 reflections
a = 7.4964 (5) Å	θ = 2.0–28.5°
b = 17.8845 (14) Å	µ = 1.76 mm⁻¹
c = 14.1931 (9) Å	T = 100 K
β = 115.144 (3)°	Block, brown
V = 1722.5 (2) Å³	0.24 × 0.11 × 0.1 mm
Z = 4

Data collection top

Bruker X8 APEXII 4K Kappa CCD diffractometer	3784 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ϕ and ω scans	θ_max = 28.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −9→10
T_min = 0.678, T_max = 0.844	k = −24→23
41366 measured reflections	l = −19→19
4341 independent 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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.069	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0257P)² + 2.6185P] where P = (F_o² + 2F_c²)/3
4341 reflections	(Δ/σ)_max = 0.002
253 parameters	Δρ_max = 1.38 e Å⁻³
11 restraints	Δρ_min = −0.92 e Å⁻³

Crystal data top

[Fe₂(C₅H₅)₂(CHO₂)(CO)₄]BF₄	V = 1722.5 (2) Å³
M_r = 485.75	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.4964 (5) Å	µ = 1.76 mm⁻¹
b = 17.8845 (14) Å	T = 100 K
c = 14.1931 (9) Å	0.24 × 0.11 × 0.1 mm
β = 115.144 (3)°

Data collection top

Bruker X8 APEXII 4K Kappa CCD diffractometer	4341 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	3784 reflections with I > 2σ(I)
T_min = 0.678, T_max = 0.844	R_int = 0.048
41366 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	11 restraints
wR(F²) = 0.069	H-atom parameters constrained
S = 1.02	Δρ_max = 1.38 e Å⁻³
4341 reflections	Δρ_min = −0.92 e Å⁻³
253 parameters

Special details top

Experimental. All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.95–1.00 Å and with U_iso(H) = 1.2U_eq(C).

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. 244_ALERT_4_C Low 'Solvent' U_eq as Compared to Neighbors for B1 912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 26 003_ALERT_ _G # Space-Group NOTED. 232_ALERT_2_G Hirshfeld Test Diff (M—X) Fe1 – C7.. 5.63 su 232_ALERT_2_G Hirshfeld Test Diff (M—X) Fe2 – C14.. 5.38 su 232_ALERT_2_G Hirshfeld Test Diff (M—X) Fe2 – C15.. 5.63 su DELU and SIMU restraints used. 790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd. # 2 B F4 860_ALERT_3_G Note: Number of Least-Squares Restraints ······. 11 NOTED.

