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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): m177.
Published online 2007 December 12. doi:  10.1107/S1600536807065634
PMCID: PMC2915112

N′-Ferrocenyl-2-hydroxy­benzohydrazide

Abstract

The title complex, [Fe(C5H5)(C13H11N2O3)], was prepared via self-assembly using ferrocenyl hydrazide and ethyl salicylate. The compound is potentially a tridentate ferrocene-based ligand. The conformation of the mol­ecule allows the formation of an intra­molecular N—H(...)O hydrogen bond involving the hydroxyl group. The CONHNHCO unit and the rings bonded to it are nearly coplanar. The crystal structure is stabilized by inter­molecular O—H(...)O(carbon­yl) and N—H(...)O(carbon­yl) hydrogen bonds.

Related literature

For related literature about applications of ferrocene complexes, see: Beer (1992 [triangle]); Beer & Smith (1997 [triangle]); Long (1995 [triangle]); Miller & Epstein (1994 [triangle]); Nguyen et al. (1999 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0m177-scheme1.jpg

Experimental

Crystal data

  • [Fe(C5H5)(C13H11N2O3)]
  • M r = 364.18
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m177-efi1.jpg
  • a = 20.680 (3) Å
  • b = 9.9673 (15) Å
  • c = 16.941 (3) Å
  • β = 121.704 (3)°
  • V = 2970.8 (8) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 1.03 mm−1
  • T = 293 (2) K
  • 0.20 × 0.18 × 0.16 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.820, T max = 0.852
  • 7479 measured reflections
  • 2611 independent reflections
  • 1053 reflections with I > 2σ(I)
  • R int = 0.129

Refinement

  • R[F 2 > 2σ(F 2)] = 0.049
  • wR(F 2) = 0.086
  • S = 0.57
  • 2611 reflections
  • 230 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.48 e Å−3
  • Δρmin = −0.34 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT-Plus (Bruker, 2000 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a [triangle]); molecular graphics: SHELXTL (Sheldrick, 1997b [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807065634/bh2153sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807065634/bh2153Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was financially supported by the Foundation of the Educational Department of Henan Province (No. 2007150012).

supplementary crystallographic information

Comment

The synthesis, isolation and characterization of ferrocene in 1951 marked an important milestone in the evolution of modern organometallic chemistry. Potential applications in material sciences, such as molecular sensors (Beer, 1992; Beer & Smith, 1997), molecular magnetic materials (Miller & Epstein, 1994), and nonlinear optical materials (Nguyen et al., 1999; Long, 1995) attracted much attention. We report here the crystal structure of the title compound, (I), a new ferrocene-based complex (Fig. 1).

The title compound belongs to space group C2/c. The bond lengths O1?C11 and O2?C12 are 1.240 (5) and 1.233 (4) Å, respectively, as excepted for double bonds. The bond length O3—C18, 1.349 (5) Å, corresponds to a single bond. The N1—C11 and N2—C12 bond distances are 1.340 (5) and 1.343 (5) Å, respectively, which make clear they are in the normal range for N—C single bonds. The bond length N1—N2 = 1.381 (4) Å is also consistent with a single N—N bond. An intramolecular N2—H2B···O3 hydrogen bond is observed in the molecular structure.

In the crystal, molecules are connected by intermolecular hydrogen bonds involving carbonyl O atoms O2 and O3 as acceptor and N—H or O—H groups as donors.

Experimental

All reagents were commercially available and of analytical grade. Ferrocenyl hydrazide (1.22 g, 5 mmol) and ethyl salicylate (0.83 g, 5 mmol) were mixed in ethanol and refluxed for 7 h. The resulting red solid was filtered, washed with ethanol and dried under reduced pressure. Anal. Calc. for C18H16FeN2O3: C 59.37, H 4.43, N 7.69%. Found: C 59.48, H 4.31, N 7.52%.

Refinement

H atoms bonded to C atoms were positioned geometrically and refined as riding on their carrier atoms, with C—H bond lengths fixed to 0.93 (benzene ring) or 0.98 Å (Cp rings), and Uiso(H) = 1.2Ueq(carrier C). H atoms bonded to heteroatoms N1, N2 and O3 were located in a difference map and were freely refined as isotropic atoms, with restricted bond lengths: N—H = 0.87 (1) Å and O—H = 0.82 (1) Å.

Figures

Fig. 1.
The molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level.

Crystal data

[Fe(C5H5)(C13H11N2O3)]F000 = 1504
Mr = 364.18Dx = 1.628 Mg m3
Monoclinic, C2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 397 reflections
a = 20.680 (3) Åθ = 2.3–28.0º
b = 9.9673 (15) ŵ = 1.04 mm1
c = 16.941 (3) ÅT = 293 (2) K
β = 121.704 (3)ºBlock, red
V = 2970.8 (8) Å30.20 × 0.18 × 0.16 mm
Z = 8

Data collection

Bruker SMART APEX CCD area-detector diffractometer2611 independent reflections
Radiation source: fine-focus sealed tube1053 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.129
T = 293(2) Kθmax = 25.0º
0.3° wide ω scansθmin = 2.3º
Absorption correction: multi-scan(SADABS; Bruker, 2000)h = −24→18
Tmin = 0.820, Tmax = 0.852k = −11→11
7479 measured reflectionsl = −20→20

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.086  w = 1/[σ2(Fo2) + (0.02P)2] where P = (Fo2 + 2Fc2)/3
S = 0.57(Δ/σ)max < 0.001
2611 reflectionsΔρmax = 0.48 e Å3
230 parametersΔρmin = −0.34 e Å3
3 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

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

xyzUiso*/Ueq
Fe10.94540 (4)0.77786 (6)0.86429 (4)0.03507 (19)
O10.83150 (16)0.4726 (3)0.79890 (19)0.0410 (9)
O20.92978 (15)0.2865 (3)0.63670 (17)0.0437 (8)
O30.75985 (16)0.1341 (3)0.6733 (2)0.0417 (8)
H3B0.7289 (10)0.099 (3)0.683 (2)0.060 (9)*
N10.9235 (2)0.3971 (3)0.7765 (2)0.0308 (10)
H1B0.9700 (8)0.387 (4)0.790 (2)0.058 (16)*
N20.87479 (18)0.2969 (4)0.7205 (2)0.0340 (9)
H2B0.8365 (9)0.276 (3)0.7248 (17)0.034 (5)*
C10.8498 (3)0.8152 (5)0.7406 (3)0.0489 (14)
H1A0.81510.74730.69700.059*
C20.8456 (3)0.8730 (4)0.8133 (3)0.0432 (13)
H2A0.80710.85300.82870.052*
C30.9052 (3)0.9656 (4)0.8594 (3)0.0451 (14)
H3A0.91611.02160.91260.054*
C40.9463 (3)0.9629 (4)0.8144 (3)0.0454 (14)
H4A0.99191.01600.83220.055*
C50.9131 (3)0.8688 (5)0.7419 (3)0.0529 (15)
H5A0.93020.84620.69950.064*
C61.0186 (3)0.6269 (4)0.8847 (3)0.0376 (13)
H6A1.03600.60110.84300.045*
C71.0541 (2)0.7191 (4)0.9589 (3)0.0415 (13)
H7A1.10020.77060.97670.050*
C81.0106 (3)0.7288 (4)1.0008 (3)0.0444 (13)
H8A1.02160.78651.05330.053*
C90.9489 (3)0.6410 (4)0.9538 (3)0.0337 (12)
H9A0.90930.62610.96810.040*
C100.9534 (3)0.5776 (4)0.8825 (3)0.0304 (12)
C110.8976 (3)0.4797 (4)0.8161 (3)0.0302 (12)
C120.8800 (2)0.2468 (4)0.6504 (3)0.0272 (11)
C130.8246 (2)0.1417 (4)0.5917 (3)0.0269 (11)
C140.8305 (3)0.0933 (4)0.5195 (3)0.0388 (13)
H14A0.86740.12840.50970.047*
C150.7828 (3)−0.0064 (4)0.4615 (3)0.0490 (15)
H15A0.7875−0.03720.41290.059*
C160.7285 (3)−0.0601 (4)0.4754 (3)0.0422 (14)
H16A0.6968−0.12830.43710.051*
C170.7214 (2)−0.0123 (4)0.5463 (3)0.0375 (13)
H17A0.6845−0.04850.55560.045*
C180.7675 (3)0.0877 (4)0.6038 (3)0.0300 (12)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Fe10.0332 (4)0.0339 (3)0.0390 (4)0.0019 (4)0.0195 (3)−0.0003 (4)
O10.0258 (18)0.0442 (19)0.058 (2)−0.0049 (17)0.0251 (17)−0.0128 (15)
O20.0409 (17)0.061 (2)0.0440 (17)−0.0154 (18)0.0328 (15)−0.0120 (16)
O30.0369 (18)0.052 (2)0.0518 (19)−0.0128 (17)0.0345 (16)−0.0080 (16)
N10.026 (2)0.029 (2)0.043 (2)0.000 (2)0.022 (2)−0.0085 (17)
N20.029 (2)0.038 (2)0.043 (2)−0.005 (2)0.0246 (18)−0.0056 (19)
C10.043 (3)0.058 (3)0.031 (3)0.006 (3)0.010 (3)0.001 (2)
C20.044 (3)0.037 (3)0.056 (3)0.013 (3)0.031 (3)0.010 (2)
C30.049 (3)0.031 (3)0.059 (3)−0.007 (3)0.031 (3)−0.007 (2)
C40.042 (3)0.036 (3)0.066 (4)0.002 (3)0.034 (3)0.011 (3)
C50.051 (3)0.069 (4)0.048 (3)0.019 (3)0.032 (3)0.021 (3)
C60.033 (3)0.044 (3)0.033 (3)0.010 (3)0.016 (2)−0.003 (2)
C70.021 (2)0.033 (3)0.048 (3)0.011 (3)0.002 (2)0.005 (3)
C80.049 (3)0.039 (3)0.040 (3)0.000 (3)0.020 (3)−0.006 (2)
C90.039 (3)0.029 (3)0.038 (3)0.002 (2)0.024 (2)−0.002 (2)
C100.028 (3)0.027 (2)0.037 (3)−0.001 (2)0.018 (2)−0.005 (2)
C110.033 (3)0.028 (3)0.027 (3)0.001 (3)0.013 (2)0.003 (2)
C120.024 (2)0.030 (3)0.031 (2)0.005 (2)0.016 (2)0.008 (2)
C130.025 (3)0.023 (2)0.032 (3)0.000 (2)0.014 (2)0.002 (2)
C140.038 (3)0.042 (3)0.046 (3)0.000 (3)0.028 (3)0.000 (2)
C150.052 (4)0.056 (3)0.045 (3)−0.006 (3)0.030 (3)−0.014 (3)
C160.038 (3)0.043 (3)0.044 (3)−0.017 (3)0.021 (3)−0.019 (2)
C170.033 (3)0.040 (3)0.041 (3)−0.012 (2)0.020 (3)−0.007 (2)
C180.034 (3)0.030 (3)0.031 (3)0.005 (2)0.020 (2)0.002 (2)

Geometric parameters (Å, °)

Fe1—C22.008 (4)C3—H3A0.9800
Fe1—C92.013 (4)C4—C51.405 (6)
Fe1—C102.014 (4)C4—H4A0.9800
Fe1—C12.021 (4)C5—H5A0.9800
Fe1—C52.028 (5)C6—C71.412 (5)
Fe1—C62.031 (4)C6—C101.416 (6)
Fe1—C32.031 (4)C6—H6A0.9800
Fe1—C82.031 (4)C7—C81.412 (6)
Fe1—C42.033 (4)C7—H7A0.9800
Fe1—C72.045 (4)C8—C91.400 (5)
O1—C111.240 (5)C8—H8A0.9800
O2—C121.233 (4)C9—C101.410 (5)
O3—C181.349 (5)C9—H9A0.9800
O3—H3B0.822 (10)C10—C111.478 (5)
N1—C111.340 (5)C12—C131.484 (5)
N1—N21.381 (4)C13—C141.379 (6)
N1—H1B0.871 (10)C13—C181.407 (6)
N2—C121.343 (5)C14—C151.381 (5)
N2—H2B0.860 (10)C14—H14A0.9300
C1—C51.402 (6)C15—C161.373 (6)
C1—C21.404 (6)C15—H15A0.9300
C1—H1A0.9800C16—C171.370 (6)
C2—C31.403 (6)C16—H16A0.9300
C2—H2A0.9800C17—C181.369 (5)
C3—C41.410 (6)C17—H17A0.9300
C2—Fe1—C9105.43 (18)C4—C3—H3A126.6
C2—Fe1—C10121.17 (19)Fe1—C3—H3A126.6
C9—Fe1—C1041.01 (16)C5—C4—C3109.2 (4)
C2—Fe1—C140.79 (16)C5—C4—Fe169.5 (3)
C9—Fe1—C1122.31 (19)C3—C4—Fe169.6 (3)
C10—Fe1—C1107.34 (18)C5—C4—H4A125.4
C2—Fe1—C568.7 (2)C3—C4—H4A125.4
C9—Fe1—C5159.32 (19)Fe1—C4—H4A125.4
C10—Fe1—C5123.77 (19)C1—C5—C4107.0 (5)
C1—Fe1—C540.53 (17)C1—C5—Fe169.5 (3)
C2—Fe1—C6158.24 (18)C4—C5—Fe170.0 (3)
C9—Fe1—C668.96 (18)C1—C5—H5A126.5
C10—Fe1—C640.98 (16)C4—C5—H5A126.5
C1—Fe1—C6123.23 (18)Fe1—C5—H5A126.5
C5—Fe1—C6108.72 (19)C7—C6—C10107.0 (4)
C2—Fe1—C340.66 (16)C7—C6—Fe170.3 (2)
C9—Fe1—C3120.45 (18)C10—C6—Fe168.9 (2)
C10—Fe1—C3156.7 (2)C7—C6—H6A126.5
C1—Fe1—C368.42 (18)C10—C6—H6A126.5
C5—Fe1—C368.83 (19)Fe1—C6—H6A126.5
C6—Fe1—C3160.36 (19)C8—C7—C6108.7 (4)
C2—Fe1—C8121.38 (19)C8—C7—Fe169.2 (2)
C9—Fe1—C840.51 (16)C6—C7—Fe169.2 (2)
C10—Fe1—C868.62 (17)C8—C7—H7A125.6
C1—Fe1—C8158.0 (2)C6—C7—H7A125.6
C5—Fe1—C8159.5 (2)Fe1—C7—H7A125.6
C6—Fe1—C868.81 (18)C9—C8—C7107.6 (4)
C3—Fe1—C8106.29 (19)C9—C8—Fe169.0 (2)
C2—Fe1—C467.96 (18)C7—C8—Fe170.2 (2)
C9—Fe1—C4157.47 (19)C9—C8—H8A126.2
C10—Fe1—C4160.9 (2)C7—C8—H8A126.2
C1—Fe1—C467.63 (19)Fe1—C8—H8A126.2
C5—Fe1—C440.48 (17)C8—C9—C10108.4 (4)
C6—Fe1—C4125.03 (19)C8—C9—Fe170.5 (2)
C3—Fe1—C440.59 (17)C10—C9—Fe169.5 (2)
C8—Fe1—C4123.09 (19)C8—C9—H9A125.8
C2—Fe1—C7158.59 (19)C10—C9—H9A125.8
