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Acta Cryst. (2008). E64, m177    [ doi:10.1107/S1600536807065634 ]

N'-Ferrocenyl-2-hydroxybenzohydrazide

Y. Xu, C.-L. Chen, J. Zhou and M.-X. Li

Abstract top

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.

Comment top

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.

Related literature top

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

Experimental top

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 top

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.

Computing details top

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

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level.
N'-Ferrocenyl-2-hydroxybenzohydrazide top
Crystal data top
[Fe(C5H5)(C13H11N2O3)]F000 = 1504
Mr = 364.18Dx = 1.628 Mg m−3
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 mm−1
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 top
Bruker SMART APEX CCD area-detector
diffractometer		2611 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 top
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 Å−3
230 parametersΔρmin = −0.34 e Å−3
3 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Fe(C5H5)(C13H11N2O3)]V = 2970.8 (8) Å3
Mr = 364.18Z = 8
Monoclinic, C2/cMo Kα
a = 20.680 (3) ŵ = 1.04 mm−1
b = 9.9673 (15) ÅT = 293 (2) K
c = 16.941 (3) Å0.20 × 0.18 × 0.16 mm
β = 121.704 (3)º
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		2611 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		1053 reflections with I > 2σ(I)
Tmin = 0.820, Tmax = 0.852Rint = 0.129
7479 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0493 restraints
wR(F2) = 0.086H atoms treated by a mixture of
independent and constrained refinement
S = 0.57Δρmax = 0.48 e Å−3
2611 reflectionsΔρmin = −0.34 e Å−3
230 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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) top
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, °) top
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, °) top
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.
Table 1
Hydrogen-bond geometry (Å, °) top
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.
Acknowledgements top

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

references
References top

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