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

	x	y	z	U_iso*/U_eq
C1	−0.3243 (3)	0.92926 (11)	0.07899 (14)	0.0147 (4)
H1	−0.3337	0.88	0.0438	0.018*
C2	−0.1969 (3)	0.99018 (11)	0.08289 (14)	0.0150 (4)
H2	−0.1025	0.9911	0.05	0.018*
C3	−0.2325 (3)	1.04957 (11)	0.13869 (14)	0.0153 (4)
H3	−0.1677	1.0998	0.1522	0.018*
C4	−0.3832 (3)	1.02592 (11)	0.16890 (14)	0.0152 (4)
H4	−0.44	1.0562	0.2088	0.018*
C5	−0.4380 (3)	0.95243 (11)	0.13173 (14)	0.0153 (4)
H5	−0.5392	0.9214	0.1421	0.018*
C6	0.0115 (3)	1.01353 (10)	0.34237 (14)	0.0146 (3)
C7	0.0791 (3)	0.90816 (11)	0.23422 (15)	0.0161 (3)
C8	−0.0601 (3)	0.85414 (10)	0.39906 (14)	0.0137 (3)
H8	−0.0936	0.8167	0.4362	0.016*
C9	0.3687 (3)	0.72050 (11)	0.53224 (15)	0.0179 (4)
H9	0.2698	0.6817	0.5283	0.021*
C10	0.5315 (3)	0.74607 (11)	0.62519 (15)	0.0175 (4)
H10	0.5666	0.7279	0.6975	0.021*
C11	0.6362 (3)	0.79995 (12)	0.59592 (16)	0.0188 (4)
H11	0.7579	0.8268	0.644	0.023*
C12	0.5394 (3)	0.80858 (12)	0.48493 (16)	0.0189 (4)
H12	0.5807	0.8426	0.4419	0.023*
C13	0.3781 (3)	0.75852 (11)	0.44746 (15)	0.0185 (4)
H13	0.2831	0.7523	0.3728	0.022*
C14	0.2328 (3)	0.82195 (10)	0.63946 (15)	0.0151 (3)
C15	0.4344 (3)	0.92972 (11)	0.59175 (14)	0.0150 (3)
B1	−0.1687 (3)	0.64951 (14)	0.37678 (18)	0.0201 (4)
F1	−0.06516 (18)	0.69395 (7)	0.33590 (9)	0.0219 (3)
F2	−0.2175 (2)	0.58267 (8)	0.32135 (15)	0.0431 (4)
F3	−0.3406 (2)	0.68494 (8)	0.36527 (13)	0.0340 (3)
F4	−0.0473 (2)	0.63435 (12)	0.47950 (12)	0.0510 (5)
Fe1	−0.13319 (4)	0.955840 (14)	0.233347 (19)	0.01069 (7)
Fe2	0.34774 (4)	0.835389 (14)	0.552967 (19)	0.01083 (7)
O1	0.1019 (2)	1.05243 (8)	0.40890 (12)	0.0232 (3)
O2	0.2129 (2)	0.88085 (9)	0.23040 (12)	0.0250 (3)
O3	−0.19470 (19)	0.88025 (8)	0.31758 (10)	0.0149 (3)
O4	0.11643 (19)	0.87505 (7)	0.43390 (10)	0.0139 (3)
O5	0.1671 (2)	0.80908 (9)	0.69662 (11)	0.0228 (3)
O6	0.4921 (2)	0.98874 (8)	0.61515 (12)	0.0241 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0144 (9)	0.0155 (9)	0.0115 (8)	0.0002 (7)	0.0029 (7)	−0.0001 (7)
C2	0.0149 (9)	0.0174 (9)	0.0111 (8)	0.0007 (7)	0.0042 (7)	0.0031 (7)
C3	0.0153 (9)	0.0138 (8)	0.0145 (8)	0.0018 (7)	0.0041 (7)	0.0036 (7)
C4	0.0123 (8)	0.0191 (9)	0.0121 (8)	0.0046 (7)	0.0031 (7)	0.0021 (7)
C5	0.0101 (8)	0.0201 (9)	0.0132 (8)	0.0011 (7)	0.0023 (7)	0.0035 (7)
C6	0.0135 (9)	0.0144 (8)	0.0140 (8)	0.0020 (6)	0.0038 (7)	0.0019 (6)
C7	0.0138 (8)	0.0185 (9)	0.0153 (8)	0.0018 (6)	0.0055 (7)	0.0015 (7)
C8	0.0148 (9)	0.0133 (8)	0.0142 (8)	0.0011 (7)	0.0074 (7)	0.0012 (7)
C9	0.0151 (9)	0.0130 (9)	0.0222 (9)	0.0028 (7)	0.0046 (8)	−0.0033 (7)
C10	0.0152 (9)	0.0150 (9)	0.0188 (9)	0.0057 (7)	0.0038 (7)	0.0005 (7)
C11	0.0111 (9)	0.0205 (9)	0.0218 (9)	0.0037 (7)	0.0041 (7)	−0.0013 (8)
C12	0.0155 (9)	0.0238 (10)	0.0208 (9)	0.0031 (8)	0.0109 (8)	−0.0021 (8)
C13	0.0167 (9)	0.0212 (10)	0.0161 (9)	0.0061 (8)	0.0053 (7)	−0.0053 (7)
C14	0.0159 (9)	0.0145 (8)	0.0147 (8)	0.0029 (7)	0.0063 (7)	0.0013 (7)
C15	0.0143 (9)	0.0170 (7)	0.0130 (8)	0.0005 (7)	0.0051 (7)	−0.0005 (6)
B1	0.0165 (11)	0.0222 (11)	0.0202 (10)	−0.0014 (9)	0.0064 (9)	0.0029 (9)
F1	0.0215 (6)	0.0243 (6)	0.0217 (6)	−0.0017 (5)	0.0110 (5)	0.0033 (5)
F2	0.0262 (8)	0.0265 (7)	0.0816 (12)	−0.0079 (6)	0.0275 (8)	−0.0190 (8)
F3	0.0321 (8)	0.0294 (7)	0.0534 (9)	0.0073 (6)	0.0307 (7)	0.0015 (6)
F4	0.0333 (9)	0.0855 (13)	0.0248 (7)	−0.0234 (9)	0.0032 (6)	0.0205 (8)
Fe1	0.00883 (12)	0.01172 (13)	0.01071 (12)	0.00072 (9)	0.00336 (10)	0.00103 (9)
Fe2	0.00995 (13)	0.01173 (13)	0.01013 (12)	0.00130 (9)	0.00361 (10)	0.00004 (9)
O1	0.0228 (8)	0.0187 (7)	0.0208 (7)	−0.0012 (6)	0.0020 (6)	−0.0026 (6)
O2	0.0186 (7)	0.0328 (9)	0.0259 (8)	0.0080 (6)	0.0118 (6)	0.0032 (6)
O3	0.0112 (6)	0.0164 (6)	0.0152 (6)	0.0000 (5)	0.0037 (5)	0.0038 (5)
O4	0.0118 (6)	0.0156 (6)	0.0129 (6)	0.0012 (5)	0.0039 (5)	0.0022 (5)
O5	0.0274 (8)	0.0251 (8)	0.0212 (7)	0.0040 (6)	0.0153 (7)	0.0045 (6)
O6	0.0277 (8)	0.0187 (7)	0.0245 (7)	−0.0037 (6)	0.0097 (7)	−0.0031 (6)