C9—Fe1—C768.03 (18)Fe1—C9—H9A125.8
C10—Fe1—C768.14 (18)C9—C10—C6108.2 (4)
C1—Fe1—C7159.89 (19)C9—C10—C11124.8 (4)
C5—Fe1—C7124.4 (2)C6—C10—C11127.0 (4)
C6—Fe1—C740.55 (15)C9—C10—Fe169.5 (2)
C3—Fe1—C7123.62 (18)C6—C10—Fe170.2 (2)
C8—Fe1—C740.54 (16)C11—C10—Fe1124.7 (3)
C4—Fe1—C7109.83 (19)O1—C11—N1121.9 (4)
C18—O3—H3B120 (3)O1—C11—C10122.7 (4)
C11—N1—N2116.7 (4)N1—C11—C10115.3 (4)
C11—N1—H1B128 (2)O2—C12—N2120.7 (4)
N2—N1—H1B114 (2)O2—C12—C13121.8 (4)
C12—N2—N1120.5 (3)N2—C12—C13117.6 (4)
C12—N2—H2B119 (2)C14—C13—C18117.9 (4)
N1—N2—H2B120 (2)C14—C13—C12116.4 (4)
C5—C1—C2108.5 (4)C18—C13—C12125.7 (4)
C5—C1—Fe170.0 (3)C13—C14—C15121.4 (5)
C2—C1—Fe169.1 (3)C13—C14—H14A119.3
C5—C1—H1A125.7C15—C14—H14A119.3
C2—C1—H1A125.7C16—C15—C14120.1 (5)
Fe1—C1—H1A125.7C16—C15—H15A120.0
C3—C2—C1108.5 (4)C14—C15—H15A120.0
C3—C2—Fe170.6 (3)C17—C16—C15119.3 (4)
C1—C2—Fe170.1 (3)C17—C16—H16A120.3
C3—C2—H2A125.8C15—C16—H16A120.3
C1—C2—H2A125.8C18—C17—C16121.4 (4)
Fe1—C2—H2A125.8C18—C17—H17A119.3
C2—C3—C4106.8 (4)C16—C17—H17A119.3
C2—C3—Fe168.8 (2)O3—C18—C17120.8 (4)
C4—C3—Fe169.8 (3)O3—C18—C13119.2 (4)
C2—C3—H3A126.6C17—C18—C13120.0 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2B···O30.860 (10)1.95 (2)2.631 (4)135 (3)
O3—H3B···O1i0.822 (10)1.908 (15)2.705 (4)163 (4)
N1—H1B···O2ii0.871 (10)2.03 (2)2.810 (4)148 (4)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BH2153).

References

  • Beer, P. D. (1992). Adv. Inorg. Chem.39, 79–157.
  • Beer, P. D. & Smith, D. K. (1997). Prog. Inorg. Chem.46, 1–8.
  • Bruker (2000). SMART (Version 5.054), SAINT-Plus (Version 6.22) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.
  • Long, N. J. (1995). Angew. Chem. Int. Ed. Engl.34, 21–38.
  • Miller, J. S. & Epstein, A. J. (1994). Angew. Chem. Int. Ed. Engl.33, 385–415.
  • Nguyen, P., Gómez-Elipe, P. & Manners, I. (1999). Chem. Rev.99, 1515–1548. [PubMed]
  • Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97 University of Göttingen, Germany.
  • Sheldrick, G. M. (1997b). SHELXTL Bruker AXS Inc., Madison, Wisconsin, USA.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography