Crystal structure of (ferrocenylmeth­yl)di­methyl­ammonium hydrogen oxalate

Ndiaye, M.; Samb, A.; Diop, L.; Maris, T.

doi:10.1107/S205698901501333X

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Volume 71| Part 8| August 2015| Pages 947-949

https://doi.org/10.1107/S205698901501333X

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Crystal structure of (ferrocenylmethyl)dimethylammonium hydrogen oxalate

Mamadou Ndiaye,^a Abdoulaye Samb,^a Libasse Diop ^b ^* and Thierry Maris ^c

^aLaboratoire des Produits Naturels, Département de Chimie, Faculté des Sciences et Techniques, Université Cheikh Anta Diop, Dakar, Senegal, ^bLaboratoire de Chimie Minérale et Analytique, Département de Chimie, Faculté des Sciences et Techniques, Université Cheikh Anta Diop, Dakar, Senegal, and ^cDépartement de Chimie, Université de Montréal, 2900 Boulevard Édouard-Montpetit, Montréal, Québec, H3C 3J7, Canada
^*Correspondence e-mail: dlibasse@gmail.com,

Edited by M. Weil, Vienna University of Technology, Austria (Received 3 July 2015; accepted 11 July 2015; online 17 July 2015)

The crystal structure of the title salt, [Fe(C₅H₅)(C₈H₁₃N)](HC₂O₄), consists of discrete (ferrocenylmethyl)dimethylammonium cations and hydrogen oxalate anions. The anions are connected through a strong O—H⋯O hydrogen bond, forming linear chains running parallel to [100]. The cations are linked to the anions through bifurcated N—H⋯(O,O′) hydrogen bonds. Weak C—H⋯π interactions between neighbouring ferrocenyl moieties are also observed.

Keywords: crystal structure; hydrogen oxalate; (ferrocenylmethyl)dimethylammonium; bifurcated hydrogen bond; C—H⋯π interactions.

CCDC reference: 1412152

1. Chemical context

Our group has been working on the interactions between alkylammonium ions with oxalic acid, and we have recently reported the crystal structure of (H₃C)₂NH⁺·HC₂O₄⁻·0.5H₂C₂O₄ (Diallo et al., 2015 ). Numerous other reports have described crystal structures containing acidic or neutral oxalate molecules interacting with a protonated amine, see for example: Vaidhyanathan et al. (2002 ); Braga et al. (2013 ); Said et al. (2006 ); Hathwar et al. (2010 ); Matulková et al. (2008 ); Olenik et al. (2003 ); Anda et al. (2004 ). Braga et al. have reported several structures of columnar metallocenium sandwich compounds interacting with hydrogen oxalate (Braga et al., 2002 ). However, none of these structures features the hydrogen oxalate anion alone. It is crystallized either with neutral oxalic acid and/or a water molecule. The crystal structure of the title salt, [Fe(C₅H₅)(C₈H₁₃N)]⁺·[HC₂O₄]⁻, (I), features only the hydrogen oxalate anion. This compound was obtained when studying the interaction of (ferrocenylmethyl)dimethylamine and oxalic acid in aqueous solution.

2. Structural commentary

The asymmetric unit of (I) contains one hydrogen oxalate anion and one (ferrocenylmethyl)dimethylammonium cation (Fig. 1). As previously observed in structures featuring this cation (Wang, 2010 ; Guo, 2006 ; Guo et al., 2006a ,b ), the two Cp rings exhibit a nearly eclipsed conformation. They are planar and almost parallel, as demonstrated by the dihedral angle of 0.96 (5)° between their least-square planes. The Fe—C distances range from 2.0394 (10) to 2.0578 (12) Å. The Fe binding with the Cp rings is somewhat asymmetric as suggested by both the Fe⋯Cp plane distances [1.6601 (6) and 1.6514 (6) Å for the unsubstituted and the substituted ligand, respectively], and the Cp1–Fe–Cp2 dihedral angle of 170.96 (3)°. This behaviour was previously described as a consequence of an electron-withdrawal effect of the methyldimethylamine group that results in the less electron-rich substituted ring being slightly closer to the metal (Winter & Wolmershäuser, 1998 ). The oxalate anion is essentially planar and the dihedral angle between carboxylate and the carboxyl groups is only 4.6 (3)°. The C—OH bond is at 1.3052 (13) significantly longer than the other three C—O bonds with an mean of 1.24 (2) Å.

