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Acta Cryst. (2007). E63, m2961    [ doi:10.1107/S1600536807055407 ]

1,5:1',5'-Bis[1,1'-(ferrocene-1,1'-diyl)diethylidyne]dicarbonohydrazide dihydrate

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

Abstract top

In the title complex, [Fe2(C15H16N4O)2]·2H2O, two ferrocene units are bridged by two Schiff base linkers. This molecule lies on an inversion centre, and the asymmetric unit also contains a solvent water molecule. In the crystal structure, complexes and water molecules are connected through weak N-H...O, O-H...O, O-H...N and N-H...N hydrogen bonds.

Comment top

Much attention has been paid to the chemistry of ferrocene complexes because of their potential applications in material sciences, such as molecular sensors (Beer, 1992; Beer & Smith, 1997), molecular magnetic devices (Miller & Epstein, 1994) and nonlinear optical materials (Nguyen et al., 1999; Long, 1995). In continuation of our research work in the assembly and properties of ferrocene-containing Schiff base compounds (Li et al., 2006), we report here the crystal structure analysis of a bis-ferrocene Schiff base compound, (I).

The compound is a cyclic bis-ferrocene complex lying on an inversion centre. The asymmetric unit is completed with a lattice water molecule. The Fe—Cring bond lengths range from 2.024 (3) to 2.043 (3) Å (average: 2.034 Å) and are within the expected range (Seiler & Dunitz, 1979; Mammano et al., 1977). The average intra C≐C bond length and C≐ C≐C angle in cyclopentadienyl groups are 1.411 Å and 108°, which are similar to dimensions reported in the literature (Abuhijleh & Woods, 1992; Takusagawa & Koetzle, 1979). The cyclopentadienyl rings in each ferrocenyl fragment are planar and nearly parallel, with a dihedral angle of 3.7 ° at Fe1. The bond lengths N1—C11 and N4—C14 are within the normal range for C═N double bonds, while the N2—C13 and N3—C13 bond lengths suggest that they are single N—C bonds. In addition, the bond length C13═O1 is 1.216 (3) Å, consistent with a carbonyl functionality. Moreover, N1—N2 and N3—N4 bond distances are within the normal range for N—N single bonds. The two side chains are parallel by symmetry, with a torsion angle C11—C10···C4—C14i of about −61.6 ° [symmetry code: (i) −x, −y, −z].

In the crystal structure, molecules are connected by four different kinds of intra- and intermolecular hydrogen bonds. Besides the intramolecular N2—H2N···N4 and the intermolecular N3—H3N···O1ii interaction present in the ligand [symmetry code: (ii) −x, y, −z − 1/2], there are two hydrogen bonds involving the water molecule.

Related literature top

For related literature, see: Abuhijleh & Woods (1992); Beer (1992); Beer & Smith (1997); Li et al. (2006); Long (1995); Mammano et al. (1977); Miller & Epstein (1994); Nguyen et al. (1999); Seiler & Dunitz (1979); Takusagawa & Koetzle (1979).

Experimental top

All reagents were commercially available and of analytical grade. Diacetylferrocene (0.54 g, 2 mmol) and carbohydrazide (0.18 g, 2 mmol) were mixed in ethanol (15 ml). Five drops of acetic acid were added and the solution was refluxed for 4 h. Then, the solution was cooled to room temperature. Subsequently the dark-red solid formed was filtered off, washed with ethanol and dried in vacuo (yield: 96%). Analysis calculated for C30H36Fe2N8O4: C 52.60, H 5.26, N 16.36%; found: C 52.44, H 5.24, N 16.26%.

