research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

Synthesis and crystal structure of 1,1′-bis­­{[4-(pyridin-2-yl)-1,2,3-triazol-1-yl]meth­yl}ferrocene, and its complexation with CuI

CROSSMARK_Color_square_no_text.svg

aDepartment of Chemistry & Physical Sciences, Nicholls State University, Thibodaux, Louisiana 70301, USA, and bDepartment of Chemistry, Louisiana State University, Baton Rouge, Louisiana, 70803, USA
*Correspondence e-mail: uttam.pokharel@nicholls.edu

Edited by S. Parkin, University of Kentucky, USA (Received 5 August 2020; accepted 28 August 2020; online 4 September 2020)

The title compound, [Fe(C13H11N4)2], was synthesized starting from 1,1′-ferro­cene­di­carb­oxy­lic acid in a three-step reaction sequence. The di­carb­oxy­lic acid was reduced to 1,1′-ferrocenedi­methanol using LiAlH4 and subsequently converted to 1,1′-bis­(azido­meth­yl)ferrocene in the presence of NaN3. The diazide was treated with 2-ethynyl­pyridine under `click' conditions to give the title compound in 75% yield. The FeII center lies on an inversion center in the crystal. The two pyridyl­triazole wings are oriented in an anti conformation and positioned exo from the FeII center. In the solid state, the mol­ecules inter­act by C—H⋯N, C—H⋯π, and ππ inter­actions. The complexation of the ligand with [Cu(CH3CN)4](PF6) gives a tetra­nuclear dimeric complex.

1. Chemical context

Metal–organic supra­molecular chemistry is an emerging area in inorganic chemistry: the structurally challenging functional supra­molecules can be constructed from the self-assembly of multidentate organic ligands and transition-metal ions in relatively few synthetic steps (Cook & Stang, 2015[Cook, T. R. & Stang, P. J. (2015). Chem. Rev. 115, 7001-7045.]). Such supra­molecules are designed by careful selection of the conformational flexibility of the linker groups in multidentate ligands, and the coordination preference of transition-metal ions. We have recently studied the self-assemblies of m-xylylene- or 2,7-naphthalene­bis­(methyl­ene)-bridged tetra­dentate bis­(pyridyl­triazole) ligands with CuII ions to give discrete [2 + 2] metallocycles (Pokharel et al., 2013[Pokharel, U. R., Fronczek, F. R. & Maverick, A. W. (2013). Dalton Trans. 42, 14064-14067.], 2014[Pokharel, U. R., Fronczek, F. R. & Maverick, A. W. (2014). Nat. Commun. 5, 5883.]). In a continuation of our work, we became inter­ested in the design of metalloligands, i.e., metal-containing organic linkers, to produce mixed-metal complexes with different topologies.

[Scheme 1]

Ferrocene, a well-known metallocene, exhibits high thermal stability, reversible electrochemistry, and conformational flexibility, making it an ideal precursor for the development of polymetallic metallo­supra­molecular complexes (Astruc, 2017[Astruc, D. (2017). Eur. J. Inorg. Chem. 2017, 6-29.]). Introduction of the iron(II) center as the structural component of the ligand allows the study of electronic coupling between metal centers in heterometallic metallo­supra­molecular assemblies. Although 1,1′-disubstituted ferrocenes featuring the pyridyl moiety as a donor group have been exploited in metallo­supra­molecular assemblies (Quinodoz et al., 2004[Quinodoz, B., Labat, G., Stoeckli-Evans, H. & von Zelewsky, A. (2004). Inorg. Chem. 43, 7994-8004.]; Buda et al., 1998[Buda, M., Moutet, J.-C., Saint-Aman, E., De Cian, A., Fischer, J. & Ziessel, R. (1998). Inorg. Chem. 37, 4146-4148.]; Ion et al., 2002[Ion, A., Buda, M., Moutet, J.-C., Saint-Aman, E., Royal, G., Gautier-Luneau, I., Bonin, M. & Ziessel, R. (2002). Eur. J. Inorg. Chem. pp. 1357-1366.]; Lindner et al., 2003[Lindner, E., Zong, R., Eichele, K., Weisser, U. & Ströbele, M. (2003). Eur. J. Inorg. Chem. pp. 705-712.]; Sachsinger & Hall, 1997[Sachsinger, N. & Hall, C. D. (1997). J. Organomet. Chem. 531, 61-65.]), the ferrocene-bridged bis­(pyridyl­triazole)-based tetra­dentate ligands are relatively new in coordination chemistry (Findlay et al., 2018[Findlay, J. A., McAdam, C. J., Sutton, J. J., Preston, D., Gordon, K. C. & Crowley, J. D. (2018). Inorg. Chem. 57, 3602-3614.]; Manck et al., 2017[Manck, S., Röger, M., van der Meer, M. & Sarkar, B. (2017). Eur. J. Inorg. Chem. pp. 477-482.]; Romero et al., 2011[Romero, T., Orenes, R. A., Espinosa, A., Tárraga, A. & Molina, P. (2011). Inorg. Chem. 50, 8214-8224.]). Herein, we report the synthesis of the 1,1′-bis­(methyl­ene­pyridyl­triazole) ferrocene ligand starting from 1,1′-ferrocenedi­carb­oxy­lic acid in a three-step sequence and its complexation with CuI ions (Fig. 1[link]).

