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

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.041
• wR factor = 0.076
• Data-to-parameter ratio = 12.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O1     -   C13     ..       5.63 su
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Fe1         (3)       3.93

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

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—C_ring 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

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).

S2. Experimental

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%.

S3. Refinement

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 U_iso(H) = 1.2U_eq(carrier C) for cyclopentadienyl and U_iso(H) = 1.5U_eq(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 U_iso(H) = 1.2U_eq(carrier N) or U_iso(H) = 1.5U_eq(O1W).

Computing details

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

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

Bis(ferrocene-1,1'-diacetyl-carbohydrazide) dihydrate

Crystal data

[Fe2(C15H16N4O)2]·2H2O	F(000) = 1424
Mr = 684.37	Dx = 1.523 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 398 reflections
a = 28.708 (4) Å	θ = 1.7–28.1°
b = 7.9756 (11) Å	µ = 1.02 mm^−1
c = 15.305 (2) Å	T = 293 K
β = 121.576 (2)°	Irregular, red
V = 2985.5 (7) Å^3	0.20 × 0.18 × 0.16 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2636 independent reflections
Radiation source: fine-focus sealed tube	1718 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.070
0.3° wide ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −22→34
Tmin = 0.822, Tmax = 0.853	k = −9→9
7443 measured reflections	l = −18→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 0.81	w = 1/[σ^2(Fo^2) + (0.0303P)^2] where P = (Fo^2 + 2Fc^2)/3
2636 reflections	(Δ/σ)max < 0.001
213 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

