Bis­[1-(2,4-di­chloro­benzoyl­hydrazono­methyl)­ferrocene(1-)]­nickel(II)

The title complex, [Ni(C₁₈H₁₃Cl₂FeN₂O)₂], results from the reaction of Ni(OAc)₂·4H₂O (Ac is acetyl) and 2,4-di­chloro­benzoyl­hydrazine in an­hydro­us ethanol. The complex mol­ecule is centrosymmetric, with the enolizable O atom and the azomethine N atom of the ligand coordinating to the nickel ion to form a five-membered chelate ring. The N₂O₂ coordinating atoms and the central Ni ion are coplanar.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.036
• wR factor = 0.094
• Data-to-parameter ratio = 13.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

Schiff bases from acylhydrazine and their complexes have strong antitumour and antivirus activities (Ali et al., 1984), while the ferrocenyl group can improve these properties (Ali et al., 1973). Some ferrocene derivatives are excellent non-linear optical materials (Long, 1995) because they can act as strong electron donors and contain electron-flow bridges. Due to the possible wide-ranging uses, the structures of these compounds are of interest. In the present work, we report a new crystal structure of an Ni complexe of a ferrocene derivative, (I).

In (I), the Ni atom is located at a center of symmetry (Fig. 1). The sum of the interior angles in the chelate ring is 540.0 (3)°, so the five atoms involved are coplanar. The sum of the three bond angles around C12 is 359.8 (2)°, which shows that atom C12 has almost sp² hybridization. The Ni—O and Ni—N bond distances are normal (Table 1). As expected, the C12—O1 bond length [1.304 (3) Å] lies between those of a C—O single bond and a C═O double bond. The bond lengths N1—C11 [1.299 (3) Å] and N2—C12 [1.305 (3) Å] are identical and close to that of typical C═N (1.30 Å). Those data shows that the –CH═N—N═C—O fragment of the ligand remains as a conjugated system even after the loss of an H atom from its enolized carbonyl O atom. There are intramolecular non-traditional hydrogen bonds (Table 2). There are also intermolecular close contacts between the Cl and O atoms; O1···Cl2(x, 1/2 − y, −1/2 + z) 3.212 (2) Å (Fig. 2).

S2. Experimental

Ferrocenecarboxaldehyde was dissolved in anhydrous ethanol and the resulting solution was added dropwise to a solution of 2,4-dichlorobenzoylhydrazine in anhydrous ethanol under stirring and reflux. A red precipitate appeared immediately and the reaction mixture was allowed to reflux for 2 h under stirring. The mixture was cooled to room temperature and the product collected on a Buchner funnel, washed twice with ethanol and diethyl ether, respectively, recrystallized from anhydrous ethanol and dried in vacuo. The product obtained was dissolved in anhydrous ethanol, then a solution of Ni(OAc)₂·4H₂O in anhydrous ethanol was added dropwise to it under stirring at room temperature. The mixture was stirred continuously for 20 min at room temperature and for 6–8 h under reflux. A red solid formed, was filtered off, and the filtrate collected. After four weeks, red crystals of (I) suitable for diffraction analysis had precipitated from the mother solution.

S3. Refinement

The positions of all H atoms were fixed geometrically and refined as riding on their parent atoms (C—H 0.93 Å).

Computing details

Data collection: CAD-4 SDP/VAX (Enraf-Nonius, 1989); cell refinement: CAD-4 SDP/VAX; data reduction: TEXSAN (Molecular Structure Corporation, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.
	Fig. 2. A packing diagram of (I), showing the Cl···O short contacts.

(I)

Crystal data

[Ni(C18H13Cl2FeN2O)2]	F(000) = 868
Mr = 858.82	Dx = 1.631 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 7.032 (1) Å	θ = 12.1–14.9°
b = 22.455 (4) Å	µ = 1.70 mm^−1
c = 11.075 (2) Å	T = 293 K
β = 91.36 (3)°	Block, red
V = 1748.3 (5) Å^3	0.3 × 0.25 × 0.2 mm
Z = 2

Data collection

Enraf-Nonius CAD-4 diffractometer	2869 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.056
Graphite monochromator	θmax = 25.0°, θmin = 1.8°
ω/2θ scans	h = −8→8
Absorption correction: ψ scan (North et al., 1968)	k = 0→26
Tmin = 0.599, Tmax = 0.716	l = 0→13
5629 measured reflections	5 standard reflections every 300 reflections
3082 independent reflections	intensity decay: none

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.01P)^2] where P = (Fo^2 + 2Fc^2)/3
3082 reflections	(Δ/σ)max = 0.001
223 parameters	Δρmax = 0.17 e Å^−3
0 restraints	Δρmin = −0.76 e Å^−3

Special details

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 structure was solved by direct methods (Sheldrick, 1990) and successive difference Fourier syntheses. 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 (Ų)

	x	y	z	Uiso*/Ueq
Ni1	1.0000	0.5000	0.0000	0.04017 (14)
Fe1	0.43926 (6)	0.588888 (18)	0.31346 (3)	0.04755 (14)
Cl1	0.57023 (12)	0.32689 (4)	0.17712 (10)	0.0783 (3)
Cl2	1.04987 (16)	0.20171 (4)	0.46311 (10)	0.0853 (3)
O1	1.0429 (3)	0.42910 (8)	0.08031 (17)	0.0456 (4)
N1	0.7827 (3)	0.50276 (9)	0.09227 (19)	0.0411 (5)
N2	0.7607 (3)	0.45365 (10)	0.1710 (2)	0.0478 (5)
C1	0.4726 (4)	0.54552 (12)	0.1523 (2)	0.0436 (6)
C2	0.3918 (4)	0.50612 (12)	0.2412 (3)	0.0504 (7)
H2	0.4444	0.4706	0.2696	0.060*
C3	0.2196 (4)	0.53150 (14)	0.2765 (3)	0.0582 (8)
H3	0.1382	0.5155	0.3329	0.070*
C4	0.1895 (4)	0.58517 (15)	0.2129 (3)	0.0613 (8)
H4	0.0845	0.6100	0.2197	0.074*
C5	0.3451 (4)	0.59492 (13)	0.1372 (3)	0.0530 (7)
H5	0.3618	0.6275	0.0867	0.064*
C6	0.6994 (5)	0.61289 (18)	0.3808 (4)	0.0744 (10)
H6	0.8149	0.6040	0.3459	0.089*
C7	0.6053 (5)	0.57744 (17)	0.4664 (3)	0.0715 (9)
H7	0.6470	0.5411	0.4975	0.086*
C8	0.4394 (6)	0.60700 (19)	0.4951 (3)	0.0766 (11)
H8	0.3500	0.5937	0.5495	0.092*
C9	0.4282 (7)	0.66016 (18)	0.4288 (4)	0.0860 (12)
H9	0.3305	0.6880	0.4321	0.103*
C10	0.5874 (6)	0.66429 (17)	0.3574 (3)	0.0793 (11)
H10	0.6153	0.6950	0.3042	0.095*
C11	0.6500 (4)	0.54300 (12)	0.0885 (2)	0.0429 (6)
H11	0.6721	0.5749	0.0373	0.051*
C12	0.9064 (4)	0.41871 (11)	0.1551 (2)	0.0417 (6)
C13	1.1072 (4)	0.35503 (13)	0.2872 (3)	0.0569 (8)
H13	1.2025	0.3831	0.2761	0.068*
C14	1.1472 (5)	0.30587 (13)	0.3578 (3)	0.0594 (8)
H14	1.2671	0.3007	0.3937	0.071*
C15	1.0048 (5)	0.26434 (13)	0.3741 (3)	0.0546 (7)
C16	0.8277 (5)	0.27134 (13)	0.3190 (3)	0.0580 (8)
H16	0.7336	0.2428	0.3292	0.070*
C17	0.7919 (4)	0.32114 (12)	0.2484 (3)	0.0492 (7)
C18	0.9311 (4)	0.36445 (11)	0.2321 (2)	0.0434 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0513 (3)	0.0307 (3)	0.0387 (3)	0.00051 (18)	0.0050 (2)	0.00209 (18)
Fe1	0.0564 (3)	0.0447 (3)	0.0416 (2)	0.00424 (16)	0.00318 (19)	−0.00301 (17)
Cl1	0.0571 (5)	0.0640 (6)	0.1131 (8)	−0.0117 (4)	−0.0126 (5)	0.0252 (5)
Cl2	0.1123 (8)	0.0593 (6)	0.0833 (7)	−0.0073 (5)	−0.0168 (5)	0.0354 (5)
O1	0.0545 (11)	0.0347 (10)	0.0478 (11)	0.0015 (8)	0.0082 (9)	0.0054 (8)
N1	0.0493 (13)	0.0336 (11)	0.0404 (12)	0.0000 (9)	0.0011 (10)	−0.0007 (9)
N2	0.0584 (14)	0.0375 (12)	0.0477 (13)	0.0010 (10)	0.0043 (11)	0.0030 (10)
C1	0.0506 (15)	0.0446 (14)	0.0353 (13)	0.0047 (11)	−0.0012 (11)	−0.0031 (11)
C2	0.0545 (17)	0.0424 (16)	0.0542 (17)	−0.0029 (11)	0.0009 (13)	−0.0010 (12)
C3	0.0506 (18)	0.067 (2)	0.0573 (19)	−0.0056 (14)	0.0046 (14)	0.0010 (15)
C4	0.0479 (18)	0.071 (2)	0.065 (2)	0.0122 (14)	−0.0005 (15)	−0.0032 (16)
C5	0.0556 (18)	0.0581 (18)	0.0452 (16)	0.0112 (13)	0.0004 (13)	0.0019 (13)
C6	0.063 (2)	0.088 (3)	0.073 (2)	−0.0139 (19)	−0.0044 (18)	−0.017 (2)
C7	0.092 (3)	0.068 (2)	0.054 (2)	−0.0029 (19)	−0.0179 (18)	−0.0031 (17)
C8	0.093 (3)	0.093 (3)	0.0440 (19)	−0.008 (2)	0.0051 (17)	−0.0210 (18)
C9	0.096 (3)	0.073 (3)	0.076 (3)	0.017 (2)	0.005 (2)	−0.027 (2)
C10	0.114 (3)	0.059 (2)	0.065 (2)	−0.020 (2)	−0.009 (2)	−0.0026 (17)
C11	0.0530 (16)	0.0392 (14)	0.0367 (13)	−0.0002 (11)	0.0055 (12)	0.0002 (11)
C12	0.0537 (16)	0.0314 (13)	0.0399 (14)	−0.0042 (11)	0.0006 (12)	−0.0014 (10)
C13	0.0604 (19)	0.0406 (16)	0.069 (2)	−0.0055 (12)	−0.0089 (15)	0.0063 (14)
C14	0.069 (2)	0.0454 (17)	0.063 (2)	−0.0063 (14)	−0.0158 (15)	0.0084 (14)
C15	0.071 (2)	0.0446 (16)	0.0486 (16)	0.0004 (14)	−0.0002 (14)	0.0100 (13)
C16	0.069 (2)	0.0447 (16)	0.0599 (19)	−0.0087 (14)	0.0036 (16)	0.0115 (14)
C17	0.0588 (18)	0.0409 (15)	0.0478 (16)	−0.0001 (12)	0.0016 (13)	0.0051 (12)
C18	0.0533 (16)	0.0367 (14)	0.0404 (15)	0.0000 (11)	0.0066 (12)	−0.0016 (11)

Geometric parameters (Å, º)