Figure 1
The molecular components in the structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radii. Fe–Cp interactions and hydrogen bonds are shown as dashed lines.

3. Supramolecular features

The hydrogen oxalate anions are held together via a strong intermolecular O4—H4A⋯O2 hydrogen bond, resulting in the formation of linear chains running parallel to [100] (Fig. 2). Within a chain, successive hydrogen oxalate anions are rotated by 30.89 (11)°. The cation is linked to the anionic chain through a bifurcated N1—H1⋯(O1,O4) hydrogen bond (Table 1). In addition to Coulomb forces and hydrogen bonds, a weak C—H⋯π interaction involving the centroid Cg2 of the Cp ligand (C6–C10; Table 1) is present and consolidates the three-dimensional supramolecular network.

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the Cp ligand C6–C10.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.878 (15)	1.981 (15)	2.8180 (11)	158.9 (14)
N1—H1⋯O4	0.878 (15)	2.346 (15)	2.8958 (11)	120.8 (11)
O4—H4A⋯O2ⁱ	0.96 (2)	1.52 (2)	2.4776 (11)	174.1 (18)
C2—H2⋯Cg2ⁱⁱ	0.935 (19)	2.743 (19)	3.6564 (13)	165.8 (13)
Symmetry codes: (i) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Figure 2
Partial packing diagram in the structure of the title compound viewed along [001]. The chains running along [100] as defined by the hydrogen-bonded hydrogen oxalate anions and the (ferrocenylmethyl)dimethylammonium cations linked by a bifurcated hydrogen bond are shown. Hydrogen bonds are shown as black lines.

4. Database survey

A search in the Cambridge Structural database (Version 5.36 with three updates, Groom & Allen, 2014 ) returned only eight entries for seven independent crystal structures containing the (ferrocenylmethyl)dimethylammonium cation. These include simple salts with Cl⁻ (Winter & Wolmershäuser, 1998) and its hydrated form (Guo et al., 2006a), Br⁻ (Wang, 2010), NO₃⁻ (Guo et al., 2006b), sulfate pentahydrate (Guo, 2006), tetrachloridozincate monohydrate (Gibbons & Trotter, 1971 ) and a benzene solvate with dodecaborane (Yongmao et al., 1983 ). The investigation of hydrogen-bonded hydrogen oxalate chains returned 119 unique structures of which 32 are characterized by a bifurcated hydrogen bond with an ammonium counter-cation.

5. Synthesis and crystallization

Crystals of the title compound were obtained by slow evaporation of an aqueous solution in which (ferrocenylmethyl)dimethylamine was mixed with oxalic acid in a 1:2 ratio.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All hydrogen atoms were located in difference Fourier maps and were freely refined.

Table 2
Experimental details

Crystal data
Chemical formula	[Fe(C₅H₅)(C₈H₁₃N)](C₂HO₄)
M_r	333.16
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	100
a, b, c (Å)	11.2225 (3), 14.8991 (4), 17.2727 (5)
V (Å³)	2888.08 (14)
Z	8
Radiation type	Ga Kα, λ = 1.34139 Å
μ (mm⁻¹)	5.72
Crystal size (mm)	0.15 × 0.13 × 0.09

Data collection
Diffractometer	Bruker Venture Metaljet
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.585, 0.752
No. of measured, independent and observed [I > 2σ(I)] reflections	56674, 3323, 3150
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.062, 1.03
No. of reflections	3323
No. of parameters	266
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.19
Computer programs: APEX2 and SAINT (Bruker, 2014 ), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1412152

