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Recrystallization of the title compound, [Fe(C5H5)(C14H13N2O3)], from a mixture of n-hexane and dichloro­methane gave the new polymorph, denoted (I), which crystallizes in the same space group (P\overline{1}) as the previously reported structure, denoted (II). The Fe—C distances in (I) range from 2.015 (3) to 2.048 (2) Å and the average value of the C—C bond lengths in the two cyclo­penta­dienyl (Cp) rings is 1.403 (13) Å. As indicated by the smallest C—Cg1—Cg2—C torsion angle of 1.4° (Cg1 and Cg2 are the centroids of the two Cp rings), the orientation of the Cp rings in (I) is more eclipsed than in the case of (II), for which the value was 15.3°. Despite the pronounced conformational similarity between (I) and (II), the formation of self-complementary N—H...O hydrogen-bonded dimers represents the only structural motif common to the two polymorphs. In the extended structure, mol­ecules of (I) utilize C—H...O hydrogen bonds and, unlike (II), an extensive set of inter­molecular C—H...π inter­actions. Fingerprint plots based on Hirshfeld surfaces are used to compare the packing of the two polymorphs.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112000765/fa3265sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112000765/fa3265Isup2.hkl
Contains datablock I

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S0108270112000765/fa3265sup3.pdf
Supplementary material

CCDC reference: 867004

Comment top

Ferrocene, an unnatural compound, has attracted intense attention by chemists since its discovery in 1951 (Kealy & Pauson, 1951; Miller et al., 1952) and particularly after its first functionalization by Friedel–Crafts acylation (Woodward et al., 1952). This interest is a consequence of several unique properties of ferrocene and its derivatives, including nontoxicity, easy handling, outstanding stability in both aqueous and non-aqueous media etc. The most attractive feature of these compounds is their ease of functionalization: following classical organic protocols one can synthesize a `double' of any known compound in which the aromatic unit is substituted by ferrocene.

Ferrocene exists in three polymorphic forms, one at room temperature, which is monoclinic (Seiler & Dunitz, 1979a; Takusagawa & Koetzle, 1979) and two at low temperature, triclinic and orthorhombic (Seiler & Dunitz, 1979b, 1982). At the molecular level, the ferrocene molecules within these forms differ only in the relative orientation of the two cyclopentadienyl (Cp) rings (Braga et al., 1998). The low rotation barrier of the Cp rings accounts for the considerable flexibility of the ferrocene (Fc) unit, which can be further related with [to] the evident structural polymorphism of Fc-containing compounds. Aliphatic substituents, when present on Fc units, add to the overall structural flexibility which plays an important role in the polymorphism of these compounds. A CSD (Cambridge Structural Database, Version ? update?; Allen, 2002) survey of Fc-containing crystal structures, for which the special text string `polymorphism' has been registered, retrieved 78 different compounds. Among these structures there are 16 examples in which the polymorphs crystallize in the same space group.

We report here a new polymorph of 1-ferrocenyl-3-(3-nitroanilino)propan-1-one obtained by recrystallization from a mixture of n-hexane and dichloromethane. The novel polymorph, denoted (I) (Fig. 1), as well as the previously described polymorph, denoted (II) (Damljanović et al., 2011), crystallizes in the space group P1, with one molecule in the asymmetric unit. The unit cells of (I) and (II) display similar volumes but differ significantly in axis lengths and angles. The previously reported examples of monosubstituted 3-arylamino-1-ferrocenylpropan-1-ones (Damljanović et al., 2011) indicate the existence of two molecular conformations, mostly dependent on the position of the substituent on the arylamino group. The molecules (I) and (II) belong to the same conformational type and exhibit only slight structural dissimilarity, but they display a significant packing polymorphism. For (I) the bond distances (Table 1) within the Fc unit are as expected for monosubstituted derivatives. The C—C bonds in the substituted cyclopentadienyl ring, Cp1, are slightly longer than those in the unsubstituted ring, Cp2. One should however take into account that the apparently shorter C—C bonds in the unsubstituted ring may be a result of the strong libration in this ring, as demonstrated by the elongated ellipsoids. Disorder of the Cp rings in ferrocene is a well known phenomenon which is initially described by Seiler & Dunitz, (1979a). The longest Cp bonds are C1—C2 [1.437 (3) Å] and C1—C5 [1.429 (3) Å] vicinal to the substituent at C1 (Fig. 1). As previously observed in similar monosubstituted Fc-based compounds (Ratković et al., 2010) the metal atom could be considered as positioned slightly closer to the substituted Cp1 ring (Fe1—Cg1 = 1.64 Å and Fe1—Cg2 = 1.65 Å). The Cp1 and Cp2 rings are almost parallel, with a dihedral angle of 1.3 (2)°, similar to the value of 2.3 (4)° for (II). The most pronounced difference in the Fc units of (I) and (II) concerns the mutual orientation of Cp rings. The C1—Cg1—Cg2—C6 torsion angle of 1.4° in (I) and 15.3° in (II) indicates a more significant deviation from an eclipsed conformation in the case of (II). Bond lengths and angles within the substituents are similar in (I) and (II). Torsion angles (Table 2) indicate small but noticeable differences in the conformation of the C1–C14 chains which are enabled by free rotation around the corresponding single bonds. These differences accompany a slight variation in the Cp2/Ph dihedral angle, 85.7 (1) and 82.7 (2)° for (I) and (II), respectively. A good gauge of the conformational differences between (I) and (II) is the relative displacement of the arylamino atom N1 from the plane Fe1/Cg2/C6, which bisects Cp2 and contains the Fe1 atom [(I) 0.55, (II) 2.05 Å, see Fig. S1 in Supplementary materials].

In the packing of the two polymorphs, the strongest intermolecular N1—H1n···O1 interactions, formed between their aliphatic moieties, link the centrosymmetrically related molecules into dimers characterized by the same, cyclic R22(12) motif (Etter, 1990). The N1—H1n···O1 hydrogen bond in (I) is somewhat shorter [N1···O1 = 3.018 (2) Å in (I) and 3.133 (6) Å in (II)] and displays better directionality than the analogous interaction in (II). Each of the N1—H1n···O1 interactions in (II) is additionally supported by a C6—H6···O1 interaction, while in (I) the relative disposition of the neighbouring molecules obviate this interaction (see Fig. S2 in Supplementary materials). The dimer mediated by N1—H1n···O1i [symmetry code: (i) -x+1, -y+2, -z+1] is the only motif common to the two structures. This interaction involves the strongest donor and acceptor and represents the best initial aggregation mode for this compound. Beyond that, the polymorphs (I) and (II) display pronounced differences. In (II) the strongest remaining acceptors, the nitro O atoms, interact with a pair of C—H donors, one from each Cp ring of the Fc unit. In this manner the bent configuration of the molecule is utilized to form a macrocyclic motif centred at (1/2, 1/2, 1/2) (Fig. 2, bottom). This motif is not seen for (I); indeed, in (I), the same pair of C—H donors is involved in a pair of C—H···π interactions toward the neighbouring benzene ring, forming an infinite chain parallel to b. Fig. 2 shows the dimers common to (I) and (II) interconnected by C—H···π [(I), Fig. 2, top] and C—H···O [(II), Fig. 2, bottom] interactions, respectively. In (I), the nitro O atoms have a completely different role from that observed for (II). Atom O2 in (I) is involved in an acceptor-bifurcated hydrogen bond (both H···O < 2.6 Å), with benzene C15—H15 and aliphatic C13—H13a as donors. The interaction to acceptor O3 is weaker and involves cyclopentadienyl C7—H7 as donor. This is the only interaction between the Fc moiety and NO2 in (I), in contrast to (II), for which there are three. While Fc in (I) has an important role in the C—H···π interactions, both as a C—H donor and as a π acceptor, in (II) only one intermolecular C—H···π interaction is observed (Table 3, see Fig. S3 in Supplementary materials).