[Figure 1]
Figure 1
The synthetic scheme showing the formation of the title compound and its complexation with CuI.

1,1′-Ferrocenedi­methanol, 2, was synthesized by reduction of 1,1′-ferrocenedi­carb­oxy­lic acid, 1, in the presence of LiAlH4. The diol was treated with sodium azide in acetic acid following published procedures (Casas-Solvas et al., 2009[Casas-Solvas, J. M., Ortiz-Salmerón, E., Giménez-Martínez, J. J., García-Fuentes, L., Capitán-Vallvey, L. F., Santoyo-González, F. & Vargas-Berenguel, A. (2009). Chem. Eur. J. 15, 710-725.]) to give 1,1′-bis­(azido­meth­yl)ferrocene, 3 as a viscous liquid. The compound showed a strong IR absorption at 2093 cm−1, indicating the formation of the desired diazide (Casas-Solvas et al., 2009[Casas-Solvas, J. M., Ortiz-Salmerón, E., Giménez-Martínez, J. J., García-Fuentes, L., Capitán-Vallvey, L. F., Santoyo-González, F. & Vargas-Berenguel, A. (2009). Chem. Eur. J. 15, 710-725.]). The diazide was treated with 2-ethynyl­pyridine under `click' conditions (Pokharel et al., 2013[Pokharel, U. R., Fronczek, F. R. & Maverick, A. W. (2013). Dalton Trans. 42, 14064-14067.]) to give the title compound in 75% yield. This new tetra­dentate ligand based on ferrocene is obtained as an air-stable light-brown crystalline powder.

2. Structural commentary

The asymmetric unit of the title compound contains one half of the mol­ecule since the FeII center is on an inversion center, as shown in Fig. 2[link]. The symmetry in the mol­ecule was also apparent in the NMR data where only one set of signals was found for the protons and carbons of the cyclo­penta­dienyl (Cp) rings, methyl­ene groups, and the pyridyl­triazole units. The Fe—C(Cp) bond lengths are in the range 2.0349 (12)–2.0471 (13) Å [average 2.0498 (13) Å] with the Fe⋯Cp-centroid distance being 1.6550 (6) Å. The Fe—C bond to the substituted carbon [Fe—C1 2.0349 (12)] is shorter than the remaining Fe—C bond lengths, as is seen in similar 1,1′-disubstituted ferrocene derivatives (Glidewell et al., 1994[Glidewell, C., Zakaria, C. M., Ferguson, G. & Gallagher, J. F. (1994). Acta Cryst. C50, 233-238.]). The conformation of the ferrocenyl unit is exactly staggered by inversion symmetry, and the centrosymmetry also makes the Cp—Fe—Cp linkage linear and the Cp rings parallel. The Csp3 atom, C6, is displaced towards the FeII center by 0.044 (3) Å from the least-squares plane of the Cp ring. The CCp—Csp3 and CCp—N bond lengths involving C6 are 1.4910 (19) and 1.4700 (18) Å, respectively. The pyridyl­triazole moiety is oriented exo from the FeII center, with the least-squares planes of the Cp and triazole rings forming a dihedral angle of 65.68 (5)°. The nitro­gen donor atoms of the pyridyl­triazole units adopt an anti conformation, as is often observed in this type of chelating ligand (Crowley & Bandeen, 2010[Crowley, J. D. & Bandeen, P. H. (2010). Dalton Trans. 39, 612-623.]). The pyridyl and triazole units deviate slightly from coplanarity, with the N3—C7—C9—N4 torsion angle being 167.64 (13)°.

[Figure 2]
Figure 2
Mol­ecular structure of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Unlabeled atoms are generated by the symmetry operation 1 − x, 1 − y, 1 − z.