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

	x	y	z	Uiso*/Ueq
Fe1	0.177935 (16)	0.15125 (6)	0.29805 (3)	0.03626 (15)
N1	0.05413 (9)	0.3357 (3)	0.05970 (17)	0.0385 (6)
O1	0.03726 (8)	0.4466 (3)	−0.12140 (14)	0.0466 (6)
C1	0.21068 (14)	0.0616 (5)	0.2179 (3)	0.0588 (10)
H1A	0.2170	0.1263	0.1706	0.071*
N2	0.00660 (10)	0.3018 (3)	−0.03320 (19)	0.0403 (7)
H2N	−0.0201 (12)	0.258 (4)	−0.033 (2)	0.048*
C2	0.24803 (13)	0.0413 (5)	0.3234 (3)	0.0577 (10)
H2A	0.2848	0.0901	0.3624	0.069*
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*
C3	0.22351 (12)	−0.0580 (4)	0.3637 (3)	0.0498 (9)
H3A	0.2402	−0.0909	0.4357	0.060*
N4	−0.08668 (10)	0.2442 (3)	−0.20452 (18)	0.0384 (6)
C4	0.16983 (12)	−0.1025 (4)	0.2821 (2)	0.0400 (8)
C5	0.16302 (13)	−0.0266 (4)	0.1917 (2)	0.0477 (9)
H5A	0.1302	−0.0338	0.1229	0.057*
C6	0.12439 (12)	0.2452 (4)	0.3353 (2)	0.0392 (8)
H6A	0.1012	0.1788	0.3515	0.047*
C7	0.17748 (13)	0.3007 (4)	0.4061 (2)	0.0453 (9)
H7A	0.1977	0.2797	0.4801	0.054*
C8	0.19695 (13)	0.3893 (4)	0.3529 (2)	0.0473 (9)
H8A	0.2330	0.4420	0.3833	0.057*
C9	0.15578 (12)	0.3895 (4)	0.2476 (2)	0.0443 (9)
H9A	0.1582	0.4430	0.1925	0.053*
C10	0.11016 (12)	0.2996 (4)	0.2359 (2)	0.0365 (8)
C11	0.05932 (12)	0.2640 (4)	0.1388 (2)	0.0356 (7)
C12	0.01811 (12)	0.1501 (4)	0.1399 (2)	0.0523 (9)
H12A	0.0057	0.0696	0.0855	0.079*
H12B	−0.0124	0.2151	0.1303	0.079*
H12C	0.0346	0.0928	0.2045	0.079*
C13	0.00185 (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	−0.1691	0.1713	−0.4445	0.090*
H15B	−0.1059	0.1935	−0.3948	0.090*
H15C	−0.1424	0.3489	−0.4077	0.090*
O1W	0.11076 (12)	0.6713 (4)	0.03268 (19)	0.0670 (8)
H1WB	0.1098 (17)	0.667 (6)	0.082 (3)	0.100*
H1WA	0.0909 (16)	0.601 (5)	−0.007 (3)	0.100*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0310 (3)	0.0420 (3)	0.0316 (3)	−0.0025 (2)	0.0135 (2)	−0.0047 (2)
N1	0.0337 (15)	0.0457 (16)	0.0271 (14)	−0.0024 (12)	0.0098 (12)	−0.0014 (13)
O1	0.0437 (14)	0.0591 (15)	0.0347 (13)	−0.0169 (12)	0.0190 (11)	−0.0079 (11)
C1	0.058 (2)	0.071 (3)	0.065 (3)	−0.013 (2)	0.044 (2)	−0.023 (2)
N2	0.0344 (17)	0.0492 (19)	0.0279 (14)	−0.0059 (12)	0.0099 (13)	0.0005 (13)
C2	0.030 (2)	0.066 (3)	0.075 (3)	−0.0046 (18)	0.027 (2)	−0.025 (2)
N3	0.0398 (16)	0.0489 (18)	0.0268 (15)	−0.0068 (14)	0.0115 (14)	0.0002 (13)
C3	0.0325 (19)	0.050 (2)	0.048 (2)	0.0086 (16)	0.0080 (17)	−0.0084 (18)
N4	0.0344 (16)	0.0410 (16)	0.0315 (15)	−0.0029 (12)	0.0115 (13)	−0.0023 (12)
C4	0.038 (2)	0.036 (2)	0.036 (2)	0.0024 (14)	0.0127 (17)	−0.0087 (14)
C5	0.046 (2)	0.056 (2)	0.040 (2)	−0.0061 (17)	0.0216 (17)	−0.0167 (17)
C6	0.040 (2)	0.047 (2)	0.0307 (18)	0.0049 (15)	0.0182 (16)	−0.0014 (15)
C7	0.049 (2)	0.047 (2)	0.0292 (18)	0.0089 (16)	0.0132 (17)	−0.0038 (15)
C8	0.041 (2)	0.044 (2)	0.041 (2)	−0.0066 (15)	0.0112 (17)	−0.0093 (16)
C9	0.042 (2)	0.044 (2)	0.0358 (19)	−0.0049 (15)	0.0128 (16)	0.0078 (15)
C10	0.038 (2)	0.041 (2)	0.0254 (17)	0.0064 (14)	0.0130 (15)	0.0015 (14)
C11	0.0341 (19)	0.0357 (18)	0.0328 (18)	0.0046 (14)	0.0146 (15)	−0.0004 (15)
C12	0.043 (2)	0.061 (2)	0.045 (2)	−0.0050 (18)	0.0174 (17)	0.0080 (18)
C13	0.043 (2)	0.037 (2)	0.0298 (18)	0.0005 (16)	0.0144 (16)	−0.0053 (15)
C14	0.039 (2)	0.0340 (19)	0.0343 (19)	0.0040 (14)	0.0104 (16)	−0.0012 (14)
C15	0.059 (2)	0.063 (3)	0.038 (2)	−0.0139 (19)	0.0119 (18)	−0.0026 (18)
O1W	0.0757 (19)	0.076 (2)	0.0496 (18)	−0.0255 (14)	0.0330 (16)	−0.0168 (15)

Geometric parameters (Å, º)

Fe1—C9	2.024 (3)	N4—C14	1.280 (3)
Fe1—C1	2.026 (3)	C4—C5	1.426 (4)
Fe1—C5	2.028 (3)	C4—C14^i	1.456 (4)
Fe1—C8	2.032 (3)	C5—H5A	0.9800
Fe1—C3	2.032 (3)	C6—C7	1.401 (4)
Fe1—C4	2.037 (3)	C6—C10	1.421 (4)
Fe1—C2	2.037 (3)	C6—H6A	0.9800
Fe1—C10	2.038 (3)	C7—C8	1.396 (4)
Fe1—C6	2.042 (3)	C7—H7A	0.9800
Fe1—C7	2.043 (3)	C8—C9	1.414 (4)
N1—C11	1.275 (3)	C8—H8A	0.9800
N1—N2	1.387 (3)	C9—C10	1.419 (4)
O1—C13	1.216 (3)	C9—H9A	0.9800
C1—C5	1.397 (4)	C10—C11	1.465 (4)
C1—C2	1.403 (4)	C11—C12	1.498 (4)
C1—H1A	0.9800	C12—H12A	0.9600
N2—C13	1.352 (4)	C12—H12B	0.9600
N2—H2N	0.84 (3)	C12—H12C	0.9600
C2—C3	1.399 (5)	C14—C4^i	1.456 (4)
C2—H2A	0.9800	C14—C15	1.503 (4)
N3—C13	1.366 (4)	C15—H15A	0.9600
N3—N4	1.374 (3)	C15—H15B	0.9600
N3—H3N	0.87 (3)	C15—H15C	0.9600
C3—C4	1.430 (4)	O1W—H1WB	0.78 (4)
C3—H3A	0.9800	O1W—H1WA	0.80 (4)
C9—Fe1—C1	104.65 (14)	C4—C3—H3A	125.8
C9—Fe1—C5	117.27 (13)	Fe1—C3—H3A	125.8
C1—Fe1—C5	40.32 (12)	C14—N4—N3	118.2 (3)
C9—Fe1—C8	40.82 (11)	C5—C4—C3	106.2 (3)
C1—Fe1—C8	118.07 (14)	C5—C4—C14^i	126.2 (3)
C5—Fe1—C8	152.04 (14)	C3—C4—C14^i	127.5 (3)
C9—Fe1—C3	162.16 (13)	C5—C4—Fe1	69.12 (18)
C1—Fe1—C3	68.09 (15)	C3—C4—Fe1	69.24 (17)
C5—Fe1—C3	68.48 (13)	C14^i—C4—Fe1	123.7 (2)
C8—Fe1—C3	126.80 (13)	C1—C5—C4	108.6 (3)
C9—Fe1—C4	153.31 (12)	C1—C5—Fe1	69.78 (18)
C1—Fe1—C4	68.71 (14)	C4—C5—Fe1	69.81 (17)
C5—Fe1—C4	41.07 (12)	C1—C5—H5A	125.7
C8—Fe1—C4	165.25 (12)	C4—C5—H5A	125.7
C3—Fe1—C4	41.15 (11)	Fe1—C5—H5A	125.7
C9—Fe1—C2	123.95 (15)	C7—C6—C10	108.5 (3)
C1—Fe1—C2	40.40 (13)	C7—C6—Fe1	70.02 (18)
C5—Fe1—C2	67.93 (13)	C10—C6—Fe1	69.47 (17)
C8—Fe1—C2	107.38 (14)	C7—C6—H6A	125.7
C3—Fe1—C2	40.22 (13)	C10—C6—H6A	125.7
C4—Fe1—C2	68.56 (13)	Fe1—C6—H6A	125.7
C9—Fe1—C10	40.91 (12)	C8—C7—C6	108.3 (3)
C1—Fe1—C10	123.67 (14)	C8—C7—Fe1	69.50 (18)
C5—Fe1—C10	106.42 (12)	C6—C7—Fe1	69.87 (17)
C8—Fe1—C10	68.56 (12)	C8—C7—H7A	125.8
C3—Fe1—C10	156.62 (13)	C6—C7—H7A	125.8
C4—Fe1—C10	119.98 (12)	Fe1—C7—H7A	125.8
C2—Fe1—C10	160.94 (14)	C7—C8—C9	108.3 (3)
C9—Fe1—C6	68.27 (13)	C7—C8—Fe1	70.42 (18)
C1—Fe1—C6	162.62 (13)	C9—C8—Fe1	69.30 (17)
C5—Fe1—C6	127.40 (13)	C7—C8—H8A	125.8
C8—Fe1—C6	67.67 (13)	C9—C8—H8A	125.8
C3—Fe1—C6	123.19 (14)	Fe1—C8—H8A	125.8
C4—Fe1—C6	110.05 (13)	C8—C9—C10	108.0 (3)
C2—Fe1—C6	156.61 (13)	C8—C9—Fe1	69.88 (17)
C10—Fe1—C6	40.78 (11)	C10—C9—Fe1	70.08 (17)
C9—Fe1—C7	68.12 (13)	C8—C9—H9A	126.0
C1—Fe1—C7	153.75 (14)	C10—C9—H9A	126.0
C5—Fe1—C7	165.66 (14)	Fe1—C9—H9A	126.0
C8—Fe1—C7	40.08 (12)	C9—C10—C6	106.9 (3)
C3—Fe1—C7	110.74 (13)	C9—C10—C11	126.1 (3)
C4—Fe1—C7	128.88 (13)	C6—C10—C11	127.0 (3)
C2—Fe1—C7	121.40 (13)	C9—C10—Fe1	69.02 (17)
C10—Fe1—C7	68.29 (12)	C6—C10—Fe1	69.75 (16)
C6—Fe1—C7	40.11 (11)	C11—C10—Fe1	124.1 (2)
C11—N1—N2	116.7 (3)	N1—C11—C10	115.8 (3)
C5—C1—C2	108.4 (3)	N1—C11—C12	125.6 (3)
C5—C1—Fe1	69.90 (18)	C10—C11—C12	118.7 (3)
C2—C1—Fe1	70.23 (19)	C11—C12—H12A	109.5
C5—C1—H1A	125.8	C11—C12—H12B	109.5
C2—C1—H1A	125.8	H12A—C12—H12B	109.5
Fe1—C1—H1A	125.8	C11—C12—H12C	109.5
C13—N2—N1	117.8 (3)	H12A—C12—H12C	109.5
C13—N2—H2N	122 (2)	H12B—C12—H12C	109.5
N1—N2—H2N	119 (2)	O1—C13—N2	124.6 (3)
C3—C2—C1	108.4 (3)	O1—C13—N3	120.5 (3)
C3—C2—Fe1	69.70 (18)	N2—C13—N3	114.9 (3)
C1—C2—Fe1	69.38 (19)	N4—C14—C4^i	116.4 (3)
C3—C2—H2A	125.8	N4—C14—C15	124.6 (3)
C1—C2—H2A	125.8	C4^i—C14—C15	118.9 (3)
Fe1—C2—H2A	125.8	C14—C15—H15A	109.5
C13—N3—N4	120.1 (3)	C14—C15—H15B	109.5
C13—N3—H3N	116 (2)	H15A—C15—H15B	109.5
N4—N3—H3N	123 (2)	C14—C15—H15C	109.5
C2—C3—C4	108.4 (3)	H15A—C15—H15C	109.5
C2—C3—Fe1	70.1 (2)	H15B—C15—H15C	109.5
C4—C3—Fe1	69.61 (17)	H1WB—O1W—H1WA	109 (4)
C2—C3—H3A	125.8

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···N4	0.84 (3)	2.30 (3)	2.628 (3)	104 (2)
N3—H3N···O1^ii	0.87 (3)	2.06 (3)	2.908 (3)	164 (3)
O1W—H1WA···O1	0.80 (4)	2.04 (4)	2.831 (3)	172 (4)
O1W—H1WB···N4^iii	0.78 (4)	2.39 (4)	3.123 (4)	156 (4)

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