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S205698901501333X/wm5182sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901501333X/wm5182Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); 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); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

(Ferrocenylmethyl)dimethylammonium hydrogen oxalate top

Crystal data top

[Fe(C₅H₅)(C₈H₁₃N)](C₂HO₄)	D_x = 1.532 Mg m⁻³
M_r = 333.16	Ga Kα radiation, λ = 1.34139 Å
Orthorhombic, Pbca	Cell parameters from 9948 reflections
a = 11.2225 (3) Å	θ = 4.8–60.7°
b = 14.8991 (4) Å	µ = 5.72 mm⁻¹
c = 17.2727 (5) Å	T = 100 K
V = 2888.08 (14) Å³	Block, clear light orange
Z = 8	0.15 × 0.13 × 0.09 mm
F(000) = 1392

Data collection top

Bruker Venture Metaljet diffractometer	3323 independent reflections
Radiation source: Metal Jet, Gallium Liquid Metal Jet Source	3150 reflections with I > 2σ(I)
Helios MX Mirror Optics monochromator	R_int = 0.034
Detector resolution: 10.24 pixels mm^-1	θ_max = 60.7°, θ_min = 4.5°
ω and φ scans	h = −14→14
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −17→19
T_min = 0.585, T_max = 0.752	l = −22→22
56674 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.022	All H-atom parameters refined
wR(F²) = 0.062	w = 1/[σ²(F_o²) + (0.0388P)² + 0.8916P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.002
3323 reflections	Δρ_max = 0.45 e Å⁻³
266 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints

Special details top

Experimental. X-ray crystallographic data for I were collected from a single-crystal sample, which was mounted on a loop fiber. Data were collected using a Bruker Venture diffractometer equipped with a Photon 100 CMOS Detector, a Helios MX optics and a Kappa goniometer. The crystal-to-detector distance was 4.0 cm, and the data collection was carried out in 1024 x 1024 pixel mode.

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.

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

	x	y	z	U_iso*/U_eq
Fe1	0.34931 (2)	0.64806 (2)	0.49469 (2)	0.01187 (7)
N1	0.11135 (8)	0.53481 (6)	0.31389 (5)	0.01286 (17)
C1	0.22887 (9)	0.57630 (6)	0.43156 (6)	0.01299 (19)
C2	0.17883 (11)	0.60032 (8)	0.50499 (6)	0.0150 (2)
C3	0.25259 (10)	0.56311 (7)	0.56398 (6)	0.0164 (2)
C4	0.34734 (9)	0.51541 (7)	0.52776 (7)	0.0161 (2)
C5	0.33275 (9)	0.52304 (7)	0.44578 (6)	0.0143 (2)
C6	0.35605 (10)	0.77834 (8)	0.45550 (7)	0.0199 (2)
C7	0.35680 (10)	0.77649 (8)	0.53827 (7)	0.0199 (2)
C8	0.45806 (10)	0.72650 (7)	0.56226 (6)	0.0193 (2)
C9	0.52010 (11)	0.69741 (8)	0.49491 (6)	0.0193 (2)
C10	0.45688 (11)	0.72947 (7)	0.42883 (6)	0.0200 (2)
C11	0.18587 (9)	0.60523 (7)	0.35384 (6)	0.0148 (2)
C12	0.07459 (11)	0.56695 (8)	0.23563 (7)	0.0209 (2)
C13	0.00554 (10)	0.50895 (8)	0.36082 (7)	0.0218 (2)
O1	0.30103 (6)	0.41777 (5)	0.27870 (5)	0.01774 (16)
O2	0.38177 (7)	0.28665 (5)	0.24336 (5)	0.01896 (17)
O3	0.15744 (6)	0.21661 (5)	0.23000 (5)	0.01636 (16)
O4	0.08414 (7)	0.35313 (5)	0.25702 (5)	0.01652 (16)
C14	0.29562 (9)	0.33826 (7)	0.25759 (6)	0.01189 (19)
C15	0.16996 (9)	0.29528 (7)	0.24647 (6)	0.01225 (19)
H11A	0.1366 (12)	0.6592 (9)	0.3575 (8)	0.015 (3)*
H5	0.3823 (13)	0.4963 (9)	0.4076 (8)	0.019 (3)*
H9	0.5900 (18)	0.6637 (12)	0.4949 (8)	0.029 (4)*
H4	0.4109 (12)	0.4842 (9)	0.5532 (8)	0.017 (3)*
H6	0.2957 (14)	0.8082 (10)	0.4249 (9)	0.025 (4)*
H1	0.1581 (12)	0.4881 (10)	0.3079 (9)	0.024 (4)*
H2	0.1122 (18)	0.6365 (12)	0.5139 (9)	0.030 (4)*
H11B	0.2507 (12)	0.6154 (9)	0.3202 (8)	0.017 (3)*
H8	0.4786 (14)	0.7118 (10)	0.6155 (9)	0.029 (4)*
H12A	0.0229 (15)	0.6170 (11)	0.2419 (9)	0.032 (4)*
H3	0.2436 (14)	0.5700 (9)	0.6199 (9)	0.027 (4)*
H13A	−0.0415 (15)	0.4691 (11)	0.3319 (9)	0.034 (4)*
H10	0.4764 (15)	0.7189 (10)	0.3752 (9)	0.032 (4)*
H13B	0.0345 (15)	0.4801 (11)	0.4091 (10)	0.033 (4)*
H7	0.2965 (14)	0.8042 (10)	0.5702 (9)	0.028 (4)*
H13C	−0.0372 (14)	0.5622 (10)	0.3732 (9)	0.029 (4)*
H12B	0.1486 (14)	0.5830 (11)	0.2080 (10)	0.031 (4)*
H12C	0.0350 (13)	0.5191 (10)	0.2088 (8)	0.021 (3)*
H4A	0.007 (2)	0.3250 (12)	0.2542 (11)	0.049 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.01085 (10)	0.01291 (10)	0.01184 (10)	−0.00209 (5)	0.00031 (5)	−0.00109 (5)
N1	0.0108 (4)	0.0125 (4)	0.0152 (4)	−0.0001 (3)	−0.0009 (3)	−0.0013 (3)
C1	0.0113 (4)	0.0122 (4)	0.0155 (5)	−0.0030 (4)	0.0000 (4)	−0.0007 (4)
C2	0.0121 (5)	0.0148 (5)	0.0182 (5)	−0.0015 (4)	0.0028 (4)	−0.0012 (4)
C3	0.0174 (5)	0.0168 (5)	0.0150 (5)	−0.0041 (4)	0.0022 (4)	0.0004 (4)
C4	0.0156 (5)	0.0150 (5)	0.0175 (5)	−0.0010 (4)	−0.0016 (4)	0.0016 (4)
C5	0.0122 (4)	0.0145 (5)	0.0160 (5)	−0.0008 (4)	0.0006 (4)	−0.0025 (4)
C6	0.0229 (6)	0.0147 (5)	0.0220 (6)	−0.0039 (4)	−0.0035 (4)	0.0015 (4)
C7	0.0211 (5)	0.0164 (5)	0.0222 (6)	−0.0040 (4)	0.0007 (4)	−0.0064 (4)
C8	0.0200 (5)	0.0206 (5)	0.0173 (5)	−0.0078 (4)	−0.0029 (4)	−0.0012 (4)
C9	0.0131 (5)	0.0184 (5)	0.0264 (6)	−0.0052 (4)	0.0008 (4)	−0.0013 (4)
C10	0.0238 (6)	0.0191 (5)	0.0170 (5)	−0.0093 (4)	0.0039 (4)	−0.0012 (4)
C11	0.0151 (5)	0.0127 (5)	0.0167 (5)	−0.0034 (4)	−0.0027 (4)	0.0002 (4)
C12	0.0258 (6)	0.0178 (5)	0.0189 (5)	0.0016 (4)	−0.0083 (5)	0.0000 (4)
C13	0.0142 (5)	0.0258 (6)	0.0254 (6)	−0.0067 (5)	0.0060 (4)	−0.0091 (5)
O1	0.0121 (3)	0.0154 (3)	0.0257 (4)	−0.0010 (3)	0.0006 (3)	−0.0054 (3)
O2	0.0099 (3)	0.0153 (4)	0.0317 (4)	0.0007 (3)	0.0018 (3)	−0.0011 (3)
O3	0.0143 (4)	0.0129 (3)	0.0219 (4)	−0.0006 (3)	−0.0025 (3)	−0.0002 (3)
O4	0.0088 (3)	0.0149 (4)	0.0258 (4)	0.0005 (3)	−0.0001 (3)	−0.0020 (3)
C14	0.0099 (4)	0.0146 (4)	0.0112 (4)	−0.0006 (4)	−0.0001 (3)	0.0024 (4)
C15	0.0106 (4)	0.0142 (4)	0.0120 (4)	−0.0001 (4)	−0.0008 (3)	0.0022 (4)

Geometric parameters (Å, º) top

Fe1—C1	2.0394 (10)	C6—C7	1.4298 (19)
Fe1—C2	2.0490 (12)	C6—C10	1.4223 (17)
Fe1—C3	2.0524 (10)	C6—H6	0.967 (16)
Fe1—C4	2.0574 (11)	C7—C8	1.4206 (17)
Fe1—C5	2.0538 (11)	C7—H7	0.965 (16)
Fe1—C6	2.0570 (12)	C8—C9	1.4233 (16)
Fe1—C7	2.0578 (12)	C8—H8	0.974 (16)
Fe1—C8	2.0536 (11)	C9—C10	1.4263 (16)
Fe1—C9	2.0528 (12)	C9—H9	0.93 (2)
Fe1—C10	2.0549 (11)	C10—H10	0.965 (16)
N1—C11	1.5087 (12)	C11—H11A	0.978 (13)
N1—C12	1.4923 (13)	C11—H11B	0.943 (14)
N1—C13	1.4885 (13)	C12—H12A	0.951 (17)
N1—H1	0.878 (15)	C12—H12B	0.987 (17)
C1—C2	1.4324 (14)	C12—H12C	0.959 (15)
C1—C5	1.4316 (14)	C13—H13A	0.939 (17)
C1—C11	1.4902 (14)	C13—H13B	0.992 (17)
C2—C3	1.4251 (15)	C13—H13C	0.951 (15)
C2—H2	0.935 (19)	O1—C14	1.2410 (12)
C3—C4	1.4237 (15)	O2—C14	1.2595 (13)
C3—H3	0.976 (15)	O3—C15	1.2144 (14)
C4—C5	1.4299 (15)	O4—C15	1.3052 (13)
C4—H4	0.958 (14)	O4—H4A	0.96 (2)
C5—H5	0.950 (15)	C14—C15	1.5607 (14)

C1—Fe1—C2	41.02 (4)	C4—C3—H3	124.4 (9)
C1—Fe1—C3	68.77 (4)	Fe1—C4—H4	125.8 (8)
C1—Fe1—C4	68.76 (4)	C3—C4—Fe1	69.54 (6)
C1—Fe1—C5	40.94 (4)	C3—C4—C5	108.05 (9)
C1—Fe1—C6	110.06 (4)	C3—C4—H4	126.7 (8)
C1—Fe1—C7	135.24 (4)	C5—C4—Fe1	69.51 (6)
C1—Fe1—C8	174.93 (4)	C5—C4—H4	125.3 (8)
C1—Fe1—C9	143.86 (4)	Fe1—C5—H5	127.8 (8)
C1—Fe1—C10	113.75 (4)	C1—C5—Fe1	68.99 (6)
C2—Fe1—C3	40.66 (4)	C1—C5—H5	126.2 (9)
C2—Fe1—C4	68.43 (4)	C4—C5—Fe1	69.78 (6)
C2—Fe1—C5	68.67 (4)	C4—C5—C1	107.89 (9)
C2—Fe1—C6	112.98 (5)	C4—C5—H5	125.9 (9)
C2—Fe1—C7	109.22 (4)	Fe1—C6—H6	126.0 (9)
C2—Fe1—C8	134.68 (4)	C7—C6—Fe1	69.70 (6)
C2—Fe1—C9	174.88 (4)	C7—C6—H6	124.0 (9)
C2—Fe1—C10	143.28 (5)	C10—C6—Fe1	69.68 (6)
C3—Fe1—C4	40.54 (4)	C10—C6—C7	108.02 (10)
C3—Fe1—C5	68.45 (4)	C10—C6—H6	128.0 (9)
C3—Fe1—C6	142.49 (5)	Fe1—C7—H7	125.3 (9)
C3—Fe1—C7	112.44 (5)	C6—C7—Fe1	69.64 (6)
C3—Fe1—C8	109.50 (4)	C6—C7—H7	124.0 (9)
C3—Fe1—C9	135.53 (5)	C8—C7—Fe1	69.63 (6)
C3—Fe1—C10	175.95 (5)	C8—C7—C6	107.85 (10)
C4—Fe1—C7	142.38 (5)	C8—C7—H7	128.2 (9)
C5—Fe1—C4	40.71 (4)	Fe1—C8—H8	123.4 (9)
C5—Fe1—C6	136.37 (5)	C7—C8—Fe1	69.95 (6)
C5—Fe1—C7	175.92 (5)	C7—C8—C9	108.21 (10)
C5—Fe1—C10	111.15 (4)	C7—C8—H8	125.7 (9)
C6—Fe1—C4	176.56 (5)	C9—C8—Fe1	69.69 (6)
C6—Fe1—C7	40.67 (5)	C9—C8—H8	126.0 (9)
C8—Fe1—C4	113.28 (5)	Fe1—C9—H9	126.3 (11)
C8—Fe1—C5	143.48 (5)	C8—C9—Fe1	69.75 (6)
C8—Fe1—C6	68.18 (5)	C8—C9—C10	107.99 (11)
C8—Fe1—C7	40.43 (5)	C8—C9—H9	125.2 (9)
C8—Fe1—C10	68.26 (5)	C10—C9—Fe1	69.76 (6)
C9—Fe1—C4	110.71 (5)	C10—C9—H9	126.8 (9)
C9—Fe1—C5	114.21 (4)	Fe1—C10—H10	124.6 (9)
C9—Fe1—C6	68.18 (5)	C6—C10—Fe1	69.84 (6)
C9—Fe1—C7	68.17 (5)	C6—C10—C9	107.94 (10)
C9—Fe1—C8	40.56 (4)	C6—C10—H10	125.1 (10)
C9—Fe1—C10	40.64 (5)	C9—C10—Fe1	69.60 (6)
C10—Fe1—C4	136.64 (5)	C9—C10—H10	126.9 (10)
C10—Fe1—C6	40.47 (5)	N1—C11—H11A	106.7 (8)
C10—Fe1—C7	68.26 (5)	N1—C11—H11B	104.9 (8)
C11—N1—H1	105.9 (9)	C1—C11—N1	112.98 (8)
C12—N1—C11	110.15 (8)	C1—C11—H11A	111.3 (9)
C12—N1—H1	108.2 (10)	C1—C11—H11B	110.6 (8)
C13—N1—C11	111.91 (8)	H11A—C11—H11B	110.1 (11)
C13—N1—C12	110.84 (9)	N1—C12—H12A	108.5 (9)
C13—N1—H1	109.6 (10)	N1—C12—H12B	106.5 (10)
C2—C1—Fe1	69.85 (6)	N1—C12—H12C	109.1 (8)
C2—C1—C11	126.76 (9)	H12A—C12—H12B	112.3 (14)
C5—C1—Fe1	70.07 (6)	H12A—C12—H12C	110.8 (13)
C5—C1—C2	107.80 (9)	H12B—C12—H12C	109.7 (13)
C5—C1—C11	125.35 (9)	N1—C13—H13A	108.8 (10)
C11—C1—Fe1	123.00 (7)	N1—C13—H13B	107.9 (10)
Fe1—C2—H2	124.2 (11)	N1—C13—H13C	108.0 (9)
C1—C2—Fe1	69.13 (6)	H13A—C13—H13B	111.0 (13)
C1—C2—H2	127.2 (10)	H13A—C13—H13C	111.3 (13)
C3—C2—Fe1	69.80 (6)	H13B—C13—H13C	109.7 (12)
C3—C2—C1	107.95 (10)	C15—O4—H4A	111.6 (11)
C3—C2—H2	124.8 (10)	O1—C14—O2	127.06 (10)
Fe1—C3—H3	124.5 (9)	O1—C14—C15	118.16 (9)
C2—C3—Fe1	69.54 (6)	O2—C14—C15	114.78 (8)
C2—C3—H3	127.3 (9)	O3—C15—O4	125.78 (9)
C4—C3—Fe1	69.92 (6)	O3—C15—C14	121.97 (9)
C4—C3—C2	108.29 (10)	O4—C15—C14	112.25 (8)