3. Supra­molecular features

The crystal structure of the title compound is consolidated by inter­molecular C—H⋯N (Table 1[link]), C—H⋯π, and ππ inter­actions (Figs. 3[link] and 4[link]). The triazole carbon C8 forms a C—H⋯N inter­action, with a C⋯N distance of 3.601 (2) Å to triazole N3 (at x − 1, y, z) and the Cp carbon atom C5 forms a C—H⋯N inter­action with a C⋯N distance of 3.4240 (19) Å to triazole N2 (at x − 1, y, z). These two contacts form a ring with graph-set motif R22(9) (Etter et al., 1990[Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256-262.]). In addition, the triazole carbon C3 forms a C—H⋯N inter­action with a C⋯N distance of 3.4625 (19) Å to pyridyl nitro­gen N4 (at x, y + 1, z). Thus, the C—H⋯N contacts form a two-dimensional network normal to [001]. The pyridyl­triazole moieties stack in an anti-parallel fashion about inversion centers. The pyridyl moiety of one mol­ecule has a ππ interaction with the triazole moiety of another mol­ecule with a dihedral angle of 11.27 (10)° and centroid–centroid distance of 3.790 Å (symmetry operation 2 − x, −y, −z). In addition, there are also C—H⋯π inter­actions between the hydrogen atom of the pyridyl moiety with the cyclo­penta­dienyl ring [H12⋯Cp(centroid) = 2.692 Å; symmetry operation 2 − x, −y, −z;]. These two inter­actions thus form centrosymmetric dimers, illustrated in Fig. 4[link].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C8—H8⋯N3i 0.95 2.68 3.601 (2) 163
C5—H5⋯N2i 0.95 2.51 3.4240 (19) 160
C3—H3⋯N4ii 0.95 2.73 3.4625 (19) 135
C12—H12⋯Cpcentroidiii 0.95 2.69 3.4861 (15) 142
Symmetry codes: (i) x-1, y, z; (ii) x, y+1, z; (iii) -x+2, -y, -z.
[Figure 3]
Figure 3
The C—H⋯N network, with displacement ellipsoids at the 50% probability level.
[Figure 4]
Figure 4
The C—H⋯π and ππ inter­actions, viewed along the a axis. Displacement ellipsoids are shown at the 50% probability level.

4. Database survey

A search of the Cambridge Structural Database (Version 5.41, update of March 2020; Groom et al., 2016[Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171-179.]) for bis­(pyridyl­triazole) with a ferrocene linker gave no results. However, the structure of ferrocene attached to one methyl­ene­pyridyl­triazole, BULQIJ (Crowley et al., 2010[Crowley, J. D., Bandeen, P. H. & Hanton, L. R. (2010). Polyhedron, 29, 70-83.]) has been reported. The two pyridyl­triazole units connected with organic linkers, namely m-xylylene, VAJVIN (Najar et al., 2010[Najar, A. M., Tidmarsh, I. S. & Ward, M. D. (2010). CrystEngComm, 12, 3642-3650.]), and p-xylylene as chloro­form solvate, FUJJOK (Crowley & Bandeen, 2010[Crowley, J. D. & Bandeen, P. H. (2010). Dalton Trans. 39, 612-623.]) have also been reported.

5. Complexation with CuI

Complexation of the ligand 4 with CuI was performed under a nitro­gen atmosphere. When [Cu(CH3CN)4]PF6 was added to a suspension of the ligand in DMF in a 1:1 ratio, the mixture was completely soluble, indicating the formation of a complex. To avoid oxidation of the complex, the resultant solution was diffused with diethyl ether vapor under nitro­gen for 3 d. Under these conditions, a bright-yellow microcrystalline solid was formed. At room temperature, the 1H NMR spectrum of the complex showed a simple pattern containing the same set of signals for the ligand, indicative of the presence of one single species in solution. Compared to the spectrum of the free ligand, the proton signals of the complex, especially for the pyridyl­triazole coordination pocket, are shifted downfield (Fig. 5[link]). Similar retaining of the number of signals and the coupling patterns in the 1H NMR spectrum was observed in xylylene-linked bis­(pyridyl­triazole) ligands and their AgI complexes (Crowley & Bandeen, 2010[Crowley, J. D. & Bandeen, P. H. (2010). Dalton Trans. 39, 612-623.]). To further explore the nature of the complex in solution, we examined a MeOH/DMSO solution of the complex by positive-ion electrospray mass spectrometry (ESMS). The ESMS spectrum of the complex contains a peak at 1273.0915 corresponding to [Cu2L2](PF6)+ with a similar isotopic pattern as the theoretical simulation (Fig. 6[link]), indicating the formation of the [2 + 2] complex. Disappointingly, despite obtaining crystalline material, our attempts to obtain crystals suitable for single-crystal X-ray analysis failed.

[Figure 5]
Figure 5
1H NMR spectra of ligand 4 (bottom) and its CuI complex, 5 (top). Both spectra are clipped on the same chemical shift ranges.
[Figure 6]
Figure 6
A portion of the high-resolution ESI–MS spectrum of complex 5