Refinement top

All H atoms bonded to C atoms were positioned geometrically and refined as riding to their carrier atoms, with C—H = 0.96–0.98 Å and Uiso(H) = 1.2Ueq(carrier C) for cyclopentadienyl and Uiso(H) = 1.5Ueq(carrier C) for methyl groups. H atoms for amine groups and water molecule were found in a difference map and refined with free coordinates and Uiso(H) = 1.2Ueq(carrier N) or Uiso(H) = 1.5Ueq(O1W).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom displacement ellipsoids drawn at the 50% probability level.
Bis(ferrocene-1,1'-diacetyl-carbohydrazide) dihydrate top
Crystal data top
[Fe2(C15H16N4O)2]·2H2OF000 = 1424
Mr = 684.37Dx = 1.523 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 398 reflections
a = 28.708 (4) Åθ = 1.7–28.1º
b = 7.9756 (11) ŵ = 1.02 mm−1
c = 15.305 (2) ÅT = 293 (2) K
β = 121.576 (2)ºIrregular, red
V = 2985.5 (7) Å30.20 × 0.18 × 0.16 mm
Z = 4
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		2636 independent reflections
Radiation source: fine-focus sealed tube1718 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.070
T = 293(2) Kθmax = 25.0º
0.3° wide ω scansθmin = 1.7º
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −22→34
Tmin = 0.822, Tmax = 0.853k = −9→9
7443 measured reflectionsl = −18→17
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)] = 0.041H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.076  w = 1/[σ2(Fo2) + (0.0303P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.81(Δ/σ)max < 0.001
2636 reflectionsΔρmax = 0.38 e Å−3
213 parametersΔρmin = −0.25 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Fe2(C15H16N4O)2]·2H2OV = 2985.5 (7) Å3
Mr = 684.37Z = 4
Monoclinic, C2/cMo Kα
a = 28.708 (4) ŵ = 1.02 mm−1
b = 7.9756 (11) ÅT = 293 (2) K
c = 15.305 (2) Å0.20 × 0.18 × 0.16 mm
β = 121.576 (2)º
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		2636 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		1718 reflections with I > 2σ(I)
Tmin = 0.822, Tmax = 0.853Rint = 0.070
7443 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.041213 parameters
wR(F2) = 0.076H atoms treated by a mixture of
independent and constrained refinement
S = 0.81Δρmax = 0.38 e Å−3
2636 reflectionsΔρmin = −0.25 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Fe10.177935 (16)0.15125 (6)0.29805 (3)0.03626 (15)
N10.05413 (9)0.3357 (3)0.05970 (17)0.0385 (6)
O10.03726 (8)0.4466 (3)−0.12140 (14)0.0466 (6)