Geometric parameters (Å, º) top

C1—C5	1.414 (3)	C9—Fe2	2.0910 (19)
C1—C2	1.434 (3)	C9—H9	1
C1—Fe1	2.1002 (18)	C10—C11	1.412 (3)
C1—H1	1	C10—Fe2	2.0737 (19)
C2—C3	1.416 (3)	C10—H10	0.9999
C2—Fe1	2.0732 (18)	C11—C12	1.435 (3)
C2—H2	1	C11—Fe2	2.0805 (19)
C3—C4	1.432 (3)	C11—H11	0.9999
C3—Fe1	2.0783 (19)	C12—C13	1.414 (3)
C3—H3	1	C12—Fe2	2.0990 (19)
C4—C5	1.411 (3)	C12—H12	1.0001
C4—Fe1	2.1125 (19)	C13—Fe2	2.1152 (19)
C4—H4	1.0001	C13—H13	1.0001
C5—Fe1	2.1224 (19)	C14—O5	1.137 (2)
C5—H5	1	C14—Fe2	1.7906 (19)
C6—O1	1.136 (2)	C15—O6	1.135 (2)
C6—Fe1	1.7915 (19)	C15—Fe2	1.808 (2)
C7—O2	1.138 (2)	B1—F4	1.378 (3)
C7—Fe1	1.8009 (19)	B1—F3	1.382 (3)
C8—O4	1.256 (2)	B1—F2	1.392 (3)
C8—O3	1.258 (2)	B1—F1	1.397 (3)
C8—H8	0.95	Fe1—O3	1.9844 (13)
C9—C13	1.410 (3)	Fe2—O4	1.9686 (13)
C9—C10	1.439 (3)

C5—C1—C2	107.34 (17)	O6—C15—Fe2	178.34 (18)
C5—C1—Fe1	71.28 (11)	F4—B1—F3	112.2 (2)
C2—C1—Fe1	68.89 (10)	F4—B1—F2	109.0 (2)
C5—C1—H1	126.3	F3—B1—F2	108.60 (18)
C2—C1—H1	126.3	F4—B1—F1	108.53 (18)
Fe1—C1—H1	126.3	F3—B1—F1	110.15 (18)
C3—C2—C1	108.10 (16)	F2—B1—F1	108.22 (18)
C3—C2—Fe1	70.24 (10)	C6—Fe1—C7	93.30 (9)
C1—C2—Fe1	70.92 (10)	C6—Fe1—O3	94.73 (7)
C3—C2—H2	125.9	C7—Fe1—O3	95.98 (7)
C1—C2—H2	125.9	C6—Fe1—C2	120.60 (8)
Fe1—C2—H2	125.9	C7—Fe1—C2	87.91 (8)
C2—C3—C4	107.81 (17)	O3—Fe1—C2	144.23 (7)
C2—C3—Fe1	69.86 (10)	C6—Fe1—C3	90.74 (8)
C4—C3—Fe1	71.32 (11)	C7—Fe1—C3	117.34 (8)
C2—C3—H3	126.1	O3—Fe1—C3	145.87 (7)
C4—C3—H3	126.1	C2—Fe1—C3	39.90 (7)
Fe1—C3—H3	126.1	C6—Fe1—C1	157.78 (8)
C5—C4—C3	107.74 (17)	C7—Fe1—C1	96.27 (8)
C5—C4—Fe1	70.92 (11)	O3—Fe1—C1	104.12 (7)
C3—C4—Fe1	68.74 (11)	C2—Fe1—C1	40.19 (7)
C5—C4—H4	126.1	C3—Fe1—C1	67.05 (7)
C3—C4—H4	126.1	C6—Fe1—C4	97.62 (8)
Fe1—C4—H4	126.1	C7—Fe1—C4	154.51 (8)
C4—C5—C1	109.00 (17)	O3—Fe1—C4	105.94 (7)
C4—C5—Fe1	70.16 (11)	C2—Fe1—C4	66.70 (7)
C1—C5—Fe1	69.59 (11)	C3—Fe1—C4	39.94 (7)
C4—C5—H5	125.5	C1—Fe1—C4	66.18 (7)
C1—C5—H5	125.5	C6—Fe1—C5	133.28 (8)
Fe1—C5—H5	125.5	C7—Fe1—C5	133.17 (8)
O1—C6—Fe1	177.30 (17)	O3—Fe1—C5	86.05 (7)
O2—C7—Fe1	176.01 (18)	C2—Fe1—C5	66.31 (7)
O4—C8—O3	123.42 (17)	C3—Fe1—C5	66.25 (8)
O4—C8—H8	118.3	C1—Fe1—C5	39.13 (7)
O3—C8—H8	118.3	C4—Fe1—C5	38.92 (7)
C13—C9—C10	107.38 (18)	C14—Fe2—C15	97.58 (9)
C13—C9—Fe2	71.35 (11)	C14—Fe2—O4	97.58 (7)
C10—C9—Fe2	69.14 (11)	C15—Fe2—O4	89.81 (7)
C13—C9—H9	126.3	C14—Fe2—C10	88.27 (8)
C10—C9—H9	126.3	C15—Fe2—C10	119.41 (8)
Fe2—C9—H9	126.3	O4—Fe2—C10	149.28 (7)
C11—C10—C9	107.94 (18)	C14—Fe2—C11	120.08 (9)
C11—C10—Fe2	70.39 (11)	C15—Fe2—C11	90.05 (9)
C9—C10—Fe2	70.43 (11)	O4—Fe2—C11	142.00 (7)
C11—C10—H10	126	C10—Fe2—C11	39.74 (8)
C9—C10—H10	126	C14—Fe2—C9	92.94 (8)
Fe2—C10—H10	126	C15—Fe2—C9	157.11 (8)
C10—C11—C12	108.14 (18)	O4—Fe2—C9	108.95 (7)
C10—C11—Fe2	69.87 (11)	C10—Fe2—C9	40.43 (8)
C12—C11—Fe2	70.61 (11)	C11—Fe2—C9	67.11 (8)
C10—C11—H11	125.9	C14—Fe2—C12	155.18 (8)
C12—C11—H11	125.9	C15—Fe2—C12	97.22 (8)
Fe2—C11—H11	125.9	O4—Fe2—C12	102.29 (7)
C13—C12—C11	107.30 (18)	C10—Fe2—C12	67.08 (8)
C13—C12—Fe2	71.01 (11)	C11—Fe2—C12	40.17 (8)
C11—C12—Fe2	69.22 (11)	C9—Fe2—C12	66.65 (8)
C13—C12—H12	126.4	C14—Fe2—C13	128.76 (9)
C11—C12—H12	126.3	C15—Fe2—C13	133.58 (8)
Fe2—C12—H12	126.3	O4—Fe2—C13	86.96 (7)
C9—C13—C12	109.22 (17)	C10—Fe2—C13	66.45 (8)
C9—C13—Fe2	69.49 (11)	C11—Fe2—C13	66.32 (8)
C12—C13—Fe2	69.77 (11)	C9—Fe2—C13	39.16 (8)
C9—C13—H13	125.4	C12—Fe2—C13	39.21 (8)
C12—C13—H13	125.4	C8—O3—Fe1	120.38 (12)
Fe2—C13—H13	125.4	C8—O4—Fe2	128.81 (12)
O5—C14—Fe2	175.35 (17)

C5—C1—C2—C3	0.6 (2)	C1—C5—Fe1—O3	−118.19 (11)
Fe1—C1—C2—C3	−60.70 (13)	C4—C5—Fe1—C2	−81.72 (12)
C5—C1—C2—Fe1	61.25 (13)	C1—C5—Fe1—C2	38.52 (11)
C1—C2—C3—C4	−0.4 (2)	C4—C5—Fe1—C3	−37.96 (11)
Fe1—C2—C3—C4	−61.56 (13)	C1—C5—Fe1—C3	82.28 (12)
C1—C2—C3—Fe1	61.13 (13)	C4—C5—Fe1—C1	−120.24 (16)
C2—C3—C4—C5	0.2 (2)	C1—C5—Fe1—C4	120.24 (16)
Fe1—C3—C4—C5	−60.48 (13)	C11—C10—Fe2—C14	−145.14 (13)
C2—C3—C4—Fe1	60.63 (13)	C9—C10—Fe2—C14	96.58 (13)
C3—C4—C5—C1	0.2 (2)	C11—C10—Fe2—C15	−47.42 (14)
Fe1—C4—C5—C1	−58.91 (13)	C9—C10—Fe2—C15	−165.69 (12)
C3—C4—C5—Fe1	59.11 (13)	C11—C10—Fe2—O4	112.87 (15)
C2—C1—C5—C4	−0.5 (2)	C9—C10—Fe2—O4	−5.4 (2)
Fe1—C1—C5—C4	59.26 (13)	C9—C10—Fe2—C11	−118.28 (17)
C2—C1—C5—Fe1	−59.72 (12)	C11—C10—Fe2—C9	118.28 (17)
C13—C9—C10—C11	0.8 (2)	C11—C10—Fe2—C12	37.90 (12)
Fe2—C9—C10—C11	−60.69 (14)	C9—C10—Fe2—C12	−80.38 (13)
C13—C9—C10—Fe2	61.45 (13)	C11—C10—Fe2—C13	80.73 (13)
C9—C10—C11—C12	0.2 (2)	C9—C10—Fe2—C13	−37.55 (12)
Fe2—C10—C11—C12	−60.52 (14)	C10—C11—Fe2—C14	41.31 (15)
C9—C10—C11—Fe2	60.72 (13)	C12—C11—Fe2—C14	160.03 (12)
C10—C11—C12—C13	−1.1 (2)	C10—C11—Fe2—C15	140.10 (12)
Fe2—C11—C12—C13	−61.14 (13)	C12—C11—Fe2—C15	−101.18 (13)
C10—C11—C12—Fe2	60.05 (14)	C10—C11—Fe2—O4	−130.14 (13)
C10—C9—C13—C12	−1.5 (2)	C12—C11—Fe2—O4	−11.43 (18)
Fe2—C9—C13—C12	58.58 (14)	C12—C11—Fe2—C10	118.72 (17)
C10—C9—C13—Fe2	−60.04 (13)	C10—C11—Fe2—C9	−38.31 (12)
C11—C12—C13—C9	1.6 (2)	C12—C11—Fe2—C9	80.41 (13)
Fe2—C12—C13—C9	−58.41 (14)	C10—C11—Fe2—C12	−118.72 (17)
C11—C12—C13—Fe2	59.99 (13)	C10—C11—Fe2—C13	−81.09 (13)
C3—C2—Fe1—C6	−46.86 (14)	C12—C11—Fe2—C13	37.62 (12)
C1—C2—Fe1—C6	−165.13 (12)	C13—C9—Fe2—C14	158.36 (13)
C3—C2—Fe1—C7	−139.46 (12)	C10—C9—Fe2—C14	−83.87 (13)
C1—C2—Fe1—C7	102.27 (12)	C13—C9—Fe2—C15	−84.2 (2)
C3—C2—Fe1—O3	123.20 (13)	C10—C9—Fe2—C15	33.6 (3)
C1—C2—Fe1—O3	4.93 (17)	C13—C9—Fe2—O4	59.31 (13)
C1—C2—Fe1—C3	−118.27 (16)	C10—C9—Fe2—O4	177.08 (11)
C3—C2—Fe1—C1	118.27 (16)	C13—C9—Fe2—C10	−117.77 (17)
C3—C2—Fe1—C4	38.15 (11)	C13—C9—Fe2—C11	−80.10 (13)
C1—C2—Fe1—C4	−80.12 (12)	C10—C9—Fe2—C11	37.67 (12)
C3—C2—Fe1—C5	80.75 (12)	C13—C9—Fe2—C12	−36.25 (12)
C1—C2—Fe1—C5	−37.52 (11)	C10—C9—Fe2—C12	81.52 (13)
C2—C3—Fe1—C6	141.09 (12)	C10—C9—Fe2—C13	117.77 (17)
C4—C3—Fe1—C6	−101.01 (12)	C13—C12—Fe2—C14	73.1 (2)
C2—C3—Fe1—C7	46.98 (14)	C11—C12—Fe2—C14	−44.7 (3)
C4—C3—Fe1—C7	164.89 (11)	C13—C12—Fe2—C15	−160.72 (12)
C2—C3—Fe1—O3	−119.34 (13)	C11—C12—Fe2—C15	81.44 (13)
C4—C3—Fe1—O3	−1.44 (18)	C13—C12—Fe2—O4	−69.34 (12)
C4—C3—Fe1—C2	117.90 (16)	C11—C12—Fe2—O4	172.83 (12)
C2—C3—Fe1—C1	−38.12 (11)	C13—C12—Fe2—C10	80.34 (13)
C4—C3—Fe1—C1	79.78 (12)	C11—C12—Fe2—C10	−37.50 (12)
C2—C3—Fe1—C4	−117.90 (16)	C13—C12—Fe2—C11	117.83 (18)
C2—C3—Fe1—C5	−80.90 (12)	C13—C12—Fe2—C9	36.20 (12)
C4—C3—Fe1—C5	37.01 (11)	C11—C12—Fe2—C9	−81.63 (13)
C5—C1—Fe1—C6	−82.2 (2)	C11—C12—Fe2—C13	−117.83 (18)
C2—C1—Fe1—C6	35.7 (3)	C9—C13—Fe2—C14	−28.18 (16)
C5—C1—Fe1—C7	162.86 (12)	C12—C13—Fe2—C14	−149.00 (13)
C2—C1—Fe1—C7	−79.23 (12)	C9—C13—Fe2—C15	147.70 (13)
C5—C1—Fe1—O3	65.06 (12)	C12—C13—Fe2—C15	26.88 (17)
C2—C1—Fe1—O3	−177.03 (11)	C9—C13—Fe2—O4	−125.46 (12)
C5—C1—Fe1—C2	−117.91 (16)	C12—C13—Fe2—O4	113.72 (12)
C5—C1—Fe1—C3	−80.07 (12)	C9—C13—Fe2—C10	38.75 (12)
C2—C1—Fe1—C3	37.84 (11)	C12—C13—Fe2—C10	−82.07 (13)
C5—C1—Fe1—C4	−36.39 (11)	C9—C13—Fe2—C11	82.29 (13)
C2—C1—Fe1—C4	81.52 (12)	C12—C13—Fe2—C11	−38.53 (12)
C2—C1—Fe1—C5	117.91 (16)	C12—C13—Fe2—C9	−120.82 (17)
C5—C4—Fe1—C6	−159.28 (12)	C9—C13—Fe2—C12	120.82 (17)
C3—C4—Fe1—C6	81.99 (12)	O4—C8—O3—Fe1	2.3 (2)
C5—C4—Fe1—C7	86.2 (2)	C6—Fe1—O3—C8	−47.85 (15)
C3—C4—Fe1—C7	−32.6 (2)	C7—Fe1—O3—C8	45.98 (15)
C5—C4—Fe1—O3	−62.12 (12)	C2—Fe1—O3—C8	140.73 (15)
C3—C4—Fe1—O3	179.16 (10)	C3—Fe1—O3—C8	−146.20 (15)
C5—C4—Fe1—C2	80.61 (12)	C1—Fe1—O3—C8	144.01 (14)
C3—C4—Fe1—C2	−38.11 (11)	C4—Fe1—O3—C8	−147.16 (14)
C5—C4—Fe1—C3	118.72 (16)	C5—Fe1—O3—C8	179.01 (15)
C5—C4—Fe1—C1	36.58 (11)	O3—C8—O4—Fe2	−174.87 (13)
C3—C4—Fe1—C1	−82.14 (12)	C14—Fe2—O4—C8	−40.67 (17)
C3—C4—Fe1—C5	−118.72 (16)	C15—Fe2—O4—C8	−138.29 (16)
C4—C5—Fe1—C6	28.79 (16)	C10—Fe2—O4—C8	58.8 (2)
C1—C5—Fe1—C6	149.03 (12)	C11—Fe2—O4—C8	131.88 (16)
C4—C5—Fe1—C7	−143.93 (12)	C9—Fe2—O4—C8	55.10 (17)
C1—C5—Fe1—C7	−23.69 (16)	C12—Fe2—O4—C8	124.36 (16)
C4—C5—Fe1—O3	121.58 (11)	C13—Fe2—O4—C8	88.04 (16)

Experimental details

Crystal data
Chemical formula	[Fe₂(C₅H₅)₂(CHO₂)(CO)₄]BF₄
M_r	485.75
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.4964 (5), 17.8845 (14), 14.1931 (9)
β (°)	115.144 (3)
V (Å³)	1722.5 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.76
Crystal size (mm)	0.24 × 0.11 × 0.1

Data collection
Diffractometer	Bruker X8 APEXII 4K Kappa CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.678, 0.844
No. of measured, independent and observed [I > 2σ(I)] reflections	41366, 4341, 3784
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.672

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.069, 1.02
No. of reflections	4341
No. of parameters	253
No. of restraints	11
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.38, −0.92

Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SAINT-Plus and XPREP (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Acknowledgements

The authors gratefully acknowledge the University of Johannesburg for funding and Dr Ilia Guzei for helping with structure refinement.

References

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