6. Synthesis and crystallization

Synthesis of 1,1′-bis­(hy­droxy­meth­yl)ferrocene, 2. To a stirred solution of 1,1′-ferrocenedi­carb­oxy­lic acid (4.00 g, 14.59 mmol) in dry THF (400.0 mL), 1.0 M LiAlH4 (58.38 mL, 58.38 mmol) was added dropwise at room temperature under N2. The reaction vigorously produced hydrogen gas. The reaction mixture was refluxed for 2 h, by which time the starting compound was consumed, as evidenced by TLC. The reaction was again cooled to room temperature, and ethyl acetate (5 mL) and water (10 mL) were added in sequence with constant stirring. The product was extracted with ethyl acetate (4 × 150 mL). The combined organic layer was dried with anhydrous MgSO4 and volatiles removed in vacuo to give 2 (3.46 g, 96%) as a brown solid. The analytically pure product was obtained by recrystallization from toluene upon cooling. 1H NMR (acetone-d6, 400 MHz, ppm): δ 4.07 (t, 4H, 3J = 1.6 Hz, Cp), 4.13 (t, 4H, 3J = 1.6 Hz, Cp), 4.19 (t, 2H, 3J = 6.0 Hz, OH), 4.30 (d, 4H, 3J = 6.0 Hz, CH2). 13C NMR (acetone-d6, 100 MHz, ppm): δ 67.4, 67.7, 69.6, 89.7.

Synthesis of 1,1′-bis­(azido­meth­yl)ferrocene, 3. Caution! Organic azides with low C/N ratio are potentially dangerous. However, we did not encounter any problem during the synthesis of diazide and its subsequent derivatization. To a stirred solution of 1,1′-hy­droxy­methyl­ferrocene (1.50 g, 6.09 mmol) in glacial acetic acid (7.5 mL), sodium azide (2.23 g, 36.5 mmol) was added. The reaction was stirred for 3 h at 323 K under nitro­gen. The reaction mixture was neutralized with a saturated solution of sodium bicarbonate. The product was extracted with chloro­form (2 × 50 mL). The organic phase was dried with anhydrous MgSO4 and the volatiles removed in vacuo to give 3 (1.50 g, 83%) as a viscous liquid. IR (ATR, cm−1): 2092 (s), 1733 (w), 1240 (m). 1H NMR (CDCl3, 400 MHz, ppm): δ 4.10 (s, 4H, CH2), 4.19 (t, 3J = 2.0 Hz, Cp), 4.22 (t, 3J = 2.0 Hz, Cp).

Synthesis of 1,1′-bis­(pyridyl­triazolylmeth­yl)ferrocene, 4. To a stirred solution of 1,1′-bis­(azido­meth­yl)ferrocene (1.00 g, 3.34 mmol) in a mixture of DMF and water (4:1) (20 mL), Na2CO3 (354 mg, 3.34 mmol), CuSO4·5H2O (333 mg, 1.33 mmol), ascorbic acid (468 mg, 2.66 mmol), and 2-ethynyl­pyridine (862 mg, 8.36 mmol) were added in sequence. The reaction mixture was stirred for 20 h at room temperature, and then poured into an NH3/EDTA solution (2.00 g of Na2H2EDTA·2H2O in 5 mL of 28% aqueous NH3, diluted to 100 mL with H2O) and the mixture extracted with chloro­form (3 x 100 mL). The organic layer was collected, dried over MgSO4, and evaporated to dryness. The crude product was purified by trituration with cold diethyl ether to give 4 (1.26 g, 75%) as a light-brown solid. X-ray quality crystals of the compound were obtained by vapor diffusion of diethyl ether into its solution in chloro­form, m.p.: decomposes above 463 K. 1H NMR (CDCl3, 400 MHz, ppm): δ 4.24 (t, 4H, 3J = 2.0 Hz, Cp), 4.32 (t, 4H, 3J = 2.0 Hz, Cp), 5.33 (s, 4H, CH2),7.21(td, 2H, 3J = 5.2 Hz, 4J = 2.0 Hz, Ar), 7.75 (td, 2H, 3J = 8.0 Hz, 4J = 2.0 Hz, Ar), 8.05 (s, 2H, triazole-H), 8.15 (d, 2H, 3J = 7.6 Hz, Ar), 8.53 (d, 2H, 3J = 4.0 Hz, Ar) 13C NMR (CDCl3, 100 MHz, ppm): δ 49.8, 69.8, 70.2, 81.9, 120.3, 121.5, 122.9, 137.0, 148.4, 149.4, 150.2. HRESI–MS: m/z = 501.1416 [4+H]+ (calculated for C26H23FeN8 501.1442), 523.1238 [4+Na]+ (calculated for C26H23FeN8 523.1261).