C10.21068 (14)0.0616 (5)0.2179 (3)0.0588 (10)
H1A0.21700.12630.17060.071*
N20.00660 (10)0.3018 (3)−0.03320 (19)0.0403 (7)
H2N−0.0201 (12)0.258 (4)−0.033 (2)0.048*
C20.24803 (13)0.0413 (5)0.3234 (3)0.0577 (10)
H2A0.28480.09010.36240.069*
N3−0.04608 (10)0.3296 (3)−0.20789 (18)0.0414 (7)
H3N−0.0501 (12)0.371 (4)−0.264 (2)0.050*
C30.22351 (12)−0.0580 (4)0.3637 (3)0.0498 (9)
H3A0.2402−0.09090.43570.060*
N4−0.08668 (10)0.2442 (3)−0.20452 (18)0.0384 (6)
C40.16983 (12)−0.1025 (4)0.2821 (2)0.0400 (8)
C50.16302 (13)−0.0266 (4)0.1917 (2)0.0477 (9)
H5A0.1302−0.03380.12290.057*
C60.12439 (12)0.2452 (4)0.3353 (2)0.0392 (8)
H6A0.10120.17880.35150.047*
C70.17748 (13)0.3007 (4)0.4061 (2)0.0453 (9)
H7A0.19770.27970.48010.054*
C80.19695 (13)0.3893 (4)0.3529 (2)0.0473 (9)
H8A0.23300.44200.38330.057*
C90.15578 (12)0.3895 (4)0.2476 (2)0.0443 (9)
H9A0.15820.44300.19250.053*
C100.11016 (12)0.2996 (4)0.2359 (2)0.0365 (8)
C110.05932 (12)0.2640 (4)0.1388 (2)0.0356 (7)
C120.01811 (12)0.1501 (4)0.1399 (2)0.0523 (9)
H12A0.00570.06960.08550.079*
H12B−0.01240.21510.13030.079*
H12C0.03460.09280.20450.079*
C130.00185 (13)0.3665 (4)−0.1192 (2)0.0388 (8)
C14−0.12873 (13)0.1977 (4)−0.2894 (2)0.0400 (8)
C15−0.13729 (14)0.2308 (4)−0.3935 (2)0.0597 (10)
H15A−0.16910.1713−0.44450.090*
H15B−0.10590.1935−0.39480.090*
H15C−0.14240.3489−0.40770.090*
O1W0.11076 (12)0.6713 (4)0.03268 (19)0.0670 (8)
H1WB0.1098 (17)0.667 (6)0.082 (3)0.100*
H1WA0.0909 (16)0.601 (5)−0.007 (3)0.100*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0310 (3)0.0420 (3)0.0316 (3)−0.0025 (2)0.0135 (2)−0.0047 (2)
N10.0337 (15)0.0457 (16)0.0271 (14)−0.0024 (12)0.0098 (12)−0.0014 (13)
O10.0437 (14)0.0591 (15)0.0347 (13)−0.0169 (12)0.0190 (11)−0.0079 (11)
C10.058 (2)0.071 (3)0.065 (3)−0.013 (2)0.044 (2)−0.023 (2)
N20.0344 (17)0.0492 (19)0.0279 (14)−0.0059 (12)0.0099 (13)0.0005 (13)
C20.030 (2)0.066 (3)0.075 (3)−0.0046 (18)0.027 (2)−0.025 (2)
N30.0398 (16)0.0489 (18)0.0268 (15)−0.0068 (14)0.0115 (14)0.0002 (13)
C30.0325 (19)0.050 (2)0.048 (2)0.0086 (16)0.0080 (17)−0.0084 (18)
N40.0344 (16)0.0410 (16)0.0315 (15)−0.0029 (12)0.0115 (13)−0.0023 (12)
C40.038 (2)0.036 (2)0.036 (2)0.0024 (14)0.0127 (17)−0.0087 (14)
C50.046 (2)0.056 (2)0.040 (2)−0.0061 (17)0.0216 (17)−0.0167 (17)
C60.040 (2)0.047 (2)0.0307 (18)0.0049 (15)0.0182 (16)−0.0014 (15)
C70.049 (2)0.047 (2)0.0292 (18)0.0089 (16)0.0132 (17)−0.0038 (15)
C80.041 (2)0.044 (2)0.041 (2)−0.0066 (15)0.0112 (17)−0.0093 (16)
C90.042 (2)0.044 (2)0.0358 (19)−0.0049 (15)0.0128 (16)0.0078 (15)
C100.038 (2)0.041 (2)0.0254 (17)0.0064 (14)0.0130 (15)0.0015 (14)
C110.0341 (19)0.0357 (18)0.0328 (18)0.0046 (14)0.0146 (15)−0.0004 (15)
C120.043 (2)0.061 (2)0.045 (2)−0.0050 (18)0.0174 (17)0.0080 (18)
C130.043 (2)0.037 (2)0.0298 (18)0.0005 (16)0.0144 (16)−0.0053 (15)
C140.039 (2)0.0340 (19)0.0343 (19)0.0040 (14)0.0104 (16)−0.0012 (14)
C150.059 (2)0.063 (3)0.038 (2)−0.0139 (19)0.0119 (18)−0.0026 (18)
O1W0.0757 (19)0.076 (2)0.0496 (18)−0.0255 (14)0.0330 (16)−0.0168 (15)
Geometric parameters (Å, °) top
Fe1—C92.024 (3)N4—C141.280 (3)
Fe1—C12.026 (3)C4—C51.426 (4)
Fe1—C52.028 (3)C4—C14i1.456 (4)
Fe1—C82.032 (3)C5—H5A0.9800
Fe1—C32.032 (3)C6—C71.401 (4)
Fe1—C42.037 (3)C6—C101.421 (4)
Fe1—C22.037 (3)C6—H6A0.9800
Fe1—C102.038 (3)C7—C81.396 (4)
Fe1—C62.042 (3)C7—H7A0.9800
Fe1—C72.043 (3)C8—C91.414 (4)
N1—C111.275 (3)C8—H8A0.9800
N1—N21.387 (3)C9—C101.419 (4)
O1—C131.216 (3)C9—H9A0.9800
C1—C51.397 (4)C10—C111.465 (4)
C1—C21.403 (4)C11—C121.498 (4)
C1—H1A0.9800C12—H12A0.9600
N2—C131.352 (4)C12—H12B0.9600
N2—H2N0.84 (3)C12—H12C0.9600
C2—C31.399 (5)C14—C4i1.456 (4)
C2—H2A0.9800C14—C151.503 (4)
N3—C131.366 (4)C15—H15A0.9600
N3—N41.374 (3)C15—H15B0.9600
N3—H3N0.87 (3)C15—H15C0.9600
C3—C41.430 (4)O1W—H1WB0.78 (4)
C3—H3A0.9800O1W—H1WA0.80 (4)
C9—Fe1—C1104.65 (14)C4—C3—H3A125.8
C9—Fe1—C5117.27 (13)Fe1—C3—H3A125.8
C1—Fe1—C540.32 (12)C14—N4—N3118.2 (3)
C9—Fe1—C840.82 (11)C5—C4—C3106.2 (3)
C1—Fe1—C8118.07 (14)C5—C4—C14i126.2 (3)
C5—Fe1—C8152.04 (14)C3—C4—C14i127.5 (3)
C9—Fe1—C3162.16 (13)C5—C4—Fe169.12 (18)
C1—Fe1—C368.09 (15)C3—C4—Fe169.24 (17)
C5—Fe1—C368.48 (13)C14i—C4—Fe1123.7 (2)
C8—Fe1—C3126.80 (13)C1—C5—C4108.6 (3)
C9—Fe1—C4153.31 (12)C1—C5—Fe169.78 (18)
C1—Fe1—C468.71 (14)C4—C5—Fe169.81 (17)
C5—Fe1—C441.07 (12)C1—C5—H5A125.7
C8—Fe1—C4165.25 (12)C4—C5—H5A125.7
C3—Fe1—C441.15 (11)Fe1—C5—H5A125.7
C9—Fe1—C2123.95 (15)C7—C6—C10108.5 (3)
C1—Fe1—C240.40 (13)C7—C6—Fe170.02 (18)
C5—Fe1—C267.93 (13)C10—C6—Fe169.47 (17)
C8—Fe1—C2107.38 (14)C7—C6—H6A125.7
C3—Fe1—C240.22 (13)C10—C6—H6A125.7
C4—Fe1—C268.56 (13)Fe1—C6—H6A125.7
C9—Fe1—C1040.91 (12)C8—C7—C6108.3 (3)
C1—Fe1—C10123.67 (14)C8—C7—Fe169.50 (18)
C5—Fe1—C10106.42 (12)C6—C7—Fe169.87 (17)
C8—Fe1—C1068.56 (12)C8—C7—H7A125.8
C3—Fe1—C10156.62 (13)C6—C7—H7A125.8
C4—Fe1—C10119.98 (12)Fe1—C7—H7A125.8
C2—Fe1—C10160.94 (14)C7—C8—C9108.3 (3)
C9—Fe1—C668.27 (13)C7—C8—Fe170.42 (18)
C1—Fe1—C6162.62 (13)C9—C8—Fe169.30 (17)
C5—Fe1—C6127.40 (13)C7—C8—H8A125.8
C8—Fe1—C667.67 (13)C9—C8—H8A125.8
C3—Fe1—C6123.19 (14)Fe1—C8—H8A125.8
C4—Fe1—C6110.05 (13)C8—C9—C10108.0 (3)
C2—Fe1—C6156.61 (13)C8—C9—Fe169.88 (17)
C10—Fe1—C640.78 (11)C10—C9—Fe170.08 (17)
C9—Fe1—C768.12 (13)C8—C9—H9A126.0
C1—Fe1—C7153.75 (14)C10—C9—H9A126.0
C5—Fe1—C7165.66 (14)Fe1—C9—H9A126.0
C8—Fe1—C740.08 (12)C9—C10—C6106.9 (3)
C3—Fe1—C7110.74 (13)C9—C10—C11126.1 (3)
C4—Fe1—C7128.88 (13)C6—C10—C11127.0 (3)
C2—Fe1—C7121.40 (13)C9—C10—Fe169.02 (17)
C10—Fe1—C768.29 (12)C6—C10—Fe169.75 (16)
C6—Fe1—C740.11 (11)C11—C10—Fe1124.1 (2)
C11—N1—N2116.7 (3)N1—C11—C10115.8 (3)
C5—C1—C2108.4 (3)N1—C11—C12125.6 (3)
C5—C1—Fe169.90 (18)C10—C11—C12118.7 (3)
C2—C1—Fe170.23 (19)C11—C12—H12A109.5
C5—C1—H1A125.8C11—C12—H12B109.5
C2—C1—H1A125.8H12A—C12—H12B109.5
Fe1—C1—H1A125.8C11—C12—H12C109.5
C13—N2—N1117.8 (3)H12A—C12—H12C109.5
C13—N2—H2N122 (2)H12B—C12—H12C109.5
N1—N2—H2N119 (2)O1—C13—N2124.6 (3)
C3—C2—C1108.4 (3)O1—C13—N3120.5 (3)
C3—C2—Fe169.70 (18)N2—C13—N3114.9 (3)
C1—C2—Fe169.38 (19)N4—C14—C4i116.4 (3)
C3—C2—H2A125.8N4—C14—C15124.6 (3)
C1—C2—H2A125.8C4i—C14—C15118.9 (3)
Fe1—C2—H2A125.8C14—C15—H15A109.5
C13—N3—N4120.1 (3)C14—C15—H15B109.5
C13—N3—H3N116 (2)H15A—C15—H15B109.5
N4—N3—H3N123 (2)C14—C15—H15C109.5
C2—C3—C4108.4 (3)H15A—C15—H15C109.5
C2—C3—Fe170.1 (2)H15B—C15—H15C109.5
C4—C3—Fe169.61 (17)H1WB—O1W—H1WA109 (4)
C2—C3—H3A125.8
Symmetry codes: (i) −x, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···N40.84 (3)2.30 (3)2.628 (3)104 (2)
N3—H3N···O1ii0.87 (3)2.06 (3)2.908 (3)164 (3)
O1W—H1WA···O10.80 (4)2.04 (4)2.831 (3)172 (4)
O1W—H1WB···N4iii0.78 (4)2.39 (4)3.123 (4)156 (4)
Symmetry codes: (ii) −x, y, −z−1/2; (iii) −x, −y+1, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···N40.84 (3)2.30 (3)2.628 (3)104 (2)
N3—H3N···O1i0.87 (3)2.06 (3)2.908 (3)164 (3)
O1W—H1WA···O10.80 (4)2.04 (4)2.831 (3)172 (4)
O1W—H1WB···N4ii0.78 (4)2.39 (4)3.123 (4)156 (4)
Symmetry codes: (i) −x, y, −z−1/2; (ii) −x, −y+1, −z.
Acknowledgements top

This work received financial support from the Natural Science Foundation of Henan Province (grant No. 0611011900) and the Foundation of Educational Department of Henan Province (grant No. 2007150012).

references
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