Fe1—C1—C2—C3	−59.20 (8)	C5—C1—C11—N1	83.77 (12)
Fe1—C1—C5—C4	59.14 (7)	C6—C7—C8—Fe1	−59.36 (7)
Fe1—C1—C11—N1	171.61 (7)	C6—C7—C8—C9	0.04 (12)
Fe1—C2—C3—C4	−59.38 (7)	C7—C6—C10—Fe1	59.37 (7)
Fe1—C3—C4—C5	−59.03 (7)	C7—C6—C10—C9	−0.03 (12)
Fe1—C4—C5—C1	−58.64 (7)	C7—C8—C9—Fe1	−59.56 (8)
Fe1—C6—C7—C8	59.36 (7)	C7—C8—C9—C10	−0.06 (13)
Fe1—C6—C10—C9	−59.40 (8)	C8—C9—C10—Fe1	−59.50 (8)
Fe1—C7—C8—C9	59.40 (8)	C8—C9—C10—C6	0.05 (13)
Fe1—C8—C9—C10	59.50 (8)	C10—C6—C7—Fe1	−59.36 (7)
Fe1—C9—C10—C6	59.55 (8)	C10—C6—C7—C8	0.00 (11)
C1—C2—C3—Fe1	58.79 (8)	C11—C1—C2—Fe1	−116.75 (10)
C1—C2—C3—C4	−0.59 (13)	C11—C1—C2—C3	−175.95 (9)
C2—C1—C5—Fe1	−59.91 (7)	C11—C1—C5—Fe1	116.95 (10)
C2—C1—C5—C4	−0.78 (11)	C11—C1—C5—C4	176.08 (9)
C2—C1—C11—N1	−99.97 (12)	C12—N1—C11—C1	−178.23 (9)
C2—C3—C4—Fe1	59.15 (8)	C13—N1—C11—C1	57.99 (12)
C2—C3—C4—C5	0.11 (12)	O1—C14—C15—O3	−175.95 (10)
C3—C4—C5—Fe1	59.05 (7)	O1—C14—C15—O4	3.94 (13)
C3—C4—C5—C1	0.41 (11)	O2—C14—C15—O3	4.30 (14)
C5—C1—C2—Fe1	60.05 (7)	O2—C14—C15—O4	−175.81 (9)
C5—C1—C2—C3	0.85 (12)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the Cp ligand C6–C10.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.878 (15)	1.981 (15)	2.8180 (11)	158.9 (14)
N1—H1···O4	0.878 (15)	2.346 (15)	2.8958 (11)	120.8 (11)
C11—H11B···O3ⁱ	0.943 (14)	2.401 (14)	3.2282 (13)	146.3 (11)
C12—H12A···O3ⁱⁱ	0.951 (17)	2.556 (17)	3.4792 (14)	163.8 (13)
C13—H13A···O4	0.939 (17)	2.578 (16)	3.0631 (14)	112.5 (12)
O4—H4A···O2ⁱⁱⁱ	0.96 (2)	1.52 (2)	2.4776 (11)	174.1 (18)
C2—H2···Cg2^iv	0.935 (19)	2.743 (19)	3.6564 (13)	165.8 (13)

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

Acknowledgements

The authors acknowledge the Cheikh Anta Diop University of Dakar (Sénégal), the Canada Foundation for Innovation and Université de Montréal for financial support.

References

Anda, C., Llobet, A., Martell, A. E., Reibenspies, J., Berni, E. & Solans, X. (2004). Inorg. Chem. 43, 2793–2802. Web of Science CSD CrossRef PubMed CAS Google Scholar
Braga, D., Chelazzi, L., Ciabatti, L. & Grepioni, F. (2013). New J. Chem. 37, 97–104. Web of Science CSD CrossRef CAS Google Scholar
Braga, D., Eckert, M., Fraccastoro, M., Maini, L., Grepioni, F., Caneschi, A. & Sessoli, R. (2002). New J. Chem. 26, 1280–1286. Web of Science CSD CrossRef CAS Google Scholar
Bruker (2014). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Diallo, W., Gueye, N., Crochet, A., Plasseraud, L. & Cattey, H. (2015). Acta Cryst. E71, 473–475. CSD CrossRef IUCr Journals Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gibbons, C. S. & Trotter, J. (1971). J. Chem. Soc. A, pp. 2659–2662. CSD CrossRef Web of Science Google Scholar
Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671. Web of Science CSD CrossRef CAS Google Scholar
Guo, H.-X. (2006). Acta Cryst. C62, m504–m506. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Guo, H.-X., Yang, L.-M. & Zhang, S.-D. (2006a). Acta Cryst. E62, m1338–m1339. Web of Science CSD CrossRef IUCr Journals Google Scholar
Guo, H.-X., Zhou, X.-J., Lin, Z.-X. & Liu, J.-M. (2006b). Acta Cryst. E62, m1770–m1772. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hathwar, V. R., Pal, R. & Guru Row, T. N. (2010). Cryst. Growth Des. 10, 3306–3310. Web of Science CSD CrossRef CAS Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Matulková, I., Němec, I., Teubner, K., Němec, P. & Mička, Z. (2008). J. Mol. Struct. 873, 46–60. Google Scholar
Olenik, B., Smolka, T., Boese, R. & Sustmann, R. (2003). Cryst. Growth Des. 3, 183–188. Web of Science CSD CrossRef CAS Google Scholar
Said, F. F., Ong, T.-G., Bazinet, P., Yap, G. P. A. & Richeson, D. S. (2006). Cryst. Growth Des. 6, 1848–1857. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Vaidhyanathan, R., Natarajan, S. & Rao, C. N. R. (2002). J. Mol. Struct. 608, 123–133. Web of Science CSD CrossRef CAS Google Scholar
Wang, B. (2010). Acta Cryst. E66, m686. Web of Science CSD CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Winter, R. F. & Wolmershäuser, G. (1998). J. Organomet. Chem. 570, 201–218. Web of Science CSD CrossRef CAS Google Scholar
Yongmao, Z., Zhaoping, C., Zhiwei, C., Kezhen, P., Guomin, Z., Zhaogui, Z. & Huaxue, Z. (1983). Chin. J. Struct. Chem. 2, 201–204. Google Scholar