Synthesis of CuI complex of 1,1′-bis­(pyridyl­triazolylmeth­yl)ferrocene, 5. To a nitro­gen-purged stirred suspension of 4 (100 mg, 0.20 mmol) in DMF (10 mL), [Cu(CH3CN)4](PF6) (77 mg, 0.20 mmol) was added. The reaction produced a clear yellow solution, which was stirred for 2 h at room temperature. The reaction mixture was diffused with nitro­gen-purged diethyl ether using a cannula for 3 d. The solution was deca­nted and the product was washed with diethyl ether and dried under a slow stream of nitro­gen to give 5 (142 mg, 100%) as a yellow microcrystalline solid. A 1H NMR sample was prepared by dissolving the compound in DMSO-d6 and transferring the solution into an NMR tube under nitro­gen. 1H NMR (DMSO-d6, 400 MHz, ppm): δ 4.21 (br, 8H, Cp), 4.29 (br, 8H, Cp), 5.43 (s, 5.42, 8H, CH2, 7.45 (br, 4H, Ar), 7.90 (s, 4H, triazole-H), 8.04 (br, 4H, Ar), 8.43 (br, 4H, Ar), 9.05 (br, 4H, Ar). HRESI–MS: m/z = 1273.0915 (Cu242](PF6)+ (calculated for C52H44Cu2F6Fe2N16P 1273.0914), 563.0650 [Cu4](PF6)+ (calculated for C26H22CuFeN8 563.0660).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. All H atoms were located in difference maps and then treated as riding in geometrically idealized positions with C—H distances of 0.95 Å (0.99 Å for CH2) and with Uiso(H) =1.2Ueq for the attached C atom.

Table 2
Experimental details

Crystal data
Chemical formula [Fe(C13H11N4)2]
Mr 502.36
Crystal system, space group Triclinic, P[\overline{1}]
Temperature (K) 90
a, b, c (Å) 5.7905 (3), 9.7461 (5), 10.1720 (4)
α, β, γ (°) 82.064 (3), 84.754 (4), 77.739 (4)
V3) 554.44 (5)
Z 1
Radiation type Mo Kα
μ (mm−1) 0.71
Crystal size (mm) 0.12 × 0.09 × 0.08
 
Data collection
Diffractometer Bruker Kappa APEXII DUO CCD
Absorption correction Multi-scan (SADABS; Krause et al., 2015[Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3-10.])
Tmin, Tmax 0.857, 0.945
No. of measured, independent and observed [I > 2σ(I)] reflections 7058, 4199, 3569
Rint 0.020
(sin θ/λ)max−1) 0.769
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.099, 1.06
No. of reflections 4199
No. of parameters 160
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.98, −0.29
Computer programs: APEX3 and SAINT (Bruker, 2016[Bruker (2016). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014/7 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), Mercury (Macrae et al., 2020[Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226-235.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).