The differences in the overall patterns of interactions in the crystal structures of polymorphs (I) and (II) are best illustrated through Hirshfeld surfaces (see Fig. S4 in Supplementary materials) and the corresponding fingerprint plots (Fig. 3; Wolff et al., 2007; Spackman & McKinnon, 2002). This two-dimensional mapping summarizes the intermolecular interactions present in the crystal structures and reflects the influences of the different crystal environments on the two polymorphs. The values de and di are defined as the distances from a point on the Hirshfeld surface to the nearest atoms external and internal to the surface, respectively. For each (de,di) pair, the fingerprint plot gives its frequency of occurrence in the structure, using colour to represent frequency. As discussed by Spackman & Jayatilaka (2009), various types of interactions in a molecular structure give rise to characteristic patterns in the fingerprint plot. The fingerprint plots for (I) and (II) show distinctly different shapes; however, the dominant feature on each of them is a pair of sharp spikes corresponding to the shortest O···H contacts. Taking into account the de and di values it is clear that polymorph (I) exhibits shorter hydrogen-bonding interactions. Moreover, a systematic shift of the whole pattern to shorter contacts in (I) suggests a more dense packing in the case of this polymorph. This accords with the densities Dcalc of 1.475 and 1.462 Mg m-3 for (I) and (II), respectively. If the density of the different polymorphs is considered as a measure of their relative stabilities (Braga et al., 1998), one can conclude that polymorph (I) is the more stable of the two. An important feature in the fingerprint plot of (I), which is lacking in (II), is the wing-like accumulation at the top left and bottom right of the graph, corresponding to the C—H···π interactions. The region between the spikes corresponds to the H···H contacts, which are obviously more numerous for (I). The shortest intermolecular H···H distance (2.42 Å) is found between H1n (attached to N1) and cyclopentadienyl H5 (located in the vicinity of the O acceptor interacting with H1n). The percentage contributions of the H···O contacts to the fingerprint plot is 24.8% for (I) and slightly higher in the case of (II) (27.1%). On the other hand, the contribution of H···C contacts is higher for polymorph (I), 19.1% in comparison to (II), 13.1%, in agreement with the greater number of observed C—H···π interactions (see Fig. S3 in Supplementary materials).

In summary, the two polymorphs of 1-ferrocenyl-3-(3-nitroanilino)propan-1-one represent the infrequent case in which polymorphs of Fc compounds crystallize with the same space group. Indeed, the molecules in polymorphs (I) and (II) exhibit almost the same conformation, and form similar centrosymmetric dimers; nevertheless, they display completely different three-dimensional packing which is based entirely on weak noncovalent interactions. [Author: please supply supplementary figures S1–S4 referred to in the text]

Related literature top

For related literature, see: Allen (2002); Braga et al. (1998); Damljanović et al. (2011); Etter (1990); Kealy & Pauson (1951); Miller et al. (1952); Ratković et al. (2010); Seiler & Dunitz (1979a, 1979b, 1982); Spackman & Jayatilaka (2009); Spackman & McKinnon (2002); Takusagawa & Koetzle (1979); Woodward et al. (1952).

Experimental top

Polymorph (I) was synthesized according to the previously reported procedure of Damljanović et al. (2011). The solid product obtained following column chromatography was dissolved in a small amount of dichloromethane (2–3 ml), and to this solution n-hexane was added carefully until the first appearance of turbidity. One or two drops of dichloromethane were then added to obtain a clear solution, which was allowed to evaporate slowly at room temperature, producing crystals of (I).

Refinement top

H atoms bonded to C atoms were placed at calculated positions, with C—H distances fixed at 0.93 Å for aromatic Csp2 atoms and at 0.97 Å for methylene Csp3 atoms. The corresponding isotropic displacement parameters of the H atoms were set equal to 1.2Ueq and 1.5Ueq of the parent Csp2 and Csp3 atoms, respectively. The H atom attached to N1 was located by difference Fourier synthesis, then the N—H bond length was idealized to 0.86 Å and the H atom constrained to ride on its parent atom with its isotropic displacement parameter freely refined.

In order to compare the Hirshfeld fingerprint plots for two polymorphs on the same grounds the corresponding N—H bond in (II) was elongated to the identical value of 0.86 Å. The refinement of (II) was then continued until the convergence in the same manner as for (I). The parameters for (II) given in Table 3 are slightly altered from the original publication (Damljanović et al., 2011) due to this modification.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999), PLATON (Spek, 2009) and PARST (Nardelli, 1995).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing atom-numbering scheme. Displacement ellipsoids are drawn at the 35% probability level.
[Figure 2] Fig. 2. The N1—H1···O1 hydrogen-bonded dimers of (I) (top) and (II) (bottom), interconnected by corresponding C—H···π and C—H···O interactions, respectively. The H atoms not involved in intermolecular interactions have been excluded for the sake of clarity.
[Figure 3] Fig. 3. Fingerprint plots of (I) and (II).
(I) top
Crystal data top
[Fe(C5H5)(C14H13N2O3)]Z = 2
Mr = 378.20F(000) = 392
Triclinic, P1Dx = 1.475 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.6075 (3) ÅCell parameters from 3324 reflections
b = 10.1342 (7) Åθ = 3.1–29.0°
c = 11.9062 (6) ŵ = 0.91 mm1
α = 73.805 (5)°T = 293 K
β = 81.350 (4)°Prismatic, orange
γ = 75.891 (5)°0.22 × 0.18 × 0.15 mm
V = 851.55 (8) Å3
Data collection top
Oxford Diffraction Xcalibur Sapphire3 Gemini
diffractometer
3884 independent reflections
Radiation source: Enhance (Mo) X-ray Source3147 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
Detector resolution: 16.3280 pixels mm-1θmax = 29.1°, θmin = 3.1°
ω scansh = 1010
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
k = 1312
Tmin = 0.933, Tmax = 1.000l = 1516
6735 measured reflections
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)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0311P)2 + 0.2595P]
where P = (Fo2 + 2Fc2)/3
3884 reflections(Δ/σ)max = 0.001
227 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = 0.34 e Å3
Crystal data top
[Fe(C5H5)(C14H13N2O3)]γ = 75.891 (5)°
Mr = 378.20V = 851.55 (8) Å3
Triclinic, P1Z = 2
a = 7.6075 (3) ÅMo Kα radiation
b = 10.1342 (7) ŵ = 0.91 mm1
c = 11.9062 (6) ÅT = 293 K
α = 73.805 (5)°0.22 × 0.18 × 0.15 mm
β = 81.350 (4)°
Data collection top
Oxford Diffraction Xcalibur Sapphire3 Gemini
diffractometer
3884 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
3147 reflections with I > 2σ(I)
Tmin = 0.933, Tmax = 1.000Rint = 0.021
6735 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.091H-atom parameters constrained
S = 1.05Δρmax = 0.21 e Å3
3884 reflectionsΔρmin = 0.34 e Å3
227 parameters
Special details top

Experimental. Absorption correction: Multi-scan absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm (Oxford Diffraction Ltd., 2009).

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. The atoms C7, C8 and C9 within the unsubstituted Cp ring of the Fc unit display somewhat higher Ueq as compared to neighbors. Disorder of the Cp rings in ferrocene is a well known phenomenon which is initially described by Seiler & Dunitz, 1979a. 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
xyzUiso*/Ueq
Fe10.65225 (4)1.14397 (4)0.76098 (3)0.04718 (12)
O10.3426 (2)1.05452 (16)0.58461 (12)0.0457 (4)
O20.7072 (3)0.4375 (3)1.02377 (17)0.1031 (9)
O30.9843 (3)0.3401 (2)0.99515 (18)0.0869 (7)
N10.5278 (2)0.74588 (19)0.63420 (15)0.0452 (4)
H1N0.54350.80680.56890.052 (7)*
N20.8463 (3)0.4210 (2)0.96107 (18)0.0563 (5)
C10.3961 (3)1.1380 (2)0.73799 (18)0.0405 (5)
C20.4113 (3)1.1279 (3)0.8591 (2)0.0543 (6)
H20.39091.05380.92270.065*
C30.4630 (3)1.2508 (3)0.8638 (3)0.0665 (8)
H30.48211.27170.93170.080*
C40.4807 (3)1.3363 (3)0.7493 (3)0.0654 (8)
H40.51421.42290.72850.078*
C50.4391 (3)1.2689 (2)0.6712 (2)0.0507 (6)
H50.43951.30340.59010.061*
C60.8310 (3)0.9880 (4)0.7031 (4)0.0887 (12)
H60.79990.92340.67150.106*
C70.8465 (4)0.9725 (5)0.8219 (5)0.1093 (15)
H70.82870.89630.88410.131*
C80.8947 (4)1.0964 (6)0.8277 (4)0.1076 (16)
H80.91401.11710.89560.129*
C90.9079 (4)1.1790 (4)0.7183 (5)0.0945 (12)
H90.93851.26660.69800.113*
C100.8695 (4)1.1147 (4)0.6416 (3)0.0796 (9)
H100.86941.15090.56070.096*
C110.3621 (2)1.0305 (2)0.68866 (17)0.0366 (4)
C120.3518 (3)0.8879 (2)0.76954 (17)0.0411 (5)
H12A0.23990.89620.82080.049*
H12B0.45260.85670.81840.049*
C130.3575 (3)0.7786 (2)0.70398 (19)0.0437 (5)
H13A0.33590.69300.76030.052*
H13B0.25950.81200.65280.052*
C140.6844 (3)0.6661 (2)0.68266 (17)0.0370 (4)
C150.6878 (3)0.5892 (2)0.79941 (17)0.0372 (4)
H150.58230.59430.85030.045*
C160.8500 (3)0.5051 (2)0.83859 (18)0.0418 (5)
C171.0115 (3)0.4946 (3)0.7700 (2)0.0532 (6)
H171.11860.43750.79950.064*
C181.0078 (3)0.5730 (3)0.6546 (2)0.0573 (6)
H181.11510.56880.60530.069*
C190.8502 (3)0.6564 (2)0.6113 (2)0.0491 (5)
H190.85230.70770.53330.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.03079 (17)0.0510 (2)0.0608 (2)0.00111 (13)0.00370 (14)0.02243 (17)
O10.0540 (9)0.0431 (9)0.0344 (8)0.0106 (7)0.0079 (7)0.0017 (7)
O20.0606 (12)0.149 (2)0.0507 (11)0.0027 (13)0.0005 (10)0.0338 (13)
O30.0794 (14)0.0777 (14)0.0735 (13)0.0178 (11)0.0269 (11)0.0099 (11)
N10.0509 (11)0.0401 (10)0.0340 (9)0.0045 (8)0.0047 (8)0.0034 (8)
N20.0564 (12)0.0531 (12)0.0493 (12)0.0059 (10)0.0157 (10)0.0042 (10)
C10.0281 (9)0.0457 (12)0.0430 (11)0.0004 (9)0.0023 (8)0.0115 (10)
C20.0362 (11)0.0757 (18)0.0486 (13)0.0006 (11)0.0015 (10)0.0228 (13)
C30.0430 (13)0.089 (2)0.0768 (19)0.0073 (13)0.0108 (13)0.0511 (18)
C40.0497 (14)0.0538 (16)0.101 (2)0.0021 (12)0.0154 (14)0.0401 (17)
C50.0471 (12)0.0414 (13)0.0608 (15)0.0001 (10)0.0118 (11)0.0125 (12)
C60.0354 (14)0.074 (2)0.174 (4)0.0085 (14)0.0154 (19)0.074 (3)
C70.0495 (18)0.084 (3)0.136 (4)0.0258 (18)0.009 (2)0.022 (3)
C80.0435 (17)0.167 (5)0.119 (3)0.025 (2)0.029 (2)0.076 (3)
C90.0391 (15)0.089 (3)0.174 (4)0.0163 (15)0.004 (2)0.068 (3)
C100.0491 (15)0.098 (3)0.089 (2)0.0133 (16)0.0176 (14)0.034 (2)
C110.0241 (9)0.0412 (11)0.0359 (11)0.0002 (8)0.0004 (8)0.0031 (9)
C120.0324 (10)0.0460 (12)0.0340 (10)0.0046 (9)0.0015 (8)0.0016 (10)
C130.0390 (11)0.0401 (12)0.0447 (12)0.0097 (9)0.0098 (9)0.0055 (10)
C140.0446 (11)0.0294 (10)0.0361 (10)0.0107 (9)0.0018 (9)0.0054 (9)
C150.0381 (10)0.0331 (10)0.0364 (10)0.0081 (8)0.0002 (8)0.0037 (9)
C160.0436 (11)0.0367 (11)0.0408 (11)0.0072 (9)0.0060 (9)0.0029 (10)
C170.0399 (12)0.0497 (14)0.0623 (15)0.0006 (10)0.0055 (11)0.0099 (12)
C180.0455 (13)0.0587 (16)0.0588 (15)0.0101 (11)0.0130 (11)0.0106 (13)
C190.0539 (13)0.0451 (13)0.0410 (12)0.0115 (11)0.0053 (10)0.0032 (10)
Geometric parameters (Å, º) top
Fe1—C82.015 (3)C6—C101.366 (5)
Fe1—C72.024 (3)C6—C71.398 (5)
Fe1—C12.025 (2)C6—H60.9300
Fe1—C62.025 (3)C7—C81.413 (6)
Fe1—C92.026 (3)C7—H70.9300
Fe1—C102.032 (3)C8—C91.342 (5)
Fe1—C52.035 (2)C8—H80.9300
Fe1—C22.036 (2)C9—C101.360 (4)
Fe1—C42.046 (2)C9—H90.9300
Fe1—C32.048 (2)C10—H100.9300
O1—C111.219 (2)C11—C121.509 (3)
O2—N21.205 (3)C12—C131.512 (3)
O3—N21.209 (2)C12—H12A0.9700
N1—C131.449 (3)C12—H12B0.9700
N1—C141.372 (3)C13—H13A0.9700
N1—H1N0.8600C13—H13B0.9700
N2—C161.470 (3)C14—C151.392 (3)
C1—C51.429 (3)C14—C191.409 (3)
C1—C21.437 (3)C15—C161.380 (3)
C1—C111.463 (3)C15—H150.9300
C2—C31.412 (4)C16—C171.368 (3)
C2—H20.9300C17—C181.382 (3)
C3—C41.404 (4)C17—H170.9300
C3—H30.9300C18—C191.366 (3)
C4—C51.407 (3)C18—H180.9300
C4—H40.9300C19—H190.9300
C5—H50.9300
C8—Fe1—C740.97 (17)C5—C4—H4125.8
C8—Fe1—C1161.33 (19)Fe1—C4—H4126.4
C7—Fe1—C1124.49 (16)C4—C5—C1108.1 (2)
C8—Fe1—C667.42 (15)C4—C5—Fe170.25 (14)
C7—Fe1—C640.40 (15)C1—C5—Fe169.02 (12)
C1—Fe1—C6109.31 (11)C4—C5—H5125.9
C8—Fe1—C938.80 (16)C1—C5—H5125.9
C7—Fe1—C966.91 (16)Fe1—C5—H5126.4
C1—Fe1—C9158.51 (16)C10—C6—C7108.0 (3)
C6—Fe1—C966.26 (13)C10—C6—Fe170.60 (17)
C8—Fe1—C1066.02 (15)C7—C6—Fe169.76 (18)
C7—Fe1—C1066.90 (15)C10—C6—H6126.0
C1—Fe1—C10124.00 (11)C7—C6—H6126.0
C6—Fe1—C1039.34 (14)Fe1—C6—H6125.2
C9—Fe1—C1039.16 (13)C6—C7—C8105.8 (4)
C8—Fe1—C5156.4 (2)C6—C7—Fe169.84 (18)
C7—Fe1—C5159.91 (19)C8—C7—Fe169.16 (18)
C1—Fe1—C541.22 (9)C6—C7—H7127.1
C6—Fe1—C5123.04 (15)C8—C7—H7127.1
C9—Fe1—C5121.83 (16)Fe1—C7—H7125.5
C10—Fe1—C5107.46 (12)C9—C8—C7108.2 (4)
C8—Fe1—C2124.46 (16)C9—C8—Fe171.07 (19)
C7—Fe1—C2109.85 (13)C7—C8—Fe169.87 (19)
C1—Fe1—C241.43 (8)C9—C8—H8125.9
C6—Fe1—C2126.30 (13)C7—C8—H8125.9
C9—Fe1—C2158.25 (15)Fe1—C8—H8124.8
C10—Fe1—C2161.49 (13)C8—C9—C10109.4 (4)
C5—Fe1—C268.98 (10)C8—C9—Fe170.1 (2)
C8—Fe1—C4121.81 (17)C10—C9—Fe170.64 (17)
C7—Fe1—C4159.3 (2)C8—C9—H9125.3
C1—Fe1—C468.69 (10)C10—C9—H9125.3
C6—Fe1—C4157.15 (17)Fe1—C9—H9125.5
C9—Fe1—C4106.76 (13)C9—C10—C6108.7 (4)
C10—Fe1—C4121.55 (14)C9—C10—Fe170.20 (18)
C5—Fe1—C440.35 (10)C6—C10—Fe170.06 (17)
C2—Fe1—C468.26 (12)C9—C10—H10125.7
C8—Fe1—C3108.47 (13)C6—C10—H10125.7
C7—Fe1—C3125.06 (17)Fe1—C10—H10125.7
C1—Fe1—C368.66 (9)O1—C11—C1121.19 (19)
C6—Fe1—C3162.16 (17)O1—C11—C12120.3 (2)
C9—Fe1—C3122.25 (13)N1—C13—C12114.00 (18)
C10—Fe1—C3156.63 (14)C14—N1—C13122.85 (17)
C5—Fe1—C367.93 (10)C1—C11—C12118.54 (18)
C2—Fe1—C340.46 (11)C11—C12—C13112.79 (17)
C4—Fe1—C340.12 (12)C11—C12—H12A109.0
C14—N1—H1N115.2C13—C12—H12A109.0
C13—N1—H1N115.9C11—C12—H12B109.0
O2—N2—O3122.8 (2)C13—C12—H12B109.0
O2—N2—C16118.67 (19)H12A—C12—H12B107.8
O3—N2—C16118.5 (2)N1—C13—H13A108.8
C5—C1—C2107.1 (2)C12—C13—H13A108.8
C5—C1—C11125.22 (19)N1—C13—H13B108.8
C2—C1—C11127.4 (2)C12—C13—H13B108.8
C5—C1—Fe169.76 (12)H13A—C13—H13B107.6
C2—C1—Fe169.70 (12)N1—C14—C15123.11 (19)
C11—C1—Fe1121.05 (13)N1—C14—C19119.36 (19)
C3—C2—C1107.5 (2)C15—C14—C19117.49 (19)
C3—C2—Fe170.23 (14)C16—C15—C14119.03 (19)
C1—C2—Fe168.87 (12)C16—C15—H15120.5
C3—C2—H2126.3C14—C15—H15120.5
C1—C2—H2126.3C17—C16—C15123.9 (2)
Fe1—C2—H2126.2C17—C16—N2118.69 (19)
C4—C3—C2108.8 (2)C15—C16—N2117.38 (19)
C4—C3—Fe169.85 (15)C16—C17—C18116.7 (2)
C2—C3—Fe169.32 (13)C16—C17—H17121.6
C4—C3—H3125.6C18—C17—H17121.6
C2—C3—H3125.6C19—C18—C17121.5 (2)
Fe1—C3—H3126.8C19—C18—H18119.2
C3—C4—C5108.5 (3)C17—C18—H18119.2
C3—C4—Fe170.02 (15)C18—C19—C14121.3 (2)
C5—C4—Fe169.41 (13)C18—C19—H19119.4
C3—C4—H4125.8C14—C19—H19119.4
O1—C11—C1—C510.7 (3)C2—C1—C11—C124.0 (3)
C1—C11—C12—C13167.40 (16)C5—C1—C11—O110.7 (3)
C11—C12—C13—N165.2 (2)C5—C1—C11—C12169.19 (18)
C12—C13—N1—C1474.4 (3)O1—C11—C12—C1312.5 (3)
N1—C14—C15—C16176.06 (19)O2—N2—C16—C156.0 (3)
C13—N1—C14—C1511.7 (3)O2—N2—C16—C17174.9 (3)
C13—N1—C14—C19170.5 (2)O3—N2—C16—C15175.5 (2)
C1—C11—C12—C13167.40 (16)O3—N2—C16—C173.7 (3)
C14—N1—C13—C1274.4 (3)C11—C1—C5—C4173.94 (18)

Experimental details

Crystal data
Chemical formula[Fe(C5H5)(C14H13N2O3)]
Mr378.20
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)7.6075 (3), 10.1342 (7), 11.9062 (6)
α, β, γ (°)73.805 (5), 81.350 (4), 75.891 (5)
V3)851.55 (8)
Z2
Radiation typeMo Kα
µ (mm1)0.91
Crystal size (mm)0.22 × 0.18 × 0.15
Data collection
DiffractometerOxford Diffraction Xcalibur Sapphire3 Gemini
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Tmin, Tmax0.933, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
6735, 3884, 3147
Rint0.021
(sin θ/λ)max1)0.684
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.091, 1.05
No. of reflections3884
No. of parameters227
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.21, 0.34

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999), PLATON (Spek, 2009) and PARST (Nardelli, 1995).

Selected geometric parameters (Å, º) top
O1—C111.219 (2)N2—C161.470 (3)
O2—N21.205 (3)C1—C111.463 (3)
O3—N21.209 (2)C11—C121.509 (3)
N1—C131.449 (3)C12—C131.512 (3)
N1—C141.372 (3)
O1—C11—C1121.19 (19)C14—N1—C13122.85 (17)
O1—C11—C12120.3 (2)C1—C11—C12118.54 (18)
N1—C13—C12114.00 (18)C11—C12—C13112.79 (17)
Selected torsion angles for (I) and (II) top
Torsion angle(I)(II)
C1—C11—C12—C13-167.4 (2)-164.4 (4)
C5—C1—C11—C12169.2 (2)178.8 (5)
C11—C12—C13—N165.2 (2)67.4 (7)
C12—C13—N1—C1474.4 (3)68.7 (8)
C13—N1—C14—C1511.7 (3)13.0 (9)
O1—C11—C12—C1312.5 (3)17.6 (7)
Geometrical parameters (Å,°) for intermolecular interactions top
D—H···AD—HH···AD···AD—H···AH···Cg
(I)
N1—H1n···O1i0.862.183.018 (2)165
C19—H19···O1i0.932.643.361 (2)135
C13—H13a···O2ii0.972.553.411 (3)147
C15—H15···O2ii0.932.513.422 (3)168
C7—H7···O3iii0.932.623.383 (4)140
C17—H17···C3iv0.932.903.824 (3)1732.87
C17—H17···C4iv0.932.733.541 (3)1462.87
C12—H12A···C7v0.932.903.724 (4)1433.06
C12—H12A···C8v0.932.913.903 (3)1373.06
C4—H4···C14vi0.932.943.857 (4)1603.31
C4—H4···C15vi0.932.743.536 (4)1443.31
C9—H9···C17vi0.932.873.780 (5)1443.19
(II)
N1—H1n···O1i0.862.343.133 (6)154
C6—H6···O1i0.932.703.601 (6)163
C19—H19···O1i0.932.643.388 (7)138
C9—H9···O2ii0.932.663.444 (10)143
C4—H4···O3ii0.932.653.273 (10)125
C18—H18···C7iii0.932.783.577 (15)1453.23
Only contacts with H···C < 3.0 Å were considered as potential intermolecular C—H···π interactions. H···Cg, represents the distance between the H atom and the centroid of the aromatic ring.

(I): i = -x+1,-y+2,-z+1; ii = -x+1,-y+1,-z+2; iii = -x+2,-y+1,-z+2. iv = x+1, y-1, z; v = x-1, y, z; vi = x, y+1, z;

(II): i = -x+2,-y+1,-z; ii = -x+1,-y+1,-z+1; iii = -x+2,-y+1,-z+1.
 

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