Ni1—O1^i	1.8450 (17)	C3—H3	0.9300
Ni1—O1	1.8450 (17)	C4—C5	1.411 (4)
Ni1—N1^i	1.859 (2)	C4—H4	0.9300
Ni1—N1	1.859 (2)	C5—H5	0.9300
Fe1—C6	2.032 (4)	C6—C7	1.414 (5)
Fe1—C10	2.041 (4)	C6—C10	1.418 (6)
Fe1—C3	2.045 (3)	C6—H6	0.9300
Fe1—C2	2.048 (3)	C7—C8	1.386 (5)
Fe1—C9	2.050 (4)	C7—H7	0.9300
Fe1—C7	2.050 (4)	C8—C9	1.403 (6)
Fe1—C5	2.051 (3)	C8—H8	0.9300
Fe1—C1	2.052 (3)	C9—C10	1.389 (5)
Fe1—C8	2.052 (3)	C9—H9	0.9300
Fe1—C4	2.059 (3)	C10—H10	0.9300
Cl1—C17	1.735 (3)	C11—H11	0.9300
Cl2—C15	1.742 (3)	C12—C18	1.495 (3)
O1—C12	1.304 (3)	C13—C14	1.378 (4)
N1—C11	1.299 (3)	C13—C18	1.383 (4)
N1—N2	1.416 (3)	C13—H13	0.9300
N2—C12	1.305 (3)	C14—C15	1.383 (4)
C1—C5	1.434 (4)	C14—H14	0.9300
C1—C11	1.449 (4)	C15—C16	1.383 (4)
C1—C2	1.450 (4)	C16—C17	1.384 (4)
C2—C3	1.402 (4)	C16—H16	0.9300
C2—H2	0.9300	C17—C18	1.395 (4)
C3—C4	1.409 (4)
O1^i—Ni1—O1	180.00 (11)	C4—C3—Fe1	70.44 (19)
O1^i—Ni1—N1^i	83.73 (8)	C2—C3—H3	125.4
O1—Ni1—N1^i	96.27 (8)	C4—C3—H3	125.4
O1^i—Ni1—N1	96.27 (8)	Fe1—C3—H3	125.7
O1—Ni1—N1	83.73 (8)	C3—C4—C5	108.7 (3)
N1^i—Ni1—N1	180.00 (12)	C3—C4—Fe1	69.39 (19)
C6—Fe1—C10	40.74 (16)	C5—C4—Fe1	69.62 (18)
C6—Fe1—C3	155.44 (15)	C3—C4—H4	125.7
C10—Fe1—C3	161.66 (16)	C5—C4—H4	125.7
C6—Fe1—C2	121.41 (15)	Fe1—C4—H4	126.9
C10—Fe1—C2	157.48 (15)	C4—C5—C1	107.6 (3)
C3—Fe1—C2	40.06 (12)	C4—C5—Fe1	70.22 (19)
C6—Fe1—C9	67.13 (17)	C1—C5—Fe1	69.57 (16)
C10—Fe1—C9	39.70 (16)	C4—C5—H5	126.2
C3—Fe1—C9	125.23 (16)	C1—C5—H5	126.2
C2—Fe1—C9	160.67 (15)	Fe1—C5—H5	125.6
C6—Fe1—C7	40.53 (15)	C7—C6—C10	108.3 (4)
C10—Fe1—C7	68.26 (16)	C7—C6—Fe1	70.5 (2)
C3—Fe1—C7	119.92 (14)	C10—C6—Fe1	70.0 (2)
C2—Fe1—C7	107.05 (14)	C7—C6—H6	125.8
C9—Fe1—C7	67.20 (17)	C10—C6—H6	125.8
C6—Fe1—C5	126.84 (14)	Fe1—C6—H6	125.3
C10—Fe1—C5	108.88 (14)	C8—C7—C6	107.1 (4)
C3—Fe1—C5	68.03 (13)	C8—C7—Fe1	70.3 (2)
C2—Fe1—C5	69.03 (12)	C6—C7—Fe1	69.0 (2)
C9—Fe1—C5	121.68 (15)	C8—C7—H7	126.5
C7—Fe1—C5	163.58 (14)	C6—C7—H7	126.5
C6—Fe1—C1	108.97 (14)	Fe1—C7—H7	125.8
C10—Fe1—C1	122.21 (14)	C7—C8—C9	108.9 (4)
C3—Fe1—C1	68.16 (12)	C7—C8—Fe1	70.18 (19)
C2—Fe1—C1	41.43 (11)	C9—C8—Fe1	69.9 (2)
C9—Fe1—C1	156.83 (15)	C7—C8—H8	125.5
C7—Fe1—C1	125.78 (14)	C9—C8—H8	125.5
C5—Fe1—C1	40.90 (11)	Fe1—C8—H8	125.9
C6—Fe1—C8	66.92 (16)	C10—C9—C8	108.6 (4)
C10—Fe1—C8	67.27 (16)	C10—C9—Fe1	69.8 (2)
C3—Fe1—C8	107.69 (15)	C8—C9—Fe1	70.1 (2)
C2—Fe1—C8	123.99 (15)	C10—C9—H9	125.7
C9—Fe1—C8	39.99 (16)	C8—C9—H9	125.7
C7—Fe1—C8	39.48 (15)	Fe1—C9—H9	126.0
C5—Fe1—C8	155.85 (15)	C9—C10—C6	107.0 (4)
C1—Fe1—C8	161.71 (15)	C9—C10—Fe1	70.5 (2)
C6—Fe1—C4	163.41 (15)	C6—C10—Fe1	69.3 (2)
C10—Fe1—C4	125.92 (16)	C9—C10—H10	126.5
C3—Fe1—C4	40.17 (12)	C6—C10—H10	126.5
C2—Fe1—C4	67.84 (13)	Fe1—C10—H10	125.3
C9—Fe1—C4	108.91 (16)	N1—C11—C1	129.6 (2)
C7—Fe1—C4	154.61 (14)	N1—C11—H11	115.2
C5—Fe1—C4	40.17 (12)	C1—C11—H11	115.2
C1—Fe1—C4	67.90 (12)	O1—C12—N2	124.7 (2)
C8—Fe1—C4	121.24 (15)	O1—C12—C18	115.5 (2)
C12—O1—Ni1	110.27 (16)	N2—C12—C18	119.6 (2)
C11—N1—N2	118.2 (2)	C14—C13—C18	122.8 (3)
C11—N1—Ni1	127.21 (18)	C14—C13—H13	118.6
N2—N1—Ni1	114.56 (16)	C18—C13—H13	118.6
C12—N2—N1	106.7 (2)	C13—C14—C15	118.4 (3)
C5—C1—C11	121.1 (2)	C13—C14—H14	120.8
C5—C1—C2	107.3 (2)	C15—C14—H14	120.8
C11—C1—C2	131.5 (3)	C16—C15—C14	120.9 (3)
C5—C1—Fe1	69.52 (16)	C16—C15—Cl2	119.4 (2)
C11—C1—Fe1	124.0 (2)	C14—C15—Cl2	119.7 (3)
C2—C1—Fe1	69.13 (15)	C15—C16—C17	119.4 (3)
C3—C2—C1	107.2 (3)	C15—C16—H16	120.3
C3—C2—Fe1	69.88 (17)	C17—C16—H16	120.3
C1—C2—Fe1	69.44 (15)	C16—C17—C18	121.1 (3)
C3—C2—H2	126.4	C16—C17—Cl1	117.8 (2)
C1—C2—H2	126.4	C18—C17—Cl1	121.0 (2)
Fe1—C2—H2	125.9	C13—C18—C17	117.4 (3)
C2—C3—C4	109.2 (3)	C13—C18—C12	117.8 (2)
C2—C3—Fe1	70.06 (17)	C17—C18—C12	124.7 (3)

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N2	0.93	2.53	2.969 (4)	109
C11—H11···O1^i	0.93	2.42	2.957 (3)	117

Symmetry code: (i) −x+2, −y+1, −z.