1,1'-Bis{[4-(pyridin-2-yl)-1,2,3-triazol-1-yl]methyl}ferrocene top
Crystal data top
[Fe(C13H11N4)2]Z = 1
Mr = 502.36F(000) = 260
Triclinic, P1Dx = 1.505 Mg m3
a = 5.7905 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.7461 (5) ÅCell parameters from 2644 reflections
c = 10.1720 (4) Åθ = 3.1–33.1°
α = 82.064 (3)°µ = 0.71 mm1
β = 84.754 (4)°T = 90 K
γ = 77.739 (4)°Fragment, orange
V = 554.44 (5) Å30.12 × 0.09 × 0.08 mm
Data collection top
Bruker Kappa APEXII DUO CCD
diffractometer
4199 independent reflections
Radiation source: fine-focus sealed tube3569 reflections with I > 2σ(I)
TRIUMPH curved graphite monochromatorRint = 0.020
φ and ω scansθmax = 33.2°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Krause et al., 2015)
h = 88
Tmin = 0.857, Tmax = 0.945k = 1414
7058 measured reflectionsl = 1515
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0526P)2 + 0.140P]
where P = (Fo2 + 2Fc2)/3
4199 reflections(Δ/σ)max < 0.001
160 parametersΔρmax = 0.98 e Å3
0 restraintsΔρmin = 0.29 e Å3
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
xyzUiso*/Ueq
Fe10.50000.50000.50000.00859 (7)
N10.9431 (2)0.11300 (13)0.36213 (12)0.0173 (2)
N21.1757 (2)0.11615 (13)0.34215 (13)0.0203 (2)
N31.2663 (2)0.03069 (13)0.25245 (13)0.0175 (2)
N40.9549 (2)0.19933 (13)0.11559 (13)0.0166 (2)
C10.6904 (2)0.34473 (13)0.39618 (12)0.0123 (2)
C20.7999 (2)0.46543 (16)0.37622 (14)0.0162 (3)
H20.95560.46680.39760.019*
C30.6341 (3)0.58282 (15)0.31869 (14)0.0186 (3)
H30.65950.67650.29520.022*
C40.4251 (3)0.53559 (15)0.30257 (13)0.0169 (3)
H40.28560.59230.26630.020*
C50.4585 (2)0.38965 (14)0.34947 (13)0.0132 (2)
H50.34580.33160.34980.016*
C60.7950 (3)0.19952 (16)0.45781 (15)0.0242 (3)
H6A0.89210.20670.53080.029*
H6B0.66550.15170.49700.029*
C71.0906 (2)0.02744 (13)0.21606 (13)0.0125 (2)
C80.8819 (2)0.02524 (15)0.28631 (14)0.0156 (2)
H80.73000.00430.28200.019*
C91.1331 (2)0.13233 (13)0.12183 (13)0.0119 (2)
C101.3477 (2)0.16117 (14)0.04578 (13)0.0141 (2)
H101.47130.11320.05410.017*
C111.3757 (3)0.26115 (15)0.04177 (14)0.0166 (3)
H111.51780.28110.09650.020*
C121.1936 (3)0.33183 (15)0.04847 (14)0.0185 (3)
H121.20900.40180.10690.022*
C130.9891 (3)0.29783 (16)0.03193 (15)0.0187 (3)
H130.86560.34720.02770.022*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.00934 (12)0.00722 (12)0.00860 (12)0.00031 (8)0.00181 (8)0.00256 (8)
N10.0209 (6)0.0119 (5)0.0147 (5)0.0053 (4)0.0018 (4)0.0026 (4)
N20.0243 (6)0.0143 (5)0.0223 (6)0.0015 (5)0.0000 (5)0.0067 (4)
N30.0180 (6)0.0138 (5)0.0212 (6)0.0032 (4)0.0011 (4)0.0060 (4)
N40.0155 (5)0.0146 (5)0.0198 (5)0.0033 (4)0.0001 (4)0.0029 (4)
C10.0141 (5)0.0101 (5)0.0108 (5)0.0027 (4)0.0007 (4)0.0033 (4)
C20.0120 (6)0.0241 (7)0.0148 (6)0.0060 (5)0.0042 (4)0.0096 (5)
C30.0287 (7)0.0127 (6)0.0140 (6)0.0066 (5)0.0100 (5)0.0036 (5)
C40.0191 (6)0.0175 (6)0.0103 (5)0.0047 (5)0.0009 (5)0.0010 (4)
C50.0130 (5)0.0163 (6)0.0112 (5)0.0033 (4)0.0012 (4)0.0052 (4)
C60.0351 (8)0.0164 (6)0.0128 (6)0.0116 (6)0.0029 (6)0.0020 (5)
C70.0135 (5)0.0094 (5)0.0130 (5)0.0005 (4)0.0005 (4)0.0011 (4)
C80.0152 (6)0.0135 (6)0.0148 (6)0.0026 (5)0.0000 (5)0.0001 (4)
C90.0134 (5)0.0089 (5)0.0120 (5)0.0001 (4)0.0002 (4)0.0005 (4)
C100.0149 (6)0.0127 (6)0.0141 (5)0.0018 (4)0.0011 (4)0.0019 (4)
C110.0175 (6)0.0181 (6)0.0129 (6)0.0003 (5)0.0019 (5)0.0042 (5)
C120.0255 (7)0.0147 (6)0.0154 (6)0.0023 (5)0.0018 (5)0.0047 (5)
C130.0204 (7)0.0166 (6)0.0211 (6)0.0063 (5)0.0026 (5)0.0042 (5)
Geometric parameters (Å, º) top
Fe1—C12.0349 (12)C2—C31.423 (2)
Fe1—C1i2.0349 (12)C2—H20.9500
Fe1—C22.0453 (13)C3—C41.413 (2)
Fe1—C2i2.0453 (13)C3—H30.9500
Fe1—C52.0471 (13)C4—C51.4145 (19)
Fe1—C5i2.0471 (13)C4—H40.9500
Fe1—C42.0602 (13)C5—H50.9500
Fe1—C4i2.0603 (13)C6—H6A0.9900
Fe1—C32.0614 (13)C6—H6B0.9900
Fe1—C3i2.0614 (13)C7—C81.3837 (18)
N1—C81.3466 (19)C7—C91.4646 (18)
N1—N21.3497 (19)C8—H80.9500
N1—C61.4700 (18)C9—C101.3987 (18)
N2—N31.3185 (17)C10—C111.3838 (19)
N3—C71.3656 (18)C10—H100.9500
N4—C131.3412 (19)C11—C121.388 (2)
N4—C91.3435 (18)C11—H110.9500
C1—C51.4248 (19)C12—C131.382 (2)
C1—C21.4334 (19)C12—H120.9500
C1—C61.4910 (19)C13—H130.9500
C1—Fe1—C1i180.0C5—C1—Fe170.03 (7)
C1—Fe1—C241.13 (5)C2—C1—Fe169.83 (7)
C1i—Fe1—C2138.87 (5)C6—C1—Fe1124.11 (9)
C1—Fe1—C2i138.87 (5)C3—C2—C1107.90 (12)
C1i—Fe1—C2i41.13 (5)C3—C2—Fe170.34 (8)
C2—Fe1—C2i180.0C1—C2—Fe169.04 (7)
C1—Fe1—C540.86 (5)C3—C2—H2126.0
C1i—Fe1—C5139.14 (5)C1—C2—H2126.0
C2—Fe1—C568.47 (5)Fe1—C2—H2126.1
C2i—Fe1—C5111.53 (5)C4—C3—C2108.01 (12)
C1—Fe1—C5i139.14 (5)C4—C3—Fe169.90 (8)
C1i—Fe1—C5i40.85 (5)C2—C3—Fe169.12 (8)
C2—Fe1—C5i111.53 (5)C4—C3—H3126.0
C2i—Fe1—C5i68.47 (5)C2—C3—H3126.0
C5—Fe1—C5i180.00 (7)Fe1—C3—H3126.5
C1—Fe1—C468.35 (5)C3—C4—C5108.52 (12)
C1i—Fe1—C4111.65 (5)C3—C4—Fe169.99 (8)
C2—Fe1—C467.96 (6)C5—C4—Fe169.36 (7)
C2i—Fe1—C4112.04 (6)C3—C4—H4125.7
C5—Fe1—C440.29 (6)C5—C4—H4125.7
C5i—Fe1—C4139.71 (6)Fe1—C4—H4126.5
C1—Fe1—C4i111.65 (5)C4—C5—C1108.24 (12)
C1i—Fe1—C4i68.35 (5)C4—C5—Fe170.36 (8)
C2—Fe1—C4i112.04 (6)C1—C5—Fe169.11 (7)
C2i—Fe1—C4i67.96 (6)C4—C5—H5125.9
C5—Fe1—C4i139.71 (6)C1—C5—H5125.9
C5i—Fe1—C4i40.29 (5)Fe1—C5—H5126.2
C4—Fe1—C4i180.00 (8)N1—C6—C1112.79 (12)
C1—Fe1—C368.63 (5)N1—C6—H6A109.0
C1i—Fe1—C3111.37 (5)C1—C6—H6A109.0
C2—Fe1—C340.54 (6)N1—C6—H6B109.0
C2i—Fe1—C3139.46 (6)C1—C6—H6B109.0
C5—Fe1—C367.93 (6)H6A—C6—H6B107.8
C5i—Fe1—C3112.07 (6)N3—C7—C8108.55 (12)
C4—Fe1—C340.11 (6)N3—C7—C9122.77 (12)
C4i—Fe1—C3139.89 (6)C8—C7—C9128.62 (13)
C1—Fe1—C3i111.37 (5)N1—C8—C7104.22 (12)
C1i—Fe1—C3i68.63 (5)N1—C8—H8127.9
C2—Fe1—C3i139.46 (6)C7—C8—H8127.9
C2i—Fe1—C3i40.54 (6)N4—C9—C10122.94 (12)
C5—Fe1—C3i112.07 (6)N4—C9—C7115.54 (12)
C5i—Fe1—C3i67.93 (6)C10—C9—C7121.50 (12)
C4—Fe1—C3i139.89 (6)C11—C10—C9118.52 (13)
C4i—Fe1—C3i40.11 (6)C11—C10—H10120.7
C3—Fe1—C3i180.0C9—C10—H10120.7
C8—N1—N2111.35 (11)C10—C11—C12119.08 (13)
C8—N1—C6129.20 (14)C10—C11—H11120.5
N2—N1—C6119.45 (13)C12—C11—H11120.5
N3—N2—N1107.30 (12)C13—C12—C11118.35 (13)
N2—N3—C7108.57 (12)C13—C12—H12120.8
C13—N4—C9117.19 (12)C11—C12—H12120.8
C5—C1—C2107.33 (12)N4—C13—C12123.89 (14)
C5—C1—C6125.82 (13)N4—C13—H13118.1
C2—C1—C6126.83 (14)C12—C13—H13118.1
C8—N1—N2—N30.31 (16)N2—N1—C6—C188.89 (17)
C6—N1—N2—N3179.79 (12)C5—C1—C6—N196.79 (18)
N1—N2—N3—C70.34 (15)C2—C1—C6—N185.10 (18)
C5—C1—C2—C30.44 (14)Fe1—C1—C6—N1174.35 (11)
C6—C1—C2—C3177.96 (12)N2—N3—C7—C80.26 (16)
Fe1—C1—C2—C359.84 (9)N2—N3—C7—C9177.32 (12)
C5—C1—C2—Fe160.28 (9)N2—N1—C8—C70.15 (15)
C6—C1—C2—Fe1118.12 (13)C6—N1—C8—C7179.97 (13)
C1—C2—C3—C40.26 (15)N3—C7—C8—N10.06 (15)
Fe1—C2—C3—C459.29 (9)C9—C7—C8—N1177.33 (13)
C1—C2—C3—Fe159.03 (9)C13—N4—C9—C100.0 (2)
C2—C3—C4—C50.02 (15)C13—N4—C9—C7178.92 (12)
Fe1—C3—C4—C558.82 (9)N3—C7—C9—N4167.64 (13)
C2—C3—C4—Fe158.81 (9)C8—C7—C9—N49.4 (2)
C3—C4—C5—C10.29 (15)N3—C7—C9—C1011.3 (2)
Fe1—C4—C5—C158.92 (9)C8—C7—C9—C10171.60 (13)
C3—C4—C5—Fe159.21 (9)N4—C9—C10—C111.4 (2)
C2—C1—C5—C40.45 (14)C7—C9—C10—C11179.75 (12)
C6—C1—C5—C4177.97 (12)C9—C10—C11—C121.7 (2)
Fe1—C1—C5—C459.70 (9)C10—C11—C12—C130.8 (2)
C2—C1—C5—Fe160.15 (9)C9—N4—C13—C121.1 (2)
C6—C1—C5—Fe1118.27 (13)C11—C12—C13—N40.6 (2)
C8—N1—C6—C191.24 (19)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8···N3ii0.952.683.601 (2)163
C5—H5···N2ii0.952.513.4240 (19)160
C3—H3···N4iii0.952.733.4625 (19)135
C12—H12···Cpcentroidiv0.952.693.4861 (15)142
Symmetry codes: (ii) x1, y, z; (iii) x, y+1, z; (iv) x+2, y, z.
 

Acknowledgements

The authors are grateful to the Department of Chemistry, Louisiana State University for providing access to single-crystal X-ray analysis of the reported compound without any cost.

Funding information

Funding for this research was provided by: Nicholls Research Council, Nicholls State University (USA) (grant to Uttam Pokharel).

References

First citationAstruc, D. (2017). Eur. J. Inorg. Chem. 2017, 6–29.  Web of Science CrossRef CAS Google Scholar
First citationBruker (2016). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBuda, M., Moutet, J.-C., Saint-Aman, E., De Cian, A., Fischer, J. & Ziessel, R. (1998). Inorg. Chem. 37, 4146–4148.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationCasas-Solvas, J. M., Ortiz-Salmerón, E., Giménez-Martínez, J. J., García-Fuentes, L., Capitán-Vallvey, L. F., Santoyo-González, F. & Vargas-Berenguel, A. (2009). Chem. Eur. J. 15, 710–725.  Web of Science PubMed CAS Google Scholar
First citationCook, T. R. & Stang, P. J. (2015). Chem. Rev. 115, 7001–7045.  Web of Science CrossRef CAS PubMed Google Scholar
First citationCrowley, J. D. & Bandeen, P. H. (2010). Dalton Trans. 39, 612–623.  Web of Science CSD CrossRef CAS Google Scholar
First citationCrowley, J. D., Bandeen, P. H. & Hanton, L. R. (2010). Polyhedron, 29, 70–83.  Web of Science CSD CrossRef CAS Google Scholar
First citationEtter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262.  CrossRef ICSD CAS Web of Science IUCr Journals Google Scholar
First citationFindlay, J. A., McAdam, C. J., Sutton, J. J., Preston, D., Gordon, K. C. & Crowley, J. D. (2018). Inorg. Chem. 57, 3602–3614.  Web of Science CSD CrossRef CAS PubMed Google Scholar
First citationGlidewell, C., Zakaria, C. M., Ferguson, G. & Gallagher, J. F. (1994). Acta Cryst. C50, 233–238.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationGroom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179.  Web of Science CrossRef IUCr Journals Google Scholar
First citationIon, A., Buda, M., Moutet, J.-C., Saint-Aman, E., Royal, G., Gautier-Luneau, I., Bonin, M. & Ziessel, R. (2002). Eur. J. Inorg. Chem. pp. 1357–1366.  CrossRef Google Scholar
First citationKrause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10.  Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
First citationLindner, E., Zong, R., Eichele, K., Weisser, U. & Ströbele, M. (2003). Eur. J. Inorg. Chem. pp. 705–712.  CSD CrossRef Google Scholar
First citationMacrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationManck, S., Röger, M., van der Meer, M. & Sarkar, B. (2017). Eur. J. Inorg. Chem. pp. 477–482.  Web of Science CSD CrossRef Google Scholar
First citationNajar, A. M., Tidmarsh, I. S. & Ward, M. D. (2010). CrystEngComm, 12, 3642–3650.  Web of Science CSD CrossRef CAS Google Scholar
First citationPokharel, U. R., Fronczek, F. R. & Maverick, A. W. (2013). Dalton Trans. 42, 14064–14067.  Web of Science CSD CrossRef CAS PubMed Google Scholar
First citationPokharel, U. R., Fronczek, F. R. & Maverick, A. W. (2014). Nat. Commun. 5, 5883.  Web of Science CSD CrossRef PubMed Google Scholar
First citationQuinodoz, B., Labat, G., Stoeckli-Evans, H. & von Zelewsky, A. (2004). Inorg. Chem. 43, 7994–8004.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationRomero, T., Orenes, R. A., Espinosa, A., Tárraga, A. & Molina, P. (2011). Inorg. Chem. 50, 8214–8224.  Web of Science CSD CrossRef CAS PubMed Google Scholar
First citationSachsinger, N. & Hall, C. D. (1997). J. Organomet. Chem. 531, 61–65.  CrossRef CAS Web of Science Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds